WO2022231006A1 - Oxidation hair dye - Google Patents

Oxidation hair dye Download PDF

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Publication number
WO2022231006A1
WO2022231006A1 PCT/JP2022/019463 JP2022019463W WO2022231006A1 WO 2022231006 A1 WO2022231006 A1 WO 2022231006A1 JP 2022019463 W JP2022019463 W JP 2022019463W WO 2022231006 A1 WO2022231006 A1 WO 2022231006A1
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WIPO (PCT)
Prior art keywords
mass
hair dye
less
oxidative hair
dye
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Application number
PCT/JP2022/019463
Other languages
French (fr)
Japanese (ja)
Inventor
圭実 伊藤
誠 唐渡
朋也 園田
Original Assignee
ホーユー株式会社
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Publication date
Priority claimed from JP2021194667A external-priority patent/JP2022171541A/en
Priority claimed from JP2021194670A external-priority patent/JP2022171544A/en
Application filed by ホーユー株式会社 filed Critical ホーユー株式会社
Publication of WO2022231006A1 publication Critical patent/WO2022231006A1/en

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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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20—Halogens; Compounds thereof
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • 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
    • A61K8/86—Polyethers
    • 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
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the present invention relates to an oxidation hair dye containing a coupler.
  • the oxidation dye polymer inside the hair does not decompose easily, the decolorization performance is low. It was necessary to destain using an agent. Furthermore, in some cases, a single destaining treatment cannot be sufficiently destained.
  • Oxidative hair dyes have been known which are used for re-dyeing the hair to a clear and bright tone by decomposing the dark tone oxidation dye polymer inside the hair without performing destaining treatment with a destaining agent.
  • the oxidative hair dye disclosed in Patent Document 1 contains a diamine-based dye intermediate or the like as a main component of the dye, thereby improving the hair dyeing power.
  • a first object of the present invention is to provide an oxidative hair dye that improves hair dyeing power, maintains destaining performance, and suppresses background staining.
  • a second object of the present invention is to provide an oxidative hair dye capable of improving destaining performance and improving levelness of dyeing.
  • the oxidative hair dye of the present invention for solving the first problem is an oxidative hair dye containing (A) a coupler, wherein the oxidative hair dye has a component (A) content of (B) The mass ratio (B/A) of the content of the dye intermediate is 0.4 or less, (A) contains 0.3 mass% or more of the component, and (C) the nonionic surfactant is C1) Characterized by containing a nonionic surfactant with an HLB of less than 10.
  • the oxidative hair dye of the present invention is specified to contain a nonionic surfactant having an HLB of less than 10 as the ratio of the coupler to the dye intermediate, the content of the coupler, and the nonionic surfactant. Therefore, it is possible to improve the hair dyeing power and suppress the background stain while maintaining the destaining performance.
  • component (C) contains component (C1) and (C2) a nonionic surfactant having an HLB of 10 or more. It is characterized by being two or more nonionic surfactants. According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power, and can suppress background staining while maintaining the destaining performance.
  • one embodiment of the oxidative hair dye of the present invention for solving the first problem is characterized in that the oxidative hair dye contains (D) an iodine compound. According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power by containing the iodine compound.
  • the oxidative hair dye of the present invention contains (E) a polyhydric alcohol in an amount of 0.5 based on the mass of the oxidative hair dye. It is characterized by containing not more than mass % or not containing (E) polyhydric alcohol. According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power.
  • the oxidative hair dye of the present invention for solving the second problem is an oxidative hair dye obtained by mixing the first agent and the second agent, and containing (A) a coupler.
  • the mass ratio (B/A) of the content of the dye intermediate (B) to the content of the component (A) is 0.4 or less, and the content of the component (A) is 0.3% by mass or more.
  • the oxidative hair dye of the present invention has a volume increase rate of 30% or more, and by increasing the volume of the oxidative hair dye, it is possible to suppress uneven application even with a limited amount of agent, and even dyeing can be achieved. can improve sexuality.
  • one embodiment of the oxidative hair dye of the present invention for solving the second problem described above contains 2,4-diaminophenoxyethanol as the component (A), and 2,4-diaminophenoxyethanol in the oxidative hair dye.
  • the content of diaminophenoxyethanol is 0.3% by mass or more. According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power.
  • one embodiment of the oxidative hair dye of the present invention for solving the second problem is characterized by further containing (F) a catalyst and (G) an oxidizing agent.
  • the oxidative hair dye of the present invention foams due to the reaction between the catalyst and the oxidizing agent, and can improve the hair dyeing power.
  • the content of the component (F) is 0.005% by mass or more and 0.25% by mass or less. Characterized by according to this feature, the oxidative hair dye of the present invention can appropriately control the amount of foaming caused by the catalyst and the oxidizing agent, and further improve the uniformity of dyeing.
  • an oxidative hair dye that improves hair dyeing power, maintains de-dyeing performance, and further suppresses background staining.
  • Oxidative hair dyes are distributed by dividing the oxidizing agent and the oxidative dye into separate agents, and the oxidative dye develops color inside the hair.
  • a first agent containing an oxidation dye and a second agent containing a peroxide are provided, and these agents are mixed and used.
  • mixing and using means applying a plurality of agents to the hair in one application operation, and not only the operation of mixing and using immediately before, but also the first agent and the second agent. is taken on a comb or the like and mixed on the hair using a comb or the like.
  • the oxidative hair dye of the present invention is a multi-component oxidative hair dye, preferably a two-component oxidative hair dye.
  • a two-component oxidative hair dye consists of a first component containing an oxidation dye and a second component containing an oxidizing agent.
  • the oxidative hair dye of the present invention refers to a multi-component oxidative hair dye, for example, the state of a mixture of a first agent and a second agent, and the composition thereof means, for example, the first agent and the second agent.
  • the composition of the mixture is shown.
  • the oxidative hair dye is typically a two-agent type consisting of a first agent and a second agent. It may be a drug formula.
  • the first agent of a two-agent type is divided into two agents, one containing a coupler and an optional alkaline agent, and the other having a composition other than that, to constitute a three-agent oxidative hair dye. good too. In this case, emulsion stability is further improved.
  • an applicator such as a comb, brush, brush, or applicator may be used to apply the oxidative hair dye to the hair. may be applied to
  • first embodiment and “second embodiment”
  • POE indicates a polyoxyethylene chain
  • POP indicates a polyoxypropylene chain
  • the numbers in parentheses following these indicate the number of added moles.
  • the numbers in parentheses following alkyl indicate the number of carbon atoms in the fatty acid chain.
  • the lower limit is preferably 2000 mPa ⁇ s or more, more preferably 5000 mPa ⁇ s or more, and still more preferably 10000 mPa ⁇ s or more.
  • the upper limit is preferably 50,000 mPa ⁇ s or less, more preferably 40,000 mPa ⁇ s or less, and still more preferably 30,000 mPa ⁇ s or less, from the viewpoint of operability when applied to hair.
  • the viscosity of the oxidative hair dye can be adjusted by adding an anionic surfactant, a cationic surfactant, or a thickening agent such as a water-soluble polymer.
  • the oxidative hair dye according to the first embodiment contains (A) a coupler and (C) a nonionic surfactant, (B) a dye intermediate, (D) an iodine compound or/and (E) a polyhydric alcohol may contain. Furthermore, it may contain components other than components (A) to (E).
  • Each component used in the oxidative hair dye according to the first embodiment will be described in detail below.
  • the content (% by mass) of each component indicates the content in the oxidative hair dye in which each agent is mixed, unless otherwise specified.
  • the oxidative hair dye according to the first embodiment contains (A) a coupler.
  • (A) Couplers mainly include m-diamines, aminophenols and diphenols, and specific examples include resorcinol, 5-amino-o-cresol, m-aminophenol, ⁇ -naphthol (1 -naphthol), 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, N, Examples include N-diethyl-m-aminophenol, phenylmethylpyrazolone, 1,5-dihydroxynaphthalene, catechol, pyrogallol, phloroglucin, gallic acid, hydroquinone, 3,3'-iminodiphenyl, tannic acid and salts
  • the (A) coupler according to the first embodiment is preferably 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5-(2-hydroxyethylamino)-2-methylphenol, 1-naphthol, 5 -Amino-o-cresol, 1,5-dihydroxynaphthalene, m-aminophenol, and salts thereof can be used.
  • 2,4-diaminophenoxyethanol and salts thereof are particularly preferred. It is presumed that 2,4-diaminophenoxyethanol further improves hair dyeing power due to a synergistic effect with (C1) a nonionic surfactant having an HLB of less than 10.0, which will be described later.
  • the content of component (A) in the oxidative hair dye according to the first embodiment is not particularly limited, but is, for example, 0.3% by mass or more.
  • the lower limit is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.6% by mass or more, and still more preferably 0.7% by mass or more.
  • the upper limit is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, even more preferably 5.0% by mass or less, and most preferably 3.5% by mass or less.
  • the content is 0.3% by mass or more, the hair dyeing power is improved, and when the content is 10.0% by mass or less, the destaining performance can be further improved, and the effect of suppressing background stains can be improved.
  • the (A) coupler is a salt
  • the content of the (A) coupler is the value in the desalted form.
  • the preferred amount of 2,4-diaminophenoxyethanol in the oxidative hair dye as the component (A) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of hair dyeing power. It is 0.15% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.25% by mass or more.
  • the upper limit is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 3.0% by mass or less, and even more preferably 2.0% by mass, from the viewpoint of the effect of suppressing background stains. % or less.
  • the content of component (B) in the oxidative hair dye according to the first embodiment is not particularly limited, but for example, the mass ratio (B /A) is from 0.0 to 0.4.
  • the upper limit is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less.
  • a mass ratio of 0.0 means that the oxidative hair dye does not substantially contain the component (B).
  • the content used for calculating the above mass ratio is the value of the desalted form of both the (A) component and the (B) component.
  • the upper limit of the content of the dye intermediate (B) in the oxidative hair dye according to the first embodiment is appropriately set within the range of the mass ratio (B/A) of the content, but preferably 1 0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and particularly preferably the oxidative hair dye does not substantially contain (B) the dye intermediate. be.
  • “substantially does not contain” means that the content is 0.1% by mass or less.
  • the content of the dye intermediate (B) is 1.0% by mass or less, the destaining performance can be further improved.
  • the (B) dye intermediate is a salt
  • the content of the (B) dye intermediate is the value in the desalted form.
  • the oxidative hair dye according to the first embodiment contains (C1) a nonionic surfactant having an HLB of less than 10 as (C) a nonionic surfactant.
  • the hair dyeing power can be improved, and the effect of suppressing background stains can be improved.
  • nonionic surfactants include ether-type nonionic surfactants (POE alkyl ethers, POE alkylphenyl ethers, POE/POP alkyl ethers, etc.), ester-type nonionic surfactants (POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, polyglycerin fatty acid esters, monoglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, etc.), alkyl glucosides (alkyl polyglucosides, etc.) etc.
  • ether-type nonionic surfactants POE alkyl ethers, POE alkylphenyl ethers, POE/POP alkyl ethers, etc.
  • ester-type nonionic surfactants POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty
  • ether-type nonionic surfactants include POE cetyl ether (ceteth), POE stearyl ether (steareth), POE behenyl ether, POE oleyl ether (oleth), POE lauryl ether (laureth), POE octyldodecyl ether, POE hexyl decyl ether, POE isostearyl ether, POE nonylphenyl ether, POE octylphenyl ether, POE.POP cetyl ether, POE.POP decyltetradecyl ether and the like.
  • ester-type nonionic surfactants include POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monopalmitate, POE sorbitan monolaurate, POE sorbitan trioleate, POE glycerol monostearate, and monomyristin.
  • POE glycerin POE sorbitol tetraoleate, POE sorbitol hexastearate, POE sorbitol monolaurate, POE sorbitol beeswax, polyethylene glycol monooleate, polyethylene glycol monostearate, polyethylene glycol monolaurate, lipophilic glycerol monooleate, Lipophilic glyceryl monostearate, self-emulsifying glyceryl monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, sucrose fatty acid ester, decaglyceryl monolaurate, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl monomyristate and the like.
  • alkyl glucosides include alkyl (8-16) glucoside, POE methyl glucoside, POE methyl dioleate glucoside, and the like.
  • the (C) component of the oxidative hair dye according to the first embodiment includes (C1) one or more nonionic surfactants with an HLB of less than 10.0 and (C2) one nonionic surfactant with an HLB of 10.0 or more. It is preferable to contain two or more species having at least one species. As a result, it is possible to further improve the hair dyeing power and to suppress the stain on the skin.
  • nonionic surfactants having an HLB of less than 10.0 include POE (2) cetyl ether ⁇ 8.0>, POE (2) stearyl ether ⁇ 8.0>, POE (4) stearyl ether ⁇ 9 .0>, POE (5) behenyl ether ⁇ 7.0>, POE (2) oleyl ether ⁇ 7.5>, POE (2) lauryl ether ⁇ 9.5>, POE (1) POP (4) cetyl ether ⁇ 9.5> can be mentioned.
  • (C1) is preferably POE (2) cetyl ether ⁇ 8.0>, POE (2) stearyl ether ⁇ 8.0>, POE (4 ) stearyl ether ⁇ 9.0>, POE (5) behenyl ether ⁇ 7.0>, POE (1) POP (4) cetyl ether ⁇ 9.5>.
  • the numerical value in ⁇ > is the measured value of HLB, and the same applies to the numerical value in ⁇ > below.
  • ester-type nonionic surfactants with an HLB of less than 10.0, polyoxyethylene glyceryl stearate ⁇ 9.5>, POE tetraoleate (6) sorbitol ⁇ 8.5>, POE (6) sorbitol beeswax ⁇ 7 .5>, POE (20) sorbitol beeswax ⁇ 9.5>, polyethylene glycol monooleate (6E.0.) ⁇ 8.5>, polyethylene glycol monostearate (2E.O.) ⁇ 4.0>, Polyethylene glycol monostearate ⁇ 6.5>, glyceryl monostearate ⁇ 3.0>, glyceryl monostearate ⁇ 4.0>, glyceryl monostearate (self-emulsifying type) ⁇ 8.0>, glyceryl monostearate (Self-emulsifying type) ⁇ 5.5>, sorbitan monooleate ⁇ 4.5>, sorbitan sesquioleate ⁇ 9
  • (C2) As ether-type nonionic surfactants with an HLB of 10.0 or more, POE (30) cetyl ether ⁇ 19.5>, POE (25) cetyl ether ⁇ 18.5>, POE (20) cetyl ether ⁇ 17.0 >, POE (15) cetyl ether ⁇ 15.5>, POE (10) cetyl ether ⁇ 13.5>, POE (5.5) cetyl ether ⁇ 10.5>, POE (20) stearyl ether ⁇ 18.0 >, POE (30) behenyl ether ⁇ 18.5>, POE (20) behenyl ether ⁇ 16.5>, POE (10) behenyl ether ⁇ 10.0>, POE (10) oleyl ether ⁇ 14.5>, POE (15) oleyl ether ⁇ 16.0>, POE (20) oleyl ether ⁇ 17.0>, POE (50) oleyl ether ⁇ 18.0>, POE (9) lauryl ether
  • the (C2) component according to the first embodiment is preferably POE (30) cetyl ether ⁇ 19.5>, POE (25) cetyl ether ⁇ 18. 5> and POE (20) cetyl ether ⁇ 17.0>.
  • ester-type nonionic surfactants having an HLB of 10.0 or more include POE tetraoleate (60) sorbitol ⁇ 14.0>, POE tetraoleate (30) sorbitol ⁇ 11.5>, and POE tetraoleate.
  • the HLB value of the present invention is an actual measurement value.
  • the HLB value is according to W.W. C. Conceived by Griffin, it is a numerical value given to nonionic surfactants, and represents the balance of strength between the lipophilic group (alkyl group) and the hydrophilic group (ethylene oxide chain) of the nonionic surfactant. It is.
  • As the HLB value a measured value calculated by an emulsification method is used (see "Handbook - Cosmetics/Materials for Pharmaceutical Preparations" Nikko Chemicals Co., Ltd. (published February 1, 1977)).
  • sorbitan monostearate for example, NIKKOL SS-10 manufactured by Nikko Chemicals Co., Ltd., HLB value 4.7
  • polyoxyethylene sorbitan monostearate for example, Nikko Chemicals NIKKOL TS-10, HLB value 14.9
  • Liquid paraffin is used as the material to be emulsified. Liquid paraffin should be measured on a case-by-case basis if variations are expected depending on the type or lot. Liquid paraffin is emulsified with the two types of surfactants described above, the optimum ratio of surfactants is determined, and the required HLB value of liquid paraffin (HLB value to be emulsified) is determined.
  • a calculation formula is shown in Formula (1).
  • the required HLB value of normal liquid paraffin is about 10.1 to 10.3, depending on the type and lot.
  • the HLB value of the unknown surfactant is measured using liquid paraffin from which the required HLB value was determined. If the unknown surfactant is hydrophilic, it is combined with sorbitan monostearate, and if the unknown surfactant is hydrophobic, it is combined with polyoxyethylene sorbitan monostearate to emulsify the liquid paraffin and stabilize it. An optimum ratio at a certain point is determined and calculated by applying the HLB value of the unknown surfactant to the above formula (1) as x.
  • the mass ratio (( C)/((A)+(B))) is between 0.1 and 30.0.
  • the lower limit is preferably 0.3 or more, more preferably 0.5 or more.
  • the upper limit is preferably 25.0 or less, more preferably 20.0 or less.
  • the HLB value of component (C1) is not particularly limited as long as it is less than 10.0.
  • the lower limit is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, and most preferably 7.0 or more, and the upper limit is preferably 9.9 or less. It is more preferably 9.8 or less, still more preferably 9.7 or less.
  • the HLB value of component (C2) is not particularly limited as long as it is 10.0 or more, but is, for example, 10.0 or more and less than 20.0.
  • the lower limit is preferably 11.0 or more, more preferably 12.5 or more, still more preferably 14.0 or more, and most preferably 15.5 or more, and the upper limit is preferably 19.9 or less.
  • the component (C1) and the component (C2) are within the above range, the emulsification stability of the oxidative hair dye can be improved, while the hair dyeing power and the effect of suppressing background stains can be improved.
  • the mass ratio (C1)/(C2) of the content of component (C1) to the content of component (C2) is 1.0 to 8.0.
  • the lower limit is preferably 1.0 or more, more preferably 1.25 or more, still more preferably 1.5 or more, and most preferably 1.75 or more, and the upper limit is preferably 7.0 or less. It is more preferably 6.0 or less, still more preferably 5.0 or less.
  • iodine compounds include alkali metal salts of iodine compounds such as potassium iodide, sodium iodide, lithium iodide and ammonium iodide, hydrogen iodide, cesium iodide and silver iodide. From the viewpoint of hair dyeing power, potassium iodide, sodium iodide and ammonium iodide are particularly preferred.
  • natural materials containing iodine for example, extracts containing iodine compounds such as iodine garlic extract may be applied.
  • One (D) component may be used alone, or two or more (D) components may be used in combination.
  • the content of (D) the iodine compound in the oxidative hair dye after mixing the agents is not particularly limited, but is, for example, 0.001 to 5.0% by mass.
  • the lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.015% by mass or more, and most preferably 0.02% by mass or more
  • the upper limit is , preferably 4.5% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less.
  • the iodine compound preferably acts with the (A) coupler in the presence of a nonionic surfactant having an HLB value of less than 10.0, which is the component (C1), to improve hair dyeing power. effective.
  • a nonionic surfactant having an HLB value of less than 10.0, which is the component (C1), to improve hair dyeing power.
  • the mass ratio ((D)/((A)+(B ))) is between 0.005 and 1.0.
  • the lower limit is preferably 0.01 or more, more preferably 0.015 or more.
  • the upper limit is preferably 0.8 or less, more preferably 0.5 or less.
  • the mass ratio (D/C) of the content of the (D) iodine compound to the content of the (C) nonionic surfactant it is possible to improve the antifouling effect.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol (eg, PEG400, PEG1000, PEG1500, PEG1540, etc.), polypropylene glycol, isoprene glycol, 1,3- butylene glycol and the like.
  • glycerin include glycerin, diglycerin, polyglycerin and the like.
  • the content of component (E) in the oxidation hair dye according to the first embodiment is not particularly limited, but is 0.0 to 2.0% by mass.
  • the upper limit is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. By making it 2.0% by mass or less, the hair dyeing power can be improved.
  • 0.0 mass % means not containing (E) component substantially.
  • the oxidative hair dye according to the first embodiment may contain a direct dye.
  • a direct dye is a compound having a color, and is not particularly limited as long as it adheres to or permeates the hair to dye the hair. Examples thereof include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes and disperse dyes. It is preferable to contain an acid dye from the viewpoint of improving the hair dyeing power. These direct dyes may be blended alone or in combination of two or more depending on the desired color tone of the hair.
  • acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227 and Red No. 230. (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3 , Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, and Black No. 401.
  • Basic Blue 3 Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 75, Basic Blue 99, Basic Blue 124 , Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet11:1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, etc.
  • natural dyes include gardenia pigments, turmeric pigments, annatto pigments, sodium copper chlorophyllin, paprika pigments, lac pigments, and henna.
  • nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, and picrin. acids, salts thereof, and the like.
  • picramic acid and 4-nitro-o-phenylenediamine are preferred from the viewpoint of improving hair dyeing power.
  • HC dyes include HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No. 12, HC Blue No.13, HC Blue No.16, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No. 15, etc.
  • disperse dyes include Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 and the like.
  • the content of the direct dye in the oxidative hair dye is not particularly limited, but is preferably 0.001% by mass or more and 20.0% by mass or less.
  • the lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more.
  • the upper limit is more preferably 15.0% by mass or less, still more preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.
  • the oxidative hair dye according to the first embodiment may contain an alkaline agent.
  • the alkaline agent has the effect of swelling the hair and promoting the permeation of the dye and the oxidizing agent, and has the effect of improving the hair dyeing power.
  • alkaline agents include alkanolamines, ammonia, silicates, carbonates, hydrogencarbonates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, alkali metals or alkaline earths. Metal hydroxides and the like are exemplified.
  • examples of alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine
  • examples of silicate include sodium silicate, potassium silicate, and the like.
  • Examples of carbonate include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate, and the like.
  • Examples of hydrogencarbonate include sodium hydrogencarbonate and ammonium hydrogencarbonate.
  • examples of metasilicate include sodium metasilicate and potassium metasilicate.
  • examples of phosphates include primary ammonium phosphate, secondary ammonium phosphate, disodium monohydrogen phosphate, and trisodium phosphate.
  • Examples of sulfates include ammonium sulfate.
  • alkaline agents include ammonia, monoethanolamine, ammonium carbonate, and ammonium hydrogencarbonate, from the viewpoint of improving the hair dyeing power.
  • the content of the alkaline agent in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.5 to 10.0% by mass.
  • the lower limit is more preferably 0.75% by mass or more, and still more preferably 1.0% by mass or more.
  • the upper limit is more preferably 7.0% by mass or less, and even more preferably 5.0% by mass or less.
  • the oxidative hair dye according to the first embodiment may contain an oily component.
  • oily component When it contains an oily component, it is possible to improve the effect of suppressing background stains.
  • oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, and fluorine oils. One or two or more of these oily components can be selected and used.
  • the oxidative hair dye according to the first embodiment preferably includes cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, arachyl alcohol, and behenyl alcohol from the viewpoint of emulsion stability and operability.
  • higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, and lanolin fatty acid.
  • alkyl glyceryl ethers include batyl alcohol, chimyl alcohol, selachyl alcohol, and isostearyl glyceryl ether.
  • (PEG/PPG/butylene/dimethicone) copolymer) amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like.
  • amino-modified silicones include, for example, aminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane/dimethylsiloxane copolymer (INCI name: amodimethicone), Aminoethylaminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: trimethylsilyl amodimethicone) and the like.
  • aminopropylmethylsiloxane/dimethylsiloxane copolymer INCI name: aminopropyldimethicone
  • aminoethylaminopropylsiloxane/dimethylsiloxane copolymer INCI name: amodimethicone
  • Alkyl quaternary ammonium salts such as alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, amine salts such as Arcobel-type tertiary amine salts, cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts salts, benzethonium chloride and the like.
  • Alkyl quaternary ammonium salts are preferred, monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts are more preferred, and monoalkyl quaternary ammonium salts are particularly preferred.
  • Monoalkyl-type quaternary ammonium salts include, for example, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharine chloride, Stearyltrimethylammonium, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di-POE (2) oleylmethylammonium chloride, di-POE stearylmethylammonium chloride, POE (1) chloride POP(25) diethylmethylammonium, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate and
  • anionic surfactants include alkyl ether sulfates, POE alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefinsulfonates, alkanesulfonates, and saturated or unsaturated fatty acid salts. , alkyl or alkenyl ether carboxylates, ⁇ -sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinates.
  • Counter ions for the anionic groups of these surfactants may be, for example, sodium ions, potassium ions, and triethanolamine.
  • Amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
  • Specific examples of amino acid type amphoteric surfactants include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethyl Imidazolinium Betaine, Undecyl Hydroxyethylimidazolinium Betaine Sodium, Alkyldiaminoethylglycine Hydrochloride, N-Cocoate Acyl-N'-Carboxyethyl-N'-Hydroxyethylethylenediamine Sodium, N-Cocoate Acyl-N '-Carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-coconut fatty acid acyl-N'-carboxyme
  • betaine-type amphoteric surfactants include, for example, coconut oil alkylbetaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amidopropyl betaine, palm aminoacetate betaine type amphoteric surfactants such as oil fatty acid amidopropyl betaine, lauramidopropyl betaine, ricinoleic acid amidopropyl betaine, stearyldihydroxyethyl betaine; and sulfobetaine type amphoteric surfactants such as lauryl hydroxysulfobetaine. .
  • solubilizer may be used alone, or two or more solubilizers may be used in combination.
  • water is preferably applied because it has excellent ability to dissolve other components in the first agent.
  • the content of water in the mixture (oxidative hair dye) (content at the time of use) is preferably 40.0% by mass or more, more preferably 50.0% by mass or more. is.
  • the mixture attached to the hair bundle was washed away with water, and the hair bundle was shampooed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.) twice and rinsed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.). rinse) was applied once. Subsequently, the hair tresses were dried with warm air to obtain dyed hair tresses of each example.
  • Example 1-1 when comparing Example 1-1 with Example 1-4 and Example 1-5, among the components (A), 2,4-diaminophenoxyethanol has a higher hair dyeing power and texture. It can be confirmed that both the stain and the dirt are good results. Further, by comparing Examples 1-4 and 1-6, it can be confirmed that the non-containing component (B) can suppress background stains.
  • Example 1-9 where the ratio of (C1)/(C2) is 1.0 , Compared to Comparative Example 1-1 in Table 1, the evaluation of the background stain is improved, but when the ratio of (C1) / (C2) is 1.5 or more, the evaluation of the hair dyeing power and the evaluation of the background stain is improved. Improvement can be confirmed.
  • Example 1-1 As shown in Tables 7 and 8, from Example 1-1, Example 1-11, Example 1-12, Example 1-1-11 to Example 1-1-13, (E) many It can be confirmed that the hair dyeing power is superior when the alcohol does not contain the alcohol. In addition, it can be confirmed that the hair dyeing power is improved by blending the component (D) from Examples 1-1, 1-13, 1-1-9, and 1-1-10. .
  • An embodiment (second embodiment) of the present invention for solving the second problem is an oxidative hair dye obtained by mixing a first agent and a second agent, comprising (A) a coupler and the mass ratio (B/A) of the content of the dye intermediate (B) to the content of the component (A) is 0.4 or less, and the content of the component (A) is 0.3 mass % or more, and a volume increase rate of 30% or more after 20 minutes of mixing the first part and the second part.
  • the oxidative hair dye according to the second embodiment can improve destaining performance.
  • the oxidative hair dye according to the second embodiment has a volume increase rate of 30% or more, and by increasing the volume of the oxidative hair dye, it is possible to suppress uneven application even with a limited amount of the agent. It is possible to improve the levelness of dyeing.
  • the oxidative hair dye according to the second embodiment self-foams when the first agent and the second agent are mixed, or increases in volume due to foam formation by the user during mixing.
  • self-foaming is preferable from the viewpoint of hair dyeing power.
  • Examples of self-foaming by mixing an oxidative hair dye include generation of oxygen by mixing an oxidizing agent and a catalyst that decomposes the oxidizing agent, and generation of carbon dioxide by mixing a carbonate and an acid capable of decomposing the carbonate. be done.
  • Examples of such self-foaming include self-foaming due to reaction between an oxidizing agent and an iodine compound that is a catalyst for decomposing the oxidizing agent.
  • Formation of foam by the user includes filling the oxidative hair dye into a shaking container and shaking to form foam, and includes foam formation by a known foaming device such as a non-aerosol foamer. be done.
  • the oxidative hair dye according to the second embodiment has a volume increase rate of 30% or more after 20 minutes of mixing.
  • the lower limit of the volume increase rate is preferably 50% or more, more preferably 70 or more, from the viewpoint of improving uniformity of dyeing.
  • the upper limit is preferably 350% or less, more preferably 200% or less, from the viewpoint of improving the hair dyeing power.
  • the "volume increase rate 20 minutes after mixing” refers to the volume of the oxidative hair dye 20 minutes after the contact between the first part and the second part during mixing compared to before mixing.
  • volume increase rate (%) [( ⁇ - ⁇ )/ ⁇ ] ⁇ 100
  • the mixing ratio of the first component and the second component is the concentration of each component in the mixture of the oxidative hair dye.
  • the ratio is appropriately set in consideration of properties, application method, etc., preferably 0.1 to 10:1, more preferably 0.5 to 2:1.
  • the dosage form of the oxidative hair dye according to the second embodiment is not particularly limited as long as it can be applied to hair. , cream-like and the like. From the viewpoints of ease of removal with a brush and improved spreadability and adhesion to the hair and excellent application operability, it is preferable to use a cream-like or foam-like form.
  • the components used in the oxidation hair dye according to the second embodiment are exemplified below.
  • the numerical value of mass% indicating the content of the component is the numerical value in the dosage form including them, and unless otherwise noted, each agent was mixed The content in the oxidation hair dye is shown.
  • the oxidative hair dye according to the second embodiment contains (A) a coupler.
  • couplers include 2,4-diaminophenoxyethanol, resorcinol, 5-amino-o-cresol, m-aminophenol, ⁇ -naphthol (1-naphthol), 5-(2-hydroxyethylamino )-2-methylphenol, m-phenylenediamine, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, N,N-diethyl-m-aminophenol, phenylmethylpyrazolone, 1,5-dihydroxynaphthalene , salts thereof, and the like.
  • salts include hydrochlorides, sulfates, and the like.
  • One (A) component may be used alone, or two or more (A) components may be used in combination.
  • the (A) coupler according to the second embodiment is preferably 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5-(2-hydroxyethylamino)-2-methylphenol, 1-naphthol, 5 -Amino-o-cresol, 1,5-dihydroxynaphthalene, m-aminophenol, and salts thereof can be used.
  • the (A) coupler is contained in an amount of 0.3% by mass or more in the oxidation hair dye according to the second embodiment.
  • the hair dyeing power of the oxidative hair dye can be improved.
  • the lower limit is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.6% by mass or more, and even more preferably 0.7% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and most preferably 3.5% by mass or less, from the viewpoint of improving destaining performance.
  • the content of (A) coupler is 10% by mass or less, the destaining performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved.
  • the (A) coupler is a salt, the content of the (A) coupler is the value in the desalted form.
  • the content of 2,4-diaminophenoxyethanol in the oxidative hair dye according to the second embodiment is 0.3% by mass or more. This can improve the hair dyeing power.
  • the content of 2,4-diaminophenoxyethanol is 0.3% by mass or more, unevenness in application tends to increase, but in the oxidation hair dye according to the second embodiment, the volume increase rate is 30%. As described above, since the volume of the oxidative hair dye is increased, unevenness in application is suppressed, and uniformity of dyeing is improved.
  • the oxidative hair dye according to the second embodiment may contain (B) a dye intermediate.
  • Dye intermediates include dye precursors that are primarily o- or p-phenylenediamines or aminophenols, and are usually colorless or weakly colored compounds per se.
  • p-phenylenediamine, toluene-2,5-diamine p-toluylenediamine
  • N-phenyl-p-phenylenediamine N-phenyl-p-phenylenediamine
  • 4,4′-diaminodiphenylamine p-aminophenol, o-amino Phenol, p-methylaminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chloro-p-phenylenediamine
  • 4-amino-m- Examples include cresol, 2-amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol and salts thereof.
  • the oxidation dyes include acid addition salts of the above compounds.
  • Acid addition salts include inorganic acid addition salts such as hydrochlorides and sulfates, and organic acid addition salts such as acetates.
  • the content of the acid addition salt of the oxidation dye is not particularly limited, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less from the viewpoint of emulsion stability.
  • One or more of these oxidation dyes can be selected and used according to the desired color tone.
  • the mass ratio (B/A) of the content of all (B) dye intermediates to the content of (A) couplers is 0.4 or less, preferably 0. 0.3 or less, more preferably 0.2 or less, and still more preferably 0.1 or less.
  • the mass ratio (B/A) is 0.4 or less, destaining performance can be improved.
  • the content used for calculating the above mass ratio is the value of the desalted form of both (A) and (B).
  • the upper limit of the content of the dye intermediate (B) in the oxidative hair dye according to the second embodiment is appropriately set within the range of the mass ratio (B/A) of the content, preferably 1 % by mass or less, more preferably 0.5 mass % or less, still more preferably 0.2 mass % or less, and particularly preferably the oxidative hair dye does not substantially contain (B) dye intermediates.
  • B) When the content of the dye intermediate is 1% by mass or less, the destaining performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved.
  • the (B) dye intermediate is a salt, the content of the (B) dye intermediate is the value in the desalted form.
  • the oxidative hair dye according to the second embodiment preferably contains (F) a catalyst that decomposes the oxidizing agent.
  • the catalyst that decomposes the oxidant reacts when mixed with the oxidant, resulting in self-foaming of the oxidative hair dye.
  • Such (F) catalysts include iodine compounds, metal compounds, non-metal catalysts, and the like.
  • iodine compounds include iodine (I 2 ), iodine compounds with counter ions released in a solubilizer, and compounds that release iodine during use.
  • iodine compounds include alkali metal salts of iodine compounds such as potassium iodide, sodium iodide, lithium iodide and ammonium iodide, hydrogen iodide, cesium iodide and silver iodide.
  • natural materials containing iodine for example, extracts containing iodine compounds such as iodine garlic extract may be applied.
  • One iodine compound may be used alone, or two or more iodine compounds may be used in combination.
  • the metal compound is preferably a metal iodine compound, including metal compounds such as iron, copper, silver, platinum, lithium, cerium, cobalt, manganese, nickel, vanadium, sodium, and potassium.
  • metal compounds include vanadium oxysulfate hydrate, copper chloride, copper sulfate, potassium chloride, calcium nitrate, lithium chloride, magnesium acetate, potassium dichromate, barium nitrate, cobalt chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide, and the like.
  • non-metallic catalysts examples include activated carbon, enzymes such as catalase and peroxidase, and dry yeast containing them.
  • the component (F) according to the second embodiment is preferably an iodine compound, preferably sodium iodide, potassium iodide or ammonium iodide, more preferably potassium iodide or ammonium iodide.
  • the content of (F) catalyst in the oxidation hair dye according to the second embodiment is not particularly limited, but is, for example, 0.001 to 5% by mass.
  • the lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more.
  • the upper limit is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, from the viewpoint of suppressing a decrease in hair dyeing power due to excessive foaming.
  • the iodine compound which is the component (F) has the effect of improving the hair dyeing power by decomposing hydrogen peroxide and promoting the polymerization of the oxidation dye by the iodine that constitutes the iodine compound.
  • the lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more.
  • the oxidative hair dye according to the second embodiment may contain carbonate.
  • Carbonates react and self-foam when carbonates are mixed with decomposable acids.
  • Examples of carbonates include, but are not limited to, carbonate ions such as alkali metal salts such as potassium and sodium, beryllium salts, magnesium salts, alkaline earth metal salts such as calcium, and ammonium salts.
  • Alkali metal salts such as potassium and sodium hydrogencarbonate ions, beryllium salts, magnesium salts, alkaline earth metal salts such as calcium, and ammonium salts.
  • alkali metal salts such as potassium and sodium carbonate ions, magnesium salts, alkaline earth metal salts such as calcium carbonate ions, ammonium salts, and potassium and sodium bicarbonate ions are preferably used from the viewpoint of the amount of foaming.
  • alkali metal salts such as magnesium salts, alkaline earth metal salts such as calcium, or carbonates selected from ammonium salts, more preferably potassium or sodium alkali metal salts or ammonium salts of carbonate ions, carbonate It is a carbonate selected from potassium hydrogen ion, alkali metal salt of sodium, and ammonium salt.
  • These carbonates may contain at least one or two or more.
  • the carbonate content for the purpose of self-foaming is not particularly limited, but is, for example, 0.5 to 15% by mass.
  • the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 7.5% by mass or less, from the viewpoint of suppressing a decrease in hair dyeing power due to volume increase due to excessive foaming.
  • Acids capable of decomposing the above carbonates are not particularly limited, but organic acids such as glycolic acid, acetic acid, citric acid, lactic acid and hydroxyethanediphosphonic acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide and the like. Inorganic acid etc. are mentioned. Among these, citric acid, lactic acid, hydroxyethanediphosphonic acid, benzoic acid, phosphoric acid and hydrogen peroxide are preferred, and hydroxyethanediphosphonic acid and phosphoric acid are more preferred. These acids may contain at least one or two or more.
  • Divalent metal salts other than carbonates can improve the foamability and foam sustainability by assisting the mixing of the carbonate-containing agent with other agents.
  • Such divalent metal salts are not particularly limited regardless of whether they are typical metals or transition metals, and include hydrochlorides, sulfates, lactates, acetates and bromates of magnesium, calcium, barium and zinc.
  • divalent metal salts other than carbonates preferred are divalent metal salts selected from hydrochlorides, sulfates and bromates of magnesium, calcium, barium, or zinc, more preferably magnesium, A divalent metal salt selected from calcium hydrochloride or sulfate. At least one or more of these divalent metal salts other than carbonates may be contained.
  • the oxidative hair dye according to the second embodiment preferably contains (G) an oxidizing agent.
  • the oxidizing agent reacts with the (F) catalyst that decomposes the oxidizing agent to generate oxygen and foam.
  • the oxidizing agent is usually contained in the second agent of the oxidative hair dye.
  • the (G) oxidizing agent according to the second embodiment include, for example, hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, Ammonium Sulfate, Potassium Persulfate, Sodium Persulfate, Sodium Peroxide, Potassium Peroxide, Magnesium Peroxide, Barium Peroxide, Calcium Peroxide, Strontium Peroxide, Sulfate Hydrogen Peroxide Adduct, Phosphate Hydrogen Peroxide Adducts, hydrogen peroxide adducts of pyrophosphates, and the like can be mentioned.
  • One oxidizing agent may be used alone, or two or more oxidizing agents may be used in combination.
  • the content of (G) the oxidizing agent in the second part of the oxidative hair dye according to the second embodiment is appropriately set, but is preferably 0.1% by mass or more, more preferably 1.0%. % by mass or more, more preferably 2.0% by mass or more.
  • the content of the oxidizing agent in the second agent is preferably 15.0% by mass or less, more preferably 9.0% by mass or less, and even more preferably 6.0% by mass or less.
  • hair damage and the like can be further suppressed.
  • Alkaline agents have the effect of swelling the hair and promoting the penetration of dyes and oxidizing agents.
  • Alkali agents include, for example, alkanolamines, ammonia, silicates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, hydroxides of alkali metals or alkaline earth metals. exemplified.
  • alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine
  • examples of silicate include sodium silicate, potassium silicate, and the like.
  • Examples of carbonate include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate, and the like.
  • Examples of hydrogencarbonate include sodium hydrogencarbonate and ammonium hydrogencarbonate.
  • Examples of metasilicate include sodium metasilicate and potassium metasilicate.
  • Examples of phosphates include primary ammonium phosphate, secondary ammonium phosphate, disodium monohydrogen phosphate, and trisodium phosphate.
  • Examples of sulfates include ammonium sulfate.
  • AMP 2-amino-2-methyl-1-propanol
  • guanidine 2-amino-2-methyl-1,3-propanediol
  • basic amino acids examples thereof include arginine, lysine and salts thereof
  • hydroxides of alkali metals or alkaline earth metals include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • the content of the alkaline agent in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.5 to 10% by mass.
  • the lower limit is more preferably 0.75% by mass, and still more preferably 1% by mass or more.
  • the upper limit is more preferably 7% by mass or less, and even more preferably 5% by mass or less.
  • the oxidative hair dye according to the second embodiment may contain the following components, if necessary, in addition to the above components.
  • Other ingredients include, for example, direct dyes, oily ingredients, surfactants, antioxidants such as anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, sugars such as sorbitol and maltose, polyethylene glycol, and dipropylene glycol.
  • polyhydric alcohols such as ethylenediaminehydroxyethyl triacetic acid trisodium dihydrate, chelating agents such as hydroxyethanediphosphonic acid tetrasodium salt, acids, pH adjusters, hair growth ingredients, plant extracts, crude drug extracts, amino acids and peptides , urea, vitamins, fragrances, and UV absorbers.
  • the oxidative hair dye according to the second embodiment may contain a direct dye.
  • a direct dye is a compound having a color, and is not particularly limited as long as it adheres to or permeates the hair to dye the hair. Examples thereof include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes and disperse dyes. From the viewpoint of hair dyeing power, it is preferable to contain an acid dye. These direct dyes may be blended alone or in combination of two or more depending on the desired color tone of the hair.
  • acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227 and Red No. 230. (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3 , Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, and Black No. 401.
  • Basic Blue 3 Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 75, Basic Blue 99, Basic Blue 124 , Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet11:1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, etc.
  • natural dyes include gardenia pigments, turmeric pigments, annatto pigments, sodium copper chlorophyllin, paprika pigments, lac pigments, and henna.
  • nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, and picrin. acids, salts thereof, and the like.
  • HC dyes include HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No. 12, HC Blue No.13, HC Blue No.16, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No. 15, etc.
  • disperse dyes include Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 and the like.
  • the content of the direct dye in the oxidation hair dye according to the second embodiment is not particularly limited, but is preferably 0.001% by mass or more and 20.0% by mass or less.
  • the lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more.
  • the upper limit is more preferably 15.0% by mass or less, still more preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.
  • the oxidative hair dye according to the second embodiment may contain an oily component.
  • oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, fluorine oils and the like. One or two or more of these oily components can be selected and used.
  • higher alcohols examples include cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachyl alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, 2-hexyldecanol, and isostearyl alcohol.
  • Fats and oils are triglycerides, that is, triesters of fatty acids and glycerin.
  • triglycerides that is, triesters of fatty acids and glycerin.
  • Waxes are esters of higher fatty acids and higher alcohols. Examples include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, wart wax, kapok wax, and shellac wax.
  • Hydrocarbons are compounds consisting of carbon and hydrogen. Examples include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, ozokerite, ceresin, polyethylene, ⁇ -olefin oligomer, polybutene, synthetic squalane, squalene, hydrogenated squalane, limonene, and turpentine oil.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolin fatty acid. is mentioned.
  • Esters are compounds obtained by the dehydration reaction of fatty acids and alcohols.
  • Silicone oil is a synthetic polymer in which silicon and oxygen with organic groups are alternately linked by chemical bonds.
  • dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxy end groups (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, average Highly polymerized silicone having a degree of polymerization of 650 to 10000, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like can be mentioned.
  • amino-modified silicones include, for example, aminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane/dimethylsiloxane copolymer (INCI name: amodimethicone), Aminoethylaminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: trimethylsilyl amodimethicone) and the like.
  • aminopropylmethylsiloxane/dimethylsiloxane copolymer INCI name: aminopropyldimethicone
  • aminoethylaminopropylsiloxane/dimethylsiloxane copolymer INCI name: amodimethicone
  • the content of the oil component in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.1 to 20% by mass.
  • the lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass or more.
  • the upper limit is more preferably 17% by mass or less, still more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less.
  • Surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • anionic surfactants include alkyl ether sulfates, POE alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefinsulfonates, alkanesulfonates, and saturated or unsaturated fatty acid salts. , alkyl or alkenyl ether carboxylates, ⁇ -sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinates.
  • Counter ions for the anionic groups of these surfactants may be, for example, sodium ions, potassium ions, and triethanolamine.
  • the content of the anionic surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.01 to 5% by mass.
  • the lower limit is more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.07% by mass or more, and particularly 0.1% by mass or more.
  • the upper limit is more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2.5% by mass or less, and particularly preferably 2% by mass or less.
  • cationic surfactants include monoalkyl-type quaternary ammonium salts, dialkyl-type quaternary ammonium salts, trialkyl-type quaternary ammonium salts, benzalkonium-type quaternary ammonium salts, and monoalkyl ether-type quaternary ammonium salts.
  • Alkyl quaternary ammonium salts such as alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, amine salts such as Arcobel-type tertiary amine salts, cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts salts, benzethonium chloride and the like.
  • Alkyl quaternary ammonium salts are preferred, monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts are more preferred, and monoalkyl quaternary ammonium salts are particularly preferred.
  • Monoalkyl-type quaternary ammonium salts include, for example, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharine chloride, Stearyltrimethylammonium, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di-POE (2) oleylmethylammonium chloride, di-POE stearylmethylammonium chloride, POE (1) chloride POP(25) diethylmethylammonium, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate and
  • dialkyl-type quaternary ammonium salts include dialkyl(12-15) dimethylammonium chloride, dialkyl(12-18) dimethylammonium chloride, dialkyl(14-18) dimethylammonium chloride, dicocoyldimethylammonium chloride, and dicetyl chloride. dimethylammonium, distearyldimethylammonium chloride, isostearyllauryldimethylammonium chloride and the like.
  • the content of the cationic surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.01 to 10% by mass.
  • the lower limit is more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.07% by mass or more, and particularly preferably 0.1% by mass or more. is.
  • the upper limit is more preferably 7.5% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1.5% by mass or less.
  • nonionic surfactants include POE alkyl ethers, POE alkylphenyl ethers, POE/POP alkyl ethers, POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, and polyglycerin fatty acid esters. monoglycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkylpolyglucosides, and the like.
  • Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, and POE phytosterol.
  • the number of repeating units of POE and POP is, for example, 2 to 100, and any one can be used as long as it exhibits surface activity.
  • the content of the nonionic surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.001 to 30% by mass.
  • the lower limit is more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. is.
  • the upper limit is more preferably 20% by mass or less, still more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 5% by mass or less.
  • Amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
  • Specific examples of amino acid type amphoteric surfactants include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethyl Imidazolinium Betaine, Undecyl Hydroxyethylimidazolinium Betaine Sodium, Alkyldiaminoethylglycine Hydrochloride, N-Cocoate Acyl-N'-Carboxyethyl-N'-Hydroxyethylethylenediamine Sodium, N-Cocoate Acyl-N '-Carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-coconut fatty acid acyl-N'-carboxyme
  • betaine-type amphoteric surfactants include, for example, coconut oil alkylbetaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amidopropyl betaine, palm aminoacetate betaine type amphoteric surfactants such as oil fatty acid amidopropyl betaine, lauramidopropyl betaine, ricinoleic acid amidopropyl betaine, stearyldihydroxyethyl betaine; and sulfobetaine type amphoteric surfactants such as lauryl hydroxysulfobetaine. .
  • the content of the amphoteric surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.001 to 5% by mass.
  • the lower limit is more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. is.
  • the upper limit is more preferably 3% by mass or less, and still more preferably 2.5% by mass or less.
  • the total content of all surfactants in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.01 to 50% by mass.
  • the lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more.
  • the upper limit is more preferably 40% by mass or less, still more preferably 30% by mass or less.
  • the oxidation hair dye according to the second embodiment does not substantially contain dye intermediates and contains only couplers as oxidation dyes, or couplers are contained in a predetermined ratio or more to all dye intermediates. contains. Therefore, destaining performance can be improved.
  • the polymer of dye intermediates or the polymer of dye intermediates and couplers, has the characteristic that it is difficult to decompose with alkaline agents and oxidizing agents, so there was a problem that the hair could not be dyed in bright colors from the next time onwards.
  • the oxidative hair dye according to the second embodiment contains substantially no dye intermediates and contains only a coupler as an oxidative dye, or contains a coupler at a predetermined ratio or more with respect to all dye intermediates. By forming a polymer that is easily decomposed by an alkaline agent, it has excellent destaining performance and less influence on subsequent hair coloring. As a result, various hair colors can be enjoyed without considering the next hair color.
  • the oxidative hair dye according to the second embodiment does not substantially contain dye intermediates, or the content thereof is very small. may also be used for
  • the oxidation hair dye according to the second embodiment has a volume increase rate of 30% or more after 20 minutes of mixing. However, uneven coating can be suppressed, and levelness can be improved.
  • the 2,4-diaminophenoxyethanol in the table below is obtained by neutralizing the raw material 2,4-diaminophenoxyethanol hydrochloride using NaOH as a pH adjuster. Since 2,4-diaminophenoxyethanol hydrochloride produces 2 mol of hydrochloric acid per 1 mol, it was neutralized by adding 2,4-diaminophenoxyethanol hydrochloride:NaOH at a ratio of 1:2 (molar ratio). That is, the first agent contains 2,4-diaminophenoxyethanol in a free form.
  • the first agent and the second agent shown in Tables 9 and 10 were mixed at a mass ratio of 1:1 in the combination shown in Table 11, and the volume increase rate of the oxidative hair dye mixture of each example was evaluated. Evaluation was performed by putting 5 g of the first agent and 5 g of the second agent into a 100 mL graduated cylinder, stirring with a glass rod until uniform, and measuring in advance at 25 ° C. before mixing the first agent and the second agent.
  • the volume increase rate was calculated by measuring and comparing the sum of the volumes and the volume of the mixture of the first part and the second part (oxidation hair dye) after 20 minutes, and evaluated according to the following criteria. This evaluation result is shown in the "volume increase rate" column of Table 11.
  • the dyed hair tresses of each example obtained as described above are destained according to a conventional method using a more general decolorizing/destaining agent, "Lece Powder Bleach” (manufactured by Hoyu Co., Ltd.). A destained hair tress was obtained by carrying out.
  • each example (Examples 2-1 to 2-10) was confirmed to be excellent in destaining performance.
  • the amount of potassium iodide, which is the (F) catalyst that decomposes the oxidizing agent is preferably 0.005% by mass or more from the viewpoint of foaming amount.
  • the oxidative hair dye of the present invention can be used as a hair dye for dyeing human body hair such as head hair, beard, eyebrows and shin hair. In addition, it may be used for dyeing body hair of animals such as pets.
  • the oxidative hair dye of the present invention can be used as a hair dye for coloring and a hair dye for self-coloring in beauty salons, barber shops, and the like.

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Abstract

According to one aspect, the present invention addresses the problem of providing an oxidation hair dye in which contamination of the scalp is suppressed while hair-coloring strength is improved.　In order to solve the aforementioned problem, there is provided an oxidation hair dye containing (A) a coupler, the oxidation hair dye being characterized in that the mass ratio (B/A) of the amount of (B) a dye intermediate to the amount of the (A) component is 0.4 or less, and the (A) component is contained at 0.3 mass% or greater, and the oxidation hair dye moreover being characterized by containing, as (C) a non-ionic surfactant, (C1) a non-ionic surfactant having having an HLB of less than 10.

Description

酸化染毛剤oxidative hair dye
　本発明は、カプラーを含有する酸化染毛剤に関する。 The present invention relates to an oxidation hair dye containing a coupler.
　例えばアルカリ剤及び酸化染料を含有する第１剤と、酸化剤、例えば過酸化水素を含有する第２剤とから構成される酸化染毛剤が知られている。アルカリ剤は、第２剤に含有される酸化剤の作用を促進するとともに、毛髪を膨潤させて毛髪への染料の浸透性を向上させる。酸化剤は、毛髪中のメラニン色素を分解するとともに、毛髪内部で酸化染料重合体を形成させる。アルカリ剤が除去された後、毛髪のキューティクルが閉じて、酸化染料重合体が毛髪内部に封入される。 For example, an oxidative hair dye comprising a first agent containing an alkaline agent and an oxidation dye and a second agent containing an oxidizing agent such as hydrogen peroxide is known. The alkaline agent promotes the action of the oxidizing agent contained in the second agent, and also swells the hair to improve the penetration of the dye into the hair. The oxidizing agent decomposes the melanin pigment in the hair and forms an oxidation dye polymer inside the hair. After the alkaline agent is removed, the hair cuticle is closed and the oxidation dye polymer is enclosed inside the hair.
　毛髪内部の酸化染料重合体は、容易に分解しないため、脱染性能が低く、通常酸化染毛剤を用いて染毛処理を行った後、別の色に再染毛する場合、一旦脱染剤を用いて脱染処理する必要があった。さらに一度の脱染処理では十分に脱染できない場合もあった。 Since the oxidation dye polymer inside the hair does not decompose easily, the decolorization performance is low. It was necessary to destain using an agent. Furthermore, in some cases, a single destaining treatment cannot be sufficiently destained.
　従来より、毛髪内部の暗い色調の酸化染料重合体を脱染剤による脱染処理を行うことなく分解させ、毛髪をクリアな明るい色調に再染色するために用いられる酸化染毛剤が知られている。例えば特許文献１に開示される酸化染毛剤は、染料の主成分としてジアミン系の染料中間体等を含有することにより、染毛力を向上させている。 Oxidative hair dyes have been known which are used for re-dyeing the hair to a clear and bright tone by decomposing the dark tone oxidation dye polymer inside the hair without performing destaining treatment with a destaining agent. there is For example, the oxidative hair dye disclosed in Patent Document 1 contains a diamine-based dye intermediate or the like as a main component of the dye, thereby improving the hair dyeing power.
国際公開第２００９／０５７２２８号WO2009/057228
（第１の課題）
　しかしながら、染毛力を向上させると、地肌が汚れるという問題がある。
　そこで、本発明の第１の課題は、染毛力を向上させ、脱染性能を維持しつつ、さらに地肌汚れを抑制した酸化染毛剤を提供することである。 (First issue)
However, when the hair dyeing power is improved, there is a problem that the skin becomes dirty.
Accordingly, a first object of the present invention is to provide an oxidative hair dye that improves hair dyeing power, maintains destaining performance, and suppresses background staining.
（第２の課題）
　本発明の第２の課題は、脱染性能を向上でき、さらに均染性を向上できる酸化染毛剤を提供することである。 (Second issue)
A second object of the present invention is to provide an oxidative hair dye capable of improving destaining performance and improving levelness of dyeing.
（第１の課題を解決するための手段）
　発明者は、上記第１の課題に対して鋭意検討した結果、酸化染料として染料中間体をカプラーに対して所定量含有しかつノニオン界面活性剤として、ＨＬＢ１０未満のノニオン界面活性剤を含有することにより、染毛力を向上させ、脱染性能を維持したまま、地肌汚れを抑制できることを見出して、本発明を完成させた。 (Means for solving the first problem)
As a result of intensive studies on the above first problem, the inventors have found that a predetermined amount of a dye intermediate as an oxidation dye is contained in a coupler and a nonionic surfactant having an HLB of less than 10 is contained as a nonionic surfactant. Thus, the present invention was completed by discovering that the hair dyeing power can be improved and the background stain can be suppressed while maintaining the destaining performance.
　すなわち、上記第１の課題を解決するための本発明の酸化染毛剤は、（Ａ）カプラーを含有する酸化染毛剤であって、酸化染毛剤は、（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）が０．４以下であり、（Ａ）成分は０．３質量％以上含有し、（Ｃ）ノニオン性界面活性剤として、（Ｃ１）ＨＬＢ１０未満のノニオン界面活性剤を含有することを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、カプラーと染料中間体との比率、カプラーの含有量及びノニオン界面活性剤として、ＨＬＢ１０未満のノニオン界面活性剤を含有することを特定することにより、染毛力を向上させ、脱染性能を維持したまま、地肌汚れを抑制することができる。 That is, the oxidative hair dye of the present invention for solving the first problem is an oxidative hair dye containing (A) a coupler, wherein the oxidative hair dye has a component (A) content of (B) The mass ratio (B/A) of the content of the dye intermediate is 0.4 or less, (A) contains 0.3 mass% or more of the component, and (C) the nonionic surfactant is C1) Characterized by containing a nonionic surfactant with an HLB of less than 10.
According to this feature, the oxidative hair dye of the present invention is specified to contain a nonionic surfactant having an HLB of less than 10 as the ratio of the coupler to the dye intermediate, the content of the coupler, and the nonionic surfactant. Therefore, it is possible to improve the hair dyeing power and suppress the background stain while maintaining the destaining performance.
　また、上記第１の課題を解決するための本発明の酸化染毛剤の一実施態様は、（Ｃ）成分は、（Ｃ１）成分と、（Ｃ２）ＨＬＢ１０以上のノニオン界面活性剤とを含有する、２種以上のノニオン界面活性剤であることを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、より染毛力を向上することができ、脱染性能を維持したまま、かつ地肌汚れを抑制することができる。 In one embodiment of the oxidative hair dye of the present invention for solving the first problem, component (C) contains component (C1) and (C2) a nonionic surfactant having an HLB of 10 or more. It is characterized by being two or more nonionic surfactants.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power, and can suppress background staining while maintaining the destaining performance.
　また、上記第１の課題を解決するための本発明の酸化染毛剤の一実施態様は、（Ｃ）成分は、（Ｃ２）の含有量に対する（Ｃ１）成分の含有量の質量比（Ｃ１）／（Ｃ２）が、１．５以上であることを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、より染毛力を向上することができ、脱染性能を維持したまま、かつ地肌汚れを抑制することができる。 Further, in one embodiment of the oxidative hair dye of the present invention for solving the first problem, the component (C) is the mass ratio of the content of the component (C1) to the content of (C2) (C1 )/(C2) is 1.5 or more.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power, and can suppress background staining while maintaining the destaining performance.
　また、上記第１の課題を解決するための本発明の酸化染毛剤の一実施態様は、酸化染毛剤は、（Ｄ）ヨウ素化合物を含有していることを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、ヨウ素化合物を含有することにより、より染毛力を向上することができる。 Further, one embodiment of the oxidative hair dye of the present invention for solving the first problem is characterized in that the oxidative hair dye contains (D) an iodine compound.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power by containing the iodine compound.
　さらに、上記第１の課題を解決するための本発明の酸化染毛剤の一実施態様は、酸化染毛剤は、（Ｅ）多価アルコールを酸化染毛剤の質量に対して０．５質量％以下含有している、又は、（Ｅ）多価アルコールを含有しないことを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、より染毛力を向上させることができる。 Furthermore, in one embodiment of the oxidative hair dye of the present invention for solving the first problem, the oxidative hair dye contains (E) a polyhydric alcohol in an amount of 0.5 based on the mass of the oxidative hair dye. It is characterized by containing not more than mass % or not containing (E) polyhydric alcohol.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power.
（第２の課題を解決するための手段）
　発明者は、上記第２の課題に対して鋭意検討した結果、カプラーの含有量に対する染料中間体の比率を特定の質量比とし、さらに発泡後の体積増加率を特定値以上とすることにより、脱染性能と均染性を向上できることを見出して、本発明を完成させた。 (Means for solving the second problem)
As a result of intensive studies on the second problem, the inventors have found that by setting the ratio of the dye intermediate to the content of the coupler to a specific mass ratio and by setting the volume increase rate after foaming to a specific value or more, The inventors have found that the destaining performance and levelness of dyeing can be improved, and completed the present invention.
　すなわち、上記第２の課題を解決するための本発明の酸化染毛剤は、第１剤と第２剤を混合することにより得られる酸化染毛剤であって、（Ａ）カプラーを含有し、（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）が０．４以下であり、前記（Ａ）成分の含有量が０．３質量％以上であり、前記第１剤と第２剤を混合し、混合の２０分後における体積増加率が３０％以上であることを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、脱染性能を向上することができる。さらに、本発明の酸化染毛剤は、体積増加率が３０％以上として、酸化染毛剤の体積を増加させることにより、限られた量の剤でも塗りムラを抑制することができ、均染性を向上することができる。 That is, the oxidative hair dye of the present invention for solving the second problem is an oxidative hair dye obtained by mixing the first agent and the second agent, and containing (A) a coupler. , The mass ratio (B/A) of the content of the dye intermediate (B) to the content of the component (A) is 0.4 or less, and the content of the component (A) is 0.3% by mass or more. A volume increase rate of 30% or more after 20 minutes of mixing the first agent and the second agent.
According to this feature, the oxidative hair dye of the present invention can improve destaining performance. Furthermore, the oxidative hair dye of the present invention has a volume increase rate of 30% or more, and by increasing the volume of the oxidative hair dye, it is possible to suppress uneven application even with a limited amount of agent, and even dyeing can be achieved. can improve sexuality.
　また、上記第２の課題を解決するための本発明の酸化染毛剤の一実施態様は、前記（Ａ）成分として２，４－ジアミノフェノキシエタノールを含有し、酸化染毛剤中の２，４－ジアミノフェノキシエタノールの含有量が０．３質量％以上であることを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、染毛力をより向上することができる。 Further, one embodiment of the oxidative hair dye of the present invention for solving the second problem described above contains 2,4-diaminophenoxyethanol as the component (A), and 2,4-diaminophenoxyethanol in the oxidative hair dye. - The content of diaminophenoxyethanol is 0.3% by mass or more.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power.
　また、上記第２の課題を解決するための本発明の酸化染毛剤の一実施態様は、さらに（Ｆ）触媒、及び（Ｇ）酸化剤を含有することを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、触媒と酸化剤の反応により発泡し、染毛力を向上することができる。 Further, one embodiment of the oxidative hair dye of the present invention for solving the second problem is characterized by further containing (F) a catalyst and (G) an oxidizing agent.
According to this feature, the oxidative hair dye of the present invention foams due to the reaction between the catalyst and the oxidizing agent, and can improve the hair dyeing power.
　また、上記第２の課題を解決するための本発明の酸化染毛剤の一実施態様は、前記（Ｆ）成分の含有量が０．００５質量％以上０．２５質量％以下であることを特徴とする。
　この特徴によれば、本発明の酸化染毛剤は、触媒と酸化剤による発泡量を適切に制御し、均染性をより向上することができる。 Further, in one embodiment of the oxidative hair dye of the present invention for solving the second problem, the content of the component (F) is 0.005% by mass or more and 0.25% by mass or less. Characterized by
According to this feature, the oxidative hair dye of the present invention can appropriately control the amount of foaming caused by the catalyst and the oxidizing agent, and further improve the uniformity of dyeing.
　上記第１の課題を解決するための本発明によれば、染毛力を向上させ、脱染性能を維持しつつ、さらに地肌汚れを抑制した酸化染毛剤を提供することができる。 According to the present invention for solving the first problem, it is possible to provide an oxidative hair dye that improves hair dyeing power, maintains de-dyeing performance, and further suppresses background staining.
　上記第２の課題を解決するための本発明によれば、脱染性能を向上し、さらに均染性を向上できる酸化染毛剤を提供することができる。 According to the present invention for solving the second problem, it is possible to provide an oxidative hair dye that can improve the destaining performance and further improve the levelness of dyeing.
　酸化染毛剤は、酸化剤と酸化染料を別の剤に分けて流通し、酸化染料を毛髪内部で発色させるものである。通常、酸化染料を含有する第１剤と、過酸化物を含有する第２剤を備え、これらの剤を混合して使用する。ここで、「混合して使用する」とは、一度の塗布操作で複数の剤を毛髪に適用することを意味し、直前に混合して使用する操作だけでなく、第１剤と第２剤をコーム等に取り、毛髪上でコーム等を用いて混合する操作も含む概念である。 　Oxidative hair dyes are distributed by dividing the oxidizing agent and the oxidative dye into separate agents, and the oxidative dye develops color inside the hair. Generally, a first agent containing an oxidation dye and a second agent containing a peroxide are provided, and these agents are mixed and used. Here, "mixing and using" means applying a plurality of agents to the hair in one application operation, and not only the operation of mixing and using immediately before, but also the first agent and the second agent. is taken on a comb or the like and mixed on the hair using a comb or the like.
　本発明の酸化染毛剤は、多剤式酸化染毛剤、好ましくは２剤式酸化染毛剤の酸化染毛剤である。２剤式酸化染毛剤は、酸化染料を含む第１剤及び酸化剤を含む第２剤からなり、使用に際して、第１剤と第２剤が混合されて使用される。以下、本発明の酸化染毛剤は、多剤式の酸化染毛剤の、例えば第１剤と第２剤の混合物の状態を示し、その組成とは、例えば第１剤と第２剤の混合物の組成を示す。
　なお、酸化染毛剤は、上記のように、第１剤及び第２剤からなる２剤式のものが代表的であるが、本発明における酸化染毛剤としては、３剤以上からなる多剤式であってもよい。例えば、２剤式の第１剤について、カプラー及び任意成分であるアルカリ剤を含有する剤と、それ以外の組成を有する剤の２つに分け、３剤式の酸化染毛剤として構成してもよい。この場合、乳化安定性がより向上する。 The oxidative hair dye of the present invention is a multi-component oxidative hair dye, preferably a two-component oxidative hair dye. A two-component oxidative hair dye consists of a first component containing an oxidation dye and a second component containing an oxidizing agent. Hereinafter, the oxidative hair dye of the present invention refers to a multi-component oxidative hair dye, for example, the state of a mixture of a first agent and a second agent, and the composition thereof means, for example, the first agent and the second agent. The composition of the mixture is shown.
As described above, the oxidative hair dye is typically a two-agent type consisting of a first agent and a second agent. It may be a drug formula. For example, the first agent of a two-agent type is divided into two agents, one containing a coupler and an optional alkaline agent, and the other having a composition other than that, to constitute a three-agent oxidative hair dye. good too. In this case, emulsion stability is further improved.
　また、本発明における酸化染毛剤を毛髪に適用する手段としては、櫛、ブラシ、刷毛、アプリケーター等の塗布具を用いて毛髪に適用したり、手袋を着用した手で酸化染毛剤を毛髪に適用したりしてもよい。 As means for applying the oxidative hair dye of the present invention to the hair, an applicator such as a comb, brush, brush, or applicator may be used to apply the oxidative hair dye to the hair. may be applied to
　以下、第１及び第２の課題を解決するための本発明に係る各実施態様（以下、「第１の実施態様」、「第２の実施態様」と呼ぶ）について、本発明を実施するための最良の形態を含めて説明する。
　なお、以下の記載において、ＰＯＥはポリオキシエチレン鎖、ＰＯＰはポリオキシプロピレン鎖を示し、これに続くカッコ内の数字は、その付加モル数を示している。また、アルキルに続くカッコ内の数字は、脂肪酸鎖の炭素数を示している。 Hereinafter, each embodiment (hereinafter referred to as "first embodiment" and "second embodiment") according to the present invention for solving the first and second problems will be described. including the best mode.
In the following description, POE indicates a polyoxyethylene chain, POP indicates a polyoxypropylene chain, and the numbers in parentheses following these indicate the number of added moles. Also, the numbers in parentheses following alkyl indicate the number of carbon atoms in the fatty acid chain.
〔第１の実施態様〕
　第１の課題を解決するための本発明に係る実施態様（第１の実施態様）は、（Ａ）カプラーを含有する酸化染毛剤であって、酸化染毛剤は、（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）が０．４以下であり、（Ａ）成分は０．３質量％以上含有し、（Ｃ）ノニオン性界面活性剤として、（Ｃ１）ＨＬＢ１０未満のノニオン界面活性剤を含有することを特徴とする。
　第１の実施態様に係る酸化染毛剤は、カプラーと染料中間体との比率、カプラーの含有量及びノニオン界面活性剤として、（Ｃ１）ＨＬＢ１０未満のノニオン界面活性剤を含有することを特定することにより、染毛力を向上させ、脱染性能を維持したまま、かつ地肌汚れを抑制することができる酸化染毛剤とすることができる。　 [First embodiment]
An embodiment (first embodiment) of the present invention for solving the first problem is an oxidative hair dye containing (A) a coupler, wherein the oxidative hair dye comprises component (A) The mass ratio (B/A) of the content of the dye intermediate (B) to the content is 0.4 or less, (A) contains 0.3% by mass or more, and (C) a nonionic surfactant (C1) containing a nonionic surfactant having an HLB of less than 10.
The oxidative hair dye according to the first embodiment is specified to contain (C1) a nonionic surfactant with an HLB of less than 10 as the ratio of the coupler to the dye intermediate, the content of the coupler, and the nonionic surfactant. As a result, it is possible to obtain an oxidative hair dye that can improve the hair dyeing power, maintain the destaining performance, and suppress background stains.
　第１の実施態様に係る酸化染毛剤における第１剤の粘度は、特に限定されないが、好ましくは、１０～１０００００ｍＰａ・ｓである。また、第２剤の粘度は、特に限定されないが、好ましくは、１０～１０００００ｍＰａ・ｓである。なお、第１剤及び第２剤の粘度は、ＴＶＢ－１０型粘度計などのＢ型粘度計を用いて測定することができ、２５℃、１分間の条件でそれぞれの粘度に適したローターを用いて測定することができる。
　また、第１の実施態様に係る酸化染毛剤における粘度は、特に制限されないが、２５℃における粘度が、例えば、１０００～１０００００ｍＰａ・ｓである。垂れ落ち抑制の観点から、下限値は、好ましくは２０００ｍＰａ・ｓ以上であり、より好ましくは５０００ｍＰａ・ｓ以上であり、さらに好ましくは１００００ｍＰａ・ｓ以上である。毛髪への適用の際の操作性の観点から、上限値は、好ましくは５００００ｍＰａ・ｓ以下であり、より好ましくは４００００ｍＰａ・ｓ以下であり、さらに好ましくは３００００ｍＰａ・ｓ以下である。酸化染毛剤の粘度は、アニオン性界面活性剤、カチオン性界面活性剤の添加、水溶性ポリマーなどの増粘剤の添加などにより調整することができる。酸化染毛剤の混合粘度は、ＴＶＢ－１０型粘度計などのＢ型粘度計を用いて行うことができ、２５℃、１分間の条件でそれぞれの粘度に適したローターを用いて測定することができる。 Although the viscosity of the first agent in the oxidative hair dye according to the first embodiment is not particularly limited, it is preferably 10 to 100000 mPa·s. Although the viscosity of the second agent is not particularly limited, it is preferably 10 to 100000 mPa·s. The viscosity of the first agent and the second agent can be measured using a B-type viscometer such as a TVB-10 type viscometer, and a rotor suitable for each viscosity under the conditions of 25 ° C. and 1 minute can be measured using
The viscosity of the oxidative hair dye according to the first embodiment is not particularly limited, but the viscosity at 25° C. is, for example, 1000 to 100000 mPa·s. From the viewpoint of suppressing dripping, the lower limit is preferably 2000 mPa·s or more, more preferably 5000 mPa·s or more, and still more preferably 10000 mPa·s or more. The upper limit is preferably 50,000 mPa·s or less, more preferably 40,000 mPa·s or less, and still more preferably 30,000 mPa·s or less, from the viewpoint of operability when applied to hair. The viscosity of the oxidative hair dye can be adjusted by adding an anionic surfactant, a cationic surfactant, or a thickening agent such as a water-soluble polymer. The mixed viscosity of the oxidative hair dye can be measured using a B-type viscometer such as a TVB-10 type viscometer, and measured at 25° C. for 1 minute using a rotor suitable for each viscosity. can be done.
　第１の実施態様に係る酸化染毛剤の形態及び酸化染毛剤を形成する各剤の形態は、どのような形態であってもよい。
　２剤式の酸化染毛剤の第１剤と第２剤の混合比は、酸化染毛剤の各成分の濃度、混合性、適用方法等を考慮して適宜設定されるが、好ましくは０．１～１０：１で、より好ましくは０．５～２：１である。酸化染毛剤の剤型は、毛髪に適用できる剤型であれば特に限定されず、例えば２５℃において、液状、クリーム状、ジェル状等の剤型とすることが挙げられる。また、各剤の混合後の酸化染毛剤が、液状、クリーム状、ジェル状等の塗布性を有する剤型であればよく、一部の剤に粉末状や固形状のものが含まれていてもよい。また、使用時に泡状やミスト状としてもよい。泡状とする場合には、エアゾールフォーマー容器、ノンエアゾールフォーマー容器、振とう容器等を使用すればよい。ミスト状とする場合には、噴霧器を使用すればよい。 The form of the oxidative hair dye according to the first embodiment and the form of each agent forming the oxidative hair dye may be of any form.
The mixing ratio of the first part and the second part of the two-component oxidative hair dye is appropriately set in consideration of the concentration, mixability, application method, etc. of each component of the oxidative hair dye, but is preferably 0. .1 to 10:1, more preferably 0.5 to 2:1. The dosage form of the oxidative hair dye is not particularly limited as long as it is applicable to hair, and examples thereof include liquid, cream, and gel dosage forms at 25°C. In addition, the oxidative hair dye after mixing each agent may be in a liquid, cream, gel, or other form that has applicability, and some agents include powders and solids. may Moreover, it may be foamy or misty at the time of use. When foaming, an aerosol foamer container, a non-aerosol foamer container, a shaking container, or the like may be used. In the case of forming a mist, a sprayer may be used.
　第１の実施態様に係る酸化染毛剤は、（Ａ）カプラー及び（Ｃ）ノニオン界面活性剤を含有し、（Ｂ）染料中間体、（Ｄ）ヨウ素化合物又は／及び（Ｅ）多価アルコールを含有してもよい。さらに、（Ａ）成分～（Ｅ）成分以外のその他の成分を含有してもよい。
　以下、第１の実施態様に係る酸化染毛剤に使用する各成分について、詳細に説明する。なお、各成分の含有量（質量％）については、特に断りがない場合には、各剤を混合した酸化染毛剤中の含有量を示す。 The oxidative hair dye according to the first embodiment contains (A) a coupler and (C) a nonionic surfactant, (B) a dye intermediate, (D) an iodine compound or/and (E) a polyhydric alcohol may contain. Furthermore, it may contain components other than components (A) to (E).
Each component used in the oxidative hair dye according to the first embodiment will be described in detail below. The content (% by mass) of each component indicates the content in the oxidative hair dye in which each agent is mixed, unless otherwise specified.
［（Ａ）カプラー］
　第１の実施態様に係る酸化染毛剤は、（Ａ）カプラーを含有する。（Ａ）カプラーとしては、主としてｍ－ジアミン類、アミノフェノール類又はジフェノール類が挙げられ、具体例としては、例えばレゾルシン、５－アミノ－ｏ－クレゾール、ｍ－アミノフェノール、α－ナフトール（１－ナフトール）、５－（２－ヒドロキシエチルアミノ）－２－メチルフェノール、ｍ－フェニレンジアミン、２，４－ジアミノフェノキシエタノール、トルエン－３，４－ジアミン、２，６－ジアミノピリジン、ジフェニルアミン、Ｎ，Ｎ－ジエチル－ｍ－アミノフェノール、フェニルメチルピラゾロン、１，５－ジヒドロキシナフタレン、カテコール、ピロガロール、フロログルシン、没食子酸、ハイドロキノン、３，３’－イミノジフェニール、タンニン酸及びそれらの塩等が例示される。
　なお、１種の（Ａ）成分を単独で使用してもよく、２種以上の（Ａ）成分を組み合わせて使用してもよい。 [(A) Coupler]
The oxidative hair dye according to the first embodiment contains (A) a coupler. (A) Couplers mainly include m-diamines, aminophenols and diphenols, and specific examples include resorcinol, 5-amino-o-cresol, m-aminophenol, α-naphthol (1 -naphthol), 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, N, Examples include N-diethyl-m-aminophenol, phenylmethylpyrazolone, 1,5-dihydroxynaphthalene, catechol, pyrogallol, phloroglucin, gallic acid, hydroquinone, 3,3'-iminodiphenyl, tannic acid and salts thereof. be.
In addition, one type of component (A) may be used alone, or two or more types of component (A) may be used in combination.
　第１の実施態様に係る（Ａ）カプラーとしては、好ましくは２，４－ジアミノフェノキシエタノール、２，６－ジアミノピリジン、５－（２－ヒドロキシエチルアミノ）－２－メチルフェノール、１－ナフトール、５－アミノ－ｏ－クレゾール、１，５－ジヒドロキシナフタレン、ｍ－アミノフェノール、及びそれらの塩が使用できる。その中でも、特に好ましくは、２，４－ジアミノフェノキシエタノール及びその塩である。２，４－ジアミノフェノキシエタノールは、後述する（Ｃ１）ＨＬＢ１０．０未満のノニオン界面活性剤との相乗効果により、染毛力をより向上させると推測される。 The (A) coupler according to the first embodiment is preferably 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5-(2-hydroxyethylamino)-2-methylphenol, 1-naphthol, 5 -Amino-o-cresol, 1,5-dihydroxynaphthalene, m-aminophenol, and salts thereof can be used. Among them, 2,4-diaminophenoxyethanol and salts thereof are particularly preferred. It is presumed that 2,4-diaminophenoxyethanol further improves hair dyeing power due to a synergistic effect with (C1) a nonionic surfactant having an HLB of less than 10.0, which will be described later.
　第１の実施態様に係る酸化染毛剤中の（Ａ）成分の含有量は、特に制限されないが、例えば、０．３質量％以上である。下限値として、好ましくは０．４質量％以上、より好ましくは０．５質量％以上、さらに好ましくは０．６質量％以上であり、さらにより好ましくは０．７質量％以上である。上限値として、好ましくは１０．０質量％以下、より好ましくは７．０質量％以下であり、さらに好ましくは５．０質量％以下であり、最も好ましくは３．５質量％以下である。０．３質量％以上とすることにより染毛力が向上し、１０．０質量％以下とすることにより、脱染性能をより向上でき、地肌汚れの抑制効果を向上させることができる。
　なお、（Ａ）カプラーが塩である場合、（Ａ）カプラーの含有量はその脱塩型での値とする。 The content of component (A) in the oxidative hair dye according to the first embodiment is not particularly limited, but is, for example, 0.3% by mass or more. The lower limit is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.6% by mass or more, and still more preferably 0.7% by mass or more. The upper limit is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, even more preferably 5.0% by mass or less, and most preferably 3.5% by mass or less. When the content is 0.3% by mass or more, the hair dyeing power is improved, and when the content is 10.0% by mass or less, the destaining performance can be further improved, and the effect of suppressing background stains can be improved.
When the (A) coupler is a salt, the content of the (A) coupler is the value in the desalted form.
　また、（Ａ）成分としての２，４－ジアミノフェノキシエタノールの酸化染毛剤中での好ましい配合量は、下限値は、染毛力の観点から、好ましくは０．１質量％以上、より好ましくは０．１５質量％以上、さらに好ましくは０．２質量％以上、よりさらに好ましくは０．２５質量％以上である。上限値は、地肌汚れの抑制効果の観点から、好ましくは５．０質量％以下、より好ましくは４．０質量％以下、さらに好ましくは３．０質量％以下、よりさらに好ましくは２．０質量％以下である。 In addition, the preferred amount of 2,4-diaminophenoxyethanol in the oxidative hair dye as the component (A) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of hair dyeing power. It is 0.15% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.25% by mass or more. The upper limit is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 3.0% by mass or less, and even more preferably 2.0% by mass, from the viewpoint of the effect of suppressing background stains. % or less.
［（Ｂ）染料中間体］
　第１の実施態様に係る酸化染毛剤は、必要により（Ｂ）染料中間体を含有することを妨げるものではない。（Ｂ）染料中間体としては、主としてｏ－又はｐ－のフェニレンジアミン類、あるいはアミノフェノール類である染料前駆物質が挙げられ、通常、それ自体は無色か又は弱く着色した化合物である。
　（Ｂ）染料中間体の具体例としては、例えばｐ－フェニレンジアミン、トルエン－２，５－ジアミン（ｐ－トルイレンジアミン）、Ｎ－フェニル－ｐ－フェニレンジアミン、４，４’－ジアミノジフェニルアミン、ｐ－アミノフェノール、ｏ－アミノフェノール、ｐ－メチルアミノフェノール、Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－ｐ－フェニレンジアミン、２－ヒドロキシエチル－ｐ－フェニレンジアミン、ｏ－クロル－ｐ－フェニレンジアミン、４－アミノ－ｍ－クレゾール、２－アミノ－４－ヒドロキシエチルアミノアニソール、１－ヒドロキシエチル－４，５－ジアミノピラゾール、２，４－ジアミノフェノール、それらの塩等が挙げられる。塩の具体例としては、例えば塩酸塩、硫酸塩等が挙げられる。
　なお、１種の（Ｂ）成分を単独で使用してもよく、２種以上の（Ｂ）成分を組み合わせて使用してもよい。
　また、第１の実施態様に係る酸化染毛剤の第１剤は、後述する酸化染料の具体例以外の染料として、例えば「医薬部外品原料規格」（２００６年６月発行、薬事日報社）に収載された酸化染料を適宜含有してもよい。 [(B) dye intermediate]
The oxidative hair dye according to the first embodiment may optionally contain (B) a dye intermediate. (B) Dye intermediates include dye precursors that are primarily o- or p-phenylenediamines or aminophenols, and are usually colorless or weakly colored compounds per se.
(B) Specific examples of dye intermediates include p-phenylenediamine, toluene-2,5-diamine (p-toluylenediamine), N-phenyl-p-phenylenediamine, 4,4′-diaminodiphenylamine, p-aminophenol, o-aminophenol, p-methylaminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chloro-p-phenylene diamine, 4-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 1-hydroxyethyl-4,5-diaminopyrazole, 2,4-diaminophenol, salts thereof and the like. Specific examples of salts include hydrochlorides, sulfates, and the like.
In addition, one type of component (B) may be used alone, or two or more types of component (B) may be used in combination.
In addition, the first agent of the oxidation hair dye according to the first embodiment is a dye other than the specific examples of the oxidation dye described later, for example, "Standards for Quasi-drug Ingredients" (published in June 2006, Yakuji Nippo Co., Ltd.) ) may be contained as appropriate.
　第１の実施態様に係る酸化染毛剤中における（Ｂ）成分の含有量は特に限定されないが、例えば、（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）は、０．０～０．４である。上限値として、好ましくは０．３以下、より好ましくは０．２以下であり、さらに好ましくは０．１以下である。
　質量比（Ｂ／Ａ）を０．４以下とすることにより、脱染性能をより向上でき、地肌汚れの抑制効果を向上させることができる。
　なお、質量比０．０とは、酸化染毛剤中に実質的に（Ｂ）成分を含有していないことを意味する。また、上記質量比の算出に用いられる含有量は、（Ａ）成分及び（Ｂ）成分ともにそれらの脱塩型での値とする。 The content of component (B) in the oxidative hair dye according to the first embodiment is not particularly limited, but for example, the mass ratio (B /A) is from 0.0 to 0.4. The upper limit is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less.
By setting the mass ratio (B/A) to 0.4 or less, the destaining performance can be further improved, and the effect of suppressing background contamination can be improved.
A mass ratio of 0.0 means that the oxidative hair dye does not substantially contain the component (B). The content used for calculating the above mass ratio is the value of the desalted form of both the (A) component and the (B) component.
　第１の実施態様に係る酸化染毛剤中における（Ｂ）染料中間体の含有量の上限は、上記含有量の質量比（Ｂ／Ａ）の範囲内において適宜設定されるが、好ましくは１．０質量％以下、より好ましくは０．５質量％以下、さらに好ましくは０．２質量％以下であり、特に好ましくは酸化染毛剤が（Ｂ）染料中間体を実質的に含有しないことである。なお、本発明において「実質的に含有しない」とは、含有量が０．１質量％以下であることを意味する。（Ｂ）染料中間体の含有量が１．０質量％以下であると、脱染性能をより向上できる。なお、（Ｂ）染料中間体が塩である場合、（Ｂ）染料中間体の含有量はその脱塩型での値とする。 The upper limit of the content of the dye intermediate (B) in the oxidative hair dye according to the first embodiment is appropriately set within the range of the mass ratio (B/A) of the content, but preferably 1 0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and particularly preferably the oxidative hair dye does not substantially contain (B) the dye intermediate. be. In the present invention, "substantially does not contain" means that the content is 0.1% by mass or less. When the content of the dye intermediate (B) is 1.0% by mass or less, the destaining performance can be further improved. When the (B) dye intermediate is a salt, the content of the (B) dye intermediate is the value in the desalted form.
［（Ｃ）ノニオン界面活性剤］
　第１の実施態様に係る酸化染毛剤は、（Ｃ）ノニオン界面活性剤として、（Ｃ１）ＨＬＢ１０未満のノニオン界面活性剤を含有する。（Ｃ）成分を含有する場合、染毛力を向上させ、地肌汚れの抑制効果を向上させることができる。
　（Ｃ）ノニオン界面活性剤の具体例としては、例えばエーテル型ノニオン界面活性剤（ＰＯＥアルキルエーテル類、ＰＯＥアルキルフェニルエーテル類、ＰＯＥ・ＰＯＰアルキルエーテル類等）、エステル型ノニオン界面活性剤（ＰＯＥソルビタン脂肪酸エステル類、ＰＯＥモノ脂肪酸エステル類、ＰＯＥグリセリン脂肪酸エステル類、ポリグリセリン脂肪酸エステル類、モノグリセリン脂肪酸エステル類、ソルビタン脂肪酸エステル類、ショ糖脂肪酸エステル類等）、アルキルグルコシド（アルキルポリグルコシド類等）等が挙げられる。 [(C) nonionic surfactant]
The oxidative hair dye according to the first embodiment contains (C1) a nonionic surfactant having an HLB of less than 10 as (C) a nonionic surfactant. When the component (C) is contained, the hair dyeing power can be improved, and the effect of suppressing background stains can be improved.
(C) Specific examples of nonionic surfactants include ether-type nonionic surfactants (POE alkyl ethers, POE alkylphenyl ethers, POE/POP alkyl ethers, etc.), ester-type nonionic surfactants (POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, polyglycerin fatty acid esters, monoglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, etc.), alkyl glucosides (alkyl polyglucosides, etc.) etc.
　エーテル型ノニオン界面活性剤の具体例としては、例えばＰＯＥセチルエーテル（セテス）、ＰＯＥステアリルエーテル（ステアレス）、ＰＯＥベヘニルエーテル、ＰＯＥオレイルエーテル（オレス）、ＰＯＥラウリルエーテル（ラウレス）、ＰＯＥオクチルドデシルエーテル、ＰＯＥヘキシルデシルエーテル、ＰＯＥイソステアリルエーテル、ＰＯＥノニルフェニルエーテル、ＰＯＥオクチルフェニルエーテル、ＰＯＥ・ＰＯＰセチルエーテル、ＰＯＥ・ＰＯＰデシルテトラデシルエーテル等が挙げられる。 Specific examples of ether-type nonionic surfactants include POE cetyl ether (ceteth), POE stearyl ether (steareth), POE behenyl ether, POE oleyl ether (oleth), POE lauryl ether (laureth), POE octyldodecyl ether, POE hexyl decyl ether, POE isostearyl ether, POE nonylphenyl ether, POE octylphenyl ether, POE.POP cetyl ether, POE.POP decyltetradecyl ether and the like.
　エステル型ノニオン界面活性剤の具体例としては、例えばモノオレイン酸ＰＯＥソルビタン、モノステアリン酸ＰＯＥソルビタン、モノパルミチン酸ＰＯＥソルビタン、モノラウリン酸ＰＯＥソルビタン、トリオレイン酸ＰＯＥソルビタン、モノステアリン酸ＰＯＥグリセリン、モノミリスチン酸ＰＯＥグリセリン、テトラオレイン酸ＰＯＥソルビット、ヘキサステアリン酸ＰＯＥソルビット、モノラウリン酸ＰＯＥソルビット、ＰＯＥソルビットミツロウ、モノオレイン酸ポリエチレングリコール、モノステアリン酸ポリエチレングリコール、モノラウリン酸ポリエチレングリコール、親油型モノオレイン酸グリセリン、親油型モノステアリン酸グリセリン、自己乳化型モノステアリン酸グリセリン、モノオレイン酸ソルビタン、セスキオレイン酸ソルビタン、トリオレイン酸ソルビタン、モノステアリン酸ソルビタン、モノパルミチン酸ソルビタン、モノラウリン酸ソルビタン、ショ糖脂肪酸エステル、モノラウリン酸デカグリセリル、モノステアリン酸デカグリセリル、モノオレイン酸デカグリセリル、モノミリスチン酸デカグリセリル等が挙げられる。 Specific examples of ester-type nonionic surfactants include POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monopalmitate, POE sorbitan monolaurate, POE sorbitan trioleate, POE glycerol monostearate, and monomyristin. acid POE glycerin, POE sorbitol tetraoleate, POE sorbitol hexastearate, POE sorbitol monolaurate, POE sorbitol beeswax, polyethylene glycol monooleate, polyethylene glycol monostearate, polyethylene glycol monolaurate, lipophilic glycerol monooleate, Lipophilic glyceryl monostearate, self-emulsifying glyceryl monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, sucrose fatty acid ester, decaglyceryl monolaurate, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl monomyristate and the like.
　アルキルグルコシドの具体例として、例えばアルキル（８～１６）グルコシド、ＰＯＥメチルグルコシド、ＰＯＥジオレイン酸メチルグルコシド等が挙げられる。 Specific examples of alkyl glucosides include alkyl (8-16) glucoside, POE methyl glucoside, POE methyl dioleate glucoside, and the like.
　第１の実施態様に係る酸化染毛剤の（Ｃ）成分は、（Ｃ１）ＨＬＢ１０．０未満のノニオン界面活性剤を１種以上と、（Ｃ２）ＨＬＢ１０．０以上のノニオン界面活性剤を１種以上と、を有する２種以上を含有することが好ましい。これにより、より染毛力を向上することができ、かつ地肌汚れを抑制することができる The (C) component of the oxidative hair dye according to the first embodiment includes (C1) one or more nonionic surfactants with an HLB of less than 10.0 and (C2) one nonionic surfactant with an HLB of 10.0 or more. It is preferable to contain two or more species having at least one species. As a result, it is possible to further improve the hair dyeing power and to suppress the stain on the skin.
　（Ｃ１）ＨＬＢ１０．０未満のノニオン界面活性剤の具体例としては、ＰＯＥ（２）セチルエーテル＜８．０＞、ＰＯＥ（２）ステアリルエーテル＜８．０＞、ＰＯＥ（４）ステアリルエーテル＜９．０＞、ＰＯＥ（５）ベヘニルエーテル＜７．０＞、ＰＯＥ（２）オレイルエーテル＜７．５＞、ＰＯＥ（２）ラウリルエーテル＜９．５＞、ＰＯＥ（１）ＰＯＰ（４）セチルエーテル＜９．５＞が挙げられる。
　これらの中でも、染毛力と乳化安定性の観点から、（Ｃ１）として、好ましくは、ＰＯＥ（２）セチルエーテル＜８．０＞、ＰＯＥ（２）ステアリルエーテル＜８．０＞、ＰＯＥ（４）ステアリルエーテル＜９．０＞、ＰＯＥ（５）ベヘニルエーテル＜７．０＞、ＰＯＥ（１）ＰＯＰ（４）セチルエーテル＜９．５＞が挙げられる。
　なお、＜＞内の数値はＨＬＢの実測値であり、以下の＜＞内の数値も同様である。 (C1) Specific examples of nonionic surfactants having an HLB of less than 10.0 include POE (2) cetyl ether <8.0>, POE (2) stearyl ether <8.0>, POE (4) stearyl ether <9 .0>, POE (5) behenyl ether <7.0>, POE (2) oleyl ether <7.5>, POE (2) lauryl ether <9.5>, POE (1) POP (4) cetyl ether <9.5> can be mentioned.
Among these, from the viewpoint of hair dyeing power and emulsion stability, (C1) is preferably POE (2) cetyl ether <8.0>, POE (2) stearyl ether <8.0>, POE (4 ) stearyl ether <9.0>, POE (5) behenyl ether <7.0>, POE (1) POP (4) cetyl ether <9.5>.
The numerical value in <> is the measured value of HLB, and the same applies to the numerical value in <> below.
　また、ＨＬＢ１０．０未満のエステル型ノニオン界面活性剤としては、ポリオキシエチレンステアリン酸グリセリル＜９．５＞、テトラオレイン酸ＰＯＥ（６）ソルビット＜８．５＞、ＰＯＥ（６）ソルビットミツロウ＜７．５＞、ＰＯＥ（２０）ソルビットミツロウ＜９．５＞、モノオレイン酸ポリエチレングリコール（６Ｅ．０．）＜８．５＞、モノステアリン酸ポリエチレングリコール（２Ｅ．Ｏ．）＜４．０＞、モノステアリン酸ポリエチレングリコール＜６．５＞、モノステアリン酸グリセリル＜３．０＞、モノステアリン酸グリセリル＜４．０＞、モノステアリン酸グリセリル（自己乳化型）＜８．０＞、モノステアリン酸グリセリル（自己乳化型）＜５．５＞、モノオレイン酸ソルビタン＜４．５＞、セスキオレイン酸ソルビタン＜４．０＞、トリオレイン酸ソルビタン＜２．０＞、モノステアリン酸ソルビタン＜４．５＞、モノステアリン酸グリセリル（自己乳化型）＜３．０＞、モノステアリン酸グリセリル＜４．０＞、モノパルミチン酸ソルビタン＜６．５＞、モノラウリン酸ソルビタン＜８．５＞が挙げられる。
　これらの中でも、染毛力と乳化安定性の観点から、第１の実施態様に係る（Ｃ１）成分として、好ましくは、ポリオキシエチレンステアリン酸グリセリル＜９．５＞、モノステアリン酸ポリエチレングリコール＜６．５＞が挙げられる。 In addition, as ester-type nonionic surfactants with an HLB of less than 10.0, polyoxyethylene glyceryl stearate <9.5>, POE tetraoleate (6) sorbitol <8.5>, POE (6) sorbitol beeswax <7 .5>, POE (20) sorbitol beeswax <9.5>, polyethylene glycol monooleate (6E.0.) <8.5>, polyethylene glycol monostearate (2E.O.) <4.0>, Polyethylene glycol monostearate <6.5>, glyceryl monostearate <3.0>, glyceryl monostearate <4.0>, glyceryl monostearate (self-emulsifying type) <8.0>, glyceryl monostearate (Self-emulsifying type) <5.5>, sorbitan monooleate <4.5>, sorbitan sesquioleate <4.0>, sorbitan trioleate <2.0>, sorbitan monostearate <4.5> , glyceryl monostearate (self-emulsifying type) <3.0>, glyceryl monostearate <4.0>, sorbitan monopalmitate <6.5>, sorbitan monolaurate <8.5>.
Among these, polyoxyethylene glyceryl stearate <9.5> and polyethylene glycol monostearate <6> are preferable as the component (C1) according to the first embodiment from the viewpoint of hair dyeing power and emulsion stability. .5>.
　（Ｃ２）ＨＬＢ１０．０以上のエーテル型ノニオン界面活性剤として、ＰＯＥ（３０）セチルエーテル＜１９．５＞、ＰＯＥ（２５）セチルエーテル＜１８．５＞、ＰＯＥ（２０）セチルエーテル＜１７．０＞、ＰＯＥ（１５）セチルエーテル＜１５．５＞、ＰＯＥ（１０）セチルエーテル＜１３．５＞、ＰＯＥ（５．５）セチルエーテル＜１０．５＞、ＰＯＥ（２０）ステアリルエーテル＜１８．０＞、ＰＯＥ（３０）ベヘニルエーテル＜１８．５＞、ＰＯＥ（２０）ベヘニルエーテル＜１６．５＞、ＰＯＥ（１０）ベヘニルエーテル＜１０．０＞、ＰＯＥ（１０）オレイルエーテル＜１４．５＞、ＰＯＥ（１５）オレイルエーテル＜１６．０＞、ＰＯＥ（２０）オレイルエーテル＜１７．０＞、ＰＯＥ（５０）オレイルエーテル＜１８．０＞、ＰＯＥ（９）ラウリルエーテル＜１４．５＞、トリＰＯＥ（４）ラウリルエーテルリン酸＜１３．０＞、ＰＯＥ（２１）ラウリルエーテル＜１９．０＞、ＰＯＥ（１０）ＰＯＰ（４）セチルエーテル＜１０．５＞、ＰＯＥ（２０）ＰＯＰ（８）セチルエーテル＜１２．５＞、ＰＯＥ（２０）ＰＯＰ（４）セチルエーテル＜１６．５＞、ＰＯＥ（２０）ＰＯＰ（６）デシルテトラデシルエーテル＜１１．０＞、ＰＯＥ（３０）ＰＯＰ（６）デシルテトラデシルエーテル＜１２．０＞が挙げられる。
　なお、染毛力と乳化安定性の観点から、第１の実施態様に係る（Ｃ２）成分として、好ましくは、ＰＯＥ（３０）セチルエーテル＜１９．５＞、ＰＯＥ（２５）セチルエーテル＜１８．５＞、ＰＯＥ（２０）セチルエーテル＜１７．０＞が挙げられる。 (C2) As ether-type nonionic surfactants with an HLB of 10.0 or more, POE (30) cetyl ether <19.5>, POE (25) cetyl ether <18.5>, POE (20) cetyl ether <17.0 >, POE (15) cetyl ether <15.5>, POE (10) cetyl ether <13.5>, POE (5.5) cetyl ether <10.5>, POE (20) stearyl ether <18.0 >, POE (30) behenyl ether <18.5>, POE (20) behenyl ether <16.5>, POE (10) behenyl ether <10.0>, POE (10) oleyl ether <14.5>, POE (15) oleyl ether <16.0>, POE (20) oleyl ether <17.0>, POE (50) oleyl ether <18.0>, POE (9) lauryl ether <14.5>, tri-POE (4) Lauryl ether phosphate <13.0>, POE (21) Lauryl ether <19.0>, POE (10) POP (4) Cetyl ether <10.5>, POE (20) POP (8) Cetyl ether <12.5>, POE(20) POP(4) cetyl ether <16.5>, POE(20) POP(6) decyltetradecyl ether <11.0>, POE(30) POP(6) decyl and tetradecyl ether <12.0>.
From the viewpoint of hair dyeing power and emulsion stability, the (C2) component according to the first embodiment is preferably POE (30) cetyl ether <19.5>, POE (25) cetyl ether <18. 5> and POE (20) cetyl ether <17.0>.
　また、ＨＬＢが１０．０以上のエステル型ノニオン界面活性剤としては、テトラオレイン酸ＰＯＥ（６０）ソルビット＜１４．０＞、テトラオレイン酸ＰＯＥ（３０）ソルビット＜１１．５＞、テトラオレイン酸ＰＯＥ（４０）ソルビット＜１２．５＞、モノラウリン酸ＰＯＥ（６）ソルビット＜１５．５＞、モノオレイン酸ポリエチレングリコール（１０Ｅ．Ｏ．）＜１１．０＞、モノステアリン酸ポリエチレングリコール（１０Ｅ．Ｏ．）＜１１．０＞、モノステアリン酸ポリエチレングリコール（２５Ｅ．Ｏ．）＜１５．０＞、モノステアリン酸ポリエチレングリコール（４０Ｅ．Ｏ．）＜１７．５＞、モノステアリン酸ポリエチレングリコール（５５Ｅ．Ｏ．）＜１８．０＞、モノステアリン酸ポリエチレングリコール＜１８．０＞、モノラウリン酸ポリエチレングリコール（１０Ｅ．Ｏ．）＜１２．５＞、モノステアリン酸グリセリル（自己乳化型）＜１０．０＞、モノラウリン酸デカグリセリル＜１５．５＞、モノステアリン酸デカグリセリル＜１５．０＞、モノステアリン酸デカグリセリル＜１２．０＞、モノオレイン酸デカグリセリル＜１２．０＞、モノミリスチン酸デカグリセリル＜１４．０＞、ポリグリセリン脂肪酸エステル＜１４．５＞が挙げられる。
　これらの中でも、染毛力と乳化安定性の観点から（Ｃ２）成分として、好ましくはポリグリセリン脂肪酸エステル＜１４．５＞が挙げられる。 Examples of ester-type nonionic surfactants having an HLB of 10.0 or more include POE tetraoleate (60) sorbitol <14.0>, POE tetraoleate (30) sorbitol <11.5>, and POE tetraoleate. (40) Sorbit <12.5>, POE monolaurate (6) Sorbit <15.5>, Polyethylene glycol monooleate (10E.O.) <11.0>, Polyethylene glycol monostearate (10E.O.) ) <11.0>, polyethylene glycol monostearate (25 E.O.) <15.0>, polyethylene glycol monostearate (40 E.O.) <17.5>, polyethylene glycol monostearate (55 E.O.) .) <18.0>, polyethylene glycol monostearate <18.0>, polyethylene glycol monolaurate (10E.O.) <12.5>, glyceryl monostearate (self-emulsifying) <10.0>, Decaglyceryl Monolaurate <15.5>, Decaglyceryl Monostearate <15.0>, Decaglyceryl Monostearate <12.0>, Decaglyceryl Monooleate <12.0>, Decaglyceryl Monomyristate <14 .0> and polyglycerin fatty acid ester <14.5>.
Among these, polyglycerin fatty acid ester <14.5> is preferably used as the component (C2) from the viewpoint of hair dyeing power and emulsion stability.
　また、本発明のＨＬＢの値は実測値である。ＨＬＢ値は、Ｗ．Ｃ．Ｇｒｉｆｆｉｎによって考えられ、ノニオン界面活性剤に対して与えられた数値であり、ノニオン界面活性剤の親油基（アルキル基）と親水基（酸化エチレン鎖）との強さのバランスを数字で表したものである。ＨＬＢ値は、乳化法から算出した実測値が用いられる（「ハンドブック－化粧品・製剤原料－」日光ケミカルズ株式会社（昭和５２年２月１日改訂版発行）参照）。実測ＨＬＢ値の測定には、界面活性剤の標準物質としてモノステアリン酸ソルビタン（例えば、日光ケミカルズ社製のＮＩＫＫＯＬ　ＳＳ－１０、ＨＬＢ値４．７）とモノステアリン酸ポリオキシエチレンソルビタン（例えば、日光ケミカルズ社製のＮＩＫＫＯＬ　ＴＳ－１０、ＨＬＢ値１４．９）を組み合わせて使用する。被乳化物には流動パラフィンを使用する。なお、流動パラフィンは種類による、又はロットによる変動が考えられる場合は、その都度測定する。流動パラフィンを上記２種類の界面活性剤で乳化し、最適な界面活性剤の割合を求め、流動パラフィンの所要ＨＬＢ値（乳化されるＨＬＢ値）を求める。計算式は数式（１）に示される。 Also, the HLB value of the present invention is an actual measurement value. The HLB value is according to W.W. C. Conceived by Griffin, it is a numerical value given to nonionic surfactants, and represents the balance of strength between the lipophilic group (alkyl group) and the hydrophilic group (ethylene oxide chain) of the nonionic surfactant. It is. As the HLB value, a measured value calculated by an emulsification method is used (see "Handbook - Cosmetics/Materials for Pharmaceutical Preparations" Nikko Chemicals Co., Ltd. (published February 1, 1977)). For measurement of actual HLB values, sorbitan monostearate (for example, NIKKOL SS-10 manufactured by Nikko Chemicals Co., Ltd., HLB value 4.7) and polyoxyethylene sorbitan monostearate (for example, Nikko Chemicals NIKKOL TS-10, HLB value 14.9) is used in combination. Liquid paraffin is used as the material to be emulsified. Liquid paraffin should be measured on a case-by-case basis if variations are expected depending on the type or lot. Liquid paraffin is emulsified with the two types of surfactants described above, the optimum ratio of surfactants is determined, and the required HLB value of liquid paraffin (HLB value to be emulsified) is determined. A calculation formula is shown in Formula (1).
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　通常流動パラフィンの所要ＨＬＢ値は、種類、及びロットにもよるが１０．１～１０．３程度である。
　次に、未知の界面活性剤のＨＬＢ値の測定は、所要ＨＬＢ値を求めた流動パラフィンを用いて測定する。未知の界面活性剤が親水性であればモノステアリン酸ソルビタンと組み合わせ、未知の界面活性剤が疎水性であればモノステアリン酸ポリオキシエチレンソルビタンと組み合わせて、上記流動パラフィンを乳化し、安定性のあるところの最適割合を求め、未知の界面活性剤のＨＬＢ値をｘとして上記数式（１）に当てはめて算出する。 The required HLB value of normal liquid paraffin is about 10.1 to 10.3, depending on the type and lot.
Next, the HLB value of the unknown surfactant is measured using liquid paraffin from which the required HLB value was determined. If the unknown surfactant is hydrophilic, it is combined with sorbitan monostearate, and if the unknown surfactant is hydrophobic, it is combined with polyoxyethylene sorbitan monostearate to emulsify the liquid paraffin and stabilize it. An optimum ratio at a certain point is determined and calculated by applying the HLB value of the unknown surfactant to the above formula (1) as x.
　第１の実施態様に係る酸化染毛剤中の（Ｃ）成分の含有量は、特に制限されないが、例えば、０．１～１０質量％である。下限値として、好ましくは０．２質量％以上、より好ましくは０．５質量％以上、さらに好ましくは１．０質量％以上であり、上限値として、好ましくは８．０質量％以下であり、より好ましくは７．０質量％以下、さらに好ましくは６．０％以下である。０．１質量％以上とすることにより染毛力が向上し、１０．０質量％以下とすることにより、地肌汚れの抑制効果を向上させることができる。 The content of component (C) in the oxidative hair dye according to the first embodiment is not particularly limited, but is, for example, 0.1 to 10% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, and the upper limit is preferably 8.0% by mass or less. More preferably 7.0% by mass or less, still more preferably 6.0% or less. When the content is 0.1% by mass or more, the hair dyeing power is improved, and when the content is 10.0% by mass or less, the effect of suppressing background stains can be improved.
　第１の実施態様に係る酸化染毛剤において、（Ａ）カプラーの含有量と（Ｂ）染料中間体の含有量との合計量に対する（Ｃ）ノニオン界面活性剤の含有量の質量比（（Ｃ）／（（Ａ）＋（Ｂ）））は、０．１以上～３０．０以下ある。下限値としては、好ましくは０．３以上、より好ましくは０．５以上である。また、上限値としては、好ましくは２５．０以下、より好ましくは２０．０以下である。
　上記の質量比を０．１以上～３０．０以下とすることで、地肌汚れの抑制効果と乳化安定性向上効果の調和がとれた酸化染毛剤とすることができる。 In the oxidative hair dye according to the first embodiment, the mass ratio (( C)/((A)+(B))) is between 0.1 and 30.0. The lower limit is preferably 0.3 or more, more preferably 0.5 or more. Also, the upper limit is preferably 25.0 or less, more preferably 20.0 or less.
By setting the above mass ratio to 0.1 or more and 30.0 or less, it is possible to obtain an oxidative hair dye that is well-balanced between the effect of suppressing background stains and the effect of improving emulsification stability.
　（Ｃ１）成分のＨＬＢの値は１０．０未満であれば特に限定されないが、例えば３．０以上～１０．０未満である。下限値としては、好ましくは４．０以上、より好ましくは５．０以上、さらに好ましくは６．０以上、最も好ましくは７．０以上であり、上限値としては、好ましくは９．９以下、より好ましくは９．８以下、さらに好ましくは９．７以下である。
　（Ｃ２）成分のＨＬＢの値は１０．０以上であれば特に限定されないが、例えば１０．０以上～２０．０未満である。下限値としては、好ましくは１１．０以上、より好ましくは１２．５以上、さらに好ましくは１４．０以上、最も好ましくは１５．５以上であり、上限値としては、好ましくは１９．９以下、より好ましくは１９．５以下、さらに好ましくは１９．０以下である。
　（Ｃ１）成分と（Ｃ２）成分が上記の範囲であれば、酸化染毛剤の乳化安定性を向上させつつ、染毛力の向上及び地肌汚れの抑制効果を向上させることできる。 The HLB value of component (C1) is not particularly limited as long as it is less than 10.0. The lower limit is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, and most preferably 7.0 or more, and the upper limit is preferably 9.9 or less. It is more preferably 9.8 or less, still more preferably 9.7 or less.
The HLB value of component (C2) is not particularly limited as long as it is 10.0 or more, but is, for example, 10.0 or more and less than 20.0. The lower limit is preferably 11.0 or more, more preferably 12.5 or more, still more preferably 14.0 or more, and most preferably 15.5 or more, and the upper limit is preferably 19.9 or less. It is more preferably 19.5 or less, still more preferably 19.0 or less.
If the component (C1) and the component (C2) are within the above range, the emulsification stability of the oxidative hair dye can be improved, while the hair dyeing power and the effect of suppressing background stains can be improved.
　また、（Ｃ２）成分の含有量に対する（Ｃ１）成分の含有量の質量比（Ｃ１）／（Ｃ２）が、１．０～８．０である。下限値として、好ましくは１．０以上、より好ましくは１．２５以上、さらに好ましくは１．５以上であり、最も好ましくは１．７５以上であり、上限値として、好ましくは７．０以下、より好ましくは６．０以下であり、さらに好ましくは５．０以下である。質量比を１．０以上とすることにより、より染毛力が向上し、質量比を８．０以下とすることにより、より地肌汚れの抑制効果を向上させることができる。 Also, the mass ratio (C1)/(C2) of the content of component (C1) to the content of component (C2) is 1.0 to 8.0. The lower limit is preferably 1.0 or more, more preferably 1.25 or more, still more preferably 1.5 or more, and most preferably 1.75 or more, and the upper limit is preferably 7.0 or less. It is more preferably 6.0 or less, still more preferably 5.0 or less. By setting the mass ratio to 1.0 or more, the hair dyeing power can be further improved, and by setting the mass ratio to 8.0 or less, the effect of suppressing background stains can be further improved.
［（Ｄ）ヨウ素化合物］
　第１の実施態様に係る酸化染毛剤は、（Ｄ）ヨウ素化合物を含有していてもよい。（Ｄ）ヨウ素化合物は、ヨウ素化合物を構成するヨウ素が過酸化水素を分解させて、酸化染料の重合を促進することで、染毛力を向上させる。（Ｄ）ヨウ素化合物としては、ヨウ素（Ｉ２）の他、可溶化剤中で遊離する対イオンを伴うヨウ素化合物、使用時にヨウ素を遊離する化合物等が挙げられる。ヨウ素化合物の具体例としては、例えばヨウ化カリウム、ヨウ化ナトリウム、ヨウ化リチウム、ヨウ化アンモニウム等のヨウ素化合物のアルカリ金属塩や、ヨウ化水素、ヨウ化セシウム、ヨウ化銀等が挙げられる。
　なお、染毛力の観点から、特に好ましくは、ヨウ化カリウム、ヨウ化ナトリウム、ヨウ化アンモニウムが挙げれらる。
　また、ヨウ素を含有する天然素材、例えばヨウ化ニンニクエキス等のヨウ素化合物を含有するエキス等を適用してもよい。１種の（Ｄ）成分を単独で使用してもよく、２種以上の（Ｄ）成分を組み合わせて使用してもよい。 [(D) Iodine compound]
The oxidative hair dye according to the first embodiment may contain (D) an iodine compound. (D) The iodine compound improves hair dyeing power by decomposing hydrogen peroxide with iodine constituting the iodine compound and promoting polymerization of the oxidation dye. Examples of (D) iodine compounds include iodine (I 2 ), iodine compounds with counter ions that are released in the solubilizer, and compounds that release iodine during use. Specific examples of iodine compounds include alkali metal salts of iodine compounds such as potassium iodide, sodium iodide, lithium iodide and ammonium iodide, hydrogen iodide, cesium iodide and silver iodide.
From the viewpoint of hair dyeing power, potassium iodide, sodium iodide and ammonium iodide are particularly preferred.
In addition, natural materials containing iodine, for example, extracts containing iodine compounds such as iodine garlic extract may be applied. One (D) component may be used alone, or two or more (D) components may be used in combination.
　第１の実施態様において、各剤が混合された後の酸化染毛剤中における（Ｄ）ヨウ素化合物の含有量は、特に限定されないが、例えば、０．００１～５．０質量％である。下限値としては、好ましくは０．００５質量％以上、より好ましくは０．０１質量％以上、さらに好ましくは０．０１５質量％以上、最も好ましくは０．０２質量％以上であり、上限値としては、好ましくは４．５質量％以下、より好ましくは３．０質量％以下、さらに好ましくは２．０質量％以下である。（Ｄ）ヨウ素化合物の含有量が０．００１質量％以上とすることにより染毛力をより向上でき、５．０質量％以下であると、脱染性能をより向上させることができる。
　特に、（Ｄ）ヨウ素化合物は、（Ｃ１）成分であるＨＬＢの値が１０．０未満のノニオン界面活性剤の存在する条件下で、（Ａ）カプラーと好適に作用し、染毛力の向上効果がある。（Ａ）カプラーとして、２，４－ジアミノフェノキシエタノールの場合、より染毛力向上の作用が発揮される。 In the first embodiment, the content of (D) the iodine compound in the oxidative hair dye after mixing the agents is not particularly limited, but is, for example, 0.001 to 5.0% by mass. The lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.015% by mass or more, and most preferably 0.02% by mass or more, and the upper limit is , preferably 4.5% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less. When the content of the (D) iodine compound is 0.001% by mass or more, the hair dyeing power can be further improved, and when it is 5.0% by mass or less, the destaining performance can be further improved.
In particular, (D) the iodine compound preferably acts with the (A) coupler in the presence of a nonionic surfactant having an HLB value of less than 10.0, which is the component (C1), to improve hair dyeing power. effective. (A) In the case of 2,4-diaminophenoxyethanol as the coupler, the effect of improving the hair dyeing power is exhibited.
　第１の実施態様において、（Ａ）カプラーの含有量と（Ｂ）染料中間体の合計の含有量に対する（Ｄ）ヨウ素化合物の含有量の質量比（（Ｄ）／（（Ａ）＋（Ｂ）））は、０．００５以上～１．０以下ある。下限値としては、好ましくは０．０１以上、より好ましくは０．０１５以上である。また、上限値としては、好ましくは０．８以下、より好ましくは０．５以下である。
　上記の質量比を０．００５以上～１．０以下とすることで、染毛力を向上させることができる。 In the first embodiment, the mass ratio ((D)/((A)+(B ))) is between 0.005 and 1.0. The lower limit is preferably 0.01 or more, more preferably 0.015 or more. Also, the upper limit is preferably 0.8 or less, more preferably 0.5 or less.
By setting the above mass ratio to 0.005 or more and 1.0 or less, hair dyeing power can be improved.
　なお、第１の実施態様に係る酸化染毛剤において、（Ｃ）ノニオン界面活性剤の含有量に対する（Ｄ）ヨウ素化合物の含有量の質量比（Ｄ／Ｃ）を適宜調整することにより、地肌汚れ抑制効果を向上できる。 In addition, in the oxidative hair dye according to the first embodiment, by appropriately adjusting the mass ratio (D/C) of the content of the (D) iodine compound to the content of the (C) nonionic surfactant, It is possible to improve the antifouling effect.
［（Ｅ）多価アルコール］
　第１の実施態様に係る酸化染毛剤は、（Ｅ）多価アルコールを含有していてもよい。（Ｅ）多価アルコールの具体例としては、例えばグリコール、グリセリン等が挙げられる。（Ｅ）成分を含有する場合、製剤安定性が向上する。
　また、これらの多価アルコールは単独で配合してもよいし、２種以上を組み合わせて配合してもよい。 [(E) polyhydric alcohol]
The oxidative hair dye according to the first embodiment may contain (E) a polyhydric alcohol. Specific examples of (E) polyhydric alcohols include glycol and glycerin. (E) When containing a component, formulation stability improves.
Moreover, these polyhydric alcohols may be blended alone, or two or more of them may be blended in combination.
　グリコールの具体例としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリエチレングリコール（例えば、ＰＥＧ４００、ＰＥＧ１０００、ＰＥＧ１５００、ＰＥＧ１５４０など）、ポリプロピレングリコール、イソプレングリコール、１，３－ブチレングリコールなどが挙げられる。
　グリセリンの具体例としては、例えば、グリセリン、ジグリセリン、ポリグリセリンなどが挙げられる。 Specific examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol (eg, PEG400, PEG1000, PEG1500, PEG1540, etc.), polypropylene glycol, isoprene glycol, 1,3- butylene glycol and the like.
Specific examples of glycerin include glycerin, diglycerin, polyglycerin and the like.
　第１の実施態様に係る酸化染毛剤中における（Ｅ）成分の含有量は特に限定されないが、０．０～２．０質量％である。上限値として、好ましくは１．０質量％以下、より好ましくは０．８質量％以下であり、さらに好ましくは０．５質量％以下である。２．０質量％以下とすることにより、染毛力を向上させることができる。なお、０．０質量％とは、実質的に（Ｅ）成分を含有しないことを意味する。 The content of component (E) in the oxidation hair dye according to the first embodiment is not particularly limited, but is 0.0 to 2.0% by mass. The upper limit is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. By making it 2.0% by mass or less, the hair dyeing power can be improved. In addition, 0.0 mass % means not containing (E) component substantially.
［直接染料］
　第１の実施態様に係る酸化染毛剤は、直接染料を含有してもよい。直接染料は、色を有する化合物であり、毛髪に付着、又は浸透して染毛する染料であれば特に制限されるものではない。例えば、酸性染料、塩基性染料、天然染料、ニトロ染料、ＨＣ染料、分散染料等が挙げられる。染毛力を向上させる観点から酸性染料を含むことが好ましい。
　また、これらの直接染料は、所望する毛髪の色調に応じて単独で配合してもよいし、２種以上を組み合わせて配合してもよい。 [Direct dye]
The oxidative hair dye according to the first embodiment may contain a direct dye. A direct dye is a compound having a color, and is not particularly limited as long as it adheres to or permeates the hair to dye the hair. Examples thereof include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes and disperse dyes. It is preferable to contain an acid dye from the viewpoint of improving the hair dyeing power.
These direct dyes may be blended alone or in combination of two or more depending on the desired color tone of the hair.
　酸性染料の具体例としては、例えば、赤色２号、赤色３号、赤色１０２号、赤色１０４号の（１）、赤色１０５号の（１）、赤色１０６号、赤色２２７号、赤色２３０号の（１）、黄色４号、黄色５号、黄色２０２号の（１）、黄色２０２号の（２）、黄色２０３号、だいだい色２０５号、だいだい色２０７号、だいだい色４０２号、緑色３号、緑色２０４号、緑色４０１号、紫色４０１号、青色１号、青色２号、青色２０２号、かっ色２０１号、黒色４０１号等が挙げられる。 Specific examples of acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227 and Red No. 230. (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3 , Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, and Black No. 401.
　塩基性染料の具体例としては、例えば、Basic Blue 3、Basic Blue 6、Basic Blue 7、Basic Blue 9、Basic Blue 26、Basic Blue 41、Basic Blue 47、Basic Blue 75、Basic Blue 99、Basic Blue 124、Basic Brown 4、Basic Brown 16、Basic Brown 17、Basic Green 1、Basic Green 4、Basic Orange 1、Basic Orange 2、Basic Orange 31、Basic Red 1、Basic Red 2、Basic Red 22、Basic Red 46、Basic Red 51、Basic Red 76、Basic Red 118、Basic Violet 1、Basic Violet 3、Basic Violet 4、Basic Violet 10、Basic Violet11:1、Basic Violet 14、Basic Violet 16、Basic Yellow 11、Basic Yellow 28、Basic Yellow 57、Basic Yellow 87等が挙げられる。 Specific examples of basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 75, Basic Blue 99, Basic Blue 124 , Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet11:1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, etc.
　天然染料の具体例としては、例えば、クチナシ色素、ウコン色素、アナトー色素、銅クロロフィリンナトリウム、パプリカ色素、ラック色素、ヘナ等が挙げられる。 Specific examples of natural dyes include gardenia pigments, turmeric pigments, annatto pigments, sodium copper chlorophyllin, paprika pigments, lac pigments, and henna.
　ニトロ染料の具体例としては、例えば、４－ニトロ－ｏ－フェニレンジアミン、２－ニトロ－ｐ－フェニレンジアミン、２－アミノ－４－ニトロフェノール、２－アミノ－５－ニトロフェノール、ピクラミン酸、ピクリン酸、及びそれらの塩等が挙げられる。本発明では、染毛力向上の観点から、好ましくはピクラミン酸、４－ニトロ－ｏ－フェニレンジアミンが挙げられる。 Specific examples of nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, and picrin. acids, salts thereof, and the like. In the present invention, picramic acid and 4-nitro-o-phenylenediamine are preferred from the viewpoint of improving hair dyeing power.
　ＨＣ染料の具体例としては、例えば、HC Blue No.2、HC Blue No.5、HC Blue No.6、HC Blue No.9、HC Blue No.10、HC Blue No.11、HC Blue No.12、HC Blue No.13、HC Blue No.16、HC Orange No.1、HC Orange No.2、HC Orange No.3、HC Red No.1、HC Red No.3、HC Red No.7、HC Red No.10、HC Red No.11、HC Red No.13、HC Red No.14、HC Violet No.1、HC Violet No.2、HC Yellow No.2、HC Yellow No.4、HC Yellow No.5、HC Yellow No.6、HC Yellow No.9、HC Yellow No.10、HC Yellow No.11、HC Yellow No.12、HC Yellow No.13、HC Yellow No.14、HC Yellow No.15等が挙げられる。 Specific examples of HC dyes include HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No. 12, HC Blue No.13, HC Blue No.16, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No. 15, etc.
　分散染料の具体例としては、例えば、Disperse Black 9、Disperse Blue 1、Disperse Blue 3、Disperse Blue 7、Disperse Brown 4、Disperse Orange 3、Disperse Red 11、Disperse Red 15、Disperse Red 17、Disperse Violet 1、Disperse Violet 4、Disperse Violet 15等が挙げられる。 Specific examples of disperse dyes include Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 and the like.
　酸化染毛剤における直接染料の含有量は、特に制限されないが、好ましくは０．００１質量％以上２０．０質量％以下である。下限値としては、より好ましくは０．０５質量％以上であり、さらに好ましくは０．１質量％以上であり、である。一方、上限値としては、より好ましくは１５．０質量％以下であり、さらに好ましくは１０．０質量％以下であり、特に好ましくは５．０質量％以下である。 The content of the direct dye in the oxidative hair dye is not particularly limited, but is preferably 0.001% by mass or more and 20.0% by mass or less. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. On the other hand, the upper limit is more preferably 15.0% by mass or less, still more preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.
［アルカリ剤］
　第１の実施態様に係る酸化染毛剤は、アルカリ剤を含有してもよい。アルカリ剤は、毛髪を膨潤させて、染料や酸化剤の浸透を促進する作用を有するものであり、染毛力を向上させる効果がある。
　アルカリ剤としては、例えば、アルカノールアミン、アンモニア、ケイ酸塩、炭酸塩、炭酸水素塩、メタケイ酸塩、リン酸塩、硫酸塩、塩化物、有機アミン、塩基性アミノ酸、アルカリ金属又はアルカリ土類金属の水酸化物等が例示される。具体的には、アルカノールアミンとしてはモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、アミノメチルプロパノール、イソプロピルアミン等が例示され、ケイ酸塩としてはケイ酸ナトリウム、ケイ酸カリウム等が例示され、炭酸塩としては炭酸ナトリウム、炭酸アンモニウム、炭酸マグネシウム、炭酸グアニジン等が例示され、炭酸水素塩としては炭酸水素ナトリウム、炭酸水素アンモニウム等が例示され、メタケイ酸塩としてはメタケイ酸ナトリウム、メタケイ酸カリウム等が例示され、リン酸塩としてはリン酸第一アンモニウム、リン酸第二アンモニウム、リン酸一水素二ナトリウム、リン酸三ナトリウム等が例示され、硫酸塩としては硫酸アンモニウムなどが例示され、塩化物としては塩化アンモニウムが例示され、有機アミンとしては２－アミノ－２－メチル－１－プロパノール（ＡＭＰ）、２－アミノ－２－メチル－１，３－プロパンジオール、グアニジンが例示され、塩基性アミノ酸としてはアルギニン、リジン及びそれらの塩等が例示され、アルカリ金属又はアルカリ土類金属の水酸化物としては水酸化カルシウム、水酸化マグネシウム、水酸化ナトリウム、水酸化カリウム等が例示される。本発明では、染毛力向上の観点から、アルカリ剤として、好ましくは、アンモニア、モノエタノールアミン、炭酸アンモニウム、炭酸水素アンモニウムが挙げられる。 [Alkaline agent]
The oxidative hair dye according to the first embodiment may contain an alkaline agent. The alkaline agent has the effect of swelling the hair and promoting the permeation of the dye and the oxidizing agent, and has the effect of improving the hair dyeing power.
Examples of alkaline agents include alkanolamines, ammonia, silicates, carbonates, hydrogencarbonates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, alkali metals or alkaline earths. Metal hydroxides and the like are exemplified. Specifically, examples of alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine, and examples of silicate include sodium silicate, potassium silicate, and the like. Examples of carbonate include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate, and the like. Examples of hydrogencarbonate include sodium hydrogencarbonate and ammonium hydrogencarbonate. Examples of metasilicate include sodium metasilicate and potassium metasilicate. Examples of phosphates include primary ammonium phosphate, secondary ammonium phosphate, disodium monohydrogen phosphate, and trisodium phosphate. Examples of sulfates include ammonium sulfate. is exemplified by ammonium chloride, and organic amines are exemplified by 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, guanidine, and basic amino acids. Examples thereof include arginine, lysine and salts thereof, and examples of hydroxides of alkali metals or alkaline earth metals include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide and the like. In the present invention, preferred alkaline agents include ammonia, monoethanolamine, ammonium carbonate, and ammonium hydrogencarbonate, from the viewpoint of improving the hair dyeing power.
　第１の実施態様に係る酸化染毛剤におけるアルカリ剤の含有量は、特に制限されないが、好ましくは０．５～１０．０質量％である。下限値として、より好ましくは０．７５質量％以上であり、さらに好ましくは１．０質量％以上である。上限値として、より好ましくは７．０質量％以下であり、さらに好ましくは５．０質量％以下である。 The content of the alkaline agent in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.5 to 10.0% by mass. The lower limit is more preferably 0.75% by mass or more, and still more preferably 1.0% by mass or more. The upper limit is more preferably 7.0% by mass or less, and even more preferably 5.0% by mass or less.
［油性成分］
　第１の実施態様に係る酸化染毛剤は、油性成分を含有してもよい。油性成分を含有する場合、地肌汚れ抑制効果を向上させることができる。油性成分としては、例えば高級アルコール、油脂、ロウ類、炭化水素、高級脂肪酸、エステル類、シリコーン油、フッ素油等が例示される。これらの油性成分から、１種又は２種以上を選んで用いることができる。 [Oil component]
The oxidative hair dye according to the first embodiment may contain an oily component. When it contains an oily component, it is possible to improve the effect of suppressing background stains. Examples of oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, and fluorine oils. One or two or more of these oily components can be selected and used.
　高級アルコールとしては、例えば、セチルアルコール（セタノール）、２－ヘキシルデカノール、ステアリルアルコール、イソステアリルアルコール、セトステアリルアルコール、オレイルアルコール、アラキルアルコール、ベヘニルアルコール、２－オクチルドデカノール、ラウリルアルコール、ミリスチルアルコール、デシルテトラデカノール、ラノリンアルコール、フィトステロール、フィトスタノール、コレステロール、コレスタノール、ラノステロール、エルゴステロール、リノレイルアルコール、リノレニルアルコール等が挙げられる。第１の実施態様に係る酸化染毛剤では、乳化安定性及び操作性の観点から、好ましくはセチルアルコール（セタノール）、ステアリルアルコール、セトステアリルアルコール、アラキルアルコール、ベヘニルアルコールが挙げられる。 Examples of higher alcohols include cetyl alcohol (cetanol), 2-hexyldecanol, stearyl alcohol, isostearyl alcohol, cetostearyl alcohol, oleyl alcohol, arachyl alcohol, behenyl alcohol, 2-octyldodecanol, lauryl alcohol, myristyl alcohol, and decyl alcohol. Tetradecanol, lanolin alcohol, phytosterol, phytostanol, cholesterol, cholestanol, lanosterol, ergosterol, linoleyl alcohol, linolenyl alcohol and the like. The oxidative hair dye according to the first embodiment preferably includes cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, arachyl alcohol, and behenyl alcohol from the viewpoint of emulsion stability and operability.
　油脂は、トリグリセリドすなわち脂肪酸とグリセリンとのトリエステルである。オリーブ油、ローズヒップ油、ツバキ油、シア脂、マカデミアナッツ油、アーモンド油、茶実油、サザンカ油、サフラワー油、ヒマワリ油、大豆油、綿実油、ゴマ油、牛脂、カカオ脂、トウモロコシ油、落花生油、ナタネ油、コメヌカ油、コメ胚芽油、小麦胚芽油、ハトムギ油、ブドウ種子油、アボカド油、カロット油、ヒマシ油、アマニ油、ヤシ油、ミンク油、卵黄油、アルガニアスピノサ核油、ラノリン、月見草油等が挙げられる。 Fats and oils are triglycerides, that is, triesters of fatty acids and glycerin. Olive oil, rosehip oil, camellia oil, shea butter, macadamia nut oil, almond oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef tallow, cocoa butter, corn oil, peanut oil, Rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, avocado oil, carrot oil, castor oil, linseed oil, coconut oil, mink oil, egg yolk oil, argania spinosa kernel oil, lanolin, Evening primrose oil and the like can be mentioned.
　ロウ類は、高級脂肪酸と高級アルコールのエステルである。ロウ類の具体例としては、例えばミツロウ（蜜蝋）、キャンデリラロウ、カルナウバロウ、ホホバ油、ラノリン、鯨ロウ、コメヌカロウ、サトウキビロウ、パームロウ、モンタンロウ、綿ロウ、ベイベリーロウ、イボタロウ、カポックロウ、セラックロウ、ラノリンロウ、等が挙げられる。 Waxes are esters of higher fatty acids and higher alcohols. Specific examples of waxes include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, wart wax, kapok wax, shellac wax, lanolin wax, etc.
　炭化水素は、炭素と水素とよりなる化合物である。炭化水素の具体例としては、例えば流動パラフィン、パラフィン、マイクロクリスタリンワックス、ワセリン、イソパラフィン類、オゾケライト、セレシン、ポリエチレン、α－オレフィンオリゴマー、ポリブテン、合成スクワラン、スクワレン、水添スクワラン、リモネン、テレビン油、ポリイソブテン、水添ポリイソブテン、ミネラルオイル等が挙げられる。本発明では、染毛力及び地肌汚れの観点から、好ましくは、流動パラフィン、ワセリンが挙げられる。 A hydrocarbon is a compound consisting of carbon and hydrogen. Specific examples of hydrocarbons include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, ozokerite, ceresin, polyethylene, α-olefin oligomer, polybutene, synthetic squalane, squalene, hydrogenated squalane, limonene, turpentine oil, and polyisobutene. , hydrogenated polyisobutene, mineral oil, and the like. In the present invention, liquid paraffin and vaseline are preferred from the viewpoint of hair dyeing power and staining of the skin.
　高級脂肪酸の具体例としては、例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、イソステアリン酸、１２－ヒドロキシステアリン酸、オレイン酸、ラノリン脂肪酸等が挙げられる。アルキルグリセリルエーテルの具体例としては、例えばバチルアルコール、キミルアルコール、セラキルアルコール、イソステアリルグリセリルエーテル等が挙げられる。 Specific examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, and lanolin fatty acid. Specific examples of alkyl glyceryl ethers include batyl alcohol, chimyl alcohol, selachyl alcohol, and isostearyl glyceryl ether.
　エステル類は、脂肪酸とアルコールとの脱水反応によって得られる化合物である。エステルの具体例としては、例えばアジピン酸ジイソプロピル、ミリスチン酸イソプロピル、オクタン酸セチル、イソノナン酸イソノニル、ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、ステアリン酸ステアリル、ミリスチン酸ミリスチル、ミリスチン酸イソトリデシル、パルミチン酸２－エチルへキシル、リシノール酸オクチルドデシル、１０～３０の炭素数を有する脂肪酸コレステリル／ラノステリル、乳酸セチル、酢酸ラノリン、ジ－２－エチルヘキサン酸エチレングリコール、ペンタエリスリトール脂肪酸エステル、ジペンタエリスリトール脂肪酸エステル、カプリン酸セチル、トリカプリル酸グリセリル、リンゴ酸ジイソステアリル、コハク酸ジオクチル、２－エチルヘキサン酸セチル、アジピン酸－２－ヘキシルデシル、イソオクタン酸セチル、セバシン酸ジイソプロピル、エチルヘキサン酸セチル、ステアリン酸ブチル、イソステアリン酸イソセチル、ラウリン酸ヘキシル、オレイン酸デシル、乳酸ラウリル、乳酸オクチルドデシル、モノイソステアリン酸Ｎ－アルキルグリコール、ラノリン誘導体等が挙げられる。 Esters are compounds obtained by the dehydration reaction of fatty acids and alcohols. Specific examples of esters include diisopropyl adipate, isopropyl myristate, cetyl octanoate, isononyl isononanoate, octyldodecyl myristate, isopropyl palmitate, stearyl stearate, myristyl myristate, isotridecyl myristate, and 2-ethyl palmitate. Hexyl, octyldodecyl ricinoleate, fatty acid cholesteryl/lanosteryl having 10 to 30 carbon atoms, cetyl lactate, lanolin acetate, ethylene glycol di-2-ethylhexanoate, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, capric acid Cetyl, glyceryl tricaprylate, diisostearyl malate, dioctyl succinate, cetyl 2-ethylhexanoate, 2-hexyldecyl adipate, cetyl isooctanoate, diisopropyl sebacate, cetyl ethylhexanoate, butyl stearate, isostearic acid Examples include isocetyl, hexyl laurate, decyl oleate, lauryl lactate, octyldodecyl lactate, N-alkyl glycol monoisostearate, lanolin derivatives and the like.
　シリコーン油は、有機基のついたケイ素と酸素が化学結合により交互に連なった合成高分子である。シリコーン油の具体例としては、例えばジメチルポリシロキサン（ジメチコン）、メチルフェニルポリシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、末端水酸基変性ジメチルポリシロキサン、高重合シリコーン、ポリエーテル変性シリコーン（例えば、（ＰＥＧ／ＰＰＧ／ブチレン／ジメチコン）コポリマー）、アミノ変性シリコーン、ベタイン変性シリコーン、アルキル変性シリコーン、アルコキシ変性シリコーン、メルカプト変性シリコーン、カルボキシ変性シリコーン、フッ素変性シリコーン等が挙げられる。 Silicone oil is a synthetic polymer in which silicon and oxygen with organic groups are alternately linked by chemical bonds. Specific examples of silicone oils include dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, terminal hydroxyl group-modified dimethylpolysiloxane, highly polymerized silicone, polyether-modified silicone (e.g. , (PEG/PPG/butylene/dimethicone) copolymer), amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like.
　上記のうち、アミノ変性シリコーンとしては、例えば、アミノプロピルメチルシロキサン・ジメチルシロキサン共重合体（INCI名：アミノプロピルジメチコン）、アミノエチルアミノプロピルシロキサン・ジメチルシロキサン共重合体（INCI名：アモジメチコン）、アミノエチルアミノプロピルメチルシロキサン・ジメチルシロキサン共重合体（INCI名：トリメチルシリルアモジメチコン）等が挙げられる。 Among the above, amino-modified silicones include, for example, aminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane/dimethylsiloxane copolymer (INCI name: amodimethicone), Aminoethylaminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: trimethylsilyl amodimethicone) and the like.
　第１の実施態様に係る酸化染毛剤における油性成分の含有量は、特に制限されないが、好ましくは０．１～３０．０質量％である。下限値として、より好ましくは０．２質量％以上であり、更に好ましくは０．５質量％以上である。上限値としては、より好ましくは２０．０質量％以下であり、更に好ましくは１０．０質量％以下である。 The content of the oil component in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.1 to 30.0% by mass. The lower limit is more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more. The upper limit is more preferably 20.0% by mass or less, and even more preferably 10.0% by mass or less.
［その他の成分］
　第１の実施態様に係る酸化染毛剤は、上記成分以外にも、必要に応じて以下の成分を含有してもよい。
　その他の成分としては、例えば、（Ｃ）成分を除くその他の界面活性剤、（Ｅ）成分を除く可溶化剤、無水亜硫酸ナトリウム等の酸化防止剤、フェノキシエタノール、安息香酸ナトリウム等の防腐剤、エチレンジアミンヒドロキシエチル三酢酸三ナトリウム二水塩、ヒドロキシエタンジホスホン酸四ナトリウム液等のキレート剤、酸、ｐＨ調整剤、育毛成分、植物抽出物、生薬抽出物、アミノ酸・ペプチド、尿素、ビタミン類、香料、及び紫外線吸収剤が挙げられる。 [Other ingredients]
The oxidative hair dye according to the first embodiment may contain the following components, if necessary, in addition to the above components.
Other components include, for example, surfactants other than component (C), solubilizers other than component (E), antioxidants such as anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, and ethylenediamine. Chelating agents such as trisodium hydroxyethyl triacetate dihydrate, tetrasodium hydroxyethanediphosphonate solution, acids, pH adjusters, hair growth ingredients, plant extracts, crude drug extracts, amino acids/peptides, urea, vitamins, fragrance , and UV absorbers.
［その他の界面活性剤］
　第１の実施態様に係る酸化染毛剤は、（Ｃ）成分を除くその他の界面活性剤を含有してもよい。界面活性剤を含有する場合、乳化安定性をさらに向上させることができる。その他の界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、両性界面活性剤が挙げられる。 [Other surfactants]
The oxidative hair dye according to the first embodiment may contain surfactants other than the component (C). When a surfactant is contained, the emulsion stability can be further improved. Other surfactants include cationic surfactants, anionic surfactants and amphoteric surfactants.
　カチオン性界面活性剤としては、例えば、モノアルキル型４級アンモニウム塩、ジアルキル型４級アンモニウム塩、トリアルキル型４級アンモニウム塩、ベンザルコニウム型４級アンモニウム塩、モノアルキルエーテル型４級アンモニウム塩等のアルキル４級アンモニウム塩類、アルキルアミン塩、脂肪酸アミドアミン塩、エステル含有３級アミン塩、アーコベル型３級アミン塩等のアミン塩類、アルキルピリジニウム塩、アルキルイソキノリウム塩等の環式４級アンモニウム塩類、塩化ベンゼトニウム等が挙げられる。 Examples of cationic surfactants include monoalkyl-type quaternary ammonium salts, dialkyl-type quaternary ammonium salts, trialkyl-type quaternary ammonium salts, benzalkonium-type quaternary ammonium salts, and monoalkyl ether-type quaternary ammonium salts. Alkyl quaternary ammonium salts such as alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, amine salts such as Arcobel-type tertiary amine salts, cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts salts, benzethonium chloride and the like.
　好ましくは、アルキル４級アンモニウム塩類であり、更に好ましくは、モノアルキル型４級アンモニウム塩、ジアルキル型４級アンモニウム塩であり、特に好ましくは、モノアルキル型４級アンモニウム塩である。 Alkyl quaternary ammonium salts are preferred, monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts are more preferred, and monoalkyl quaternary ammonium salts are particularly preferred.
　モノアルキル型４級アンモニウム塩としては、例えば、塩化ラウリルトリメチルアンモニウム、臭化ラウリルトリメチルアンモニウム、塩化アルキル（１６，１８）トリメチルアンモニウム、塩化セチルトリメチルアンモニウム、臭化セチルトリメチルアンモニウム、セチルトリメチルアンモニウムサッカリン、塩化ステアリルトリメチルアンモニウム、臭化ステアリルトリメチルアンモニウム、塩化ベヘニルトリメチルアンモニウム、ステアリルトリメチルアンモニウムサッカリン、塩化アルキル（２８）トリメチルアンモニウム、塩化ジＰＯＥ（２）オレイルメチルアンモニウム、塩化ジＰＯＥステアリルメチルアンモニウム、塩化ＰＯＥ（１）ＰＯＰ（２５）ジエチルメチルアンモニウム、塩化ＰＯＰメチルジエチルアンモニウム、塩化メタクリロイルオキシエチルトリメチルアンモニウム、メチル硫酸ベヘニルトリメチルアンモニウム等が挙げられる。特に好ましくは、塩化ステアリルトリメチルアンモニウム、塩化アルキル（１６，１８）トリメチルアンモニウム、塩化セチルトリメチルアンモニウムである。 Monoalkyl-type quaternary ammonium salts include, for example, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharine chloride, Stearyltrimethylammonium, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di-POE (2) oleylmethylammonium chloride, di-POE stearylmethylammonium chloride, POE (1) chloride POP(25) diethylmethylammonium, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate and the like. Particularly preferred are stearyltrimethylammonium chloride, alkyl(16,18)trimethylammonium chloride and cetyltrimethylammonium chloride.
　ジアルキル型４級アンモニウム塩としては、例えば、塩化ジアルキル（１２～１５）ジメチルアンモニウム、塩化ジアルキル（１２～１８）ジメチルアンモニウム、塩化ジアルキル（１４～１８）ジメチルアンモニウム、塩化ジココイルジメチルアンモニウム、塩化ジセチルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化イソステアリルラウリルジメチルアンモニウム等が挙げられる。 Examples of dialkyl-type quaternary ammonium salts include dialkyl(12-15) dimethylammonium chloride, dialkyl(12-18) dimethylammonium chloride, dialkyl(14-18) dimethylammonium chloride, dicocoyldimethylammonium chloride, and dicetyl chloride. dimethylammonium, distearyldimethylammonium chloride, isostearyllauryldimethylammonium chloride and the like.
　第１の実施態様に係る酸化染毛剤におけるカチオン性界面活性剤の含有量は、特に制限されないが、好ましくは０．００１～１０．０質量％である。下限値として、より好ましくは０．０１質量％以上であり、更に好ましくは０．０５質量％以上である。上限値として、より好ましくは５．０質量％以下であり、更に好ましくは３．０質量％以下である。 The content of the cationic surfactant in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.001 to 10.0% by mass. The lower limit is more preferably 0.01% by mass or more, and still more preferably 0.05% by mass or more. The upper limit is more preferably 5.0% by mass or less, and still more preferably 3.0% by mass or less.
　アニオン性界面活性剤としては、例えば、アルキルエーテル硫酸塩、ＰＯＥアルキルエーテル硫酸塩、アルキル硫酸塩、アルケニルエーテル硫酸塩、アルケニル硫酸塩、オレフィンスルホン酸塩、アルカンスルホン酸塩、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－スルホン脂肪酸塩、Ｎ－アシルアミノ酸型界面活性剤、リン酸モノ又はジエステル型界面活性剤、及びスルホコハク酸エステルが例示される。これらの界面活性剤のアニオン基の対イオンは、例えばナトリウムイオン、カリウムイオン、及びトリエタノールアミンのいずれであってもよい。 Examples of anionic surfactants include alkyl ether sulfates, POE alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefinsulfonates, alkanesulfonates, and saturated or unsaturated fatty acid salts. , alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinates. Counter ions for the anionic groups of these surfactants may be, for example, sodium ions, potassium ions, and triethanolamine.
　より具体的には、ラウリル硫酸ナトリウム、ミリスチル硫酸ナトリウム、ラウリル硫酸カリウム、ラウリル硫酸アンモニウム、ラウリル硫酸トリエタノールアミン、セチル硫酸ナトリウム、ステアリル硫酸ナトリウム、ＰＯＥラウリルエーテル硫酸ナトリウム、ＰＯＥラウリルエーテル硫酸トリエタノールアミン、ＰＯＥラウリルエーテル硫酸アンモニウム、ＰＯＥステアリルエーテル硫酸ナトリウム、ステアロイルメチルタウリンナトリウム、ドデシルベンゼンスルホン酸トリエタノールアミン、テトラデセンスルホン酸ナトリウム、ラウリルリン酸ナトリウム、ＰＯＥラウリルエ－テルリン酸及びその塩、Ｎ－ラウロイルグルタミン酸塩類（ラウロイルグルタミン酸ナトリウム等）、Ｎ－ラウロイルメチル－β－アラニン塩、Ｎ－アシルグリシン塩、Ｎ－アシルグルタミン酸塩、高級脂肪酸であるラウリン酸、ミリスチン酸及びこれらの高級脂肪酸の塩が例示され、１又は２種以上を使用することができる。 More specifically, sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, POE sodium lauryl ether sulfate, POE lauryl ether sulfate triethanolamine, POE Ammonium lauryl ether sulfate, POE sodium stearyl ether sulfate, sodium stearoyl methyl taurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecene sulfonate, sodium lauryl phosphate, POE lauryl ether - telluric acid and its salts, N-lauroyl glutamates (lauroyl sodium glutamate, etc.), N-lauroylmethyl-β-alanine salts, N-acylglycine salts, N-acylglutamate salts, higher fatty acids such as lauric acid, myristic acid and salts of these higher fatty acids, 1 or 2 More than one species can be used.
　第１の実施態様に係る酸化染毛剤におけるアニオン性界面活性剤の含有量は、特に制限されないが、好ましくは０．０１～５．０質量％である。下限値として、より好ましくは０．０５質量％以上であり、更に好ましくは０．１質量％以上である。上限値として、より好ましくは３．０質量％以下であり、更に好ましくは１．５質量％以下である。 The content of the anionic surfactant in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.01 to 5.0% by mass. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 3.0% by mass or less, and still more preferably 1.5% by mass or less.
　両性界面活性剤としては、アミノ酸型両性界面活性剤、ベタイン型両性界面活性剤が挙げられる。
　アミノ酸型両性界面活性剤の具体例としては、例えば、Ｎ－ラウロイル－Ｎ′－カルボキシメチル－Ｎ′－ヒドロキシエチルエチレンジアミンナトリウム（ラウロアンホ酢酸Ｎａ）、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチルイミダゾリニウムベタイン、ウンデシルヒドロキシエチルイミダゾリニウムベタインナトリウム、塩酸アルキルジアミノエチルグリシン、Ｎ－ヤシ油脂肪酸アシル－Ｎ′－カルボキシエチル－Ｎ′－ヒドロキシエチルエチレンジアミンナトリウム、Ｎ－ヤシ油脂肪酸アシル－Ｎ′－カルボキシエトキシエチル－Ｎ′－カルボキシエチルエチレンジアミン二ナトリウム、Ｎ－ヤシ油脂肪酸アシル－Ｎ′－カルボキシメトキシエチル－Ｎ′－カルボキシメチルエチレンジアミン二ナトリウム、ラウリルジアミノエチルグリシンナトリウム、パーム油脂肪酸アシル－Ｎ－カルボキシエチル－Ｎ－ヒドロキシエチルエチレンジアミンナトリウム等のグリシン型両性界面活性剤；ラウリルアミノプロピオン酸ナトリウム、ラウリルアミノジプロピオン酸ナトリウム、ラウリルアミノプロピオン酸トリエタノールアミン等のアミノプロピオン酸型両性界面活性剤；等が挙げられる。
　ベタイン型両性界面活性剤の具体例としては、例えば、ヤシ油アルキルベタイン、ラウリルジメチルアミノ酢酸ベタイン、ミリスチルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ステアリルジメチルベタインナトリウム、ヤシ油脂肪酸アミドプロピルベタイン、パーム油脂肪酸アミドプロピルベタイン、ラウリン酸アミドプロピルベタイン、リシノレイン酸アミドプロピルベタイン、ステアリルジヒドロキシエチルベタイン等のアミノ酢酸ベタイン型両性界面活性剤；ラウリルヒドロキシスルホベタイン等のスルホベタイン型両性界面活性剤等が挙げられる。 Amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
Specific examples of amino acid type amphoteric surfactants include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethyl Imidazolinium Betaine, Undecyl Hydroxyethylimidazolinium Betaine Sodium, Alkyldiaminoethylglycine Hydrochloride, N-Cocoate Acyl-N'-Carboxyethyl-N'-Hydroxyethylethylenediamine Sodium, N-Cocoate Acyl-N '-Carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-coconut fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, sodium lauryldiaminoethylglycinate, palm oil fatty acid acyl-N - glycine-type amphoteric surfactants such as sodium carboxyethyl-N-hydroxyethylethylenediamine; aminopropionic acid-type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, triethanolamine laurylaminopropionate; etc.
Specific examples of betaine-type amphoteric surfactants include, for example, coconut oil alkylbetaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amidopropyl betaine, palm aminoacetate betaine type amphoteric surfactants such as oil fatty acid amidopropyl betaine, lauramidopropyl betaine, ricinoleic acid amidopropyl betaine, stearyldihydroxyethyl betaine; and sulfobetaine type amphoteric surfactants such as lauryl hydroxysulfobetaine. .
　第１の実施態様に係る酸化染毛剤における両性界面活性剤の含有量は、特に制限されないが、好ましくは０．００１～５．０質量％である。下限値として、より好ましくは０．００５質量％以上であり、更に好ましくは０．０１質量％以上である。上限値として、より好ましくは３．０質量％以下であり、更に好ましくは２．５質量％以下である。 The content of the amphoteric surfactant in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.001 to 5.0% by mass. The lower limit is more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more. The upper limit is more preferably 3.0% by mass or less, and still more preferably 2.5% by mass or less.
　第１の実施態様に係る酸化染毛剤における全ての界面活性剤の総含有量としては、特に制限されないが、好ましくは０．０１～５０．０質量％である。下限値として、より好ましくは０．０５質量％以上であり、更に好ましくは０．１質量％以上である。上限値として、より好ましくは４０．０質量％以下であり、更に好ましくは３０．０質量％以下である。 The total content of all surfactants in the oxidative hair dye according to the first embodiment is not particularly limited, but is preferably 0.01 to 50.0% by mass. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 40.0% by mass or less, and still more preferably 30.0% by mass or less.
［可溶化剤］
　可溶化剤は、例えば、剤型を液状等にする場合に配合される。使用される可溶化剤の例としては、例えば水及び有機溶媒（溶剤）が挙げられる。有機溶媒の具体例としては、例えばエタノール、ｎ－プロパノール、イソプロパノール、メチルセロソルブ、エチルセロソルブ、メチルカルビトール、エチルカルビトール、ベンジルアルコール、フェネチルアルコール、γ－フェニルプロピルアルコール、ケイ皮アルコール、アニスアルコール、ｐ－メチルベンジルアルコール、α－ジメチルフェネチルアルコール、α－フェニルエタノール、エチレングリコールフェニルエーテル（フェノキシエタノール）、フェノキシイソプロパノール、２－ベンジルオキシエタノール、Ｎ－アルキルピロリドン、炭酸アルキレン、アルキルエーテル等が挙げられる。１種の可溶化剤を単独で使用してもよく、２種以上の可溶化剤を組み合わせて使用してもよい。
　なお、可溶化剤としては、第１剤中のその他の成分を溶解する能力に優れることから、水が好ましく適用される。溶媒として水が用いられる場合、混合物（酸化染毛剤）中における水の含有量（使用時の含有量）は、好ましくは４０．０質量％以上であり、より好ましくは５０．０質量％以上である。 [Solubilizer]
A solubilizer is added, for example, when the dosage form is liquid. Examples of solubilizers used include, for example, water and organic solvents (solvents). Specific examples of organic solvents include ethanol, n-propanol, isopropanol, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamic alcohol, anise alcohol, p-methylbenzyl alcohol, α-dimethylphenethyl alcohol, α-phenylethanol, ethylene glycol phenyl ether (phenoxyethanol), phenoxyisopropanol, 2-benzyloxyethanol, N-alkylpyrrolidone, alkylene carbonate, alkyl ether and the like. One solubilizer may be used alone, or two or more solubilizers may be used in combination.
As the solubilizer, water is preferably applied because it has excellent ability to dissolve other components in the first agent. When water is used as a solvent, the content of water in the mixture (oxidative hair dye) (content at the time of use) is preferably 40.0% by mass or more, more preferably 50.0% by mass or more. is.
　以下、実施例及び比較例を挙げて前記第１の実施態様を更に具体的に説明する。なお、本発明は、実施例欄記載の構成に限定されるものではなく、また、これらの実施例によって本発明の技術範囲が限定されるものでもない。 Hereinafter, the first embodiment will be described more specifically with examples and comparative examples. It should be noted that the present invention is not limited to the configurations described in the Examples column, and the technical scope of the present invention is not limited by these Examples.
［試験例：酸化染毛剤の評価について］
（酸化染毛剤の調製）
　第１の実施態様に係る酸化染毛剤として、表１～表８に示す各成分を含有するクリーム状の第１剤と、クリーム状の第２剤をそれぞれ調製した。以下、各表における各成分を示す欄中の数値は当該欄の成分の含有量を示し、その単位は質量％である。 [Test example: Evaluation of oxidative hair dye]
(Preparation of oxidative hair dye)
As the oxidative hair dye according to the first embodiment, a cream-like first agent containing each component shown in Tables 1 to 8 and a cream-like second agent were prepared. Hereinafter, the numerical values in the columns indicating each component in each table indicate the content of the component in that column, and the unit is % by mass.
　以下、表中の２，４－ジアミノフェノキシエタノールは、原料である２，４－ジアミノフェノキシエタノール塩酸塩を、ｐＨ調整剤としてＮａＯＨを用いて中和したものである。２，４－ジアミノフェノキシエタノール塩酸塩は１モルあたり２モルの塩酸を生じるため、２，４－ジアミノフェノキシエタノール塩酸塩：ＮａＯＨ＝１：２（モル比）の割合で配合することにより中和した。つまり、第１剤中には２，４－ジアミノフェノキシエタノールがフリー態として含有される。 The 2,4-diaminophenoxyethanol in the table below is obtained by neutralizing the raw material 2,4-diaminophenoxyethanol hydrochloride using NaOH as a pH adjuster. Since 2,4-diaminophenoxyethanol hydrochloride produces 2 mol of hydrochloric acid per 1 mol, it was neutralized by adding 2,4-diaminophenoxyethanol hydrochloride:NaOH at a ratio of 1:2 (molar ratio). That is, the first agent contains 2,4-diaminophenoxyethanol in a free form.
（酸化染毛剤による染毛処理）
　下記表１～表８に示す各実施例及び各比較例について、第１剤及び第２剤を、１：１の質量比で混合して、各例の酸化染毛剤の混合物を調製した。長さ１０ｃｍの評価用の白毛の毛束サンプル（ビューラックス社製）（以下、単に「毛束」という。）１ｇに対して、得られた混合物３ｇを刷毛を用いて塗布した。混合物を毛束に塗布してから４０分後に、毛束に付着した混合物を水で洗い流し、毛束にシャンプー（ホーユー社製のビゲントリートメントシャンプー）を２回、及びリンス（ホーユー社製のビゲントリートメントリンス）を１回施した。続いて、毛束を温風で乾燥し、各例の染毛処理毛束を得た。 (Hair dyeing treatment with oxidative hair dye)
For each example and each comparative example shown in Tables 1 to 8 below, the first agent and the second agent were mixed at a mass ratio of 1:1 to prepare a mixture of the oxidation hair dye of each example. Using a brush, 3 g of the resulting mixture was applied to 1 g of a white hair bundle sample (manufactured by Beaulux Co., Ltd.) for evaluation (hereinafter simply referred to as "hair bundle") having a length of 10 cm. 40 minutes after applying the mixture to the hair bundle, the mixture attached to the hair bundle was washed away with water, and the hair bundle was shampooed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.) twice and rinsed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.). rinse) was applied once. Subsequently, the hair tresses were dried with warm air to obtain dyed hair tresses of each example.
　染毛処理が施された各例の毛束について、上記染毛処理の翌日、下記に示す方法に従い、脱染性能及び染毛力について評価を行った。 On the next day after the hair dyeing treatment, the hair tresses of each example subjected to the hair dyeing treatment were evaluated for de-dyeing performance and hair dyeing power according to the method shown below.
（脱染性能の評価）
　上記のように得られた各例の染毛処理毛束に対し、更に一般的な脱色・脱染剤である「レセパウダーブリーチ」（ホーユー社製）を用いて、常法に従い脱染処理を行うことにより脱染処理毛束を得た。 (Evaluation of destaining performance)
The dyed hair tresses of each example obtained as described above are destained according to a conventional method using a more general decolorizing/destaining agent, "Lece Powder Bleach" (manufactured by Hoyu Co., Ltd.). A destained hair tress was obtained by carrying out.
　そして、パネラー１０名が、脱染処理毛束の染毛色調について、脱染性が良好であるか否かを標準光源下で目視にて、脱染性能を評価し、以下の基準で判断した。脱染性能が優れる場合を、優れる（５点）、脱染性能が良好な場合を、良好（４点）、脱染性能がやや良好な場合を、可（３点）、脱染性能がやや悪い場合を、やや不良（２点）、脱染性能が悪い場合を、不良（１点）の５段階で採点し、各パネラーの採点結果について平均値を算出し、平均値が４．７点以上を「非常に優れる：６」、４．０点以上４．７点未満を「優れる：５」、３．３点以上４．０点未満を「良好：４」、２．６点以上３．３点未満を「可：３」、１．９点以上２．６点未満を「やや不良：２」、及び１．９点未満を「不良：１」とし、評価結果とした。その結果を表１～表８の「脱染性能」欄に示した。 Then, 10 panelists evaluated the destaining performance visually under a standard light source to determine whether the dyed color tone of the destained hair tresses had good destaining properties, and judged according to the following criteria. . Excellent destaining performance (5 points), good destaining performance (4 points), somewhat good destaining performance (3 points), slightly destaining performance Scored in 5 stages of poor (2 points) for poor destaining performance and poor (1 point) for poor destaining performance, calculated the average value of the scoring results of each panelist, and averaged 4.7 points. Above is "very excellent: 6", 4.0 points or more and less than 4.7 points is "excellent: 5", 3.3 points or more and less than 4.0 points is "good: 4", 2.6 points or more 3 The evaluation results were defined as "good: 3" for less than 3 points, "slightly unsatisfactory: 2" for 1.9 to less than 2.6 points, and "bad: 1" for less than 1.9 points. The results are shown in the "Destaining Performance" column of Tables 1 to 8.
（染毛力の評価）
　上記のように得られた各例の染毛処理毛束について、パネラー１０名が、標準光源下で目視にて発色度合いを、以下の基準で評価することにより、発色が良いか否かについて判断した。非常に良く染まっている（５点）、良く染まっている（４点）、染まっている（３点）、染まりが僅かに浅い（２点）、染まりが浅い（１点）の５段階で採点し、各パネラーの採点結果について平均値を算出し、平均値が４．６点以上を「優れる：５」、３．６点以上４．６点未満を「良好：４」、２．６点以上３．６点未満を「可：３」、１．６点以上２．６点未満を「やや不良：２」、及び１．６点未満を「不良：１」とし、評価結果とした。その結果を表１～表８の「染毛力」欄に示した。 (Evaluation of hair dyeing power)
Regarding the dyed hair tresses of each example obtained as described above, 10 panelists visually evaluated the degree of color development under a standard light source according to the following criteria to determine whether the color development was good. did. Very well dyed (5 points), well dyed (4 points), dyed (3 points), slightly dyed (2 points), lightly dyed (1 point) Then, the average value is calculated for the scoring results of each panelist, and the average value is 4.6 points or more as “excellent: 5”, 3.6 points or more and less than 4.6 points as “good: 4”, 2.6 points The evaluation results were defined as "good: 3" if less than 3.6 points, "slightly unsatisfactory: 2" if 1.6 points or more and less than 2.6 points, and "bad: 1" if less than 1.6 points. The results are shown in the "hair dyeing power" column of Tables 1 to 8.
（地肌汚れ抑制の評価）
　表１～表８に示す第１剤と第２剤を１：１で混合して酸化染毛剤０．１ｇを腕内側部に直径１ｃｍの円形状に塗布し、４０分間放置した後、水洗した。更に、ホーユー社製のビゲントリートメントシャンプー組成物を使用し、塗布部分を２回洗浄処理した。このときの腕内側部をパネラー５名が目視で観察し、以下の基準で評価することにより、地肌が汚れ難いか否かを判断した。地肌汚れが抑制される（５点）、地肌汚れ度合としては十分で基準値（４点）、地肌汚れ度合としては許容範囲内（３点）、地肌汚れは目立つが許容範囲内（２点）、地肌汚れが著しく目立ち、洗浄後も長時間皮膚に色素が残留する（１点）の５段階で採点し、評価結果とした。その結果を表１～表８の「地肌汚れ」欄に示した。 (Evaluation of Suppression of Background Stain)
The first and second agents shown in Tables 1 to 8 were mixed at a ratio of 1:1, and 0.1 g of the oxidation hair dye was applied to the inner arm in a circular shape with a diameter of 1 cm, left for 40 minutes, and then washed with water. did. Further, the applied portion was washed twice using Bigen Treatment Shampoo Composition manufactured by Hoyu. Five panelists visually observed the inner side of the arm at this time, and evaluated according to the following criteria to determine whether or not the skin was difficult to stain. Background dirt is suppressed (5 points), the degree of background dirt is sufficient and the standard value (4 points), the degree of background dirt is within the allowable range (3 points), and the background dirt is conspicuous but within the allowable range (2 points). , The background stain is conspicuous, and the pigment remains on the skin for a long time even after washing (1 point). The results are shown in Tables 1 to 8 in the "Skin Stain" column.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１～表４に示されるように、実施例１－１～実施例１－３及び実施例１－１－１～実施例１－１－８と比較例１－１とを比較すると、（Ｃ１）成分を含有することで染毛力、地肌汚れの評価が良好になることが確認できる。また、実施例１－１と実施例１－２を比較すると、（Ｂ）成分を含有しない場合であっても、同じ評価の染毛力が得られ、地肌汚れを抑制できることが確認できる。 As shown in Tables 1 to 4, when comparing Examples 1-1 to 1-3 and Examples 1-1-1 to 1-1-8 with Comparative Example 1-1, ( It can be confirmed that the inclusion of the component C1) improves the evaluation of the hair dyeing power and the staining of the background. Further, when comparing Example 1-1 and Example 1-2, it can be confirmed that the hair dyeing power of the same evaluation can be obtained and the background stain can be suppressed even when the component (B) is not contained.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表５に示されるように、実施例１－１と実施例１－４、実施例１－５とを比較すると、（Ａ）成分の中でも、２，４－ジアミノフェノキシエタノールが、染毛力と地肌汚れ共に、良好な結果であることが確認できる。また、実施例１－４と実施例１－６とを比較すると、（Ｂ）成分を含有しない方が、地肌汚れを抑制できることが確認できる。 As shown in Table 5, when comparing Example 1-1 with Example 1-4 and Example 1-5, among the components (A), 2,4-diaminophenoxyethanol has a higher hair dyeing power and texture. It can be confirmed that both the stain and the dirt are good results. Further, by comparing Examples 1-4 and 1-6, it can be confirmed that the non-containing component (B) can suppress background stains.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表６に示されるように、実施例１－１と実施例１－７～実施例１－１０とを比較すると、（Ｃ１）／（Ｃ２）の比が１．０の実施例１－９では、表１の比較例１－１と比較して、地肌汚れの評価が改善されるが、（Ｃ１）／（Ｃ２）の比が１．５以上になると、染毛力及び地肌汚れの評価の改善が確認できる。 As shown in Table 6, when comparing Example 1-1 with Examples 1-7 to 1-10, in Example 1-9 where the ratio of (C1)/(C2) is 1.0 , Compared to Comparative Example 1-1 in Table 1, the evaluation of the background stain is improved, but when the ratio of (C1) / (C2) is 1.5 or more, the evaluation of the hair dyeing power and the evaluation of the background stain is improved. Improvement can be confirmed.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表７及び表８に示されるように、実施例１－１、実施例１－１１、実施例１－１２、実施例１－１－１１～実施例１－１－１３から、（Ｅ）多価アルコールを含有しない方が染毛力に優れることが確認できる。また、実施例１－１、実施例１－１３、実施例１－１－９、実施例１－１－１０から（Ｄ）成分を配合することで、染毛力が向上することが確認できる。 As shown in Tables 7 and 8, from Example 1-1, Example 1-11, Example 1-12, Example 1-1-11 to Example 1-1-13, (E) many It can be confirmed that the hair dyeing power is superior when the alcohol does not contain the alcohol. In addition, it can be confirmed that the hair dyeing power is improved by blending the component (D) from Examples 1-1, 1-13, 1-1-9, and 1-1-10. .
〔第２の実施態様〕
　第２の課題を解決するための本発明に係る実施態様（第２の実施態様）は、第１剤と第２剤を混合することにより得られる酸化染毛剤であって、（Ａ）カプラーを含有し、（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）が０．４以下であり、前記（Ａ）成分の含有量が０．３質量％以上であり、前記第１剤と第２剤を混合し、混合の２０分後における体積増加率が３０％以上であることを特徴とする。
　第２の実施態様に係る酸化染毛剤は、脱染性能を向上することができる。さらに、第２の実施態様に係る酸化染毛剤は、体積増加率を３０％以上として、酸化染毛剤の体積を増加させることにより、限られた量の剤でも塗りムラを抑制することができ、均染性を向上することができる。 [Second embodiment]
An embodiment (second embodiment) of the present invention for solving the second problem is an oxidative hair dye obtained by mixing a first agent and a second agent, comprising (A) a coupler and the mass ratio (B/A) of the content of the dye intermediate (B) to the content of the component (A) is 0.4 or less, and the content of the component (A) is 0.3 mass % or more, and a volume increase rate of 30% or more after 20 minutes of mixing the first part and the second part.
The oxidative hair dye according to the second embodiment can improve destaining performance. Furthermore, the oxidative hair dye according to the second embodiment has a volume increase rate of 30% or more, and by increasing the volume of the oxidative hair dye, it is possible to suppress uneven application even with a limited amount of the agent. It is possible to improve the levelness of dyeing.
　第２の実施態様に係る酸化染毛剤は、第１剤と第２剤の混合の際に自己発泡するか、又は混合する際の使用者による泡の形成により体積が増加する。これらの中でも、染毛力の観点から自己発泡が好ましい。酸化染毛剤の混合による自己発泡としては、例えば、酸化剤と酸化剤を分解する触媒の混合による酸素の発生、炭酸塩と炭酸塩を分解可能な酸の混合による炭酸ガスの発生などが挙げられる。このような自己発泡の例としては、酸化剤と酸化剤を分解する触媒であるヨウ素化合物の反応による自己発泡などが挙げられる。使用者による泡の形成としては、酸化染毛剤を振とう容器に充填して振とうにより泡を形成することが挙げられ、ノンエアゾールフォーマー等の公知の起泡装置による泡の形成が挙げられる。 The oxidative hair dye according to the second embodiment self-foams when the first agent and the second agent are mixed, or increases in volume due to foam formation by the user during mixing. Among these, self-foaming is preferable from the viewpoint of hair dyeing power. Examples of self-foaming by mixing an oxidative hair dye include generation of oxygen by mixing an oxidizing agent and a catalyst that decomposes the oxidizing agent, and generation of carbon dioxide by mixing a carbonate and an acid capable of decomposing the carbonate. be done. Examples of such self-foaming include self-foaming due to reaction between an oxidizing agent and an iodine compound that is a catalyst for decomposing the oxidizing agent. Formation of foam by the user includes filling the oxidative hair dye into a shaking container and shaking to form foam, and includes foam formation by a known foaming device such as a non-aerosol foamer. be done.
　第２の実施態様に係る酸化染毛剤は、混合の２０分後における体積増加率が３０％以上である。体積増加率の下限値としては、均染性の向上の観点から、好ましくは５０％以上であり、より好ましくは７０以上である。上限値としては、染毛力の向上の観点から好ましくは３５０％以下であり、より好ましくは２００％以下である。
　ここで、「混合の２０分後における体積増加率」とは、混合前と比べ、混合の際に第１剤と第２剤が接触した時から２０分後における酸化染毛剤の体積に係る増加率であり、混合前に予め測定した第１剤、第２剤それぞれの体積の和（ｍＬ）をα、第１剤、第２剤の接触直後から２０分経過後の酸化染毛剤の体積（ｍＬ）をβとしたとき、以下の式で求められる。
　　　　　体積増加率（％）＝［（β―α）／α］×１００ The oxidative hair dye according to the second embodiment has a volume increase rate of 30% or more after 20 minutes of mixing. The lower limit of the volume increase rate is preferably 50% or more, more preferably 70 or more, from the viewpoint of improving uniformity of dyeing. The upper limit is preferably 350% or less, more preferably 200% or less, from the viewpoint of improving the hair dyeing power.
Here, the "volume increase rate 20 minutes after mixing" refers to the volume of the oxidative hair dye 20 minutes after the contact between the first part and the second part during mixing compared to before mixing. is the rate of increase, and the sum (mL) of the volume of each of the first and second agents measured in advance before mixing is α, and the oxidation hair dye after 20 minutes from immediately after contact with the first and second agents When the volume (mL) is β, it is obtained by the following formula.
Volume increase rate (%) = [(β-α)/α] × 100
　第２の実施態様に係る酸化染毛剤を２剤式の酸化染毛剤とした場合、第１剤と第２剤の混合比は、酸化染毛剤の混合物中の各成分の濃度、混合性、適用方法等を考慮して適宜設定されるが、好ましくは０．１～１０：１で、より好ましくは０．５～２：１である。
　また、第２の実施態様に係る酸化染毛剤の剤型は、毛髪に適用できる剤型であれば特に限定されず、具体例としては、２５℃における剤型が、例えばゲル状、フォーム状、クリーム状等となるものが挙げられる。なお、刷毛での取り易さや、毛髪への伸び及び密着性が向上して塗布操作性に優れるという観点から、クリーム状、フォーム状とすることが好ましい。 When the oxidative hair dye according to the second embodiment is a two-component oxidative hair dye, the mixing ratio of the first component and the second component is the concentration of each component in the mixture of the oxidative hair dye. The ratio is appropriately set in consideration of properties, application method, etc., preferably 0.1 to 10:1, more preferably 0.5 to 2:1.
Further, the dosage form of the oxidative hair dye according to the second embodiment is not particularly limited as long as it can be applied to hair. , cream-like and the like. From the viewpoints of ease of removal with a brush and improved spreadability and adhesion to the hair and excellent application operability, it is preferable to use a cream-like or foam-like form.
　以下、第２の実施態様に係る酸化染毛剤に使用する成分について例示する。なお、成分の含有量を示す質量％の数値は、水等の可溶化剤を使用する場合、それらも含めた剤型中における数値であり、特に断りがない場合には、各剤を混合した酸化染毛剤中の含有量を示す。 The components used in the oxidation hair dye according to the second embodiment are exemplified below. In addition, when using a solubilizer such as water, the numerical value of mass% indicating the content of the component is the numerical value in the dosage form including them, and unless otherwise noted, each agent was mixed The content in the oxidation hair dye is shown.
［（Ａ）カプラー］
　第２の実施態様に係る酸化染毛剤は、（Ａ）カプラーを含有する。
　（Ａ）カプラーの具体例としては、例えば２，４－ジアミノフェノキシエタノール、レゾルシン、５－アミノ－ｏ－クレゾール、ｍ－アミノフェノール、α－ナフトール（１－ナフトール）、５－（２－ヒドロキシエチルアミノ）－２－メチルフェノール、ｍ－フェニレンジアミン、トルエン－３，４－ジアミン、２，６－ジアミノピリジン、ジフェニルアミン、Ｎ，Ｎ－ジエチル－ｍ－アミノフェノール、フェニルメチルピラゾロン、１，５－ジヒドロキシナフタレン、それらの塩等が挙げられる。塩の具体例としては、例えば塩酸塩、硫酸塩等が挙げられる。１種の（Ａ）成分を単独で使用してもよく、２種以上の（Ａ）成分を組み合わせて使用してもよい。
　第２の実施態様に係る（Ａ）カプラーとしては、好ましくは２，４－ジアミノフェノキシエタノール、２，６－ジアミノピリジン、５－（２－ヒドロキシエチルアミノ）－２－メチルフェノール、１－ナフトール、５－アミノ－ｏ－クレゾール、１，５－ジヒドロキシナフタレン、ｍ－アミノフェノール、及びそれらの塩が使用できる。 [(A) Coupler]
The oxidative hair dye according to the second embodiment contains (A) a coupler.
(A) Specific examples of couplers include 2,4-diaminophenoxyethanol, resorcinol, 5-amino-o-cresol, m-aminophenol, α-naphthol (1-naphthol), 5-(2-hydroxyethylamino )-2-methylphenol, m-phenylenediamine, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, N,N-diethyl-m-aminophenol, phenylmethylpyrazolone, 1,5-dihydroxynaphthalene , salts thereof, and the like. Specific examples of salts include hydrochlorides, sulfates, and the like. One (A) component may be used alone, or two or more (A) components may be used in combination.
The (A) coupler according to the second embodiment is preferably 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5-(2-hydroxyethylamino)-2-methylphenol, 1-naphthol, 5 -Amino-o-cresol, 1,5-dihydroxynaphthalene, m-aminophenol, and salts thereof can be used.
　第２の実施態様に係る酸化染毛剤中には、（Ａ）カプラーは０．３質量％以上含有される。これにより、酸化染毛剤の染毛力を向上することができる。染毛力の観点から、下限値は、好ましくは０．４質量％以上、より好ましくは０．５質量％以上、さらに好ましくは０．６質量％以上、よりさらに好ましくは０．７質量％以上である。上限値は、脱染性能の向上の観点から、好ましくは１０質量％以下、より好ましくは７質量％以下、さらに好ましくは５質量％以下、最も好ましくは３．５質量％以下である。（Ａ）カプラーの含有量が１０質量％以下であると、脱染性能をより向上でき、可溶化剤を使用する場合、可溶化剤に対する溶解性を向上できる。なお、（Ａ）カプラーが塩である場合、（Ａ）カプラーの含有量はその脱塩型での値とする。 The (A) coupler is contained in an amount of 0.3% by mass or more in the oxidation hair dye according to the second embodiment. Thereby, the hair dyeing power of the oxidative hair dye can be improved. From the viewpoint of hair dyeing power, the lower limit is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.6% by mass or more, and even more preferably 0.7% by mass or more. is. The upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and most preferably 3.5% by mass or less, from the viewpoint of improving destaining performance. When the content of (A) coupler is 10% by mass or less, the destaining performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the (A) coupler is a salt, the content of the (A) coupler is the value in the desalted form.
　また、第２の実施態様に係る酸化染毛剤中の２，４－ジアミノフェノキシエタノールの含有量が０．３質量％以上であることが好ましい。これにより染毛力を向上することができる。２，４－ジアミノフェノキシエタノールの含有量が０．３質量％以上であると、塗りムラが多くなる傾向があるが、第２の実施態様に係る酸化染毛剤においては、体積増加率が３０％以上であり、酸化染毛剤の体積が増加しているため、塗りムラが抑制され、均染性が向上される。 Further, it is preferable that the content of 2,4-diaminophenoxyethanol in the oxidative hair dye according to the second embodiment is 0.3% by mass or more. This can improve the hair dyeing power. When the content of 2,4-diaminophenoxyethanol is 0.3% by mass or more, unevenness in application tends to increase, but in the oxidation hair dye according to the second embodiment, the volume increase rate is 30%. As described above, since the volume of the oxidative hair dye is increased, unevenness in application is suppressed, and uniformity of dyeing is improved.
［（Ｂ）染料中間体］
　第２の実施態様に係る酸化染毛剤は（Ｂ）染料中間体を含有してもよい。（Ｂ）染料中間体としては、主としてｏ－又はｐ－のフェニレンジアミン類あるいはアミノフェノール類である染料前駆物質が挙げられ、通常、それ自体は無色か又は弱く着色した化合物である。
　具体的には、ｐ－フェニレンジアミン、トルエン－２，５－ジアミン（ｐ－トルイレンジアミン）、Ｎ－フェニル－ｐ－フェニレンジアミン、４，４’－ジアミノジフェニルアミン、ｐ－アミノフェノール、ｏ－アミノフェノール、ｐ－メチルアミノフェノール、Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－ｐ－フェニレンジアミン、２－ヒドロキシエチル－ｐ－フェニレンジアミン、ｏ－クロル－ｐ－フェニレンジアミン、４－アミノ－ｍ－クレゾール、２－アミノ－４－ヒドロキシエチルアミノアニソール、２，４－ジアミノフェノール及びそれらの塩類等が例示される。 [(B) dye intermediate]
The oxidative hair dye according to the second embodiment may contain (B) a dye intermediate. (B) Dye intermediates include dye precursors that are primarily o- or p-phenylenediamines or aminophenols, and are usually colorless or weakly colored compounds per se.
Specifically, p-phenylenediamine, toluene-2,5-diamine (p-toluylenediamine), N-phenyl-p-phenylenediamine, 4,4′-diaminodiphenylamine, p-aminophenol, o-amino Phenol, p-methylaminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chloro-p-phenylenediamine, 4-amino-m- Examples include cresol, 2-amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol and salts thereof.
　酸化染料には、上記した各化合物の酸付加塩等が含まれる。酸付加塩としては、塩酸塩、硫酸塩等の無機酸の付加塩、酢酸塩等の有機酸の付加塩が挙げられる。酸化染料の酸付加塩の含有量は、特に制限されないが、乳化安定性の観点から、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下である。 The oxidation dyes include acid addition salts of the above compounds. Acid addition salts include inorganic acid addition salts such as hydrochlorides and sulfates, and organic acid addition salts such as acetates. Although the content of the acid addition salt of the oxidation dye is not particularly limited, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less from the viewpoint of emulsion stability.
　これらの酸化染料は、所望する色調に応じて１種又は２種以上を選択して使用することができる。 One or more of these oxidation dyes can be selected and used according to the desired color tone.
　第２の実施態様に係る酸化染毛剤中において、（Ａ）カプラーの含有量に対する全（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）は、０．４以下、好ましくは０．３以下、より好ましくは０．２以下、さらに好ましくは０．１以下である。かかる質量比（Ｂ／Ａ）が０．４以下であると、脱染性能を向上できる。なお、（Ａ）カプラー及び（Ｂ）染料中間体が塩である場合、上記質量比の算出に用いられる含有量は、（Ａ），（Ｂ）ともにそれらの脱塩型での値とする。 In the oxidation hair dye according to the second embodiment, the mass ratio (B/A) of the content of all (B) dye intermediates to the content of (A) couplers is 0.4 or less, preferably 0. 0.3 or less, more preferably 0.2 or less, and still more preferably 0.1 or less. When the mass ratio (B/A) is 0.4 or less, destaining performance can be improved. When (A) the coupler and (B) the dye intermediate are salts, the content used for calculating the above mass ratio is the value of the desalted form of both (A) and (B).
　第２の実施態様に係る酸化染毛剤中における（Ｂ）染料中間体の含有量の上限は、上記含有量の質量比（Ｂ／Ａ）の範囲内において適宜設定されるが、好ましくは１質量％以下、より好ましくは０．５質量％以下、さらに好ましくは０．２質量％以下であり、特に好ましくは酸化染毛剤が（Ｂ）染料中間体を実質的に含有しないことである。（Ｂ）染料中間体の含有量が１質量％以下であると、脱染性能をより向上でき、可溶化剤を使用する場合、可溶化剤に対する溶解性を向上できる。なお、（Ｂ）染料中間体が塩である場合、（Ｂ）染料中間体の含有量はその脱塩型での値とする。 The upper limit of the content of the dye intermediate (B) in the oxidative hair dye according to the second embodiment is appropriately set within the range of the mass ratio (B/A) of the content, preferably 1 % by mass or less, more preferably 0.5 mass % or less, still more preferably 0.2 mass % or less, and particularly preferably the oxidative hair dye does not substantially contain (B) dye intermediates. (B) When the content of the dye intermediate is 1% by mass or less, the destaining performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the (B) dye intermediate is a salt, the content of the (B) dye intermediate is the value in the desalted form.
［（Ｆ）触媒］
　第２の実施態様に係る酸化染毛剤は、酸化剤を分解する（Ｆ）触媒を含有することが好ましい。酸化剤を分解する触媒は、酸化剤と混合した際に反応し、その結果、酸化染毛剤が自己発泡する。このような（Ｆ）触媒としては、ヨウ素化合物、金属化合物、非金属触媒、などが挙げられる。 [(F) catalyst]
The oxidative hair dye according to the second embodiment preferably contains (F) a catalyst that decomposes the oxidizing agent. The catalyst that decomposes the oxidant reacts when mixed with the oxidant, resulting in self-foaming of the oxidative hair dye. Such (F) catalysts include iodine compounds, metal compounds, non-metal catalysts, and the like.
　ヨウ素化合物としては、ヨウ素（Ｉ２）の他、可溶化剤中で遊離する対イオンを伴うヨウ素化合物、使用時にヨウ素を遊離する化合物等が挙げられる。ヨウ素化合物の具体例としては、例えばヨウ化カリウム、ヨウ化ナトリウム、ヨウ化リチウム、ヨウ化アンモニウム等のヨウ素化合物のアルカリ金属塩や、ヨウ化水素、ヨウ化セシウム、ヨウ化銀等が挙げられる。また、ヨウ素を含有する天然素材、例えばヨウ化ニンニクエキス等のヨウ素化合物を含有するエキス等を適用してもよい。一種のヨウ素化合物を単独で使用してもよく、二種以上のヨウ素化合物を組み合わせて使用してもよい。 Examples of iodine compounds include iodine (I 2 ), iodine compounds with counter ions released in a solubilizer, and compounds that release iodine during use. Specific examples of iodine compounds include alkali metal salts of iodine compounds such as potassium iodide, sodium iodide, lithium iodide and ammonium iodide, hydrogen iodide, cesium iodide and silver iodide. In addition, natural materials containing iodine, for example, extracts containing iodine compounds such as iodine garlic extract may be applied. One iodine compound may be used alone, or two or more iodine compounds may be used in combination.
　金属化合物としては、鉄、銅、銀、白金、リチウム、セリウム、コバルト、マンガン、ニッケル、バナジウム、ナトリウム、カリウムなどの金属化合物が挙げられる、金属のヨウ素化合物が好ましい。金属化合物の具体例としては、オキシ硫酸バナジウム水和物、塩化銅、硫酸銅、塩化カリウム、硝酸カルシウム、塩化リチウム、酢酸マグネシウム、重クロム酸カリウム、硝酸バリウム、塩化コバルト、硫酸セリウム、塩化セリウム、硫酸バナジウム、二酸化マンガンなどが挙げられる。 The metal compound is preferably a metal iodine compound, including metal compounds such as iron, copper, silver, platinum, lithium, cerium, cobalt, manganese, nickel, vanadium, sodium, and potassium. Specific examples of metal compounds include vanadium oxysulfate hydrate, copper chloride, copper sulfate, potassium chloride, calcium nitrate, lithium chloride, magnesium acetate, potassium dichromate, barium nitrate, cobalt chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide, and the like.
　非金属触媒としては、活性炭、カタラーゼ、ペルオキシダーゼなどの酵素、それらを含むドライイーストなどが挙げられる。 Examples of non-metallic catalysts include activated carbon, enzymes such as catalase and peroxidase, and dry yeast containing them.
　第２の実施態様に係る（Ｆ）成分としては、染毛力の観点から、ヨウ素化合物が好ましく、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化アンモニウムが好ましく、ヨウ化カリウム、ヨウ化アンモニウムがより好ましい。 From the viewpoint of hair dyeing power, the component (F) according to the second embodiment is preferably an iodine compound, preferably sodium iodide, potassium iodide or ammonium iodide, more preferably potassium iodide or ammonium iodide. .
　第２の実施態様に係る酸化染毛剤中における（Ｆ）触媒の含有量は、特に制限されないが、例えば０．００１～５質量％である。下限値は、発泡量の観点から、好ましくは０．００５質量％以上であり、より好ましくは０．０１質量％以上、さらに好ましくは０．０２質量％以上である。上限値は、過大な発泡による染毛力の低下を抑制する観点から、好ましくは、０．３質量％以下、より好ましくは０．２５質量％以下である。 The content of (F) catalyst in the oxidation hair dye according to the second embodiment is not particularly limited, but is, for example, 0.001 to 5% by mass. From the viewpoint of foaming amount, the lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more. The upper limit is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, from the viewpoint of suppressing a decrease in hair dyeing power due to excessive foaming.
　また、（Ｆ）成分であるヨウ素化合物は、ヨウ素化合物を構成するヨウ素が過酸化水素を分解させて、酸化染料の重合を促進することで、染毛力を向上させる効果を有する。この観点から、下限値は、好ましくは０．００１質量％以上であり、より好ましくは０．０１質量％以上である。 In addition, the iodine compound, which is the component (F), has the effect of improving the hair dyeing power by decomposing hydrogen peroxide and promoting the polymerization of the oxidation dye by the iodine that constitutes the iodine compound. From this point of view, the lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more.
［炭酸塩］
　第２の実施態様に係る酸化染毛剤は、炭酸塩を含有してもよい。炭酸塩は、炭酸塩を分解可能な酸と混合した際に反応して自己発泡する。
　炭酸塩としては、特に限定されないが、炭酸イオンのカリウム、ナトリウムなどのアルカリ金属塩類、ベリリウム塩、マグネシウム塩、カルシウムなどのアルカリ土類金属塩類、またはアンモニウム塩などが挙げられる。炭酸水素イオンのカリウム、ナトリウムなどのアルカリ金属塩類、ベリリウム塩、マグネシウム塩、カルシウムなどのアルカリ土類金属塩類、または、アンモニウム塩などが挙げられる。これら炭酸塩のうち、好ましくは、発泡量の観点から、炭酸イオンのカリウム、ナトリウムなどのアルカリ金属塩類、マグネシウム塩、カルシウムなどのアルカリ土類金属塩類、またはアンモニウム塩、炭酸水素イオンのカリウム、ナトリウムなどのアルカリ金属塩類、マグネシウム塩、カルシウムなどのアルカリ土類金属塩類、またはアンモニウム塩から選択される炭酸塩であり、より好ましくは、炭酸イオンのカリウム、ナトリウムのアルカリ金属塩、またはアンモニウム塩、炭酸水素イオンのカリウム、ナトリウムのアルカリ金属塩、アンモニウム塩から選択される炭酸塩である。これらの炭酸塩は、少なくとも１または２種以上を含有してもよい。 [Carbonate]
The oxidative hair dye according to the second embodiment may contain carbonate. Carbonates react and self-foam when carbonates are mixed with decomposable acids.
Examples of carbonates include, but are not limited to, carbonate ions such as alkali metal salts such as potassium and sodium, beryllium salts, magnesium salts, alkaline earth metal salts such as calcium, and ammonium salts. Alkali metal salts such as potassium and sodium hydrogencarbonate ions, beryllium salts, magnesium salts, alkaline earth metal salts such as calcium, and ammonium salts. Among these carbonates, alkali metal salts such as potassium and sodium carbonate ions, magnesium salts, alkaline earth metal salts such as calcium carbonate ions, ammonium salts, and potassium and sodium bicarbonate ions are preferably used from the viewpoint of the amount of foaming. alkali metal salts such as magnesium salts, alkaline earth metal salts such as calcium, or carbonates selected from ammonium salts, more preferably potassium or sodium alkali metal salts or ammonium salts of carbonate ions, carbonate It is a carbonate selected from potassium hydrogen ion, alkali metal salt of sodium, and ammonium salt. These carbonates may contain at least one or two or more.
　第２の実施態様に係る酸化染毛剤において、自己発泡を目的とした場合の炭酸塩の含有量は、特に制限されないが、例えば０．５～１５質量％である。下限値は、発泡量の観点から、好ましくは１質量％以上であり、より好ましくは２質量％以上である。上限値は、過大な発泡による体積増加による染毛力の低下を抑制する観点から、好ましくは、１０質量％以下であり、より好ましくは７．５質量％以下である。 In the oxidative hair dye according to the second embodiment, the carbonate content for the purpose of self-foaming is not particularly limited, but is, for example, 0.5 to 15% by mass. From the viewpoint of foaming amount, the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 7.5% by mass or less, from the viewpoint of suppressing a decrease in hair dyeing power due to volume increase due to excessive foaming.
　上記した炭酸塩を分解可能な酸は、特に制限されないが、グリコール酸、酢酸、クエン酸、乳酸、ヒドロキシエタンジホスホン酸などの有機酸、リン酸、塩酸、硫酸、硝酸、過酸化水素などの無機酸などが挙げられる。これらの中でも、好ましくはクエン酸、乳酸、ヒドロキシエタンジホスホン酸、安息香酸、リン酸、過酸化水素であり、より好ましくはヒドロキシエタンジホスホン酸、リン酸である。これらの酸は、少なくとも１または２種以上を含有してもよい。 Acids capable of decomposing the above carbonates are not particularly limited, but organic acids such as glycolic acid, acetic acid, citric acid, lactic acid and hydroxyethanediphosphonic acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide and the like. Inorganic acid etc. are mentioned. Among these, citric acid, lactic acid, hydroxyethanediphosphonic acid, benzoic acid, phosphoric acid and hydrogen peroxide are preferred, and hydroxyethanediphosphonic acid and phosphoric acid are more preferred. These acids may contain at least one or two or more.
　炭酸塩による自己発泡を用いる場合、さらに炭酸塩以外の２価金属塩を含有することが好ましい。炭酸塩以外の２価金属塩は炭酸塩を含有する剤と他の剤との混合を補助することにより、発泡性、泡の持続性を向上させることができる。このような２価金属塩は、典型金属、遷移金属を問わず特に限定されないが、マグネシウム、カルシウム、バリウムおよび亜鉛の塩酸塩、硫酸塩、乳酸塩、酢酸塩および臭素酸塩などが挙げられる。これら炭酸塩以外の２価金属塩のうち、好ましくは、マグネシウム、カルシウム、バリウム、または亜鉛の塩酸塩、硫酸塩および臭素酸塩から選択される２価金属塩であり、より好ましくは、マグネシウム、カルシウムの塩酸塩または硫酸塩から選択される２価金属塩である。これらの炭酸塩以外の２価金属塩は、少なくとも１または２種以上を含有してもよい。 When using self-foaming with carbonate, it is preferable to further contain a divalent metal salt other than carbonate. Divalent metal salts other than carbonates can improve the foamability and foam sustainability by assisting the mixing of the carbonate-containing agent with other agents. Such divalent metal salts are not particularly limited regardless of whether they are typical metals or transition metals, and include hydrochlorides, sulfates, lactates, acetates and bromates of magnesium, calcium, barium and zinc. Among these divalent metal salts other than carbonates, preferred are divalent metal salts selected from hydrochlorides, sulfates and bromates of magnesium, calcium, barium, or zinc, more preferably magnesium, A divalent metal salt selected from calcium hydrochloride or sulfate. At least one or more of these divalent metal salts other than carbonates may be contained.
［（Ｇ）酸化剤］
　第２の実施態様に係る酸化染毛剤は、（Ｇ）酸化剤を含有することが好ましい。（Ｇ）酸化剤は、酸化剤を分解する（Ｆ）触媒との反応により酸素を発生し、発泡する。（Ｇ）酸化剤は、通常、酸化染毛剤の第２剤に含有される。
　第２の実施態様に係る（Ｇ）酸化剤の具体例としては、例えば過酸化水素、過酸化尿素、過酸化メラミン、過炭酸ナトリウム、過炭酸カリウム、過ホウ酸ナトリウム、過ホウ酸カリウム、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム、過酸化ナトリウム、過酸化カリウム、過酸化マグネシウム、過酸化バリウム、過酸化カルシウム、過酸化ストロンチウム、硫酸塩の過酸化水素付加物、リン酸塩の過酸化水素付加物、ピロリン酸塩の過酸化水素付加物等が挙げられる。１種の酸化剤を単独で使用してもよく、２種以上の酸化剤を組み合わせて使用してもよい。 [(G) oxidizing agent]
The oxidative hair dye according to the second embodiment preferably contains (G) an oxidizing agent. (G) The oxidizing agent reacts with the (F) catalyst that decomposes the oxidizing agent to generate oxygen and foam. (G) The oxidizing agent is usually contained in the second agent of the oxidative hair dye.
Specific examples of the (G) oxidizing agent according to the second embodiment include, for example, hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, Ammonium Sulfate, Potassium Persulfate, Sodium Persulfate, Sodium Peroxide, Potassium Peroxide, Magnesium Peroxide, Barium Peroxide, Calcium Peroxide, Strontium Peroxide, Sulfate Hydrogen Peroxide Adduct, Phosphate Hydrogen Peroxide Adducts, hydrogen peroxide adducts of pyrophosphates, and the like can be mentioned. One oxidizing agent may be used alone, or two or more oxidizing agents may be used in combination.
　第２の実施態様に係る酸化染毛剤の第２剤中における（Ｇ）酸化剤の含有量は、適宜設定されるが、好ましくは０．１質量％以上であり、より好ましくは１．０質量％以上であり、さらに好ましくは２．０質量％以上である。酸化剤の含有量が０．１質量％以上の場合、メラニンの脱色性をより向上することができる。また、第２剤中における酸化剤の含有量は、好ましくは１５．０質量％以下であり、より好ましくは９．０質量％以下であり、さらに好ましくは６．０質量％以下である。酸化剤の含有量が１５．０質量％以下の場合、毛髪の損傷等をより抑制することができる。 The content of (G) the oxidizing agent in the second part of the oxidative hair dye according to the second embodiment is appropriately set, but is preferably 0.1% by mass or more, more preferably 1.0%. % by mass or more, more preferably 2.0% by mass or more. When the content of the oxidizing agent is 0.1% by mass or more, the decolorization of melanin can be further improved. Also, the content of the oxidizing agent in the second agent is preferably 15.0% by mass or less, more preferably 9.0% by mass or less, and even more preferably 6.0% by mass or less. When the content of the oxidizing agent is 15.0% by mass or less, hair damage and the like can be further suppressed.
[アルカリ剤]
　アルカリ剤は、毛髪を膨潤させて、染料や酸化剤の浸透を促進する作用を有するものである。
　アルカリ剤としては、例えば、アルカノールアミン、アンモニア、ケイ酸塩、メタケイ酸塩、リン酸塩、硫酸塩、塩化物、有機アミン、塩基性アミノ酸、アルカリ金属又はアルカリ土類金属の水酸化物等が例示される。具体的には、アルカノールアミンとしてはモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、アミノメチルプロパノール、イソプロピルアミン等が例示され、ケイ酸塩としてはケイ酸ナトリウム、ケイ酸カリウム等が例示され、炭酸塩としては炭酸ナトリウム、炭酸アンモニウム、炭酸マグネシウム、炭酸グアニジン等が例示され、炭酸水素塩としては炭酸水素ナトリウム、炭酸水素アンモニウム等が例示され、メタケイ酸塩としてはメタケイ酸ナトリウム、メタケイ酸カリウム等が例示され、リン酸塩としてはリン酸第一アンモニウム、リン酸第二アンモニウム、リン酸一水素二ナトリウム、リン酸三ナトリウム等が例示され、硫酸塩としては硫酸アンモニウムなどが例示され、塩化物としては塩化アンモニウムが例示され、有機アミンとしては２－アミノ－２－メチル－１－プロパノール（ＡＭＰ）、２－アミノ－２－メチル－１，３－プロパンジオール、グアニジンが例示され、塩基性アミノ酸としてはアルギニン、リジン及びそれらの塩等が例示され、アルカリ金属又はアルカリ土類金属の水酸化物としては水酸化カルシウム、水酸化マグネシウム、水酸化ナトリウム、水酸化カリウム等が例示される。 [Alkaline agent]
Alkaline agents have the effect of swelling the hair and promoting the penetration of dyes and oxidizing agents.
Alkali agents include, for example, alkanolamines, ammonia, silicates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, hydroxides of alkali metals or alkaline earth metals. exemplified. Specifically, examples of alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine, and examples of silicate include sodium silicate, potassium silicate, and the like. Examples of carbonate include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate, and the like. Examples of hydrogencarbonate include sodium hydrogencarbonate and ammonium hydrogencarbonate. Examples of metasilicate include sodium metasilicate and potassium metasilicate. Examples of phosphates include primary ammonium phosphate, secondary ammonium phosphate, disodium monohydrogen phosphate, and trisodium phosphate. Examples of sulfates include ammonium sulfate. is exemplified by ammonium chloride, and organic amines are exemplified by 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, guanidine, and basic amino acids. Examples thereof include arginine, lysine and salts thereof, and examples of hydroxides of alkali metals or alkaline earth metals include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide and the like.
　第２の実施態様に係る酸化染毛剤におけるアルカリ剤の含有量は、特に制限されないが、好ましくは０．５～１０質量％である。下限値として、より好ましくは０．７５質量％であり、さらに好ましくは１質量％以上である。上限値として、より好ましくは７質量％以下であり、さらに好ましくは５質量％以下である。 The content of the alkaline agent in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.5 to 10% by mass. The lower limit is more preferably 0.75% by mass, and still more preferably 1% by mass or more. The upper limit is more preferably 7% by mass or less, and even more preferably 5% by mass or less.
［その他の成分］
　第２の実施態様に係る酸化染毛剤は、上記成分以外にも、必要に応じて以下の成分を含有してもよい。
　その他の成分としては、例えば、直接染料、油性成分、界面活性剤、無水亜硫酸ナトリウム等の酸化防止剤、フェノキシエタノール、安息香酸ナトリウム等の防腐剤、ソルビトール、マルトース等の糖類、ポリエチレングリコール、ジプロピレングリコール等の多価アルコール、エチレンジアミンヒドロキシエチル三酢酸三ナトリウム二水塩、ヒドロキシエタンジホスホン酸四ナトリウム液等のキレート剤、酸、ｐＨ調整剤、育毛成分、植物抽出物、生薬抽出物、アミノ酸・ペプチド、尿素、ビタミン類、香料、及び紫外線吸収剤が挙げられる。 [Other ingredients]
The oxidative hair dye according to the second embodiment may contain the following components, if necessary, in addition to the above components.
Other ingredients include, for example, direct dyes, oily ingredients, surfactants, antioxidants such as anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, sugars such as sorbitol and maltose, polyethylene glycol, and dipropylene glycol. polyhydric alcohols such as ethylenediaminehydroxyethyl triacetic acid trisodium dihydrate, chelating agents such as hydroxyethanediphosphonic acid tetrasodium salt, acids, pH adjusters, hair growth ingredients, plant extracts, crude drug extracts, amino acids and peptides , urea, vitamins, fragrances, and UV absorbers.
＜直接染料＞
　第２の実施態様に係る酸化染毛剤は、直接染料を含有してもよい。直接染料は、色を有する化合物であり、毛髪に付着、又は浸透して染毛する染料であれば特に制限されるものではない。例えば、酸性染料、塩基性染料、天然染料、ニトロ染料、ＨＣ染料、分散染料等が挙げられる。染毛力の観点から酸性染料を含むことが好ましい。
　また、これらの直接染料は、所望する毛髪の色調に応じて単独で配合してもよいし、２種以上を組み合わせて配合してもよい。 <Direct dye>
The oxidative hair dye according to the second embodiment may contain a direct dye. A direct dye is a compound having a color, and is not particularly limited as long as it adheres to or permeates the hair to dye the hair. Examples thereof include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes and disperse dyes. From the viewpoint of hair dyeing power, it is preferable to contain an acid dye.
These direct dyes may be blended alone or in combination of two or more depending on the desired color tone of the hair.
　酸性染料の具体例としては、例えば、赤色２号、赤色３号、赤色１０２号、赤色１０４号の（１）、赤色１０５号の（１）、赤色１０６号、赤色２２７号、赤色２３０号の（１）、黄色４号、黄色５号、黄色２０２号の（１）、黄色２０２号の（２）、黄色２０３号、だいだい色２０５号、だいだい色２０７号、だいだい色４０２号、緑色３号、緑色２０４号、緑色４０１号、紫色４０１号、青色１号、青色２号、青色２０２号、かっ色２０１号、黒色４０１号等が挙げられる。 Specific examples of acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227 and Red No. 230. (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3 , Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, and Black No. 401.
　塩基性染料の具体例としては、例えば、Basic Blue 3、Basic Blue 6、Basic Blue 7、Basic Blue 9、Basic Blue 26、Basic Blue 41、Basic Blue 47、Basic Blue 75、Basic Blue 99、Basic Blue 124、Basic Brown 4、Basic Brown 16、Basic Brown 17、Basic Green 1、Basic Green 4、Basic Orange 1、Basic Orange 2、Basic Orange 31、Basic Red 1、Basic Red 2、Basic Red 22、Basic Red 46、Basic Red 51、Basic Red 76、Basic Red 118、Basic Violet 1、Basic Violet 3、Basic Violet 4、Basic Violet 10、Basic Violet11:1、Basic Violet 14、Basic Violet 16、Basic Yellow 11、Basic Yellow 28、Basic Yellow 57、Basic Yellow 87等が挙げられる。 Specific examples of basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 75, Basic Blue 99, Basic Blue 124 , Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet11:1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, etc.
　天然染料の具体例としては、例えば、クチナシ色素、ウコン色素、アナトー色素、銅クロロフィリンナトリウム、パプリカ色素、ラック色素、ヘナ等が挙げられる。 Specific examples of natural dyes include gardenia pigments, turmeric pigments, annatto pigments, sodium copper chlorophyllin, paprika pigments, lac pigments, and henna.
　ニトロ染料の具体例としては、例えば、４－ニトロ－ｏ－フェニレンジアミン、２－ニトロ－ｐ－フェニレンジアミン、２－アミノ－４－ニトロフェノール、２－アミノ－５－ニトロフェノール、ピクラミン酸、ピクリン酸、及びそれらの塩等が挙げられる。 Specific examples of nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, and picrin. acids, salts thereof, and the like.
　ＨＣ染料の具体例としては、例えば、HC Blue No.2、HC Blue No.5、HC Blue No.6、HC Blue No.9、HC Blue No.10、HC Blue No.11、HC Blue No.12、HC Blue No.13、HC Blue No.16、HC Orange No.1、HC Orange No.2、HC Orange No.3、HC Red No.1、HC Red No.3、HC Red No.7、HC Red No.10、HC Red No.11、HC Red No.13、HC Red No.14、HC Violet No.1、HC Violet No.2、HC Yellow No.2、HC Yellow No.4、HC Yellow No.5、HC Yellow No.6、HC Yellow No.9、HC Yellow No.10、HC Yellow No.11、HC Yellow No.12、HC Yellow No.13、HC Yellow No.14、HC Yellow No.15等が挙げられる。 Specific examples of HC dyes include HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No. 12, HC Blue No.13, HC Blue No.16, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No. 15, etc.
　分散染料の具体例としては、例えば、Disperse Black 9、Disperse Blue 1、Disperse Blue 3、Disperse Blue 7、Disperse Brown 4、Disperse Orange 3、Disperse Red 11、Disperse Red 15、Disperse Red 17、Disperse Violet 1、Disperse Violet 4、Disperse Violet 15等が挙げられる。 Specific examples of disperse dyes include Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 and the like.
　第２の実施態様に係る酸化染毛剤における直接染料の含有量は、特に制限されないが、好ましくは０．００１質量％以上２０．０質量％以下である。下限値としては、より好ましくは０．０５質量％以上であり、さらに好ましくは０．１質量％以上である。一方、上限値としては、より好ましくは１５．０質量％以下であり、さらに好ましくは１０．０質量％以下であり、特に好ましくは５．０質量％以下である。 The content of the direct dye in the oxidation hair dye according to the second embodiment is not particularly limited, but is preferably 0.001% by mass or more and 20.0% by mass or less. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. On the other hand, the upper limit is more preferably 15.0% by mass or less, still more preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.
＜油性成分＞
　第２の実施態様に係る酸化染毛剤は、油性成分を含有してもよい。油性成分としては、例えば、高級アルコール、油脂、ロウ類、炭化水素、高級脂肪酸、エステル類、シリコーン油、フッ素油等が例示される。これらの油性成分から、１種又は２種以上を選んで用いることができる。 <Oil component>
The oxidative hair dye according to the second embodiment may contain an oily component. Examples of oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, fluorine oils and the like. One or two or more of these oily components can be selected and used.
　高級アルコールとしては、例えば、セチルアルコール（セタノール）、ステアリルアルコール、セトステアリルアルコール、オレイルアルコール、リノレイルアルコール、リノレニルアルコール、アラキルアルコール、ベヘニルアルコール、ラウリルアルコール、ミリスチルアルコール、２－ヘキシルデカノール、イソステアリルアルコール、２－オクチルドデカノール、デシルテトラデカノール、フィトステロール、フィトスタノール、コレステロール、コレスタノール、ラノステロール、エルゴステロール等が挙げられる。 Examples of higher alcohols include cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachyl alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, 2-hexyldecanol, and isostearyl alcohol. alcohol, 2-octyldodecanol, decyltetradecanol, phytosterol, phytostanol, cholesterol, cholestanol, lanosterol, ergosterol and the like.
　油脂は、トリグリセリド、すなわち脂肪酸とグリセリンとのトリエステルである。例えば、オリーブ油、ローズヒップ油、ツバキ油、シア脂、マカデミアナッツ油、アーモンド油、茶実油、サザンカ油、サフラワー油、ヒマワリ油、大豆油、綿実油、ゴマ油、牛脂、カカオ脂、トウモロコシ油、落花生油、ナタネ油、コメヌカ油、コメ胚芽油、小麦胚芽油、ハトムギ油、ブドウ種子油、アボカド油、カロット油、ヒマシ油、アマニ油、ヤシ油、ミンク油、卵黄油等が挙げられる。 Fats and oils are triglycerides, that is, triesters of fatty acids and glycerin. For example, olive oil, rosehip oil, camellia oil, shea butter, macadamia nut oil, almond oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef tallow, cocoa butter, corn oil, peanut oil. oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, avocado oil, carrot oil, castor oil, linseed oil, coconut oil, mink oil, egg yolk oil and the like.
　ロウ類は、高級脂肪酸と高級アルコールのエステルである。例えば、ミツロウ（蜜蝋）、キャンデリラロウ、カルナウバロウ、ホホバ油、ラノリン、鯨ロウ、コメヌカロウ、サトウキビロウ、パームロウ、モンタンロウ、綿ロウ、ベイベリーロウ、イボタロウ、カポックロウ、セラックロウ等が挙げられる。 Waxes are esters of higher fatty acids and higher alcohols. Examples include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, wart wax, kapok wax, and shellac wax.
　炭化水素は、炭素と水素よりなる化合物である。例えば、流動パラフィン、パラフィン、マイクロクリスタリンワックス、ワセリン、イソパラフィン類、オゾケライト、セレシン、ポリエチレン、α－オレフィンオリゴマー、ポリブテン、合成スクワラン、スクワレン、水添スクワラン、リモネン、テレビン油等が挙げられる。 　Hydrocarbons are compounds consisting of carbon and hydrogen. Examples include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, ozokerite, ceresin, polyethylene, α-olefin oligomer, polybutene, synthetic squalane, squalene, hydrogenated squalane, limonene, and turpentine oil.
　高級脂肪酸としては、例えば、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、イソステアリン酸、ヒドロキシステアリン酸、１２－ヒドロキシステアリン酸、オレイン酸、ウンデシレン酸、リノール酸、リシノール酸、ラノリン脂肪酸等が挙げられる。 Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolin fatty acid. is mentioned.
　エステル類は、脂肪酸とアルコールとの脱水反応によって得られる化合物である。例えば、アジピン酸ジイソプロピル、アジピン酸－２－ヘキシルデシル、ミリスチン酸イソプロピル、ミリスチン酸ミリスチル、オクタン酸セチル、イソオクタン酸セチル、イソノナン酸イソノニル、セバシン酸ジイソプロピル、パルミチン酸イソプロピル、パルミチン酸２－エチルへキシル、２－エチルヘキサン酸セチル、ステアリン酸ブチル、イソステアリン酸イソセチル、ラウリン酸ヘキシル、オレイン酸デシル、脂肪酸（Ｃ１０－３０）（コレステリル／ラノステリル）、乳酸ラウリル、乳酸オクチルドデシル、酢酸ラノリン、ジペンタエリスリトール脂肪酸エステル、モノイソステアリン酸Ｎ－アルキルグリコール、ラノリン誘導体等が挙げられる。 Esters are compounds obtained by the dehydration reaction of fatty acids and alcohols. For example, diisopropyl adipate, 2-hexyldecyl adipate, isopropyl myristate, myristyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, diisopropyl sebacate, isopropyl palmitate, 2-ethylhexyl palmitate, Cetyl 2-ethylhexanoate, butyl stearate, isocetyl isostearate, hexyl laurate, decyl oleate, fatty acid (C10-30) (cholesteryl/lanosteryl), lauryl lactate, octyldodecyl lactate, lanolin acetate, dipentaerythritol fatty acid ester , N-alkyl glycol monoisostearate, lanolin derivatives and the like.
　シリコーン油は、有機基のついたケイ素と酸素が化学結合により交互に連なった合成高分子である。例えば、ジメチルポリシロキサン（INCI名：ジメチコン）、ヒドロキシ末端基を有するジメチルポリシロキサン（INCI名：ジメチコノール）、メチルフェニルポリシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、ポリエーテル変性シリコーン、平均重合度が６５０～１００００の高重合シリコーン、アミノ変性シリコーン、ベタイン変性シリコーン、アルキル変性シリコーン、アルコキシ変性シリコーン、メルカプト変性シリコーン、カルボキシ変性シリコーン、フッ素変性シリコーン等が挙げられる。 Silicone oil is a synthetic polymer in which silicon and oxygen with organic groups are alternately linked by chemical bonds. For example, dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxy end groups (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, average Highly polymerized silicone having a degree of polymerization of 650 to 10000, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like can be mentioned.
　上記のうち、アミノ変性シリコーンとしては、例えば、アミノプロピルメチルシロキサン・ジメチルシロキサン共重合体（INCI名：アミノプロピルジメチコン）、アミノエチルアミノプロピルシロキサン・ジメチルシロキサン共重合体（INCI名：アモジメチコン）、アミノエチルアミノプロピルメチルシロキサン・ジメチルシロキサン共重合体（INCI名：トリメチルシリルアモジメチコン）等が挙げられる。 Among the above, amino-modified silicones include, for example, aminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane/dimethylsiloxane copolymer (INCI name: amodimethicone), Aminoethylaminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: trimethylsilyl amodimethicone) and the like.
　第２の実施態様に係る酸化染毛剤における油性成分の含有量は、特に制限されないが、好ましくは０．１～２０質量％である。下限値として、より好ましくは０．２質量％以上であり、さらに好ましくは０．５質量％以上であり、よりさらに好ましくは１質量％以上であり、特に好ましくは２質量％以上である。上限値としては、より好ましくは１７質量％以下であり、さらに好ましくは１５質量％以下であり、よりさらに好ましくは１２質量以下であり、特に好ましくは１０質量％以下である。 The content of the oil component in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.1 to 20% by mass. The lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit is more preferably 17% by mass or less, still more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less.
＜界面活性剤＞
　界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤が挙げられる。 <Surfactant>
Surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
　アニオン性界面活性剤としては、例えば、アルキルエーテル硫酸塩、ＰＯＥアルキルエーテル硫酸塩、アルキル硫酸塩、アルケニルエーテル硫酸塩、アルケニル硫酸塩、オレフィンスルホン酸塩、アルカンスルホン酸塩、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－スルホン脂肪酸塩、Ｎ－アシルアミノ酸型界面活性剤、リン酸モノ又はジエステル型界面活性剤、及びスルホコハク酸エステルが例示される。これらの界面活性剤のアニオン基の対イオンは、例えばナトリウムイオン、カリウムイオン、及びトリエタノールアミンのいずれであってもよい。 Examples of anionic surfactants include alkyl ether sulfates, POE alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefinsulfonates, alkanesulfonates, and saturated or unsaturated fatty acid salts. , alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinates. Counter ions for the anionic groups of these surfactants may be, for example, sodium ions, potassium ions, and triethanolamine.
　より具体的には、ラウリル硫酸ナトリウム、ミリスチル硫酸ナトリウム、ラウリル硫酸カリウム、ラウリル硫酸アンモニウム、ラウリル硫酸トリエタノールアミン、セチル硫酸ナトリウム、ステアリル硫酸ナトリウム、ＰＯＥラウリルエーテル硫酸ナトリウム、ＰＯＥラウリルエーテル硫酸トリエタノールアミン、ＰＯＥラウリルエーテル硫酸アンモニウム、ＰＯＥステアリルエーテル硫酸ナトリウム、ステアロイルメチルタウリンナトリウム、ドデシルベンゼンスルホン酸トリエタノールアミン、テトラデセンスルホン酸ナトリウム、ラウリルリン酸ナトリウム、ＰＯＥラウリルエ－テルリン酸及びその塩、Ｎ－ラウロイルグルタミン酸塩類（ラウロイルグルタミン酸ナトリウム等）、Ｎ－ラウロイルメチル－β－アラニン塩、Ｎ－アシルグリシン塩、Ｎ－アシルグルタミン酸塩、高級脂肪酸であるラウリン酸、ミリスチン酸及びこれらの高級脂肪酸の塩が例示される。これらのアニオン性界面活性剤は１又は２種以上を使用することができる。 More specifically, sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, POE sodium lauryl ether sulfate, POE lauryl ether sulfate triethanolamine, POE Ammonium lauryl ether sulfate, POE sodium stearyl ether sulfate, sodium stearoyl methyl taurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecene sulfonate, sodium lauryl phosphate, POE lauryl ether - telluric acid and its salts, N-lauroyl glutamates (lauroyl sodium glutamate, etc.), N-lauroylmethyl-β-alanine salts, N-acylglycinates, N-acylglutamates, higher fatty acids such as lauric acid and myristic acid, and salts of these higher fatty acids. One or more of these anionic surfactants can be used.
　第２の実施態様に係る酸化染毛剤におけるアニオン性界面活性剤の含有量は、特に制限されないが、好ましくは０．０１～５質量％である。下限値として、より好ましくは０．０３質量％以上であり、さらに好ましくは０．０５質量％以上であり、よりさらに好ましくは０．０７質量％以上であり、特に０．１質量％以上である。上限値として、より好ましくは４質量％以下であり、さらに好ましくは３質量％以下であり、よりさらに好ましくは２．５質量％以下であり、特に好ましくは２質量％以下である。 The content of the anionic surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.01 to 5% by mass. The lower limit is more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.07% by mass or more, and particularly 0.1% by mass or more. . The upper limit is more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2.5% by mass or less, and particularly preferably 2% by mass or less.
　カチオン性界面活性剤としては、例えば、モノアルキル型４級アンモニウム塩、ジアルキル型４級アンモニウム塩、トリアルキル型４級アンモニウム塩、ベンザルコニウム型４級アンモニウム塩、モノアルキルエーテル型４級アンモニウム塩等のアルキル４級アンモニウム塩類、アルキルアミン塩、脂肪酸アミドアミン塩、エステル含有３級アミン塩、アーコベル型３級アミン塩等のアミン塩類、アルキルピリジニウム塩、アルキルイソキノリウム塩等の環式４級アンモニウム塩類、塩化ベンゼトニウム等が挙げられる。 Examples of cationic surfactants include monoalkyl-type quaternary ammonium salts, dialkyl-type quaternary ammonium salts, trialkyl-type quaternary ammonium salts, benzalkonium-type quaternary ammonium salts, and monoalkyl ether-type quaternary ammonium salts. Alkyl quaternary ammonium salts such as alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, amine salts such as Arcobel-type tertiary amine salts, cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts salts, benzethonium chloride and the like.
　好ましくは、アルキル４級アンモニウム塩類であり、更に好ましくは、モノアルキル型４級アンモニウム塩、ジアルキル型４級アンモニウム塩であり、特に好ましくは、モノアルキル型４級アンモニウム塩である。 Alkyl quaternary ammonium salts are preferred, monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts are more preferred, and monoalkyl quaternary ammonium salts are particularly preferred.
　モノアルキル型４級アンモニウム塩としては、例えば、塩化ラウリルトリメチルアンモニウム、臭化ラウリルトリメチルアンモニウム、塩化アルキル（１６，１８）トリメチルアンモニウム、塩化セチルトリメチルアンモニウム、臭化セチルトリメチルアンモニウム、セチルトリメチルアンモニウムサッカリン、塩化ステアリルトリメチルアンモニウム、臭化ステアリルトリメチルアンモニウム、塩化ベヘニルトリメチルアンモニウム、ステアリルトリメチルアンモニウムサッカリン、塩化アルキル（２８）トリメチルアンモニウム、塩化ジＰＯＥ（２）オレイルメチルアンモニウム、塩化ジＰＯＥステアリルメチルアンモニウム、塩化ＰＯＥ（１）ＰＯＰ（２５）ジエチルメチルアンモニウム、塩化ＰＯＰメチルジエチルアンモニウム、塩化メタクリロイルオキシエチルトリメチルアンモニウム、メチル硫酸ベヘニルトリメチルアンモニウム等が挙げられる。特に好ましくは、塩化ステアリルトリメチルアンモニウム、塩化アルキル（１６，１８）トリメチルアンモニウム、塩化セチルトリメチルアンモニウムである。 Monoalkyl-type quaternary ammonium salts include, for example, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharine chloride, Stearyltrimethylammonium, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di-POE (2) oleylmethylammonium chloride, di-POE stearylmethylammonium chloride, POE (1) chloride POP(25) diethylmethylammonium, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate and the like. Particularly preferred are stearyltrimethylammonium chloride, alkyl(16,18)trimethylammonium chloride and cetyltrimethylammonium chloride.
　ジアルキル型４級アンモニウム塩としては、例えば、塩化ジアルキル（１２～１５）ジメチルアンモニウム、塩化ジアルキル（１２～１８）ジメチルアンモニウム、塩化ジアルキル（１４～１８）ジメチルアンモニウム、塩化ジココイルジメチルアンモニウム、塩化ジセチルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化イソステアリルラウリルジメチルアンモニウム等が挙げられる。 Examples of dialkyl-type quaternary ammonium salts include dialkyl(12-15) dimethylammonium chloride, dialkyl(12-18) dimethylammonium chloride, dialkyl(14-18) dimethylammonium chloride, dicocoyldimethylammonium chloride, and dicetyl chloride. dimethylammonium, distearyldimethylammonium chloride, isostearyllauryldimethylammonium chloride and the like.
　また、第２の実施態様に係る酸化染毛剤におけるカチオン性界面活性剤の含有量は、特に制限されないが、好ましくは０．０１～１０質量％である。下限値として、より好ましくは０．０３質量％以上であり、さらに好ましくは０．０５質量％以上であり、よりさらに好ましくは０．０７質量％以上であり、特に好ましくは０．１質量％以上である。上限値として、より好ましくは７.５質量％以下であり、さらに好ましくは５質量％以下であり、よりさらに好ましくは３質量％以下であり、特に好ましくは１．５質量％以下である。 The content of the cationic surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.01 to 10% by mass. The lower limit is more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.07% by mass or more, and particularly preferably 0.1% by mass or more. is. The upper limit is more preferably 7.5% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1.5% by mass or less.
　ノニオン性界面活性剤としては、例えば、ＰＯＥアルキルエーテル類、ＰＯＥアルキルフェニルエーテル類、ＰＯＥ・ＰＯＰアルキルエーテル類、ＰＯＥソルビタン脂肪酸エステル類、ＰＯＥモノ脂肪酸エステル類、ＰＯＥグリセリン脂肪酸エステル類、ポリグリセリン脂肪酸エステル類、モノグリセリン脂肪酸エステル類、ソルビタン脂肪酸エステル類、ショ糖脂肪酸エステル類、アルキルポリグルコシド類等が挙げられる。ＰＯＥアルキルエーテル類の具体例としては、ＰＯＥラウリルエーテル、ＰＯＥセチルエーテル、ＰＯＥステアリルエーテル、ＰＯＥベヘニルエーテル、ＰＯＥラノリン、ＰＯＥフィトステロール等が挙げられる。
　なお、ＰＯＥ、ＰＯＰの繰り返し単位数としては、例えば、２～１００が挙げられ、界面活性作用を示すものであればいずれのものも使用可能である。 Examples of nonionic surfactants include POE alkyl ethers, POE alkylphenyl ethers, POE/POP alkyl ethers, POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, and polyglycerin fatty acid esters. monoglycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkylpolyglucosides, and the like. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, and POE phytosterol.
The number of repeating units of POE and POP is, for example, 2 to 100, and any one can be used as long as it exhibits surface activity.
　また、第２の実施態様に係る酸化染毛剤におけるノニオン性界面活性剤の含有量は、特に制限されないが、好ましくは０．００１～３０質量％である。下限値として、より好ましくは０．０１質量％以上であり、更に好ましくは０．０５質量％以上であり、よりさらに好ましくは０．１質量％以上であり、特に好ましくは０．２質量％以上である。上限値として、より好ましくは２０質量％以下であり、さらに好ましくは１０質量％以下であり、よりさらに好ましくは７質量％以下であり、特に好ましくは５質量％以下である。 Also, the content of the nonionic surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.001 to 30% by mass. The lower limit is more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. is. The upper limit is more preferably 20% by mass or less, still more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 5% by mass or less.
　両性界面活性剤としては、アミノ酸型両性界面活性剤、ベタイン型両性界面活性剤が挙げられる。
　アミノ酸型両性界面活性剤の具体例としては、例えば、Ｎ－ラウロイル－Ｎ′－カルボキシメチル－Ｎ′－ヒドロキシエチルエチレンジアミンナトリウム（ラウロアンホ酢酸Ｎａ）、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチルイミダゾリニウムベタイン、ウンデシルヒドロキシエチルイミダゾリニウムベタインナトリウム、塩酸アルキルジアミノエチルグリシン、Ｎ－ヤシ油脂肪酸アシル－Ｎ′－カルボキシエチル－Ｎ′－ヒドロキシエチルエチレンジアミンナトリウム、Ｎ－ヤシ油脂肪酸アシル－Ｎ′－カルボキシエトキシエチル－Ｎ′－カルボキシエチルエチレンジアミン二ナトリウム、Ｎ－ヤシ油脂肪酸アシル－Ｎ′－カルボキシメトキシエチル－Ｎ′－カルボキシメチルエチレンジアミン二ナトリウム、ラウリルジアミノエチルグリシンナトリウム、パーム油脂肪酸アシル－Ｎ－カルボキシエチル－Ｎ－ヒドロキシエチルエチレンジアミンナトリウム等のグリシン型両性界面活性剤；ラウリルアミノプロピオン酸ナトリウム、ラウリルアミノジプロピオン酸ナトリウム、ラウリルアミノプロピオン酸トリエタノールアミン等のアミノプロピオン酸型両性界面活性剤；等が挙げられる。
　ベタイン型両性界面活性剤の具体例としては、例えば、ヤシ油アルキルベタイン、ラウリルジメチルアミノ酢酸ベタイン、ミリスチルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ステアリルジメチルベタインナトリウム、ヤシ油脂肪酸アミドプロピルベタイン、パーム油脂肪酸アミドプロピルベタイン、ラウリン酸アミドプロピルベタイン、リシノレイン酸アミドプロピルベタイン、ステアリルジヒドロキシエチルベタイン等のアミノ酢酸ベタイン型両性界面活性剤；ラウリルヒドロキシスルホベタイン等のスルホベタイン型両性界面活性剤等が挙げられる。 Amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
Specific examples of amino acid type amphoteric surfactants include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethyl Imidazolinium Betaine, Undecyl Hydroxyethylimidazolinium Betaine Sodium, Alkyldiaminoethylglycine Hydrochloride, N-Cocoate Acyl-N'-Carboxyethyl-N'-Hydroxyethylethylenediamine Sodium, N-Cocoate Acyl-N '-Carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-coconut fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, sodium lauryldiaminoethylglycinate, palm oil fatty acid acyl-N - glycine-type amphoteric surfactants such as sodium carboxyethyl-N-hydroxyethylethylenediamine; aminopropionic acid-type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, triethanolamine laurylaminopropionate; etc.
Specific examples of betaine-type amphoteric surfactants include, for example, coconut oil alkylbetaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amidopropyl betaine, palm aminoacetate betaine type amphoteric surfactants such as oil fatty acid amidopropyl betaine, lauramidopropyl betaine, ricinoleic acid amidopropyl betaine, stearyldihydroxyethyl betaine; and sulfobetaine type amphoteric surfactants such as lauryl hydroxysulfobetaine. .
　さらに、第２の実施態様に係る酸化染毛剤における両性界面活性剤の含有量は、特に制限されないが、好ましくは０．００１～５質量％である。下限値として、より好ましくは０．００５質量％以上であり、さらに好ましくは０．０１質量％以上であり、よりさらに好ましくは０．０５質量％以上であり、特に好ましくは０．１質量％以上である。上限値として、より好ましくは３質量％以下であり、更に好ましくは２．５質量％以下である。 Furthermore, the content of the amphoteric surfactant in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.001 to 5% by mass. The lower limit is more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. is. The upper limit is more preferably 3% by mass or less, and still more preferably 2.5% by mass or less.
　第２の実施態様に係る酸化染毛剤における全ての界面活性剤の総含有量としては、特に制限されないが、好ましくは０．０１～５０質量％である。下限値として、より好ましくは０．０５質量％以上であり、更に好ましくは０．１質量％以上である。上限値として、より好ましくは４０質量％以下であり、更に好ましくは３０質量％以下である。 The total content of all surfactants in the oxidative hair dye according to the second embodiment is not particularly limited, but is preferably 0.01 to 50% by mass. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 40% by mass or less, still more preferably 30% by mass or less.
　第２の実施態様に係る酸化染毛剤の作用及び効果について説明する。 The actions and effects of the oxidative hair dye according to the second embodiment will be explained.
（１）第２の実施態様に係る酸化染毛剤は、染料中間体を実質的に含有せず、酸化染料としてカプラーのみを含有するか、又はカプラーを全染料中間体に対して所定比率以上含有する。したがって、脱染性能を向上できる。 (1) The oxidation hair dye according to the second embodiment does not substantially contain dye intermediates and contains only couplers as oxidation dyes, or couplers are contained in a predetermined ratio or more to all dye intermediates. contains. Therefore, destaining performance can be improved.
　染料中間体同士の重合体、又は染料中間体とカプラーの重合物は、アルカリ剤や酸化剤で分解されにくいといった特徴をもつため、次回以降に明るい色調に染毛処理できないという問題があった。第２の実施態様に係る酸化染毛剤は、染料中間体を実質的に含有せず、酸化染料としてカプラーのみを含有するか、又はカプラーを全染料中間体に対して所定比率以上含有することにより、アルカリ剤にて分解されやすい重合物を形成するため、脱染性能に優れ、次回以降のヘアカラーへの影響が少なくなる。それにより、次回のヘアカラーを考慮せずに様々なヘアカラーを楽しむことができる。 The polymer of dye intermediates, or the polymer of dye intermediates and couplers, has the characteristic that it is difficult to decompose with alkaline agents and oxidizing agents, so there was a problem that the hair could not be dyed in bright colors from the next time onwards. The oxidative hair dye according to the second embodiment contains substantially no dye intermediates and contains only a coupler as an oxidative dye, or contains a coupler at a predetermined ratio or more with respect to all dye intermediates. By forming a polymer that is easily decomposed by an alkaline agent, it has excellent destaining performance and less influence on subsequent hair coloring. As a result, various hair colors can be enjoyed without considering the next hair color.
（２）第２の実施態様に係る酸化染毛剤は、染料中間体を実質的に含有しない、又はその含有量が微量であるため、例えば特定の染料中間体に対してアレルギーを有する対象者にも使用できる可能性がある。 (2) The oxidative hair dye according to the second embodiment does not substantially contain dye intermediates, or the content thereof is very small. may also be used for
（３）第２の実施態様に係る酸化染毛剤は、混合２０分後の体積増加率が３０％以上であり、酸化染毛剤の体積を増加しているため、限られた量の剤でも塗りムラを抑制することができ、均染性を向上することができる。 (3) The oxidation hair dye according to the second embodiment has a volume increase rate of 30% or more after 20 minutes of mixing. However, uneven coating can be suppressed, and levelness can be improved.
　以下、実施例及び比較例を挙げて前記第２の実施態様を更に具体的に説明する。なお、本発明は、実施例欄記載の構成に限定されるものではなく、また、これらの実施例によって本発明の技術範囲が限定されるものでもない。 Hereinafter, the second embodiment will be described more specifically with examples and comparative examples. It should be noted that the present invention is not limited to the configurations described in the Examples column, and the technical scope of the present invention is not limited by these Examples.
［酸化染毛剤の評価］
（酸化染毛剤の調製）
　酸化染毛剤として、表９に示す各成分を含有するクリーム状の第１剤、表１０に示す各成分を含有する乳液状の第２剤をそれぞれ調製した。以下、各表における各成分を示す欄中の数値は当該欄の成分の含有量を示し、その単位は質量％である。 [Evaluation of oxidative hair dye]
(Preparation of oxidative hair dye)
As oxidation hair dyes, a cream-like first agent containing each component shown in Table 9 and an emulsion-like second agent containing each component shown in Table 10 were prepared. Hereinafter, the numerical values in the columns indicating each component in each table indicate the content of the component in that column, and the unit is % by mass.
　以下、表中の２，４－ジアミノフェノキシエタノールは、原料である２，４－ジアミノフェノキシエタノール塩酸塩を、ｐＨ調整剤としてＮａＯＨを用いて中和したものである。２，４－ジアミノフェノキシエタノール塩酸塩は１モルあたり２モルの塩酸を生じるため、２，４－ジアミノフェノキシエタノール塩酸塩：ＮａＯＨ＝１：２（モル比）の割合で配合することにより中和した。つまり、第１剤中には２，４－ジアミノフェノキシエタノールがフリー態として含有される。 The 2,4-diaminophenoxyethanol in the table below is obtained by neutralizing the raw material 2,4-diaminophenoxyethanol hydrochloride using NaOH as a pH adjuster. Since 2,4-diaminophenoxyethanol hydrochloride produces 2 mol of hydrochloric acid per 1 mol, it was neutralized by adding 2,4-diaminophenoxyethanol hydrochloride:NaOH at a ratio of 1:2 (molar ratio). That is, the first agent contains 2,4-diaminophenoxyethanol in a free form.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
（体積増加率の評価）
　表９及び表１０に示す第１剤及び第２剤を、表１１に示す組み合わせで１：１の質量比で混合して、各例の酸化染毛剤の混合物の体積増加率を評価した。
　評価は、１００ｍＬメスシリンダに第１剤５ｇ、第２剤５ｇをそれぞれ投入し、ガラス棒にて均一になるまで撹拌し、２５℃において混合前に予め測定した第１剤、第２剤それぞれの体積の和と、２０分後における第１剤と第２剤の混合物（酸化染毛剤）の体積とを測定して比較することにより体積増加率を算出し、以下の基準で評価した。この評価結果を表１１の「体積増加率」欄に示した。
（体積増加率の評価基準）
過大：混合２０分後の体積増加率が３５０％以上
大：混合２０分後の体積増加率が２００％以上３５０％未満
中：混合２０分後の体積増加率が５０％以上２００％未満
小：混合２０分後の体積増加率が３０％以上５０％未満
微小：混合２０分後の体積増加率が３０％未満
　なお、体積増加率は、第１剤及び第２剤の混合前後における酸化染毛剤体積の増加率であり、混合前に予め測定した第１剤、第２剤それぞれの体積の和（ｍＬ）をα、第１剤、第２剤の接触直後から２０分経過後の酸化染毛剤の体積（ｍＬ）をβとして、以下の式を用いて算出した。
　　　　　体積増加率（％）＝［（β―α）／α］×１００ (Evaluation of volume increase rate)
The first agent and the second agent shown in Tables 9 and 10 were mixed at a mass ratio of 1:1 in the combination shown in Table 11, and the volume increase rate of the oxidative hair dye mixture of each example was evaluated.
Evaluation was performed by putting 5 g of the first agent and 5 g of the second agent into a 100 mL graduated cylinder, stirring with a glass rod until uniform, and measuring in advance at 25 ° C. before mixing the first agent and the second agent. The volume increase rate was calculated by measuring and comparing the sum of the volumes and the volume of the mixture of the first part and the second part (oxidation hair dye) after 20 minutes, and evaluated according to the following criteria. This evaluation result is shown in the "volume increase rate" column of Table 11.
(Evaluation criteria for volume increase rate)
Excessive: Volume increase rate after 20 minutes of mixing is 350% or more Large: Volume increase rate after 20 minutes of mixing is 200% or more and less than 350% Medium: Volume increase rate after 20 minutes of mixing is 50% or more and less than 200% Small: Volume increase rate after 20 minutes of mixing is 30% or more and less than 50% Very small: Volume increase rate after 20 minutes of mixing is less than 30% Note that the volume increase rate is the oxidation dyeing hair before and after mixing the first agent and the second agent. It is the rate of increase in the agent volume, and the sum (mL) of the volume of each of the first agent and the second agent measured in advance before mixing is α. It was calculated using the following formula, where β is the volume (mL) of the hair agent.
Volume increase rate (%) = [(β-α)/α] × 100
（酸化染毛剤による染毛処理）
　下記表１１に示す各実施例及び各比較例について、第１剤及び第２剤を、１：１の質量比で混合して、各例の酸化染毛剤の混合物を調製した。長さ１０ｃｍの評価用の白毛の毛束サンプル（ビューラックス社製）（以下、単に「毛束」という。）１ｇに対して、得られた混合物３ｇを刷毛を用いて塗布した。混合物を毛束に塗布してから４０分後に、毛束に付着した混合物を水で洗い流し、毛束にシャンプー（ホーユー社製のビゲントリートメントシャンプー）を２回、及びリンス（ホーユー社製のビゲントリートメントリンス）を１回施した。続いて、毛束を温風で乾燥し、各例の染毛処理毛束を得た。 (Hair dyeing treatment with oxidative hair dye)
For each example and each comparative example shown in Table 11 below, the first agent and the second agent were mixed at a mass ratio of 1:1 to prepare a mixture of the oxidation hair dye of each example. Using a brush, 3 g of the resulting mixture was applied to 1 g of a white hair bundle sample (manufactured by Beaulux Co., Ltd.) for evaluation (hereinafter simply referred to as "hair bundle") having a length of 10 cm. 40 minutes after applying the mixture to the hair bundle, the mixture attached to the hair bundle was washed away with water, and the hair bundle was shampooed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.) twice and rinsed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.). rinse) was applied once. Subsequently, the hair tresses were dried with warm air to obtain dyed hair tresses of each example.
　染毛処理が施された各例の毛束について、上記染毛処理の翌日、下記に示す方法に従い、脱染性能又は染毛力について評価を行った。 On the next day after the hair dyeing treatment, the hair tresses of each example that had undergone the hair dyeing treatment were evaluated for de-dyeing performance or hair dyeing power according to the method shown below.
（脱染性能の評価）
　上記のように得られた各例の染毛処理毛束に対し、更に一般的な脱色・脱染剤である「レセパウダーブリーチ」（ホーユー社製）を用いて、常法に従い脱染処理を行うことにより脱染処理毛束を得た。 (Evaluation of destaining performance)
The dyed hair tresses of each example obtained as described above are destained according to a conventional method using a more general decolorizing/destaining agent, "Lece Powder Bleach" (manufactured by Hoyu Co., Ltd.). A destained hair tress was obtained by carrying out.
　そして、パネラー１０名が、脱染処理毛束の染毛色調について、非処理の白毛の毛束との対比により、脱染性能が良好であるか否かを標準光源下で目視にて観察した。これらの毛束との対比観察の結果を総合して、脱染性能を評価し、以下の基準で判断した。脱染性能が優れる場合を、優れる（５点）、脱染性能が良好な場合を、良好（４点）、脱染性能がやや良好な場合を、可（３点）、脱染性能がやや悪い場合を、やや不良（２点）、脱染性能が悪い場合を、不良（１点）の５段階で採点し、各パネラーの採点結果について平均値を算出し、平均値が４．７点以上を「非常に優れる：６」、４．０点以上４．７点未満を「優れる：５」、３．３点以上４．０点未満を「良好：４」、２．６点以上３．３点未満を「可：３」、１．９点以上２．６点未満を「やや不良：２」、及び１．９点未満を「不良：１」とし、評価結果とした。この評価結果を表１１の「脱染性能」欄に示した。 Then, 10 panelists visually observed under a standard light source whether or not the destaining performance was good by comparing the dyed color tone of the destained hair tresses with the untreated white hair tresses. did. The results of comparative observation with these hair tresses were combined to evaluate the destaining performance, and judgment was made according to the following criteria. Excellent destaining performance (5 points), good destaining performance (4 points), somewhat good destaining performance (3 points), slightly destaining performance Scored in 5 stages of poor (2 points) for poor destaining performance and poor (1 point) for poor destaining performance, calculated the average value of the scoring results of each panelist, and the average value was 4.7 points. Above is "very excellent: 6", 4.0 points or more and less than 4.7 points is "excellent: 5", 3.3 points or more and less than 4.0 points is "good: 4", 2.6 points or more 3 The evaluation result was defined as "Fair: 3" for less than 3 points, "Slightly poor: 2" for 1.9 to less than 2.6 points, and "Poor: 1" for less than 1.9 points. The results of this evaluation are shown in the "Destaining Performance" column of Table 11.
（均染性の評価）
　上記した脱染性能の評価と同様の方法で得られた各例の染毛処理毛束について、色ムラの程度を１０名のパネラーが目視で観察し、色ムラがあるか否かを評価（官能評価）した。具体的には、「ムラなく染まっている」場合を「４」、「ほぼムラなく染まっている」場合を「３」、「ムラが多い」場合を「２」、「ムラが非常に多い」場合を「１」とした。各パネラーの採点結果について平均値を算出し、平均値が３．６点以上を「◎」、２．６点以上３．６点未満を「〇」、1．６点以上2．６点未満を「△」、及び１．６点未満を「×」とし、評価結果とした。この評価結果を表１１の「均染性」欄に示した。 (Evaluation of levelness)
Ten panelists visually observed the degree of color unevenness of the dyed hair tresses of each example obtained in the same manner as in the evaluation of the destaining performance described above, and evaluated whether or not there was color unevenness ( sensory evaluation). Specifically, "4" for "evenly dyed", "3" for "almost evenly dyed", "2" for "a lot of unevenness", and "very much unevenness". The case was set to "1". Calculate the average value of the scoring results of each panelist, "◎" if the average value is 3.6 points or more, "○" if the average value is 2.6 points or more and less than 3.6 points, 1.6 points or more and less than 2.6 points was evaluated as "Δ", and less than 1.6 points as "×". The results of this evaluation are shown in Table 11, in the "evenness" column.
（染毛力の評価）
　上記のように得られた各例の染毛処理毛束について、パネラー１０名が、標準光源下で目視にて発色度合いを、以下の基準で評価することにより、発色が良いか否かについて判断した。非常に良く染まっている（５点）、良く染まっている（４点）、染まっている（３点）、染まりが僅かに浅い（２点）、染まりが浅い（１点）の５段階で採点し、そして、各パネラーの採点結果について平均値を算出し、平均値が４．６点以上を「優れる：５」、３．６点以上４．６点未満を「良好：４」、２．６点以上３．６点未満を「可：３」、１．６点以上２．６点未満を「やや不良：２」、及び１．６点未満を「不良：１」とし、評価結果とした。この評価結果を表１１の「染毛力」欄に示した。 (Evaluation of hair dyeing power)
Regarding the dyed hair tresses of each example obtained as described above, 10 panelists visually evaluated the degree of color development under a standard light source according to the following criteria to determine whether the color development was good. did. Very well dyed (5 points), well dyed (4 points), dyed (3 points), slightly dyed (2 points), lightly dyed (1 point) Then, the average value of the scoring results of each panelist was calculated, and the average value of 4.6 points or more was "excellent: 5", 3.6 points or more and less than 4.6 points was "good: 4". 6 points or more and less than 3.6 points are "acceptable: 3", 1.6 points or more and less than 2.6 points are "slightly poor: 2", and less than 1.6 points are "bad: 1", and the evaluation results and did. The results of this evaluation are shown in the "hair dyeing power" column of Table 11.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表１１に示されるように、各実施例（実施例２－１～実施例２－１０）は、脱染性能に優れることが確認された。 As shown in Table 11, each example (Examples 2-1 to 2-10) was confirmed to be excellent in destaining performance.
　また、混合の２０分後の体積増加率３０％以上（体積増加率の評価「小」以上）である実施例においては、塗りムラが抑制され、均染性に優れることが確認できた。発泡量の観点から酸化剤を分解する（Ｆ）触媒であるヨウ化カリウムの量は０．００５質量％以上が好ましいことが分かった。 In addition, it was confirmed that in the examples in which the volume increase rate after 20 minutes of mixing was 30% or more (the volume increase rate was evaluated as "small" or more), uneven coating was suppressed and excellent level dyeing was achieved. It was found that the amount of potassium iodide, which is the (F) catalyst that decomposes the oxidizing agent, is preferably 0.005% by mass or more from the viewpoint of foaming amount.
　また、過大な発泡（体積増加率３５０％以上）が見られた実施例２－１では、体積増加により酸化染毛剤が希釈され、染毛力が低下することが確認された。 In addition, in Example 2-1, in which excessive foaming (volume increase rate of 350% or more) was observed, it was confirmed that the oxidation hair dye was diluted due to the increase in volume, and the hair dyeing power decreased.
　本発明の酸化染毛剤は、ヒトの頭髪、髭、眉毛、すね毛等の体毛を染毛するための染毛剤として利用することができる。その他、ペット等の動物の体毛を染毛するために利用してもよい。
　本発明の酸化染毛剤は、美容室、理容室等におけるカラーリング用の染毛剤、セルフカラーリング用の染毛剤に利用することができる。
 

  The oxidative hair dye of the present invention can be used as a hair dye for dyeing human body hair such as head hair, beard, eyebrows and shin hair. In addition, it may be used for dyeing body hair of animals such as pets.
The oxidative hair dye of the present invention can be used as a hair dye for coloring and a hair dye for self-coloring in beauty salons, barber shops, and the like.

Claims (9)

  1. （Ａ）カプラーを含有する酸化染毛剤であって、
    　前記酸化染毛剤は、（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）が０．４以下であり、
    　前記（Ａ）成分は０．３質量％以上含有し、
    　（Ｃ）ノニオン性界面活性剤として、（Ｃ１）ＨＬＢ１０未満のノニオン界面活性剤を含有することを特徴とする、酸化染毛剤。     (A) an oxidative hair dye containing a coupler,
    The oxidative hair dye has a mass ratio (B/A) of the content of the dye intermediate (B) to the content of the component (A) of 0.4 or less,
    The component (A) contains 0.3% by mass or more,
    (C) An oxidative hair dye containing (C1) a nonionic surfactant having an HLB of less than 10 as a nonionic surfactant.
  2. 　前記（Ｃ）成分は、（Ｃ１）成分と、（Ｃ２）ＨＬＢ１０以上のノニオン界面活性剤とを含有する、２種以上のノニオン界面活性剤であることを特徴とする、請求項１に記載の酸化染毛剤。 2. The method according to claim 1, wherein the component (C) is two or more nonionic surfactants containing component (C1) and (C2) a nonionic surfactant having an HLB of 10 or more. Oxidative hair dye.
  3. 　前記（Ｃ）成分は、
    　（Ｃ２）成分の含有量に対する前記（Ｃ１）成分の含有量の質量比（Ｃ１）／（Ｃ２）が、１．５以上であることを特徴とする、請求項１又は２に記載の酸化染毛剤。     The component (C) is
    3. The oxidation dye according to claim 1 or 2, wherein the mass ratio (C1)/(C2) of the content of the component (C1) to the content of the component (C2) is 1.5 or more. Hair agent.
  4. 　前記酸化染毛剤は、（Ｄ）ヨウ素化合物を含有していることを特徴とする、請求項１～３のいずれか一項に記載の酸化染毛剤。 The oxidative hair dye according to any one of claims 1 to 3, characterized in that the oxidative hair dye contains (D) an iodine compound.
  5. 　前記酸化染毛剤は、（Ｅ）多価アルコールを前記酸化染毛剤の質量に対して０．５質量％以下含有している、又は、（Ｅ）多価アルコールを含有しないことを特徴とする、請求項１～４のいずれか一項に記載の酸化染毛剤。 The oxidative hair dye contains (E) a polyhydric alcohol in an amount of 0.5% by mass or less relative to the mass of the oxidative hair dye, or (E) does not contain a polyhydric alcohol. The oxidative hair dye according to any one of claims 1 to 4.
  6. 　第１剤と第２剤を混合することにより得られる酸化染毛剤であって、
    　（Ａ）カプラーを含有し、
    　（Ａ）成分の含有量に対する（Ｂ）染料中間体の含有量の質量比（Ｂ／Ａ）が０．４以下であり、
    　前記（Ａ）成分の含有量が０．３質量％以上であり、
    　前記第１剤と第２剤を混合し、混合の２０分後における体積増加率が３０％以上であることを特徴とする、酸化染毛剤。     An oxidation hair dye obtained by mixing a first agent and a second agent,
    (A) contains a coupler,
    The mass ratio (B/A) of the content of the dye intermediate (B) to the content of the component (A) is 0.4 or less,
    The content of the component (A) is 0.3% by mass or more,
    An oxidative hair dye characterized by mixing the first part and the second part and having a volume increase rate of 30% or more 20 minutes after mixing.
  7. 　前記（Ａ）成分として２，４－ジアミノフェノキシエタノールを含有し、
    　酸化染毛剤中の２，４－ジアミノフェノキシエタノールの含有量が０．３質量％以上であることを特徴とする、請求項６に記載の酸化染毛剤。     containing 2,4-diaminophenoxyethanol as the component (A),
    7. The oxidative hair dye according to claim 6, wherein the content of 2,4-diaminophenoxyethanol in the oxidative hair dye is 0.3% by mass or more.
  8. 　さらに（Ｆ）触媒、及び（Ｇ）酸化剤を含有することを特徴とする、請求項６又は７に記載の酸化染毛剤。 The oxidative hair dye according to claim 6 or 7, further comprising (F) a catalyst and (G) an oxidizing agent.
  9. 　前記（Ｆ）成分の含有量が０．００５質量％以上０．２５質量％以下であることを特徴とする、請求項８に記載の酸化染毛剤。
     

          9. The oxidative hair dye according to claim 8, wherein the content of component (F) is 0.005% by mass or more and 0.25% by mass or less.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05194162A (en) * 1991-11-26 1993-08-03 Bristol Myers Squibb Co Oxidative hair dyeing composition and method for dyeing human keratinous fiber
JP2017197505A (en) * 2016-04-28 2017-11-02 ホーユー株式会社 Oxidative hair dye composition
JP2018104334A (en) * 2016-12-26 2018-07-05 ホーユー株式会社 Composition for hair cosmetics and method for using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05194162A (en) * 1991-11-26 1993-08-03 Bristol Myers Squibb Co Oxidative hair dyeing composition and method for dyeing human keratinous fiber
JP2017197505A (en) * 2016-04-28 2017-11-02 ホーユー株式会社 Oxidative hair dye composition
JP2018104334A (en) * 2016-12-26 2018-07-05 ホーユー株式会社 Composition for hair cosmetics and method for using the same

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