US20120076745A2 - Hair cosmetic product - Google Patents

Hair cosmetic product Download PDF

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Publication number
US20120076745A2
US20120076745A2 US10/829,954 US82995404A US2012076745A2 US 20120076745 A2 US20120076745 A2 US 20120076745A2 US 82995404 A US82995404 A US 82995404A US 2012076745 A2 US2012076745 A2 US 2012076745A2
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United States
Prior art keywords
mixed liquid
agent
hair
agents
hair cosmetic
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US10/829,954
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US8153108B2 (en
US20040213752A1 (en
Inventor
Hiroyuki Fujinuma
Takashi Matsuo
Masahiko Ogawa
Tomohito Koshika
Kazuhiro Okada
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Kao Corp
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Kao Corp
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Assigned to KAO CORPORATION reassignment KAO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOSHIKA, TOMOHITO, OKADA, KAZUHIRO, FUJINUMA, HIROYUKI, MATSUO, TAKASHI, OGAWA, MASAHIKO
Publication of US20040213752A1 publication Critical patent/US20040213752A1/en
Priority to US12/849,576 priority Critical patent/US8158112B2/en
Priority to US13/308,017 priority patent/US8246936B2/en
Publication of US20120076745A2 publication Critical patent/US20120076745A2/en
Priority to US13/439,429 priority patent/US8277784B2/en
Publication of US8153108B2 publication Critical patent/US8153108B2/en
Application granted granted Critical
Priority to US13/596,348 priority patent/US20120318291A1/en
Priority to US14/050,747 priority patent/US20140034078A1/en
Priority to US14/828,702 priority patent/US20150352015A1/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22Peroxides; Oxygen; Ozone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/347Phenols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/411Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/415Aminophenols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/08Preparations for bleaching the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/432Direct dyes
    • A61K2800/4324Direct dyes in preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits
    • A61K2800/882Mixing prior to application

Definitions

  • the present invention relates to a hair bleach or hair dye cosmetic product in the form of foam.
  • liquid or cream form agents have been widely used as hair cosmetics such as hair bleaches and hair dyes, but it is difficult to apply these types of hair cosmetics uniformly to the hair.
  • special skills such as “blocking” or a “two mirror technique” are required to apply the cosmetic to the root of the hair or to the back of the head, and a lot of time is also required to do this.
  • agents in the form of foam include aerosol type hair dyes in which two agents constituting a two agent type hair dye are discharged in foam form from a discharge vessel of the type in which two aerosol cans are connected (see Japanese Patent Application Laid-Open No. 10-287534) and non-aerosol type agents in which a single agent type hair bleach is discharged from a foamer vessel such as a pump foamer or the like as a foam (see Japanese Patent Application Laid-Open No. 9-227347).
  • the first and second agents are each independently discharged from the aerosol cans; accordingly, irregular mixing of the agents tends to occur, so that there may be instances of irregular bleaching (in other words, discoloration) or non-uniform dyeing.
  • pressure-resistant vessels and caps made of metal are used in the case of aerosol type discharge vessels, these parts are oxidized and corroded by hydrogen peroxide contained in hair bleaches or hair dyes, and there is a danger that the internal pressure inside such pressure-resistant vessels may rise to an excessive pressure and result in the decomposition of this hydrogen peroxide.
  • this hair bleach is applied to the hair without activating hydrogen peroxide, so that the effect obtained in a single application is insufficient. Accordingly, in order to achieve a sufficiently clear bleaching, this hair bleach must be allowed to stand for a considerable period of time following application (e.g., applied in the morning and rinsed away in the evening or the like), and several applications must be repeated, so that the use of such hair bleaches is complicated. As a result, problems also arise in terms of stickiness of the hair while, for example, the hair bleach is allowed to stand.
  • the present invention provides a hair cosmetic product containing:
  • a two agent type hair cosmetic which has a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein at least one of the first and second agents contains a surfactant;
  • the present invention provides also a hair cosmetic product containing:
  • a two agent type hair cosmetic which has a first agent containing an alkali agent and a second agent containing hydrogen peroxide, and wherein the first and second agents are mixed immediately prior to use;
  • a foamer vessel which discharges a mixed liquid containing the first and second agents in the form of foam
  • the present invention provides a hair treatment method in which a mixed liquid of the first and second agents of the abovementioned hair cosmetic product is applied to the hair by being discharged from a foamer vessel, allowed to stand for 3 to 60 minutes, and then rinsed away.
  • the present invention has advantages such as to prevent irregular bleaching or non-uniform dyeing in a hair cosmetic product, and also allow a sufficient bleaching power or dyeing power to be obtained, by discharging a hair bleach or hair dye in foam form from a non-aerosol type foamer vessel.
  • the preferred embodiments of the present invention provides an aspect in which the first agent contains no dye, this hair cosmetic product being used for hair bleaching, and a second aspect in which the first agent contains an oxidation dye or direct dye, this hair cosmetic product being used for hair dyeing.
  • the hair cosmetic product since the first agent contains an alkali agent, the product is superior in terms of hair bleaching power or dyeing power, and a specified hair bleaching effect or dyeing effect can be obtained in a short period of time.
  • the first and second agents are discharged after being pre-mixed using a foamer vessel, there is uniform mixing of the first and second agents.
  • the mixed liquid that is discharged in the form of foam by gas-liquid mixing using the foamer vessel can easily reach the roots of the hair; however, there is no accumulation of liquid or the like in this area, and the liquid spreads throughout the hair in an appropriately thin layer. Accordingly, unlike a case of using conventional liquid or cream form hair cosmetic products, roots of the hair will not be extremely bright, and also there will be no irregular bleaching or non-uniform dyeing due to unevenness in the amount of mixed liquid that is applied.
  • any difference in color between areas of new growth and areas already dyed can be eliminated, so that a natural finish is obtained, by applying the mixed liquid that is discharged in foam form in the present invention in the vicinity of areas of new growth such as part line, hairline or the like. Furthermore, since the mixed liquid can be applied to the hair as an appropriately thin layer, damage to the hair can be reduced.
  • the hair cosmetic product of the present invention contains a two agent type hair cosmetic which has a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein at least one of the first and second agents contains a surfactant; and a foamer vessel which discharges a mixed liquid comprising the first and second agents in the form of foam.
  • the hair cosmetic product of the present invention also contains a two agent type hair cosmetic which has a first agent that contains an alkali agent, and a second agent that contains hydrogen peroxide, and which uses the first and second agents after mixing these agents immediately prior to use, and a foamer vessel which discharges a mixed liquid containing the first and second agents in the form of foam.
  • This hair cosmetic product contains a surfactant at an amount of 0.1 to 10 wt % by weight of the mixed liquid, and the viscosity of the mixed liquid at 25° C. is 1 to 300 mPa ⁇ s.
  • ammonia alkanolamines such as monoethanolamine or the like, sodium hydroxide, potassium hydroxide or the like can be used as the alkali agent contained in the first agent.
  • ammonium salts such as ammonium hydrogencarbonate, ammonium chloride or the like, or carbonates such as potassium carbonate, sodium hydrogencarbonate or the like, can be added as buffering agents.
  • the concentration of the alkali agent is appropriately set so that the pH in the mixed liquid of the first and second agents is preferably 8 to 11, more preferably 9 to 11.
  • the second agent contains hydrogen peroxide.
  • the concentration of hydrogen peroxide in the second agent is preferably 1 to 9 wt %, and is more preferably 3 to 6 wt %. In the mixed liquid of the first and second agents, this concentration is preferably 1 to 6 wt %, and is more preferably 2 to 5 wt %.
  • the pH of the second agent is preferably pH 2 to 6, and is more preferably pH 2.5 to 4.
  • the mixed liquid of the first and second agents contains water as an essential component in a preferred amount constituting the balance of the liquid.
  • the abovementioned surfactant is contained in the first agent or second agent so that a foam is easily formed by the mixing of air and the hair cosmetic in the foam discharge means of the foamer vessel, and so that this foam is stabilized. Furthermore, in cases where the first agent contains an oxidation dye or direct dye, the surfactant also acts as a solubilizing agent for such dyes. Universally known surfactants can be used as this surfactant.
  • anionic surfactants such as alkylsulfates, polyoxyethylene alkyl ether sulfates or the like
  • cationic surfactants such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides or the like
  • amphoteric surfactants such as fatty acid amide propylbetaines, alkyldimethylamine oxides, alkylcarboxymethylhydroxyethylimiazolium betaines, betaine alkyldimethylaminoacetates, sulfobetaine or the like
  • nonionic surfactants such as polyoxyethylene alkyl ethers, alkylpolyglycosides, alkylalkanolamides or the like, can be used singly or in mixtures.
  • nonionic surfactants that are contained mainly in the first agent in order to solubilize oxidation dyes or direct dyes
  • the first agent since the first agent usually contains ammonia or a carbonate, and has a high ionic strength, it is preferable to use nonionic surfactants.
  • alkylpolyglycosides or polyoxyethylene alkyl ethers are more preferable for use.
  • Alkylpolyglycosides in which the number of carbon atoms in the alkyl group is 10 to 14, and the average degree of glycoside condensation is 1 to 2
  • preferable alkylpolyglycosides may be cited as examples of preferable alkylpolyglycosides.
  • polyoxyethylene alkyl ethers in which the number of carbon atoms in the alkyl group is 10 to 14, and the degree of polymerization of the polyoxyethylene is 10 to 30, may be cited as examples of more preferable polyoxyethylene alkyl ethers.
  • anionic surfactant in order to realize good foaming that allow easy application to the hair, it is preferable to use an anionic surfactant as the surfactant.
  • Preferred anionic surfactants include polyoxyethylene alkyl ether sulfates, and preferably sodium polyoxyethylene lauryl ether sulfates.
  • amphoteric surfactants such as fatty acid amide propylbetaines, sulfobetaine or the like with such anionic surfactants is more preferable.
  • Such anionic surfactants or amphoteric surfactants are contained in the first agent or second agent; however, in view of the fact that the first agent usually contains ammonia or a carbonate, and has a high ionic strength, it is preferable that such surfactants be contained in the second agent.
  • the surfactant content in the mixed liquid of the first and second agents is 0.1 to 10 wt %.
  • a preferred content in the aspect of the present invention used for hair bleaching is 0.1 to 3 wt %; in this case, a content of 0.5 to 2.5 wt % is more preferable, and a content of 1 to 2 wt % is even more preferable.
  • a preferable content is 1 to 5 wt %, and a content of 2 to 4 wt % is more preferable.
  • the hair cosmetic product of the present invention can be used for hair bleaching; this hair cosmetic product can be used for hair dyeing by including an oxidation dye or direct dye.
  • the first agent contains an oxidation dye or direct dye.
  • oxidation dyes include dye precursors such as paraphenylenediamine, para-aminophenol, toluene-2,5-diamine, N,N-bis(2-hydroxyethyl)paraphenylenediamine, 2-(2-hydroxyethyl)paraphenylenediamine, 4-amino-3-methylphenol, 6-amino-3-methylphenol, ortho-aminophenol, 1-hydroxyethyl-4,5-diaminopyrazole and the like, and couplers such as resorcine, 2-methylresorcine, meta-aminophenol, para-amino-ortho-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, meta-phenylenediamine, 2,4-diaminophenoxyethanol, 1-naphthol and the like.
  • direct dyes include para-nitro-ortho-phenylenediamine, para-nitro-meta-phenylenediamine, basic yellow 87, basic orange
  • the first or second agent, and more preferably the second agent contain a nonvolatile hydrophilic solvent in a relatively large amount.
  • a nonvolatile hydrophilic solvent it is preferable that a solvent that has no defoaming action be used as such a nonvolatile hydrophilic solvent.
  • solvents include polyols and lower alkyl ethers of the same. Polyols with 2 to 6 carbon atoms are preferable.
  • polyols examples include glycerol, propylene glycol, dipropylene glycol, 1,3-butanediol, ethylene glycol, diethylene glycol, isoprene glycol, sorbitol and the like.
  • lower alkyl ethers of polyols include mono-lower alkyl ethers and poly-lower alkyl ethers (e.g., di-lower alkyl ethers) of the abovementioned polyols.
  • monomethyl ethers or monoethyl ethers of polyols are preferable, and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether are more preferable.
  • the content of the nonvolatile hydrophilic solvent be set at 0.1 to 30 wt % in the mixed liquid of the first and second agents.
  • a content of 5 to 30 wt % is more preferable, a content of 10 to 30 wt % is even more preferable, and a content of 12 to 25 wt % is even more preferable.
  • the first or second agent contains a higher alcohol. Foam retention is improved by such a higher alcohol, and this is effective in preventing the dripping of liquid while the two agent type cosmetic is being allowed to stand following application to the hair.
  • Compounds with 10 to 24 carbon atoms are preferable as higher alcohols; examples of such higher alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and the like. Two or more of these alcohols can be used in combination.
  • the content of the abovementioned higher alcohol be set at 0.1 to 3 wt % by weight of the mixed liquid of the first and second agent; a content of 0.2 to 2 wt % is more preferable, and a content of 0.3 to 1.5 wt % is even more preferable.
  • the first or second agent contains a cationic polymer.
  • a conditioning effect can be imparted to the hair by such a cationic polymer.
  • a cationic polymer it is preferable to cause this polymer to form a complex with an anionic surfactant in order to improve the tactile sensation during rinsing.
  • this polymer be added to the first agent separately from the second agent, which contains an anionic surfactant.
  • the cationic polymer is preferably contained in the mixed liquid of the first and second agents at an amount of 0.1 to 3 wt %, and more preferably at an amount of 0.1 to 1 wt %.
  • cationic polymer refers to a polymer which has cationic groups or groups that can be ionized into cationic groups. This term includes amphoteric polymers that are cationic on the whole.
  • examples of cationic polymers include polymers in aqueous solution that contain amino groups or ammonium groups in the side chains of the polymer chains, or that contain diallyl quaternary ammonium salts as constituent units, e.g., cationized cellulose derivatives, cationic starches, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, quaternized polyvinylpyrrolidone derivatives and the like.
  • polymers that include diallyl quaternary ammonium salts as constituent units, quaternized polyvinylpyrrolidone derivatives and cationized cellulose derivatives are preferable from the standpoints of softness and smoothness of tactile sensation during rinsing and shampooing, ability to pass the fingers through, ease of arrangement during drying, moisture retention and storage stability; from these standpoints, polymers or copolymers of diallyl quaternary ammonium salts and cationized cellulose derivatives are preferable, and polymers or copolymers of diallyl quaternary ammonium salts are more preferable.
  • the skeletons indicated by the following general formula (1) or (2) are preferable as the skeletons of such polymers of diallyl quaternary ammonium salts.
  • R 1 and R 2 may be the same or different, and indicate hydrogen atoms, alkyl groups with 1 to 18 carbon atoms, aryl groups (phenyl groups or the like), hydroxyalkyl groups, amidoalkyl groups, cyanoalkyl groups, alkoxyalkyl groups or carboalkoxyalkyl groups.
  • R 3 and R 4 may be the same or different, and indicate hydrogen atoms, alkyl groups with 1 to 3 carbon atoms or phenyl groups.
  • X ⁇ indicates an anion (chloride ion, bromide ion, iodide ion, sulfuric acid anion, sulfonic acid anion, methylsulfuric acid anion, phosphoric acid anion, nitric acid anion or the like).
  • Examples of monomers that may constitute a copolymer with diallyl quaternary ammonium salts include acrylic acid, methacrylic acid or salts or acrylamides of these acids. In particular, acrylic acid, methacrylic acid or salts of these acids are preferable. Copolymers of acrylic acid, methacrylic acid or salts of these acids with diallyl quaternary ammonium salts have a high constituent ratio of diallyl quaternary ammonium salts, and are cationic polymers overall.
  • diallyl quaternary ammonium salts examples include dimethyldiallylammonium chloride polymers (Polyquaternium-6, e.g., Mercoat 100; ONDEO Nalco Co.), dimethyldiallylammonium chloride/acrylic acid copolymers (Polyquaternum-22, e.g., Mercoat 280 and 295; ONDEO Nalco Co.), dimethyldiallylammonium chloride/acrylamide copolymers (Polyquaternium-7, e.g., Mercoat 550; ONDEO Nalco Co.) and the like.
  • Mercoat 280 and 295 are preferred.
  • R 5 indicates a hydrogen atom or an alkyl group with 1 to 3 carbon atoms
  • R 6 , R 7 and R 8 may be the same or different, and indicate hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, hydroxyalkyl groups, amidoalkyl groups, alkoxyalkyl groups or carboalkoxyalkyl groups
  • Y indicates an oxygen atom or an imino group
  • r indicates an integer of 1 to 10
  • the total of s and t indicates a number from 20 to 8,000
  • X ⁇ has the same meaning as described above.
  • the molecular weight of the quaternized polyvinylpyrrolidone derivatives used in the present invention be 10,000 to 2,000,000, and a molecular weight of 50,000 to 1,500,000 is more preferable.
  • Examples of commercially marketed products include Gafcoat 734, 755 and 755N (ISP Japan Co.).
  • A indicates the residue of an anhydroglucose unit
  • f indicates an integer from 50 to 20,000
  • each R 9 indicates a substituent group expressed by the following general formula (5).
  • R 10 and R 11 indicate alkylene groups with 2 or 3 carbon atoms
  • g indicates an integer from 0 to 10
  • h indicates an integer from 0 to 3
  • i indicates an integer from 0 to 10
  • R 12 indicates an alkylene group or a hydroxyalkylene group with 1 to 3 carbon atoms
  • R 13 , R 14 and R 15 may be the same or different, and indicate alkyl groups, aryl groups or aralkyl groups with up to 10 carbon atoms; furthermore, these groups may form a hetero-ring containing a nitrogen atom in the formula.
  • X ⁇ has the same meaning as described above.
  • the degree of cation substitution of such cationized cellulose derivatives i.e., the mean value of h per anhydroglucose unit, be 0.01 to 1, and a value of 0.02 to 0.5 is more preferable. Furthermore, the total of g+i is 1 to 3. In cases where the degree of cation substitution is less than 0.01, this degree of substitution is insufficient. On the other hand, although this value may exceed 1, from the standpoint of the reaction yield, it is preferable that this value be 1 or less. It is preferable that the molecular weight of cationized cellulose derivatives used here be 100,000 to 3,000,000.
  • Examples of commercially marketed products include Leogard G and GP (Lion Co.), Polymer JR-125, JR-400, JR-30M, LR-400 and LR-30M (Union Carbide Co.) and the like.
  • Examples of other cationized cellulose derivatives that can be used include hydroxyethylcellulose dimethyldiallylammonium chloride; examples of commercially marketed products of this type include Celcoat H-100 and L-200 (National Starch and Chemical Co.).
  • the first or second agent may contain fragrances, ultraviolet absorbing agents, metal blocking agents such as edetic acid or the like, microbicidal agents, preservatives such as methyl para-oxybenzoate or the like, stabilizing agents such as phenacetin, 1-hydroxyethane-1,1-diphosphonic acid or the like, volatile or hydrophobic solvents such as ethanol, benzyl alcohol or the like, water-soluble macromolecular compounds such as hydroxyethylcellulose or the like, silicones such as dimethylpolysiloxane, polyether-modified silicone, amodimethicone or the like, moisture-retaining agents or the like.
  • fragrances ultraviolet absorbing agents
  • metal blocking agents such as edetic acid or the like
  • microbicidal agents such as methyl para-oxybenzoate or the like
  • stabilizing agents such as phenacetin, 1-hydroxyethane-1,1-diphosphonic acid or the like
  • volatile or hydrophobic solvents such as ethanol,
  • the first and second agent are prepared so that the viscosity of the mixed liquid of these agents (taken as the value obtained following rotation for 1 minute at 30 rpm using a No. 1 rotor in a B type rotary viscometer at 25° C.; if the viscosity exceeds 160 mPa ⁇ s, taken as the value similarly obtained following rotation for 1 minute at 12 rpm) is preferably 50 mPa ⁇ s or less, more preferably 10 mPa ⁇ s or less. If the viscosity is adjusted to a value in this range, a foam volume (i.e., gas-liquid mixture ratio) that allows easy application can be realized regardless of the temperature; accordingly, such a viscosity is preferable.
  • a foam volume i.e., gas-liquid mixture ratio
  • the first and second agent are prepared so that the viscosity of the mixed liquid of these agents is 1 to 300 mPa ⁇ s at 25° C., preferably 10 to 200 mPa ⁇ s, and more preferably 30 to 120 mPa ⁇ s. If the viscosity is adjusted to a value in this range, a foam volume that allows easy application can be realized regardless of the temperature and drops of the mixed liquid can be prevented from falling down between when applying the mixed liquid to the hair and when allowing the applied mixed liquid to stand on the hair; accordingly, such a viscosity is effective.
  • the gas-liquid mixture ratio be 7 to 40 mL/g, and a ratio of 15 to 30 mL/g is more preferable. Furthermore, the gas-liquid mixture ratio referred to here is a value which can be measured as follows.
  • the gas-liquid mixture ratio is determined by measuring the weight and volume of the foam that is discharged at 25° C. For example 100 g of a mixed liquid is placed in the bottle of a squeeze foamer vessel (manufactured by Yamato Seikan K.K., volume: 150 mL, mesh coarseness (openings): 200 mesh in the mixing compartment (200 measures per inch (25.4 mm)), 255 mesh at the tip end). 20 g of foam is discharged into a 100-mL graduated cylinder from the point in time at which the residue reaches 80 g, and the volume of foam is measured 1 minute following the initial discharge. The gas-liquid mixture ratio (mL/g) is obtained by dividing this volume (mL) of the discharged foam by a weight of 20 g.
  • a water-soluble solvent such as ethanol or the like may be added, or the contents and types of the surfactant, polyol and higher alcohol may be appropriately adjusted, in order to adjust the viscosity of the mixed liquid of the first and second agent to a value in the abovementioned range.
  • the first and second agents have a liquid form; however, as long as these agents form a solution in which the viscosity of the mixed liquid of the first and second agents is 1 to 300 mPa ⁇ s at 25° C., the first agent or second agent may have the form of a powder, granules, paste or the like.
  • a persulfate such as ammonium persulfate or the like may be contained in the mixed liquid in order to heighten the hair bleaching effect.
  • the foamer vessel is a non-aerosol type vessel which is used to mix the mixed liquid of the first and second agents with air and to discharge this mixture in the form of foam without using a propellant.
  • a foamer vessel scattering of the discharged agents can also be prevented.
  • such a non-aerosol type vessel can be manufactured at a lower cost, and does not require any high-pressure gas as a propellant, whereby hair cosmetic products using such a non-aerosol type vessel can be handled more safely in the distribution step.
  • Universally known pump foamer vessels, squeeze foamer vessels, electric foam generators, cumulative pressure type foamer vessels or the like that have foam discharge means can be used as the abovementioned foamer vessel.
  • Concrete examples of such vessels include the pump foamer E3 type and F2 type (manufactured by Yamato Seikan K.K.), squeeze foamer (manufactured by Yamato Seikan K.K.), electric foam generator (manufactured by Matushita Denko), air spray foamer (manufactured by Air Spray International Co.) and the like described in Shokuhin to Yoki [Food Products and Containers] (Vol. 35, No. 10, pp. 588-593 (1994); Vol. 35, No. 11, pp. 624-627 (1994); Vol. 36, No. 3, pp. 154-158 (1995)).
  • the portions that contact the contents (inside walls of the vessel, inside walls of the foam discharge means and the like) be constructed from materials that are not corroded by alkali agents or hydrogen peroxide, and that allow oxygen generated by the decomposition of hydrogen peroxide to pass through.
  • this configuration may be devised so that containers that are separate from the foamer vessel are respectively filled with the first agent or second agent, and both agents are transferred into the foamer vessel at the time of use; on the other hand, this product configuration may also be devised so that the foamer vessel is filled with one agent, a separate container is filled with the other agent, and this other agent is transferred into the foamer vessel at the time of use.
  • the second agent be placed in a container that has gas permeability in order to prevent a rise in the internal pressure of the container caused by oxygen generated by the decomposition of the hydrogen peroxide.
  • the second agent be placed in a foamer vessel constructed from a material with oxygen permeability (e.g., polyethylene).
  • the foam form agents discharged from the foamer vessel following the mixing of the first and second agents inside this vessel may be applied directly to the hair, or may be applied to the hair using the hands or an implement such as a brush or the like.
  • the applied preparation is allowed to stand for approximately 3 to 60 minutes, preferably approximately 5 to 45 minutes, following application, and is then rinsed away.
  • rinsing is performed with water, and the hair is then dried.
  • a first agent and second agent were prepared using the compositions shown in Table 1, and the first agent and second agent thus obtained were placed in (A) a squeeze foamer (manufactured by Yamato Seikan K.K.), (B) a pump foamer (F2 type, manufactured by Yamato Seikan K.K.) or (C) an electric foam generator (Awawash, manufactured by Matsushita Denko), and mixed at a mixture ratio (weight ratio) of 1:1.5, after which the mixed liquid was discharged. 80 g of the discharged foam was applied to the hair as a whole; hair bleaching was accomplished by allowing this foam to stand for 30 minutes, and then rinsing the foam away.
  • a squeeze foamer manufactured by Yamato Seikan K.K.
  • B a pump foamer
  • F2 type manufactured by Yamato Seikan K.K.
  • C an electric foam generator
  • a first agent and second agent were prepared using the compositions shown in Table 3; the first and second agents thus obtained were placed in a squeeze foamer A and mixed at a mixture ratio (weight ratio) of 1:1.5, and these agents were then discharged in the form of foam. 80 g of the discharged foam was applied to the hair as a whole; hair dyeing was accomplished by allowing this foam to stand for 30 minutes, and then rinsing the foam away. As a result, there was no scattering of the agents, hair dyeing was accomplished without irregularity, and scalp irritation was not a problem.
  • a first agent and second agent were prepared using the compositions shown in Tables 4 and 5; the first and second agents thus obtained were placed in a squeeze foamer A and mixed at a mixture ratio (weight ratio) of 1:1.5, and these agents were then discharged in the form of foam.
  • the overall hair was dyed in the same manner as in Example 2 using 80 g of the discharged foam. As a result, there was no scattering of the agents, hair dyeing was accomplished without irregularity, and scalp irritation was not a problem.
  • the present invention provides a hair cosmetic product in which a two agent type hair bleach or two agent type hair dye is discharged in the form of foam from a non-aerosol type foamer vessel.
  • the foam of this two agent type hair bleach or two agent type hair dye that is discharged from this hair cosmetic product has a foam quality that for example shows good affinity with the hair, and has a sufficient hair bleaching power or hair dyeing power without causing irritation of the scalp or scattering of the agents. Accordingly, the preferred hair cosmetic product of the present invention makes it possible to realize a uniform hair bleaching finish or hair dyeing finish with little irregularity.

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Abstract

A hair cosmetic product has a two agent type hair cosmetic which comprises a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein at least one of the first and second agents contains a surfactant; and a foamer vessel which discharges a mixed liquid comprising the first and second agents in the form of foam. Another hair cosmetic product has a two agent type hair cosmetic which contains a first agent that includes an alkali agent and a second agent that includes hydrogen peroxide, and which is used after mixing the first and second agents immediately prior to use, and a foamer vessel from which a mixed liquid of the first and second agents is discharged in the form of foam. A surfactant is contained in the mixed liquid at an amount of 0.1 to 10 wt %, and the viscosity of the mixed liquid at 25° C. is 1 to 300 mPa·s.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a hair bleach or hair dye cosmetic product in the form of foam.
  • BACKGROUND OF THE INVENTION
  • Conventionally, liquid or cream form agents have been widely used as hair cosmetics such as hair bleaches and hair dyes, but it is difficult to apply these types of hair cosmetics uniformly to the hair. In particular, special skills such as “blocking” or a “two mirror technique” are required to apply the cosmetic to the root of the hair or to the back of the head, and a lot of time is also required to do this.
  • As a countermeasure for such problems, it has been proposed to simplify the hair dyeing operations by discharging agents in the form of foam. For example, such agents include aerosol type hair dyes in which two agents constituting a two agent type hair dye are discharged in foam form from a discharge vessel of the type in which two aerosol cans are connected (see Japanese Patent Application Laid-Open No. 10-287534) and non-aerosol type agents in which a single agent type hair bleach is discharged from a foamer vessel such as a pump foamer or the like as a foam (see Japanese Patent Application Laid-Open No. 9-227347).
  • However, in the case of agents using a discharge vessel of the type in which two aerosol cans are connected, the first and second agents are each independently discharged from the aerosol cans; accordingly, irregular mixing of the agents tends to occur, so that there may be instances of irregular bleaching (in other words, discoloration) or non-uniform dyeing. Furthermore, since pressure-resistant vessels and caps made of metal are used in the case of aerosol type discharge vessels, these parts are oxidized and corroded by hydrogen peroxide contained in hair bleaches or hair dyes, and there is a danger that the internal pressure inside such pressure-resistant vessels may rise to an excessive pressure and result in the decomposition of this hydrogen peroxide.
  • On the other hand, in the case of products in which a foamer vessel is filled with a single agent type hair bleach, this hair bleach is applied to the hair without activating hydrogen peroxide, so that the effect obtained in a single application is insufficient. Accordingly, in order to achieve a sufficiently clear bleaching, this hair bleach must be allowed to stand for a considerable period of time following application (e.g., applied in the morning and rinsed away in the evening or the like), and several applications must be repeated, so that the use of such hair bleaches is complicated. As a result, problems also arise in terms of stickiness of the hair while, for example, the hair bleach is allowed to stand.
  • SUMMARY OF THE INVENTION
  • The present invention provides a hair cosmetic product containing:
  • a two agent type hair cosmetic which has a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein at least one of the first and second agents contains a surfactant; and
  • a foamer vessel which discharges a mixed liquid comprising the first and second agents in the form of foam. The present invention provides also a hair cosmetic product containing:
  • a two agent type hair cosmetic which has a first agent containing an alkali agent and a second agent containing hydrogen peroxide, and wherein the first and second agents are mixed immediately prior to use; and
  • a foamer vessel which discharges a mixed liquid containing the first and second agents in the form of foam,
  • wherein the mixed liquid contains a surfactant at an amount of 0.1 to 10 wt %, by weight of the mixed liquid, and the viscosity of the mixed liquid at 25° C. is 1 to 300 mPa·s. Furthermore, the present invention provides a hair treatment method in which a mixed liquid of the first and second agents of the abovementioned hair cosmetic product is applied to the hair by being discharged from a foamer vessel, allowed to stand for 3 to 60 minutes, and then rinsed away.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention will be described in detail below.
  • The present invention has advantages such as to prevent irregular bleaching or non-uniform dyeing in a hair cosmetic product, and also allow a sufficient bleaching power or dyeing power to be obtained, by discharging a hair bleach or hair dye in foam form from a non-aerosol type foamer vessel.
  • In particular, the preferred embodiments of the present invention provides an aspect in which the first agent contains no dye, this hair cosmetic product being used for hair bleaching, and a second aspect in which the first agent contains an oxidation dye or direct dye, this hair cosmetic product being used for hair dyeing.
  • If this hair cosmetic product is used, since the first agent contains an alkali agent, the product is superior in terms of hair bleaching power or dyeing power, and a specified hair bleaching effect or dyeing effect can be obtained in a short period of time.
  • Furthermore, since the first and second agents are discharged after being pre-mixed using a foamer vessel, there is uniform mixing of the first and second agents. Moreover, the mixed liquid that is discharged in the form of foam by gas-liquid mixing using the foamer vessel can easily reach the roots of the hair; however, there is no accumulation of liquid or the like in this area, and the liquid spreads throughout the hair in an appropriately thin layer. Accordingly, unlike a case of using conventional liquid or cream form hair cosmetic products, roots of the hair will not be extremely bright, and also there will be no irregular bleaching or non-uniform dyeing due to unevenness in the amount of mixed liquid that is applied. Accordingly, any difference in color between areas of new growth and areas already dyed can be eliminated, so that a natural finish is obtained, by applying the mixed liquid that is discharged in foam form in the present invention in the vicinity of areas of new growth such as part line, hairline or the like. Furthermore, since the mixed liquid can be applied to the hair as an appropriately thin layer, damage to the hair can be reduced.
  • Furthermore, in the preferred embodiments of the present invention, since a non-aerosol type vessel can be used as the foamer vessel, the problems of corrosion of the vessel and a rise in internal pressure are also substantially eliminated.
  • The hair cosmetic product of the present invention contains a two agent type hair cosmetic which has a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein at least one of the first and second agents contains a surfactant; and a foamer vessel which discharges a mixed liquid comprising the first and second agents in the form of foam.
  • The hair cosmetic product of the present invention also contains a two agent type hair cosmetic which has a first agent that contains an alkali agent, and a second agent that contains hydrogen peroxide, and which uses the first and second agents after mixing these agents immediately prior to use, and a foamer vessel which discharges a mixed liquid containing the first and second agents in the form of foam. This hair cosmetic product contains a surfactant at an amount of 0.1 to 10 wt % by weight of the mixed liquid, and the viscosity of the mixed liquid at 25° C. is 1 to 300 mPa·s.
  • Here, for example, ammonia, alkanolamines such as monoethanolamine or the like, sodium hydroxide, potassium hydroxide or the like can be used as the alkali agent contained in the first agent. Furthermore, ammonium salts such as ammonium hydrogencarbonate, ammonium chloride or the like, or carbonates such as potassium carbonate, sodium hydrogencarbonate or the like, can be added as buffering agents.
  • The concentration of the alkali agent is appropriately set so that the pH in the mixed liquid of the first and second agents is preferably 8 to 11, more preferably 9 to 11.
  • Meanwhile, the second agent contains hydrogen peroxide. The concentration of hydrogen peroxide in the second agent is preferably 1 to 9 wt %, and is more preferably 3 to 6 wt %. In the mixed liquid of the first and second agents, this concentration is preferably 1 to 6 wt %, and is more preferably 2 to 5 wt %. Furthermore, in order to suppress decomposition of the hydrogen peroxide, the pH of the second agent is preferably pH 2 to 6, and is more preferably pH 2.5 to 4.
  • The mixed liquid of the first and second agents contains water as an essential component in a preferred amount constituting the balance of the liquid.
  • The abovementioned surfactant is contained in the first agent or second agent so that a foam is easily formed by the mixing of air and the hair cosmetic in the foam discharge means of the foamer vessel, and so that this foam is stabilized. Furthermore, in cases where the first agent contains an oxidation dye or direct dye, the surfactant also acts as a solubilizing agent for such dyes. Universally known surfactants can be used as this surfactant. For example, anionic surfactants such as alkylsulfates, polyoxyethylene alkyl ether sulfates or the like, cationic surfactants such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides or the like, amphoteric surfactants such as fatty acid amide propylbetaines, alkyldimethylamine oxides, alkylcarboxymethylhydroxyethylimiazolium betaines, betaine alkyldimethylaminoacetates, sulfobetaine or the like, or nonionic surfactants such as polyoxyethylene alkyl ethers, alkylpolyglycosides, alkylalkanolamides or the like, can be used singly or in mixtures.
  • In regard to surfactants that are contained mainly in the first agent in order to solubilize oxidation dyes or direct dyes, since the first agent usually contains ammonia or a carbonate, and has a high ionic strength, it is preferable to use nonionic surfactants. In particular, alkylpolyglycosides or polyoxyethylene alkyl ethers are more preferable for use. Alkylpolyglycosides in which the number of carbon atoms in the alkyl group is 10 to 14, and the average degree of glycoside condensation is 1 to 2, may be cited as examples of preferable alkylpolyglycosides. Furthermore, polyoxyethylene alkyl ethers in which the number of carbon atoms in the alkyl group is 10 to 14, and the degree of polymerization of the polyoxyethylene is 10 to 30, may be cited as examples of more preferable polyoxyethylene alkyl ethers.
  • Furthermore, in order to realize good foaming that allow easy application to the hair, it is preferable to use an anionic surfactant as the surfactant. Preferred anionic surfactants include polyoxyethylene alkyl ether sulfates, and preferably sodium polyoxyethylene lauryl ether sulfates. Furthermore, the combined use of amphoteric surfactants such as fatty acid amide propylbetaines, sulfobetaine or the like with such anionic surfactants is more preferable. Such anionic surfactants or amphoteric surfactants are contained in the first agent or second agent; however, in view of the fact that the first agent usually contains ammonia or a carbonate, and has a high ionic strength, it is preferable that such surfactants be contained in the second agent.
  • In order to obtain good foaming that allows easy application to the hair, and in order to obtain good foam stability, the surfactant content in the mixed liquid of the first and second agents is 0.1 to 10 wt %. Furthermore, a preferred content in the aspect of the present invention used for hair bleaching is 0.1 to 3 wt %; in this case, a content of 0.5 to 2.5 wt % is more preferable, and a content of 1 to 2 wt % is even more preferable. Furthermore, in the aspect of the present invention used for hair dyeing, since solubilizing the oxidation dye or direct dye may be necessary, a preferable content is 1 to 5 wt %, and a content of 2 to 4 wt % is more preferable.
  • In cases where no dye is contained in the hair cosmetic, the hair cosmetic product of the present invention can be used for hair bleaching; this hair cosmetic product can be used for hair dyeing by including an oxidation dye or direct dye. In cases where the hair cosmetic product is used for hair dyeing, the first agent contains an oxidation dye or direct dye. Examples of such oxidation dyes include dye precursors such as paraphenylenediamine, para-aminophenol, toluene-2,5-diamine, N,N-bis(2-hydroxyethyl)paraphenylenediamine, 2-(2-hydroxyethyl)paraphenylenediamine, 4-amino-3-methylphenol, 6-amino-3-methylphenol, ortho-aminophenol, 1-hydroxyethyl-4,5-diaminopyrazole and the like, and couplers such as resorcine, 2-methylresorcine, meta-aminophenol, para-amino-ortho-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, meta-phenylenediamine, 2,4-diaminophenoxyethanol, 1-naphthol and the like. Examples of direct dyes include para-nitro-ortho-phenylenediamine, para-nitro-meta-phenylenediamine, basic yellow 87, basic orange 31, basic red 12, basic red 51, basic blue 99, acid orange 7 and the like.
  • Furthermore, in the present invention, it is preferable that the first or second agent, and more preferably the second agent, contain a nonvolatile hydrophilic solvent in a relatively large amount. As a result, the irritation of the scalp caused by the concentration of irritating components such as hydrogen peroxide or the like due to the evaporation of moisture from the hair cosmetic while the cosmetic is being allowed to stand after the two agent type hair cosmetic has been applied to the hair can be alleviated. It is preferable that a solvent that has no defoaming action be used as such a nonvolatile hydrophilic solvent. Examples of such solvents include polyols and lower alkyl ethers of the same. Polyols with 2 to 6 carbon atoms are preferable. Examples of such polyols include glycerol, propylene glycol, dipropylene glycol, 1,3-butanediol, ethylene glycol, diethylene glycol, isoprene glycol, sorbitol and the like. Examples of lower alkyl ethers of polyols include mono-lower alkyl ethers and poly-lower alkyl ethers (e.g., di-lower alkyl ethers) of the abovementioned polyols. In particular, monomethyl ethers or monoethyl ethers of polyols are preferable, and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether are more preferable.
  • From the standpoint of reducing scalp irritation and obtaining good foam quality, it is preferable that the content of the nonvolatile hydrophilic solvent be set at 0.1 to 30 wt % in the mixed liquid of the first and second agents. A content of 5 to 30 wt % is more preferable, a content of 10 to 30 wt % is even more preferable, and a content of 12 to 25 wt % is even more preferable.
  • Furthermore, in the present invention, it is preferable that the first or second agent contains a higher alcohol. Foam retention is improved by such a higher alcohol, and this is effective in preventing the dripping of liquid while the two agent type cosmetic is being allowed to stand following application to the hair. Compounds with 10 to 24 carbon atoms are preferable as higher alcohols; examples of such higher alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and the like. Two or more of these alcohols can be used in combination.
  • From the standpoint of controlling liquid dripping and improving the foam quality, it is preferable that the content of the abovementioned higher alcohol be set at 0.1 to 3 wt % by weight of the mixed liquid of the first and second agent; a content of 0.2 to 2 wt % is more preferable, and a content of 0.3 to 1.5 wt % is even more preferable.
  • Furthermore, in the present invention, it is preferable that the first or second agent contains a cationic polymer. A conditioning effect can be imparted to the hair by such a cationic polymer. In cases where a cationic polymer is added, it is preferable to cause this polymer to form a complex with an anionic surfactant in order to improve the tactile sensation during rinsing. However, from the standpoint of storage stability, it is preferable that this polymer be added to the first agent separately from the second agent, which contains an anionic surfactant. The cationic polymer is preferably contained in the mixed liquid of the first and second agents at an amount of 0.1 to 3 wt %, and more preferably at an amount of 0.1 to 1 wt %.
  • Here, the term “cationic polymer” refers to a polymer which has cationic groups or groups that can be ionized into cationic groups. This term includes amphoteric polymers that are cationic on the whole. Specifically, examples of cationic polymers include polymers in aqueous solution that contain amino groups or ammonium groups in the side chains of the polymer chains, or that contain diallyl quaternary ammonium salts as constituent units, e.g., cationized cellulose derivatives, cationic starches, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, quaternized polyvinylpyrrolidone derivatives and the like. Among these compounds, polymers that include diallyl quaternary ammonium salts as constituent units, quaternized polyvinylpyrrolidone derivatives and cationized cellulose derivatives are preferable from the standpoints of softness and smoothness of tactile sensation during rinsing and shampooing, ability to pass the fingers through, ease of arrangement during drying, moisture retention and storage stability; from these standpoints, polymers or copolymers of diallyl quaternary ammonium salts and cationized cellulose derivatives are preferable, and polymers or copolymers of diallyl quaternary ammonium salts are more preferable.
  • The skeletons indicated by the following general formula (1) or (2) are preferable as the skeletons of such polymers of diallyl quaternary ammonium salts.
    Figure US20120076745A2-20120329-C00001
  • In formulae (1) and (2), R1 and R2 may be the same or different, and indicate hydrogen atoms, alkyl groups with 1 to 18 carbon atoms, aryl groups (phenyl groups or the like), hydroxyalkyl groups, amidoalkyl groups, cyanoalkyl groups, alkoxyalkyl groups or carboalkoxyalkyl groups. R3 and R4 may be the same or different, and indicate hydrogen atoms, alkyl groups with 1 to 3 carbon atoms or phenyl groups. X indicates an anion (chloride ion, bromide ion, iodide ion, sulfuric acid anion, sulfonic acid anion, methylsulfuric acid anion, phosphoric acid anion, nitric acid anion or the like).
  • Examples of monomers that may constitute a copolymer with diallyl quaternary ammonium salts include acrylic acid, methacrylic acid or salts or acrylamides of these acids. In particular, acrylic acid, methacrylic acid or salts of these acids are preferable. Copolymers of acrylic acid, methacrylic acid or salts of these acids with diallyl quaternary ammonium salts have a high constituent ratio of diallyl quaternary ammonium salts, and are cationic polymers overall.
  • Concrete examples of polymers or copolymers of diallyl quaternary ammonium salts include dimethyldiallylammonium chloride polymers (Polyquaternium-6, e.g., Mercoat 100; ONDEO Nalco Co.), dimethyldiallylammonium chloride/acrylic acid copolymers (Polyquaternum-22, e.g., Mercoat 280 and 295; ONDEO Nalco Co.), dimethyldiallylammonium chloride/acrylamide copolymers (Polyquaternium-7, e.g., Mercoat 550; ONDEO Nalco Co.) and the like. In particular, Mercoat 280 and 295 are preferred.
  • Compounds expressed by the following general formula (3) are preferable as quaternized polyvinylpyrrolidone derivatives.
    Figure US20120076745A2-20120329-C00002
  • In formula (3), R5 indicates a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, R6, R7 and R8 may be the same or different, and indicate hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, hydroxyalkyl groups, amidoalkyl groups, alkoxyalkyl groups or carboalkoxyalkyl groups, Y indicates an oxygen atom or an imino group, r indicates an integer of 1 to 10, the total of s and t indicates a number from 20 to 8,000, and X has the same meaning as described above.
  • It is preferable that the molecular weight of the quaternized polyvinylpyrrolidone derivatives used in the present invention be 10,000 to 2,000,000, and a molecular weight of 50,000 to 1,500,000 is more preferable. Examples of commercially marketed products include Gafcoat 734, 755 and 755N (ISP Japan Co.).
  • For example, compounds expressed by the following general formula (4) are preferable as cationized cellulose derivatives.
    Figure US20120076745A2-20120329-C00003
  • In formula (4), A indicates the residue of an anhydroglucose unit, f indicates an integer from 50 to 20,000, and each R9 indicates a substituent group expressed by the following general formula (5).
    Figure US20120076745A2-20120329-C00004
  • In formula (5), R10 and R11 indicate alkylene groups with 2 or 3 carbon atoms, g indicates an integer from 0 to 10, h indicates an integer from 0 to 3, i indicates an integer from 0 to 10, R12 indicates an alkylene group or a hydroxyalkylene group with 1 to 3 carbon atoms, and R13, R14 and R15 may be the same or different, and indicate alkyl groups, aryl groups or aralkyl groups with up to 10 carbon atoms; furthermore, these groups may form a hetero-ring containing a nitrogen atom in the formula. X has the same meaning as described above.
  • It is preferable that the degree of cation substitution of such cationized cellulose derivatives, i.e., the mean value of h per anhydroglucose unit, be 0.01 to 1, and a value of 0.02 to 0.5 is more preferable. Furthermore, the total of g+i is 1 to 3. In cases where the degree of cation substitution is less than 0.01, this degree of substitution is insufficient. On the other hand, although this value may exceed 1, from the standpoint of the reaction yield, it is preferable that this value be 1 or less. It is preferable that the molecular weight of cationized cellulose derivatives used here be 100,000 to 3,000,000. Examples of commercially marketed products include Leogard G and GP (Lion Co.), Polymer JR-125, JR-400, JR-30M, LR-400 and LR-30M (Union Carbide Co.) and the like. Examples of other cationized cellulose derivatives that can be used include hydroxyethylcellulose dimethyldiallylammonium chloride; examples of commercially marketed products of this type include Celcoat H-100 and L-200 (National Starch and Chemical Co.).
  • If necessary, furthermore, the first or second agent may contain fragrances, ultraviolet absorbing agents, metal blocking agents such as edetic acid or the like, microbicidal agents, preservatives such as methyl para-oxybenzoate or the like, stabilizing agents such as phenacetin, 1-hydroxyethane-1,1-diphosphonic acid or the like, volatile or hydrophobic solvents such as ethanol, benzyl alcohol or the like, water-soluble macromolecular compounds such as hydroxyethylcellulose or the like, silicones such as dimethylpolysiloxane, polyether-modified silicone, amodimethicone or the like, moisture-retaining agents or the like.
  • Furthermore, the first and second agent are prepared so that the viscosity of the mixed liquid of these agents (taken as the value obtained following rotation for 1 minute at 30 rpm using a No. 1 rotor in a B type rotary viscometer at 25° C.; if the viscosity exceeds 160 mPa·s, taken as the value similarly obtained following rotation for 1 minute at 12 rpm) is preferably 50 mPa·s or less, more preferably 10 mPa·s or less. If the viscosity is adjusted to a value in this range, a foam volume (i.e., gas-liquid mixture ratio) that allows easy application can be realized regardless of the temperature; accordingly, such a viscosity is preferable. Furthermore, the first and second agent are prepared so that the viscosity of the mixed liquid of these agents is 1 to 300 mPa·s at 25° C., preferably 10 to 200 mPa·s, and more preferably 30 to 120 mPa·s. If the viscosity is adjusted to a value in this range, a foam volume that allows easy application can be realized regardless of the temperature and drops of the mixed liquid can be prevented from falling down between when applying the mixed liquid to the hair and when allowing the applied mixed liquid to stand on the hair; accordingly, such a viscosity is effective. Here, from the standpoints of good affinity of the agents for the hair and ease of application, it is preferable that the gas-liquid mixture ratio be 7 to 40 mL/g, and a ratio of 15 to 30 mL/g is more preferable. Furthermore, the gas-liquid mixture ratio referred to here is a value which can be measured as follows.
  • First, the gas-liquid mixture ratio is determined by measuring the weight and volume of the foam that is discharged at 25° C. For example 100 g of a mixed liquid is placed in the bottle of a squeeze foamer vessel (manufactured by Yamato Seikan K.K., volume: 150 mL, mesh coarseness (openings): 200 mesh in the mixing compartment (200 measures per inch (25.4 mm)), 255 mesh at the tip end). 20 g of foam is discharged into a 100-mL graduated cylinder from the point in time at which the residue reaches 80 g, and the volume of foam is measured 1 minute following the initial discharge. The gas-liquid mixture ratio (mL/g) is obtained by dividing this volume (mL) of the discharged foam by a weight of 20 g.
  • Furthermore, adjustment of the viscosity of the mixed liquid to a value in the abovementioned range is preferable, since this facilitates squeezing when the foam is discharged by a squeeze foamer or the like. A water-soluble solvent such as ethanol or the like may be added, or the contents and types of the surfactant, polyol and higher alcohol may be appropriately adjusted, in order to adjust the viscosity of the mixed liquid of the first and second agent to a value in the abovementioned range.
  • Furthermore, it is preferable that the first and second agents have a liquid form; however, as long as these agents form a solution in which the viscosity of the mixed liquid of the first and second agents is 1 to 300 mPa·s at 25° C., the first agent or second agent may have the form of a powder, granules, paste or the like.
  • In addition, a persulfate such as ammonium persulfate or the like may be contained in the mixed liquid in order to heighten the hair bleaching effect.
  • In the present invention, the foamer vessel is a non-aerosol type vessel which is used to mix the mixed liquid of the first and second agents with air and to discharge this mixture in the form of foam without using a propellant. As a result of the use of such a foamer vessel, scattering of the discharged agents can also be prevented. In particular, as compared with an aerosol type vessel, such a non-aerosol type vessel can be manufactured at a lower cost, and does not require any high-pressure gas as a propellant, whereby hair cosmetic products using such a non-aerosol type vessel can be handled more safely in the distribution step.
  • Universally known pump foamer vessels, squeeze foamer vessels, electric foam generators, cumulative pressure type foamer vessels or the like that have foam discharge means can be used as the abovementioned foamer vessel. Concrete examples of such vessels include the pump foamer E3 type and F2 type (manufactured by Yamato Seikan K.K.), squeeze foamer (manufactured by Yamato Seikan K.K.), electric foam generator (manufactured by Matushita Denko), air spray foamer (manufactured by Air Spray International Co.) and the like described in Shokuhin to Yoki [Food Products and Containers] (Vol. 35, No. 10, pp. 588-593 (1994); Vol. 35, No. 11, pp. 624-627 (1994); Vol. 36, No. 3, pp. 154-158 (1995)).
  • In such a foamer vessel, it is preferable that the portions that contact the contents (inside walls of the vessel, inside walls of the foam discharge means and the like) be constructed from materials that are not corroded by alkali agents or hydrogen peroxide, and that allow oxygen generated by the decomposition of hydrogen peroxide to pass through.
  • In regard to the product configuration of the hair cosmetic product of the present invention containing the abovementioned first agent, second agent and foamer vessel, this configuration may be devised so that containers that are separate from the foamer vessel are respectively filled with the first agent or second agent, and both agents are transferred into the foamer vessel at the time of use; on the other hand, this product configuration may also be devised so that the foamer vessel is filled with one agent, a separate container is filled with the other agent, and this other agent is transferred into the foamer vessel at the time of use. In this case, it is preferable that the second agent be placed in a container that has gas permeability in order to prevent a rise in the internal pressure of the container caused by oxygen generated by the decomposition of the hydrogen peroxide. On the other hand, in the case of the first agent, it is necessary to use a container resistant to oxygen permeation in order to prevent oxidation of the oxidation dye and volatilization of the ammonia. Accordingly, it is preferable that the second agent be placed in a foamer vessel constructed from a material with oxygen permeability (e.g., polyethylene).
  • Furthermore, in regard to the method of use of the hair cosmetic product of the present invention, the foam form agents discharged from the foamer vessel following the mixing of the first and second agents inside this vessel may be applied directly to the hair, or may be applied to the hair using the hands or an implement such as a brush or the like. The applied preparation is allowed to stand for approximately 3 to 60 minutes, preferably approximately 5 to 45 minutes, following application, and is then rinsed away. Preferably subsequently, following appropriate shampooing or rinsing, rinsing is performed with water, and the hair is then dried.
  • The following examples further describe and demonstrate embodiments of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention.
  • EXAMPLES Examples 1A Through 1C Cosmetic Products Used for Hair Bleaching
  • A first agent and second agent were prepared using the compositions shown in Table 1, and the first agent and second agent thus obtained were placed in (A) a squeeze foamer (manufactured by Yamato Seikan K.K.), (B) a pump foamer (F2 type, manufactured by Yamato Seikan K.K.) or (C) an electric foam generator (Awawash, manufactured by Matsushita Denko), and mixed at a mixture ratio (weight ratio) of 1:1.5, after which the mixed liquid was discharged. 80 g of the discharged foam was applied to the hair as a whole; hair bleaching was accomplished by allowing this foam to stand for 30 minutes, and then rinsing the foam away. In this case, foaming, foam duration, irritation of the scalp, irregular hair bleaching, coating properties (ease of coating, affinity for the hair) and scattering of the agents were respectively evaluated using the criteria shown below. The results obtained are shown in Table 2.
    TABLE 1
    Concentration in first
    First agent agent (wt %)
    Strong aqueous ammonia (28%) 8.0
    Ammonium hydrogencarbonate 14.0
    Methyl para-oxybenzoate 0.1
    Fragrance 0.5
    Water balance
    Concentration in second
    Second agent agent (wt %)
    Sodium polyoxyethylene (2.5) 1.9
    lauryl ether sulfate
    Lauric acid amide propylbetaine 0.05
    Laurylhydroxysulfobetaine 0.05
    Lauric acid 0.04
    Phosphoric acid (75%) Amount required to adjust
    second agent to pH 3.8
    Glycerol 30.0
    Hydrogen peroxide (35%) 16.3
    Water balance

    Surfactant concentration following mixing: 1.22 wt %

    Viscosity: 15 mPa · s

    Evaluation Criteria for Foaming
    “Superior”: Extremely uniform fine foam
    “Good”: Uniform fine foam
    “Normal”: Non-uniform coarse foam
    “Poor”: Foam not formed; moisture admixed.
    Evaluation Criteria for Foam Duration
    “Superior”: Extremely long duration; foam lasted while being allowed to stand.
    “Good”: Sufficient duration; foam lasted for some time following application.
    “Normal”: Foam showed sufficient duration so that there was no problem in application; however, foam quickly disappeared following application.
    “Poor”: Foam disappeared immediately following discharge, and liquid dripping occurred during application.
    Evaluation Criteria for Irritation of Scalp
    “Superior”: No feeling of irritation
    “Good”: Almost no feeling of irritation
    “Normal”: Irritation felt, but not at a level that could not be endured.
    “Poor”: Severe irritation felt.
    Evaluation Criteria for Irregular Hair Bleaching
    “Superior”: Extremely uniform hair bleaching possible without any irregular hair bleaching.
    “Good”: Uniform hair bleaching possible with hardly any irregular hair bleaching.
    “Normal”: Slight irregularity in hair bleaching
    “Poor”: Major irregularity in hair bleaching
    Evaluation Criteria for Coating Properties (Ease of Application, Affinity for Hair)
    “Superior”: Agents firmly penetrated to roots merely by pressing the foam on the hair.
    “Good”: Agents could easily be caused to penetrate to roots by kneading with hands.
    “Normal”: Cases occurred in which penetration of the agents was difficult depending on location, as in the roots on the back portion of the head where the quantity of hair was large.
  • “Poor”: Poor penetration; failure to coat roots and the like.
    TABLE 2
    C:
    A: B: Electric foam
    Squeeze foamer Pump foamer generator
    Foaming Good Superior Superior
    Foam duration Good Superior Superior
    Irritation of Good Good Good
    scalp
    Irregular hair Superior Superior Superior
    bleaching
    Coating Good Superior Superior
    properties
    Scattering of none none none
    agents
  • It is seen from the results in Table 2 that there was no scattering of the agents, hair bleaching was possible without irregularity, and scalp irritation was not a problem, when any of the foamer vessels A, B and C were used.
  • Furthermore, in the case of hair that showed conspicuous differences in color (brightness) between black hair in areas of new growth and bleached hair from which color was removed (as time elapsed following the final hair bleaching), this difference was eliminated, so that a natural finish could be obtained, regardless of the foamer vessel that was used.
  • Example 2 Hair Cosmetic Product Used for Hair Dyeing
  • A first agent and second agent were prepared using the compositions shown in Table 3; the first and second agents thus obtained were placed in a squeeze foamer A and mixed at a mixture ratio (weight ratio) of 1:1.5, and these agents were then discharged in the form of foam. 80 g of the discharged foam was applied to the hair as a whole; hair dyeing was accomplished by allowing this foam to stand for 30 minutes, and then rinsing the foam away. As a result, there was no scattering of the agents, hair dyeing was accomplished without irregularity, and scalp irritation was not a problem.
  • Furthermore, differences in color between black hair in areas of new growth and the color of the hair in already dyed areas were eliminated, so that a natural finish could be obtained.
    TABLE 3
    Concentration in first
    First agent agent (wt %)
    Strong aqueous ammonia (28%) 8.0
    Ammonium hydrogencarbonate 14.0
    Methyl para-oxybenzoate 0.1
    Fragrance 0.5
    Ascorbic acid 0.3
    Anhydrous sodium sulfite 0.4
    Toluene-2,5-diamine 0.5
    Resorcine 0.4
    Water balance
    Concentration in second
    Second agent agent (wt %)
    Sodium polyoxyethylene (2.5) 1.9
    lauryl ether sulfate
    Lauric acid amide propylbetaine 0.05
    Laurylhydroxysulfobetaine 0.05
    Lauric acid 0.04
    Phosphoric acid Amount required to
    adjust second agent to
    pH 3.8
    Glycerol 30.0
    Hydrogen peroxide (35%) 16.3
    Water balance

    Concentration of surfactant following mixing: 1.22 wt %

    Viscosity: 15 mPa · s
  • Examples 3 and 4 Hair Cosmetic Products Used for Hair Dyeing
  • A first agent and second agent were prepared using the compositions shown in Tables 4 and 5; the first and second agents thus obtained were placed in a squeeze foamer A and mixed at a mixture ratio (weight ratio) of 1:1.5, and these agents were then discharged in the form of foam. The overall hair was dyed in the same manner as in Example 2 using 80 g of the discharged foam. As a result, there was no scattering of the agents, hair dyeing was accomplished without irregularity, and scalp irritation was not a problem.
  • Furthermore, differences in color between black hair in areas of new growth and the color of the hair in already dyed areas were eliminated, so that a natural finish could be obtained.
    TABLE 4
    Concentration in first
    First agent agent (wt %)
    Strong aqueous ammonia (28%) 8.0
    Ammonium hydrogencarbonate 14.0
    Methyl para-oxybenzoate 0.1
    Fragrance 0.5
    Ascorbic acid 0.3
    Anhydrous sodium sulfite 0.4
    Toluene-2,5-diamine 0.5
    Resorcine 0.4
    Sodium polyoxyethylene (2.5) 1.9
    lauryl ether sulfate
    Lauric acid amide propylbetaine 0.05
    Laurylhydroxysulfobetaine 0.05
    Lauric acid 0.04
    Water balance
    Concentration in second
    Second agent agent (wt %)
    Phosphoric acid Amount required to adjust
    second agent to pH 3.8
    Glycerol 30.0
    Hydrogen peroxide (35%) 16.3
    Water balance

    Concentration of surfactant following mixing: 0.82 wt %

    Viscosity: 15 mPa · s
  • TABLE 5
    Concentration in first
    First agent agent (wt %)
    Para-aminophenol 0.8
    Meta-aminophenol 0.2
    Toluene-2,5-diamine 0.5
    Resorcine 0.6
    Strong aqueous ammonia (28%) 8.5
    Ammonium hydrogencarbonate 8.0
    Decylpoly (1.4) glycoside 3.2
    Polyoxyethylene (23) lauryl 2.0
    ether
    Propylene glycol 4.0
    Dimethyldiallylammonium chlo- 0.4
    ride acrylic acid copolymer
    Methyl para-oxybenzoate 0.1
    Tetrasodium edetate dihydrate 0.1
    Fragrance 0.5
    Ascorbic acid 0.3
    Anhydrous sodium sulfite 0.4
    Water balance
    Concentration in
    Second agent second agent (wt %)
    Sodium polyoxyethylene (2.5) 1.9
    lauryl ether sulfate
    Lauric acid amide propylbetaine 0.05
    Laurylhydroxysulfobetaine 0. 05
    Lauric acid 0.04
    Cetyl alcohol 1.5
    1-Hydroxyethane-1,1-diphos- 0.04
    phonic acid
    Phosphoric acid (75%) Amount required to
    adjust second agent to
    pH 3.8
    Sodium hydroxide solution 0.01
    (48%)
    Glycerol 20.0
    Hydrogen peroxide (35%) 16.3
    Water balance

    Concentration of surfactant following mixing: 3.30 wt %

    Viscosity: 80 mPa · s
  • The present invention provides a hair cosmetic product in which a two agent type hair bleach or two agent type hair dye is discharged in the form of foam from a non-aerosol type foamer vessel. The foam of this two agent type hair bleach or two agent type hair dye that is discharged from this hair cosmetic product has a foam quality that for example shows good affinity with the hair, and has a sufficient hair bleaching power or hair dyeing power without causing irritation of the scalp or scattering of the agents. Accordingly, the preferred hair cosmetic product of the present invention makes it possible to realize a uniform hair bleaching finish or hair dyeing finish with little irregularity.
  • The entire disclosure of the specification, claims and summary of the Japanese Patent Application No. 2003-122808, filed on Apr. 25, 2004, is hereby incorporated by reference in its entirety.

Claims (10)

1. A hair cosmetic product comprising:
a two agent type hair cosmetic which comprises a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein at least one of the first and second agents contains a surfactant; and
a foamer vessel which discharges a mixed liquid comprising the first and second agents in the form of foam.
2. The hair cosmetic product according to claim 1, wherein the first agent further comprises an oxidation dye or direct dye.
3. A hair treatment method, comprising the steps of:
discharging a mixed liquid of the first and second agents of the hair cosmetic product according to claim 1 in the form of foam from a foamer vessel;
applying the discharged mixed liquid to the hair;
allowing the applied mixed liquid to stand for 3 to 60 minutes; and
then rinsing the mixed liquid away.
4. A hair cosmetic product comprising:
a two agent type hair cosmetic which comprises a first agent containing an alkali agent and a second agent containing hydrogen peroxide, wherein the first and second agents are mixed immediately prior to use; and
a foamer vessel which discharges a mixed liquid comprising the first and second agents in the form of foam;
wherein the mixed liquid further comprises a surfactant at an amount of 0.1 to 10 wt %, by weight of the mixed liquid, and wherein the viscosity of the mixed liquid at 25° C. is 1 to 300 mPa·s.
5. The hair cosmetic product according to claim 4, wherein the first agent further comprises an oxidation dye or direct dye.
6. The hair cosmetic product according to claim 4, wherein the mixed liquid further comprises a nonvolatile hydrophilic solvent at an amount of 0.1 to 30 wt %, by weight of the mixed liquid.
7. The hair cosmetic product according to claim 6, wherein the nonvolatile hydrophilic solvent is at least one solvent selected from the group of polyols and lower alkyl ethers thereof, and mixtures thereof.
8. The hair cosmetic product according to claim 4, wherein the mixed liquid further comprises a higher alcohol at an amount of 0.1 to 3 wt %, by weight of the mixed liquid.
9. The hair cosmetic product according to claim 4, wherein the mixed liquid further comprises a cationic polymer at an amount of 0.1 to 3 wt %, by weight of the mixed liquid.
10. A hair treatment method, comprising the steps of:
discharging a mixed liquid of the first and second agents of the hair cosmetic product according to claim 4 in the form of foam from a foamer vessel;
applying the discharged mixed liquid to the hair;
allowing the applied mixed liquid to stand for 3 to 60 minutes; and
then rinsing the mixed liquid away.
US10/829,954 2003-04-25 2004-04-23 Hair cosmetic product Active 2027-11-04 US8153108B2 (en)

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US12/849,576 US8158112B2 (en) 2003-04-25 2010-08-03 Hair cosmetic product
US13/308,017 US8246936B2 (en) 2003-04-25 2011-11-30 Hair cosmetic product
US13/439,429 US8277784B2 (en) 2003-04-25 2012-04-04 Hair cosmetic product
US13/596,348 US20120318291A1 (en) 2003-04-25 2012-08-28 Hair cosmetic product
US14/050,747 US20140034078A1 (en) 2003-04-25 2013-10-10 Hair cosmetic product
US14/828,702 US20150352015A1 (en) 2003-04-25 2015-08-18 Hair cosmetic product

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