Classifications

• • 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
  • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
  • A61K8/66—Enzymes
• • 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
  • A61K8/73—Polysaccharides
  • A61K8/738—Cyclodextrins
• • 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 a hair composition in which a substance to be oxidized, an enzyme which utilizes oxygen as a substrate and does not produce hydrogen peroxide, and a cyclodextrin compound are compounded and, more particularly, it relates to a hair composition having a good stability with a lapse of time and being suitably able to be used as a reactive hairdye (a single preparation type) , a permanent-waving preparation of a single preparation type , a depilatory of a single preparation type, etc.
• catalase Japanese Laid-Open Patent Hei-8/175935
• uricase Japanese Laid-Open Patent Hei-8/217652
• the present invention has been achieved in view of the above circumstances and an object of the present invention is to offer a hair composition in which there is no damage to the hair, an excellent enzymatic action is achieved by suppression of production of aggregates, etc. by oxidase during preservation and use is simple and easy whereby usability is excellent.
• the present inventors have carried out an intensive study for achieving the above-mentioned object and, as a result, have found that , when a cyclodextrin compound is compounded with a hair composition wherein a substance to be oxidized and an oxidase which is an enzyme generating no hydrogen peroxide and utilizes oxygen as substrates are compounded, the said substance to be oxidized and the said oxidase are included in the said cyclodextrin compound whereby generation of insoluble aggregates, etc. as the time goes by is suppressed as shown in the examples mentioned later and stability with a lapse of time of the said hair composition is significantly improved.
• the present invention has been accomplished consequently.
• the present invention offers a hair composition, characterized in that, a substance to be oxidized, an oxidase which utilizes oxygen as a substrate and does not generate hydrogen peroxide, and a cyclodextrin compound are compounded therein .
• the hair composition of the present invention is such a composition wherein a substance to be oxidized and an oxidase which utilizes oxygen as a substrate and does not generate hydrogen peroxide are compounded and then a cyclodextrin compound is further compounded therewith.
• the hair composition of the present invention in terms of its form as a commercial product but it can be used as various types of hair compositions for hair such as, for example, a hairdye of a reactive type, a permanent-waving preparation of a single preparation type and a depilatory of a single preparation type.
• the enzyme is in a dissolved state in the preparation and, in the case of such a preparation, any of solution and emulsion is acceptable and, further, a propellant may be contained therein.
• the state upon use may be foams, cream, transparent gel, etc. as well and there is no particular limitation for the product form of the product.
• the substance to be oxidized used in the present invention there is no particular limitation for the substance to be oxidized used in the present invention but , depending upon the product forms such as hairdye of a reactive type, permanent- waving preparation of a single preparation type and depilatory of a single preparation type, a substance to be oxidized used therefor may be appropriately selected.
• coloring substances such as dye precursor, developer and direct dye which are used as substance to be oxidized for hairdye of a reactive type may be used.
• p-phenylenediamine or salt thereof, toluene-2 , 5-diamine or salt thereof, p- aminophenol, 5-amino-o-cresol, p-methylaminophenol sulfate, m-aminophenol , p-nitro-o-phenylenediamine, 2,6- dlaminopyridine , resorcinol, o-aminophenol and m- phenylenediamine are particularly preferred.
• a melanin precursor-like substance represented by the following formula (1) may be appropriately used as well.
• X is a hydrogen atom, NH 2 , OH or any of C ⁇ _ 6 linear or branched alkyl group, alkenyl group and alkoxy group
• Y is OH or NH 2
• X is located at 5-, 6- or 7-position in the ring and is located at ortho- position to Y.
• R 1 and R 3 may be same or different and each of them is a hydrogen atom or any of C ⁇ linear or branched alkyl group, alkenyl group and alkoxy group; and R 2 is a C 1 _ 6 linear or branched alkyl group, alkenyl group or alkoxy group or a carboxyl group.
• the compound represented by the above formula (1) are 4, 5-dihydroxyindole, 5, 6-dihydroxyindole, 6,7-dihydroxyindole, N-methyl-5 , 6-dihydroxyindole, N-ethyl- 5, 6-dihydroxyindole, N-hexyl-5, 6-dihydroxyindole, 2-methyl- 5, 6-dihydroxyindole, 3-methyl-5 , 6-dihydroxyindole, 4- hydroxyindole , 2 , 3-dimethyl-5 , 6-dihydroxyindole, 2-methyl-5- ethyl-6-hydroxyindole, 2-methyl-5-hydroxy-6- ⁇ - hydroxyethylindole , 4-hydroxypropylindole, 2 , 3-dimethyl-5, 6- dihydroxyindole , 4-hydroxy-5-methoxyindole, 6-hydroxy-7- methoxyindole , 6-hydroxy-5-methoxyindole, 6-hydroxyindole, 5-hydroxy
• a melanin precursor-like substance represented by the following formula ( 2 ) may be appropriately used as well.
• K is a hydrogen atom, NH 2 , OH or any of C 1 , 6 linear or branched alkyl group, alkenyl group and alkoxy group
• L is OH or NH 2
• K is located at 5-, 6- or 7-position in the ring and is located at ortho- position to L.
• R 4 and R 6 may be same or different and each of them is a hydrogen atom or any of C ⁇ linear or branched alkyl group, alkenyl group and alkoxy group; and R 5 is a C ⁇ _ 6 linear or branched alkyl group, alkenyl group or alkoxy group or a carboxyl group.
• Specific examples of the compound represented by the above formula (2) are 4 , 5-dihydroxyindoline, 5, 6-dihydroxyindoline, 6 , 7-dihydroxyindoline, N-methyl-5, 6-dihydroxyindoline, N- ethyl-5 , 6-dihydroxyindoline, N-hexyl-5 , 6-dihydroxyindoline, 2-methyl-5,6-dihydroxyindoline , 3-methyl-5,6- dihydroxyindoline , 4-hydroxyindoline, 2 , 3-dimethyl-5 , 6- dihydroxyindoline, 2-methyl-5-ethyl-6-hydroxyindoline, 2- methyl-5-hydroxy-6- ⁇ -hydroxyethylindoline, 4- hydroxypropylindoline, 2,3-dimethyl-5,6-dihydroxyindoline, 4-hydroxy-5-methoxyindoline, 6-hydroxy-7-methoxyindoline, 6- hydroxy-5-methoxyindoline, 6-hydroxyind
• each of the above-mentioned substances to be oxidized may be used solely or two or more thereof may be used jointly.
• a component used as a substance to be oxidized are thioglycolic acid, thioglycolate, cysteine, hydroxy ⁇ ysteine, dihydroxycysteine, acetylated cysteine and sodium sulfite. Each of them may be used solely or two or more thereof may be used jointly. Due to its object for use, the above-mentioned coloring substance is not compounded with those preparations .
• the compounding amount of the above substance to be oxidized in the hair composition of the present invention may be appropriately selected depending upon the product form of the composition and the type of the substance to be oxidized and further depending upon the degree of toning in the case of hairdye of a reactive type and upon the degree of decoloration and the waving effect in the cases of permanent-waving preparation and depilatory.
• the amount of a hairdye of a reactive type it is appropriate to compound in an amount of 0.01-10% (% by weight; hereinafter, % will be used in the same sense) or, particularly, 0.1-5% to the total composition.
• a permanent-waving preparation it is appropriate to compound in an amount of 0.01-40% or, particularly, 0.1-20% to the total composition while, in the case of a depilatory, it is appropriate to compound in an amount of 0.01-50% or, particularly, 0.1-30% to the total composition.
• the compounding amount of the substance to be oxidized is too small, it may be necessary to use a large amount of the composition for achieving the effect of the compounding sufficiently while, when the amount is too much, the compounding amount of oxidase naturally becomes small whereby the action by oxidation in use is hardly available and, moreover, stabilization may be sometimes difficult.
• WO 99/36034, WO 99/36035, WO 99/36036, WO 99/36037, WO 99/36038, WO 99/36039, WO 99/36040, WO 99/36041, WO 99/36042, WO 99/36043, WO 99/36044, WO 99/36045 and WO 99/36046 in the name of L'Oreal discloses different kind of oxidizing dyes (developed substances or oxidation bases) and coupling components (coupling agents) which can also be used according to the present invention and which are hereby incorporated by reference.
• the oxidation bases can in particular be selected among para-phenylenediamines , double bases, para-aminophenols , ortho-aminophenols and heterocyclic oxidation bases.
• R 1 represents a hydrogen atom, C 1 -C 4 -alkyl, C 1 -C 4 - monohydroxyalkyl, C 2 -C 4 -polyhydroxyalkyl, (C x - C 4 )alkoxy(C 1 -C 4 ) alkyl, C 1 -C 4 -alkyl substituted with a nitrogen-containing group, phenyl or 4 ' -aminophenyl;
• - R 2 represents a hydrogen atom, C 1 -C 4 -alkyl, C x - C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, (C : - C 4 )alkoxy(C x -C 4 ) alkyl or C 1 -C 4 alkyl substituted with a nitrogen-containing group;
• R 3 represents a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine, C 1 -C 4 alkyl
• amino, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, tri(C x -C 4 )alkylamino , monohydroxy( C ⁇ -C 4 )alkylamino , imidazolinium and ammonium can in particular be mentioned.
• para-phenylenediamines of the above formula (3) More particularly among the para-phenylenediamines of the above formula (3), the following para-phenylenediamines can be mentioned: para-phenylenediamine, paratoluylenediamine, 2- chloro para-phenylenediamine, 2, 3-dimethyl para- phenylenediamine, 2, 6-dimethyl para-phenylenediamine, 2,6- diethyl para-phenylenediamine, 2,5- dimethyl para-phenylenediamine, N,N-dimethyl para- phenylenediamine, N,N-diethyl para-phenylenediamine, N,N- dipropyl para-phenylenediamine, 4-amino N,N-diethyl 3-methyl aniline, N,N-bis ( ⁇ -hydroxyethyl) para-phenylenediamine, 4- N,N-bis- ( ⁇ -hydroxyethyl)amino 2-methyl aniline, 4-
• para-phenylenediamines of the above formula ( 3 ) the following are especially preferred: para-phenylenediamine, paratoluylenediamine, 2-isopropyl para-phenylenediamine, 2- ⁇ -hydroxyethyl para-phenylenediamine, 2- ⁇ -hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2 , 3-dimethyl para- phenylenediamine, N,N-bis- ( ⁇ -hydroxyethyl) para- phenylenediamine, 2-chloro para-phenylenediamine, 2- ⁇ - acetylaminoethyloxy para-phenylenediamine and their addition salts with an acid.
• double bases is, according to the invention, meant such compositions which include at least two aromatic nuclei carrying amino and/or hydroxyl groups.
• Z 1 and Z 2 which are identical or differ, represent a hydroxyl group or -NH 2 , which can be substituted with a C 1 -C 4 alkyl group or with a bridging group Y;
• - the bridging group Y is a linear or branched alkylene chain with 1 to 14 carbon atoms, which can be interrupted or terminated by one or more nitrogen-containing groups and/or one or more hetero atoms, such as oxygen, sulphur or nitrogen atoms, and optionally be substituted with one or more hydroxyl groups or groups;
• R 5 and R 6 represents a hydrogen or halogen atom, C x -C 4 alkyl, C ⁇ C ⁇ ono-hydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C x - C 4 aminoalkyl or a bridging group Y;
• R 7 , R 8 , R 9 , R 10 , R 11 and R 12 which are identical or differ, represent a hydrogen atom, a bridging group Y or a C 1 -C 4 alkyl group; whereby it should be understood that the compounds of the formula (4) only include a single bridging group Y per molecule.
• nitrogen-containing groups of the above formula ( 4 ) the following can in particular be mentioned: amino, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkyl-amino, trifCi- C 4 )alkylamino , monohydroxytCi-C,,)alkylamino, imidazolinium and ammonium.
• N,N -bis-( ⁇ - hydroxyethyl) N,N' -bis- ( 4 ' -aminophenyl) 1 , 3-diamino propanol
• N,N -bis- ( 4-aminophenyl) tetramethylenediamine
• N,N'-bis-(4- methylaminophenyl) tetramethylenediamine N,N' -bis-(ethyl) N,N' -bis-(ethyl) N,N' -bis-(ethyl) N,N' -bis-(ethyl) N,N' -bis-(eth
• Particularly preferred double bases of the formula ( 4 ) are N,N' -bis- ( ⁇ -hydroxyethyl) N,N' -bis- ( 4 ' -aminophenyl) 1,3- diamino propanol, 1 , 8-bis- ( 2, 5-diamino-phenoxy) -3 , 5- dioxaoctane or one of their addition salts with an acid.
• R 13 represents a hydrogen or halogen atom , C 1 -C 4 alkyl , Ci-Cmonohydroxyalkyl , ( C x - C 4 ) alkoxy ( C 1 -C 4 ) alkyl , C 1 -
• R 14 represents a hydrogen or halogen atom , C 1 -C 4 alkyl , C ⁇ - C 4 monohydroxyalkyl , C 2 - C 4 polyhydroxyalkyl , C 1 - C 4 aminoalkyl , C : - C 4 cyanoalkyl or ( C x - C 4 ) alkoxy ( C x - C 4 ) alkyl , whereby it should be understood that at least one of the groups R 13 or R 14 represents a hydrogen atom.
• para-aminophenol 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3- hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2- hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino
• 2-aminomethyl phenol 4-amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol and acid addition salts thereof.
• ortho-aminophenols suitable as oxidation bases in the dye compositions according to the invention the following can in particular be mentioned: 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol and acid addition salts thereof.
• heterocyclic bases suitable as oxidation bases in the dye compositions according to the invention the following can in particular be mentioned: pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolo- pyrimidine derivatives and acid addition salts thereof.
• compositions described for instance in the patents GB-PS 1026978 and GB-PS 1153196 can in particular be mentioned: 2,5-diamino pyridine, 2- ( 4-methoxyphenyl)amino 3-amino pyridine, 2, 3-diamino 6- methoxy pyridine, 2- ( ⁇ -methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine and the addition salts thereof.
• the compositions described for instance in the German patent DE 2359399 or the Japanese patents JP 88-169571 and JP 91-333495 or in the Patent Application WO 96/15765 can in particular be mentioned: 2, 4, 5, 6-tetra-aminopyrimidine, 4-hydroxy 2,5,6- triaminopyrimidine , 2-hydroxy 4 , 5 , 6-triaminopyrimidine, 2,4- dihydroxy 5,6-diaminopyrimidine , 2,5,6-triaminopyrimidine and their addition salts with an acid.
• 4,5-diamino 1-methyl pyrazole 3,4-diamino pyrazole, 4,5-diamino l-(4'- chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert- butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1- ( ⁇ -hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl
• pyrazolo- [ 1, 5-a] - pyrimidines of the formula (6) shown below their addition salts with an acid or base and their tautomeric forms when a tautomeric equilibrium exists:
• R , R , R 1 and R which are identical or differ, represent a hydrogen atom, C 1 -C 4 alkyl, aryl/ C, - C 4 hydroxyalkyl , C 2 -C 4 polyhydroxyalkyl, ( C 1 -C 4 ) alkoxy(C x - C 4 )alkyl, C 1 -C 4 aminoalkyl (where the amine can be protected by an acetyl, ureido or sulfonyl group) , (C 1 -C 4 ) alkylamino (C 1 -C 4 ) alkyl, di- [ (C 1 -C 4 ) alkyl] amino C 1 -C 4 alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members), hydroxy-C 1 -C 4 alkyl or di- [hydroxy( C 1 -C 4 ) alkyl ] -amino C 1 -C
• - C 4 alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members ) , hydroxy (C ⁇ C alkyl or di- [hydroxy(C 1 -C 4 )alkyl]amino-C 1 -C 4 alkyl, amino, C 1 -C 4 alkyl or di- [ (C 1 -C 4 )alkyl] -amino, a halogen atom, a carboxylic acid group or a sulfonic acid group; i is 0, 1, 2 or 3; p is 0 or 1; q is 0 or 1; n is 0 or 1 , with the proviso that the sum p + q differs from 0 ; when p + q is 2 , n has the value 0 , and the groups NR , ⁇ 1 a 5R ⁇ , x 16 and NR 17 R 18 occupy the positions (2,3); (5,6); (6,7); (3
• pyrazolo- [ 1 , 5-a] -pyrimidines of the above formula (6) the following can be mentioned in particular: pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7-diamine; 2,5-dimethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7-diamine; pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 5-diamine;
• the pyrazolo- [ 1 , 5-a] -pyrimidines of the above formula ( 6 ) can furthermore be produced by cyclisation from a hydrazine according to the syntheses described in the following references : - A. McKillop, R.J. Kobilecki, Heterocycles , 6(9), 1355,
• the oxidation base or bases represent preferably between approximately 0.0005% and approximately 12% by weight of the total weight of the dye composition according to the invention, especially between approximately 0.005% and approximately 6% by weight .
• the coupling agent or coupling agents suitable in the ready-to-use dye compositions according to the invention are such which are conventionally used in oxidation dye composition, viz. metaphenylene diamines , metaaminophenols , metadiphenols , heterocyclic coupling agents and their addition salts with an acid.
• These coupling agents can especially be selected among
• meta-aminophenol or meta-aminophenols applicable as coupling agents in the ready-to-use dye composition according to the invention is/are preferably selected from compounds of the following formula (7) and acid addition salts thereof:
• R 19 represents a hydrogen atom, C 1 -C 4 -alkyl, C ⁇ C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl
• R 20 represents a hydrogen atom, C 1 -C 4 alkyl, C ! -C 4 alkoxy or a halogen atom selected from chlorine, bromine and fluorine
• R 21 represents a hydrogen atom, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 mono-hydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C ⁇ - C 4 monohydroxyalkoxy or C 2 -C 4 poly-hydroxyalkoxy.
• meta-aminophenols of the above formula (5) the following can be mentioned in particular: meta-aminophenol,
• meta-phenylenediamine or meta-phenylenediamines applicable as coupling agents in the ready-to-use dye composition according to the invention is/are preferably selected from compounds of the following formula (8) and acid addition salts thereof :
• R 22 represents a hydrogen atom, C 1 -C 4 alkyl, C x - C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl;
• R 23 and R 24 which are identical or differ, each represents a hydrogen atom, C 1 -C 4 alkyl, C ⁇ monohydroxyalkoxy or C 2 -C 4 polyhydroxyalkoxy;
• R 25 represents a hydrogen atom, C 1 -C 4 alkoxy, C x - C 4 aminoalkoxy, C 2 - C 4 polyhydroxyalkoxy or 2 , 4-diaminophenoxyalkoxy.
• 2,4-diamino- benzene, 3 5-diamino-l-ethyl-2-methoxybenzene, 3,5-diamino- 2-methoxy-1-methyl benzene, 2 , 4-diamino-l-ethoxybenzene , l,3-bis-(2,4-diaminophenoxy) propane, bis- (2,4- diaminophenoxy) -methane, 1- ( ⁇ -aminoethyloxy) -2 , 4-diamino- benzene, 2-amino-l- ( ⁇ -hydroxy-ethyloxy)
• the meta-diphenol or meta-diphenols applicable as coupling agents in the ready-to-use dye composition according to the invention is/are preferably selected from the compounds of the following formula (9) and acid addition salts thereof:
• R 26 and R 27 which are identical or differ, each represents a hydrogen atom, C 1 -C 4 alkyl or a halogen atom selected from chlorine, bromine and fluorine.
• a halogen atom selected from chlorine, bromine and fluorine.
• the meta-diphenols of the above formula (9) the following can in particular be mentioned: 1 , 3-dihydroxy-benzene, 2-methyl-l,3-dihydroxy-benzene, 4-chloro-l , 3-dihydroxy- benzene, 2-chloro-l , 3-dihydroxybenzene, and acid addition salts thereof .
• heterocyclic coupling agents applicable in the ready-to-use dye composition according to the invention, derivatives of benzimidazole, derivatives of benzomorpholine, derivatives of sesamol, pyrazolo-azol derivatives, pyrrolo- azole derivatives, imidazolo-azole derivatives, pyrazolo- pyrimidine derivatives, derivatives of pyrazoline-3 , 5-diones , pyrrolo- [3 , 2-d]oxazole derivatives, pyrazolo- [ 3 , 4-d] -thiazole derivatives, thiazolo-azole S-oxide derivatives, thiazolo- azole S,S-dioxide derivatives and their addition salts with an acid can in particular be mentioned.
• Ri represents a hydrogen atom or C 1 -C 4 -alkyl
• R 2 represents a hydrogen atom, C 1 -C 4 alkyl or phenyl
• R 3 represents a hydroxyl, amino or methoxy group
• R 4 represents a hydrogen atom, a hydroxyl group, a methoxy group or C 1 -C 4 alkyl group, with the proviso that : when R 3 is an amino group, it is in position 4, when R 3 is in position 4, R 4 is in position 7, - when R 3 is in position 5, R 4 is in position 6.
• R, and R which are identical or differ, each represents a hydrogen atom or C 1 -C 4 -alkyl, and Z represents a hydroxyl group or an amino group.
• benzomorpholine derivatives of the above formula (II) the following can in particular be mentioned: 6-hydroxy 1 , 4-benzomorpholine, N-methyl 6-hydroxy 1,4- benzomorpholine, 6-amino 1 , 4-benzomorpholine and their acid addition salts .
• R 7 represents a hydroxyl group, an amino group, a C ⁇ - C 4 -alkylamino group, a C 1 -C 4 monohydroxyalkylamino group or a C 2 -C 4 polyhydroxyalkylamino group,
• R 8 represents a hydrogen atom, a halogen atom or a C x - 4 alkoxy group.
• the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: FR 2075583, EP-A-119860, EP-A-285274, EP-A-244 160, EP-A-578 248, GB 1 458 377, US 3 277 554, US 3 419 391, US 3 061 432, US 4 500 630, US 3 725 067, US 3 926 631, US 5 457 210, JP 84/99437, JP 83/42045, JP 84/162548, JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85/190779 as well in the following publications : Chem.
• the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: US 5256526, EP-A-557851, EP-A-578248, EP-A-518 238 , EP-A-456226 , EP-A-488909 , EP-A-488248 and in the following publications:
• the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: US 5 441 863, JP 62-279 337, JP 06-236 011 and JP 07-092632, the subject matter of which constitute an integrated part of the present application.
• the imidazolo-azole derivatives the following can in particular be mentioned:
• pyrazolo-pyrimidine derivatives the following can in particular be mentioned: pyrazolo- [ 1, 5-a] -pyrimidine-7-one, - 2, 5-dimethyl pyrazolo [1,5-a] pyrimidine-7-one, 2-methyl-6-ethoxycarbonyl pyrazolo [1,5-a] pyrimidine-7-one,
• the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: JP 07-036159, JP 07-084348 and US 4 128 425, and in the following publications: - L. WYZGOWSKA, Acta. Pol . Pharm. 1982, 39 (1-3), 83. E. HANNIG, Pharmazie, 1980, 35 (4), 231
• the compounds can in particular be mentioned which are described in the Patent Application JP 07-325 375, the subject matter of which constitute an integrated part of the present application.
• the compounds can in particular be mentioned which are described in the Patent Application JP 07-244 361 and in J. Heterocycl. Chem. 16, 13, (1979).
• the cationic direct dye(s) applicable in the ready-to-use dye composition according to the invention is/are preferably selected among cationic amino-anthraquinone dyes, cationic mono or di-azo dyes and cationic naphtoquinone dyes.
• the cationic direct dye(s) can furthermore be selected among: a) Compounds of the formula (V) :
• D represents a nitrogen atom or a group -CH
• R 19 and R 20 which are identical or differ, each represents a hydrogen atom, a C 1 -C 4 alkyl group, which can be substituted with one of the groups -CN, -OH or -NH 2 or together with a carbon atom in the benzene ring form an optionally oxygen-containing or nitrogen-containing heterocyclic group, which can be substituted with one or more C 1 -C 4 alkyl groups; or a 4'- aminophenyl group,
• R 21 and R' 21 which are identical or differ, each represents a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, cyano , C 1 -C 4 -alkoxy or acetyloxy,
• X " represents an anion, preferably selected from chloride, methylsulphate and acetate.
• A represents a group selected from the following structures A1-A19:
• R 24 represents a hydrogen atom or a C 1 -C 4 alkyl group
• R 25 represents a hydrogen atom, an alkyl group, which can be substituted with a group -CN or with an amino group, or 4 ' - aminophenyl
• R 25 represents together with R 24 an optionally oxygen and/or nitrogen-containing heterocyclic group, which can be substituted with a C 1 -C 4 alkyl group
• R 26 and R 27 which are identical or differ, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine,
• X " represents an anion, preferably selected from chloride, methylsulphate and acetate
• B represents a group selected from the following structures
• R 28 represents a C 1 -C 4 alkyl group
• R 29 and R 30 which are identical or differ , each represents a hydrogen atom or a C 1 -C 4 alkyl group
• c compounds of the following formulae (VII ) and (VII ' ) :
• R 31 represents a hydrogen atom, a C 1 -C 4 alkoxy group, a halogen atom such as bromine, chlorine, iodine or fluorine, or an amino group,
• R 32 represents a hydrogen atom or a C 1 -C 4 alkyl group, or R 32 together with a carbon atom in the benzene ring forms a heterocyclic group, which optionally includes an oxygen atom and/or is substituted with one or more C 1 -C 4 alkyl groups
• R 33 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,
• R 34 and R 35 which are identical or differ, each represents a hydrogen atom or a C 1 -C 4 alkyl group.
• X " represents an anion, preferably selected from chloride, methylsulphate and acetate,
• E represents a group selected from the following struc tures E1-E8 :
• E6 E7 E8 in which R 36 represents a C 1 -C 4 alkyl group; when m 0 and D : represents a nitrogen atom, E can also represent a group with the following structure E9: in which R 36 represents a C 1 -C 4 alkyl group.
• the cationic direct dyes of the formulae (V) , (VI) , (VII) and (VII'), which are applicable in the ready-to-use dye compositions according to the invention, are compositions known per se, which are described for instance in the Patent Applications WO 95/01772, WO 95/15144 and EP-A-0 714 954.
• the compounds with the structures (VI), (V2), (V4), (V14) and (V31) are particularly preferred.
• compositions with the structures (VIII) to (VII18) are particularly preferred.
• the cationic direct dye or dyes used according to the invention represent preferably between approximately 0.001% and approximately 10% by weight of the total weight of the ready-to-use dye composition, especially between approximately
• the acid addition salts suitable within the scope of the dye compositions according to the invention are especially selected from hydro ⁇ hlorides , hydrobromides , sulphates , tartrates , lactates and acetates.
• the oxidase used in the present invention is that which uses oxygen as a substrate and does not generate hydrogen peroxide.
• an oxidase of a four-electron reduced type has been known and its examples are catechol oxidase, amine oxidase and laccase. Each of them may be used solely or two or more thereof may be used jointly.
• Particularly preferred enzymes are laccases and related enzymes, the term "laccases and related enzymes" including enzymes comprised by the enzyme classification E.C. 1.10.3.2
• laccases and catechol oxidase enzymes comprised by E.C.
• bilirubin oxidase enzymes comprised by the enzyme classification E.C. 1.3.3.5 and mono-phenol mono-oxygenase enzymes comprised by the enzyme classification E.C. 1.14.99.1.
• Laccases are multi-copper containing enzymes that catalyze the oxidation of phenols and aromatic amines. Laccase-mediated oxidations result in the production of aryloxy-radical intermediates from suitable phenolic substrates ; the ultimate coupling of the intermediates so produced provides a combination of dimeric, oligomeric, and polymeric reaction products.
• the laccase may be derived from a microorganism, e.g. a fungus or a bacteria, or a plant.
• the laccase employed is derived from a fungus. More preferably, it is derived from a strain of Polyporus sp. , in particular a strain of P. pinsitus or P. versicolor, a strain of Myceliophthora sp., e. g. M. thermophila, a strain of Rhizoctonia sp. , in particular a strain of Rh. pratlcola or Rh. solani , a strain of Pyricularla sp, in particular P.
• the laccase may also be from a plant such as Rhus sp. , e.g. Rhus vernlclfera ,
• the oxidoreductase is a laccase such as a Polyporus sp. laccase, especially the Polyporus plnlsl tus laccase (also called Trametes vlllosa laccase) described in WO 96/00290 (from Novo Nordisk Biotec Inc. ) or a Myceliophthora sp. laccase, especially the Myceliophthora thermophila laccase described in WO 95/33836 (from Novo Nordisk Biotech Inc. ) .
• a laccase such as a Polyporus sp. laccase, especially the Polyporus plnlsl tus laccase (also called Trametes vlllosa laccase) described in WO 96/00290 (from Novo Nordisk Biotec Inc. ) or a Myceliophthora sp. laccase, especially the Myceliophthora thermophila laccase described in WO 95/33836 (from Novo Nordisk Biotech Inc. ) .
• the laccase may be a Scytalldlum sp. laccase such as the S. thermophlllum laccase described in WO 95/33837 and WO 97/19998 (from Novo Nordisk Biotech Inc. ) , the contents of which is incorporated herein by reference, or a Pyricularla sp .
• laccase such as the Pyricularla oryzae laccase which can be purchased from SIGMA under the trade name SIGMA No. L5510, or a Coprlnus sp. laccase, such as a C. cinereus laccase , especially a C. cinereus IFO 30116 laccase , or a Rhizoctonia sp. laccase, such as a Rh. solani laccase, especially the neutral Rh. solani laccase describedin WO 95/07988 (fromNovo Nordisk A/S) having a pH optimum in the range of from 6.0 to 8.5.
• the laccase may also be derived from a fungus such as Collybla , Pomes, Lentlnus, Pleurotus, Asperglllus, Neurospora, Podospora, Phlebla , e. g. P. radlata (WO 92/01046), Corlolus sp. , e. g. C. hlrsl tus (JP 2-238885), or Botrytls .
• Bilirubin oxidase may preferably be derived from a strain of Myrotheclum sp., such as M. verrucarla .
• Oxidases yielding peroxide are typically used in combination with a peroxidase to remove or at least reduce the peroxide produced.
• Suitable oxidases include glucose oxidase (E.C. 1.1.3.4), hexose oxidase (E.C. 1.1.3.5), L-amino-acid oxidase (E.C. 1.4.3.2), xylitol oxidase, galactose oxidase (E.C. 1.1.3.9), pyranose oxidase (E.C. 1.1.3.10) and alcohol oxidase (E.C. 1.1.3.13).
• an L-amino acid oxidase may be derived from a Trlchoderma sp. such as Trlchoderma harzlanu , such as the L-amino acid oxidase described in WO 94/25574 (from Novo Nordisk A/S) , or Trlchoderma vlrlde.
• a suitable glucose oxidase may originate from Asperglllus sp. , such as a strain of Asperglllus nlger, or from a strain of Cladosporlum sp. in particular Cladosporlum oxysporu .
• Hexose oxidases from the red sea-weed Chondrus crlspus (commonly known as Irishmoss) (Sullivan and Ikawa, (1973), Biochim. Biophys. Acts, 309, p. 11-22; Ikawa, (1982), Meth. in Enzymol.
• oxidise a broad spectrum of carbohydrates, such as D-glucose, D-galactose, maltose, cellobiose, lactose, D-glucose 6-phosphate, D-mannose, 2-deoxy-D-glucose, 2-deoxy-D-galactose, D-fructose, D- glucuronic acid, and D-xylose.
• carbohydrates such as D-glucose, D-galactose, maltose, cellobiose, lactose, D-glucose 6-phosphate, D-mannose, 2-deoxy-D-glucose, 2-deoxy-D-galactose, D-fructose, D- glucuronic acid, and D-xylose.
• the compounding amount of the above-mentioned oxidase in the composition of the present invention is not particular limitation but the amount may be appropriately selected depending upon the form of the product , frequency of use , treating time, titer of the enzyme, etc. and, for example, it is preferred to compound in an amount of 0.0005-20% or, more preferably, 0.001-15% to the total composition.
• the amount is too small, there is a tendency that the effect by compounding the oxidase is not sufficiently achieved while, when it is too much, there is a tendency that an increase in the effect proportional to an increase in the compounding amount is not available.
• cyclodextrin compound of the present invention cyclodextrin and its derivatives may be used.
• Cyclodextrin is a non-reducing malto-oligosaccharide having a structure wherein 6-8 glucose molecules were connected in a ring form by means of ⁇ -1 , 4-glucoside bond.
• ⁇ - , ⁇ - and ⁇ -compounds depending upon the numbers of the connected glucose molecules and any of them may be used.
• an adduct of the above cyclodextrin with propylene oxide is particularly effective and, although there is no particular limitation for the adding molar numbers thereto, 3-8 moles per molecule are preferred.
• each of such cyclodextrin compounds may be used solely or two or more thereof may be used jointly.
• the compounding amount of the cyclodextrin compound in the composition it is preferred to compound 0.1-75% or, particularly preferably, 0.5-60% to the total composition.
• the compounding amount is too small, the effect by compounding of the cyclodextrin compound may not be well achieved while , when it is too much, there is a tendency that an increase in the effect proportional to an increase in the compounding amount is not resulted.
• the hair composition of the present invention may be further compounded with a solvent .
• a solvent which has been used for various hair compositions of a single preparation type such as a hairdye of a single preparation type, a permanent-waving preparation of a single preparation type and a depilatory of a single preparation type may be used.
• alcohol such as ethanol, propanol, n-butanol, sec-butanol and isopropanol
• aromatic alcohol such as benzyl alcohol, phenoxyethanol and 2-benzyloxyethanol
• polyhydric alcohol such as ethylene glycol, propylene glycol, butylene glycol and glycerol
• aqueous ether such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol and ethyl carbitol
• cyclic ketone such as propylene carbonate, N-methylpyrrolidone, N-ethylpyrrolidone and N- hexylpyrrolidone
• formamide derivative such as N-cyclohexyl formamide and N,N-dibutyl formamide
• acid such as glycolic acid and levulinic acid.
• each of them may be used solely or two or more thereof may be used jointly.
• the compounding amount of the said solvent may be appropriately selected depending upon the type of the composition. Usually, it is appropriate to compound about 1-50% to the total composition.
• the hair composition of the present invention may be further compounded, if necessary, with other components which have been conventionally used including pH adjusting agents such as acid and alkali; various kinds of surface-active agents; ionic or nonionic and natural, synthetic or semi-synthetic high- molecular compounds; oil such as ester oil and vegetable oil; silicone derivatives; fluorine derivatives; amino acids; various salts; dandruff removers; chelating agents; antiseptics ; ultraviolet absorbers ; antibacterials ; antioxidants; perfumes; acidic dyes; and natural dyes . They may be compounded in their usual amount so far as the effect of the present invention is not deteriorated.
• pH adjusting agents such as acid and alkali
• various kinds of surface-active agents such as acid and alkali
• ionic or nonionic and natural, synthetic or semi-synthetic high- molecular compounds oil such as ester oil and vegetable oil; silicone derivatives; fluorine derivatives; amino acids; various salts
• the above-mentioned components are mixed and then dissolved, dispersed, emulsified, etc. by a conventional means to prepare a hair composition of a single preparation type such as a hairdye of a single preparation type , a depilatory of a single preparation type and a permanent-waving preparation of a single preparation type.
• a hair composition of a solvent type in a liquid form
• it can be made into any of the preparations including paste (cream), aerosol, gel, liquid, foams, etc.
• a dried tuft of white hair of goat were shampooed and dried. Each 3 g of the compositions as shown in Table 1 were applied thereto quickly and uniformly. After allowing to stand for about 20 minutes, the dyed tuft was rinsed with warm water, shampooed and dried. After drying, a dyeing index ( ⁇ E) was measured as an index for the dyeing property to the dyed tuft using a color difference meter ( SE 2000 manufactured by Nippon Denshoku) .
• the hair-dyeing index ( ⁇ E) was measured in such a manner that the values of L, a and b of the dyed tuft were measured by a color difference meter (SE2000 manufactured by Nippon Denshoku) and the color difference ( ⁇ E) from the hair which was not dyed was calculated.
• This operation was carried out for the composition of Table 1 immediately after compounding and after allowing to stand at room temperature for six months whereby the hair-dyeing property upon preservation was grasped.
• the more the ⁇ E the better the hair dyeing property.
• the hair compositions (hairdyes of a reactive type) of the present invention showed very good stability of the product and hair-dyeing property.
• a tuft of dried normal hair (about 15 cm; 10 g) was shampooed and dried. This was quickly and uniformly applied with about 5 g of each of the compositions of Table 2 and then obliquely wound on a glass rod of 3 cm in diameter and 10 cm in length so as not to overlapping the hair flow one another. After allowing to stand for about 30 minutes, the treated hair was rinsed with warm running water, shampooed and dried. After drying, the tuft was hung and the degree of waving was evaluated according to the following evaluating criteria. This operation was carried out immediately after the compounding of the composition of Table 2 and also after preserving for six months and the effect upon preservation was grasped. Criteria for Evaluation
• the hair compositions (permanent-waving preparations) of the present invention showed very good stability of the product and waving property.
• the stability of the products was good but, because of no oxidizing property, it was not possible to give waves; and, in the cases where the cyclodextrin compound was not compounded (Comparative Examples 6, 7 and 8), the waving property immediately after preparation was good but the stability of the product was poor and, when preserved at room temperature for six months , aggregates, precipitate, etc. were produced and the waving property was deteriorated as well.
• the original liquid was prepared by a conventional method according to the above formulation, charged in an aerosol can and clinched In vacuo and 2.0 kg of LPG ( a propellant) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight) whereupon a hairdye of an aerosol type was prepared.
• LPG was used at this time as a compressed gas but any of nitrogen, carbon dioxide gas. laughing gas and Flon 11, 12 and 114 may be used either solely or jointly.
• ordinary containers such as aluminum can or tin-plated can with direct- jet nozzle or piston type nozzle may be used or a double container such as a bag-in type or an EXXEL type may be used as well.
• the above hairdye was preserved at room temperature for six months , its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in blue black color and its shade was the same as that immediately after being prepared.
• the original liquid was prepared by a conventional method according to the above formulation, charged in an aerosol can and clinched In vacuo and 2.0 kg of LPG (a propellant ) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight) whereupon a hairdye of an aerosol type was prepared.
• This hairdye was preserved at room temperature for six months , its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in black color and its shade was the same as that immediately after being prepared.
• Compounding Components Compounding Amount (wt%) (Original Liquid) 2, 5-Diaminotoluene sulfate 2.0 m-Phenylenediamine 0.5 m-Aminophenol 0.5
• the original liquid was prepared by a conventional method according to the above formulation, charged in an aerosol can and clinched In vacuo and 4.0 kg of LPG (a propellant ) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight) whereupon a hairdye of an aerosol type was prepared.
• LPG a propellant
• This hairdye was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in dark brown color and its shade was the same as that immediately after being prepared.
• the original liquid was prepared by a conventional method according to the above formulation, charged in an aerosol can and clinched In vacuo and 4.0 kg of LPG (a propellant ) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight) whereupon a hairdye of an aerosol type was prepared.
• LPG a propellant
• This hairdye was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in black color and its shade was the same as that immediately after being prepared.
• Compounding Components Compounding Amount (wt%) 5 , 6-Dihydroxyindoline hydrobromide 1.0 5, 6-Dihydroxyindole hydrochloride 1.0
• the above components were mixed until the whole became homogeneous to prepare a hairdye of a cream type .
• This hairdye was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in bright brown color and its shade was the same as that immediately after being prepared.
• Liquid paraffin 1.0 Beeswax 0.5 POE(40) Hydrogenated castor oil triisostearate 0.25 POE(20) Hydrogenated castor oil triisostearate
• the above components were mixed until the whole became homogeneous to prepare a hairdye of a treatment type.
• This hairdye was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in dark gray black brown color and its shade was the same as that immediately after being prepared.
• the tuft treated with this hairdye showed a good touch and showed an excellent treatment effect as well.
• the above components were mixed by a conventional method to prepare a hairdye of a gel type. This hairdye was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed. The hair treated as such was dried using a drier whereupon the white hair was dyed in blue black color and its shade was the same as that immediately after being prepared.
• the original liquid was prepared by a conventional method according to the above formulation to prepare an original liquid for a permanent-waving preparation.
• the original liquid was charged in an aerosol can and clinched In vacuo and 2.0 kg of LPG (a propellant) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight ) whereupon a permanent-waving preparation of an aerosol type of a single preparation type was prepared.
• This permanent-waving preparation of a single preparation type was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of normal hair and the hair was wound on a curler, allowed to stand for 30 minutes, washed with water and shampooed.
• Example 20 Depilatory of a Single Preparation Type (Foamy) Compounding Components Compounding Amount (wt%) (Original Liquid) Thioglycolic acid 5.0
• the original liquid was prepared by a conventional method according to the above formulation to prepare an original liquid for a depilatory.
• the original liquid was charged in an aerosol can and clinched In vacuo and 2.0 kg of LPG (a propellant) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight) whereupon a depilatory of an aerosol type of a single preparation type was prepared.
• LPG a propellant
• This depilatory of a single preparation type was subjected to evaluation for a depilatory force by ten female panelists using a product immediately after manufacture and that preserved at room temperature for six months whereupon all panelists evaluated that this depilatory showed an excellent depilatory force for repeated use for two to three times and that such an action was unchanged before and after the preservation. Thus, it was ascertained that the said depilatory was excellent.
• Examples 21-25 and Comparative Examples 9-11 The components as shown in Table 3 were used, mixed by a conventional method so as to make the components homogeneous , the resulting original hairdye liquid was charged into a glass pressure bottle, clinched In vacuo and 2.0 kg of LPG (a propellant ) were charged so as to make the ratio of the original liquid to gas 95:5 (by weight) whereupon hairdyes (hair compositions) of an aerosol type of Examples 21-25 and Comparative Examples 9-11 were prepared. Each of the hairdye compositions was evaluated for stability upon preservation and hair-dyeing property by the same methods as mentioned already. The result is shown in Table 3 as well.
• the hairdye which is the hair composition of the present invention shows very good stability of the product and hair-dyeing property.
• the above components were mixed by a conventional method to prepare a hairdye of a gel type. This hairdye was preserved at room temperature for six months, its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed. The hair treated as such was dried using a drier whereupon the white hair was dyed in blue black color and its shade was the same as that immediately after being prepared.
• Toluene-2,5-diamine sulfate 1 m-Phenylenediamine hydrochloride 0.1 m-Aminophenol 0.8
• the original liquid was prepared by a conventional method according to the above formulation, charged in an aerosol can and clinched In vacuo and 2.0 kg of LPG (a propellant ) were charged so as to make the ratio of the original liquid to the gas 95:5 (by weight) whereupon a hairdye of an aerosol type was prepared.
• LPG was used at this time as a compressed gas but any of nitrogen, carbon dioxide gas, laughing gas and Flon 11, 12 and 114 may be used either solely or jointly.
• ordinary containers such as aluminum can or tin-plated can with direct-jet nozzle or piston type nozzle may be used or a double container such as a bag-in type or an EXXEL type may be used as well.
• the above hairdye was preserved at room temperature for six months , its appropriate amount was applied to 1.0 g of white hair and the hair was allowed to stand for 20 minutes, washed with water and shampooed.
• the hair treated as such was dried using a drier whereupon the white hair was dyed in dark brown color and its shade was the same as that immediately after being prepared.
• a hair composition which is not a mixed type where the first preparation and the second preparation are mixed but a cyclodextrin compound is compounded with a hair composition in a single preparation type where such a mixing operation is not necessary and the usability for consumers is very high whereby generation of aggregates , precipitates, etc. in the product can be prevented, stability of the product becomes very good and the function and merit by the reaction of a substance to be oxidized with oxidase are fully achieved in any of the forms of aerosol, cream, gel, liquid, etc.

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