CN103249455B - Process for dyeing keratin fibres using hydroxybenzaldehyde derivatives, oxidizing agents and alkalinizing agents in the presence of heat - Google Patents

Abstract

One subject of the invention is a process for dyeing keratin fibres, especially the hair, using i)at least one hydroxybenzaldehyde derivative, ii)at least one oxidizing agent, and iii) at least one alkalinizing agent in the presence of heat. Another subject of the invention is a cosmetic composition for dyeing keratin fibres comprising the ingredients i)to iii)as defined previously. Another subject of the invention is a multicompartment device comprising the ingredients i),ii)and iii). This dyeing process makes it possible to obtain better colorations that are chromatic, intense and long-lasting without the use of oxidation bases such as para-phenylenediamines and para-aminophenols.

Description

The diagonal egg of hydroxy benzaldehyde derivative, oxidant and basifier is used in the presence of heat The method that white fiber is dyeed

One theme of the present invention is to use in the presence of heati)At least one hydroxy benzaldehyde derivative,ii)At least one Kind of oxidant andiii)At least one basifier keratin fiber, the method that especially hair is dyeed.This colouring method Even if so that lacking oxidation base (oxidation base) such as oxidation and p-aminophenyl phenols chemical combination Thing is likely in the case of lacking active CH compounds enough obtain bright, strong, depth and lasting coloring.

It is known way that " permanent " coloring is obtained using the dye composite comprising oxidation dye precursors, the oxidation dye Material precursor is commonly known as oxidation base, such as o-phenylenediamine or oxidation, o-aminophenol class compound Or p-aminophenyl phenols compound and heterocyclic compound.These oxidation bases are colourless or slightly colored compound, Colored compound is generated when it is combined with oxidation product via oxidative condensation process.It is also known that by these oxidation base institutes The tone for obtaining can be by by these oxidation bases and colour coupler（coupler）Or coloring modifier combines to change, quality Agent or coloring modifier are especially selected from aromatic meta-diamines, m-aminophenol and an xenol, and with photostability and to Shampoo some heterocyclic compounds such as benzazolyl compounds of the hair washing with stability.

This oxidation dyeing method includes applying alkali or alkali and colour coupler and the peroxidating as oxidant to keratin fiber Hydrogen（H₂O₂Or the mixture of aqueous hydrogen peroxide solution）So as to spread, then rinse fiber.It is therefrom coloring be it is lasting, Strong, and for external factor especially light, unfavourable weather condition, washing, perspiration and rub with tolerance.

This oxidation dyeing method includes applying alkali or alkali and colour coupler and the peroxidating as oxidant to keratin fiber Hydrogen（H₂O₂Or aqueous hydrogen peroxide solution）Mixture so as to spread, then rinse fiber.It is therefrom coloring be it is lasting, Strong, and there is tolerance for external factor such as light, adverse weather condition, washing, perspiration and when rubbing.

The derivative of 5,6- dihydroxy indoles also can by "Autoxidation" generate shade, but gained coloring and not always Satisfactorily, especially send out in colourity, intensity, colour retention (remanence) or shampoo and under light expose it Discoloration aspect afterwards.

In order to obtain shade, the presence of p-phenylenediamine oxidation base is almost indispensable.

It also is known to utilize the dye composite keratin fiber comprising direct dyes is dyeed.Conventional dye used is outstanding It is nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or triarylmethane nitro benzene-type Dyestuff or natural dye.By these dyestuffs（It is the coloured and colored molecules to fiber with affinity）Apply fine to keratin Then Victor is rinsed to the time obtained needed for expecting to colour.It is bright coloring by its coloring for obtaining, but is somebody's turn to do Color is only temporary or semi-permanent, because the interactive property that direct dyes is combined with keratin fiber and straight Connect dyestuff from the desorption of fiber surface and/or core cause it to face washing or perspire when dyeing capacity it is weaker and color fastness is bad.One Modification known to kind is to apply dyestuff former rather than direct dyes that color is formed via chemical reaction to keratin fiber.Example Such as, patent US 6,790,239 and US 6,770,102 and international patent application WO 2006/131163 and WO 2006/ Aromatic aldehyde/ketone precursor is had been described in 002710, it is condensed to be formed in situ directly dye after discharging in water with active CH precursors Material.Due to the low resistance that chromophore is attacked photochemistry, these direct dyess cause the coloring of hair with the time also to photaesthesia And take off.These dyestuffs cause that gratifying coloring can not be obtained, especially in terms of colour retention.

Other documents are referred to and use in the presence of Ortho-Aminophenol type and 2,5- diaminotoluene type oxidation bases 2- Hydroxyl-or 3-methoxy-4-hydroxybenzaldehyde are dyeed to hair（FR 2 462 907 and DE 28 30 497- Schwarzkopf）.

Therefore, actual demand is to find the new paragon that keratin fiber is dyeed, and it makes it possible to ideally Obtain uniform, strong in the case of not using conventional aromatic amine such as oxidation and p-aminophenyl phenols compound Strong and/or bright with dark-toned coloring, the coloring will have with light resistance to unfavorable weather conditions Resistance, has persistence relative to washing operation and perspiration, and it will not be stained and in oxidant such as aqueous hydrogen peroxide solution In the presence of it is sufficiently stable so as to make the simultaneously blast of the fiber with above-mentioned advantage.

This purpose is achieved by the present invention, and a theme of the present invention is the side that keratin fiber is dyeed Method, it includes：

A) apply to keratin fiber：

i)The hydroxy benzaldehyde derivative of at least one formula (I) and its salt of organic or inorganic acid or alkali, and its solvent Compound such as hydrate：

In formula (I)：

R¹、R²、R³、R⁴And R⁵May be the same or different, represent hydrogen or halogen atom or selected from following group：

Hydroxyl；

Straight or branched (C₁-C₅) alkyl, it is optionally substituted, and is especially replaced by least one hydroxyl；

Straight or branched (C₁-C₅) alkoxyl；

Carboxyl-C (O)-OH or carboxylate radical-C (O)-O^-, M⁺；Wherein M⁺Represent cation counterbalancing ion such as alkali metal or alkali Earth metal or ammonium ion；

Carbamoyl-O-C (O)-NR_aR_b, wherein R_aAnd R_bMay be the same or different, represent hydrogen atom or straight or branched (C₁-C₅) alkyl；Particularly-O-C (O)-NH₂；

Amide groups-C (O)-NR⁶R⁷Or-NR⁶–C(O)–R⁷, wherein R⁶And R⁷May be the same or different, represent hydrogen atom or (C₁-C₅) alkyl, particularly-C (O)-NH₂；

Ester group-C (O)-O-R⁸Or-O-C (O)-R⁸, wherein R⁸Represent (C₁-C₅) alkyl, particularly-C (O)-O-R⁸；

▪(C₁-C₅) alkyl-carbonyl；

Aldehyde radical-C (O) H；And

Amino N R_aR_b, wherein R_aAnd R_bAs defined before this；

Or R¹And R²Or R²And R³Or R³And R⁴6 yuan are formed together with the carbon atom being connected with them（It is miscellaneous）Aryl such as benzene Base；

Condition is two group R¹Or R³At least one of represent hydroxyl；Wherein work as R¹When representing hydroxyl, then R²Or R³Or R⁴Or R⁵Represent hydrogen atom；And work as R³When representing hydroxyl, R¹Or R²Or R⁴Or R⁵Represent hydrogen atom；

ii)At least one chemical oxidizing agent；With

iii) At least one basifier；

B) and then higher than 30 DEG C, being preferably between keratin fiber at a temperature of between 30 DEG C and 80 DEG C carries out hot place Reason；

It should be understood that formula (I) hydroxy benzaldehyde derivative is relative to compositioni)、ii)Withiii)Gross weight or methods described The total concentration of the gross weight of middle composition therefor is more than 1%.

Another theme of the present invention is the cosmetic composition that keratin fiber is dyeed, and it is included：

i)The derivative of at least one formula (I) as defined in before this；

ii)At least one chemical oxidizing agent；With

iii) At least one basifier；

It should be understood that：

The pH of-the composition is higher than 7 and is preferably ranges between 7.5 and 12；

Two group R in-formula (I) compound¹Or R³In at least one represent hydroxyl；Wherein, R is worked as¹When representing hydroxyl, then R²Or R³Or R⁴Or R⁵Represent hydrogen atom；And work as R³When representing hydroxyl, then R¹Or R²Or R⁴Or R⁵Represent hydrogen atom；

The hydroxy benzaldehyde derivative of-formula (I) is relative to compositionii)Withiii)Gross weight total concentration be more than 1%；And And

- represent selected from 3,4- 4-dihydroxy benzaldehydes when the hydroxy benzaldehyde derivative of formula (I)；4- hydroxyl -2- methoxybenzenes Formaldehyde；3,5- dimethoxy benzaldehydes；4- hydroxyl-1-naphthalene Formaldehydes；During the compound of 3,5- dimethyl -4- hydroxy benzaldehydes, then Basifieriii)It is not MEA；And

- represent when the hydroxy benzaldehyde derivative that there is following formula (I) in Ortho-Aminophenol, 2,5- diaminotoluene sulphates Selected from the compound of 3-methoxy-4-hydroxybenzaldehyde and 2- hydroxy 3-methoxybenzene formaldehyde when；Then basifieriii)It is not hydrogen Amine-oxides.

Another theme of the present invention is related to multi-compartment device, and it includes the composition as defined in before thisi)Extremelyiii)。

The composition and colouring method of the present invention has to be made one dyeing keratinous fibres and has strong, bright dyeing As a result advantage, the coloration result anti-can be washed, perspired, sebum and light, more longlasting, without damaging the fiber.Additionally, The coloring that methods described is obtained is used so that fiber has uniform color from root to end（Few coloring selectivity）.Make It is very strong with the tone obtained after the composition or method dyeing of the present invention, it is particularly at temperatures greater than room temperature, excellent Selection of land is at a temperature of between 45 DEG C and 80 DEG C.

Additionally, the coloring obtained using the composition or method of the present invention and bright conventional oxidizing condition are compatible 's.These colorings are especially lasting for the operation that shampoo is sent out.

Except otherwise indicated in non-invention, it should be understood that：

-"Aryl" represent the monocyclic or polycyclic carbon-based group of condensing comprising 6 to 22 carbon atoms or non-condensed, and its In at least one ring be aromatic ring；Preferably, aryl is phenyl, xenyl, naphthyl, indenyl, anthryl or tetralyl；Preferably, Aryl is phenyl；

-"Heteroaryl" expression is condensed or non-condensed, the 5-22 unit monocycles that are optionally cation or polycyclic moiety, and it is included 1 to 6 hetero atom selected from nitrogen, oxygen, sulphur and selenium atom, and wherein at least one ring is aromatic ring；Preferably, heteroaryl is selected from Acridinyl, benzimidazolyl, benzo double triazolyl, benzopyrazoles base, benzo pyridazinyl, benzoquinoline base, benzothiazolyl, benzene And triazolyl, benzoxazolyl, pyridine radicals, tetrazole radical, dihydro-thiazolyl, imidazopyridyl, imidazole radicals, indyl, isoquinoline Quinoline base, naphtho- imidazole radicals, Nai Bing oxazolyls, naphtho- pyrazolyl, oxadiazolyl, oxazolyl, oxazoles and pyridine radicals, phenazinyl, fen Oxazolyl, pyrazinyl, pyrazolyl, pyranose (pyrilyl), pyrazolyl triazine radical, pyridine radicals, pyrimidine radicals, pyridine-imidazole base, Pyrrole radicals, quinolyl, tetrazole radical, thiadiazolyl group, thiazolyl, thiazolopyridinyl, thiazolyl imidazole radicals, thiopyranyl (thiopyrylyl), triazolyl, xanthyl (xanthylyl) and its ammonium salt；

-"Cation heteroaryl" for defined heteroaryl before this, it is included in ring or ring outer cationic group,

Zero when electric charge be ring in electric charge when, it is incorporated to electron delocalization via mesomeric effect, and for example it is pyridine, miaow Azoles or indoline group：

Wherein R and R' are the heteroaryl substituent as defined in before this, in particular (hydroxyl) (C₁-C₈) alkyl such as methyl；

Zero when electric charge is ring exterior charging, and it is not incorporated to electron delocalization via mesomeric effect, and for example it is that ammonium or Phosphonium take For base R⁺Such as trimethyl ammonium, it is outside the heteroaryl for being considered such as pyridine radicals, indyl or imidazole radicals：

Wherein R is heteroaryl substituent and R as defined in before this⁺For ammonium R_aR_bR_cN⁺-, Phosphonium R_aR_bR_cP⁺- or ammonium R_aR_bR_cN⁺-(C₁-C₆) alkyl amino, wherein R_a、R_bAnd R_cMay be the same or different, represent hydrogen atom or (C₁-C₈) alkyl such as methyl；

-"Aryl" or "Heteroaryl" or the aryl or heteroaryl moieties of group can be taken selected from following by least one by carbon The substituent of band replaces：

● C₁-C₁₆With preferred C₁-C₈Alkyl, is optionally selected from hydroxyl, C by one or more₁-C₂Alkoxyl, (many) Hydroxyl (C₂-C₄) alkoxyl, acylamino-, the substituent group of amino, the acylamino-, amino are identical or different optional by two C of the ground with least one hydroxyl₁-C₄Alkyl replaces, or the nitrogen-atoms formation saturation that can be connected with them of the two groups or Undersaturated, optionally substituted 5-7 circle heterocycles and preferably 5 yuan or 6 circle heterocycles, the heterocycle optionally includes another and nitrogen phase Same or different hetero atom；

● halogen atom such as chlorine, fluorine or bromine；

● hydroxyl；

● (C₁-C₂) alkoxyl；

● (C₁-C₂) alkylthio group；

● (many) hydroxyl (C₂-C₄) alkoxyl；

● amino；

● 5 or 6 circle heterocycles alkyl such as cyclohexyl；

● optional 5 yuan of cation or 6 unit's heteroaryls, preferred imidazoles, it is optionally by (C₁-C₄) alkyl, preferred first Base is replaced；

● by one or two identical or different (C₁-C₆) alkyl-substituted amino, it is optionally by least following Substituent group：

I) hydroxyl；

Ii) an amino, it is optionally by one or two optionally substituted C₁-C₃Alkyl replace, the alkyl can with The nitrogen-atoms that they connect forms saturation or undersaturated, optionally substituted 5-7 circle heterocycles, and the heterocycle is optionally comprising at least One other hetero atom identical or different with nitrogen；

●-N (R)-C (O)-R', wherein group R are hydrogen atom or the (C optionally with least one hydroxyl₁-C₄) alkane Base, and group R' is (C₁-C₂) alkyl；

● R₂N-C (O)-, wherein group R may be the same or different, and represent hydrogen atom or optionally with least one hydroxyl (C₁-C₄) alkyl；

● R'-S(O)₂- N (R)-, wherein group R represents hydrogen atom or the C optionally with least one hydroxyl₁-C₄Alkane Base, and group R' represents (C₁-C₄) alkyl or phenyl；

● R₂N-S(O)₂-, wherein group R may be the same or different, and represent hydrogen atom or optionally with least one hydroxyl (C₁-C₄) alkyl；

● in acid or into salt（It is preferred that with alkali metal or substituted or unsubstituted ammonium into salt）The carboxyl of form；

● cyano group；

● comprising 1-6 carbon atom and comprising the multi-haloalkyl of 1-6 identical or different halogen atom, many halogen Substituted alkyl is such as trifluoromethyl；

-"Aryl" for the straight or branched C of saturation₁-C₁₆, preferred C₁-C₈Hydrocarbyl group such as methyl or ethyl；

- as the statement of alkyl attribute "It is optionally substituted" mean that the alkyl can be selected from following group by one or more Group replaced：I) hydroxyl；ii) (C₁-C₄) alkoxyl；Iii) acylamino-；Iv it is) optionally identical or not by one or two Same (C₁-C₆) alkyl-substituted amino, the alkyl can be optional with formation 5-7 circle heterocycles of the nitrogen-atoms with it, the heterocycle Ground includes another hetero atom identical or different with nitrogen；Or quaternary ammonium group-N v)⁺R'R''R''', An^-, wherein R', R'' and R''', may be the same or different, and represent hydrogen atom or (C₁-C₆) alkyl, or-N⁺R'R''R''' is formed optionally by (C₁-C₆) alkane The heteroaryl such as imidazoles that base replaces, An^-Represent the counter ion counterionsl gegenions of organic or inorganic acid or corresponding halide；Preferably work as alkyl When optionally replacing, by least one hydroxyl, especially methylol replaces for it；

-"Alkoxyl" for alkyl-epoxide or allcyl-O-groups, wherein alkyl is straight or branched C₁-C₁₆And it is preferred that C₁-C₈Hydrocarbyl group；

-"Alkylthio group" it is alkyl-S-group, wherein alkyl is straight or branched C₁-C₁₆And it is preferred that C₁-C₈Hydrocarbyl group；

-"Active CH" or "Active methylene group" compound be comprising " CH " or " methylene " reactive compounds of group, It can be easy to from the CH or methylene group lose or discharge proton, i.e. the carbon wherein with CH or the proton of methylene is former The cation heteroaryl Direct Bonding of son and electron deficient：

Wherein

● R represents hydrogen atom, (C₁-C₆) alkyl or aryl or electron withdraw group, particularly inhale via-M mesomeric effects Those groups of electronics, such as cyano group-CN or-C (O) OR ', wherein R ' represent C₁-C₆Alkyl or hydrogen atom；

● Het⁺Represent the cation heteroaryl with cationic charge in ring, i.e. its electric charge is incorporated to the heteroaryl Armaticity and its stablize via mesomeric effect；

Activity methene compound is especially by following formula (II₂) represent：

(II₂)

In formula (II₂) in：

R ' represents optionally substituted C₁-C₆) alkyl；

▪Represent that it may be used also with cationic charge in ring and comprising the heteroaryl of 5 to 13 ring memberses Comprising cationic nitrogen atom, comprising 1 to 3 hetero atom selected from nitrogen, oxygen and sulphur, and it is carried on the carbon atom of heteroaryl Group R-CH₂-, wherein R represents hydrogen atom or (C₁-C₆) alkyl or aryl；For example imidazoles, oxazoles, thiazole, pyridine, Pyrimidine such as 2- oxopyrimidins, quinoline, group R-CH₂- at 2 or 4 of pyridine or quinoline or in imidazoles, Evil 2,4 or 5 of azoles or thiazolyl group, or at 4 and 6 of pyrimidine such as 2- oxopyrimidins；

The limiting value of-restriction number range is included in this number range；And

- statement "At least" being understood to refer to "One（Kind）Or it is multiple（Kind）"。

I) the hydroxy benzaldehyde derivative of formula (I)

One embodiment of the invention is related to the hydroxy benzaldehyde derivative or its mixture of formula (I), wherein two Individual group R¹And/or R³At least one of represent hydroxyl, and wherein R¹、R²、R³、R⁴And R⁵Hydrogen or halogen are represented independently of one another Atom, preferred chlorine atom or selected from following group：

Hydroxyl；

Straight or branched C₁-C₄Alkyl；

Straight or branched C₁-C₄Alkoxyl, preferred methoxyl group；

Carboxyl-C (O)-OH；

Aldehyde radical-C (O) H；And

- two (C₁-C₄) alkyl amino；Or

▪ R¹And R²Or R²And R³Or R³And R⁴The virtue comprising 6 carbon atoms is formed together with the carbon atom being connected with them Ring；

Condition is to work as R¹When representing hydroxyl, then R²Or R³Or R⁴Or R⁵Represent hydrogen atom；And work as R³When representing hydroxyl, then R¹ Or R²Or R⁴Or R⁵Represent hydrogen atom.

The present invention formula (I) advantageous chemical compounds be selected from following table those：

	Title	Structure		Title	Structure
						1	3,4- dihydroxy-benzaldehyde (protocatechualdehyde)		2	Vanillin（Vanillic aldehyde）
3	4- hydroxyls-benzene -1,3- dicarbaldehydes		4	2,4- dihydroxy-benzaldehyde
						5	3,4,5- trihydroxies-benzaldehyde		6	3,5- dimethyl -4- hydroxy-benzaldehydes
7	3,4- dihydroxy -5- Methoxy-benzaldehydes		8	2,3,4- trihydroxies-benzaldehyde
						9	2,4,6- trihydroxies-benzaldehyde		10	The chloro- 2- hydroxy-benzaldehydes of 3,5- bis-
11	2,4- dihydroxy-benzaldehyde		12	4- hydroxy-benzaldehydes
						13	3,4,5- trihydroxies-benzaldehyde		14	4- hydroxy-2-methyls-benzaldehyde
15	3,4- dihydroxy -5- Methoxy-benzaldehydes		16	Vanillin
						17	The chloro- 2- hydroxy-benzaldehydes of 3,5- bis-		18	2,4,5- trihydroxies-benzaldehyde
19	2- hydroxy-3-methyls-benzaldehyde		20	4- hydroxyl -3- chlorobenzaldehydes
						21	3,4- dihydroxy-benzaldehyde		22	5- formoxyl -2- hydroxy-benzoic acids
23	3,5- di-t-butyl -2- hydroxy-benzaldehydes		24	4- hydroxyl -2,6- Dimethoxy-benzaldehydes
						25	2- hydroxy-benzaldehydes		26	4- hydroxyl -3,5- Dimethoxy-benzaldehydes
27	3,5- di-t-butyl -4- hydroxy-benzaldehydes		28	4- hydroxyls-naphthalene -1- formaldehyde
						29	Vanillin		30	1- hydroxyls-naphthalene -2- formaldehyde
31	3,5- dimethyl -4- hydroxy-benzaldehydes		32	2- hydroxyls-naphthalene -1- formaldehyde
						33	The chloro- benzaldehydes of 4- hydroxyl -2-		34	2- hydroxy-5-methyls base-benzaldehyde
35	2,4,6- trihydroxies-benzaldehyde		36	2- hydroxy-4-methyls-benzaldehyde
						37	3,5- dihydroxy-benzene -1,2- dicarbaldehydes		38	2,3- dihydroxy-benzaldehyde
39	2- Hydroxy-3-Methoxy Benzaldehydes		40	2- hydroxy-5-methyls epoxide-benzaldehyde
						41	2- hydroxy-5-methyls base-benzene -1,3- dicarbaldehydes		42	2- hydroxyl -4,6- Dimethoxy-benzaldehydes
43	4- lignocaine -2- hydroxy-benzaldehydes		44	4- hydroxyls-benzene -1,3- dicarbaldehydes

Preferably, the derivative of formula (I) is selected from the compound as defined in front table1Extremely10。

According to causing that strong, dark coloured one embodiment of the invention can be obtained, hydroxy benzaldehyde derives Thing or its mixture are selected from those of formula (II)：

In formula (II)：

R’₁Represent hydrogen atom or hydroxyl；

R’₂Represent hydrogen atom or selected from hydroxyl, aldehyde radical, straight or branched C₁-C₄Alkyl and straight or branched C₁-C₄Alkoxyl Group；

R’₄Represent hydrogen atom or selected from hydroxyl, straight or branched C₁-C₄Alkyl and straight or branched C₁-C₄The base of alkoxyl Group；

R’₅Represent hydrogen atom or hydroxyl；

Wherein, more particularly：

-R’₁=OH and R '₅=OH or straight or branched C₁-C₅Alkoxyl；And/or

-R’₂=OH or C (O) H and R '₄=OH or straight or branched C₁-C₅Alkoxyl；

- and R '₁Or R '₂Or R '₄Or R '₅Represent hydrogen atom.

Preferred compound (II) is following：

And/or the salt and/or its solvate of its organic or inorganic alkali.

According to the present invention, the hydroxy benzaldehyde derivative of formula (I) is synthesis, natural or look in natural extract Arrive.For example, there can be mentioned hydroxy benzaldehyde, for example originating from vanilla or flat leaf vanilla (Vanilla planifolia) or Tahiti vanilla (Vanilla tahitensis) extract vanillic aldehyde (3-methoxy-4-hydroxybenzaldehyde), an unusually sweet smell grass Aldehyde (3- hydroxyls -4-methoxybenzaldehyde) or ethyl vanillin (4- hydroxyl -3- ethoxy-benzaldehydes), from plus thunder Cassia (Cassia garrettiana) extract protocatechualdehyde, from Leccinum scabrum (Boletus scaber) extract Nutgall aldehyde (gallaldehyde).

According to an embodiment, the derivative of formula (I) is present in composition or method without oxidant or colour coupler In.

According to another embodiment, oxidation dye optionally exists together with colour coupler.

Observed coloring and bright conventional oxidizing condition are compatible.The coloring is sent out relative to shampoo It is lasting for operation.

In latter variant, the total concentration of the derivative of formula (I) is for example optionally present in than other oxidation dye precursors The concentration of alkali and colour coupler in mixture is high at least 10 times.

Preferably, the hydroxy benzaldehyde derivative or its mixture of formula (I) depositing in the composition or method of the present invention It is more than 1g/ for the gross weight of extract of the concentration relative to the composition comprising hydroxy benzaldehyde derivative or comprising it 100g (%), particularly between 1g % and 10g %, is preferably ranges between 1g % and 5g %.

Ii) chemical oxidizing agent ：

Colouring method of the invention, methods described uses chemical oxidizing agent.Statement " chemical oxidizing agent " is interpreted as Oxidant in addition to referring to the oxygen in from air.

Statement " chemical oxidizing agent " should more particularly be understood as referring to：

A) ozone；

B) alkali metal or quaternary ammonium persalt such as perborate, persulfate, percarbonate or peroxide phosphoric acid salt or Oxone ®；The oxidant is in particular selected from sodium perborate, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, SODIUM PERCARBONATE and potassium percarbonate；

C) aliphatic series C₁-C₆And C₆-C₂₀Aromatics organic peracid and its percarboxylic acids salt form, such as performic acid, excessively peracetic acid, benzene Formic acid derivates, trifluoroacetic acid, peroxyphthalic acid, peroxy maleic acid, Perpropionic Acid；The oxidant is specifically for second excessively Acid；

D) organic peroxide such as bisoxirane, C₁-C₆Alkyl peroxide, benzoyl peroxide, peroxidating (C₁- C₆) alkyl carboxylic acid ester, double (three) (C₁-C₆) such as double (trimethyl silyl) peroxide of aIkylsilyl groups peroxide, C₁-C₆The carbonic ester of alkyl peroxyization two, and pelargonyl group epoxide benzene sulfonic acid sodium salt, such as patent WO 19,95/,000 625 and US 4 412 Described in 934；

E) oxide anion such as nitrite anions, nitrate anion, hypochlorite, hypobromite, hypoiodous acid root, chlorite, Asia Bromate, idous acid group, chlorate anions, bromate, iodate and periodate；The oxidant is in particular selected from alkali metal hypochlorous acid Salt or periodate, such as sodium hypochlorite or sodium metaperiodate；

F) stable N-oxyl radical (NO^.) group, such as 2,2,6,6- tetra- (C₁-C₆) Alkylpiperidine subbase-epoxide, 2,2,6,6- tetra- (C₁-C₆) alkyl morpholine generation-epoxide, nitroso disulfonic acid Fremy's salt (Fr é my nitrosodisulfonate salt), Quinoline N- oxides；The oxidant is in particular selected from 2,2,6,6- tetramethyl-piperidyl epoxides.

G) multivalence iodine derivative for example iodine triacetate, iodosobenzene, three iodobenzene acetates, iodine benzylhydroperoxide derivative, Periodinane, alkyl and benzoyl hypoiodite；

It is highly preferred that the oxidant is selected from iodine triacetate, iodosobenzene, three iodobenzene acetates, iodine benzylhydroperoxide and wears This-the high iodine reagent of Martin (Dess-Martin periodinane)；

H) following organic compound：N- halosuccinimides, TCCA, N- hydroxyls phthalimide and alkyl are sub- Nitrate；

These oxidant a) to optional carrier h) may be selected from silica, alumina, charcoal and charged polymer or neutral polymerization Thing；

I) hydrogen peroxide or aqueous hydrogen peroxide solution

Or the system of generation hydrogen peroxide, for example：

I-1) urea peroxide；

I-2) the polymer complex of releasable hydrogen peroxide, such as PVP/H₂O₂（Particularly it is in powder Last form）, and US 5 008 093；US 3 376 110；Other polymer complexes described in US 5 183 901；

I-3) in suitable substrates（For example to glucose oxidase, salt is glucose or is uric acid for uricase）'s In the presence of produce hydrogen peroxide oxidizing ferment；

I-4 the metal peroxides of hydrogen peroxide, such as calper calcium peroxide or peromag) are generated in water；

I-5) perborate；Or

I-6) percarbonate.

More particularly, the chemical oxidizing agent is selected from i) hydrogen peroxide or generates the system of hydrogen peroxide, more particularly H₂O₂。

According to a preferred embodiment of the invention, methods described uses one or more body for generating hydrogen peroxide System, selected from i) urea peroxide, i-2) release hydrogen peroxide polymer complex, it is selected from PVP/H₂O₂； I-3) oxidizing ferment；I-5) perborate and i-6) percarbonate.

It is highly preferred that the composition of the present invention includes hydrogen peroxide.

Additionally, the composition comprising hydrogen peroxide or the generating agent of hydrogen peroxide also includes various assistant agents, these assistant agents lead to It is usually used in hair dye composition and following article is in title "Cosmetic compositionIt is " lower defined.

A specific embodiment of the invention, hydrogen peroxide used or generates the system of hydrogen peroxide preferably Account for 0.001% to 12% weight（Hydrogen peroxide is expressed as relative to relative to the gross weight comprising its composition）.More particularly, The hydrogen peroxide of the composition of the method for the present invention or the present invention or the content of aqueous hydrogen peroxide solution are included in every 100g (%) It is 20 volumetric concentrations between 1g and 70g in the composition of the peroxide；Be preferably ranges between 3g % and 50g % it Between, particular between 3g % and 50g %.

Iii) basifier

With the 4th component i ii) it is present in the composition of the present invention or for the basifier in the colouring method of the present invention It is for improving the pH that there is its composition.Basifier is brnsted base (Bronsted base), Luo Rui alkali (Lowry ) or lewis base (Lewis base) base.It can be inorganic or organic.

Especially, the reagent is selected from i) carbonic acid（Hydrogen）Salt；Ii) ammoniacal liquor；Iii) alkanolamine such as MEA, diethyl Hydramine, triethanolamine and its derivative；Iv) oxyethylation and/or oxypropylation ethylenediamine；V) inorganic or organic hydroxide； Vi) alkali silicate such as sodium metasilicate；Vii) amino acid, preferred basic amino acid such as arginine, lysine, ornithine, melon Propylhomoserin and histidine；And viii) under formula (III) compound：

(III)

In formula (III), W is divalence (C₁-C₁₀) alkylidene, it is optionally by least one hetero atom such as O, S or NR_eBetween Every, and/or the alkylidene optionally by least one hydroxyl or (C₁-C₄) alkyl replacement；R_a、R_b、R_c、R_dAnd R_eCan it is identical or Difference, represents hydrogen atom, (C₁-C₄) alkyl or C₁-C₄Hydroxyalkyl, it is therefore preferable to propylidene.

Inorganic or organic hydroxide is preferably chosen from a) alkali-metal hydroxide；B) hydroxide of alkaline-earth metal, Such as NaOH or potassium hydroxide；C) hydroxide of transition metal, such as hydroxide of III, IV, V and VI race metal； D) hydroxide of lanthanide series or actinides, quaternary ammonium hydroxide and hydroxide guanidine.

Hydroxide can be formed in situ, for example to form hydroxide guanidine by reacting calcium hydroxide and guanidine carbonate.

Term " carbonic acid（Hydrogen）Salt i) " is referred to：

A) alkali-metal carbonate (Met₂ ⁺, CO₃ ^2-), the carbonate (Met ' of alkaline-earth metal²⁺, CO₃ ^2-), the carbonic acid of ammonium Salt ((R ' '₄N⁺)₂, CO₃ ^2-) the carbonate ((R ' ' of Huo Phosphonium₄P⁺)₂, CO₃ ^2-), wherein Met ' represents alkaline-earth metal, and Met represents alkali Metal, and R ' ' may be the same or different, and represent hydrogen atom or optionally substituted (C₁-C₆) alkyl such as ethoxy）, and

B) bicarbonate (bicarbonate), also referred to as bicarbonate (hydrogen carbonate), it is by following formula Represent：

R’+, HCO₃ ^-, wherein R ' expression hydrogen atoms, alkali metal or ammonium atomic group R ' '₄N⁺- Huo Phosphonium atom base R ' '₄P⁺-, its Middle R ' ' may be the same or different, and represent hydrogen atom, optionally substituted (C₁-C₆) alkyl such as ethoxy, and work as R ' expression hydrogen atoms When, then bicarbonate is referred to as carbonic acid dihydric salt (CO₂, H₂O)；And

Met’²⁺ (HCO₃ ^-)₂, wherein Met ' expression alkaline-earth metal.

More particularly, basifier is selected from alkali metal or alkaline-earth metal carbonic acid（Hydrogen）Salt；Preferred as alkali carbonic acid（Hydrogen）Salt.

There can be mentioned the carbonate or bicarbonate and its mixture, particularly sodium acid carbonate of Na, K, Mg and Ca.These Bicarbonate may originate from natural water, such as from Vichy basin (Vichy basin), La Roche ripple match (La Roche Posay) The spring of water or many water of ripple (Badoit water)（See, for example, patent document FR 2 814 943）.Especially, can be mentioned that There is sodium carbonate [497-19-8]=Na₂CO₃, sodium acid carbonate or sodium bicarbonate [144-55-8]=NaHCO₃With carbonic acid sodium dihydrogen= Na(HCO₃)₂。

According to a particularly advantageous embodiment, basifier iii) selected from i) bicarbonate, particularly alkali metal or ammonium Bicarbonate；Ii) ammoniacal liquor；Iii) alkanolamine such as monoethanolamine or 2-amino-2-methyl-1-propanol, more preferably ammoniacal liquor.

Basifier preferably comprises from 10 in compositions of the every 100g (%) comprising the basifier as defined in before this^-3Extremely 2.5×10^-1Mole, particularly 0.05 to 0.5 mole %, it is therefore preferable to 0.1 to 0.25 g%（In terms of the weight of composition）.

Iv) optional sulfate：

The method of the present invention or composition can be comprising at least one sulfuric acid（Hydrogen）Salt.Term " sulfate " is understood to refer to From sulfuric acid H₂SO₄Salt, its sulfate ion be SO₄ ^2-（Referring to "Sulfites, Thiosulfates, and Dithionites",Ullmann's Encyclopedia of Industrial Chemistry；2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim - http://onlinelibrary.wiley.com/doi/ 10.1002/14356007.a25_477/pdf）.The pH of the sulfate of the present invention is neutral or or even slightly acidic（PH is between 7 And between 6.6）.

Another preferred embodiment of the invention, sulfate is formula M₂SO₃Or M ' SO₃Sulfate or formula MHSO₃ Disulfate, wherein M represents alkali metal such as Na or K or (two) (C₁-C₆) (alkyl) ammonium or three (C₁-C₆) alkylammonium such as NH₄ ⁺Or Person's formula M ' S₂O₅Disulfate, wherein M ' represent alkaline-earth metal.

The sulfate in particular alkali metal or alkaline-earth metal or ammonium, (two) (C of the present invention₁-C₆) alkylammonium or three (C₁- C₆) alkylammonium salt；Preferably, the cation counterbalancing ion of sulfate is selected from sodium ion, potassium ion and ammonium ion.

Preferably, sulfate of the invention is selected from：

A) ammonium sulfate [10196-04-0]：(NH₄)₂SO₃；

B) sodium sulphate [7757-83-7]：Na₂SO₃；With

C) niter cake [7631-90-5]：NaHSO₃。

Preferred embodiment of the invention, for the present invention composition or method in sulfate account for comprising this or About 0.001 weight % of the gross weight of the composition of these sulfate more preferably accounts for about 0.05 weight to 10 weight % Amount weight % of % to 0.1.

V) one or more optional mordant

The composition of the present invention can may include using at least one matchmaker comprising at least one mordant or the method for the present invention The supplementary step of stain.Term " mordant " is understood to refer to be generally used for textile industry and for cosmetically acceptable matchmaker Transfection reagent, it is preferably in metallic salt form, such as molysite, aluminium salt, titanium salt, calcium salt, manganese salt, mantoquita, zinc salt and strontium salt.Citing For, mordant can be ferric sulfate, manganese gluconate, copper sulphate, zinc gluconate, calcium chloride, magnesium chloride, oxalic acid titanyl potassium (potassium titanyl oxalate) or strontium acetate.Preferably, mordant used is ferric sulfate.

Especially, mordant is deposited relative to the gross weight comprising its composition with the ratio between 0.001% and 10% In being the composition.

Another specific embodiment of the invention, the colouring method and composition of the present invention are not used or included Mordant dyeing reagent.

Water：

An embodiment of the invention, water is preferably comprised in the method for the present invention.It can derive from angle egg The wetting of white fiber and/or from comprising as defined in before this compound i) to iii) composition or from one kind or Various other compositions.Preferably, water is from least one composition, and the composition is selected from such as institute before this comprising at least one The i of definition) to iv) compound.

Cosmetic composition：

The cosmetic composition of the present invention is cosmetically acceptable, i.e. it includes dye carrier, and the dye carrier leads to Often include the mixture of the mixture or organic solvent of water or water and one or more organic solvent.

Term " organic solvent " refers to that chemical modification need not be carried out to it just can be dissolved or disperse another kind of material to have Machine material.

Organic solvent：

There can be mentioned the example of machine solvent includes C₁-C₄Low-level chain triacontanol such as ethanol and isopropanol；Polyalcohol and polyalcohol Ether such as butoxy ethanol, propane diols, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hexylene glycol, and Aromatic alcohol such as phenmethylol or phenoxetol.

Organic solvent relative to dye composite gross weight preferably with about 1 weight % to 40 weight %, even more excellent The ratio of ground about 5 weight % to 30 weight % is present.

Assistant agent：

The composition of the colouring method of the present invention can also be comprising conventional use of various assistant agents in hair dye composition, example Such as anion, cation, nonionic, both sexes or zwitterionic surfactant or its mixture；Anion, cation, it is non-from Son, both sexes or amphoteric ion polymer or its mixture；Inorganic or organic thickening agent, particularly anion, cation, nonionic The thickener related to amphiphilic polymers；Antioxidant；Bleeding agent；Sequestering agent；Aromatic；Buffer；Dispersant；Adjust Agent, such as volatile or nonvolatile, modified or unmodified silicone；Film forming agent；Ceramide；Preservative or shading Agent.

The assistant agent is preferably chosen from surfactant（Such as anion or nonionic surfactant）Or its mixture And inorganic or organic thickening agent.

Above-mentioned assistant agent each relative to composition weight generally between 0.01 weight % and 40 weight %, preferably 0.1 weight Amount between amount % and 20 weight % is present.

Certainly, those skilled in the art is careful to select this or these additional compound so that with can be used for this The adverse effect of expected addition is not received or be not substantially affected by the favorable property of the composition internal association of bright colouring method.

Additional dye：

Using the component i as defined in before this) to iii) method or comprising the component i as defined in before this) to iii) Cosmetic composition of the invention it is also possible to use or comprising one or more additional direct dyes.These direct dyess are for example In direct staining it is conventional use of those, wherein there can be mentioned any commonly employed aromatics and/or non-aromatic dyestuff, for example Neutral, acid or cation nitrobenzene direct dyes；Neutral, acid or cationic azo direct dyes；In addition to 0,0-diphenol Natural direct dyes；Neutral, acid or cation quinone, particularly anthraquinone direct dyes；Azine, triarylmethane, iodine amine (indoamine), methine, styryl, porphyrin, metalloporphyrin, phthalocyanine and methinecyanines direct dyes；With fluorescence dye Material.All these additional dyes are different from the o- 2,2 '-biphenol derivative of the present invention.

In natural direct dyes, it may be mentioned that have lawsone (lawsone), juglone (juglone), indigo (indigo), isatin (isatin), curcumin (curcumin), penicillium spinulosum element (spinulosin), apigenidin Or cudbear (orcein) (apigenidin).The extract containing these natural dyes or decoction can also be utilized, particularly Opoultice or extract based on garden balsam.

Additional direct dyes for composition preferably comprises from about 0.001 weight of the gross weight comprising its composition Amount weight % of % to 10, or even more preferably about 0.05 weight % is to 5 weight %.

Using the component i as defined in before this) to iii) method composition or comprising the composition as defined in before this I) to iii) cosmetic composition of the invention it is also possible to use or comprising conventional use of a kind of in dyeing keratinous fibres or Various oxidation bases and/or one or more colour coupler.

In the oxidation base, oxidation, double (phenyl) Alkylenediamine classes are there can be mentioned Compound, p-aminophenyl phenols compound, double-p-aminophenyl phenols compound, o-aminophenol class compound, heterocyclic bases and its add Into salt.

In these colour couplers, can be specifically mentioned have m-phenylene diamine (MPD) class compound, m-aminophenyl phenols compound, connection Phenol compound, naphthyl colour coupler and heterocyclic coupler agent and its addition salts.A specific embodiment of the invention, this The method of invention and the composition of the present invention do not contain colour coupler, especially m-aminophenol.

More particularly, the method for the present invention or composition using or comprising it is at least one selected from following oxidation dye, Alkali and colour coupler：

● 2,3- diaminourea -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone and its salt, such as 2,3- diaminos Base -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone dimethanesulfonates；

● the diamino-n, n-dihydropyrazolone derivative or its addition salts of formula (IV)：

In formula (IV)：

R₁、R₂、R₃And R₄May be the same or different, represent：

- straight or branched C₁-C₆Alkyl, it is optionally selected from one or more following substituent groups：Group OR₅, base Group NR₆R₇, carboxyl, sulfonyl, formamido group CONR₆R₇, sulfonamido SO₂NR₆R₇, heteroaryl, aryl, the heteroaryl and virtue Base is optionally by (C₁-C₄) alkyl, hydroxyl, C₁-C₂Alkoxyl, amino or (two) alkyl (C₁-C₂) amino replacement；

- aryl, it is optionally by (C₁-C₄) alkyl, hydroxyl, C₁-C₂Alkoxyl, amino or (two) (C₁-C₂) alkyl amino In one or more replacement；

- 5 or 6 unit's heteroaryls, it is optionally selected from (C₁-C₄) alkyl and (C₁-C₂) one or more in alkoxyl take Generation；

R₃And R₄It is also represented by hydrogen atom；

R₅、R₆And R₇May be the same or different, represent hydrogen atom；Straight or branched C₁-C₄Alkyl, is optionally selected from following One or more substituent groups：Hydroxyl, C₁-C₂Alkoxyl, formamido group CONR₈R₉, sulfonyl SO₂R₈, optionally by (C₁-C₄) Alkyl, hydroxyl, C₁-C₂Alkoxyl, amino, (two) alkyl (C₁-C₂) amino replace aryl；Optionally by (C₁-C₄) alkyl, hydroxyl Base, C₁-C₂Alkoxyl, amino or (two) alkyl (C₁-C₂) amino replace aryl；

R₆And R₇May be the same or different, can also represent formamido group CONR₈R₉；Or sulfonyl SO₂R₈；

R₈And R₉May be the same or different, represent hydrogen atom；Straight or branched C₁-C₄Alkyl, it is optionally by hydroxyl or C₁-C₂ One or more replacements in alkoxyl；

R₁And R₂（On the one hand）, and R₃And R₄（On the other hand）The nitrogen-atoms that can be connected with them forms saturation or not 5 yuan or 7 circle heterocycles of saturation, it is optionally selected from one or more following substituent groups：Halogen atom, amino, (two) (C₁-C₄) alkyl amino, hydroxyl, carboxyl, formamido group and (C₁-C₂) alkoxyl, C₁-C₄Alkyl, the alkyl is optionally by one Individual or multiple hydroxyls, amino, (two) alkyl amino, alkoxyl, carboxyl or sulfonyl replace；

R₃And R₄5 yuan or 7 circle heterocycles can be also formed together with the nitrogen-atoms being connected with them, its carbon atom can optionally be taken The oxygen or nitrogen-atoms in generation is substituted；

More particularly, the derivative or its addition salts of formula (IV) is selected from：

4,5- diaminostilbenes, 2- dimethyl -1,2- pyrazoline -3- ketone；

4- amino -5- methylamino -1,2- dimethyl -1,2- pyrazoline -3- ketone；

4- amino -5- dimethylamino -1,2- dimethyl -1,2- pyrazoline -3- ketone；

4- amino -5- (2- ethoxys) amino -1,2- dimethyl -1,2- pyrazoline -3- ketone；

4- amino -5- (pyrrolidin-1-yl) -1,2- dimethyl -1,2- pyrazoline -3- ketone；

4- amino -5- (piperidin-1-yl) -1,2- dimethyl -1,2- pyrazoline -3- ketone；

4,5- diaminostilbenes, double (2- the ethoxys) -1,2- pyrazoline -3- ketone of 2-；

Double (2- the ethoxys) -1,2- pyrazoline -3- ketone of 4- amino -5- methylaminos -1,2-；

Double (2- the ethoxys) -1,2- pyrazoline -3- ketone of 4- amino -5- dimethylaminos -1,2-；

Double (2- the ethoxys) -1,2- pyrazoline -3- ketone of 4- amino -5- (2- ethoxys) amino -1,2-；

Double (2- the ethoxys) -1,2- pyrazoline -3- ketone of 4- amino -5- (pyrrolidin-1-yl) -1,2-；

Double (2- the ethoxys) -1,2- pyrazoline -3- ketone of 4- amino -5- (piperidin-1-yl) -1,2-；

4,5- diaminostilbenes, 2- diethyl -1,2- pyrazoline -3- ketone；

4,5- diaminostilbenes, 2- phenyl -1,2- pyrazoline -3- ketone；

4,5- diaminostilbenes-Ethyl-2-Methyl -1,2- pyrazoline -3- ketone；

4,5- diaminourea -2- ethyl -1- methyl isophthalic acids, 2- pyrazoline -3- ketone；

4,5- diaminostilbenes-phenyl -2- methyl isophthalic acids, 2- pyrazoline -3- ketone；

4,5- diaminostilbenes-(2- ethoxys) -2- methyl isophthalic acids, 2- pyrazoline -3- ketone；

4,5- diaminourea -2- (2- ethoxys) -1- methyl isophthalic acids, 2- pyrazoline -3- ketone；

2,3- diaminourea -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- methylamino -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- dimethylamino -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- ethylamino -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- isopropylamino -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- (2- ethoxys) amino -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- (2- hydroxypropyls) amino -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

Double (2- ethoxys) amino -6,7- dihydro -1H of 2- amino -3-, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- (pyrrolidin-1-yl) -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- (3- hydroxyl pyrrolidine -1- bases) -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2- amino -3- (piperidin-1-yl) -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2,3- diaminourea -6- hydroxyl -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2,3- diaminourea -6- methyl -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2,3- diaminourea -6- dimethyl -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone；

2,3- diaminourea -5,6,7,8- tetrahydrochysene -1H, 6H- pyridazines simultaneously [1,2-a] pyrazoles -1- ketone；

2,3- diaminourea -5,8- dihydro -1H, 6H- pyridazines simultaneously [1,2-a] pyrazoles -1- ketone；

● 4- (3- amino-pyrazols simultaneously [1,5-a] pyridine -2- bases) -1,1- lupetazin -1- salt, especially halogenation Thing such as 4- (3- amino-pyrazols simultaneously [1,5-a] pyridine -2- bases) -1,1- lupetazin -1- hydrochlorides；With

● the 3- amino-pyrazols of lower formula (V) simultaneously [1,5-a] pyridine derivate and its salt and its solvate：

X

In formula (V)：

○ Z₁And Z₂Independently represent：I) covalent single bond；Ii) selected from oxygen atom and group-NR₆(R₇)_pDivalent group,

- wherein p=0 or 1, wherein when p is equal to 0, then R₆Represent hydrogen atom or C₁-C₆Alkyl, or R₆Respectively with R₁And R₂With And the nitrogen-atoms connected with them forms substituted or unsubstituted, saturation or undersaturated, aromatics together or non-aromatic 5-8 units are miscellaneous Ring, it is optionally selected from N, O, S, SO comprising one or more₂With the hetero atom or group of-CO-, the heterocycle can be cation Heterocycle and/or by cation or non-cationic substituent group,

- when p is equal to 1, then-NR₆R₇- be cation group, wherein R₆And R₇Alkyl is independently represented,

Zero works as R₁For methyl when, Z₁May also indicate that divalent group-S- ,-SO- or-SO₂-；

It should be understood that Z₁And Z₂At least one of be not covalent single bond,

○ R₁And R₂Independently represent hydrogen or halogen atom or selected from following group：

- C₁-C₁₀Alkyl, it is selected from O, N, Si, S, SO and SO₂Hetero atom or group optionally replace and optionally Interval,

- C₁-C₁₀Alkyl, it is replaced and/or is spaced by cation group,

- SO₃H groups,

- 5-8 yuan of rings, its be substituted or unsubstituted, saturation, it is undersaturated or aromatics and optionally include One or more are selected from N, O, S, SO₂With the hetero atom or group of-CO-, the ring can be for cation ring and/or by cation base Group replaces,

Work as Z₁And Z₂When representing covalent bond respectively, then R₁And R₂Can also represent respectively：

- optionally substituted C₁-C₆Alkyl-carbonyl；

- group-O-CO-R ,-CO-O-R, NR-CO-R ' or-CO-NRR ', wherein R and R ' independently represent hydrogen atom or appoint Choose the C in generation₁-C₆Alkyl；

○ R₃、R₄And R₅, it may be the same or different, and represent：

- hydrogen atom；

- hydroxyl；

-C₁-C₆Alkoxyl；

-C₁-C₆Alkylthio group；

- amino；

- alkyl monosubstituted amino；

-C₁-C₆Dialkyl amido, wherein alkyl can form saturation or undersaturated, aromatics with the nitrogen-atoms being connected with them Or non-aromatic 5-8 circle heterocycles, it includes one or more selected from N, O, S, SO₂With the hetero atom or group of CO, the heterocycle can Replace for cationic heterocyclic and/or by cation group；

- optionally substituted C₁-C₆Alkyl-carbonyl；

- group-O-CO-R ,-CO-O-R, NR-CO-R ' or-CO-NRR ', wherein R and R ' are as defined in before this；

- halogen；

- group-NHSO₃H；

- optionally substituted C₁-C₄Alkyl；

- optionally substituted, saturation or undersaturated or aromatic carbon basic ring；

-R₃、R₄And R₅Saturation or undersaturated ring can in couples be formed；

Zero X represented so that can ensure that electronegative anionic counter-ion or anionic group of the derivative of formula (V),

Condition is Z₁、R₁、Z₂And R₂At least one of represent cation group.

More particularly, the derivative or its addition salts of formula (V) is selected from：

。

● the salt of 2- [(3- amino-pyrazols simultaneously [1,5-a] pyridine -2- bases) epoxide] ethanol, especially 2- [(3- amino pyrroles Azoles simultaneously [1,5-a] pyridine -2- bases) epoxide] ethylate hydrochlorate；With

● the 3- amino-pyrazols of formula (VI) the simultaneously derivative and its salt of [1,5-a] pyridine derivate and its solvate：

In formula (VI)：

○ Z₁Represent oxygen atom or group NR₆, work as Z₁Represent NR₆When, then R₁And R₆Can be with the nitrogen-atoms one being connected with them Rise and form optionally substituted, saturation or undersaturated or aromatics 5-8 circle heterocycles；

Work as R₁Represent CH₃When, Z₁May also indicate that divalent group S, SO or SO₂；

○ R₁And R₆Independently represent：

- hydrogen atom；

- optionally substituted C₁-C₁₀Alkyl, the substituent can be optionally substituted, saturation or undersaturated or aromatics 5-8 Unit（It is miscellaneous）Ring；

- optionally substituted, saturation or undersaturated or aromatics 5-8 are first（It is miscellaneous）Ring；

○ R₂、R₃、R₄And R₅Independently represent：

Hydrogen atom；

Optionally substituted C₁-C₄Alkyl；

Selected from NH₂、NHR₁₀、NR₁₁R₁₂, OH or OR₉Group, wherein R₉And R₁₀Represent optionally substituted, straight chain or prop up Chain C₁-C₆Alkyl, R₁₁And R₁₂May be the same or different, represent optionally substituted, straight or branched C₁-C₆Alkyl, R₁₁And R₁₂Can be with The nitrogen-atoms connected with them forms together saturation or undersaturated or aromatics 5-8 circle heterocycles, and it optionally includes one or many It is individual selected from N, O, S, SO₂With other hetero atoms or group of CO, the heterocycle is optionally substituted；

○ R₂、R₃、R₄、R₅Optionally substituted, saturation or undersaturated can be in couples formed with adjacent group（It is miscellaneous）Ring；

More particularly, formula (VI) or derivative or its addition salts be selected from：

● 5- [(2- ethoxys) amino] -2- methylphenols；

● 3,4- dihydro -2H-1,4- benzoxazine -6- alcohol；

● the chloro- 6- methylphenols of 3- amino -2-；

● PA -3- alcohol；

● 2- methylbenzene -1,3- glycol；

● 2- (2,4- diamino phenoxies) ethylate hydrochlorate；With

● the cation amino pyridine derivate of logical formula (VII), its addition salts and its solvate with acid：

In formula (VII), group Z₁R₁With cationic charge,

_○ Z₁For oxygen atom or group NR₂；

_○ R₂For hydrogen atom or straight or branched C₁-C₄Alkyl, benzyl or acetyl group；

_○R₁For saturation, straight or branched C₁-C₁₀Alkyl, it is replaced or is spaced by cation group, optionally by one Or multiple oxygen atoms and/or by one or more groups NR₂Interval, is optionally selected from hydroxyl, alkoxyl and C₁-C₄Hydroxyalkyl One or more substituent groups, or R₁For saturation or undersaturated or aromatic cationic 5-8 circle heterocycles, it is optionally by one Or it is multiple selected from following substituent group：C₁-C₄Alkyl, hydroxyl, C₁-C₄Alkoxyl, amino, (C₁-C₄) alkyl amino, two (C₁- C₄) alkyl amino, thio, (C₁-C₄) alkylthio group, carboxyl, (C₁-C₄) alkyl-carbonyl, sulfonyl, amide groups and C₁-C₄Hydroxyalkyl；

Work as Z₁Represent NR₂When, then

▪ R₁And R₂Saturation or undersaturated cation 5-8 circle heterocycles, institute can be formed together with the nitrogen-atoms being connected with them State heterocycle and be optionally selected from following substituent group by one or more：C₁-C₁₀Alkyl and hydroxyl, C₁-C₄Alkoxyl, amino, (C₁-C₄) alkyl amino, two (C₁-C₄) alkyl amino, thio, (C₁-C₄) alkylthio group, carboxyl, (C₁-C₄) alkyl-carbonyl, sulphonyl Base, amide groups and C₁-C₄Hydroxyalkyl, this heterocycle can include one or more selected from N or O, the hetero atom of preferred N, or

▪ R₁And R₂Saturation or undersaturated non-cationic 5-8 circle heterocycles can be formed together with the nitrogen-atoms being connected with them, The heterocycle optionally replaces and is optionally selected from one or more following substituent groups by cation group：C₁-C₁₀ Alkyl and hydroxyl, C₁-C₄Alkoxyl, amino, (C₁-C₄) alkyl amino, two (C₁-C₄) alkyl amino, thio, (C₁-C₄) alkane sulphur Base, carboxyl, (C₁-C₄) alkyl-carbonyl, sulfonyl, amide groups and C₁-C₄Hydroxyalkyl；

R is selected from hydrogen atom；Selected from the halogen of fluorine, chlorine and bromine；Straight or branched C₁-C₄Alkyl and carboxyl (- COOH) and (C₁-C₄) alkoxy carbonyl group；

An- represents anionic counter-ion or anionic group.

More particularly, the derivative or its addition salts of formula (VII) is selected from：

2- [(3,5- diamino-pyridine -2- bases) amino]-N, N, N- trimethyl second ammonium,

2- [(3,5- diamino-pyridine -2- bases) (methyl) amino]-N, N, N- trimethyl second ammonium,

1- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } -1- methyl piperidines,

1- (3,5- diamino-pyridine -2- bases)-N, N, N- trimethyl pyrrolidines -3- ammoniums,

1- { 3- [(3,5- diamino-pyridine -2- bases) amino] propyl group } -3- (2- ethoxys) -1H- imidazoles -3-,

1- { 3- [(3,5- diamino-pyridine -2- bases) amino] propyl group } -1- methyl piperidines,

1- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } -1- crassitudes,

1- { 3- [(3,5- diamino-pyridine -2- bases) amino] propyl group } -1- crassitudes,

1- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } -3- methyl isophthalic acid H- imidazoles -3-,

4- { 3- [(3,5- diamino-pyridine -2- bases) amino] propyl group } -4- methyl morpholine -4-,

4- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } -4- methyl morpholine -4-,

1- [2- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) ethyl] -1- methyl piperidines,

1- [2- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) ethyl] -1- crassitudes,

1- [2- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) ethyl] -3- methyl isophthalic acid H- imidazoles -3- ,

4- [2- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) ethyl] -4- methyl morpholine -4-,

2- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino)-N, N, N- trimethyl second ammonium, 3- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino)-N, N, N- trimethyl propyl- 1- ammonium,

2- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyoxyl }-N, N, N- trimethyl second ammonium,

3- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyoxyl }-N, N, N- trimethyl propyl- 1- ammonium,

1- (2- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyoxyl } ethyl) -1- methyl piperidines,

1- (2- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyoxyl } ethyl) -1- crassitudes,

1- { 3- [(3,5- diamino-pyridine -2- bases) amino] propyl group } -3- methyl isophthalic acid H- imidazoles -3-,

1- [3- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) propyl group] -3- methyl isophthalic acid H- imidazoles -3- ,

4- [3- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) propyl group] -1,1- lupetazin -1- ,

1- (3- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyoxyl } propyl group) -1- methyl piperidines,

4- [3- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino) propyl group] -4- methyl morpholine -4-,

3- ({ 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } amino)-N- ethyl-N-methyl-N- propyl group propyl-s 1- Ammonium,

3- [(3,5- diamino-pyridine -2- bases) amino]-N, N, N- trimethyl propyl- 1- ammonium,

3- [(3,5- diamino-pyridine -2- bases) (methyl) amino]-N, N, N- trimethyl propyl- 1- ammonium,

3- [(3,5- diamino-pyridine -2- bases) epoxide]-N, N, N- trimethyl propyl- 1- ammonium,

1- { 2- [(3,5- diamino-pyridine -2- bases) amino] ethyl } -3- (2- ethoxys) -1H- imidazoles -3-,

4- (3,5- diamino-pyridine -2- bases) -1- (2- ethoxys) -1- methyl piperazine -1-,

Double (2- ethoxys) piperazine -1- of 4- (3,5- diamino-pyridine -2- bases) -1,1-,

4- (3,5- diamino-pyridine -2- bases)-(2- Trimethylethanes)-morpholine-ammonium,

4- (3,5- diamino-pyridine -2- bases)-(2- methyl diethyl ethane)-morpholine-ammonium,

4- (3,5- diamino-pyridine -2- bases) morpholine } 2-1,1 dimethyl pyrrolidines,

(3,5- diamino-pyridine -2- bases) -3- trimethyl-piperidines-ammonium,

(3,5- diamino-pyridine -2- bases) -4- trimethyl-piperidines-ammonium and

4- (3,5- diamino-pyridine -2- bases) -1,1- lupetazin -1-.

It is present in the oxidation base in composition according to the gross weight meter of correspondent composition each generally between 0.001 Amount between weight % and 10 weight % is present.

Work as oxidation base, particularly aromatic amine such as oxidation and/or p-aminophenyl phenols compound is deposited Be the present invention composition in or during in the method for the present invention, its amount causes the hydroxyl of the formula (I) as defined in before this The ratio of the amount of the amount/oxidation base of benzaldehyde derivative is at least above 5；Preferably greater than 20.

According to a preferred embodiment of the invention, colouring method of the invention and composition do not contain oxidation base, Particularly oxidation and/or p-aminophenyl phenols compound.

The cosmetic composition of the present invention can be in various galenics (galenic form), such as powder, lotion, bubble Foam, creams or gel are suitable to any other form that keratin fiber is dyeed.Can also be packaged in without propulsion Pack in the presence of a propellant in aerosol container in the dynamic bottle (pump-action bottle) of the pump of agent or under stress and shape Into foam.

The pH of composition

Comprisingiii)The pH of the composition of basifier is higher than 7, and is preferably ranges between 8 and 12.It is especially between 8 And between 10.

If composition does not contain basifier, comprising oxidant（Such as system of hydrogen peroxide or generation hydrogen peroxide）'s The pH of composition is preferably lower than 7, more particularly between 1 and 5.

Preferably, the hydroxy benzaldehyde derivative comprising the formula as defined in before this (I) and the combination without basifier The pH of thing is less than 7 and is preferably ranges between 3 and 6.5.

A specific embodiment of the invention, comprising sulfate and with or without the composition of basifier PH is higher than 7 and is preferably ranges between 8 and 12.

Acidulant or the basifier commonly used in dyeing keratinous fibres can be passed through（As above " Iii) basifier " defined） Or the pH of these compositions is adjusted to into desired value using standard buffers system.

In the acidulant of composition, can be specifically mentioned be derived from it is following it is various acid salt those：I) hydrochloric acid HCl；Ii) hydrobromic acid HBr；Iii) sulfuric acid H₂SO₄；Iv) alkyl sulfonic acid：Alk-S(O)₂OH such as methanesulfonic acid and ethyl sulfonic acid；V) aryl Sulfonic acid：Ar-S(O)₂OH such as benzene sulfonic acid and toluenesulfonic acid；Vi) citric acid；Vii) butanedioic acid；Viii) tartaric acid；Ix) lactic acid；x) Phosphoric acid H₃PO₄；Xi) acetic acid CH₃C(O)OH；Xii) TFMS CF₃SO₃H；And xiii) tetrafluoro boric acid HBF₄。

Colouring method according to step a) and b)

Preferably, the method for the present invention does not use active CH compounds, and the composition of the present invention without active CHization Compound.

A specific embodiment of the invention, the colouring method is implemented in the following manner：

A) one or more cosmetic combinations comprising following ingredients is applied to keratin fiber with one or more steps Thing, the composition together or is independently present in the composition：

i)The hydroxy benzaldehyde derivative of at least one formula (I) as defined in before this；

ii)At least one oxidant, preferred chemical oxidizing agent；With

iii) At least one basifier；

It should be understood that：

- include compositioniii)Composition pH be alkaline pH, i.e. higher than 7；It is preferably ranges between 7.5 and 12；And

The hydroxy benzaldehyde derivative of-formula (I) is relative to comprising component i), ii) and composition iii) gross weight Total concentration is more than 1%；With

B) keratin fiber is heat-treated at a temperature of higher than 30 DEG C.

Apply to include compositioni)、ii)And/oriii)Composition the step of between stand-by period be set between 3 points Between clock and 120 minutes, it is preferably ranges between 10 minutes and 60 minutes, more particularly between 15 minutes and 45 minutes.

Keratin fiber can in advance be soaked or can not soaked in advance.

More particularly, in the method for the invention, chemical oxidizing agent such as hydrogen peroxideii)Can be with compositioni)Mixing, or apply It is added to without other compositionsii)Withiii)Composition in.

One embodiment of the invention is related to colouring method, and it includes what is implemented with one or two applying step Step a).

A step of specific embodiment of the invention, method that keratin fiber is dyeed a) by Keratin fiber applies preferably aqueous cosmetic composition of the invention to implement, and the cosmetic composition is included：

i)The derivative of at least one formula (I) as defined in before this；

ii)At least one oxidant, preferred chemical oxidizing agent；With

iii) At least one basifier；

It should be understood that：

- the composition does not preferably contain activity CH compounds；

The pH of-the composition is alkaline pH, i.e. higher than 7；It is preferably ranges between 7.5 and 12；

Two group R of-formula (I) compound¹Or R³In at least one represent hydroxyl；Wherein, R is worked as¹When representing hydroxyl, then R²Or R³Or R⁴Or R⁵Represent hydrogen atom；And work as R³When representing hydroxyl, then R¹Or R²Or R⁴Or R⁵Represent hydrogen atom；

The hydroxy benzaldehyde derivative of-formula (I) is relative to comprising compositioni)Extremelyiii)Composition gross weight it is total dense Degree is more than 1%.

Stand-by period after applying is generally set between 5 minutes and 24 hours, especially between 10 minutes and 120 Between minute, and more particularly between 15 minutes and 60 minutes, especially between 15 minutes and 45 minutes.

The step of another specific embodiment of the invention, method that keratin fiber is dyeed, a) was with two Individual step is carried out.

In the first modification, step a) includes applying to include the composition as defined in before this to the fiberi)、ii)'s Cosmetic composition, then in second step, applies to include the composition as defined in before this to the fiberiii)Change Cosmetic compositions, it should be understood that at least one in two kinds of cosmetic compositions is aqueous.

In second modification of the method that keratin fiber is dyeed, step a) includes being applied to the fiber first Plus comprising the composition as defined in before thisi)Withiii)Composition, then in second step, to the fiber apply wrap Containing as defined in before thisii)The second cosmetic composition, it should be appreciated that at least one in preferably two kinds compositions is aqueous 's.

One of the invention preferred colouring method, the step a) is utilizing compositioniii)Keratin fiber is carried out Process terminates.

The step of the inventive method a) applying temperature generally between room temperature（15 DEG C to 25 DEG C）And between 150 DEG C, especially Ground is preferably ranges between 20 DEG C and 60 DEG C between 15 DEG C and 85 DEG C.If applied at a temperature of higher than 30 DEG C Carry out, then b) the step of can save the inventive method.Preferred embodiment of the invention, a) according to the step of methods described Composition be applied to room temperature（I.e. 25 DEG C）Under carry out.

The step of the inventive method in b), according to the step of the inventive method a) apply composition after, by Higher than room temperature, i.e. at a temperature of 30 DEG C, hair is carried out particularly between heating at a temperature of between 35 DEG C and 80 DEG C Heat treatment.More particularly, between 40 DEG C and 50 DEG C, such as 45 DEG C.

In practice, the heat treatment operation of the step of the inventive method b) can be sent out using hair style cover, hair dryer or infrared ray Emitter or other standard heaters have to carry out.

Can using temperature between 60 DEG C and 220 DEG C and be preferably ranges between 120 DEG C and 200 DEG C plus hot iron plate (heating iron) stretches instrument as heating tool and hair.

One favourable aspect is related to colouring method as previously described, be first by with as defined in before this at least A kind of mordant（Referring to " V) one or more optional mordant"）Keratin fiber pre-processed one or more Mordant dyeing step.Mordant is particularly present in cosmetic composition and is applied within least 5 minutes before colouring method is implemented, The cosmetic composition includes the composition as defined in before thisi)Extremelyiii).Mordant used in particular ferric sulfate.

Another favourable aspect is related to the colouring method as previously described followed by post-processing step, the rear place Reason step is shampoo hair washing for example to be carried out with standard shampoo, is rinsed（For example use water）And/or by heat defined below at Manage to be dried keratin fiber.

Preferably, colouring method of the invention includes the composition as defined in before this by applying to keratin fiberi)Extremelyii)Composition of the invention carry out a step and carry out, be then rinsed（For example use water）, carry out shampoo with standard shampoo and wash Send out and/or be dried the post-processing step of keratin fiber.

In all specific embodiments and modification of methods described before this, mentioned composition is instant combination Thing, it can be by mixing two or more compositions temporarily, and the composition being especially mixed in staining kit comes Produce.

Dyeing apparatus or " kit "：

Another theme of the present invention is multi-compartment dyeing apparatus or " kit ".Advantageously, the kit includes containing There are 2 to 5 compartments of 2 to 5 kinds of compositions, wherein following component is distributed with：i)At least one formula (I) hydroxyl as defined in before this Benzaldehyde derivative；ii)At least one chemical oxidizing agent such as hydrogen peroxide；Withiii)At least one alkali as defined in before this Agent.

According to first modification, the kit includes three compartments, and the first two compartment is such comprising powder respectively Front defined compositioni)Withiii), the 3rd compartment include waterborne compositions such as water.In this case, compoundii)For mistake Hydrogen oxide precursor.

Or, the kit include four compartments, first three compartment respectively include powder as defined in before this Compositioni)、ii)Withiii), the 4th compartment include waterborne compositions such as water.

Another kind of modification is related to a kind of kit, and it includes three compartments, and one of compartment is comprising at least one aqueous Composition, and comprising the composition as defined in before thisi)Extremelyii)。

Another preferred embodiment is related to a kind of device, and it includes three compartments：

A () first compartment includes composition, the composition contains：

i)The hydroxy benzaldehyde derivative of at least one formula (I) as defined in before this；With

B () second compartment includes composition, the composition contains：

ii)At least one chemical oxidizing agent such as hydrogen peroxide；

C () the 3rd compartment is includediii)At least one basifier as defined in before this.

In here another embodiment, at least one in three kinds of compositions is preferably aqueous and hydroxyl of formula (I) Benzaldehyde derivative can be in powder type.

In two compartment kits, can also have such kit, it is in first compartment comprising containing such as institute before this The compound i) and iii of definition) composition, and in second compartment comprising contain as defined in before this compound ii) The composition of at least one chemical oxidizing agent such as hydrogen peroxide.

According to a modification, the device of the present invention is also comprising the additional combinations containing one or more process or mordant dyeing reagent Thing (c).

The composition of the device of the present invention is packaged in independent compartment, and it is optionally with suitable identical or different Applying instrument, for example, carefully brush, slightly brush or sponge.

Above-mentioned device can also be with being ready for use on the instrument being assigned to desired mixt on hair, such as patent FR 2 Device described in 586 913.

Dyeing Example

Embodiment A：

Prepare compositions below：

In 100g compositions：

The hydroxy benzaldehyde compound of the 3g present inventioni)；

The ammoniacal liquor of 5g 20%；

The volume hydrogen peroxide aqueous solution of 30g 20；

62g water.

Above-mentioned composition is applied with the bath raio of every 5g compositions 1g hairs.Hair tresses are containing 90% natural white (90% NW) The gray hair of hair.Composition is set to retain 15 or 30 minutes in hair tresses at 45 DEG C.Then hair tresses are rinsed, shampoo is washed Wash and be dried with hair dryer.

Colorimetric results：

Coloring to hair is visually assessed and in Minolta spectrocolorimeters (CM3600d, light source D65, angle 10 °, SCI values）The upper colorimetric measurement value for reading L*, a* and b*.

In this L*, a*, b* system, L* represents color intensity, and a* represents green/red axle, and b* represents blue/yellow Axle.The value of L is lower, and color is darker or denseer.The value of a* is higher, and tone is redder；The value of b* is higher, and tone is more yellow.

It is undressed（Control）And the dyeing hair tresses of the natural white hair after process between color change (Δ E*) By the definition according to below equation：

In this formula, L*, a* and b* represent the measured value after the natural hair dyeing containing 90% white hair, L*₀、 a₀And b *₀* the measured value of the natural hair containing 90% untreated hair is represented.

The value of Δ E is higher, and the difference compareed between hair tresses and dyeing hair tresses is bigger.

Coloring is very lasting relative to washing operation and light.

。

Embodiment B：

Prepare compositions below：

In 100g compositions：

The hydroxy benzaldehyde compound of -1.5g the present inventioni)；

- 1g alkaline agents（Monoethanolamine or NaOH, or arginine, or sodium acid carbonate, or ammonium hydrogen carbonate or 2- amino -2- Methyl isophthalic acid-propyl alcohol）；

The volume hydrogen peroxide aqueous solution of -30g 20；With

- 67.5g water.

Above-mentioned composition is applied with the bath raio of every 5g compositions 1g hairs.Hair tresses are containing 90% natural white (90% NW) The gray hair of hair.Composition is set to retain 30 minutes in hair tresses at 45 DEG C.Then hair tresses are rinsed, shampoo is washed simultaneously It is dried with hair dryer.

。

Embodiment C：

Prepare compositions below：

In 100g compositions：

The hydroxy benzaldehyde compound of -1g the present inventioni)；

The ammoniacal liquor of -2g 20%；

The volume hydrogen peroxide aqueous solution of -12g 20；With

- 85g water.

Above-mentioned composition is applied with the bath raio of every 5g compositions 1g hairs.Hair tresses are containing 90% natural white (90% NW) The gray hair of hair.Composition is set to retain 30 minutes in hair tresses at 45 DEG C.Then hair tresses are rinsed, shampoo is washed simultaneously It is dried with hair dryer.

。

Claims (21)

1. the method that keratin fiber is dyeed, it includes：

A) apply to the keratin fiber：

I) salt of the hydroxy benzaldehyde derivative of at least one formula (II) and its organic or inorganic acid or alkali：

In the formula (II)：

R’₁Represent hydrogen atom；

R’₂Represent straight or branched C₁-C₄Alkoxyl；

R’₄Represent hydrogen atom or hydroxyl；

R’₅Represent hydrogen atom or hydroxyl；

Ii) at least one chemical oxidizing agent；With

Iii) at least one basifier；

B) and then at a temperature of higher than 30 DEG C the angle egg fiber is heat-treated；

It should be understood that the hydroxy benzaldehyde derivative of formula (II) is relative to component i), ii) and gross weight iii) or methods described in The total concentration of the gross weight of composition therefor is more than 1%.

2. colouring method according to claim 1, wherein the hydroxy benzaldehyde derivative of the formula (II) is selected under Those in table：

And/or the salt of its organic or inorganic alkali.

3. colouring method according to claim 2, wherein the hydroxy benzaldehyde derivative of the formula (II) is compound 7.

4. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

A) ozone；

B) alkali metal or quaternary ammonium persalt, persulfate, percarbonate, peroxide phosphoric acid salt or

G) multivalence iodine derivative；

The optional carrier of the oxidant is selected from silica, alumina, charcoal and charged polymer or neutral polymer.

5. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

C) aliphatic series C₁-C₆With aromatics C₆-C₂₀Organic peracid, and its percarboxylic acids salt form；

The optional carrier of the oxidant is selected from silica, alumina, charcoal and charged polymer or neutral polymer.

6. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

D) organic peroxide；

The optional carrier of the oxidant is selected from silica, alumina, charcoal and charged polymer or neutral polymer.

7. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

E) oxide anion；

The optional carrier of the oxidant is selected from silica, alumina, charcoal and charged polymer or neutral polymer.

8. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

F) stable N- epoxide (NO^·) group；

The optional carrier of the oxidant is selected from silica, alumina, charcoal and charged polymer or neutral polymer.

9. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

H) following organic compound：N- halosuccinimides, TCCA, N- hydroxyl phthalimides, alkyl nitrous acid Salt；

The optional carrier of the oxidant is selected from silica, alumina, charcoal and charged polymer or neutral polymer.

10. colouring method according to claim 1 and 2, wherein ii) chemical oxidizing agent is selected from：

I) system of hydrogen peroxide or generation hydrogen peroxide.

11. colouring methods according to claim 10, wherein ii) chemical oxidizing agent is selected from：

I-1) urea peroxide；

I-2) the polymer complex of releasable hydrogen peroxide；

I-3 the oxidizing ferment of hydrogen peroxide) is produced in the presence of suitable substrates；

I-4 the metal peroxides of hydrogen peroxide) is generated in water；

I-5) perborate；Or

I-6) percarbonate.

12. colouring methods according to claim 1 and 2, wherein ii) chemical oxidizing agent be selected from hydrogen peroxide.

13. colouring methods according to claim 12, wherein the hydrogen peroxide includes the peroxide with every 100g Composition in amount between 1g and 70g exist.

14. colouring methods according to claim 12, wherein the hydrogen peroxide includes the peroxide with every 100g Composition in amount between 3g and 50g exist.

15. colouring methods according to claim 1 and 2, wherein iii) basifier is selected from：A) carbonate and bicarbonate Salt；

B) ammoniacal liquor；C) alkanolamine and its derivative；D) oxyethylation and/or oxypropylation ethylenediamine；E) inorganic or organic hydrogen Oxide；F) alkali silicate；G) amino acid；And h) under formula (III) compound：

In the formula (III), W is divalence (C₁-C₁₀) alkylidene, it is optionally selected from O, S, NR by least one_eHetero atom Or group interval, and/or the alkylidene are optionally by least one hydroxyl or (C₁-C₄) alkyl replacement；R_a、R_b、R_c、R_dAnd R_e May be the same or different, represent hydrogen atom, (C₁-C₄) alkyl or C₁-C₄Hydroxyalkyl.

16. colouring methods according to claim 1 and 2, wherein iii) basifier be ammoniacal liquor.

17. colouring methods according to claim 1 and 2, it does not use oxidation or p-aminophenyl phenols Compound.

18. colouring methods according to claim 1 and 2, it is used selected from following at least one oxidation dye, developing alkali And/or colour coupler：

● 2,3- diaminourea -6,7- dihydro -1H, 5H- pyrazolos [1,2-a] pyrazoles -1- ketone and its salt；

● the diamino-n, n-dihydropyrazolone derivative or its addition salts of formula (IV)：

In the formula (IV)：

R₁、R₂、R₃And R₄May be the same or different, represent：

- straight or branched C₁-C₆Alkyl, it is optionally selected from one or more following substituent groups：Group OR₅, group NR₆R₇, carboxyl, sulfonyl, formamido group CONR₆R₇, sulfonamido SO₂NR₆R₇, heteroaryl, aryl, the heteroaryl and aryl Optionally by (C₁-C₄) alkyl, hydroxyl, C₁-C₂Alkoxyl, amino or (two) (C₁-C₂) alkyl amino replacement；

- aryl, it is optionally by (C₁-C₄) alkyl, hydroxyl, C₁-C₂Alkoxyl, amino or (two) (C₁-C₂) in alkyl amino One or more replacements；

- 5 or 6 unit's heteroaryls, it is optionally selected from (C₁-C₄) alkyl and (C₁-C₂) one or more replacements in alkoxyl；

R₃And R₄Hydrogen atom can also be represented；

R₅、R₆And R₇May be the same or different, represent hydrogen atom；Straight or branched C₁-C₄Alkyl, it is optionally selected from following one Individual or multiple substituent groups：Hydroxyl, C₁-C₂Alkoxyl, formamido group CONR₈R₉, sulfonyl SO₂R₈, optionally by (C₁-C₄) alkane Base, hydroxyl, C₁-C₂Alkoxyl, amino, (two) alkyl (C₁-C₂) amino replace aryl；Optionally by (C₁-C₄) alkyl, hydroxyl Base, C₁-C₂Alkoxyl, amino or (two) alkyl (C₁-C₂) amino replace aryl；

R₆And R₇May be the same or different, can also represent formamido group CONR₈R₉；Or sulfonyl SO₂R₈；

R₈And R₉May be the same or different, represent hydrogen atom；Straight or branched C₁-C₄Alkyl, it is optionally by hydroxyl or C₁-C₂Alcoxyl One or more replacements in base；

One side R₁And R₂, and another aspect R₃And R₄Saturation or undersaturated 5 or 7 can be formed with the nitrogen-atoms being connected with them Circle heterocycles, it is optionally selected from one or more following substituent groups：Halogen atom, amino, (two) (C₁-C₄) alkyl amino, Hydroxyl, carboxyl, formamido group and (C₁-C₂) alkoxyl, C₁-C₄Alkyl, the alkyl is optionally by one or more hydroxyls, ammonia Base, (two) alkyl amino, alkoxyl, carboxyl or sulfonyl replace；

R₃And R₄5 or 7 circle heterocycles, the oxygen that its carbon atom can be optionally substituted can be also formed together with the nitrogen-atoms being connected with them Or nitrogen-atoms is substituted；

● the salt of 4- (3- amino-pyrazols simultaneously [1,5-a] pyridine -2- bases) -1,1- lupetazin -1-；

● the 3- amino-pyrazols of lower formula (V) simultaneously [1,5-a] pyridine derivate and its salt：

In the formula (V)：

○Z₁And Z₂Independently represent：I) covalent single bond；Ii) selected from oxygen atom and group-NR₆(R₇)_pDivalent group,

- wherein p=0 or 1, wherein when p is equal to 0, then R₆Represent hydrogen atom or C₁-C₆Alkyl, or R₆Respectively with R₁And R₂And The nitrogen-atoms connected with them forms substituted or unsubstituted, saturation or undersaturated, aromatics together or non-aromatic 5-8 units are miscellaneous Ring, it is optionally selected from N, O, S, SO comprising one or more₂With the hetero atom or group of-CO-, the heterocycle can be cation Heterocycle and/or by cation or non-cationic substituent group,

- when p is equal to 1, then-NR₆R₇- be cation group, wherein R₆And R₇Alkyl is independently represented,

Zero works as R₁For methyl when, Z₁May also indicate that divalent group-S- ,-SO- or-SO₂-；

It should be understood that Z₁And Z₂At least one of be not covalent single bond,

○R₁And R₂Independently represent hydrogen or halogen atom or selected from following group：

-C₁-C₁₀Alkyl, it is selected from O, N, Si, S, SO and SO₂Hetero atom or group optionally replace and be optionally spaced,

-C₁-C₁₀Alkyl, it is replaced and/or is spaced by cation group,

-SO₃H groups,

- 5-8 yuan of rings, it is being substituted or unsubstituted, saturated or unsaturated or aromatics and optionally comprising one Or it is multiple selected from N, O, S, SO₂With the hetero atom or group of-CO-, the ring can be cation ring and/or to be taken by cation group Generation,

Work as Z₁And Z₂When representing covalent bond respectively, then R₁And R₂Can also represent respectively：

- optionally substituted C₁-C₆Alkyl-carbonyl；

- group-O-CO-R ,-CO-O-R, NR-CO-R ' or-CO-NRR ', wherein R and R ' independently represent hydrogen atom or optionally take The C in generation₁-C₆Alkyl；

○R₃、R₄And R₅, it may be the same or different, and represent：

- hydrogen atom；

- hydroxyl；

-C₁-C₆Alkoxyl；

-C₁-C₆Alkylthio group；

- amino；

- alkyl monosubstituted amino；

-C₁-C₆Dialkyl amido, wherein alkyl can form saturation or undersaturated, aromatics or non-aromatic with the nitrogen being connected with them 5-8 circle heterocycles, it includes one or more selected from N, O, S, SO₂With the hetero atom or group of CO, the heterocycle can be cation Heterocycle and/or replaced by cation group；

- optionally substituted C₁-C₆Alkyl-carbonyl；

- group-O-CO-R ,-CO-O-R, NR-CO-R ' or-CO-NRR ', wherein R and R ' are as defined before this；

- halogen；

- group-NHSO₃H；

- optionally substituted C₁-C₄Alkyl；

- optionally substituted, saturation or undersaturated or aromatic carbon basic ring；

-R₃、R₄And R₅Saturation or undersaturated ring can in couples be formed；

Zero X represented so that can ensure that electronegative anionic counter-ion or anionic group of the derivative of formula (V),

Condition is Z₁、R₁、Z₂And R₂At least one of represent cation group：

● the salt of 2- [(3- amino-pyrazols simultaneously [1,5-a] pyridine -2- bases) epoxide] ethanol；

● the derivative and its salt of the 3- amino-pyrazols of formula (VI) simultaneously [1,5-a] pyridine derivate

In the formula (VI)：

○Z₁Represent oxygen atom or group NR₆, work as Z₁Represent NR₆When, then R₁And R₆Can together with the nitrogen-atoms being connected with them shape Into optionally substituted, saturation or undersaturated or aromatics 5-8 circle heterocycles；

Work as R₁Represent CH₃When, Z₁May also indicate that divalent group S, SO or SO₂；

○R₁And R₆Independently represent：

- hydrogen atom；

- optionally substituted C₁-C₁₀Alkyl, the substituent can be that optionally substituted, saturation or undersaturated or aromatics 5-8 are first (miscellaneous) ring；

- optionally substituted, saturation or undersaturated or aromatics 5-8 units (miscellaneous) ring；

○R₂、R₃、R₄And R₅Independently represent：

Hydrogen atom；

Optionally substituted C₁-C₄Alkyl；

Selected from NH₂、NHR₁₀、NR₁₁R₁₂, OH or OR₉Group, wherein R₉And R₁₀Represent optionally substituted, straight or branched C₁- C₆Alkyl, R₁₁And R₁₂May be the same or different, represent optionally substituted, straight or branched C₁-C₆Alkyl, R₁₁And R₁₂Can with and they The nitrogen-atoms of connection forms together saturation or undersaturated or aromatics 5-8 circle heterocycles, and it is optionally selected from comprising one or more N、O、S、SO₂With other hetero atoms or group of CO, the heterocycle is optionally substituted；

○R₂、R₃、R₄、R₅Optionally substituted, saturation or undersaturated (miscellaneous) ring can be in couples formed with adjacent group；

● 5- [(2- ethoxys) amino] -2- methylphenols；

● 3,4- dihydro -2H-1,4- benzoxazine -6- alcohol；

● the chloro- 6- methylphenols of 3- amino -2-；

● PA -3- alcohol；

● 2- methylbenzene -1,3- glycol；

● 2- (2,4- diamino phenoxies) ethylate hydrochlorate；With

● the cation amino pyridine derivate of logical formula (VII), its addition salts with acid：

In the formula (VII), group Z₁R₁With cationic charge,

○Z₁For oxygen atom or group NR₂；

○R₂For hydrogen atom or straight or branched C₁-C₄Alkyl, benzyl or acetyl group；

○R₁For saturation, straight or branched C₁-C₁₀Alkyl, it is replaced or is spaced by cation group, optionally by one or many Individual oxygen atom and/or by one or more groups NR₂Interval, is optionally selected from hydroxyl, alkoxyl and C₁-C₄The one of hydroxyalkyl Individual or multiple substituent groups, or R₁For saturation or undersaturated or aromatic cationic 5-8 circle heterocycles, it is optionally by one or many It is individual selected from following substituent group：C₁-C₄Alkyl, hydroxyl, C₁-C₄Alkoxyl, amino, (C₁-C₄) alkyl amino, two (C₁-C₄) alkane Base amino, thio, (C₁-C₄) alkylthio group, carboxyl, (C₁-C₄) alkyl-carbonyl, sulfonyl, amide groups and C₁-C₄Hydroxyalkyl；

Work as Z₁Represent NR₂When, then

·R₁And R₂Saturation or undersaturated cation 5-8 circle heterocycles can be formed together with the nitrogen-atoms being connected with them, it is described miscellaneous Ring is optionally selected from following substituent group by one or more：C₁-C₁₀Alkyl and hydroxyl, C₁-C₄Alkoxyl, amino, (C₁- C₄) alkyl amino, two (C₁-C₄) alkyl amino, thio, (C₁-C₄) alkylthio group, carboxyl, (C₁-C₄) alkyl-carbonyl, sulfonyl, acyl Amido and C₁-C₄Hydroxyalkyl, this heterocycle can include one or more hetero atoms selected from N or O, or

·R₁And R₂Saturation or undersaturated non-cationic 5-8 circle heterocycles can be formed together with the nitrogen-atoms being connected with them, it is described Heterocycle replaces and is optionally selected from one or more following substituent groups by cation group：C₁-C₁₀Alkyl and hydroxyl, C₁-C₄Alkoxyl, amino, (C₁-C₄) alkyl amino, two (C₁-C₄) alkyl amino, thio, (C₁-C₄) alkylthio group, carboxyl, (C₁- C₄) alkyl-carbonyl, sulfonyl, amide groups and C₁-C₄Hydroxyalkyl；

R is selected from hydrogen atom；Selected from the halogen of fluorine, chlorine and bromine；Straight or branched C₁-C₄Alkyl and carboxyl (- COOH) and (C₁- C₄) alkoxy carbonyl group；And

·An^-Represent anionic counter-ion or anionic group.

19. colouring methods according to claim 1 and 2, it does not use non-activated CH compounds.

20. cosmetic compositions, it is included：

I) derivative of at least one formula (II) defined in any one of claims 1 to 3；

Ii) at least one chemical oxidizing agent defined in any one of claim 1 and 4-15；With

Iii) at least one basifier defined in claim 1,16 and any one of 17；

It should be understood that：

The pH of-the composition is higher than 7；

In-formula (II) compound, R '₁Or R '₄Or R '₅Represent hydrogen atom；

The hydroxy benzaldehyde derivative of-formula (II) is relative to the component i i) and iii) gross weight total concentration be more than 1%； And

- 4- is represented when the hydroxy benzaldehyde derivative that there is following formula (II) in Ortho-Aminophenol, 2,5- diaminotoluene sulphates During hydroxy 3-methoxybenzene formaldehyde, then the basifier iii) it is not ammonium hydroxide.

A kind of 21. multi-compartment devices, it includes containing 2 to 4 kinds of compositions 2 to 4 compartments, wherein claim 1 is distributed with Component i to defined in any one of 20), ii), iii), the composition is aqueous or powdery, wherein these combination It is at least one for aqueous in thing.