Note: Descriptions are shown in the official language in which they were submitted.
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Novel p-aminophenol derivatives and the use thereof
This invention relates to new p-aminophenol derivatives, to their use
for coloring keratin fibers and to colorants containing these compounds.
By virtue of their intensive colors and good fastness properties, so
called oxidation colorants play a prominent role in the coloring of keratin
fibers, particularly human hair. Oxidation colorants contain oxidation dye
precursors, so-called primary intermediates and secondary intermediates.
The primary intermediates form the actual dyes with one another or by
coupling with one or more secondary intermediates in the presence of
oxidizing agents or atmospheric oxygen.
Good oxidation dye precursors are expected to satisfy above all the
following requirements: they must form the required color tones with
sufficient intensity and fastness during the oxidative coupling reaction. In
addition, they must be readily absorbed onto the fibers with no significant
differences - particularly in the case of human hair - between damaged and
freshly regrown hair (levelling behavior). They must be resistant to light,
heat and the effect of chemical reducing agents, for example permanent
wave lotions. Finally, if they are used to color hair, they should not overly
stain the scalp and, above all, should be toxicologically and
dermatologically safe.
The primary intermediates normally used are primary aromatic
amines containing another free or substituted hydroxy or amino group in
the para position or the ortho position, diaminopyridine derivatives,
heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-
tetraaminopyrimidine and derivatives thereof.
Special representatives are, for example, p-phenylenediamine, p-
toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis-(2-
hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5-
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diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone,
4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6
triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino
hydroxy pyrimidine and 1,3-N,N'-bis-(2'-hydroxyethyl)-N,N'-bis-(4'-amino
phenyl)-diamino-2-propanol.
The secondary intermediates are generally m-phenylenediamine
derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones
and m-aminophenols. Particularly suitable secondary intermediates are 1-
naphthol, 1,5-, 2'.,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methyl-
phenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-
phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-amino-
phenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4-
chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-4-hydroxy-
pyridine, 2-methyl resorcinol, 5-methyl resorcinol and 2-methyl-4-chloro-5-
aminophenol.
In general, natural color tones cannot be obtained with a primary
intermediate alone or with a special secondary intermediate/primary
intermediate combination. In practice, therefore, combinations of various
primary intermediates and secondary intermediates are used so that there
is a constant need for new improved dye components.
Accordingly, the problem addressed by the present invention was to
provide new primary intermediates which would satisfy the requirements
oxidation dye precursors are expected to meet to a particular degree.
It has now keen found that certain, hitherto unknown p-aminophenol
derivatives satisfy the requirements primary intermediates are expected to
meet to a particularly high degree. Thus, brilliant color tones, more
especially in the brown and red range, are obtained using these primary
intermediates with most of the known secondary intermediates. In addition,
the colors obtained are distinguished by extremely high fastness to light
and washing.
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In a first embodiment, therefore, the present invention relates to p-
aminophenol derivatives corresponding to general formula (I):
A C
R' X R2 (I)
B D
in which
- A, B, C and D independently of one another represent an -OH or -NHR
group where R is a hydrogen atom or a C» alkyl group, with the
proviso that either A or B and C or D is a hydroxy group,
- X stands for oxygen, sulfur, a sulfoxy or a sulfoxyl group and
- R' and R2 independently of one another represent hydrogen, fluorine,
chlorine, a C~.d alkyl or hydroxyalkyl group or a C2~, dihydroxyalkyl
group, preferably a C2 dihydroxyalkyl group.
These compounds can be produced by known organic synthesis
methods. Particul<~rs can be found in the following Synthesis Example.
Since all the compounds according to the invention are amino
compounds, the known acid addition salts can be prepared from them in
the usual way. Accordingly, all statements in this specification and hence
the claimed scope of protection relate both to the p-aminophenol
derivatives of formula (I) present in free form and to their water-soluble
physiologically compatible salts. Examples of such salts are the
hydrochlorides, the hydrobromides, the sulfates, the phosphates, the
acetates, the propionates, the citrates and the lactates.
Those aminophenol derivatives of formula (I) where X is an oxygen
or sulfur atom have proved to be particularly suitable for the purposes of
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the invention. Oxygen has proved to be a particularly advantageous group
X.
Those p-aminophenol derivatives corresponding to formula (I) where
the groups A, B, C; and D which are not OH groups stand for -NH2 groups
are also particularly preferred for the purposes of the invention.
In addition, hydrogen has proved to be a particularly suitable
substituent R' and R2 in p-aminophenol derivatives corresponding to
formula (I).
Finally, those p-aminophenol derivatives corresponding to formula (I)
where R' and R2 are the same, A and C are the same and B and D are the
same have also proved to be particularly suitable for the purposes of the
invention.
A compound with particularly outstanding suitability for the purposes
of the invention is 4-amino-2-(((5-amino-2-hydroxyphenyl)-methoxy)
methyl)-phenol.
In a second embodiment, the present invention relates to the use of
the above-mentioned p-aminophenol derivatives as primary intermediates
in oxidation hair colorants.
Finally, in a third embodiment, the present invention relates to
oxidation colorants for coloring keratin fibers containing secondary
intermediates and primary intermediates in a water-containing carrier,
characterized in that one of the above-mentioned p-aminophenol
derivatives is present as the primary intermediate.
Keratin fibers in the context of the present invention include pelts,
wool, feathers and, more particularly, human hair. Although the oxidation
colorants according to the invention are particularly suitable for coloring
keratin fibers, there' is basically nothing to prevent them from being used in
other fields, particularly in color photography.
The oxidation colorants according to the invention contain the
primary intermediates corresponding to formula (I) and secondary
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intermediates and, if desired, may contain other primary intermediates and
secondary intermediates.
According to the invention, preferred other primary intermediates are
p-phenylenediamine, p-toluylenediamine, p-aminophenol, 2-(2,5-
diaminophenyl)-ethanol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 1-
phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 4-
amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2,4,5,6-tetraamino-
pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triamino-
pyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-tri-
aminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol and 4,4'-
diaminodiphenylamine. 2-hydroxymethyl-4-aminophenol, bis-(2-hydroxy-5-
aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,3-
N,N'-bis-(2'-hydroxyethyl)-N,N'-(4'-aminophenyl)-diamino-1,3-propan-2-of
and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO
94108970, such as 4,5-diamino-1-(2'-hydroxyethyl)-pyrazole for example,
are also primary intermediates which may advantageously be combined
with the primary intermediates according to the invention.
Most particularly preferred other primary intermediates are p
phenylenediamine, 2,4,5,6-tetraminopyrimidine, 4,5-diamino-1-(2'
hydroxyethyl)-pyrazole, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, bis
(2-hydroxy-5-aminophenyl)-methane, 2-(2,5-diaminophenyl)-ethanol, 3-
methyl-4-aminophc:nol, 4-hydroxy-2,5,6-triaminopyrimidine, 2-aminomethyl-
4-aminophenol and p-toluylenediamine.
According to the invention, preferred secondary intermediates are 1-
naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-amino-
phenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol
monomethyl ether, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-
aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 4-chlororesorcinol, 2-
chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol,
2,5-dimethyl resorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-
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amino-3-hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine, 2-methyl-4-
chloro-5-aminophenol, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 3-amino-2-
methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis-(2-
hydroxyethylamino)-toluene, 3.4-methylenediioxyphenol, 3,4-methylene-
dioxyaniline, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethyl-
amino)-anisole and 2,6-dimethyl-3-aminphenol.
Particularly preferred secondary intermediates are 1-naphthol, m-
aminophenol, 5-amino-2-methylphenol, 3-methylsulfonylamino-2-
methylaniline, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dimethyl-3-
aminophenol, 2,4-~diaminophenoxy ethanol, 2,7-dihydroxynaphthalene, 6-
methyl-1,2,3,4-tetrahydroquinoxaline, 1,7-dihydroxynaphthalene, 2-methyl-
4-chloro-5-aminophenol, 3,4-methylenedioxyaniline, 2-methylresorcinol, 4-
chlororesorcinol, 3,4-methylenedioxyphenol, 2-amino-3-hydroxypyridine
and 2-chloro-6-methyl-3-aminophenol.
These other primary and secondary intermediates are normally used
in free form. Where they contain amino groups, however, it may be
preferable to uses them in salt form, particularly in the form of the
hydrochlorides and sulfates.
The hair colorants according to the invention contain both the
primary intermediates and the secondary intermediates in a quantity of
preferably 0.005 t.o 20% by weight and more preferably 0.1 to 5% by
weight, based on the oxidation colorant as a whole. The primary
intermediates and secondary intermediates are generally used in a
substantially equimolar ratio to one another. Although it has proved to be
of advantage to use the primary and secondary intermediates in an
equimolar ratio, there is no disadvantage in using individual oxidation dye
precursors in a certain excess so that primary intermediates and secondary
intermediates may be present in a molar ratio of 1:0.5 to 1:3 and, more
particularly, 1:1 to 1:2.
In one preferred embodiment, the hair colorants according to the
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invention contain typical substantive dyes in addition to the oxidation dye
precursors for further modifying the color tones. Substantive dyes are
normally nitrophenylendiamines, nitroaminophenols, azo dyes, anthra-
quinones or indophenols. Preferred substantive dyes are the compounds
known under the International names or trade names of HC Yellow 2, HC
Yellow 4, HC Yellaw 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC
Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC
Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic
Brown 16 and Basic Brown 17 and also 4-amino-2-nitrodiphenylamine-2'-
carboxylic acid, 6-nitra-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-
nitrotoluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol and 4-N-ethyl-
1,4-bis-(2'-hydroxyethylamino)-2-nitrobenzene hydrochloride. The color-
ants according to the invention of this embodiment preferably contain the
substantive dyes in a quantity of 0.01 to 20% by weight, based on the
colorant as a whole.
The colorants according to the invention may also contain naturally
occurring dyes such as, for example, henna red, henna neutral, henna
black, camomile blossom, sandalwood, black tea, black alder bark, sage,
logwood, madder root, catechu, sedre and alkanet.
Other dye components which may be present in the colorants
according to the invention are indoles and indolines and physiologically
compatible salts thereof. Preferred examples are 5,6-dihydroxyindole, N-
methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-di-
hydroxyindole, N-butyl-5,6-dihydroxyindole, 6-hydroxyindole, 6-aminoindole
and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-
dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxy-
indoline, N-butyl-5,6-dihydroxyindoline, 6-hydroxyindoline, 6-aminoindoline
and 4-aminoindoline.
The oxidation dye precursors or the substantive dyes optionally
present do not have to be single compounds. On the contrary, other
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components may be present in small quantities in the hair colorants
according to the invention due to the processes used to produce the
individual dyes providing these other components do not adversely affect
the coloring result or have to be ruled out for other reasons, for example
toxicological reasons.
So far as the dyes suitable for use in the hair colorants and tinting
formulations according to the invention are concerned, reference is also
expressly made to the work by Ch. Zviak, The Science of Hair Care,
Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264-
267; oxidation dye precursors), published as Volume 7 of the Series
"Dermatology" (E=d.: Ch. Culnan and H. Maibach), Marcel Dekker Inc.,
New York/Basle, 1986, and to the "Europaische Inventar der Kosmetik-
Rohstoffe" published by the Europaische Gemeinschaft and available in
disk form from the Bundesverband Deutscher Industrie- and
Handelsunternehmen fur Arzneimittel, Reformwaren and Korperpflegemittel
d.V., Mannheim.
To produce the colorants according to the invention, the oxidation
dye precursors are incorporated in a suitable water-containing carrier. For
coloring hair, such carriers are, for example, creams, emulsions, gels or
even surfactant-containing foaming solutions, for example shampoos, foam
aerosols or other formulations suitable for application to the hair.
The colorants according to the invention may also contain any of the
known active substances, additives and auxiliaries typical of such
formulations. In many cases, the colorants contain at least one surfactant,
both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants
being suitable in principle. In many cases, however, it has been found to
be of advantage to select the surfactants from anionic, zwitterionic or
nonionic surfactants.
Suitable anionic surfactants for the hair colorants according to the
invention are any anionic surface-active substances suitable for use on the
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human body. Such substances are characterized by a water-solubilizing
anionic group such as, for example, a carboxylate, sulfate, sulfonate or
phosphate group and a lipophilic alkyl group containing around 10 to 22
carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether
and amide and hydroxyl groups may also be present in the molecule. The
following are exannples of suitable anionic surfactants - in the form of the
sodium, potassium and ammonium salts and the mono-, di- and trialkanol-
ammonium salts containing 2 or 3 carbon atoms in the alkanol group:
- linear fatty acids containing 10 to 22 carbon atoms (soaps),
- ether carboxylic acids corresponding to the formula R-O-(CH2-CH20)X-
CH2-COOH, in which R is a linear alkyl group containing 10 to 22
carbon atoms and x = 0 or 1 to 16,
- acyl sarcosides containing 10 to 18 carbon atoms in the acyl group,
- acyl taurides containing 10 to 18 carbon atoms in the acyl group,
- acyl isethionatE~s containing 10 to 18 carbon atoms in the acyl group,
- sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon
atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl
esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6
oxyethyl groups,
- linear alkane sulfonates containing 12 to 18 carbon atoms,
- linear a-olefin sulfonates containing 12 to 18 carbon atoms,
- a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon
atoms,
- alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the
formula R-O(C1~2-CH20)X-S03H, in which R is a preferably linear alkyl
group containing 10 to 18 carbon atoms and x = 0 or 1 to 12,
- mixtures of surface-active hydroxysulfonates according to DE-A-37 25
030,
- sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene
glycol ethers according to DE-A-37 23 354,
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- sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms
and 1 to 6 double bonds according to DE-A-39 26 344,
- esters of tartaric acid and citric acid with alcohols in the form of
addition
products of around 2 to 15 molecules of ethylene oxide and/or
propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether
sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the
alkyl group and up to 12 glycol ether groups in the molecule and, in
particular, salts of saturated and, more particularly, unsaturated C&22
carboxylic acids, such as oleic acid, stearic acid, isostearic acid and
palmitic acid.
In the context of the invention, zwitterionic surfactants are surface-
active compounds which contain at least one quaternary ammonium group
and at least one -COO~-~ or -S03~~~ group in the molecule. Particularly
suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-
N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl
ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium
glycinates, for example cocoacylaminopropyl dimethyl ammonium
glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines
containing 8 to 18 carbon atoms in the alkyl or acyl group and
cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred
zwitterionic surfactant is the fatty acid amide derivative known by the CTFA
name of Cocamidopropyl Betaine.
Ampholytic surfactants are surface-active compounds which, in
addition to a C$_~8 alkyl or acyl group, contain at least one free amino group
and at least one -COOH or -S03H group in the molecule and which are
capable of forming inner salts. Examples of suitable ampholytic surfactants
are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N
alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines,
N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl
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aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl
group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino-
propionate, cocoacyl aminoethyl aminopropionate and C~2_~$ acyl
sarcosine.
Nonionic surfactants contain, for example, a polyol group, a poly-
alkylene glycol ether group or a combination of polyol and polyglycol ether
groups as the hydrophilic group. Examples of such compounds are
- products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5
moles of propylene oxide onto linear fatty alcohols containing 8 to 22
carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and
onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group,
- 02_22 fatty acid monoesters and diesters of products of the addition of 1
to 30 moles of ethylene oxide onto glycerol,
- C8_22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof,
- products of the addition of 5 to 60 moles of ethylene oxide onto castor
oil and hydrogenated castor oil,
- products of the addition of ethylene oxide onto sorbitan fatty acid esters,
- products of the addition of ethylene oxide onto fatty acid alkanolamides.
Examples ~of cationic surfactants suitable for use in the hair
treatment formulations according to the invention are, in particular,
quaternary ammonium compounds. Preferred quaternary ammonium
compounds are ammonium halides, such as alkyl trimethyl ammonium
chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl
ammonium chlorides, for example cetyl trimethyl ammonium chloride,
stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium
chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl
ammonium chloride and tricetyl methyl ammonium chloride. Other cationic
surfactants suitable for use in accordance with the invention are the
quaternized protein hydrolyzates.
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Also suitable for use in accordance with the invention are cationic
silicone oils such as, for example, the commercially available products Q2-
7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethi-
cone), Dow Corning 929 Emulsion (containing a hydroxylarnino-modified
silicone which is also known as Amodimethicone), SM-2059 (manufacturer:
General Electric), SLM-55067 (manufacturer: Wacker) and Abil~-Quat
3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl
siloxanes, Quaternium-80).
Alkyl amidoamines, particularly fatty acid amidoamines, such as the
stearyl amidopropyl dimethyl amine obtainable as Tego Amid7S 18, are
distinguished not only by their favorable conditioning effect, but also and in
particular by their ready biodegradability.
Quaternary ester compounds, so-called Aesterquats-, such as the
methyl hydroxyalk:yl dialkoyloxyalkyl ammonium methosulfates marketed
under the trade name of Stepantex~ and the products marketed under the
trade name of De~hyquart~, such as Dehyquart AU-46, are also readily
biodegradable.
One example of a quaternary sugar derivative suitable for use as a
cationic surfactant is the commercially available product Glucquat~100
(INCI name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).
The compounds containing alkyl groups used as surfactants may be
single compounds. In general, however, these compounds are produced
from native vegetable or animal raw materials so that mixtures with
different alkyl chain lengths dependent upon the particular raw material are
obtained.
The surfactants representing addition products of ethylene and/or
propylene oxide with fatty alcohols or derivatives of these addition products
may be both products with a Anormal= homolog distribution and products
with a narrow homolog distribution. Products with a Anormal= homolog
distribution are mixtures of homologs which are obtained in the reaction of
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fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides
or alkali metal alcoholates as catalysts. By contrast, narrow homolog
distributions are obtained when, for example, hydrotalcites, alkaline earth
metal salts of ether carboxylic acids, alkaline earth metal oxides,
hydroxides or alcoholates are used as catalysts. The use of products with
a narrow homolog distribution can be of advantage.
Other active substances, auxiliaries and additives are, for example,
- nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate
copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate
copolymers and polysiloxanes,
- cationic polymers, such as quaternized cellulose ethers, polysiloxanes
containing quaternary groups, dimethyl diallyl ammonium chloride
polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers,
dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quater-
nized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride
copolymers and quaternized polyvinyl alcohol,
- zwitterionic and amphoteric polymers such as, for example, acrylamido-
propyl/trimethyl ammonium chloride/acrylate copolymers and octyl
acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2-
hydroxypropyl rnethacrylate copolymers,
- anionic polymers such as, for example, polyacrylic acids, crosslinked
polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl
pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl
maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic
anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl
acrylamide terpolymers,
- thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum
arabic, karaya c,~um, locust bean gum, linseed gums, dextrans, cellulose
derivatives, for example methyl cellulose, hydroxyalkyl cellulose and
carboxymethyl cellulose, starch fractions and derivatives, such as
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amylose, amylopectin and dextrins, clays such as, for example,
bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl
alcohol,
- structurants, such as glucose and malefic acid,
- hair-conditioning compounds, such as phospholipids, for example soya
lecithin, egg lecithin and kephalins, and also silicone oils,
- protein hydrolyzates, more particularly elastin, collagen, keratin, milk
protein, soya protein and wheat protein hydrolyzates, condensation
products thereof with fatty acids and quaternized protein hydrolyzates,
- perfume oils, dimethyl isosorbide and cyclodextrins,
- solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene
glycol, glycerol and diethylene glycol,
- antidandruff agents, such as piroctone olamine and zinc omadine,
- other substances for adjusting the pH value,
- active substances, such as panthenol, pantothenic acid, allantoin,
pyrrolidone carboxylic acids and salts thereof, plant extracts and
vitamins,
- cholesterol,
- UV filters,
- consistency factors, such as sugar esters, polyol esters or polyol alkyl
ethers,
- fats and waxes, such as spermaceti, beeswax, montan wax, paraffins,
fatty alcohols and fatty acid esters,
- fatty acid alkanolamides,
- complexing agents, such as EDTA, NTA and phosphonic acids,
- swelling and penetration agents, such as glycerol, propylene glycol
monoethyl ether, carbanates, hydrogen carbonates, guanidines, ureas
and primary, secondary and tertiary phosphates,
- opacifiers, such as latex,
- pearlizers, such as ethylene glycol mono- and distearate,
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- propellents, such as propane/butane mixtures, N20, dimethyl ether,
C02 and air and
- antioxidants.
To produce the colorants according to the invention, the constituents
of the water-containing carrier are used in the usual quantities for this
purpose. For example, emulsifiers are used in concentrations of 0.5 to
30% by weight while thickeners are used in concentrations of 0.1 to 25% by
weight, based on the colorant as a whole.
In principle, the color can be oxidatively developed with atmospheric
oxygen. However, a chemical oxidizing agent is preferably used,
particularly when human hair is to be not only colored, but also lightened.
Particularly suitable oxidizing agents are persulfates, chlorites and, in
particular, hydrogen peroxide or addition products thereof with urea,
melamine or sodium borate. Oxidation may also be carried out with
enzymes. In this case, the enzymes may be used to transfer atmospheric
oxygen to the primary intermediate or to enhance the effect of an oxidizing
agent present in small quantities. One example of an enzymatic process is
the procedure whereby the effect of small quantities (for example 1 % and
less, based on the formulation as a whole) of hydrogen peroxide is
enhanced by peroxidases.
The preparation of the oxidizing agent is preferably mixed with the
preparation of the oxidation dye precursors immediately before coloring of
the hair. The ready-to-use hair coloring preparation formed should
preferably have a pH value in the range from 6 to 10. In a particularly
preferred embodiment, the hair colorant is used in a mildly alkaline
medium. The application temperatures may be in the range from 15 to
40°C. After a contact time of about 5 to 30 minutes, the hair colorant
is
removed from the hair to be colored by rinsing. There is no need for the
hair to be washed with a shampoo where a carrier of high surfactant
content, for example a coloring shampoo, has been used.
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The following Examples are intended to illustrate the invention.
Examples
1. Synthesis Example
Synthesis of 4-amino-2-(((5-amino-2-hydroxyphenyl~-methoxy~-methy~-
hp enol
Diazonium solution (solution A):
10.35 g (0.115 mole) of sodium nitrite in 125 ml of water were added
at a temperature of +5°C to a solution consisting of 26 g (0.15 mole)
of
sulfanilic acid and 75 ml (0.15 mole) of 2N sodium hydroxide. 131 ml (0.38
mole) of 10% hydrochloric acid were added dropwise while cooling (+5°C)
over a period of 3G minutes.
Solution A was added dropwise to an ice-cooled solution consisting
of 17.25 g (0.075 rnole) of bis-(2-hydroxybenzyl)-ether in 120 ml (0.3 mole)
of 10% sodium hydroxide. After the addition, the whole was stirred for 1.5
hours at 20°C.
69 g (0.4 mole) of sodium dithionite were then added over a period
of 2 minutes. After 20 minutes at 75°C, the product was filtered off
under
suction and washed with water. The product was obtained in the form of
colorless crystals with a melting point of 175°C (decomp.).
2. Coloring
A cream base with the following composition was first prepared [all
quantities are in g, unless otherwise indicated]:
tallow fatty alcohol 17.0
Lorol~techn.' 4.0
Texapon~N 282 40.0
Dehyton~K3 25.0
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Eumulgin~B 24 1.5
distilled water 12.5
' C~2_~8 fatty alcohol (HENKEL)
2 Sodium lauryl ether sulfate (ca. 28% active substance; /NCI name:
Sodium Laureth Sulfate) (HENKEL)
Fatty acid amide derivative with a betaine structure corresponding to the
following formula: R-CONH(CH2)3N+(CH3)2CHZC00) (ca. 30% active
substance; /NCI name Cocoamidopropyl Betaine) (HENKEL)
4 Cetyl stearyl alcohol containing ca. 20 moles EO (/NCI name:
Ceteareth-20) (HENKEL)
The following hair coloring cream emulsion was then prepared on
the basis of this cream:
cream base 50.0
primary intermediate 7.5 mmoles*
secondary intermediate 7.5 mmoles*
Na2S03 (inhibitor) 1.0
(NH4)2S04 1.0
conc. ammonia solution to pH 10
water to 100
* unless otherwise indicated
The ingredients were mixed in the order listed. Substantive dyes
were optionally added with corresponding reductions in the water content.
After addition of the oxidation dye precursors and the inhibitor, the
emulsion was first adjusted to pH 10 with concentrated ammonia solution
and was then made up with water to 100 g.
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The color was oxidatively developed with 3% hydrogen peroxide
solution as the oxidizing solution. To this end, 50 g of hydrogen peroxide
solution (3%) were added to and mixed with 100 g of the emulsion.
The coloring cream was applied to approximately 5 cm long tresses
of standardized, 90% grey but not specially pretreated human hair and left
thereon for 30 minutes at 32°C. On completion of the coloring process,
the
hair was rinsed, washed with a normal shampoo and dried. The following
primary and secondary intermediates and substantive dyes were used for
coloring:
Primary intermediates
~ 4-amino-2-(((5-amino-2-hydroxyphenyl)-methoxy)-methyl)-phenol (E1)
~ 2,4,5,6-tetraaminopyrimidine (E2)
~ 4,5-diamino-1-(2-hydroxyethyl)-pyrazole (E3)
~ p-phenylenediamine
~ N,N-bis-(2-hydroxyethyl)-p-phenylenediamine (E5)
~ 4-hydroxy-2,5,Ei-triaminopyrimidine (E6)
~ p-toluylenediamine
~ 2-(2,5-diaminophenyl)-ethanol (E8)
~ 2-aminomethyl-~4-aminophenol (E9)
~ 4-amino-3-methylphenol
~ bis-(2-hydroxy-5-aminophenyl)-methane (E11 )
Secondary intermediates
~ 1-naphthol (K1)
~ 2-methyl-5-aminophenol (K2)
~ 2-chloro-6-methyl-3-aminophenol (K3)
~ 2-amino-3-hydroxypyridine (K4)
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~ 2,6-dimethyl-3-aminophenol (K5)
~ m-aminophenol (K6)
~ 2,7-dihydroxynaphthalene (K7)
~ 4-chlororesorcinol (K8)
~ 2-methyl-4-chloro-5-aminophenol (K9)
~ 6-methyl-1,2,3,4-tetrahydroquinoxaline (K10)
~ 2-methyl resorcinol (K11 )
~ 3-amino-2-methylamino-6-methoxypyridine (K12)
~ 2,4-diaminophenoxyethanol (K13)
~ 3-methylsulfonylamino-2-methyl aniline (K14)
~ 1,7-dihydroxynaphthalene (K15)
~ 3,4-methylenedioxyphenol (K16)
~ 3,4-methylenedioxyaniline (K17)
~ m-phenylenediamine (K18)
Substantive dyes
~ 6-nitro-1,2,3,4-tetrahydroquinoxaline (D1)
~ 2-nitro-4-aminodiphenylamine-2'-carboxylic acid (D2)
~ 2-amino-6-chloro-4.-nitrophenol (D3)
~ 2-nitro-1-amino-4-bis-(2-hydroxyethyl)-aminobenzene (D4)
~ 2-nitro-1-(2-hydroxyethyl)-amino-4-methylbenzene (D5)
~ 2-(2'-hydroxyethylamino)-4,6-dinitrobenzene (D6)
~ 1-(2'-hydroxyethyl)-amino-2-nitro-4-bis-(2-hydroxyethyl)-aminobenzene
(D7)
~ 1-(2-hydroxyethyl)-amino-2-nitro-4-aminobenzene (D8)
~ 4-(2-nitrophenyl)-aminophenol (D9)
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The following colors were obtained:
Primary Secondary Substantive dye Hair color
intermediateintermediate
E 1 K1 - Grey-red
E1 K2 - Grey-orange
E 1 K3 - Brown-red
E1 K4 - Light orange
E1 K5 - Grey-red
E1 K6 - Topaz yellow
E1+E3 K1+K~ - Old pink
E1+E2 K2+K7a - Flat violet
E1+E6a K8+K9a - Grey-red
E1+E7 K10+K~ - Champagne
E1+E4 K12 - Black
E1+E5a K5+K13a - Black-blue
E1+E8a K12+K~ - Blue-grey
E1+E9a K15+K~16 0.1% by weight D1 Brown-orange
-
E1+E10a K17 0.3% by weight D2 Flat red
E1+E11a K18 0.1% by weight D3 Hair brown
E1 K3 0.1 % by weight D4 + Copper
0.1 %
by weight D5
E1 K3 0.1 % by weight D6 + Tomato red
0.1 %
by weight D7
E1 K9 0.1 % by weight D8 + Lacquer red
0.1 %
by weight D9
a 0.375 mmole
