U.S. patent application number 14/110567 was filed with the patent office on 2014-04-10 for hair treatment method.
This patent application is currently assigned to L'OREAL. The applicant listed for this patent is Maryse Chaisy, Stefania Nuzzo, Fabrice Osolin, Gabin Vic. Invention is credited to Maryse Chaisy, Stefania Nuzzo, Fabrice Osolin, Gabin Vic.
Application Number | 20140096786 14/110567 |
Document ID | / |
Family ID | 44549570 |
Filed Date | 2014-04-10 |
United States Patent
Application |
20140096786 |
Kind Code |
A1 |
Nuzzo; Stefania ; et
al. |
April 10, 2014 |
HAIR TREATMENT METHOD
Abstract
The present invention provides a method of treating hair, the
method comprising the following steps: applying a composition to
the hair, the composition comprising one or more active ingredients
selected from the following: hair conditioning agents; reducing
agents; organic or inorganic bases; hair dyes; abrasive solid
particles; and moisturizing agents; and combing the hair using a
motor-driven combing device (10) comprising spikes that are driven
in an oscillating motion.
Inventors: |
Nuzzo; Stefania; (Paris,
FR) ; Vic; Gabin; (Semoy, FR) ; Osolin;
Fabrice; (Fanconville, FR) ; Chaisy; Maryse;
(Fresneaux Montchevreuil, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Nuzzo; Stefania
Vic; Gabin
Osolin; Fabrice
Chaisy; Maryse |
Paris
Semoy
Fanconville
Fresneaux Montchevreuil |
|
FR
FR
FR
FR |
|
|
Assignee: |
L'OREAL
Paris
FR
|
Family ID: |
44549570 |
Appl. No.: |
14/110567 |
Filed: |
April 5, 2012 |
PCT Filed: |
April 5, 2012 |
PCT NO: |
PCT/IB2012/051692 |
371 Date: |
December 18, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61476785 |
Apr 19, 2011 |
|
|
|
Current U.S.
Class: |
132/207 ;
132/202; 132/208 |
Current CPC
Class: |
A45D 7/00 20130101; A46B
5/0029 20130101; A61H 2201/1685 20130101; A61H 7/005 20130101; A61Q
5/06 20130101; A45D 7/04 20130101; A45D 2019/0033 20130101; A61K
8/416 20130101; A46B 13/02 20130101; A61H 2205/021 20130101; A46B
13/023 20130101; A61H 2201/1463 20130101; A46B 9/023 20130101; A46B
2200/102 20130101; A45D 19/02 20130101; A45D 2019/0041 20130101;
A45D 24/007 20130101; A46B 13/04 20130101; A61H 2201/149 20130101;
A61K 2800/87 20130101; A61K 8/891 20130101; A61H 2201/1215
20130101 |
Class at
Publication: |
132/207 ;
132/202; 132/208 |
International
Class: |
A45D 7/04 20060101
A45D007/04; A45D 24/00 20060101 A45D024/00; A46B 13/02 20060101
A46B013/02; A45D 19/02 20060101 A45D019/02 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 8, 2011 |
FR |
11 53108 |
Claims
1. A method for treating hair, the method comprising: applying a
composition to the hair, combing the hair using a motor-driven
combing device, wherein the composition comprises at least one
active ingredient selected from the group consisting of a hair
conditioning agent, a reducing agent, an organic or inorganic base,
a hair dye, an abrasive solid particle, and a moisturizing agent,
and the motor-driven combing device comprises a flexible diaphragm
carrying spikes in contact with the hair, and a drive mechanism
enabling the flexible diaphragm to be deformed periodically to
generate an oscillating movement of the spikes.
2. The method according to claim 1, wherein the hair is combed by
the motor-driven device after applying some of the composition to
the hair.
3. The method according to claim 1, wherein the hair is combed by
the motor-driven device before applying some of the composition to
the hair.
4. The method according to claim 1, wherein a frequency of
oscillation of the flexible diaphragm is from 0.5 Hz to 200 Hz.
5. The method according to claim 1, wherein an envelope surface
defined by free ends of the spikes is concave towards scalp with a
radius of curvature that varies with deformations of the flexible
diaphragm.
6. The method according to claim 1, wherein a travel axis of the
flexible diaphragm is perpendicular to scalp at least while combing
base of hair.
7. The method according to claim 1, wherein the spikes are made
from a thermoplastic material.
8. The method according to claim 1, wherein the composition
comprises at least one hair dye selected from the group consisting
of a synthetic direct dye, a natural dye, and an oxidation dye
precursor.
9. The method according to claim 1, wherein the composition
comprises at least one reducing agent selected from the group
consisting of phosphine, an alkaline sulfite, an alkaline
bisulfite, and a thiol.
10. The method according to claim 1, wherein the composition
comprises at least one organic or inorganic base selected from the
group consisting of an alkali or alkaline-earth hydroxide, a
transition metal, and an organic hydroxide.
11. The method according to claim 1, wherein the composition
comprises at least one hair conditioning agent selected from the
group consisting of a non-silicone cationic polymer, a non-silicone
cationic surfactant, a silicone, a linear or branched C8-C30
hydrocarbon, a linear or branched C8-C30 fatty alcohol, an ester of
a C8-C30 fatty acid and a C1-C30 mono-alcohol or polyol, a
ceramide, and a ceramide analog.
12. The method according to claim 1, wherein the composition
comprises at least one abrasive solid particle selected from the
group consisting of a natural material and a synthetic
material.
13. The method according to claim 1, wherein the composition
comprises at least one moisturizing agent selected from the group
consisting of a urea, a urea derivative, and a polyol.
14. The method according to claim 1, wherein said combing lasts for
a period of from 1 minute to 5 minutes.
15. The method according to claim 1, wherein the active ingredient
is more than 0.001% by weight relative to a total composition
weight, the active ingredient is applied alone or with other
ingredients, and when the active ingredient is applied with other
ingredients, the active ingredient optionally is up to 50% of the
total composition weight.
16. The method according to claim 1, wherein the composition
comprises an abrasive solid particle which is a natural material of
mineral or vegetable origin.
Description
[0001] The present invention relates to methods, devices and kits
for treating hair.
[0002] Tools for cleaning or massaging the hair are known from U.S.
Pat. No. 6,283,930 B, JP 2002-363039 A, JP 2005-046190 A, CN 2010
44658 Y and JP 11070019 A.
[0003] European application EP 1 825 842 A1 describes a massage
device for massaging the scalp when washing the hair, for example,
and envisages using it at the same time as shampoo is used.
[0004] The application US 2009/0182249 A1 discloses a device for
massaging the scalp, comprising a reservoir that can accommodate a
liquid such as a shampoo or a lotion for stimulating hair growth.
Various devices for massaging the scalp are also disclosed in the
publications EP 1 972 317 A1, EP 1 964 537 A1, and EP 2 080 500
A1.
[0005] There is a need for a method and for a treatment kit that
can be used to improve the efficacy of the active ingredients in
hair treatments.
[0006] In first exemplary embodiments the invention provides a
cosmetic hair treatment method comprising the steps consisting in:
[0007] applying a composition to the hair, the composition
comprising one or more active ingredients selected from the
following: [0008] hair conditioning agents; [0009] reducing agents;
[0010] organic or inorganic bases; [0011] hair dyes; [0012]
abrasive solid particles; and [0013] moisturizing agents; and
[0014] combing the hair using a motor-driven combing device
comprising spikes that are driven in an oscillating motion.
[0015] Hair combing using a motor-driven device can be carried out
after applying the composition of the invention to the hair,
preferably in the presence of the composition on the hair.
[0016] Hair combing using a motor-driven device may be carried out
before applying the composition of the invention to the hair, in
particular after wetting the hair or after applying a composition
not including any active ingredient of the invention. By way of
example, combing may be carried out less than 60 minutes before
applying the composition containing the active ingredient of the
invention.
[0017] Applying the method to frizzy or curly hair in association
with the composition containing the active ingredient results in a
very distinct reduction in volume and density, in better
disentangling, and in a smoother feel.
[0018] Preferably, the combing device is characterized in that it
includes a flexible diaphragm carrying spikes and a drive mechanism
that enables the diaphragm to deform periodically in order to
generate movement of the spikes.
[0019] The drive mechanism preferably includes a connecting rod
that is driven in oscillating motion, which connecting rod is
connected at one end to a member that is driven in rotation by an
electric motor and is connected directly or indirectly at its other
end to the flexible diaphragm, in particular in a central region
thereof.
[0020] The frequency of oscillation of the diaphragm preferably
lies in the range 0.5 Hz [Hertz] to 200 Hz, better preferably in
the range 1 Hz to 20 Hz, the limits of the ranges being included in
the ranges.
[0021] The envelope surface defined by the free ends of the spikes
may be a surface that is concave towards the scalp, with a radius
of curvature that varies as a function of the deformations of the
diaphragm.
[0022] During oscillation of the diaphragm, at least some of the
spikes rub against the hair. Performance is improved by rubbing
these spikes on the hair in combination with using the composition.
The invention enables a superior effect to be achieved than that
obtained manually. The travel axis of the flexible diaphragm, i.e.
the axis of the oscillating movement, may be substantially
perpendicular to the scalp during combing, at least while combing
the base of hair.
[0023] Preferably, the spikes are made out of a thermoplastic
material.
[0024] In other exemplary embodiments the invention provides a
cosmetic hair treatment method comprising the steps consisting in:
[0025] applying a composition to the hair, the composition
comprising one or more active ingredients selected from the
following: [0026] hair conditioning agents; [0027] reducing agents;
[0028] organic or inorganic bases; [0029] hair dyes; [0030]
abrasive solid particles; and [0031] moisturizing agents; and
[0032] combing the hair for a period of 1 minute to 5 minutes using
a motor-driven combing device comprising spikes that are driven in
an oscillating motion.
[0033] In other exemplary embodiments the invention also provides a
motor-driven combing device for carrying out one of the above
methods.
[0034] The invention also provides a motor-driven combing device
comprising: a flexible diaphragm carrying spikes adapted to come
into contact with the hair; a drive mechanism enabling the
diaphragm to deform periodically in order to generate movement of
the spikes in contact with the hair; and a reservoir containing a
composition for application, in the form of a pre-filled removable
cartridge.
Active Ingredients
[0035] The composition of the invention applied to the hair may
contain at least one of the following active ingredients.
[0036] The active ingredient or ingredients may be applied alone or
in combination with other ingredients. When applied in combination,
the active ingredient may represent up to 50% by weight of the
total composition weight, preferably up to 20% by weight of the
total composition weight.
[0037] The active ingredient or ingredients may represent more than
0.001%, preferably more than 0.1%, more preferably more than 0.2%;
and more particularly more than 0.5% by weight relative to the
total composition weight.
Hair Dyes
[0038] The term "hair dye" as used in the present invention means
synthetic direct dyes, natural dyes, and precursors of oxidation
dyes.
[0039] These hair dyes may be non-ionic or ionic, in particular
cationic or anionic.
[0040] The precursor or precursors of the oxidation dyes present in
the composition of the present invention may be selected from
oxidation bases and coupling agents in conventional use in
oxidation dyeing.
[0041] The oxidation base or bases may be selected from
para-phenylenediamines, bis-phenylalkylenediamines,
para-aminophenols, bis-para-aminophenols, ortho-aminophenols,
ortho-phenylenediamines, heterocyclic bases, and their addition
salts.
[0042] Examples of para-phenylenediamines that may be mentioned are
para-phenylenediamine, para-toluenediamine, 2-chloro
para-phenylenediamine, 2,3-dimethyl para-phenylenediamine,
2,6-dimethyl para-phenylenediamine, 2,6-diethyl
para-phenylenediamine, 2,5-dimethyl para-phenylenediamine,
N,N-dimethyl para-phenylenediamine, N,N-diethyl
para-phenylenediamine, N,N-dipropyl para-phenylenediamine, 4-amino
N,N-diethyl 3-methyl aniline, N,N-bis-(.beta.-hydroxyethyl)
para-phenylenediamine, 4-N,N-bis-(.beta.-hydroxyethyl)amino
2-methyl aniline, 4-N,N-bis-(.beta.-hydroxyethyl)amino 2-chloro
aniline, 2-.beta.-hydroxyethyl para-phenylenediamine, 2-fluoro
para-phenylenediamine, 2-isopropyl para-phenylenediamine,
N-(.beta.-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl
para-phenylenediamine, N,N-dimethyl 3-methyl para-phenylenediamine,
N,N-(ethyl, .beta.-hydroxyethyl) para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl) para-phenylenediamine,
N-(4'-aminophenyl) para-phenylenediamine, N-phenyl
para-phenylenediamine, 2-.beta.-hydroxyethyloxy
para-phenylenediamine, 2-.beta.-acetylaminoethyloxy
para-phenylenediamine, N-(.beta.-methoxyethyl)
para-phenylene-diamine, 4-aminophenyl pyrrolidine, 2-thienyl
para-phenylenediamine, 2-.beta.-hydroxyethylamino 5-amino toluene,
3-hydroxy 1-(4'-aminophenyl)pyrrolidine, and their addition
salts.
[0043] Particularly preferred examples of the above-mentioned
para-phenylenediamines are para-phenylenediamine,
para-toluenediamine, 2-isopropyl para-phenylenediamine,
2-.beta.-hydroxyethyl para-phenylenediamine,
2-.beta.-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl
para-phenylenediamine, 2,6-diethyl para-phenylenediamine,
2,3-dimethyl para-phenylenediamine, N,N-bis-(.beta.-hydroxyethyl)
para-phenylenediamine, 2-chloro para-phenylenediamine,
2-.beta.-acetylaminoethyloxy para-phenylenediamine, and their
addition salts.
[0044] Examples of bis-phenylalkylenediamines that may be mentioned
are N,N'-bis-(.beta.-hydroxyethyl) N,N'-bis-(4'-aminophenyl)
1,3-diamino propanol, N,N'-bis-(.beta.-hydroxyethyl)
N,N'-bis-(4'-aminophenyl) ethylenediamine,
N,N'-bis-(4-aminophenyl)tetramethylenediamine,
N,N'-bis-(.beta.-hydroxyethyl)
N,N'-bis-(4-aminophenyl)tetramethylenediamine,
N,N'-bis-(4-methyl-aminophenyl)tetramethylenediamine,
N,N'-bis-(ethyl) N,N'-bis-(4'-amino, 3'-methylphenyl)
ethylenediamine, 1,8-bis-(2,5-diamino phenoxy)-3,6-dioxaoctane, and
their addition salts.
[0045] More particular examples of para-aminophenols that may be
mentioned are para-aminophenol, 4-amino 3-methyl phenol, 4-amino
3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl
phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl
phenol, 4-amino 2-aminomethyl phenol, 4-amino
2-(.beta.-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro
phenol, and their addition salts.
[0046] Examples of ortho-aminophenols that may be mentioned are
2-aminophenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol,
5-acetamido 2-aminophenol, and their addition salts.
[0047] Examples of heterocyclic bases that may be mentioned are
pyridine derivatives, pyrimidine derivatives and pyrazolic
derivatives.
[0048] Examples of pyridine derivatives that may be mentioned are
the compounds described, for example, in patents GB 1 026 978 and
GB 1 153 196, such as 2,5-diamino pyridine,
2-(4-methoxyphenyl)amino 3-amino pyridine, 2,3-diamino 6-methoxy
pyridine, 2-(.beta.-methoxyethyl)amino 3-amino 6-methoxy pyridine,
3,4-diamino pyridine, and their addition salts.
[0049] Other pyridinic oxidation bases that may be used in the
present invention are 3-amino pyrazolo-[1,5-a]-pyridine oxidation
bases, or their addition salts, as described in patent application
FR 2 801 308, for example. Examples that may be mentioned are
pyrazolo[1,5-a]pyridin-3-ylamine; 2-acetylamino
pyrazolo-[1,5-a]pyridin-3-ylamine;
2-morpholin-4-yl-pyrazolo[1,5-a]pyridin-3-ylamine;
3-amino-pyrazolo[1,5-a]pyridin-2-carboxylic acid;
2-methoxy-pyrazolo[1,5-a]pyridine-3-ylamino;
(3-amino-pyrazolo[1,5-a]pyridine-7-yl)-methanol;
2-(3-amino-pyrazolo[1,5-a]pyridine-5-yl)-ethanol;
2-(3-amino-pyrazolo[1,5-a]pyridine-7-yl)-ethanol;
(3-amino-pyrazolo[1,5-a]pyridine-2-yl)-methanol;
3,6-diamino-pyrazolo[1,5-a]pyridine;
3,4-diamino-pyrazolo[1,5-a]pyridine;
pyrazolo[1,5-a]pyridine-3,7-diamine;
7-morpholin-4-yl-pyrazolo[1,5-a]pyridin-3-ylamine;
pyrazolo[1,5-a]pyridine-3,5-diamine;
5-morpholin-4-yl-pyrazolo[1,5-a]pyridin-3-ylamine;
2-[(3-amino-pyrazolo[1,5-a]pyridin-5-yl)-(2-hydroxyethyl)-amino]-ethanol;
2-[(3-amino-pyrazolo[1,5-a]pyridin-7-yl)-(2-hydroxyethyl)-amino]-ethanol;
3-amino-pyrazolo[1,5-a]pyridine-5-ol;
3-amino-pyrazolo[1,5-a]pyridine-4-ol;
3-amino-pyrazolo[1,5-a]pyridine-6-ol;
3-amino-pyrazolo[1,5-a]pyridine-7-ol; as well as their addition
salts.
[0050] Examples of pyrimidine derivatives that may be mentioned are
the compounds described, for example, in patents DE 23 59 399; JP
88-169571; JP 05-63124; EP 0 770 375 or patent application WO
96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy
2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine,
2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and
pyrazolo-pyrimidine derivatives such as those mentioned in patent
application FR-A-2 750 048; in which some that may be mentioned are
pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; 2,5-dimethyl
pyrazolo-[1,5-a]-pyrimidine-3,7-diamine;
pyrazolo-[1,5-a]-pyrimidine-3,5-diamine; 2,7-dimethyl
pyrazolo-[1,5-a]-pyrimidine-3,5-diamine; 3-amino
pyrazolo-[1,5-a]-pyrimidin-7-ol; 3-amino
pyrazolo-[1,5-a]-pyrimidin-5-ol; 2-(3-amino
pyrazolo-[1,5-a]-pyrimidin-7-ylamino)-ethanol, 2-(7-amino
pyrazolo-[1,5-a]-pyrimidin-3-ylamino)-ethanol,
2-[(3-amino-pyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethan-
ol,
2-[(7-amino-pyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-et-
hanol, 5,6-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine,
2,6-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine,
2,5,N7,N7-tetramethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine,
3-amino-5-methyl-7-imidazolylpropylamino
pyrazolo-[1,5-a]-pyrimidine, and their addition salts, and their
tautomeric forms when a tautomeric equilibrium exists.
[0051] Examples of pyrazolic derivatives that may be mentioned are
the compounds described in patents DE 38 43 892, DE 41 33 957 and
patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE
195 43 988, such as 4,5-diamino 1-(.beta.-hydroxyethyl) pyrazole,
4,5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole, 4,5-diamino
1-(4'-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole,
4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl
3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole,
1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl
1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole,
4,5-diamino 1-(.beta.-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino
1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-(4'-methoxyphenyl)
pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino
3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl
1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole,
4-amino 5-(2'-aminoethyl)amino 1,3-dimethyl pyrazole,
3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole,
3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino
4-(.beta.-hydroxyethyl)amino 1-methyl pyrazole,
2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, and
their addition salts.
[0052] The coupling agent or agents present in the composition of
the present invention may be selected from meta-phenylenediamines,
meta-aminophenols, meta-diphenols, naphthalenic coupling agents,
heterocyclic coupling agents, and their addition salts.
[0053] Examples that may be mentioned are 3-aminophenol, 2-methyl
5-aminophenol, 2-methyl 5-(.beta.-hydroxyethylamino) phenol,
2-chloro 6-methyl 3-aminophenol, 1,3-dihydroxy benzene,
1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene,
2,4-diamino 1-(.beta.-hydroxyethyloxy) benzene, 2-amino
4-(.beta.-hydroxyethylamino) 1-methoxybenzene, 1,3-diaminobenzene,
1,3-bis-(2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido
1-dimethylaminobenzene, sesamol,
1-.beta.-hydroxyethylamino-3,4-methylenedioxybenzene,
.alpha.-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy
indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine,
6-hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxy pyridine,
1-N-(.beta.-hydroxyethyl)amino-3,4-methylene dioxybenzene,
2,6-bis-(.beta.-hydroxyethylamino) toluene, and their addition
salts.
[0054] In general, addition salts of oxidation bases and coupling
agents that may be used in the context of the invention are in
particular selected from addition salts with an acid such as
hydrochlorides, hydrobromides, sulfates, citrates, succinates,
tartrates, lactates, (C.sub.1-C.sub.4)alkyl sulfonates, and in
particular methylsulfonates, tosylates, benzenesulfonates,
phosphates, and acetates, and addition salts with a base such as
sodium hydroxide, potassium hydroxide, ammonia, amines, or
alkanolamines.
[0055] The term "natural dyes" means any dye or dye precursor that
occurs naturally and that is produced either by extraction (and
possibly purification) from a plant matrix, or by chemical
synthesis.
[0056] In contrast, the term "synthetic dyes" means any dye that
does not occur naturally.
[0057] Examples of suitable synthetic direct dyes that may be
mentioned are azo direct dyes; methine dyes; carbonyl dyes; azine
dyes; nitro(hetero)aryl dyes; tri-(hetero)aryl methane dyes; used
alone or as a mixture.
[0058] More particularly, azo dyes include an --N.dbd.N-- function
in which both nitrogen atoms are not simultaneously engaged in a
cycle. However, it is also possible for one of the two nitrogen
atoms of the --N.dbd.N-- concatenation to be engaged in a
cycle.
[0059] Dyes of the methine family are more particularly compounds
comprising at least one concatenation selected from >C.dbd.C<
and --N.dbd.C< in which both atoms are not simultaneously
engaged in one cycle. However, it should be pointed out that one of
the atoms of the concatenations, nitrogen or carbon, may be engaged
in a cycle. More particularly, dyes of this family derive from
compounds of the true methane type (comprising one or more of the
above-mentioned --C.dbd.C-- concatenations); of the azomethine type
(including at least one or more --C.dbd.N-- concatenations) with,
for example, azacarbocyanins and their isomers, or
diazacarbocyanins and their isomers, tetraazacarbocyanins; of the
mono- and di-arylmethane type; indoamines (or diphenylamines);
indophenols; indoanilines.
[0060] Examples of dyes of the carbonyl family that may be
mentioned are dyes selected from acridone, benzoquinone,
anthraquinone, naphthoquinone, benzanthrone, anthranthrone,
pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone,
idanthrone, flavone, (iso)violanthrone, isoindolinone,
benzimidazolone, isoquinolinone, anthrapyridone,
pyrazoloquinazolone, perinone, quinacridone, quinophthalone,
indigoid, thioindigo, naphthalimide, anthrapyrimidine,
diketopyrrolopyrrole, and coumarin.
[0061] Particular examples of dyes of the azine family that may be
mentioned are azine, xanthene, thioxanthene, fluorindine, acridine,
(di)oxazine, (di)thiazine, and pyronine.
[0062] More particular nitro (hetero)aromatic dyes are nitrobenzene
direct dyes or nitropyridine dyes.
[0063] Regarding porphyrin or phthalocyanin dyes, it is possible to
use cationic or non-cationic compounds, optionally including one or
more metals or metallic ions such as alkali and alkaline-earth
metals, zinc, or silicon, for example.
[0064] Particularly suitable examples of direct dyes that may be
mentioned are nitrated dyes of the benzene series; azo direct dyes;
methine dyes; azomethine dyes, more particularly with
diazacarbocyanins and their isomers and tetraazacarbocyanins
(tetraazapentamethines); quinone direct dyes and in particular
anthraquinone, naphthoquinone or benzoquinone dyes; azine direct
dyes; xanthene dyes; triarylmethane dyes; indoamine dyes; indigoid
dyes; and phthalocyanins and porphyrins; used alone or as a
mixture.
[0065] Preferably, the direct dyes are selected from nitro dyes of
the benzene series; azo dyes; azomethines with diazacarbocyanins
and their isomers, tetraazacarbocyanins (tetraazapentamethines);
anthraquinone direct dyes; and triarylmethane direct dyes; used
alone or as a mixture.
[0066] Still more preferably, said direct dyes are selected from
nitro dyes of the benzene series; azo direct dyes; azomethines with
diazacarbocyanins and their isomers, and tetraazacarbocyanins
(tetraazapentamethines); alone or as a mixture.
[0067] Non-limiting examples of nitrobenzene direct dyes that may
be used in accordance with the invention that may be mentioned are
the following compounds: [0068] 1,4-diamino-2-nitrobenzene; [0069]
1-amino-2 nitro-4-.beta.-hydroxyethylaminobenzene; [0070] 1-amino-2
nitro-4-bis(.beta.-hydroxyethyl)-aminobenzene; [0071]
1,4-bis(.beta.-hydroxyethylamino)-2-nitrobenzene; [0072]
1-.beta.-hydroxyethylamino-2-nitro-4-bis-(.beta.-hydroxyethylamino)-benze-
ne; [0073] 1-.beta.-hydroxyethylamino-2-nitro-4-aminobenzene;
[0074]
1-.beta.-hydroxyethylamino-2-nitro-4-(ethyl)(.beta.-hydroxyethyl)-aminobe-
nzene; [0075]
1-amino-3-methyl-4-.beta.-hydroxyethylamino-6-nitrobenzene; [0076]
1-amino-2-nitro-4-.beta.-hydroxyethylamino-5-chlorobenzene; [0077]
1,2-diamino-4-nitrobenzene; [0078]
1-amino-2-.beta.-hydroxyethylamino-5-nitrobenzene; [0079]
1,2-bis-(.beta.-hydroxyethylamino)-4-nitrobenzene; [0080]
1-amino-2-tris-(hydroxymethyl)-methylamino-5-nitrobenzene; [0081]
1-hydroxy-2-amino-5-nitrobenzene; [0082]
1-hydroxy-2-amino-4-nitrobenzene; [0083]
1-hydroxy-3-nitro-4-aminobenzene; [0084]
1-hydroxy-2-amino-4,6-dinitrobenzene; [0085]
1-.beta.-hydroxyethyloxy-2-.beta.-hydroxyethylamino-5-nitrobenzene;
[0086] 1-methoxy-2-.beta.-hydroxyethylamino-5-nitrobenzene; [0087]
1-.beta.-hydroxyethyloxy-3-methylamino-4-nitrobenzene; [0088]
1-.beta..quadrature..gamma.-dihydroxypropyloxy-3-methylamino-4-nitrobenze-
ne; [0089]
1-.beta.-hydroxyethylamino-4-.beta.,.gamma.-dihydroxypropyloxy--
2-nitrobenzene; [0090]
1-.beta..quadrature..gamma.-dihydroxypropylamino-4-trifluoromethyl-2-nitr-
obenzene; [0091]
1-.beta.-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene; [0092]
1-.beta.-hydroxyethylamino-3-methyl-2-nitrobenzene; [0093]
1-.beta.-aminoethylamino-5-methoxy-2-nitrobenzene; [0094]
1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene; [0095]
1-hydroxy-2-chloro-6-amino-4-nitrobenzene; [0096]
1-hydroxy-6-bis-(.beta.-hydroxyethyl)-amino-3-nitrobenzene; [0097]
1-.beta.-hydroxyethylamino-2-nitrobenzene; and [0098]
1-hydroxy-4-.beta.-hydroxyethylamino-3-nitrobenzene.
[0099] Examples of azo, azomethine, methine direct dyes that may be
used in accordance with the invention and that may be mentioned are
the cationic dyes described in patent applications WO 95/15144, WO
95/01772, and EP 7 149 54; FR 2 189 006, FR 2 285 851, FR 2 140
205, EP 1 378 544, and EP 1 674 073.
[0100] As an example, the synthetic direct dye or dyes may be
selected from cationic monochromophoric direct dyes of the azo;
methine; azomethine type with diazacarbocyanins and their isomers,
tetraazacarbocyanins; and anthraquinones; used alone or as a
mixture.
[0101] Thus, cationic direct dyes with the following formulae may
in particular be mentioned:
##STR00001##
in which: [0102] D represents a nitrogen atom or the group --CH;
[0103] R.sub.1 and R.sub.2, which may be identical or different,
represent a hydrogen atom; a C.sub.1-C.sub.4 alkyl radical possibly
substituted with a --CN, --OH or --NH.sub.2 radical or form a
heterocycle, optionally oxygen-containing or nitrogen-containing,
with a carbon atom of the benzene ring, possibly substituted with
one or more C.sub.1-C.sub.4 alkyl radicals; or a 4'-aminophenyl
radical; [0104] R.sub.3 and R'.sub.3, which may be identical or
different, represent a hydrogen atom or halogen atom selected from
chlorine, bromine, iodine and fluorine, or a cyano, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, or acetyloxy radical; [0105] X-
represents an anion, preferably selected from the chloride, methyl
sulfate, and acetate; [0106] A represents a group selected from the
following structures:
##STR00002##
[0106] in which R.sub.4 represents a C.sub.1-C.sub.4 alkyl radical,
possibly substituted with a hydroxyl radical;
##STR00003##
in which: [0107] R.sub.5 represents a hydrogen atom, a
C.sub.1-C.sub.4 alkoxy radical, a halogen atom such as bromine,
chlorine, iodine, or fluorine; [0108] R.sub.6 represents a hydrogen
atom, a C.sub.1-C.sub.4 alkyl radical or forms, with a carbon atom
of the benzene ring, a heterocycle that optionally contains oxygen
and/or is substituted with one or more C.sub.1-C.sub.4 alkyl
groups; [0109] R.sub.7 represents a hydrogen atom or halogen atom
such as bromine, chlorine, iodine, or fluorine; [0110] D.sub.1 and
D.sub.2, which may be identical or different, represent a nitrogen
atom or the group --CH; [0111] m=0 or 1; [0112] X.sup.- represents
a cosmetically acceptable anion preferably selected from chloride,
methyl sulfate and acetate; [0113] E represents a group selected
from the following structures:
##STR00004##
[0113] in which R' represents a C.sub.1-C.sub.4 alkyl radical;
[0114] when m=0 and D.sub.1 represents a nitrogen atom, then E may
also designate a group with the following structure:
##STR00005##
[0114] in which R' represents a C.sub.1-C.sub.4 alkyl radical.
[0115] More particular examples of the above-mentioned compounds
are as follows:
##STR00006##
[0116] X.sup.- representing a cosmetically acceptable anion or
mixture of anions.
[0117] Other dyes that may be used in accordance with the invention
that may also be mentioned from azo direct dyes include the
following dyes, described in the COLOR INDEX INTERNATIONAL 3rd
edition: [0118] Disperse Red 17; [0119] Disperse Red 13; [0120]
Basic Red 22; [0121] Basic Red 76; [0122] Basic Yellow 57; [0123]
Basic Brown 16; [0124] Basic Brown 17; [0125] Disperse Green 9;
[0126] Disperse Black 9; [0127] Solvent Black 3; [0128] Disperse
Blue 148; [0129] Disperse Violet 63; and [0130] Solvent Orange 7.
1-(4'-aminodiphenylazo)-2-methyl-4
bis-(.beta.-hydroxyethyl)aminobenzene (INCI name: HC Yellow 7) may
also be mentioned.
[0131] Examples of direct quinone dyes that may be mentioned are
the following dyes: [0132] Disperse Red 15; [0133] Solvent Violet
13; [0134] Solvent Blue 14; [0135] Disperse Violet 1; [0136]
Disperse Violet 4; [0137] Disperse Blue 1; [0138] Disperse Violet
8; [0139] Disperse Blue 3; [0140] Disperse Red 11; [0141] Disperse
Blue 7; [0142] Disperse Blue 14; [0143] Basic Blue 22; [0144]
Disperse Violet 15; [0145] Disperse Blue 377; [0146] Disperse Blue
60; and [0147] Basic Blue 99; as well as the following compounds:
[0148] 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone;
[0149] 1-aminopropylamino-4-methylaminoanthraquinone; [0150]
1-aminopropylaminoanthraquinone; [0151]
5-.beta.-hydroxyethyl-1,4-diaminoanthraquinone; [0152]
2-aminoethylaminoanthraquinone; and [0153]
1,4-bis-(.beta..gamma.-dihydroxypropylamino)-anthraquinone.
[0154] The coumarin Disperse Yellow 82 may also be mentioned.
[0155] Examples of azine dyes that may be mentioned are the
following compounds: [0156] Basic Blue 17; [0157] Basic Red 2; and
[0158] Solvent Orange 15.
[0159] Examples of triarylmethane dyes that may be used in
accordance with the invention and that may be mentioned are the
following compounds: [0160] Basic Green 1; [0161] Basic Violet 3;
[0162] Basic Violet 14; [0163] Basic Blue 7; and [0164] Basic Blue
26.
[0165] Examples of indoamine dyes that may be used in accordance
with the invention and that may be mentioned are the following
compounds: [0166]
2-.beta.-hydroxyethylamino-5-[bis-(.beta.-4'-hydroxyethyl)amino]anilino-1-
,4-benzoquinone; [0167]
2-.beta.-hydroxyethylamino-5-(2'-methoxy-4'-amino)anilino-1,4-benzoquinon-
e; [0168]
3-N(2'-chloro-4'-hydroxy)phenyl-acetylamino-6-methoxy-1,4-benzoq-
uinone imine; [0169]
3-N(3'-chloro-4'-methylamino)phenyl-ureido-6-methyl-1,4-benzoquinone
imine; and [0170]
3-[4'-N-(ethylcarbamylmethyl)-amino]-phenyl-ureido-6-methyl-1,4-benzoquin-
one imine.
[0171] Preferably, the direct cationic dyes are selected from
direct dyes of the following types: azo; methine; azomethine with
diazacarbocyanins and their isomers, tetraazacarbocyanins
(tetraazapentamethines); anthraquinone; used alone or as a
mixture.
[0172] Examples of direct anionic dyes that may in particular be
mentioned are those described in the COLOR INDEX INTERNATIONAL 3rd
edition listed under ACID and in particular: [0173] Disperse Red
17; [0174] Acid Yellow 9; [0175] Acid Black 1; [0176] Acid Yellow
36; [0177] Acid Orange 7; [0178] Acid Red 33; [0179] Acid Red 35;
[0180] Acid Yellow 23; [0181] Acid Orange 24; [0182] Acid Violet
43; [0183] Acid Blue 62; [0184] Acid Blue 9; [0185] Acid Violet 49;
and [0186] Acid Blue 7.
[0187] Particular natural dye or dyes that may be used to carry out
the invention are preferably selected from lawsone, juglone,
alizarin, purpurin, carminic acid, kermesic acid, laccaic acid,
purpurogallin, anthragallol, protocatechaldehyde, indigo, isatin,
curcumin, spinusolin, chlorophylls, chlorophyllins, orceins,
hematein, hematoxylin, brazilin, brazilein, carthame dyes (such as
carthamin, for example), flavonoids (with morin, apigenidin,
santal, for example), anthocyans (of the apigeninidin type),
carotenoids, tannins, sorghum, and cochineal carmine, or mixtures
thereof.
[0188] It is also possible to use extracts or decoctions containing
natural dyes, in particular henna-based extracts.
[0189] Preferably, the natural dye or dyes are selected from
lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid,
laccaic acid, purpurogallin, protocatechaldehyde, indigo, isatin,
curcumin, spinulosin, apigenidin, chlorophyllin, sorghum, orceins,
cochineal carmine, hematein, hematoxylin, braziline, and brazilein,
and mixtures thereof.
[0190] These dyes may optionally be used in the presence of
mordants (for example salts of zinc, manganese, aluminum, iron
etc.).
Reducing Agents
[0191] The composition may contain at least one reducing agent
capable of reducing disulfide bonds in the hair.
[0192] It is possible to use a reducing agent of the phosphine or
sulfite or alkaline bisulfite type. Advantageously, a thiol
reducing agent is used.
[0193] Preferably, the thiol or thiols used as reducing agents in
the reducing composition are selected from aminothiols such as
cysteine and its derivatives, such as N-acetylcysteine, cysteamine
and its derivatives, preferably its C.sub.1-C.sub.4 acylated
derivatives such as N-acetyl cysteamine and N-propionyl cysteamine,
and non-amino-containing thiols such as thiolactic acid and its
esters, such as glycerol monothiolactate, thioglycolic acid and its
esters, such as glycerol or glycol monothioglycolate, and
thioglycerol.
[0194] When the thiol has at least one carboxylic acid function, if
appropriate it is possible to use said thiol in the form of one or
more of its salts, such as alkali metal or ammonium salts. It is
thus possible to use thioglycolate ammonium as the thiol. If the
thiol has an amino group, it would be possible to use said thiol in
the form of one or more of its salts such as aminothiol halides.
Thus, the thiol used in the context of the present invention may be
L-cysteine hydrochloride.
[0195] Aminothiols that may be used in the reducing composition
used in accordance with the invention and that may also be
mentioned are N-mercapto-alkylamides of sugars, such as
N-(mercapto-2-ethyl)gluconamide, pantheteine,
N-(mercaptoalkyl).omega.-hydroxyalkylamides such as those described
in patent application EP-A-354 835 and N-mono- or
N,N-dialkylmercapto 4-butyramides such as those described in patent
application EP-A-368 763, aminomercaptoalkylamides such as those
described in patent application EP-A-432 000 and alkylaminomercapto
alkylamides such as those described in patent application EP-A-514
282. Examples of non-aminated thiols used in the invention that may
also be mentioned are 2-hydroxypropyl thioglycolate (2/3) and
2-hydroxy-1-methylethyl thioglycolate (67/33) described in patent
application FR-A-2 679 448, .beta.-mercaptopropionic acid and its
derivatives, and thiomalic acid.
[0196] It is possible to use a thiol-containing reducing agent, in
particular thioglycolic acid or cysteine.
Organic or Inorganic Bases
[0197] For straightening, it is also possible to use strong bases
such as alkali or alkaline-earth metal hydroxides, transition metal
hydroxides or organic hydroxides. By way of example, examples of
hydroxides that may be mentioned are sodium hydroxide, lithium
hydroxide, calcium hydroxide, magnesium hydroxide, barium
hydroxide, strontium hydroxide, manganese hydroxide, zinc
hydroxide, and guanidinium hydroxide. Preferred hydroxides are
sodium hydroxide, calcium hydroxide, lithium hydroxide and
guanidinium hydroxide.
Conditioning Agents
[0198] The conditioning agent may be selected from the group
comprising non-silicone cationic polymers, non-silicone cationic
surfactants, silicones, in particular organosiloxanes, linear or
branched C.sub.8-C.sub.30 hydrocarbons, linear or branched
C.sub.8-C.sub.30 fatty alcohols, esters of C.sub.8-C.sub.30 fatty
acids and C.sub.1-C.sub.30 monoalcohols or polyols including esters
of C.sub.8-C.sub.30 fatty acids and C.sub.8-C.sub.30 fatty
alcohols, esters of C.sub.1-C.sub.7 acids or dibasic acids and
C.sub.8-C.sub.30 fatty alcohols, ceramides or ceramide analogs, and
mixtures of these compounds.
[0199] The term "cationic non-silicone polymer" means a polymer
having no silicon atoms in its structure, charged positively when
it is contained in the composition of the invention. This polymer
may carry one or more permanent positive charges or contain one or
more cationizable functions in the composition of the
invention.
[0200] The cationic polymer or polymers that may be used as
conditioning agents of the present invention are preferably
selected from polymers comprising primary, secondary, tertiary,
and/or quaternary groups forming part of the polymer chain or
directly bonded thereto, and having a molecular weight (MW) in the
range 500 to approximately 5,000,000, preferably in the range 1000
to 3,000,000.
[0201] When the conditioning agent is a cationic polymer, it is
preferably selected from those containing motifs comprising
primary, secondary, tertiary, and/or quaternary amine groups that
may either form part of the main polymer chain or be carried by a
lateral substituent bonded directly thereto.
[0202] More particular examples of cationic polymers that may be
mentioned are polymers of the polyamine, polyaminoamide, and
quaternary polyammonium type. These are known products. They are
described, for example, in French patents numbers 2 505 348 and 2
542 997.
[0203] Some of these polymers that may be mentioned are:
[0204] (1) homopolymers or copolymers derived from acrylic or
methacrylic esters or amides and comprising at least one of the
motifs with the following formulae:
##STR00007##
in which: [0205] R.sub.3 and R.sub.4, which may be identical or
different, represent hydrogen or an alkyl group containing 1 to 6
carbon atoms, preferably methyl or ethyl; [0206] R.sub.5, which may
be identical or different, designate a hydrogen atom or a CH.sub.3
radical; [0207] A, which may be identical or different, represent a
linear or branched alkyl group containing 1 to 6 carbon atoms,
preferably 2 or 3 carbon atoms or a hydroxyalkyl group containing 1
to 4 carbon atoms; [0208] R.sub.6, R.sub.7, R.sub.8, which may be
identical or different, represent an alkyl group containing 1 to 18
carbon atoms or a benzyl radical, preferably an alkyl group
containing 1 to 6 carbon atoms; and [0209] X designates an anion
derived from an organic or inorganic acid such as a methosulfate
anion or a halide such as chloride or bromide.
[0210] The copolymers of family (1) may further contain one or more
motifs deriving from co-monomers that may be selected from the
family of acrylamides, methacrylamides, acrylamides, diacetone
acrylamides, and acrylamides and methacrylamides substituted on the
nitrogen with lower (C.sub.1-C.sub.4)alkyls, acrylic or methacrylic
acids or their esters, vinyllactams such as vinylpyrrolidone or
vinylcaprolactam, and vinyl esters.
[0211] Thus, copolymers of family (1) that may be mentioned
include: [0212] copolymers of acrylamide and dimethylaminoethyl
methacrylate quaternized with dimethyl sulfate or with a dimethyl
halide such as that sold under the trade name HERCOFLOC by the
supplier HERCULES; [0213] copolymers of acrylamide and
methacryloyloxyethyltrimethyl ammonium chloride described, for
example, in patent application EP-A-080 976 and sold under the
trade name BINA QUAT P 100 by the supplier CIBA GEIGY; [0214] the
copolymer of acrylamide and methacryloyloxyethyltrimethyl ammonium
methosulfate sold under the trade name RETEN by the supplier
HERCULES; [0215] quaternized or non-quaternized
vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate
copolymers such as the products sold under the trade name "GAFQUAT"
by the supplier ISP such as, for example, "GAFQUAT 734" or "GAFQUAT
755", or the products designated as "COPOLYMER 845, 958, and 937".
These polymers are described in detail in French patents 2 077 143
and 2 393 573; [0216] dimethyl amino ethyl
methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers such as
the product sold under the trade name GAFFIX VC 713 by the supplier
ISP; [0217] vinylpyrrolidone/methacrylamidopropyl dimethylamine
copolymers, in particular as sold under the trade name STYLEZE CC
10 by ISP. [0218] and vinylpyrrolidone/quaternized dimethylamino
propyl methacrylamide copolymers such as the product sold under the
trade name "GAFQUAT HS 100" by the supplier ISP; and [0219]
cross-linked polymers of
methacryloyloxy(C.sub.1-C.sub.4)alkyl(C.sub.1-C.sub.4)trialkyl
ammonium salts such as the polymers obtained by homopolymerization
of dimethylaminoethylmethacrylate quaternized by methyl chloride,
or by copolymerization of acrylamide with
dimethylaminoethylmethacrylate quaternized by methyl chloride, the
homo- or copolymerization being followed by cross-linking with a
compound containing an olefinically unsaturated bond, in particular
methylene bis-acrylamide. More particularly, an
acrylamide/methacryloyloxyethyl trimethylammonium chloride
cross-linked polymer (20/80 by weight) may be used in the form of a
dispersion containing 50% by weight of said copolymer in mineral
oil. This dispersion is sold under the name "SALCARE.RTM. SC 92" by
the supplier CIBA. It is also possible to use a cross-linked
homopolymer of methacryloyloxyethyl trimethylammonium chloride, for
example in dispersion in mineral oil or in a liquid ester. These
dispersions are provided under the names "SALCARE.RTM. SC 95" and
"SALCARE.RTM. SC 96" by the supplier CIBA;
[0220] (2) polymers constituted by piperazinyl motifs and divalent
alkylene or hydroxyalkylene radicals with straight or branched
chains, possibly interrupted by oxygen, sulfur or nitrogen atoms or
aromatic or heterocyclic cycles as well as the oxidation and/or
quaternization products of said polymers. Such polymers are in
particular described in French patents 2 162 025 and 2 280 361;
[0221] (3) polyaminoamides that are soluble in water prepared, in
particular, by polycondensation of an acid compound with a
polyamine; these polyaminoamides may be cross-linked with an
epihalohydrin, a diepoxide, a dianhydride, an unsaturated
dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a
bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or an
oligomer resulting from the reaction of a bifunctional compound
that is reactive towards a bis-halohydrin, a bis-azetidinium, a
bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a
diepoxide or a bis-unsaturated derivative; the cross-linking agent
is used in proportions of 0.025 to 0.35 moles per amine group of
the polyaminoamide; these polyaminoamides may be alkylated or, if
they comprise one or more tertiary amine functions, they may be
quaternized. Such polymers are in particular described in French
patents 2 252 840 and 2 368 508;
[0222] (4) derivatives of polyaminoamides resulting from
condensation of polyalkylene polyamines with polycarboxylic acids
followed by alkylation with functional agents. Examples that may be
mentioned are adipic acid-dialkylaminohydroxyalkyldialkylene
triamine polymers in which the alkyl radical contains 1 to 4 carbon
atoms and preferably designates methyl, ethyl or propyl. Such
polymers are described in particular in French patent 1 583
363;
[0223] More particular examples of these derivatives that may be
mentioned are adipic acid/dimethylamino-hydroxypropyl/diethylene
triamine polymers provided under the trade name "Cartaretine F, F4,
or F8" by the supplier Sandoz.
[0224] (5) polymers obtained by reacting a polyalkylene polyamine
comprising two primary amine groups and at least one secondary
amine group with a dicarboxylic acid selected from diglycolic acid
and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon
atoms. The molar ratio between the polyalkylene polyamine and the
dicarboxylic acid is in the range 0.8:1 to 1.4; the resulting
polyaminoamide is reacted with epichlorhydrin in a molar ratio of
epichlorhydrin to the second amine group of the polyaminoamide in
the range 0.5:1 to 1.8:1. Such polymers are described in particular
in American patents U.S. Pat. No. 3,227,615 and U.S. Pat. No.
2,961,347;
[0225] Polymers of this type are in particular sold under the trade
name "Hercosett 57" by the supplier Hercules Inc. or under the
trade name "PD 170" or "Delsette 101" by the supplier Hercules for
an adipic acid/epoxypropyl/diethylene-triamine copolymer.
[0226] (6) alkyl diallyl amine or dialkyl diallyl ammonium
cyclopolymers such as homopolymers or copolymers comprising motifs
with formulae (V) or (V) as the principal constituent of the
chain:
##STR00008##
in which formulae k and t equal 0 or 1, the sum k+t being equal to
1; R.sub.12 designates a hydrogen atom or a methyl radical;
R.sub.10 and R.sub.11, independently of each other, designate an
alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group in
which the alkyl group preferably contains 1 to 5 carbon atoms, a
lower (C.sub.1-C.sub.4)amidoalkyl group, or R.sub.10 and R.sub.11
may, together with the nitrogen atom to which they are attached,
designate heterocyclic groups such as piperidinyl or morpholinyl;
and Y-- is an anion such as bromide, chloride, acetate, borate,
citrate, tartrate, bisulfate, bisulfite, sulfate, or phosphate.
These polymers are in particular described in French patent 2 080
759 and in its certificate of addition 2 190 406; [0227] R.sub.10
and R.sub.11, independently of each other, preferably designate an
alkyl group containing 1 to 4 carbon atoms and more particularly 1
carbon atom;
[0228] More particular examples of polymers as defined above that
may be mentioned are the dimethyldiallyl ammonium chloride
homopolymer sold under the trade name "Merquat 100" by the supplier
NALCO (and its homologs with low mass average molecular weights)
and copolymers of diallyldimethylammonium chloride and acrylamide
sold under the trade name "MERQUAT 550".
[0229] (7) the quaternary diammonium polymer containing recurring
motifs with formula:
##STR00009##
in which formula (VII): [0230] R.sub.13, R.sub.14, R.sub.15, and
R.sub.16, which may be identical or different, represent aliphatic,
alicyclic, or arylaliphatic radicals containing 1 to 20 carbon
atoms or lower hydroxyalkylaliphatic radicals, or R.sub.13,
R.sub.14, R.sub.15 and R.sub.16, together or separately,
constitute, together with the nitrogen atoms to which they are
attached, heterocycles optionally containing a second heteroatom
other than nitrogen or R.sub.13, R.sub.14, R.sub.15 and R.sub.16
represent a linear or branched C.sub.1-C.sub.6 alkyl radical
substituted with a nitrile, ester, acyl, amide or
--CO--O--R.sub.17-D or --CO--NH--R.sub.17-D group where R.sub.17 is
an alkylene and D is a quaternary ammonium group; [0231] A.sub.1
and B.sub.1 represent polymethylene groups containing 2 to 20
carbon atoms that may be linear or branched, saturated or
unsaturated, and may contain, linked to or interposed in the main
chain, one or more aromatic rings, one or more oxygen or sulfur
atoms or sulfoxide, sulfone, disulfide, amino, alkylamino,
hydroxyl, quaternary ammonium, ureido, amide or ester groups; and
[0232] X.sup.- designates an anion derived from an organic or
inorganic acid; [0233] A.sub.1, R.sub.13, and R.sub.15 may, with
the two nitrogen atoms to which they are attached, form a
piperazine cycle; further, if A.sub.1 designates a linear or
branched, saturated or unsaturated alkylene or hydroxyalkylene
radical, B.sub.1 may also designate a group
(CH.sub.2).sub.n--CO-D-OC--(CH.sub.2).sub.p--; where n and p are
integers in the range approximately 2 to 20; and [0234] D
designates:
[0235] a) a glycol residue with formula: --O--Z--O--, where Z
designates a linear or branched hydrocarbon radical or a group
having one of the following formulae:
(CH.sub.2--CH.sub.2--O).sub.x--CH.sub.2--CH.sub.2--
[CH.sub.2--CH(CH.sub.3)--O].sub.y--CH.sub.2--CH(CH.sub.3)--
where x and y designate an integer in the range 1 to 4,
representing a predetermined, unique degree of polymerization or
any nucleic from 1 to 4 representing a mean degree of
polymerization;
[0236] b) a bis-secondary diamine residue such as a piperazine
derivative;
[0237] c) a bis-primary diamine residue with formula:
--NH--Y--NH--, where Y designates a linear or branched hydrocarbon
radical, or the bivalent radical
CH.sub.2--CH.sub.2--S--S--CH.sub.2--CH.sub.2--;
[0238] d) a ureylene group with formula: --NH--CO--NH--; and
[0239] X.sup.- is preferably an anion such as chloride or
bromide.
[0240] These polymers have a number average molecular mass that is
generally in the range 1000 to 100,000.
[0241] Polymers of this type are described in particular in French
patents 2 320 330, 2 270 846, 2 316 271, 2 336 434, and 2 413 907,
and in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547,
3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990,
3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945,
and 4,027,020.
[0242] More particularly, polymers constituted by recurring motifs
with the following formula may be used:
##STR00010##
in which R.sub.18, R.sub.19, R.sub.20 and R.sub.21, which may be
identical or different, designate an alkyl or hydroxyalkyl radical
containing approximately 1 to 4 carbon atoms, r and s are integers
in the range approximately 2 to 20 and, X.sup.- is an anion derived
from an organic or inorganic acid.
[0243] A particularly preferred compound with formula (VIII) is
that in which R.sub.18, R.sub.19, R.sub.20 and R.sub.21, represent
a methyl radical and r=3, s=6 and X.dbd.Cl, known as Hexadimethrine
chloride using the INCI nomenclature (CTFA).
[0244] (8) quaternary polyammonium polymers constituted by motifs
with formula (IX):
##STR00011##
in which formula: [0245] R.sub.22, R.sub.20, R.sub.24 and R.sub.25,
which may be identical or different, represent a hydrogen atom or a
methyl, ethyl, propyl, .beta.-hydroxyethyl, .beta.-hydroxypropyl or
--CH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH radical; where:
[0246] p is equal to 0 or to an integer in the range 1 to 6,
provided that R.sub.22, R.sub.20, R.sub.24, and R.sub.25 do not
simultaneously represent a hydrogen atom; [0247] t and u, which may
be identical or different, are integers in the range 1 to 6; [0248]
v is equal to 0 or an integer in the range 1 to 34; [0249] X.sup.-
designates an anion such as a halide; [0250] A designates a radical
of a dihalide or, preferably, represents
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--.
[0251] Such compounds are described in particular in patent
application EP-A-122 324.
[0252] Examples of the above that may be mentioned include the
products "Mirapol.RTM. A 15", "Mirapol.RTM. AD1", "Mirapol.RTM.
AZ1" and "Mirapol.RTM. 175" provided by the supplier Miranol;
[0253] (9) Quaternary vinylpyrrolidone and vinylimidazole polymers
such as the products provided under the trade names Luviquat.RTM.
FC 905, FC 550, and FC 370 by the supplier B.A.S.F, for
example;
[0254] (10) Cationic polysaccharides, in particular celluloses and
cationic galactomannan gums.
[0255] More particular examples of cationic polysaccharides that
may be mentioned are derivatives of cellulose ethers comprising
quaternary ammonium groups, cationic copolymers of cellulose or
cellulose derivatives grafted with a hydrosoluble quaternary
ammonium monomer and cationic galactomannan gums.
[0256] Derivatives of cellulose ethers comprising quaternary
ammonium groups have been described in French patent 1 492 597.
These polymers are also defined in the CTFA dictionary as
quaternary ammonium hydroxyethylcellulose compounds that have
reacted with an epoxide substituted with a trimethylammonium
group.
[0257] Cationic cellulose copolymers or cellulose derivatives
grafted with a hydrosoluble quaternary ammonium monomer are
described in particular in the patent U.S. Pat. No. 4,131,576, such
as hydroxyalkyl celluloses, for example hydroxymethyl-,
hydroxyethyl- or hydroxypropyl-celluloses grafted in particular
with a methacryloylethyl trimethylammonium salt,
methacrylamidopropyl trimethylammonium salt, or
dimethyl-diallylammonium salt.
[0258] Cationic galactomannan gums are described more particularly
in patents U.S. Pat. Nos. 3,589,578 and 4,031,307, in particular
guar gums containing cationic trialkylammonium groups. As an
example, guar gums modified by a salt (for example chloride) of
2,3-epoxypropyl trimethylammonium may be used.
[0259] Other cationic polymers that may be used in the context of
the invention are cationic proteins or cationic protein
hydrolysates, polyalkyleneimines, in particular polyethyleneimines,
polymers containing vinylpyridine or vinylpyridinium motifs,
condensates of polyamines and epichlorhydrin, quaternary
polyureylenes, and chitin derivatives.
[0260] Particular examples of cationic proteins or protein
hydrolysates are chemically modified polypeptides carrying
quaternary ammonium groups at the chain end or grafted thereto.
Their molecular mass may, for example, be from 1500 to 10,000, in
particular from approximately 2000 to 5000. Particular examples of
these compounds that may be mentioned are as follows:
[0261] Preferably, these polypeptides are of vegetable origin.
[0262] The following may in particular be mentioned: [0263]
hydrolysates of wheat, soya, or rice protein modified by
cocodimonium hydroxypropyl groups; [0264] hydrolysates of protein,
soya, jojoba, oats, or rice wheat modified by hydroxypropyl
trimonium groups; [0265] hydrolysates of wheat, soya, or jojoba
protein modified by laurdimonium hydroxypropyl groups; and [0266]
hydrolysates of jojoba, soya, or rice protein modified by
steardimonium hydroxypropyl groups.
[0267] Examples of these products that may be mentioned include the
products provided by the supplier COGNIS under the trade name
GLUADIN WQ, by the supplier CRODA under the trade names
HYDROTRITICUM WQ PE or CROQUAT SOYA.
[0268] Preferred examples of cationic polymers that could be used
in the context of the present invention are cationic cyclopolymers,
in particular homopolymers or copolymers of dimethyldiallylammonium
chloride, sold under the trade names "MERQUAT 100", "MERQUAT 550"
and "MERQUAT S" by the supplier NALCO, quaternary vinylpyrrolidone
and vinylimidazole polymers and cationic polysaccharides, and
mixtures thereof.
Non-Silicone Cationic Surfactants
[0269] The conditioning agent or agents that may be used in
accordance with the invention may be selected from non-silicone
cationic surfactants.
[0270] The term "non-silicone cationic surfactant" means a
surfactant having no silicon atoms in its structure and positively
charged when it is contained in the composition of the invention.
This surfactant may carry one or more permanent positive charges or
contain one or more cationizable functions in the composition of
the invention.
[0271] The cationic surfactant or surfactants suitable for use as
conditioning agents in the context of the present invention are
preferably selected from primary, secondary, or tertiary fatty
amines, possibly polyoxyalkylenated, or their salts, quaternary
ammonium salts, and mixtures thereof.
[0272] The fatty amines generally comprise at least one
C.sub.8-C.sub.30 hydrocarbon chain. Examples of fatty amines that
may be used in accordance with the invention that may be mentioned
are stearyl amidopropyl dimethylamine and distearylamine.
[0273] Examples of quaternary ammonium salts that may in particular
be mentioned are as follows: [0274] those with the following
general formula (XII):
##STR00012##
[0274] (XII) in which the radicals R.sub.8 to R.sub.11, which may
be identical or different, represent a linear or branched aliphatic
radical containing 1 to 30 carbon atoms or an aromatic radical such
as aryl or alkylaryl, at least one of radicals R.sub.8 to R.sub.11
designating a radical containing 8 to 30 carbon atoms, preferably
12 to 24 carbon atoms. The aliphatic radicals may comprise
heteroatoms such as oxygen, nitrogen, sulfur or the halogens.
Examples of aliphatic radicals are selected from C.sub.1-C.sub.30
alkyl, C.sub.1-C.sub.30 alkoxy, (C.sub.2-C.sub.6)polyoxyalkylene,
C.sub.1-C.sub.30 alkylamide,
(C.sub.12-C.sub.22)alkyl(C.sub.2-C.sub.6)amidoalkyl,
(C.sub.12-C.sub.22)alkyl acetate, and C.sub.1-C.sub.30
hydroxyalkyl; X.sup.- is an anion selected from the group formed by
halides, phosphates, acetates, lactates, (C.sub.2-C.sub.6)alkyl
sulfates, and alkyl- or alkylaryl-sulfonates.
[0275] Preferred examples of quaternary ammonium salts with formula
(XII) are tetraalkylammonium chlorides such as, for example,
dialkyldimethylammonium or alkyltrimethylammonium chlorides in
which the alkyl radical comprises approximately 12 to 22 carbon
atoms, in particular behenyltrimethylammonium,
distearyldimethylammonium, cetyltrimethylammonium,
benzyldimethylstearylammonium chlorides or, alternateively,
palmitylamidopropyltrimethylammonium chloride or
stearamidopropyldimethyl-(myristyl acetate)-ammonium chloride such
that sold under the trade name CERAPHYL.RTM. 70 by the supplier VAN
DYK; [0276] quaternary ammonium salts of imidazoline such as, for
example, those with the following formula (XIII):
##STR00013##
[0276] in which R.sub.12 represents an alkenyl or alkyl radical
containing 8 to 30 carbon atoms, for example fatty acid derivatives
from tallow, R.sub.13 represents a hydrogen atom, a C.sub.1-C.sub.4
alkyl radical or an alkenyl or alkyl radical containing 8 to 30
carbon atoms, R.sub.14 represents a C.sub.1-C.sub.4 alkyl radical,
R.sub.15 represents a hydrogen atom, a C.sub.1-C.sub.4 alkyl
radical, X.sup.- is an anion selected from the group formed by
halides, phosphates, acetates, lactates, alkylsulfates, alkyl- or
alkylaryl-sulfonates. Preferably, R.sub.12 and R.sub.13 designate a
mixture of alkenyl or alkyl radicals containing 12 to 21 carbon
atoms, for example fatty acid derivatives from tallow, R.sub.14
designates a methyl radical, R.sub.15 designates a hydrogen atom.
An example of such a product is that sold under the trade name
REWOQUAT.RTM. W 75 by the supplier REWO; [0277] quaternary di- or
triammonium salts, in particular with formula (XIV):
##STR00014##
[0277] in which R.sub.16 designates an alkyl radical containing
approximately 16 to 30 carbon atoms optionally hydroxylated and/or
interrupted by one or more oxygen atoms, R.sub.17 is selected from
hydrogen or an alkyl radical containing 1 to 4 carbon atoms or a
(R.sub.16a)(R.sub.17a)(R.sub.18a)N--(CH.sub.2).sub.3-- group,
R.sub.16a, R.sub.17a, R.sub.18a, R.sub.18, R.sub.19, R.sub.20, and
R.sub.21, which may be identical or different, being selected from
hydrogen or an alkyl radical containing 1 to 4 carbon atoms, and
X.sup.- is an anion selected from the group formed by halides,
acetates, phosphates, nitrates and methylsulfates. Examples of such
compounds are Finquat CT-P promoted by the supplier FINETEX
(Quaternium 89), Finquat CT promoted by the supplier FINETEX
(Quaternium 75); [0278] quaternary ammonium salts containing at
least one ester function, such as those with the following formula
(XV):
##STR00015##
[0278] in which: [0279] R.sub.22 is selected from C.sub.1-C.sub.6
alkyl radicals and C.sub.1-C.sub.6 hydroxyalkyl or dihydroxyalkyl
radicals; [0280] R.sub.23 is selected from: [0281] the radical
[0281] ##STR00016## [0282] radicals R.sub.27, which are linear or
branched, saturated or unsaturated C.sub.1-C.sub.22 hydrocarbon
radicals; [0283] the hydrogen atom; [0284] R.sub.25 is selected
from: [0285] the radical
[0285] ##STR00017## [0286] radicals R.sub.29, which are linear or
branched, saturated or unsaturated C.sub.1-C.sub.6 hydrocarbon
radicals; [0287] the hydrogen atom; [0288] R.sub.24, R.sub.26, and
R.sub.28, which may be identical or different, are selected from
linear or branched, saturated or unsaturated C.sub.7-C.sub.21
hydrocarbon radicals; [0289] r, s, and t, which may be identical or
different, are integers from 2 to 6; [0290] y is an integer from 1
to 10; [0291] x and z, which may be identical or different, are
integers from 0 to 10; [0292] X.sup.- is a simple or complex
organic or inorganic anion; [0293] provided that the sum x+y+z is
equal to 1 to 15, that when x is equal to 0 then R.sub.23
designates R.sub.27 and that when z is equal to 0 then R.sub.25
designates R.sub.29.
[0294] The R.sub.22 alkyl radicals may be linear or branched, more
particularly linear.
[0295] Preferably, R.sub.22 designates a methyl, ethyl,
hydroxyethyl, or dihydroxypropyl radical, and more particularly a
methyl or ethyl radical.
[0296] Advantageously, the sum x+y+z is equal to a value in the
range 1 to 10.
[0297] When R.sub.23 is a hydrocarbon radical R.sub.27, it may be
long and contain 12 to 22 carbon atoms, or short and contain 1 to 3
carbon atoms.
[0298] When R.sub.25 is a hydrocarbon radical R.sub.29, it
preferably contains 1 to 3 carbon atoms.
[0299] Advantageously, R.sub.24, R.sub.26, and R.sub.28, which may
be identical or different, are selected from linear or branched,
saturated, or unsaturated C.sub.11-C.sub.21 hydrocarbon radicals,
and more particularly from linear or branched, saturated or
unsaturated alkyl and alkenyl C.sub.11-C.sub.21 radicals.
[0300] Preferably, x and z, which may be identical or different,
are equal to 0 or 1.
[0301] Advantageously, y is equal to 1.
[0302] Preferably, r, s and t, which may be identical or different,
are equal to 2 or 3, still more particularly equal to 2.
[0303] The anion X.sup.- is preferably a halide (chloride, bromide
or iodide) or an alkylsulfate, more particularly methylsulfate.
However, it is possible to use the methanesulfonate, phosphate,
nitrate, tosylate, an anion derived from an organic acid such as
the acetate or lactate, or any other anion compatible with the
ammonium possessing an ester function.
[0304] Still more particularly, the anion X.sup.- is the chloride
or the methylsulfate.
[0305] More particularly, in the composition of the invention,
ammonium salts with formula (XV) are used in which: [0306] R.sub.22
designates a methyl or ethyl radical; [0307] x and y are equal to
1; [0308] z is equal to 0 or 1; [0309] r, s and t are equal to 2;
[0310] R.sub.23 is selected from: [0311] the radical
[0311] ##STR00018## [0312] methyl, ethyl, or C.sub.14-C.sub.22
hydrocarbon radicals; [0313] the hydrogen atom; [0314] R.sub.25 is
selected from: [0315] the radical
[0315] ##STR00019## [0316] the hydrogen atom; [0317] R.sub.24,
R.sub.26, and R.sub.28, which may be identical or different, are
selected from linear or branched, saturated or unsaturated
C.sub.13-C.sub.17 hydrocarbon radicals, and preferably from linear
or branched, saturated or unsaturated C.sub.13-C.sub.17 alkyl and
alkenyl radicals.
[0318] Advantageously, the hydrocarbon radicals are linear.
[0319] Examples that may be mentioned are compounds with formula
(XV) such as salts (in particular chloride or methylsulfate) of
diacyloxyethyl-dimethylammonium, of
diacyloxyethyl-hydroxyethyl-methylammonium, of
monoacyloxyethyl-dihydroxyethyl-methylammonium, of
triacyloxyethyl-methylammonium, or of
monoacyloxyethyl-hydroxyethyl-dimethylammonium, and mixtures
thereof. The acyl radicals preferably contain 14 to 18 carbon atoms
and more particularly originate from a vegetable oil such as palm
oil or sunflower oil. When the compound contains several acyl
radicals, they may be identical or different.
[0320] Said products are obtained, for example, by direct
esterification of triethanolamine, of triisopropanolamine, of
alkyldiethanolamine, or of alkyldiisopropanolamine optionally
oxyalkylenated on C.sub.10-C.sub.30 fatty acids or on
C.sub.10-C.sub.30 fatty acid mixtures of animal or vegetable
origin, or by transesterification of their methyl esters. This
esterification is followed by quaternization using an alkylation
agent such as an alkyl halide (preferably methyl or ethyl), a
dialkyl sulfate (preferably methyl or ethyl), methyl
methanesulfonate, methyl para-toluenesulfonate, or glycol, or
glycerol chlorhydrin.
[0321] By way of example, such compounds are sold under the trade
names DEHYQUART.RTM. by the supplier HENKEL, STEPANQUAT.RTM. by the
supplier STEPAN, NOXAMIUM.RTM. by the supplier CECA, or
REWOQUAT.RTM. WE 18 by the supplier REWO-WITCO.
[0322] The composition of the invention may, for example, contain a
mixture of quaternary ammonium mono-, di- and trimester salts with
a majority by weight of diester salts.
[0323] It is also possible to use ammonium salts containing at
least one ester function as described in U.S. Pat. No. 4,874,554
and U.S. Pat. No. 4,137,180.
[0324] Particularly preferred cationic surfactant(s) that may be
used in the invention are selected from compounds with formula
(XII) or with formula (XV).
[0325] Preferred examples of cationic surfactants that may be
present in the composition of the invention include cetyl trimethyl
ammonium, behenyl trimethyl ammonium, dipalmitoylethyl hydroxyethyl
methyl ammonium, distearoylethyl hydroxyethyl methyl ammonium,
methyl(C.sub.9-C.sub.19)alkyl, (C.sub.10-C.sub.20)alkyl
amidoethylimidazolium, and stearamidopropyldimethylamine salts, a
salt of stearamidopropyl dimethylammonium, and mixtures
thereof.
Silicones
[0326] Non-limiting examples of silicones that may be used as
conditioning agents of the present invention that may be mentioned
are:
I. Volatile Silicones:
[0327] These have a boiling point in the range 60.degree. C. to
260.degree. C. This type of silicone includes:
[0328] (i) cyclic silicones containing 3 to 7 silicon atoms, and
preferably 4 to 5.
[0329] It may, for example, be the octamethylcyclo-tetrasiloxane
sold under the name "VOLATILE SILICONE 7207.RTM." by the supplier
UNION CARBIDE or "SILBIONE 70045 V2.RTM." by the supplier RHONE
POULENC, the decamethylcyclopentasiloxane sold under the name
"VOLATILE SILICONE 7158.RTM." by the supplier UNION CARBIDE,
"SILBIONE 70045 V5.RTM." by the supplier RHONE POULENC, and also
their mixtures. Cyclopolymers of the
dimethylsiloxane/methylalkylsiloxane type, such as "SILICONE
VOLATILE FZ 3109.RTM." sold by the supplier UNION CARBIDE, which is
a dimethylsiloxane/methyloctylsiloxane cyclocopolymer, may also be
mentioned;
[0330] (ii) linear volatile silicones containing 2 to 9 silicon
atoms and having a viscosity of 5.times.10.sup.-6 m.sup.2/s [square
meters per second] or less at 25.degree. C.
[0331] It may, for example, be the hexamethyldisiloxane sold under
the trade name "SILBIONE 70041 V0,65.RTM." by the supplier RHONE
POULENC. This type of product is described in the article by TODD
& BYERS, "Volatile silicone fluids for cosmetics", Cosmetics
and Toiletries, Vol. 91, January 76, pp. 27-32.
II. Non-Volatile Silicones
[0332] These are principally constituted by polyalkylsiloxanes,
polyarylsiloxanes, polyalkylarylsiloxanes and organomodified
polysiloxanes, and also their mixtures. They may be in the form of
oils, gums or resins.
[0333] Examples of polyalkylsiloxanes that may be mentioned are
principally linear polydimethylsiloxanes with a viscosity of more
than 5.times.10.sup.-6 m.sup.2/s, and preferably less than 2.6
m.sup.2/s, i.e.: [0334] with terminal trimethylsilyl groups,
non-limiting examples of which are "SILBIONE.RTM." oils from the
70047 series sold by the supplier RHONE POULENC, Wacker Belsil DM
60000 oil from WACKER, or certain "VISCASIL.RTM." liquids from the
supplier GENERAL ELECTRIC; [0335] with terminal trihydroxysilyl
groups, such as oils from the "48 V.RTM." series from the supplier
RHONE POULENC.
[0336] In this class of polyalkylsiloxanes, mention can also be
made of polyalkylsiloxanes provided by the supplier GOLDSCHMIDT
under the trade names "ABILWAX 9800.RTM." and "ABILWAX 9801.RTM.",
which are poly(C.sub.1-C.sub.20)alkylsiloxanes.
[0337] Examples of polyalkylarylsiloxanes that may be mentioned are
polydimethylphenylsiloxanes, linear and/or branched
polydimethyldiphenylsiloxanes with a viscosity of 10.sup.-5 to
5.times.10.sup.-2 m.sup.2/s such as, for example: [0338]
"RHODORSIL.RTM." oil 763 from RHONE POULENC; [0339] "SILBIONE.RTM."
oils from the 70641 series from RHONE POULENC, such as "SILBIONE
70641 V30.RTM." and "SILBIONE 70641 V200.RTM." oils; [0340] the
product "DC 556.RTM." Cosmetic Grad Fluid from DOW CORNING; [0341]
silicones from the series PK de BAYER, such as "PK20.RTM."; [0342]
silicones from the series PN, PH de BAYER, such as "PN 1000.RTM."
and "PH 1000.RTM."; and [0343] certain oils from the SF series from
GENERAL ELECTRIC, such as "SF 1250.RTM.", "SF 1265.RTM.", "SF
1154.RTM.", "SF 1023.RTM.".
[0344] The silicone gums of the present invention are
polydiorganosiloxanes with a high number average molecular mass in
the range 200,000 to 1,000,000, used alone or as a mixture in a
solvent selected from volatile silicones, polydimethylsiloxane oils
(PDMS), polyphenylmethylsiloxanes (PPMS) oils, isoparaffins,
methylene chloride, pentane, dodecane, tridecane, tetradecane, or
mixtures thereof.
[0345] Examples that may be mentioned are compounds containing the
following structures: [0346]
poly[(dimethylsiloxane)/(methylvinylsiloxane)]gums; [0347]
poly[(dimethylsiloxane)/(diphenylsiloxane)] gums; [0348]
poly[(dihydrogeno dimethylsiloxane)/(divinylsiloxane)] gums; [0349]
poly[(dimethylsiloxane)/(phenylmethylsiloxane)] gums; [0350]
poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)]
gums.
[0351] Mirasil DM 300 000 from Rhodia may be mentioned.
[0352] The following non-limiting examples may also be
mentioned:
[0353] 1) mixtures formed from a polydimethylsiloxane hydroxylated
at the chain end (DIMETHICONOL in the CTFA nomenclature), and a
cyclic polydimethylsiloxane (CYCLOMETHICONE in the CTFA
nomenclature), such as the products "Q2 1401.RTM." or DOW CORNING
1501 FLUID provided by the supplier DOW CORNING;
[0354] 2) mixtures formed from a polydimethylsiloxane gum with a
cyclic silicone, such as the product "SF 1214 SILICONE FLUID.RTM."
from GENERAL ELECTRIC, which is a "SE 30 .RTM." gum with a MW of
500000 (number average) dissolved in "SF 1202 SILICONE FLUID.RTM."
(decamethylcyclopentasiloxane);
[0355] 3) mixtures of two PDMS with different viscosities, in
particular a PDMS gum and a PDMS oil, such as the products "SF
1236.RTM." and "CF 1241.RTM." from the supplier GENERAL ELECTRIC.
The product "SF 1236.RTM." is a mixture of a "SE 30.RTM." gum as
defined above with a viscosity of 20 m.sup.2/s and a "SF 96.RTM."
oil with a viscosity of 5.times.10.sup.6 m.sup.2/s (15% of "SE
30.RTM." gum and 85% of "SF 96.RTM." oil).
[0356] The product "CF 1241.RTM." is a mixture of a "SE 30.RTM."
(33%) gum and a PDMS (67%) with a viscosity of 10.sup.-3
m.sup.2/s.
[0357] The organopolysiloxane resins that may be used in accordance
with the invention are cross-linked siloxane systems comprising the
units: R.sub.2SiO.sub.2/2, RSiO.sub.3/2 and SiO.sub.4/2 in which R
represents a hydrocarbon group containing 1 to 6 carbon atoms or a
phenyl group. Particularly preferred examples of these products are
those in which R designates a lower alkyl radical or a phenyl
radical.
[0358] Examples of these resins that may be mentioned are the
product sold under the trade name "DOW CORNING 593.RTM." or those
sold under the trade names "SILICONE FLUID SS 4230" and "SILICONE
FLUID SS 4267" by the supplier GENERAL ELECTRIC and that are
dimethyl/trimethylpolysiloxanes.
[0359] The organomodified silicones of the present invention are
silicones as defined above, comprising in their general structure
one or more organo-functional groups bonded directly to the
siloxane chain or bound via a hydrocarbon radical.
[0360] Examples that may be mentioned are silicones comprising:
[0361] a) perfluorinated groups such as trifluoroalkyls such as,
for example, those provided by the supplier GENERAL ELECTRIC under
the trade names "FF.150 FLUOROSILICONE FLUID.RTM." or by the
supplier SHIN ETSU under the trade names "X-22-819.RTM.",
"X-22-82.RTM.", "X-22-821.RTM." and "X-22-822.RTM.";
[0362] b) hydroxyacylamino groups such as, for example, those
described in patent application EP 0 342 834 and in particular the
silicone sold by the supplier DOW CORNING under the trade name
"Q2-8413.RTM.";
[0363] c) thiol groups such as in the silicones "X 2-8360.RTM."
from the supplier DOW CORNING or "GP 72A.RTM." and "GP 71.RTM."
from GENESEE;
[0364] d) non-quaternized amino groups, such as in "GP 4 SILICONE
FLUID.RTM." from GENESEE, "GP 7100.RTM." from GENESEE, "Q2
8220.RTM." from DOW CORNING, "AFL 40.RTM." from UNION CARBIDE or
the silicone known as "Amodimethicone" in the CTFA dictionary;
[0365] e) carboxylate groups, such as the products described in
patent EP 186 507 from CHISSO CORPORATION;
[0366] f) hydroxyl groups such as polyorganosiloxanes with a
C.sub.2-C.sub.18 hydroxyalkyl function described, for example, in
patent application FR 85/16334; more particularly mention may be
made of the product supplied by Dow Corning under the name DC
190;
[0367] g) alkoxy groups such as those in the silicone copolymer "F
755.RTM." from SWS SILICONES and the products "ABILWAX 2428.RTM.",
"ABILWAX 2434.RTM.", "ABILWAX 2440.RTM." from the supplier
GOLDSCHMIDT;
[0368] h) (C.sub.8-C.sub.22) acyloxy(C.sub.2-C.sub.18)alkyl groups
such as the polyorganopolysiloxanes described in patent application
FR 88/17433, for example;
[0369] i) quaternary ammonium groups such as in the products "X2 81
08.RTM." and "X2 81 09.RTM.", the product "ABIL K 3270.RTM." from
the supplier GOLDSCHMIDT;
[0370] j) amphoteric or betaine groups, such as those in the
product provided by the supplier GOLDSCHMIDT under the trade name
"ABIL B 9950.RTM.";
[0371] k) bisulfite groups such as in the products provided by the
supplier GOLDSCHMIDT under the trade names "ABIL S 201.RTM." and
"ABIL S 255.RTM."; and
[0372] l) polyethyleneoxy and/or polypropyleneoxy groups optionally
comprising C.sub.6-C.sub.24 alkyl groups, such as products known as
dimethicone copolyol provided by the supplier DOW CORNING under the
trade name DC 1248 or SILWET L 722, L 7500, L 77, L 711 oils from
the supplier UNION CARBIDE and the (C.sub.12)alkyl methicone
copolyol provided by the supplier DOW CORNING under the trade name
Q2 5200;
[0373] In accordance with the invention, it is also possible to use
silicones comprising a polysiloxane portion and a portion
constituted by an organic non-silicone chain, one of the two
portions constituting the main chain of the polymer, the other
being grafted onto said principal chain. These polymers are, for
example, described in patent applications EP-A-412 704, EP-A-412
707, EP-A-640 105 and WO 95/00578, EP-A-582 152 and WO 93/23009 and
in U.S. Pat. Nos. 4,693,935, 4,728,571, and 4,972,037. These
polymers are preferably anionic or non-ionic.
[0374] Examples of such polymers are copolymers that can be
obtained by radical polymerization from a mixture of monomers
constituted by:
[0375] a) 50% to 90% by weight of tertiobutyl acrylate;
[0376] b) 0 to 40% by weight of acrylic acid;
[0377] c) 5% to 40% by weight of silicone macromer with
formula:
##STR00020##
with v being a number from 5 to 700; the percentages by weight are
calculated relative to the total monomer weight.
[0378] Other particular examples of graft silicone polymers are
polydimethylsiloxanes (PDMS) onto which mixed polymer motifs are
grafted, via a linker of the thiopropylene type, which mixed
polymer motifs are of the poly(meth)acrylic and alkyl
poly(meth)acrylate types, and polydimethylsiloxanes (PDMS), onto
which polymer motifs of the poly isobutyl(meth)acrylate type are
grafted via a thiopropylene type linker.
[0379] In accordance with the invention, all of the silicones may
also be used in the form of emulsions, nanoemulsions or
microemulsions.
[0380] Particularly preferred polyorganosiloxanes of the invention
are: [0381] non-volatile silicones selected from the
polydialkylsiloxane family with terminal trimethylsilyl groups,
such as oils with a viscosity in the range 0.2 m.sup.2/s to 2.5
m.sup.2/s at 25.degree. C., for example oils from the DC200 series
from DOW CORNING, in particular that with a viscosity of 60,000
Cst, from the SILBIONE 70047 series, more particularly 70,047 V
500,000 oil provided by the supplier RHODIA CHIMIE,
polydialkylsiloxanes with terminal dimethylsilanol groups such as
dimethiconol or polyalkylarylsiloxanes such as SILBIONE 70641 V 200
oil provided by the supplier RHODIA CHIMIE; and [0382]
polysiloxanes with amine groups such as aminodimethicones or
trimethylsilylamodimethicone.
[0383] The viscosities of the silicones may in particular be
determined using the standard ASTM D445-97 (viscometry).
Hydrocarbons
[0384] When the conditioning agent of the composition of the
invention is a hydrocarbon, it is a linear or branched
C.sub.8-C.sub.300 hydrocarbon.
[0385] Particular examples of hydrocarbons that are liquid at
ambient temperature that fall within this definition that can be
mentioned are isododecane, isohexadecane and its isomers (such as
2,2,4,4,6,6-heptamethylnonane), isoeicosane, isotetracosane,
isomers of said compounds, n-dodecane, n-nonane, n-undecane,
n-tridecane, n-pentadecane, vaseline oil and mixtures of said
hydrocarbons.
[0386] Preferably, vaseline oil, isododecane or one of its isomers
is used in the invention.
Fatty Alcohols
[0387] When the conditioning agent is a fatty alcohol, it is of the
linear or branched, saturated or unsaturated C.sub.8-C.sub.30 type.
Examples of these that may be mentioned are 2-butyl octanol, lauric
alcohol, oleic alcohol, isocetyl alcohol, isostearic alcohol,
behenyl alcohol, stearyl alcohol, cetyl alcohol, and mixtures
thereof.
Fatty Esters
[0388] When the conditioning agent is a fatty ester, it may either
be an ester of a C.sub.8-C.sub.30 fatty acid and C.sub.1-C.sub.30
monoalcohols or polyols including esters of C.sub.8-C.sub.30 fatty
acids and C.sub.8-C.sub.30 fatty alcohols, or an ester of a
C.sub.1-C.sub.7 dibasic acid and a C.sub.8-C.sub.30 fatty
alcohol.
[0389] Examples of such esters that may be mentioned are ethyl,
isopropyl, 2-ethylhexyl and 2-octyldecyl palmitate, isopropyl,
butyl, cetyl and 2-octyldecyl myristate, butyl and hexyl stearate,
hexyl and 2-hexyldecyl laurate, isononyl isononanoate, dioctyl
malate, dioctyl, myristyl myristate, stearyl myristate, cetyl
palmitate, myristyl stearate, stearyl stearate, cetyl stearate, and
mixtures thereof.
[0390] It is also possible to mention natural or synthetic
triglycerides, in particular vegetable oils such as rapeseed oil,
avocado oil, olive oil, sunflower oil, argan oil, or grapeseed
oil.
Ceramides
[0391] Ceramides or ceramide analogs, such as glycoceramides, that
can be used as a conditioning agent in the compositions of the
invention are known per se and are natural or synthetic molecules
that may have the following general formula (XIX):
##STR00021##
in which: [0392] R.sub.1 designates a, linear or branched,
saturated or unsaturated alkyl radical derived from
C.sub.14-C.sub.30 fatty acids, said radical possibly being
substituted with a hydroxyl group in the alpha position, or a
hydroxyl group in the omega position esterified by a saturated or
unsaturated C.sub.16-C.sub.30 fatty acid; [0393] R.sub.2 designates
a hydrogen atom or a (glycosyl).sub.n, (galactosyl).sub.m or
sulfogalactosyl radical, in which n is an integer in the range 1 to
4 and m is an integer in the range 1 to 8; and [0394] R.sub.3
designates a C.sub.15-C.sub.26 hydrocarbon radical, saturated or
unsaturated in the alpha position, said radical possibly
substituted with one or more C.sub.1-C.sub.14 alkyl radicals;
[0395] it being understood that with natural ceramides or
glycoceramides, R.sub.3 may also designate a C.sub.15-C.sub.26
alpha-hydroxyalkyl radical, the hydroxyl group optionally being
esterified by a C.sub.16-C.sub.30 alpha-hydroxyacid.
[0396] Ceramides that are preferred in the context of the present
invention are those described by DOWNING in Arch. Dermatol, Vol.
123, 1381-1384, 1987, or those described in French patent FR 2 673
179.
[0397] A more particularly preferred ceramide or more particularly
preferred ceramides of the invention are compounds for which
R.sub.1 designates a saturated or unsaturated alkyl derivative of
C.sub.16-C.sub.22 fatty acids; R.sub.2 designates a hydrogen atom;
and R.sub.3 designates a saturated C.sub.15 linear radical.
[0398] Examples of such compounds are: [0399]
N-linoleoyldihydrosphingosine; [0400] N-oleoyldihydrosphingosine;
[0401] N-palmitoyldihydrosphingosine; [0402]
N-stearoyldihydrosphingosine; [0403] N-behenoyldihydrosphingosine;
or
[0404] mixtures of these compounds.
[0405] Still more preferably, ceramides are used for which R.sub.1
designates a saturated or unsaturated alkyl radical derived from
fatty acids; R.sub.2 designates a galactosyl or sulfogalactosyl
radical; and R.sub.3 designates a
--CH.dbd.CH--(CH.sub.2).sub.12--CH.sub.3 group.
[0406] An example that may be mentioned is the product constituted
by a mixture of these compounds, sold under the trade name GLYCOCER
by the supplier WAITAKI INTERNATIONAL BIOSCIENCES.
Abrasive Solid Particles
[0407] The term "abrasive solid particles" means particles with a
hardness that is greater than or equal to that of hair. As an
example, the abrasive solid particles may have a hardness of 3 or
more on the Mohs scale, or even 4 or more, for example 5 or more on
the Mohs scale.
[0408] The solid particles may be selected from natural materials,
in particular of mineral or vegetable origin, or from synthetic
materials. The abrasive solid particles may, for example, be
selected from the following materials, although this list is not
limiting: [0409] inorganic and/or metallic particles such as boron
nitride in the cubic form (Borazon.RTM.), aluminosilicate, zircon,
mixed aluminum oxides such as emery, zinc oxide, aluminum oxides
such as aluminas or corundum, titanium oxide, mica titanium oxide,
carbides, in particular silicon carbide (carborundum), or other
metallic oxides, metals and metal alloys such as iron shot, steel,
in particular pearlite; silicates such as glass, quartz or sand,
calcium carbonate (for example bora bora sand or Rose de Brignoles
marble) or magnesium carbonate, sodium chloride, pumice stone,
amorphous silica, diamond, or ceramics; [0410] organic particles
such as fruit kernels, especially apricot, for example
Scrubami.RTM. apricot, wood cellulose, for example ground bamboo,
coconut shell, for example Coconut exfoliator; polyamides, in
particular Nylon-6, sugars; polyethylenes; polypropylenes; and
[0411] mixed particles combining organic and inorganic compounds,
and particles coated with the compounds described above.
[0412] The solid particles may have a flattened, spherical,
elongate, polyhedral or irregular shape. The solid particles may,
for example, originate from powdered pumice stone grains, powdered
diamond, powdered fruit kernels, powdered coconut shells,
microbeads, for example alumina microbeads, glass microbeads,
polyamide microbeads, in particular Nylon-6, or from fibers, in
particular polyamide fibers and hardwood cellulose fibers.
Moisturizing Agents
[0413] The moisturizing agents are preferably selected from urea,
urea derivatives such as hydroxyethylurea, polyols such as
glycerin, propyleneglycol or sorbitol, polyethylene glycols.
[0414] Preferably, the composition of the invention comprises at
least one conditioning agent or at least one reducing agent or at
least one organic or inorganic base, or at least one hair dye.
[0415] Still more preferably, the composition of the invention
comprises at least one hair conditioning agent.
[0416] The cosmetic hair composition used in accordance with the
invention may also contain other compounds that are normal in the
hair cosmetics field, such as vitamins and pro-vitamins including
panthenol, sunscreens, organic or inorganic pigments, which may
optionally be colored, pearlizing and opacifying agents,
sequestrating agents, plasticizers, solubilizing agents,
anti-oxidants, hydroxyacids, fragrances, non-ionic, anionic,
cationic or amphoteric surfactants, non-ionic, anionic, cationic or
amphoteric polymers, short chain alkanols such as ethanol or
isopropanol, acidifying agents and preservatives.
[0417] The compositions of the invention may be aqueous or
anhydrous. They may be in the form of powders, liquids, gels,
milks, creams or non-powdery solids. They may optionally be sprayed
onto the hair using an aerosol or a pump bottle.
[0418] The method of the invention may be implemented in a
plurality of variant embodiments.
[0419] In first variant exemplary embodiments, the hair is combed
using a motor-driven device after applying the composition of the
invention to the hair, the composition possibly being present on
the hair.
[0420] In second variant exemplary embodiments, the hair is combed
using a motor-driven device before applying the composition of the
invention to the hair. In these variant exemplary embodiments,
combing is carried out after wetting the hair or after applying a
composition not comprising active ingredients of the invention.
[0421] The first variant exemplary embodiments are preferred. The
method according to these variant exemplary embodiments may also
include a subsequent step of applying of a composition with or
without active ingredients of the invention.
[0422] The treatment may optionally be followed by rinsing.
[0423] Finally, the hair is dried or left to dry.
[0424] The method of the invention may be repeated several times.
In general, the method of the invention is applied once or
twice.
[0425] The invention is particularly suitable for curly or frizzy
hair.
[0426] The invention can be better understood from the following
description of non-limiting examples made with reference to the
accompanying drawings in which:
[0427] FIG. 1 represents an example of a combing device of the
invention;
[0428] FIG. 2 represents the device of FIG. 1 in diagrammatic
section;
[0429] FIG. 3 diagrammatically illustrates the deformation of the
diaphragm during operation of the device;
[0430] FIG. 4 illustrates the use of the device
[0431] FIG. 5 is a diagrammatic and perspective representation of a
variant embodiment of a combing device; and
[0432] FIGS. 6A and 6B represent a head of hair respectively with
one side treated in accordance with the invention and the other
side treated conventionally.
[0433] The motor-driven combing device represented in FIGS. 1 and 2
comprise a hand piece 10 that can receive a detachable diaphragm 20
carrying spikes 21.
[0434] The combing device may be offered to the user with a
charging unit 30 for recharging a battery 18 contained in the hand
piece 10.
[0435] In the example illustrated, the device is similar to those
promoted under the trade name NEO or FLEX by TWINBIRD and to that
described in particular in patent application US 2009/0182249 A1; a
section of it is reproduced in FIG. 2.
[0436] It can be seen in this figure that the hand piece comprises
a geared electric motor 11 driving a drive member 12 in rotation on
which is articulated a rod 13, connected to the diaphragm 20 by
means, for example, of a hook 15 that is engaged in a portion in
relief 22 provided on the inner face of the diaphragm 20.
[0437] Its periphery may be attached to a rim 16 of the casing of
the hand piece 10.
[0438] In FIG. 2, it can be seen that a block 23 of an elastically,
deformable, porous material forming a reservoir may be disposed on
the inner face side of the diaphragm, but in a variant embodiment,
this material is absent. Openings 25 may allow communication
between the outside of the diaphragm 20, between the spikes 21, and
the block 23.
[0439] As illustrated, the hand piece may include a switch 17 that
can start the electric motor 11 that is powered via the battery
18.
[0440] The spikes 21 may have different heights, generally being
shorter in the central region of the diaphragm and longer at its
periphery, to provide the envelope surface touching the free ends
of the spikes 21 with a generally concave shape.
[0441] As illustrated, the spikes 21 may be distributed into two
groups, namely a first group 21a disposed in the central region
with spikes that are oriented parallel to the axis X of movement of
the portion in relief, and a second group 21b with spikes disposed
about the first, the respective longitudinal axes of which extend
obliquely outwardly relative to the axis X.
[0442] The spikes 21 may be disposed in concentric rows to the
circumference of the diaphragm. Thus, the spikes 21 are not aligned
and when the combing device is moved along a lock of hair in a
direction perpendicular to or obliquely to its major axis Y, the
hair that passes between the spikes 21 follows a non-rectilinear
path.
[0443] During operation of the device, the rod 13 is driven in an
oscillating motion from top to bottom in FIG. 2, which causes
periodic deformation of the diaphragm 20, the periphery of the
diaphragm 20 remaining fixed relative to the hand piece 10 while
its central region oscillates along the axis X with a maximum
amplitude.
[0444] As illustrated in FIG. 3, the oscillations of the diaphragm
20 generate a rubbing action of the spikes 21 on the hair that,
combined with the use of the composition of the invention, can
achieve results that are superior using the composition alone or
the combing device alone.
[0445] To use the combing device, as illustrated in FIG. 4, the
user may apply the composition to the wetted hair and comb the
hair, for example by passing it a few times from the base to the
tips.
EXAMPLE
[0446] The protocol was as follows:
[0447] a) applying a composition A comprising 1% active ingredient
of a polydimethysiloxane, or B comprising 0.5% active ingredient of
trimetylcetylammonium chloride to wetted hair, for example of the
African or Caucasian type;
[0448] b) distribution of the composition using the hands and
combing by hand or a comb on a first side of the head, and using
the NEO device from the supplier TWINBIRD on the other side of the
head, for 2 minutes;
[0449] c) rinsing; and
[0450] d) drying.
[0451] Applying the method, particularly to frizzy or curly hair in
association with compositions A or B containing the active
ingredient shows, as illustrated in FIGS. 6A and 6B, better
individualization of the hair, resulting in a very clear reduction
in volume and density compared with massage using the hands. Better
disentangling and a smoother feel was also observed. This effect
lasted through several shampooings.
[0452] Steps a) and b) could also be repeated after step c) then
terminated by steps c) and d).
[0453] The scope of the invention also encompasses using a combing
device comprising, as illustrated in FIG. 5, a removable reservoir
40 containing the composition to be applied during use of the
combing device. The reservoir 40 is, for example, pre-filled with
composition and is supplied to the operator in the form of a
cartridge to be placed in the hand piece 10.
[0454] The composition from the reservoir is distributed, for
example, by means of a pump actuated by the same motor as that
which deforms the diaphragm.
[0455] The expression "comprising at least one" should be construed
as being equivalent to "comprising one or more".
* * * * *