U.S. patent application number 08/985213 was filed with the patent office on 2002-01-31 for aerosol device based on alcoholic compositions of fixing materials.
Invention is credited to MINOU, PATRICK, SAMAIN, HENRI.
Application Number | 20020012632 08/985213 |
Document ID | / |
Family ID | 9497932 |
Filed Date | 2002-01-31 |
United States Patent
Application |
20020012632 |
Kind Code |
A1 |
SAMAIN, HENRI ; et
al. |
January 31, 2002 |
AEROSOL DEVICE BASED ON ALCOHOLIC COMPOSITIONS OF FIXING
MATERIALS
Abstract
An aerosol device comprising a container containing an aerosol
composition including a liquid phase containing at least one fixing
material in a suitable solvent and a propellant and a means for
distributing the aerosol composition, where the fixing material has
a glass transition temperature (Tg) of greater than or equal to
30.degree. C., and the aerosol device is suitable for obtaining a
solids flow rate for the aerosol composition ranging from
approximately 4 to approximately 17 mg/s and a wetting power for
the aerosol composition of greater than or equal to 50 mg/s, and a
process for treating keratin fibers using the aerosol device.
Inventors: |
SAMAIN, HENRI; (BIEVRES,
FR) ; MINOU, PATRICK; (COURBEVOIE, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT
& DUNNER
1300 I STREET, N.W.
WASHINGTON
DC
200053315
|
Family ID: |
9497932 |
Appl. No.: |
08/985213 |
Filed: |
December 4, 1997 |
Current U.S.
Class: |
424/45 ;
424/400 |
Current CPC
Class: |
A61Q 5/06 20130101; A61K
8/8147 20130101; A61K 8/046 20130101; A61K 8/8158 20130101 |
Class at
Publication: |
424/45 ;
424/400 |
International
Class: |
A61K 009/12; A61K
009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 4, 1996 |
FR |
9614329 |
Claims
We claim:
1. An aerosol device, comprising: a container containing an aerosol
composition, said composition comprising a liquid phase containing
at least one fixing material in a suitable solvent and a
propellant, wherein said at least one fixing material has a glass
transition temperature (Tg) of greater than or equal to 30.degree.
C.; and a means for distributing said aerosol composition, wherein
said aerosol device is suitable for obtaining a solids flow rate
for said aerosol composition ranging from approximately 4 to
approximately 17 mg/s and a wetting power for said aerosol
composition of greater than or equal to 50 mg/s.
2. An aerosol device according to claim 1, wherein said aerosol
device is suitable for obtaining a solids flow rate of less than 16
mg/s.
3. An aerosol device according to claim 2, wherein said aerosol
device is suitable for obtaining a solids flow rate ranging from 6
to 15 mg/s.
4. An aerosol device according to claim 1, wherein said aerosol
device is suitable for obtaining a wetting power ranging from 50
mg/s to 125 mg/s.
5. An aerosol device according to claim 1, wherein said aerosol
composition has a solids concentration (C.sub.S) ranging from 0.4
to 5% by weight relative to the total weight of said aerosol
composition.
6. An aerosol device according to claim 5, wherein said solids
concentration ranges from 0.6 to 3.25% by weight relative to the
total weight of said aerosol composition.
7. An aerosol device according to claim 1, wherein said aerosol
composition has a flow rate (F.sub.AC) ranging from approximately
500 to approximately 700 mg/s.
8. An aerosol device according to claim 7, wherein said flow rate
is approximately 550 mg/s.
9. An aerosol device according to claim 1, wherein said aerosol
composition has a fluid/propellant weight ratio of greater than
1.
10. An aerosol device according to claim 9, wherein said
fluid/propellant weight ratio ranges from 1.2 to 3.
11. An aerosol device according to claim 1, wherein said at least
one fixing material comprises at least one fixing polymer.
12. An aerosol device according to claim 11, wherein said at least
one fixing polymer is an anionic, cationic, amphoteric or nonionic
polymer.
13. An aerosol device according to claim 12, wherein said at least
one fixing polymer is an anionic or amphoteric polymer.
14. An aerosol device according to claim 1, wherein said suitable
solvent contains at least 50% by volume of alcohol.
15. An aerosol device according to claim 14, wherein said suitable
solvent contains at least 70% by volume of alcohol.
16. A process for treating a keratin fiber comprising applying to
said keratin fiber a composition comprising at least one fixing
material having a glass transition temperature (Tg) of greater than
or equal to 30.degree. C., said applying being accomplished by a
suitable device capable of obtaining a solids flow rate for said
composition ranging from approximately 4 to approximately 17 mg/s
and a wetting power for said composition of greater than or equal
to 50 mg/s.
Description
[0001] The present invention relates to novel aerosol devices
intended for fixing the hair.
[0002] The hair products for shaping and/or holding the hair style
which are most widely available on the cosmetics market are spray
compositions essentially consisting of a solution, usually an
alcoholic or aqueous solution, and one or more materials, generally
polymer resins, whose function is to form welds between the hairs,
these materials also being known as fixing materials, as a mixture
with various cosmetic adjuvants. This solution is generally
packaged either in a suitable aerosol container placed under
pressure with the aid of a propellant, or in a pump-dispenser
bottle.
[0003] The fixing materials are generally fixing polymers, that is
to say film-forming polymers that are soluble in water and in
alcohol, such as polyvinylpyrrolidone, the vinylpyrrolidone/vinyl
acetate copolymers described in particular in U.S. Pat. Nos.
3,929,735 and 3,770,683, vinyl acetate/crotonic acid copolymers and
anionic or amphoteric acrylic resins. These materials make it
possible to obtain the fixing effect easily but, on the other hand,
after brushing or combing, hair under the usual lacquer conditions
looks stiff and feels coarse, or even sticky.
[0004] These drawbacks are associated with several parameters,
among which mention may be made of the nature of the fixing
polymer(s), or alternatively the nature of the welds. In order to
overcome these drawbacks, it is thus possible to alter these two
parameters without, however, decreasing the desired fixing effect.
In order to improve the cosmetic properties of the fixing
materials, it has been proposed to combine different polymers, for
example as discussed in documents WO 94/12148, WO 96/06592 and U.S.
Pat. No. 5,158,762.
[0005] The inventors have now found, surprisingly, that by
appropriately selecting the fixing polymers and the diffusion
parameters for the compositions, it is possible to decrease the
size of the welds.
[0006] The present invention thus relates to a novel aerosol device
intended to fix the hair, which makes it possible to decrease the
size of the welds and thus to provide excellent cosmetic properties
such as softness, disentangling and feel while at the same time
retaining good fixing and/or shaping qualities for the hair
style.
[0007] The aerosol device according to the invention comprises a
container containing an aerosol composition including, on the one
hand, a liquid phase (or fluid) containing at least one fixing
material in a suitable solvent and, on the other hand, a
propellant, and a means for distributing the aerosol composition,
the fixing material having a glass transition temperature (Tg) of
greater than or equal to 30.degree. C., and the device being
suitable for obtaining a solids flow rate ranging from
approximately 4 to approximately 17 mg/s and a wetting power
greater than or equal to 50 mg/s.
[0008] The distribution means generally includes a distribution
valve controlled by a distribution head, which itself comprises a
nozzle through which the aerosol composition is vaporized.
[0009] The terms "Tg", "solids flow rate" and "wetting power" as
understood according to the present invention are defined
below.
[0010] According to the present invention, the term glass
transition temperature (Tg) is understood to refer to the Tg of the
fixing material in the dry extract, the dry extract consisting of
all of the non-volatile materials in the fluid, or solids.
[0011] According to the present invention, the solids flow rate
(F.sub.S) corresponds to the amount of dry extract which leaves the
aerosol device per unit time. This solids flow rate is expressed in
mg/s and is calculated by multiplying the solids concentration in
the aerosol composition (C.sub.S) by the flow rate of the aerosol
composition at the nozzle outlet (F.sub.AC):
F.sub.S=C.sub.S.times.F.sub.AC
[0012] The solids concentration in the aerosol composition
(C.sub.S) corresponds to the amount of solids relative to 100 g of
aerosol composition (fluid+propellant). The solids concentration is
expressed as a percentage and is measured after spraying by
evaporation of the volatile components of the spray residue for 1
hour 30 at 105.degree. C.
[0013] The flow rate of aerosol composition (FAC) corresponds to
the amount of aerosol composition (fluid+propellant) leaving the
aerosol device per unit time. It is expressed in mg/s and is
measured by the difference between the weight of aerosol before
(M.sub.0) and after (M.sub.1) spraying for 10 seconds:
F.sub.AC=(M.sub.0-M.sub.1)/10.
[0014] According to the present invention, the wetting power
corresponds to the amount of product received on a sheet of plastic
placed 35 cm away from the nozzle of the aerosol device for a given
unit of time. In this case, the product comprises the solids plus
some of the solvent which has not evaporated in the course of the
trajectory plus, optionally, some of the propellant which has not
evaporated. This wetting power is expressed in mg/s and is
measured, according to the invention, by the following method:
[0015] a sheet of plastic 21 cm.times.23 cm in size is suspended
vertically from a precision balance ({fraction (1/1000)}), the
sheet being connected to the balance via the upper edge (generally
by a balance hook inserted into a perforation placed at the center
of the width and 1 cm from the upper edge), and held vertically by
applying a weight centered on the lower edge (generally by means of
a clamp fixed and centered on the lower edge);
[0016] a block is placed behind the lower edge of the sheet in
order to keep the sheet vertical during impact of the product;
[0017] the aerosol device is placed vertically such that the
composition diffusion nozzle is positioned at the center of and 35
cm away from the vertical sheet, for vaporization of the product
perpendicular to the sheet;
[0018] the composition is vaporized for 5 seconds
[0019] the amount of product received on the vertical sheet is
measured as soon as the vaporization has ended.
[0020] For greater precision, it is possible to use a suitable
device comprising a means for supporting the aerosol device and
means allowing the three-dimensional control of the position of the
nozzle relative to the vertical sheet. This device can also be
equipped with a pneumatic device for controlling the spray (firing
and duration), so as to control the duration of the vaporization
precisely. The whole assembly can be controlled by computer.
[0021] In order to avoid environmental disturbances, the trajectory
of the product between the nozzle and the sheet will advantageously
be protected horizontally and vertically by the walls of a tunnel
of appropriate dimensions.
[0022] Lastly, vaporization of the product is advantageously
carried out under a controlled atmosphere, preferably at a
temperature of 20.degree. C. and a relative humidity of 50%.
[0023] According to a preferred embodiment of the invention, the
aerosol device according to the invention is suitable for obtaining
a solids flow rate of less than 16 mg/s, preferably ranging from 6
to 15 mg/s.
[0024] Advantageously, the aerosol device according to the
invention is suitable for obtaining a wetting power ranging from 50
mg/s to 125 mg/s.
[0025] The solids flow rate and wetting power characteristics of
the aerosol devices according to the invention depend, on the one
hand, on the aerosol composition, and, on the other hand, on the
means of distribution, the two needing to be suitable in order to
obtain the desired characteristics. Among the parameters liable to
influence these characteristics, mention will be made more
particularly of the solids concentration (C.sub.S), the flow rate
of aerosol composition (F.sub.AC) and the phase of the aerosol
composition.
[0026] Advantageously, the solids concentration (C.sub.S) ranges
from 0.4 to 5% by weight relative to the total weight of the
aerosol composition (fluid+propellant), preferably from 0.6 to
3.25% by weight.
[0027] The flow rate of aerosol composition (F.sub.AC) will, in
this case, be suitable for obtaining a solids flow rate (F.sub.S)
as defined above. Preferably, the F.sub.S will range from 500 to
700 mg/s, more preferably in the region of 550 mg/s.
[0028] The phase of the aerosol composition is preferably a long
phase, that is to say that the fluid/propellant weight ratio is
greater than 1, more preferably ranging from 1.2 to 3.
[0029] The fixing material comprises at least one fixing polymer,
alone or in combination with common cosmetic additives, for example
plasticizers, or neutralizing agents.
[0030] According to the invention, any fixing polymer known per se
can be used. A fixing polymer selected from anionic, cationic,
amphoteric and nonionic polymers and mixtures thereof can be used
in particular. The fixing polymers can be used in solubilized form
or in the form of dispersions of solid polymer particles.
[0031] The cationic fixing polymers which can be used according to
the present invention are preferably selected from polymers
containing primary, secondary, tertiary and/or quaternary amine
groups forming part of the polymer chain or connected directly
thereto, and having a molecular weight preferably ranging from
about 500 to about 5,000,000 and more preferably from 1000 to
3,000,000.
[0032] According to the present invention, the fixing polymers are
preferably anionic or amphoteric polymers.
[0033] The anionic fixing polymers generally used are polymers
containing groups derived from carboxylic acid, sulphonic acid or
phosphoric acid and have a weight-average molecular weight ranging
from approximately 500 to approximately 5,000,000. The carboxylic
groups are provided by unsaturated mono- or dicarboxylic acids
monomers such as those corresponding to the formula (II): 1
[0034] in which:
[0035] n is an integer from 0 to 10,
[0036] A.sub.1 denotes a methylene group, optionally connected to
the carbon atom of the unsaturated group, or to the neighboring
methylene group when n is greater than 1, via a hetero atom such as
oxygen or sulphur,
[0037] R.sub.10 denotes a hydrogen atom or a phenyl or benzyl
group,
[0038] R.sub.8 denotes a hydrogen atom or a lower alkyl or carboxyl
group, and
[0039] R.sub.9 denotes a hydrogen atom, a lower alkyl group or a
--CH.sub.2--COOH, phenyl or benzyl group.
[0040] In the abovementioned formula, a lower alkyl radical
preferably denotes a group having 1 to 4 carbon atoms and in
particular methyl and ethyl.
[0041] The anionic fixing polymers containing carboxylic groups
which are preferred according to the invention are:
[0042] A) Homo- or copolymers of acrylic or methacrylic acid or
salts thereof and in particular the products sold under the names
VERSICOL E or K by the company Allied Colloid and ULTRAHOLD by the
company BASF. The copolymers of acrylic acid and of acrylamide sold
in the form of their sodium salt under the names RETEN 421, 423 or
425 by the company Hercules, the sodium salts of
polyhydroxycarboxylic acids.
[0043] B) Copolymers of acrylic or methacrylic acids with a
monoethylenic monomer such as ethylene, styrene, vinyl esters,
acrylic acid esters or methacrylic acid esters. These copolymers
can be grafted onto a polyalkylene glycol such as polyethylene
glycol and optionally crosslinked. Such polymers are described in
particular in French patent 1,222,944 and German patent application
2,330,956, the disclosures of which are specifically incorporated
by reference herein. Mention may be made in particular of the
copolymers containing an optionally N-alkylated and/or
hydroxyalkylated acrylamide unit in their chain as described in
particular in Luxembourg patent applications 75370 and 75371, the
disclosure of which is specifically incorporated by reference
herein, or sold under the name QUADRAMER by the company American
Cyanamid. Mention may also be made of copolymers of acrylic acid
and of C.sub.1-C.sub.4 alkyl methacrylate and terpolymers of
vinylpyrrolidone, of (meth)acrylic acid and of (meth)acrylate of
C.sub.1-C.sub.20 alkyl, for example lauryl (such as the product
sold by the company ISP under the name ACRYLIDONE LM), tert-butyl
(LUVIFLEX VBM 70 sold by BASF) or methyl (STEPANHOLD EXTRA sold by
Stepan) and methacrylic acid/ethyl acrylate/tert-butyl acrylate
terpolymers such as the product sold under the name LUVIMER 100 P
by the company BASF.
[0044] C) Copolymers derived from crotonic acid such as those
containing vinyl acetate or propionate units in their chain and
optionally other monomers such as allylic esters or methallylic
esters, vinyl ether or vinyl ester of a linear or branched
saturated carboxylic acid with a long hydrocarbon chain such as
those containing at least 5 carbon atoms, it being possible for
these polymers optionally to be grafted and crosslinked, or
alternatively a vinyl, allylic or methallylic ester of an .alpha.-
or .beta.-cyclic carboxylic acid. Such polymers are described,
inter alia, in French patents 1,222,944, 1,580,545, 2,265,782,
2,265,781, 1,564,110 and 2,439,798, the disclosures of which are
specifically incorporated by reference herein. Commercial products
falling into this class are the resins 28-29-30, 26-13-14 and
28-13-10 sold by the company National Starch.
[0045] D) Copolymers derived from C4-C8 monounsaturated carboxylic
acids or anhydrides selected from:
[0046] copolymers comprising (i) one or more maleic, fumaric or
itaconic acids or anhydrides and (ii) at least one monomer selected
from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl
derivatives, acrylic acid and its esters, the anhydride functions
of these copolymers optionally being monoesterified or
monoamidated. Such polymers are described in particular in U.S.
Pat. Nos. 2,047,398, 2,723,248 and 2,102,113 and GB patent 839,805,
the disclosures of which are specifically incorporated by reference
herein, and in particular those sold under the names GANTREZ AN or
ES and AVANTAGE CP by the company ISP;
[0047] copolymers comprising (i) one or more maleic, citraconic or
itaconic anhydrides and (ii) one or more monomers selected from
allylic or methallylic esters optionally containing one or more
acrylamide, methacrylamide, a-olefin, acrylic or methacrylic ester,
acrylic or methacrylic acid or vinylpyrrolidone groups in their
chain,
[0048] the anhydride functions of these copolymers optionally being
monoesterified or monoamidated.
[0049] These polymers are described, for example, in French patents
2,350,384 and 2,357,241, the disclosures of which are specifically
incorporated by reference herein.
[0050] E) Polyacrylamides containing carboxylate groups.
[0051] The polymers comprising sulphonic groups are polymers
containing vinylsulphonic, styrenesulphonic, naphthalenesulphonic
or acrylamidoalkylsulphonic units.
[0052] These polymers can be selected in particular from:
[0053] polyvinylsulphonic acid salts having a weight-average
molecular weight ranging from approximately 1000 to approximately
100,000, as well as the copolymers with an unsaturated comonomer
such as acrylic or methacrylic acids and their esters, as well as
acrylamide or its derivatives, vinyl ethers and
vinylpyrrolidone;
[0054] polystyrenesulphonic acid salts, the sodium salts having a
weight-average molecular weight of about 500,000 and about 100,000,
which are sold respectively under the names FLEXAN 500 and FLEXAN
130 by National Starch. These compounds are described in patent FR
2,198,719, the disclosure of which is specifically incorporated by
reference herein;
[0055] polyacrylamidesulphonic acid salts, those mentioned in U.S.
Pat. No. 4,128,631, the disclosure of which is specifically
incorporated by reference herein, and more particularly
polyacrylamidoethylpropanesulphon- ic acid sold under the name
COSMEDIA POLYMER HSP 1180 by Henkel.
[0056] According to the invention the anionic fixing polymers are
preferably selected from acrylic acid copolymers such as the
acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold
in particular under the name ULTRAHOLD STRONG by the company BASF,
copolymers derived from crotonic acid such as the vinyl
acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the
crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold
in particular under the name RESIN 28-29-30 by the company National
Starch, polymers derived from maleic, fumaric or itaconic acids or
anhydrides with vinyl esters, vinyl ethers, vinyl halides,
phenylvinyl derivatives or acrylic acid and its esters, such as the
methyl vinyl ether/maleic anhydride monoesterified copolymers sold,
for example, under the name GANTREZ by the company ISP, the
copolymers of methacrylic acid and of methyl methacrylate sold
under the name EUDRAGIT L by the company Rohm Pharma, the
copolymers of methacrylic acid/methyl methacrylate/C.sub.1-C.sub.4
alkyl acrylate/acrylic acid or C.sub.1-C.sub.4 hydroxyalkyl
methacrylate which are sold in the form of dispersions under the
name AMERHOLD DR 25 by the company Amerchol or under the name
ACUDYNE 255 by the company Rohm & Haas, the copolymers of
methacrylic acid and of ethyl acrylate sold under the name LUVIMER
MAEX or MAE by the company BASF and the vinyl acetate/crotonic acid
copolymers and the vinyl acetate/crotonic acid copolymers grafted
with polyethylene glycol, sold under the name ARISTOFLEX A by the
company BASF.
[0057] The anionic fixing polymers which are more particularly
preferred are selected from the monoesterified methyl vinyl
ether/maleic anhydride copolymers sold under the name GANTREZ ES
425 by the company ISP, the acrylic acid/ethyl
acrylate/N-tert-butylacrylamide terpolymers sold under the name
ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic
acid and of methyl methacrylate sold under the name EUDRAGIT L by
the company Rohm Pharma, the vinyl acetate/vinyl
tert-butylbenzoate/crotonic acid terpolymers and the crotonic
acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the
name RESIN 28-29-30 by the company National Starch, the copolymers
of methacrylic acid and of ethyl acrylate sold under the name
LUVIMER MAEX or MAE by the company BASF and the vinyl
pyrrolidone/acrylic acid/lauryl methacrylate terpolymers sold under
the name ACRYLIDONE LM by the company ISP.
[0058] The amphoteric fixing polymers which can be used in
accordance with the invention can be selected from polymers
containing units B and C distributed randomly in the polymer chain,
in which B denotes a unit derived from a monomer containing at
least one basic nitrogen atom and C denotes a unit derived from an
acid monomer containing one or more carboxylic or sulphonic groups,
or alternatively B and C can denote groups derived from
carboxybetaine or sulphobetaine zwitterionic monomers; B and C can
also denote a cationic polymer chain containing primary, secondary,
tertiary or quaternary amine groups, in which at least one of the
amine groups bears a carboxylic or sulphonic group connected via a
hydrocarbon radical or alternatively B and C form part of a chain
of a polymer containing an .alpha.,.beta.-dicarboxylic ethylene
unit in which one of the carboxylic groups has been made to react
with a polyamine containing one or more primary or secondary amine
groups.
[0059] The amphoteric fixing polymers corresponding to the
definition given above which are more particularly preferred are
selected from the following polymers:
[0060] (1) Polymers resulting from the copolymerization of a
monomer derived from a vinyl compound bearing a carboxylic group
such as, more particularly, acrylic acid, methacrylic acid, maleic
acid, a-chloroacrylic acid, and a basic monomer derived from a
substituted vinyl compound containing at least one basic atom, such
as, more particularly, dialkylaminoalkyl methacrylate and acrylate,
dialkylaminoalkylmethacrylamides and -acrylamides. Such compounds
are described in U.S. Patent No. 3,836,537, the disclosure of which
is specifically incorporated by reference herein.
[0061] (2) Polymers containing units derived from:
[0062] a) at least one monomer selected from acrylamides and
methacrylamides substituted on the nitrogen with an alkyl
radical,
[0063] b) at least one acidic comonomer containing one or more
reactive carboxylic groups, and
[0064] c) at least one basic comonomer such as esters containing
primary, secondary, tertiary and quaternary amine substituents of
acrylic and methacrylic acids and the product of quaternization of
dimethylaminoethyl methacrylate with dimethyl or diethyl
sulphate.
[0065] The N-substituted acrylamides or methacrylamides which are
more particularly preferred according to the invention are groups
in which the alkyl radicals contain from 2 to 12 carbon atoms and
more particularly N-ethylacrylamide, N-tert-butylacrylamide,
N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide,
N-dodecylacrylamide and the corresponding methacrylamides.
[0066] The acidic comonomers are selected more particularly from
acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
maleic acid and fumaric acid and alkyl monoesters, having from 1 to
4 carbon atoms, of maleic or fumaric acids or anhydrides.
[0067] The preferred basic comonomers are aminoethyl,
butylaminoethyl, N,N'-dimethylaminoethyl and N-tert-butylaminoethyl
methacrylates.
[0068] The copolymers whose CTFA (4th edition, 1991) name is
octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer
such as the products sold under the name AMPHOMER or LOVOCRYL 47 by
the company National Starch are particularly used.
[0069] (3) crosslinked and alkylated polyamino amides partially or
totally derived from polyamino amides of formula (III):
CO--R.sub.10--CO--Z (III)
[0070] in which:
[0071] R.sub.10 represents a divalent radical derived from a
saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid
containing an ethylenic double bond, an ester of a lower alkanol,
having from 1 to 6 carbon atoms, of these acids or a radical
derived from the addition of any one of the acids to a bis(primary)
or bis(secondary) amine, and
[0072] Z denotes a bis(primary), mono- or bis(secondary)
polyalkylene-polyamine radical and preferably represents:
[0073] a) in proportions of from 60 to 100 mol %, the radical
--NH(CH.sub.2).sub.x--NH.sub.p (IV)
[0074] where x=2 and p=2 or 3, or alternatively x=3 and p=2
[0075] this radical being derived from diethylenetriamine, from
triethylenetetraamine or from dipropylenetriamine;
[0076] b) in proportions of from 0 to 40 mol %, the radical (IV)
above in which x=2 and p=1 and which is derived from
ethylenediamine, or the radical derived from piperazine: 2
[0077] c) in proportions of from 0 to 20 mol %, the
--NH--(CH.sub.2).sub.6--NH-- radical derived from
hexamethylenediamine, these polyamino amines being crosslinked by
addition of a difunctional crosslinking agent selected from
epihalohydrines, diepoxides, dianhydrides and bis-unsaturated
derivatives, using from 0.025 to 0.35 mol of crosslinking agent per
amine group of the polyamino amide and alkylated by the action of
acrylic acid, chloroacetic acid or an alkane sultone, or salts
thereof.
[0078] The saturated carboxylic acids are preferably selected from
acids having from 6 to 10 carbon atoms, such as adipic acid,
2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid,
terephthalic acid, acids containing an ethylenic double bond such
as, for example, acrylic acid, methacrylic acid and itaconic
acid.
[0079] The alkane sultones used in the alkylation are preferably
propane sultone or butane sultone, the salts of the alkylating
agents are preferably the sodium or potassium salts.
[0080] (4) polymers containing zwitterionic units of formula (V):
3
[0081] in which:
[0082] R.sub.11 denotes a polymerizable unsaturated group such as
an acrylate, methacrylate, acrylamide or methacrylamide group,
[0083] y and z represent an integer ranging from 1 to 3,
[0084] R.sub.12 and R.sub.13 represent a hydrogen atom, methyl,
ethyl or propyl,
[0085] R.sub.14 and R.sub.15 represent a hydrogen atom or an alkyl
radical such that the sum of the carbon atoms in R.sub.14 and
R.sub.15 does not exceed 10.
[0086] The polymers comprising such units can also contain units
derived from non-zwitterionic monomers such as dimethyl or
diethylaminoethyl acrylate or methacrylate or alkyl acrylates or
methacrylates, acrylamides or methacrylamides or vinyl acetate.
[0087] By way of example, mention may be made of the copolymer of
methyl methacrylate/dimethyl carboxymethylammonio methyl
ethylmethacrylate such as the product sold under the name DIAFORMER
Z301 by the company Sandoz.
[0088] (5) Polymers derived from chitosan containing monomer units
corresponding to the following formulae: 4
[0089] the unit D being present in a concentration ranging from 0
to 30%,
[0090] the unit E in a concentration ranging from 5 to 50%, and
[0091] the unit F in a concentration ranging from 30 to 90%,
[0092] it being understood that, in this unit F, R,.sub.6
represents a radical of formula: 5
[0093] in which,
[0094] if q=0, R.sub.17, R.sub.18 and R.sub.19 each independently
represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino
residue, a monoalkylamine residue or a dialkylamine residue which
are optionally interrupted by one or more nitrogen atoms and/or
optionally substituted with one or more amine, hydroxyl, carboxyl,
alkylthio or sulphonic groups, an alkylthio residue in which the
alkyl group bears an amino residue, at least one of the radicals
R.sub.17, R.sub.18 and R.sub.19 being, in this case, a hydrogen
atom;
[0095] or, if q=1, R.sub.17, R.sub.18 and R.sub.19 each
independently represent a hydrogen atom, as well as the salts
formed by these compounds with bases or acids.
[0096] (6) Polymers derived from the N-carboxyalkylation of
chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan
sold under the name "EVALSAN" by the company Jan Dekker.
[0097] (7) Polymers corresponding to the formula (Vl) are
described, for example, in French patent 1,400,366, the disclosure
of which is specifically incorporated by reference herein: 6
[0098] in which:
[0099] R.sub.20 represents a hydrogen atom, a CH.sub.30,
CH.sub.3CH.sub.2O or phenyl radical,
[0100] R.sub.21 denotes hydrogen or a lower alkyl radical such as
methyl or ethyl,
[0101] R.sub.22 denotes hydrogen or a lower alkyl radical such as
methyl or ethyl,
[0102] R.sub.23 denotes a lower alkyl radical such as methyl or
ethyl or a radical corresponding to the formula:
--R.sub.24--N(R.sub.22).sub.2, wherein R.sub.22 can be the same or
different,
[0103] R.sub.24 representing a --CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--CH.sub.2-- or --CH.sub.2--CH(CH.sub.3)--
group, and the higher homologues of these radicals containing up to
6 carbon atoms.
[0104] (8) Amphoteric polymers of the type --D--X--D--X selected
from:
[0105] a) polymers obtained by the action of chloroacetic acid or
sodium chloroacetate on compounds containing at least one unit of
formula:
--D--X--D--X--D-- (VII)
[0106] where D denotes a radical 7
[0107] and X denotes the symbol E or E', E or E', which may be
identical or different, denotes a divalent radical which is an
alkylene radical containing a straight or branched chain containing
up to 7 carbon atoms in the main chain, which is unsubstituted or
substituted with hydroxyl groups and which can contain, in addition
to the oxygen, nitrogen and sulphur atoms, from 1 to 3 aromatic
and/or heterocyclic rings; the oxygen, nitrogen and sulphur atoms
being present in the form of ether, thioether, sulphoxide,
sulphone, sulphonium, alkylamine or alkenylamine groups, hydroxyl,
benzylamine, amine oxide, quaternary ammonium, amide, imide,
alcohol, ester and/or urethane groups.
[0108] b) Polymers of formula: --D--X--D--X--(VII') in which D
denotes a radical 8
[0109] and X denotes the symbol E or E' and at least once E', E
having the meaning given above and E' is a divalent radical which
is an alkylene radical with a straight or branched chain having up
to 7 carbon atoms in the main chain, which is unsubstituted or
substituted with one or more hydroxyl radicals and containing one
or more nitrogen atoms, the nitrogen atom being substituted with an
alkyl chain which is optionally interrupted by an oxygen atom and
necessarily containing one or more carboxyl functions or one or
more hydroxyl functions and betainized by reaction with
chloroacetic acid or sodium chloroacetate.
[0110] (9) (C.sub.1-C.sub.5)alkyl vinyl ether/maleic anhydride
copolymers partially modified by semiamidation with an
N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or
by semiesterification with an N,N-dialkanolamine. These copolymers
can also contain other vinyl comonomers such as
vinylcaprolactam.
[0111] The amphoteric fixing polymers which are particularly
preferred according to the invention are those of family (3), such
as the copolymers whose CTFA name is
octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,
such as the products sold under the names AMPHOMER, AMPHOMER LV 71
or LOVOCRYL 47 by the company National Starch and those of family
(4) such as the copolymer of methyl methacrylate/dimethyl
carboxymethylammonio methyl ethylmethacrylate, sold, for example,
under the name DIAFORMER Z301 by the company Sandoz.
[0112] The anionic or amphoteric fixing polymers can, if necessary,
be partially or totally neutralized. The neutralizing agents are,
for example, sodium hydroxide, potassium hydroxide,
2-amino-2-methyl-1-propan- ol, monoethanolamine, triethanolamine or
triisopropanolamine and inorganic or organic acids such as
hydrochloric acid or citric acid.
[0113] Advantageously, the appropriate solvent contains at least
50% by volume of alcohol, preferably at least 70% by volume of
alcohol. According to the invention, the term alcohol is understood
to refer to a C.sub.1-C.sub.4 aliphatic alcohol, preferably
ethanol.
[0114] The propellant comprises the compressed or liquefied gases
usually used for the preparation of aerosol compositions. Air,
carbon dioxide or nitrogen, which are compressed, or alternatively
a gas which may or may not be soluble in the composition, such as
dimethyl ether, hydrocarbons and mixtures thereof, will preferably
be used.
[0115] Depending on the aerosol composition (fluid+propellant), a
person skilled in the art will know how to select the appropriate
distribution means in order to obtain the desired solids flow rate
and wetting power characteristics.
[0116] The specific characteristics defined above (C.sub.S and
phase) can be obtained by selecting the appropriate distribution
means and/or by varying the formulation.
[0117] The appropriate valves for the specific compositions above
are, in particular, straight valves with a nozzle having a diameter
ranging from 0.35 to 0.60 mm, preferably from 0.40 to 0.50 mm,
advantageously with no internal restriction or any additional
uptake of gas. These are, in particular, the valves sold under the
name COSTER T104 RA36/014 by the company Coster or the valve
PRECISION EXPERIMENTAL 15130, comprising a nozzle and a valve body
0.46 mm in diameter with no additional gas uptake, from the company
Precision.
[0118] The appropriate diffusers for the specific compositions
above are, in particular, the push-button dispensers sold under the
name PRECISION 216903-40AD29 by the company Precision.
[0119] The present invention also relates to a process for treating
keratin fibers, in which a composition comprising a fixing material
having a glass transition temperature (Tg) of greater than or equal
to 30.degree. C. is applied to the fibers by means of an
appropriate device in order to obtain a solids flow rate ranging
from approximately 4 to approximately 17 mg/s and a wetting power
of greater than or equal to 50 mg/s.
[0120] The examples below allow the invention to be illustrated
without, however, limiting its scope.
EXAMPLE 1
Importance of the "Wetting Power" for Lacquering
[0121] The two aerosol devices below were prepared:
[0122] Device 1 (According to the Invention)
[0123] The following fluid was prepared:
[0124] Composition A
1 Acrylic acid/ethyl acrylate/N-tert-butylacrylamide 3.10 g
terpolymer sold under the name ULTRAHOLD STRONG by the company BASF
2-Amino-2-methyl-1-propanol q.s. Neutralization Ethanol q.s. 100.00
g
[0125] 65 g of this fluid were introduced into an aerosol can which
was then fitted with a PRECISION EXPERIMENTAL 15130 valve, after
which 35 g of dimethyl ether were added as propellant and a
PRECISION 216903-40AD29 bush-button dispenser.
[0126] The characteristics of this device were as follows:
2 Tg of the fixing material 51.degree. C. F.sub.S 11 mg/s Wetting
power 55 mg/s F.sub.AC 550 mg/s
[0127] Device 2 (Comparative)
[0128] The following fluid was prepared:
[0129] Composition B
3 Acrylic acid/ethyl acrylate/N-tert-butylacrylamide 4.28 g
terpolymer sold under the name ULTRAHOLD STRONG by the company BASF
2-Amino-2-methyl-1-propanol q.s. Neutralization Ethanol q.s. 100.00
g
[0130] 35 g of this fluid and 20 g of pentane were introduced into
an aerosol can which was fitted with a PRECISION P155/590 valve
(sold by the company Precision), after which 43 g of dimethyl ether
were added as propellant, and a PRECISION 21 6943-40 push-button
dispenser (sold by the company Precision).
[0131] The characteristics of this device were as follows:
4 Tg of the fixing material 51.degree. C. F.sub.S 11 mg/s Wetting
power 10 mg/s F.sub.AC 700 mg/s
[0132] These two devices were tested on heads (20 s per head). The
tests showed that only the device according to the invention
allowed a desired cosmetic fixing effect to be obtained. In
contrast, device 2 (comparative) did not allow a satisfactory
cosmetic fixing result to be obtained.
Example 2
Importance of the "Tg" for Obtaining Good Cosmetic Properties
[0133] The following fluids were prepared:
[0134] Composition C
5 VA/vinyl butylbenzoate/crotonates copolymer (CTFA) 4.28 g
2-Amino-2-methyl-1-propanol q.s. Neutralization Tripropylene glycol
monomethyl ether 0.29 g Ethanol q.s. 100.00 g
[0135] Composition D
6 VA/vinyl butylbenzoate/crotonates copolymer (CTFA) 4.28 g
2-Amino-2-methyl-1-propanol q.s. Neutralization Ethanol q.s. 100.00
g
[0136] The aerosol devices 3 and 4 were prepared by introducing 65
g of compositions C and D respectively into aerosol cans. The two
cans were fitted with a PRECISION EXPERIMENTAL 15130 valve and 35 g
of dimethyl ether as propellant, and a PRECISION 216903-40AD29
push-button dispenser were then added.
[0137] For the two devices, the F.sub.S was 14.3 mg/s and the
wetting power was 62 mg/s.
[0138] The Tg values of the fixing materials in the two devices
were as follows:
7 Tg device 3 (comparative) 23.degree. C. Tg device 4 (according to
the invention) 41.degree. C.
[0139] The performance levels of the two devices were compared by
spraying the two compositions on 10 heads in half-head tests. In
all cases, the fixing powers were satisfactory and comparable. On
the other hand, the side treated with device 4 according to the
invention felt more pleasant than the side treated with comparative
device 3, and likewise the disentangling was easier on the side
treated with device 4 according to the invention, and the feel
after disentangling was also considered to be more pleasant.
Example 3
Importance of the "F.sub.S" for Obtaining Good Cosmetic
Properties
[0140] The following two fluids were prepared:
[0141] Composition E
8 VA/vinyl butylbenzoate/crotonates copolymer (CTFA) 4.00 g
2-Amino-2-methyl-1-propanol q.s. Neutralization Ethanol q.s. 100.00
g
[0142] Composition F
9 VA/vinyl butylbenzoate/crotonates copolymer (CTFA) 5.00 g
2-Amino-2-methyl-1-propanol q.s. Neutralization Ethanol q.s. 100.00
g
[0143] Aerosol devices 5 and 6 were prepared by introducing 65 g of
compositions E and F respectively into aerosol cans. The two cans
were fitted with a PRECISION EXPERIMENTAL 15130 valve and 35 g of
dimethyl ether as propellant, and a PRECISION 216903-40AD29
push-button dispenser were then added.
[0144] For the two devices, the Tg of the fixing material was
41.degree. C. and the wetting power was 62 mg/s.
[0145] The F.sub.S values of the fixing materials in the two
devices were as follows:
10 F.sub.S device 5 (according to the invention) 15.0 mg/s F.sub.S
device 6 (comparative) 18.5 mg/s
[0146] The performance levels of the two devices were compared by
spraying the two compositions on 10 heads in half-head tests. In
all cases, the fixing powers were satisfactory and comparable. On
the other hand, the side treated with device 5 according to the
invention felt more pleasant than the side treated with comparative
device 6, and likewise the disentangling was easier on the side
treated with device 5 according to the invention, and the feel
after disentangling was also considered to be more pleasant.
Example 4
Comparisons
[0147] The disentangling properties obtained with device 4 (65 g of
composition D, PRECISION EXPERIMENTAL valve 15130, 35 g of dimethyl
ether, PRECISION 216903-40AD29 push-button dispenser) were compared
with those of commercial devices.
11 Wetting Disen- Device Tg F.sub.S power tangling Device 4
41.degree. C. 14.3 mg/s 62 mg/s +++ *Pantene Pro V .RTM. 50.degree.
C. 17.4 mg/s >190 mg/s ++ **Aqua Net .RTM. 23.degree. C. 16.8
mg/s 190 mg/s + **Elnett .RTM. Fixation <30.degree. C. >20
mg/s 40 mg/s ++ Forte *Sold by Procter & Gamble **Sold by
Faberg ***Sold by L'Oral + to +++ represent an increasing scale of
the disentangling qualities of the various compositions.
[0148] The results of the above table are in accordance with those
results observed in Examples 1 to 3, in which only the device
satisfying the three characteristics of "Tg", "F.sub.S" and
"wetting power" according to the invention allows both strong
fixing and improved cosmetic properties to be obtained.
* * * * *