U.S. patent application number 13/453530 was filed with the patent office on 2012-12-27 for composition for shaping keratin fibers containing starches modified with propylene oxide.
Invention is credited to Carine Dogan, Lydiane Huet, Thorsten Knappe, Ralf Roenisch, Mathias Schriefers, MATTHIAS SCHWEINSBERG.
Application Number | 20120328532 13/453530 |
Document ID | / |
Family ID | 43648714 |
Filed Date | 2012-12-27 |
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United States Patent
Application |
20120328532 |
Kind Code |
A1 |
SCHWEINSBERG; MATTHIAS ; et
al. |
December 27, 2012 |
COMPOSITION FOR SHAPING KERATIN FIBERS CONTAINING STARCHES MODIFIED
WITH PROPYLENE OXIDE
Abstract
Cosmetic agents for temporarily reshaping keratin fibers,
particularly human hair, containing in a cosmetic carrier at least
one starch modified with propylene oxide, the starch having an
average molecular weight (weight-average) of 50 to 2,500 kDa and a
propylene oxide content of 4 to 6 wt. % (based on weight of the
starch modified with propylene oxide), wherein the agents achieve
styling with a good degree of hold and elevated flexibility. The
propylene oxide-modified starches are based on renewable raw
materials. Here, effective styling agents for hair can be provided
without having to rely on setting polymers obtained from fossil
fuels.
Inventors: |
SCHWEINSBERG; MATTHIAS;
(Hamburg, DE) ; Roenisch; Ralf; (Wuppertal,
DE) ; Schriefers; Mathias; (Moenchengladbach, DE)
; Huet; Lydiane; (Strassburg, FR) ; Dogan;
Carine; (Vigneux sur Seine, FR) ; Knappe;
Thorsten; (Scenefeld, DE) |
Family ID: |
43648714 |
Appl. No.: |
13/453530 |
Filed: |
April 23, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/EP2010/065862 |
Oct 21, 2010 |
|
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13453530 |
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Current U.S.
Class: |
424/47 ;
424/70.13 |
Current CPC
Class: |
A61K 8/608 20130101;
A61K 8/046 20130101; A61K 8/732 20130101; A61K 8/8152 20130101;
A61K 8/8158 20130101; A61Q 5/06 20130101; A61K 2800/5422 20130101;
A61K 8/8147 20130101; A61K 2800/5424 20130101 |
Class at
Publication: |
424/47 ;
424/70.13 |
International
Class: |
A61K 8/73 20060101
A61K008/73; A61Q 5/06 20060101 A61Q005/06 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 22, 2009 |
DE |
10 2009 045 925.1 |
Oct 22, 2009 |
DE |
10 2009 045 933.2 |
Claims
1. Cosmetic agent for temporarily reshaping keratin fibers
comprising in a cosmetic carrier at least one starch modified with
propylene oxide, wherein the modified starch has an average
molecular weight (weight-average) of 50 to 2,500 kDa and a
propylene oxide content of 4 to 6 wt. % based on weight of the
modified starch.
2. Cosmetic agent according to claim 1, wherein the modified starch
is gelatinized.
3. Cosmetic agent according to claim 1, wherein the modified starch
is uncrosslinked.
4. Cosmetic agent according to claim 1, wherein the modified starch
has an average molecular weight (weight-average) of 100 to 2,000
kDa.
5. Cosmetic agent according to claim 1, wherein, in a 43 wt. %
solution in water, the modified starch has a viscosity from 150 to
1,500,000 mPas based on Brookfield viscometer with spindle #7 at
20.degree. C. and 20 rpm.
6. Cosmetic agent according to claim 1, wherein the modified starch
is a tapioca starch modified with propylene oxide, a potato starch
modified with propylene oxide, or a mixture thereof.
7. Cosmetic agent according to claim 1, wherein the modified starch
is present in an amount of 0.01 wt. % to 40 wt. %, based on total
weight of the agent.
8. Cosmetic agent according to claim 1 further comprising at least
one polymer chosen from film-forming polymers and setting
polymers.
9. Cosmetic agent according to claim 1 further comprising at least
one compound of formula (II),
HO--CH.sub.2--(CHOH).sub.n--CH.sub.2--OH (II) wherein n is an
integer from 1 to 4.
10. Cosmetic agent according to claim 1 further comprising at least
one propellant.
11. Method for temporarily reshaping keratin fibers comprising
applying a cosmetic agent according to claim 1 onto the keratin
fibers.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of International
Application No. PCT/EP2010/065862 filed 21 Oct. 2010, which claims
priority to German Patent Application Nos. 10 2009 045 925.1 and 10
2009 045 933.2, both filed 22 Oct. 2009, each of which are
incorporated herein by reference.
[0002] The present invention relates to cosmetic agents for
temporarily reshaping keratin fibers, containing in a cosmetic
carrier at least one starch modified with propylene oxide and
having an average molecular weight (weight-average) of 50 to 2,500
kDa and a propylene oxide content of 4 to 6 wt. % (based on weight
of the starch modified with propylene oxide).
[0003] Agents for temporary shaping typically contain synthetic
polymers as the shaping component. Preparations containing a
dissolved or dispersed polymer can be applied to hair by propellant
gases or by a pump mechanism. Hair gels and hair waxes, however,
are generally not applied directly onto the hair but are rather
distributed in the hair using a comb or the hands.
[0004] Synthetic polymers typically used in agents for temporary
shaping are produced from appropriate synthetically obtainable
monomers. These monomers are obtained from fossil substances such
as petroleum by conversion into the corresponding polymer building
blocks, inter alia with input of energy. In a more sustainable
approach to nature as our habitat and to resources, it remains
desirable to use only those cosmetic raw materials for cosmetic
products which can be obtained from "renewable" raw materials using
the least possible energy. However, synthetic polymers can only be
reduced in quantity or substituted if the replacement provides the
characteristics desired for the intended application and ensures
that the keratin-containing fibres adequately maintain a stable
shape.
[0005] Moreover, naturally based replacement polymers should
maintain the bounce and silkiness of keratin-containing fibers
which have been set in shape. Formation of polymer particles which
are visible to the naked eye on keratin-containing fibers must be
avoided. Furthermore, the keratin-containing fibers must not look
dull, but should instead have a natural gloss.
[0006] The present invention provides a cosmetic composition with a
shape-setting action which brings about improved or equivalent
shape setting and does not exhibit the above-stated disadvantages.
In so doing, it is intended to make little or, if possible, no use
of synthetic polymers based on fossil raw materials.
[0007] The present invention accordingly firstly provides a
cosmetic agent for temporarily reshaping keratin fibers,
particularly human hair, containing in a cosmetic carrier at least
one starch modified with propylene oxide, wherein the starch has an
average molecular weight (weight-average) of 50 to 2,500 kDa and a
propylene oxide content of 4 to 6 wt. % (based on weight of the
starch modified with propylene oxide). These agents exhibit
excellent parameters for use on hair. The starch can be
incorporated into the agents by simple mixing virtually without
input of heat at a temperature of at most 30.degree. C.
[0008] Keratin fibers according to the invention refer to furs,
wool, feathers and particularly human hair.
[0009] Starch is a storage carbohydrate which is stored by many
plants in the form of starch grains (granules) ranging in size from
1 to 200 .mu.m in various plant parts, for example, in tubers or
roots, cereal seeds, fruits and in the medulla. Starch modified
with propylene oxide which can be used according to the invention
can be obtained from starch from potatoes, maize, rice, peas,
acorns, chestnuts, barley, wheat, bananas, sago, millet, sorghum,
oats, barley, rye, beans, sweet potato, arrowroot or manioc.
Particularly pronounced effects according to the invention are
achieved using tapioca starch modified with propylene oxide, potato
starch modified with propylene oxide or mixtures of both of these
starches. It is very particularly preferred to use potato starch
modified with propylene oxide as the corresponding modified
starch.
[0010] Starch belongs to the homoglycan family and is a
polycondensation product of D-glucose. Starch consists of three
structurally different polymers: d-glucopyranose, namely amylose,
amylopectin and an "intermediate fraction". Higher plants contain 0
to 45 wt. % of amylose relative to dry solids.
[0011] The intermediate fraction, also referred to as "abnormal
amylopectin", lies structurally between amylose and amylopectin.
The quantities stated for amylopectin for the purposes of the
present application include the intermediate fraction.
[0012] It is preferred for the starch modified with propylene oxide
to have an amylose content of less than 25 wt. %, particularly less
than 20 wt. %, based on total weight of the starch. It was found
that, in order to achieve the effect according to the invention, a
particularly suitable starch is one having 17 to 22 wt. % amylose
and 78 to 83 wt. % amylopectin.
[0013] Amylose consists of predominantly linear
.alpha.-1,4-glycosidically linked d-glucose M.sub.r 50,000-150,000.
The resultant chains formation double helices in the starch.
[0014] In addition to the .alpha.-1,4 linkages described for
amylose, amylopectin also contains from 4 to 6% of .alpha.-1,6
bonds as branch points. The average distance between the branch
points amounts for instance to 12 to 17 glucose units. The molar
mass of 10.sup.7 to 710.sup.8 corresponds to approx. 10.sup.5
glucose units, amylopectin accordingly being among the largest
biopolymers. Said branches are distributed within the molecule in
such a way that a cluster structure with relatively short side
chains develops. Two of these side chains in each case form a
double helix. Due to the numerous branch points, amylopectin is
relatively readily soluble in water.
[0015] According to the invention, a starch modified with propylene
oxide is taken to mean a reaction product of a starch with
propylene oxide. Such a reaction product comprises at least one
structural unit of formula (I),
##STR00001##
wherein at least one of R, R' or R'' is a group of the formula
##STR00002##
where n 0 and at most 2 of R, R', R'' are a hydrogen atom. A bond
marked with the symbol * in the formulae of the present application
corresponds to a free valence of the corresponding structural unit.
Starches modified with propylene oxide are, for example, prepared
by reacting a native starch with propylene oxide. Prior to
modification with propylene oxide, the starch may have been
subjected to various physical or chemical processes such as heat
treatment, shearing or cleavage by thermal treatment, acid
hydrolysis, oxidation, or enzymatic treatment, etc.
[0016] It is preferred for the starch modified with propylene oxide
when used in the agent according to the invention not to be present
as individual starch grains (granules). Accordingly, the starch
grains are opened up, for example, by heat or shearing, and the
corresponding polysaccharide molecules are released therefrom. The
released polysaccharide molecules can be modified with propylene
oxide after or before release.
[0017] In a preferred embodiment, the propoxylated starch is
gelatinized. If an aqueous suspension of starch is heated or
compressed at a critical temperature or pressure, tangential
swelling of the bodies is observed accompanied by loss of
birefringence, a modified X-ray structure and an abrupt increase in
the viscosity of the solution. This phenomenon is known as
gelatinization.
[0018] Starches according to the invention modified with propylene
oxide are present in the agent in a molecular weight distribution.
Molecular weight distribution is determined experimentally by gel
filtration chromatography against dextran. One important feature of
the invention is the weight-average molecular weight of the
propylene oxide-modified starches present in the agent. This
weight-average is an average molecular weight which takes account
of the total weight of the molecules of different molecular weight,
and not merely the number of molecules. The "weight fraction"
w.sub.i=(N.sub.iM.sub.i)/[.SIGMA.(N.sub.iM.sub.i)]
is first defined in order to calculate the weight average
statistically. This indicates the proportion by weight of
macromolecules in the sample consisting of i segments (e.g.,
monomer building blocks) of mass M.sub.i consist and occur N.sub.i
times in the sample. The following equation accordingly applies to
the weight-average molecular weight
M.sub.w=.SIGMA.w.sub.iM.sub.i:
M.sub.w=[.SIGMA.(N.sub.iM.sup.2.sub.i)]/[.SIGMA.(N.sub.iM.sub.i)].
[0019] Particularly preferred agents are those having starches
modified with propylene oxide and which have an average molecular
weight (weight-average) of 100 to 2,000 kDa, particularly 500 to
1,800 kDa, very preferably 700 to 1,000 kDa.
[0020] It is particularly preferred for the starch modified with
propylene oxide to be uncrosslinked. Crosslinking of starch
modified with propylene oxide is present when the linear or
branched polysaccharide macromolecules of the starch are covalently
linked by a crosslinking agent to form a three-dimensional,
insoluble polymer network which is then only swellable. Native
starch is generally regarded as uncrosslinked and, should
crosslinking be desired, would require artificial crosslinking by
chemical synthesis. Such artificial crosslinking can be carried out
with crosslinking agents such as epichlorohydrin. (Propylene
oxide-modified) starches which do not exhibit such crosslinking are
uncrosslinked.
[0021] In order to achieve a lower molecular weight, for example,
100 to 400 kDa or 200 to 300 kDa, the starches are subjected to
mechanical cleavage, enzymatic cleavage (particularly with
.alpha.-amylase, .beta.-amylase, glucoamylase or debranching
enzymes), cleavage by acid hydrolysis (particularly with
hydrochloric acid, sulfuric acid or phosphoric acid), thermal
cleavage or reaction with oxidizing agents (such as periodate,
hypochlorite, chromic acid, permanganate, nitrogen dioxide,
hydrogen peroxide or organic percarboxylic acid, preferably with
hydrogen peroxide). Kneaders, extruders, stator/rotor devices
and/or stirrers are suitable for mechanically cleaving starch.
[0022] Oxidative cleavage using hydrogen peroxide is preferably
suitable. To accomplish this, starch modified with propylene oxide
is placed in water, heated to 50 to 70.degree. C., hydrogen
peroxide is added, and the mixture stirred at 70 to 85.degree. C.
for 2 to 5 hours.
[0023] The starch's propylene oxide content has an impact on
styling hold and styling flexibility as well as on the stability of
the cosmetic agent. It has surprisingly been found that ideal
application parameters are obtained when the modified starch has,
based on weight of the starch, a propylene oxide content of 4 to 6
wt. %. Propylene oxide content can, for example, be determined,
once Hodges cleavage has been carried out, according to DIN EN
13268.
[0024] It has furthermore been found that cosmetic agents which are
ideally suitable for the invention are those in which, in a 43 wt.
% solution in water (i.e., a 43 wt. % aqueous solution), the
modified starch exhibits a viscosity from 150 to 1,500,000 mPas
(Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
Ideally suitable propylene oxide-modified polysaccharides exhibit
viscosities of 3,000 to 200,000 mPas, particularly 10,000 to
100,000 mPas, very preferably 40,000 to 70,000 mPas (measured under
the above-stated conditions).
[0025] It is preferred for the cosmetic agent to contain the
polysaccharide modified with propylene oxide in an amount of 0.01
wt. % to 40 wt. %, more preferably 0.5 wt. % to 10 wt. %, very
preferably 2 wt. % to 6 wt. %, based on total weight of the
agent.
[0026] Agents according to the invention preferably comprise foams
or gels as the cosmetic carrier and therefore are preferably in the
form of a foam or gel. Excellent setting can be achieved with the
starches. Furthermore, gels produced with the modified starches
additionally achieve superb transparency.
[0027] Very particularly preferred cosmetic agents according to the
invention comply with at least one of the following embodiments A)
to R):
[0028] A): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked starch modified with propylene oxide,
the starch having an average molecular weight (weight-average) of
50 to 2,500 kDa and a propylene oxide content of 4 to 6 wt. %
(based on weight of the modified starch).
[0029] B): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked starch modified with propylene oxide,
the starch having an average molecular weight (weight-average) of
700 to 1,000 kDa and a propylene oxide content of 4 to 6 wt. %
(based on weight of the modified starch).
[0030] C): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked starch modified with propylene oxide,
the starch having an average molecular weight (weight-average) of
50 to 2,500 kDa, a propylene oxide content of 4 to 6 wt. % (based
on weight of the modified starch) and a viscosity of 3,000 to
200,000 mPas (in a 43 wt. % aqueous solution, Brookfield
viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0031] D): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked starch modified with propylene oxide,
the starch having an average molecular weight (weight-average) of
50 to 2,500 kDa, a propylene oxide content of 4 to 6 wt. % (based
on weight of the modified starch) and a viscosity of 10,000 to
100,000 mPas (in a 43 wt. % aqueous solution, Brookfield
viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0032] E): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked starch modified with propylene oxide,
the starch having an average molecular weight (weight-average) of
700 to 1,000 kDa, a propylene oxide content of 4 to 6 wt. % (based
on weight of the modified starch) and a viscosity of 3,000 to
200,000 mPas (in a 43 wt. % aqueous solution, Brookfield
viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0033] F): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked starch modified with propylene oxide,
the starch having an average molecular weight (weight-average) of
700 to 1,000 kDa, a propylene oxide content of 4 to 6 wt. % (based
on weight of the modified starch) and a viscosity of 10,000 to
100,000 mPas (in a 43 wt. % aqueous solution, Brookfield
viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0034] G): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked tapioca starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 50 to 2,500 kDa and a propylene oxide content
of 4 to 6 wt. % (based on weight of the modified starch).
[0035] H): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked tapioca starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 700 to 1,000 kDa and a propylene oxide content
of 4 to 6 wt. % (based on weight of the modified starch).
[0036] I): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked tapioca starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 50 to 2,500 kDa, a propylene oxide content of 4
to 6 wt. % (based on weight of the modified starch) and a viscosity
of 3,000 to 200,000 mPas (in a 43 wt. % aqueous solution,
Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0037] J): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked tapioca starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 50 to 2,500 kDa, a propylene oxide content of 4
to 6 wt. % (based on weight of the modified starch) and a viscosity
of 10,000 to 100,000 mPas (in a 43 wt. % aqueous solution,
Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0038] K): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked tapioca starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 700 to 1,000 kDa, a propylene oxide content of
4 to 6 wt. % (based on weight of the modified starch) and a
viscosity of 3,000 to 200,000 mPas (in a 43 wt. % aqueous solution,
Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0039] L): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked tapioca starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 700 to 1,000 kDa, a propylene oxide content of
4 to 6 wt. % (based on weight of the modified starch) and a
viscosity of 10,000 to 100,000 mPas (in a 43 wt. % aqueous
solution, Brookfield viscometer, spindle #7 at 20.degree. C. and 20
rpm).
[0040] M): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one potato starch modified with propylene oxide, the
starch having an average molecular weight (weight-average) of 50 to
2,500 kDa and a propylene oxide content of 4 to 6 wt. % (relative
to the weight of the starch modified with propylene oxide).
[0041] N): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one potato starch modified with propylene oxide, the
starch having an average molecular weight (weight-average) of 700
to 1,000 kDa and a propylene oxide content of 4 to 6 wt. % (based
on weight of the modified starch).
[0042] O): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked potato starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 50 to 2,500 kDa, a propylene oxide content of 4
to 6 wt. % (based on weight of the modified starch) and a viscosity
of 3,000 to 200,000 mPas (in a 43 wt. % aqueous solution,
Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0043] P): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked potato starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 50 to 2,500 kDa, a propylene oxide content of 4
to 6 wt. % (based on weight of the modified starch) and a viscosity
of 10,000 to 100,000 mPas (in a 43 wt. % aqueous solution,
Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0044] Q): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked potato starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 700 to 1,000 kDa, a propylene oxide content of
4 to 6 wt. % (based on weight of the modified starch) and a
viscosity of 3,000 to 200,000 mPas (in a 43 wt. % aqueous solution,
Brookfield viscometer, spindle #7 at 20.degree. C. and 20 rpm).
[0045] R): A cosmetic agent for temporarily reshaping keratin
fibers, particularly human hair, comprising in a cosmetic carrier
at least one uncrosslinked potato starch modified with propylene
oxide, the starch having an average molecular weight
(weight-average) of 700 to 1,000 kDa, a propylene oxide content of
4 to 6 wt. % (based on weight of the modified starch) and a
viscosity of 10,000 to 100,000 mPas (in a 43 wt. % aqueous
solution, Brookfield viscometer, spindle #7 at 20.degree. C. and 20
rpm).
[0046] For the above-stated embodiments, the preferred features of
the agent according to the invention apply mutatis mutandis, as do
in particular the quantities used.
[0047] In addition to starch modified with propylene oxide
(particularly that modified with propylene oxide according to
embodiments A) to R)), the cosmetic agent according to the
invention preferably also contains at least one polymer chosen from
film-forming polymers or setting polymers. In this way, it is
possible, for example, to finely tune the reshaping result and
conditioning of the fibers. These additional polymers differ from
starches modified with propylene oxide and can have an anionic,
amphoteric, nonionic, permanently cationic or temporarily cationic
(preferably nonionic, permanently cationic or temporarily cationic)
charge.
[0048] Polymers according to the invention refer to compounds
synthesized from a plurality of molecules wherein one kind or a
plurality of species of atoms or atomic groups ("constitutive
units", "basic building blocks" or "repeat units") is repeatedly
arranged adjacent one another and have a molecular weight of at
least 10,000 g/mol. The polymers are obtained by polyreaction,
which can proceed artificially (i.e., synthetically) or
naturally.
[0049] Film-forming polymers refer to those polymers which, on
drying, leave behind a continuous film on the skin, hair or nails.
Such film formers can be used in a wide variety of cosmetic
products, such as face masks, make-up, hair fixatives, hairsprays,
hair gels, hair waxes, hair tonics, shampoos or nail polishes.
Particular preference is given to those polymers having sufficient
solubility in water, alcohol or water/alcohol mixtures. Thus,
corresponding solutions can be produced which may be simply applied
or further processed.
[0050] Film-forming polymers further refer to those polymers
capable of, when applied in a 0.01 to 20 wt. % aqueous, alcoholic
or aqueous-alcoholic solution, depositing a transparent polymer
film on the hair.
[0051] Hair-setting polymers assist in holding or building up the
volume and fullness of the overall hairstyle. These polymers are
simultaneously also film-forming polymers and therefore generally
typical substances for shaping hair treatment agents such as hair
setting preparations, hair mousses, hair waxes, and hair sprays.
Film formation in this respect can occur only at points and connect
only a few fibres together.
[0052] Additional cationic film-forming and/or cationic setting
polymers can be chosen from cationic, quaternized cellulose
derivatives. Cationic, quaternized celluloses which are
advantageous for the purposes of the invention are generally those
having more than one permanent cationic charge in a side chain.
[0053] Among these, emphasis should be placed on those cationic
cellulose derivatives produced by reaction of hydroxyethylcellulose
with a dimethyldiallylammonium reactant (particularly
dimethyldiallylammonium chloride), optionally in the presence of
further reactants. Among these cationic celluloses, cationic
celluloses which are particularly suitable are those with the INCI
name Polyquaternium-4, distributed, for example, under the names
Celquat.RTM. H 100, Celquat.RTM. L 200 by National Starch.
[0054] Additional cationic film-forming and/or cationic setting
polymers which are suitable are those having at least one
structural unit of formula (M-I) and at least one structural unit
of the formula (M-VI), and optionally at least one structural unit
of the formula (M-V)
##STR00003##
wherein R.sup.1 and R.sup.4 are, mutually independently, a hydrogen
atom or a methyl group, A.sup.1 and A.sup.2 are, mutually
independently, a 1,2-ethanediyl, 1,3-propanediyl or 1,4-butanediyl
group, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are, mutually
independently, a (C.sub.1 to C.sub.4) alkyl group, and R.sup.7 is a
(C.sub.8 to C.sub.30) alkyl group.
[0055] The positive charge of monomer (M-VI) can be offset using
any possible physiologically acceptable anions, such as chloride,
bromide, hydrogensulfate, methylsulfate, ethylsulfate,
tetrafluoroborate, phosphate, hydrogenphosphate,
dihydrogenphosphate or p-toluenesulfonate, triflate. Suitable
compounds are, for example, commercially available as [0056]
copolymers of diethylsulfate-quaternized
dimethylaminoethylmethacrylate methosulfate with vinylpyrrolidone
with the INCI name Polyquaternium-11 under the names Gafquat.RTM.
440, Gafquat.RTM.734, Gafquat.RTM.755 (in each case ISP) and
Luviquat PQ 11 PN (BASF SE), [0057] copolymers of
methacryloylaminopropyllauryldimethylammonium chloride with
vinylpyrrolidone and dimethylaminopropylmethacrylamide with the
INCI name Polyquaternium-55 under the trade names, Styleze.RTM.
W-10, Styleze.RTM. W-20 (ISP), [0058] copolymers of
N-vinylpyrrolidone, N-vinylcaprolactam,
N-(3-dimethylaminopropyl)-methacrylamide and
3-(methacryloyl)propyllauryldimethylammonium chloride (INCI name:
Polyquaternium-69) under the trade name AquaStyle.RTM. 300 (28-32
wt. % active substance in ethanol-water mixture) (ISP).
[0059] Additional film-forming and/or setting polymers chosen from
cationic polymers having at least one structural unit comprising a
permanently cationized nitrogen atom which may particularly be used
in the invention are those cationic film-forming and/or cationic
setting polymers having at least one structural element of the
formula (M1)
##STR00004##
wherein R'' is a (C.sub.1 to C.sub.4) alkyl group, particularly a
methyl group, and additionally have at least one further cationic
and/or nonionic structural element.
[0060] The positive polymer charge of the component can be offset
using any possible physiologically acceptable anions, such as
chloride, bromide, hydrogensulfate, methylsulfate, ethylsulfate,
tetrafluoroborate, phosphate, hydrogenphosphate,
dihydrogenphosphate or p-toluenesulfonate, triflate.
[0061] It is preferred for the cosmetic agent according to the
invention to additionally contain as the cationic film-forming
and/or cationic setting polymer at least one copolymer (b1) which,
in addition to at least one structural element of formula (M1),
additionally contains a structural element of formula (M-I)
##STR00005##
wherein R'' is a (C.sub.1 to C.sub.4) alkyl group, particularly a
methyl group.
[0062] The positive polymer charge of copolymers (b1) can be offset
using any possible physiologically acceptable anions, such as
chloride, bromide, hydrogensulfate, methylsulfate, ethylsulfate,
tetrafluoroborate, phosphate, hydrogenphosphate,
dihydrogenphosphate or p-toluenesulfonate, triflate.
[0063] Cationic film-forming and/or cationic setting polymers which
are very particularly preferred as copolymers (b1) contain 10 to 30
mol %, preferably 15 to 25 mol % and particularly 20 mol % of
structural units according to formula (M1) and 70 to 90 mol %,
preferably 75 to 85 mol % and particularly 80 mol % of structural
units according to formula (M-I).
[0064] Here, it is particularly preferred for copolymers (b1) to
contain, in addition to polymer units occurring from the
incorporation of structural units according to formula (M1) and
(M-I) into the copolymer, up to 5 wt. %, preferably at most 1 wt.
%, of polymer units originating from the incorporation of other
monomers. Copolymers (b1) are preferably exclusively synthesized
from structural units of formula (M1) with R''=methyl, and (M-I)
and can be described by the general formula (Poly1)
##STR00006##
wherein m and p vary depending on the molar mass of the polymer and
are not intended to imply that the copolymers are block copolymers.
Instead, structural units of formula (M1) and formula (M-I) can be
randomly distributed in the molecule.
[0065] If a chloride ion is used to offset the positive charge of
the polymer of formula (Polyl), such
N-methylvinylimidazole/vinylpyrrolidone copolymers are designated
according to INCI nomenclature as Polyquaternium-16 and are
obtainable, for example, from BASF under the trade names
Luviquat.RTM. Style, Luviquat.RTM. FC 370, Luviquat.RTM.FC 550,
Luviquat.RTM.FC 905 and Luviquat.RTM.MQ 552.
[0066] If a methosulfate is used to offset the positive charge of
the polymer of the formula (Poly1), such
N-methylvinylimidazole/vinylpyrrolidone copolymers are designated
according to INCI nomenclature as Polyquaternium-44 and are
obtainable, for example, from BASF under the trade name
Luviquat.RTM. UltraCare.
[0067] In addition to or instead of copolymer(s) (b1), cosmetic
agents according to the invention can also contain copolymers (b2)
which, based on copolymer (b1), comprise structural units of
formula (M-II) as additional structural units
##STR00007##
[0068] Further cosmetic agents which are particularly preferred
according to the invention contain as cationic film-forming and/or
cationic setting polymer at least one copolymer (b2) having at
least one structural unit according to formula (M1-a), at least one
structural unit according to formula (M-I) and at least one
structural unit according to formula (M-II)
##STR00008##
[0069] Here, it is particularly preferred for copolymers (b2) to
contain, in addition to polymer units which arise from the
incorporation of the stated structural units according to formula
(M1-a), (MI) and (M-II) into the copolymer, up to 5 wt. %,
preferably at most 1 wt. %, of polymer units originating from the
incorporation of other monomers. Copolymers (b2) are preferably
exclusively synthesized from structural units of the formulae
(M1-a), (M-I) and (M-II) and can be described by the general
formula (Poly2)
##STR00009##
wherein m, n and p vary depending on the molar mass of the polymer
and are not intended to imply that the copolymers are block
copolymers. Instead, structural units of the formulae may be
present randomly distributed in the molecule.
[0070] The positive polymer charge of component (b2) can be offset
using any possible physiologically acceptable anions, such as
chloride, bromide, hydrogensulfate, methylsulfate, ethylsulfate,
tetrafluoroborate, phosphate, hydrogenphosphate,
dihydrogenphosphate or p-toluenesulfonate, triflate.
[0071] If a methosulfate is used to offset the positive charge of
the polymer of the formula (Poly2), such
N-methylvinylimidazole/vinylpyrrolidone/vinylcaprolactam copolymers
are designated according to INCI nomenclature as Polyquaternium-46
and are obtainable, for example, from BASF under the trade name
Luviquat.RTM. Hold.
[0072] Very particularly preferred copolymers (b2) contain 1 to 20
mol %, preferably 5 to 15 mol % and particularly 10 mol % of
structural units according to formula (M1-a) and 30 to 50 mol %,
preferably 35 to 45 mol % and particularly 40 mol % of structural
units according to formula (I) and 40 to 60 mol %, preferably 45 to
55 mol % and particularly 60 mol % of structural units according to
formula (M-II).
[0073] In addition to or instead of copolymer(s) (b1) and/or (b2),
cosmetic agents according to the invention can also contain
copolymers (b3) as a film-forming cationic and/or setting cationic
polymer, wherein copolymers (b3) contain as structural units those
of formulae (M1-a) and (I) together with further structural units
from the group of vinylimidazole units and further structural units
from the group of acrylamide and/or methacrylamide units.
[0074] Further particularly preferred cosmetic agents contain as
cationic film-forming and/or cationic setting polymer at least one
copolymer (b3) having at least one structural unit according to
formula (M1-a), at least one structural unit according to formula
(M-I), at least one structural unit according to formula (M-VII),
and at least one structural unit according to formula (M-VIII)
##STR00010##
[0075] Here, it is particularly preferred for copolymers (b3) to
contain, in addition to polymer units arising from the
incorporation of the structural units according to formulae (M1-a),
(M-I), (M-VII) and (M-VIII) into the copolymer, up to 5 wt. %,
preferably at most 1 wt. %, of polymer units originating from the
incorporation of other monomers. Copolymers (b3) are preferably
exclusively synthesized from structural units of formulae (M1-a),
(M-I), (M-VII) and (M-VIII) and can be described by general formula
(Poly3)
##STR00011##
wherein m, n, o and p vary depending on the molar mass of the
polymer and are not intended to imply that the copolymers are block
copolymers. Instead, structural units of formulae (M1-a), (M-I),
(M-VII) and (M-VIII) can be present randomly distributed in the
molecule.
[0076] The positive polymer charge of component (b2) can be offset
using any possible physiologically acceptable anions, such as
chloride, bromide, hydrogensulfate, methylsulfate, ethylsulfate,
tetrafluoroborate, phosphate, hydrogenphosphate,
dihydrogenphosphate or p-toluenesulfonate, triflate.
[0077] If a methosulfate is used to offset the positive charge of
the polymer of the formula (Poly3), such
N-methylvinylimidazole/vinylpyrrolidone/vinylimidazole/methacrylamide
copolymers are designated according to INCI nomenclature as
Polyquaternium-68 and are obtainable, for example, from BASF under
the trade name Luviquat.RTM. Supreme.
[0078] Very particularly preferred copolymers (b3) contain 1 to 12
mol %, preferably 3 to 9 mol % and in particular 6 mol % of
structural units according to formula (M1-a) and 45 to 65 mol %,
preferably 50 to 60 mol % and particularly 55 mol % of structural
units according to formula (M-I) and 1 to 20 mol %, preferably 5 to
15 mol % and particularly 10 mol % of structural units according to
formula (M-VII) and 20 to 40 mol %, preferably 25 to 35 mol % and
particularly 29 mol % of structural units according to formula
(M-VIII).
[0079] Among additional film-forming cationic and/or setting
polymers chosen from cationic polymers with at least one structural
element of formula (M1), the following are considered preferred:
[0080] vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium chloride
copolymers (such as that with the INCI name Polyquaternium-16 under
the trade names Luviquat.RTM. Style, Luviquat.RTM. FC 370,
Luviquat.RTM.FC 550, Luviquat.RTM.FC 905 and Luviquat.RTM. MQ 552
(BASF SE)), [0081] vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium
methylsulfate copolymers (such as that with the INCI name
Polyquaternium-44 under the trade name Luviquat.RTM. Care (BASF
SE)), [0082]
vinylpyrrolidone/vinylcaprolactam/1-vinyl-3-methyl-1H-imidazolium
terpolymer (such as that with the INCI name Polyquaternium-46 under
the trade names Luviquat.RTM. Care or Luviquat.RTM. Hold (BASF
SE)), [0083]
vinylpyrrolidone/methacrylamide/vinylimidazole/1-vinyl-3-methyl-1H-imidaz-
olium methylsulfate copolymer (such as that with the INCI name
Polyquaternium-68 under the trade name Luviquat.RTM. Supreme (BASF
SE)), and mixtures of these polymers.
[0084] In a preferred embodiment, cosmetic agents according to the
invention contain as additional film-forming and/or setting polymer
at least one film-forming nonionic and/or setting nonionic
polymer.
[0085] According to the invention, a nonionic polymer refers to a
polymer which, in a protic solvent under standard conditions, has
substantially no structural units with permanently cationic or
anionic groups which have to be offset by counterions to obtain
electroneutrality. Cationic groups include quaternized ammonium
groups but not protonated amines. Anionic groups include carboxylic
and sulfonic acid groups.
[0086] Film-forming nonionic and/or setting nonionic polymers are
present in the agent preferably in an amount of 0.1 wt. % to 20.0
wt. %, more preferably 0.2 wt. % to 15.0 wt. %, very preferably 0.5
wt. % to 5.0 wt. %, based on total weight of the cosmetic
agent.
[0087] Film-forming nonionic and/or setting nonionic polymers are
preferably chosen from at least one polymer from [0088]
homopolymers and nonionic copolymers of N-vinylpyrrolidone, [0089]
nonionic copolymers of isobutene, [0090] nonionic copolymers of
maleic anhydride.
[0091] A preferred combination of film-forming nonionic and/or
setting nonionic polymers is one comprising at least one nonionic
copolymer of maleic anhydride and at least one polymer from
homopolymers and nonionic copolymers of N-vinylpyrrolidone.
[0092] Suitable polyvinylpyrrolidones include commercial products
such as Luviskol.RTM. K 90 or Luviskol.RTM. K 85 from BASF SE.
[0093] Suitable polyvinyl alcohols are distributed, for example,
under the trade names Elvanol.RTM. by Du Pont or Vinol.RTM. 523/540
by Air Products.
[0094] Suitable polyvinyl acetate is distributed, for example,
under the trade name Vinac.RTM. as an emulsion by Air Products.
[0095] Very particularly preferred agents according to the
invention are those having as film-forming nonionic and/or setting
nonionic polymer at least one polymer chosen from [0096] copolymers
of maleic anhydride and methyl vinyl ether, [0097]
polyvinylpyrrolidone, [0098] copolymers of N-vinylpyrrolidone and
vinyl esters of carboxylic acids with 2 to 18 carbon atoms,
particularly N-vinylpyrrolidone and vinyl acetate, [0099]
copolymers of N-vinylpyrrolidone and N-vinylimidazole and
methacrylamide, [0100] copolymers of N-vinylpyrrolidone and
N-vinylimidazole and acrylamide, [0101] copolymers of
N-vinylpyrrolidone with N,N-di(C.sub.1 to
C.sub.4)-alkylamino-(C.sub.2 to C.sub.4)-alkylacrylamide, [0102]
copolymers of N-vinylpyrrolidone with N,N-di(C.sub.1 to
C.sub.4)-alkylamino-(C.sub.2 to C.sub.4)-alkylacrylamide, or
mixtures of these polymers.
[0103] It is preferred for the molar ratio of structural units
obtained from the monomer N-vinylpyrrolidone to structural units
obtained from the monomer vinyl acetate of the polymer to be in a
range from 20:80 to 80:20, particularly from 30:70 to 60:40.
[0104] Suitable copolymers of vinylpyrrolidone and vinyl acetate
are obtainable, for example, under the trademark Luviskol.RTM. VA
37, Luviskol.RTM. VA 55, Luviskol.RTM. VA 64 and Luviskol.RTM. VA
73 from BASF SE.
[0105] Further preferred cosmetic agents according to the invention
additionally contain as nonionic film-forming and/or nonionic
setting polymer at least one copolymer (n1) having at least one
structural unit according to formula (M-I), at least one structural
unit according to formula (M-VII), and at least one structural unit
according to formula (M-VIII)
##STR00012##
[0106] Here, it is particularly preferred for these copolymers to
contain, in addition to polymer units arising from incorporation of
structural units according to formulae (M1-a), (I), (VII) and
(VIII) into the copolymer, up to 5 wt. %, preferably at most 1 wt.
%, of polymer units originating from the incorporation of other
monomers. Copolymers (n1) are preferably exclusively synthesized
from structural units of formulae (M1-a), (I), (VII) and (VIII) and
can be described by the general formula (Poly4)
##STR00013##
wherein m, n, o and p vary depending on the molar mass of the
polymer and are not intended to imply that the copolymers are block
copolymers. Instead, structural units of formulae (I), (VII) and
(VIII) can be present randomly distributed in the molecule.
[0107] One particularly preferred polymer is chosen from polymers
having the INCI name VP/Methacrylamide/Vinyl Imidazole Copolymer,
obtainable, for example, under the trade name Luviset Clear from
BASF SE.
[0108] Further suitable according to the invention are those
pulverulent compositions additionally having at least one nonionic
film-forming and/or nonionic setting polymer comprising at least
one structural unit of formula (M-I) and at least one structural
unit of formula (M-III)
##STR00014##
wherein R.sup.1 is a hydrogen atom or a methyl group, X.sup.1 is an
oxygen atom or an NH group, A.sup.1 is a 1,2-ethanediyl,
1,3-propanediyl or 1,4-butanediyl group R.sup.2 and R.sup.3 are,
mutually independently, a (C.sub.1 to C.sub.4) alkyl group.
[0109] It is particularly preferred for the above nonionic
film-forming and/or nonionic setting polymer to be chosen from at
least one polymer having at least one or a plurality of the
following features:
R.sup.1 is a methyl group, X.sup.1 is an NH group, A.sup.1 is
1,2-ethanediyl or 1,3-propanediyl, R.sup.2 and R.sup.3 are,
mutually independently, methyl or ethyl (particularly preferably
methyl).
[0110] Additional nonionic film-forming and/or nonionic setting
polymer of this embodiment is particularly preferably at least one
polymer having at least one structural unit of formula (M-I) and at
least one structural unit of formula (M-III-8),
##STR00015##
[0111] One very particularly preferred additional nonionic
film-forming and/or nonionic setting polymer of this embodiment is
a copolymer of N-vinylpyrrolidone and
N,N-dimethylaminopropylmethacrylamide, sold, for example, with the
INCI name VP/DMAPA Acrylates Copolymer, for example, under the
tradename Styleze.RTM. CC 10 by ISP.
[0112] Preferred cosmetic agents according to one embodiment are
those having at least one additional film-forming and/or setting
polymer, provided that all these additional polymers are
polysaccharide-based polymers. These additional polymers differ
from the propylene oxide-modified polysaccharides. It is preferred
that all further polymers of the cosmetic agent be chosen from
xanthan, dehydroxanthan, alginate, guar gum, gum arabic, locust
bean gum, starch, chitosan or mixtures thereof.
[0113] The additional film-forming and/or setting polymers are
preferably present in an amount of 0.5 wt. % to 30 wt. %,
particularly 2.5 wt. % to 20 wt. %, based on weight of the
agent.
[0114] In order to improve the effects according to the invention,
it is preferably suitable to add at least one compound of formula
(II),
HO--CH.sub.2--(CHOH).sub.n--CH.sub.2--OH (II)
wherein n is an integer from 1 to 4.
[0115] Agents according to the invention are particularly effective
if they contain glycerol and/or sorbitol as compounds of formula
(II).
[0116] An input of compounds of formula (II) in an amount from 0.2
to 10 wt. %, particularly 0.5 to 7 wt. % has proven
advantageous.
[0117] It is also preferred to use at least one nonionic
surfactant. According to the invention, these surfactants can
already have an emulsifying action.
[0118] Nonionic surfactants contain as hydrophilic group, for
example, a polyol group, a polyalkylene glycol ether group or a
combination of a polyol group and polyglycol ether group. Such
compounds include [0119] addition products of 2 to 100 mol of
ethylene oxide and/or 1 to 5 mol of propylene oxide onto linear or
branched fatty alcohols with 8 to 30 carbon atoms, onto fatty acids
with 8 to 30 carbon atoms and onto alkylphenols with 8 to 15 C
atoms in the alkyl group, [0120] addition products of 2 to 20 units
of glycerol onto linear or branched fatty alcohols with 8 to 30
carbon atoms in the alkyl group, onto linear or branched fatty
acids with 8 to 30 carbon atoms in the alkyl group, such as those
grades obtainable under the commercial names Dermofeel.RTM. G 10 LW
(Straetmans Chemische Produkte), [0121] addition products, end
group-terminated with a methyl or C.sub.2-C.sub.6 alkyl residue, of
2 to 50 mol of ethylene oxide and/or 1 to 5 mol of propylene oxide
onto linear and branched fatty alcohols having 8 to 30 carbon
atoms, onto fatty acids having 8 to 30 C atoms and onto
alkylphenols having 8 to 15 C atoms in the alkyl group, such as the
grades obtainable under the commercial names Dehydrol.RTM. LS,
Dehydrol.RTM. LT (Cognis), [0122] C.sub.12-C.sub.30 fatty acid
mono- and diesters of addition products of 1 to 30 mol of ethylene
oxide onto glycerol, [0123] addition products of 5 to 60 mol of
ethylene oxide onto castor oil and hardened castor oil, [0124]
polyol fatty acid esters, such as the commercial product
Hydagen.RTM. HSP (Cognis) or Sovermol grades (Cognis), [0125]
alkoxylated triglycerides, [0126] alkoxylated fatty acid alkyl
esters of the formula (E4-I)
[0126] R.sup.1CO-(OCH.sub.2CHR.sup.2).sub.wOR.sup.3 (E4-I) [0127]
wherein R.sup.1CO is a linear or branched, saturated and/or
unsaturated acyl residue having 6 to 22 carbon atoms, R.sup.2 is
hydrogen or methyl, R.sup.3 is linear or branched alkyl residues
having 1 to 4 carbon atoms and w is a number from 1 to 20, [0128]
amine oxides, [0129] hydroxy mixed ethers described, for example,
in German Patent Application No. 19738866, [0130] sorbitan fatty
acid esters and addition products of ethylene oxide onto sorbitan
fatty acid esters such as polysorbates, [0131] sugar fatty acid
esters and addition products of ethylene oxide onto sugar fatty
acid esters, [0132] addition products of ethylene oxide onto fatty
acid alkanolamides and fatty amines, [0133] sugar surfactants of
the alkyl and alkenyl oligoglycoside type of the formula
(E4-II),
[0133] R.sup.4O-[G].sub.p (E4-II) [0134] wherein R.sup.4 is an
alkyl or alkenyl residue having 4 to 22 carbon atoms, G is a sugar
residue having 5 or 6 carbon atoms and p is a number from 1 to 10.
They may be obtained according to relevant methods of preparative
organic chemistry.
[0135] Suitable nonionic surfactants which are particularly
preferred for use in the agent according to the invention are those
chosen from [0136] addition products of 2 to 20 units of glycerol
onto linear or branched fatty alcohols with 8 to 30 carbon atoms in
the alkyl group, [0137] addition products of 2 to 20 units of
glycerol onto linear or branched fatty acids with 8 to 30 carbon
atoms in the alkyl group, [0138] sugar surfactants of the alkyl and
alkenyl oligoglycoside type according to formula (E4-II) above, and
mixtures of these surfactants.
[0139] Nonionic surfactants are preferably present in the agent
according to the invention in an amount of 0.005 wt. % to 10 wt. %,
particularly 0.01 to 2 wt. %, based on weight of the agent.
[0140] Agents according to the invention can also contain at least
one plant extract. Typically, these extracts are produced by
extraction of the entire plant. However, in individual cases it may
be preferable to produce the extracts solely from the blossoms
and/or leaves of the plant. Suitable plant extracts are obtained by
extraction with organic solvents (e.g., ethanol, isopropanol,
diethyl ether, petroleum ether, benzene, chloroform) or by steam
distillation. According to the invention, preference is given to
extracts from bamboo, linseed, water lily, green tea, oak bark,
stinging nettle, witch hazel, hops, henna, chamomile, burdock root,
horsetail, hawthorn, lime blossom, almond, Aloe vera, pine-needle,
horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,
wheat, kiwi fruit, melon, orange, grapefruit, sage, rosemary,
birch, mallow, lady's smock, wild thyme, yarrow, thyme, melissa,
restharrow, coltsfoot, marsh mallow, meristem, ginseng and ginger
root. The additional plant extract is preferably present in the
agent in an amount of 0.05 wt. % to 1.0 wt. %, particularly 0.1 wt.
% to 0.5 wt. %, based on weight of the cosmetic agent.
[0141] It is preferred in particular if the agent according to the
invention is formulated as a cream so that the cosmetic agent
according to the invention additionally contains at least one oil
phase.
[0142] An oil phase according to the invention refers to a phase
which is liquid at 20.degree. C. and which, at 20.degree. C.,
dissolves in an amount of less than 1 g in 100 g of water.
[0143] The oil phase preferably has a viscosity of up to 1,000
mPas, (Brookfield, RVDV II+, 20.degree. C., 20 revolutions per
minute, spindle no. 1).
[0144] In a preferred embodiment, the oil of the oil phase is
chosen from at least one oil of [0145] plant oils, [0146] animal
oils, [0147] ester oils, [0148] liquid fatty acids and/or the
mono-, di- and trifatty acid esters of saturated and/or unsaturated
linear and/or branched C.sub.6 to C.sub.22 fatty acids with
glycerol.
[0149] Preferred vegetable oils are chosen from at least one of
amaranth oil, sunflower oil, olive oil, soy oil, rapeseed oil,
castor oil, sesame oil, almond oil, jojoba oil, orange oil, apricot
kernel oil, macadamia nut oil, wheat germ oil, peach stone oil and
the liquid fractions of coconut oil.
[0150] Preferred ester oils are chosen from esters of
C.sub.6-C.sub.30 fatty acids with C.sub.2-C.sub.30 fatty alcohols.
Monoesters of fatty acids with alcohols having 2 to 24 C atoms are
preferred. Examples of fatty acid moieties used in the esters are
caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid,
lauric acid, isotridecanoic acid, myristic acid, palmitic acid,
palmitoleic acid, stearic acid, isostearic acid, oleic acid,
elaidic acid, petroselinic acid, linoleic acid, linolenic acid,
elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and
erucic acid and the technical mixtures thereof, which are obtained,
for example, on pressure splitting of natural fats and oils, on
oxidation of aldehydes from Roelen's oxo synthesis or the
dimerization of unsaturated fatty acids. Examples of fatty alcohol
moieties in the ester oils are isopropyl alcohol, caproic alcohol,
caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl
alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol,
palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl
alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol,
linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl
alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and
the technical mixtures thereof, which are obtained, for example, on
high pressure hydrogenation of technical methyl esters based on
fats and oils or aldehydes from Roelen's oxo synthesis and as a
monomer fraction on the dimerization of unsaturated fatty alcohols.
Particularly preferred substances according to the invention are
isopropyl myristate (Rilanit.RTM. IPM), isononanoic acid
C.sub.16-18 alkyl ester (Cetiol.RTM. SN), 2-ethylhexyl palmitate
(Cegesoft.RTM. 24), stearic acid 2-ethylhexyl ester (Cetiol.RTM.
868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol
caprinate/caprylate (Cetiol.RTM. LC), n-butyl stearate, oleyl
erucate (Cetiol.RTM. J 600), isopropyl palmitate (Rilanit.RTM.
IPP), oleyl oleate (Cetiol.RTM.), lauric acid hexyl ester
(Cetiol.RTM. A), di-n-butyl adipate (Cetiol.RTM. B), myristyl
myristate (Cetiol.RTM. MM), cetearyl isononanoate (Cetiol.RTM. SN),
oleic acid decyl ester (Cetiol.RTM. V).
[0151] Mono-, di- and trifatty acid esters of saturated and/or
unsaturated linear and/or branched fatty acids with glycerol which
are preferably usable as oil in the oil phase are triglyceride
esters of capric acid and caprylic acid (INCI name: Caprylic/Capric
Triglyceride), for example, obtainable as a commercial product from
Cognis under the name Myritol.RTM. 312.
[0152] The additional oil phase is preferably present in the agent
according to the invention in an amount of 0.05 wt. % to 25 wt. %,
particularly 0.1 wt. % to 20 wt. %, based on weight of the cosmetic
agent.
[0153] Agents according to the invention which additionally contain
at least one fatty substance are also suitable.
[0154] According to the invention, fatty substances are those
compounds which, at 20.degree. C., are soluble in an amount of less
than 1 g in 100 g of water.
[0155] The fatty substance is preferably chosen from candelilla
wax, shea butter, carnauba wax, beeswax, coconut oil, C.sub.12 to
C.sub.20 fatty acids (particularly palmitic acid, stearic
acid).
[0156] The additional fatty substance is preferably present in the
agent according to the invention in an amount of 0.05 wt. % to 35
wt. %, particularly of 1 wt. % to 20 wt. %, based on weight of the
cosmetic agent.
[0157] Agents according to the invention contain their active
ingredients in a cosmetic carrier, preferably in a hydrous cosmetic
carrier, alcoholic cosmetic carrier or an aqueous-alcoholic
cosmetic carrier. For temporarily reshaping hair, such carriers
include lotions, water-in-oil emulsions, oil-in-water emulsions,
creams, gels, foams, pomades, waxes or other preparations suitable
for use on hair.
[0158] For the present invention, aqueous-alcoholic carriers
include aqueous compositions containing 3 to 70 wt. % of a
C.sub.1-C.sub.4 alcohol, particularly ethanol or isopropanol. The
agents can also contain further organic solvents such as
methoxybutanol, benzyl alcohol, diethylene glycol monoethyl ether,
1,2-propylene glycol or 1,3-propylene glycol. Any water-soluble
organic solvents are preferred.
[0159] A cationic surfactant can be used as a conditioner. Here,
preference is given to cationic surfactants such as quaternary
ammonium compounds, ester quats and the amidoamines. Preferred
quaternary ammonium compounds are ammonium halides, particularly
chlorides and bromides such as alkyltrimethylammonium chlorides,
dialkyldimethylammonium chlorides and trialkylmethylammonium
chlorides (e.g., cetyltrimethylammonium chloride,
stearyltrimethylammonium chloride, distearyldimethylammonium
chloride, lauryldimethylammonium chloride,
lauryldimethylbenzylammonium chloride and tricetylmethylammonium
chloride), and the imidazolinium compounds known under the INCI
names Quaternium-27 and Quaternium-83. Long alkyl chains of these
surfactants preferably comprise 10 to 18 carbon atoms. Since,
however, addition of surface-active substances can have a negative
effect on the hydrophobic properties of hydrophobized silicon
dioxide and thus on the stability of the cosmetic agent, the amount
of conditioning surfactant has to be carefully matched to total
composition. Preferably, no surfactant components are added.
[0160] Moreover, at least one vitamin, one provitamin, one vitamin
precursor and/or of one of the derivatives thereof can be used as
conditioner.
[0161] Preferred vitamins, provitamins and vitamin precursors
according to the invention are those conventionally assigned to the
groups A, B, C, E, F and H. Particularly preferred vitamins are
those belonging to the B group or to the vitamin B complex, very
particularly preferably vitamin B.sub.5 (pantothenic acid,
panthenol and pantolactone).
[0162] A series of carboxylic acids are also suitable as
conditioner.
[0163] Short-chain carboxylic acids in particular can be
advantageous. For the purposes of the invention, short-chain
carboxylic acids and the derivatives thereof are carboxylic acids
which can be saturated or unsaturated and/or linear or branched or
cyclic and/or aromatic and/or heterocyclic and have a molecular
weight of less than 750. Preference may be given to saturated or
unsaturated straight-chain or branched carboxylic acids with a
chain length of from 1 to 16 C atoms in the chain, very
particularly those with a chain length of from 1 to 12 C atoms.
[0164] Further suitable conditioners are protein hydrolysates
and/or the derivatives thereof, use of protein hydrolysates of
plant origin (e.g., soy, almond, pea, potato and wheat protein
hydrolysates) being preferred. Such products are obtainable, for
example, under the tradenames Gluadin.RTM. (Cognis), DiaMin.RTM.
(Diamalt), Lexein.RTM. (Inolex), Hydrosoy.RTM. (Croda),
Hydrolupin.RTM. (Croda), Hydrosesame.RTM. (Croda),
Hydrotritium.RTM. (Croda) and Crotein.RTM. (Croda).
[0165] Although use of protein hydrolysates as such is preferred,
amino acid mixtures obtained in other ways can also optionally be
used in their place. It is also possible to use derivatives of
protein hydrolysates, for example, in the form of the fatty acid
condensation products thereof. Such products are distributed, for
example, under the names Lamepon.RTM. (Cognis), Lexein.RTM.
(Inolex), Crolastin.RTM. (Croda), Crosilk.RTM. (Croda) or
Crotein.RTM. (Croda).
[0166] The teaching according to the invention comprises all
isomeric forms, such as cis-trans isomers, diastereomers and chiral
isomers.
[0167] According to the invention, it is also possible to use a
mixture of a plurality of protein hydrolysates.
[0168] Furthermore, lipids and oil bodies are suitable as
conditioners, for example, plant oils, liquid paraffin oils,
isoparaffin oils, synthetic hydrocarbons and ester oils, enzymes
and pearl extracts.
[0169] With addition of a UV filter, both the preparations
themselves and the treated fibers can be protected from the harmful
effects of UV radiation. It may therefore be advantageous to also
add at least one UV filter to the cosmetic agent. Suitable UV
filters are not subject to any general restrictions regarding
structure and physical properties. Rather, any UV filters usable in
the field of cosmetics whose absorption maximum is in the UVA
(315-400 nm), the UVB (280-315 nm) or the UVC (<280 nm) range
are suitable. UV filters with an absorption maximum in the UVB
range, particularly from approx. 280 to approx. 300 nm, are
particularly preferred.
[0170] Preferred UV filters according to the invention can be
chosen from substituted benzophenones, p-aminobenzoic acid esters,
diphenylacrylic acid esters, cinnamic acid esters, salicylic acid
esters, benzimidazoles and o-aminobenzoic acid esters. Examples
which may be mentioned here are
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the sodium salt
thereof (benzophenone-4; Uvinul.RTM.MS 40; Uvasorb.RTM.S 5).
[0171] In one particular embodiment, the cosmetic agent contains
one or more direct dyes. This makes it possible, when applying the
composition, for the treated keratin fibers not only to be
temporarily structured but also to be dyed at the same time. This
may be particularly desirable when, for example, only temporary
dyeing with conspicuous fashion colors is desired, which can be
removed again from the keratin fibers simply by washing.
[0172] Cosmetic agents according to the invention can also contain
alkalizing agents, conventionally alkali metal or alkaline earth
metal hydroxides, ammonia or organic amines. Preferred alkalizing
agents are monoethanolamine, monoisopropanolamine,
2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol,
2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and
triethanolamine and alkali metal and alkaline earth metal
hydroxides. In particular, monoethanolamine, triethanolamine and
2-amino-2-methylpropanol and 2-amino-2-methyl-1,3-propanediol are
preferred in the context of this group. .omega.-Amino acids such as
.omega.-aminocaproic acid can also be used as alkalizing
agents.
[0173] The present invention secondly provides for use of a
cosmetic agent of the first subject matter of the invention for
temporarily reshaping and/or setting the shape of keratin fibers,
particularly human hair.
[0174] The present invention thirdly provides a method for
temporarily reshaping keratin fibers, particularly human hair,
wherein a cosmetic agent of the first subject matter of the
invention is applied onto the keratin fibres.
[0175] It is preferable if, after exposure to the cosmetic agent of
the first subject matter of the invention, the keratin fibers are
not rinsed and are left on the fibers.
[0176] The following Examples are intended to explain the subject
matter of the present invention without limiting it in any way.
EXAMPLES
[0177] Unless stated otherwise, all quantities in this Examples
section are stated in weight percent. The following formulations
were prepared:
Example 1.1
"Hair Mousse"
TABLE-US-00001 [0178] Raw material E1[wt. %] E2[wt. %] Hydagen HCMF
.sup.1 0.50 -- Polyquaternium-4 -- 0.30 Polyquaternium-11 -- 1.50
Lactic acid 0.28 -- Luviskol 60/40 W NP .sup.2 10.70 -- Nonionic
starch modified with propylene oxide .sup.3 2.70 2.00 Sodium
benzoate 0.30 -- D-Panthenol 0.15 0.15 Dow Corning 939 .sup.4 0.20
0.20 Dehyquart A CA .sup.5 1.00 1.00 PEG-40 Hydrogenated Castor Oil
-- 0.30 Glycerol -- 0.15 Propane/butane 8.00 8.00 Water Ad 100 Ad
100 .sup.1 chitosan (80% deacetylated), molecular weight 50,000 to
1,000,000 g/mol, Cognis .sup.2 copolymer of N-vinylpyrrolidone and
vinyl acetate, .sup.3 potato starch, propylene oxide content: 4 wt.
% propylene oxide, viscosity: 64,000 mPa s, average molecular
weight (weight-average): 800 kDa .sup.4 approximately 32-36% active
substance, INCI name: Amodimethicone, Trideceth-12, Cetrimonium
Chloride (Dow Corning) .sup.5 trimethylhexadecylammonium chloride
(approximately 24-26% active substance; INCI name: Aqua (Water),
Cetrimonium Chloride) (Cognis)
[0179] The respective formulation ingredients except for the
propellant were mixed and the mixture introduced into an aerosol
container satisfying the following industrial parameters: aluminum
reservoir with valve product 522983 PV10697 from Precision
(Deutsche Prazisions-Ventil GmbH). The aerosol can was
appropriately sealed and the propellant introduced.
Example 1.2
"Hair Gels"
TABLE-US-00002 [0180] Raw material E4 E5 E6 E7 Disodium EDTA -- --
0.05 -- 1,2-Propanediol 6.00 -- -- -- Starch modified with
propylene 8.50 10.00 10.00 3.00 oxide .sup.6 Methylparaben 0.10 --
-- -- Aculyn 28 .sup.7 3.00 -- -- -- Aculyn 88 .sup.8 -- -- -- 1.80
Synthalen W 2000 .sup.9 -- -- -- 1.50 Polygel W 30 .sup.10 -- 3.00
-- -- Structure 2001 .sup.11 -- -- 5.00 -- PEG-40 Hydrogenated
Castor Oil 0.40 -- -- 0.20 PPG-5-Ceteth-20 -- -- 0.50 -- Euxyl K320
.sup.12 -- -- -- 1.00 Luviskol K 90 .sup.13 -- -- 12.00 -- Luviskol
K 85 .sup.14 -- 5.00 -- -- Polyethylene glycol 1500 2.00 -- -- --
Glycerol 10.00 2.75 2.00 -- D-Panthenol 0.15 -- 0.20 0.20 Neolone
PE 0.30 0.60 0.60 Triethanolamine -- -- -- 0.80 Lactic acid -- 0.10
0.30 -- Uvinul P25 .sup.15 -- -- -- 0.05 Perfume 0.15 0.20 0.20
0.20 Water Ad 100 Ad 100 Ad 100 Ad 100 .sup.6 potato starch
modified with 4.5 wt. % propylene oxide; average molecular weight
800 kDa, viscosity of a 43 wt. % solution in water 64,000 mPa s
.sup.7 copolymer of (meth)acrylic acid, (meth)acrylic acid ester
and beheneth-25 methacrylic acid ester (19-21 wt. % solids content
in water; INCI name: Acrylates/Beheneth-25 Methacrylate Copolymer)
(Rohm & Haas) .sup.8 copolymer of (meth)acrylic acid,
(meth)acrylic acid ester and steareth-20 methacrylic acid ester
(28-33 wt. % solids content in water; INCI name:
Acrylates/Steareth-20 Methacrylate Copolymer) (Rohm & Haas)
.sup.9 copolymer of (meth)acrylic acid, (meth)acrylic acid ester
and palmeth-25 methacrylic acid ester (30-32 wt. % solids content
in water; INCI name: Acrylates/Palmeth-25 Methacrylate Copolymer)
(3 V Sigma) .sup.10 copolymer of (meth)acrylic acid, (meth)acrylic
acid ester and palmeth-25 itaconic acid ester (30 wt. % solids
content in water; INCI name: Acrylates/Palmeth-25 Itaconate
Copolymer) (3 V Sigma) .sup.11 copolymer of (meth)acrylic acid,
(meth)acrylic acid ester and steareth-20 itaconic acid ester (30
wt. % solids content in water; INCI name: Acrylates/Steareth-20
Itaconate Copolymer) (3 V Sigma) .sup.12 mixture of phenoxyethanol,
methylparaben, ethylparaben, propylene glycol (Schulke & Mayr)
.sup.13 polyvinylpyrrolidone (approx. 20% solids content in water;
INCI name: PVP) (BASF) .sup.14 polyvinylpyrrolidone (approx. 20%
solids content in water; INCI name: PVP) (BASF) .sup.15
4-aminobenzoic acid ethyl ester + 25 mol ethylene oxide (INCI name:
PEG-25 PABA) (BASF SE)
2.0 Proof of Action
[0181] The following starches modified with propylene oxide were
used:
TABLE-US-00003 TABLE 1 Propylene oxide-modified starches - Average
molecular Viscosity range Name of the weight range of the of the
modified modified starch modified starch (kDa) starch [mPa s] HPS A
.sup.16 700-900 40,000-70,000 HPS B .sup.17 700-900 40,000-70,000
HPS C .sup.18 700-900 40,000-70,000 .sup.16 tapioca starch modified
with 4.5-5.5 wt. % propylene oxide .sup.17 tapioca starch modified
with 9.5-10.5 wt. % propylene oxide .sup.18 tapioca starch modified
with 19-21 wt. % propylene oxide
[0182] Polymer solutions in water, each of 5 wt. % strength of the
respective hydroxypropyl starches HPS A to C, of
polyvinylpyrrolidone (PVP) (Luviskol.RTM. K 85, BASF SE) and of
polyvinylpyrrolidone/vinyl acetate copolymer (PVP/VA)
(Luviskol.RTM. 64 W NP, BASF SE) were produced. Curl retention
measurements were then carried out on strands of hair treated
therewith. Here, strands of hair were investigated according to the
procedure described in 3.0 for determining High Humidity Curl
Retention (HHCR).
[0183] The following results were obtained:
TABLE-US-00004 TABLE 2 High humidity curl retention (HHCR) -
Polymer solution HHCR HPS A - 5 wt. % 90% HPS A - 5 wt. % 65% HPS A
- 5 wt. % 75% PVP/VA - 5 wt. % 26% PVP - 5 wt. % 23%
[0184] The strands of hair treated with agents according to the
invention exhibited hairstyle retention which was more resistant to
atmospheric humidity. Better HHCR values and better styling hold
were obtained when carrying out similar experiments with
correspondingly modified potato starch.
3.0 Performance of High Humidity Curl Retention Measurement
[0185] Standardized strands of hair from Kerling (item no. 827560)
of the "European Natural", color 6/0 type) of a length (L.sub.max)
of 220 mm and a weight of 0.6 g were used. The strands were washed
with a 12.5 wt. % sodium laureth sulfate solution by way of
preparation. The strands of hair were dried overnight in a drying
oven at 318 K.
[0186] 0.18 g of the compositions were applied onto a strand of
hair and rubbed in. The strand was then wound onto a curler
(Fripac-medis, diam. 7 mm, item no. D-1203) and dried overnight at
room temperature.
[0187] The curlers were carefully removed and the strands hung up.
The length of curls was in each case measured (L.sub.0) and the
strands placed in a conditioning cabinet. They were stored there at
294 K and a relative atmospheric humidity of 85% over a period of
24 h, after which the length of the curls was remeasured
(L.sub.t).
[0188] Five test strands per composition were correspondingly
treated and measured.
[0189] High Humidity Curl Retention (HHCR) was calculated according
to the following formula and the arithmetic mean of the HHCR values
for the 5 test strands was determined for each composition:
HHCR = L max - L t L max - L 0 ##EQU00001##
* * * * *