[0001] This invention relates to a product for permanent shaping keratin fibres consisting
of a packaging and a ready to use aqueous composition comprising at least one reducing
agent.
[0002] It is generally known that permanent shaping is carried out in two steps, the reductive
splitting of the cystein disulfide bonds in the hair by a reducing agent and the subsequent
neutralisation by application of an oxidizing agent, whereby the cystein disulfide
bonds are restored.
[0003] The reducing agent used still most frequently is thioglycolic acid also in the form
of the salts thereof, in particular its ammonium salt, although numerous other thio
compounds have been proposed for this purpose which, however, mostly have not been
successfully applied because of toxicological reasons. The reducing agents especially
of interest are thiogylcolic acid, cystein, thiolactic acid and cystamine. Another
one is glycerine monothiogylcolate (GMTG) showing very good permanent shaping effect,
however, has some toxicological problems. The reducing agents are in general used
at a concentration of 1 to 20% by weight, preferably 1 to 15% by weight. It should
be noted that regulations on the concentration of reducing agents must be followed
in those countries where authorities do so.
[0004] Compositions for permanent shaping hair are usually packed as single dose units because
of their sensibility to oxidation when contacting air. Multi-portion products are
as well available although the great stability concerns. Once products is opened and
emptied partly, remaining product is losing its effect as a reducing agent and this
certainly affects the results of the permanent shaping process. In order to overcome
such stability problem, pressurised packaging materials have found their application
which often requires use of flammable propellants limiting their effective use as
packaging for permanent shaping products. Therefore, there is a great need for multi-portion
products for permanent shaping hair. Products as single does units brings certainly
high packaging costs and waste, which is, in addition, not always environmental friendly.
Additionally, usually because of stability reasons, they have to be packed into a
multi phase products, which are mixed prior to application. This requires as well
expensive special packaging technology, which brings certainly limitations in practice.
[0005] It is, therefore, highly desirable to achieve ready to use products, without any
mixing step prior to use, for permanent shaping hair, especially from the view point
of a multi-portion product, with low cost without loosing the performance in terms
of stability and permanent shaping ability during whole life time of the product.
This invention starts form the problems as explained and aims primarily for finding
an alternative, which is more cost effective and environmental friendly and as well
be packed without using propellants. The alternative packaging makes withdrawal of
content of package in smaller portions than the whole content of the product without
affecting the stability of the remaining product
[0006] It has now been found out that a multiportion permanent shaping ready to use product
can be achieved by using a tube or a pouch confectioned with a cap which releases
its content when a pressure is applied and closes without sucking gas from its environment.
This form of preparation show advantages over the conventional packaging has been
used until now as well as over aerosol packaging proposed to solve stability problem
in the literature. Product for permanent shaping is released from packaging as it
is without forming foam.
[0007] With the term permanent shaping throughout the description and as well with the claims,
the reference is made to perming and straightening processes.
[0008] The inventors have surprisingly found out that the use of a twist cap (A) on a tube
(7) or a pouch packaging component (8) or a bottle consisting of a seal (1), temper
evident (2), thread (3) and a carrying element (4) and confectioned with a silicone
valve (5) and a retainer therefore (6) filled with a permanent shaping composition
solves the above mentioned problems. Packaging with such kind of closure cap have
been proposed in a US patent application published US 2003/0106910 A1.
[0009] Accordingly the object of the present invention is product for permanent shaping
hair consisting of a packaging and an aqueous composition wherein packaging is consisting
a twist cap (A) on a tube (7) or a pouch packaging component (8) or a bottle consisting
of a seal (1), temper evident (2), thread (3) and a carrying element (4) and confectioned
with a silicone valve (5) and a retainer therefore (6) filled with a permanent shaping
composition comprising at least one reducing agent.
[0010] Further object of the present invention is multiportion product for permanent shaping
hair consisting of a packaging and an aqueous composition wherein packaging is consisting
a twist cap (A) on a tube (7) or a pouch packaging component (8) or a bottle consisting
of a seal (1), temper evident (2), thread (3) and a carrying element (4) and confectioned
with a silicone valve (5) and a retainer therefore (6) filled with a permanent shaping
composition comprising at least one reducing agent wherein the composition can be
removed partially without effecting the stability of the remaining product.
Figure 1 presents schematically a confectioned cap (The letters B, C and D all together
are defined as spout.)
Figure 2 presents schematically individual elements of cap (The letters B, C and D
all together are defined as spout.)
Figure 3 presents schematically a tube confectioned with a cap (circled) as shown
in figures 1 and 2
Figure 4 presents schematically a pouch confectioned with a cap (circled) as shown
in figures 1 and 2
[0011] The silicone valve (5) is of heat curable liquid silicone rubber. Liquid silicone
rubber used therefore is for example Silastic 94-595 from Dow Corning.
[0012] Composition filled into the tube or pouch to obtain product is an aqueous permanent
shaping composition for hair comprising at least one reducing agent. The reducing
agents used are thiogylcolic acid, cystein, thiolactic acid, cystamine, glycerin monothiogylcolate.
Thiogylcolic acid, cystein and thiolactic acid or mixtures are the most preferred
ones at a concentration of 1 to 20% by weight and preferably 1 to 15% by weight. The
regulations from the authorities should be taken into consideration concerning the
concentration of individual reducing agent in certain countries.
[0013] The pH of the permanent shaping composition is in the range of 5 to 10 preferably
6 to 10 and more preferably 6.5 to 9.5 and most preferably 6.8 to 9.5. The pH of the
composition is adjusted preferably with ammonium hydroxide or monoethanolamine. Ammonium
carabamate and/or sodium bicarbonate are as well used for pH adjustment, in certain
case even preferred because of their buffering capacities. Both agents are not used
in acidic pH ranges. Organic and or inorganic acids may as well be used for adjusting
the pH in addition to the alkalising agents mentioned above.
[0014] According to the invention, composition for permanent shaping hair is an aqueous
solution or dispersion either clear or opaque, which can further be an emulsion or
a gel. The solution and dispersion forms with clear or opaque appearance are the most
preferred.
[0015] The viscosity of the compositions according to the invention is preferably below
5,000, in particular below 3,000, especially below 1,000 mPa.s, measured at 20°C with
a Brookfield rotation viscosimeter with an appropriate spindle.
[0016] Permanent shaping composition of the present invention can comprise surfactants of
anionic, non-ionic, amphoteric or zwitterionic and/or cationic surfactants or their
mixtures at a concentration of 0.1 to 10%, preferably 0.1 to 7.5% and more preferably
0.1 to 5% by weight, calculated to the total composition. The surfactants, especially
the nonionic ones, are especially used for solubilizing aid for insoluble lipophilic
compounds such as fragrance and oily conditioning compounds.
[0017] Suitable anionic surfactants are of the sulfate, sulfonate, carboxylate and alkyl
phosphate type, especially, of course, those customarily used in shampoo compositions,
for example, the known C
10-C
18-alkyl sulfates, and in particular the respective ether sulfates, for example, C
12-C
14-alkyl ether sulfate, lauryl ether sulfate, especially with 1 to 4 ethylene oxide
groups in the molecule, monoglyceride (ether) sulfates, fatty acid amide sulfates
obtained by ethoxylation and subsequent sulfatation of fatty acid alkanolamides, and
the alkali salts thereof, as well as the salts of long-chain mono- and dialkyl phosphates
constituting mild, skin-compatible detergents.
[0018] Additional anionic surfactants useful within the scope of the invention are α-olefin
sulfonates or the salts thereof, and in particular alkali salts of sulfosuccinic acid
semiesters, for example, the disodium salt of monooctyl sulfosuccinate and alkali
salts of long-chain monoalkyl ethoxysulfosuccinates.
[0019] Suitable surfactants of the carboxylate type are alkyl polyether carboxylic acids
and the salts thereof of the formula
R
1 - (C
2H
4O)
n- O - CH
2COOX,
wherein R
1 is a C
8-C
20-alkyl group, preferably a C
12-C
14-alkyl group, n is a number from 1 to 20, preferably 2 to 17, and X is H or preferably
a cation of the group sodium, potassium, magnesium and ammonium, which can optionally
be hydroxyalkyl-substituted, as well as alkyl amido polyether carboxylic acids of
the general formula

wherein R
1 and X have the above meanings, and n is in particular a number from 1 to 10, preferably
2.5 to 5.
[0020] Such products have been known for some time and are on the market, for example, under
the trade name "AKYPO® " and "AKYPO-SOFT® ".
[0021] Also useful are C
8-C
20-acyl isethionates, alone or in admixture with other anionic surfactants, as well
as sulfofatty acids and the esters thereof.
[0022] An overview of the anionic surfactants suiutable for compositions of the present
invention can furthermore be found in the monography of K. Schrader, "Grundlagen und
Rezepturen der Kosmetika", 2
nd Ed.(1989, Hüthig Buchverlag), pp. 595-600 and pp. 683 to 691.
[0023] Further suitable anionic surfactants are also C
8-C
22-acyl aminocarboxylic acids or the water-soluble salts thereof. Especially preferred
is N-lauroyl glutamate, in particular as sodium salt, as well as, for example, N-lauroyl
sarcosinate, N-C
12-C
18-acyl asparaginic acid, N-myristoyl sarcosinate, N-oleoyl sarcosinate, N-lauroyl methylalanine,
N-lauroyl lysine and N-lauroyl aminopropyl glycine, preferably in form of the water-soluble
alkali or ammonium, in particular the sodium salts thereof, preferably in admixture
with the above-named anionic surfactants.
[0024] Further surfactants in the permanent shaping compositions according to the invention
are nonionic surfactants, which are especially preferred as solubilizing aid for lipophilic
water insoluble compounds. Especially suited are alkyl polyglucosides of the general
formula
R
2-O-(R
3O)
n-Z
x,
wherein R
2 is an alkyl group with 8 to 18 carbon atoms, R
3 is an ethylene or propylene group, Z is a saccharide group with 5 to 6 carbon atoms,
n is a number from 0 to 10 and x is a number between 1 and 5.
[0025] Further nonionic surfactant components are, for example, long-chain fatty acid mono-and
dialkanolamides, such as coco fatty acid monoethanolamide and myristic fatty acid
monoethanolamide.
[0026] Further additionally useful nonionic surfactants are, for example, the various sorbitan
esters, such as polyethylene glycol sorbitan stearic acid ester, fatty acid polyglycol
esters or poly-condensates of ethyleneoxide and propyleneoxide, as they are on the
market, for example, under the trade name "Pluronics
R", as well as fatty alcohol ethoxylates.
[0027] Such amineoxides are state of the art, for example C
12-C
18- alkyl dimethyl amineoxides such as lauryl dimethyl amineoxide, C
12-C
18- alkyl amidopropyl or -ethyl amineoxides, C
12-C
18 -alkyl di(hydroxyethyl) or (hydroxypropyl) amineoxides, or also amineoxides with
ethyleneoxide and/or propyleneoxide groups in the alkyl chain. Such amineoxides are
on the market, for example, under the trade names "Ammonyx® ", "Aromox® " or "Genaminox®
".
[0028] Further nonionic surfactants useful in the compositions according to invention are
C
10-C
22-fafty alcohol ethoxylates. Especially suited are C
10-C
22-fatty alcohol ethers, the alkyl polyglycol ethers known by the generic terms "Laureth",
"Myristeth", "Oleth", "Ceteth", "Deceth", "Steareth" and "Ceteareth" according to
the CTFA nomenclature, including addition of the number of ethylene oxide molecules,
e.g., "Laureth-16":
The average degree of ethoxylation thereby ranges between about 2.5 and about 25,
preferably about 10 and about 20.
[0029] As solubilizing aid especially preferred are the ethoxylated hydrogenated castor
oil known with the trade name Cremophor from the company BASF, such as PEG-60 hydrogenated
castor oil.
[0030] As further surfactant component, the compositions according to the invention can
also contain amphoteric or zwitterionic surfactants. Useful as such are in particular
the various known betaines such as alkyl betaines, fatty acid amidoalkyl betaines
and sulfobetaines, for example, lauryl hydroxysulfobetaine; long-chain alkyl amino
acids, such as cocoaminoacetate, cocoaminopropionate and sodium cocoamphopropionate
and -acetate have also proven suitable.
[0031] In detail, it is possible to use betaines of the structure

wherein R
4 is a C
8-C
18-alkyl group and n is 1 to 3;
sulfobetaines of the structure

wherein R
4 and n are same as above;
and amidoalkyl betaines of the structure

wherein R
4 and n are same as above.
[0032] Permanent shaping compositions of the present invention can comprise additionally
one or more cationic surfactants, especially as conditioner, presented with the general
formula

where R
7 is a saturated or unsaturated, branched or non-branched alkyl chain with 8-22 C atoms
or
R
11 CO NH (CH
2)
n
where R
11 is saturated or unsaturated, branched or non-branched alkyl chain with 7-21 C atoms
and n has value of 1 - 4,
or
R
12 CO O (CH
2)
n
where R
12 is saturated or unsaturated, branched or non-branched alkyl chain with 7-21 C atoms
and n has value of 1 - 4, and
R
8 is H or unsaturated or saturated, branched or non-branched alkyl chain with 1 - 4
C atoms or
R
11 CO NH (CH
2)n
or
R
12 CO O (CH
2)
n
where R
11, R
12 and n are same as above.
[0033] R
9 and R
10 are H or lower alkyl chain with 1 to 4 carbon atoms, and X is anion such as chloride,
bromide, methosulfate.
[0034] Typical examples of those ingredients are cetyl trimethly ammonium chloride, stear
trimonium chloride, behentrimoinium chloride, stearamidopropyl trimonuim chloride,
dioleoylethyl dimethyl ammonium methosulfate, dioleoylethyl hydroxyethylmonium methosulfate.
[0035] The composition of the present invention comprises further hair-conditioning agents.
Conditioning agents can be selected from oily substances, non-ionic substances, cationic
polymers or their mixtures. Oily substances are selected from such as silicone oils,
either volatile or non-volatile, natural and synthetic oils. Among silicone oils those
can be added to the composition include dimethicone, dimethiconol, polydimethylsiloxane,
DC fluid ranges from Dow Corning, natural oils such as olive oil, almond oil, avocado
oil, weizenkeim oil, ricinus oil and the synthetic oils, such as mineral oil.
[0036] Non-ionic conditioning agents may be polyols such as glycerin, glycol and derivatives,
polyethyleneglycoles known with trade names Carbowax PEG from Union Carbide and Polyox
WSR range from Amerchol, polyglycerin, polyethyleneglycol mono or di fatty acid esters
having general formula
R
13 CO (O CH
2 CH
2)
n OH
R
13 CO (O CH
2 CH
2)
n O OC R
14
where R
13 and R
14 are independent from each other saturated, unsaturated or branched or non-branched
alkyl chain with 7 to 21 C atoms and n is typically 2 - 100.
[0037] Permanent shaping compositions of the present invention can contain additionally
cationic polymers as conditioning agents. Suitable polymers are those of cationic
polymers best known with their CTFA category name Polyquaternium. Typical examples
of those Polyquaternium 6, Polyquaternium 7, Polyquaternium 10, Polyquaternium 11,
Polyquaternium 16, Polyquaternium 22 and Polyquaternium 28.
[0038] As well those polymers known with their CTFA category name Quaternium are suitable.
Those are for example Quaternium-8, Quaternium-14, Quaternium-15, Quaternium-18, Quaternium-22,
Quaternium-24, Quaternium-26, Quaternium-27, Quaternium-30, Quaternium-33, Quaternium-53,
Quaternium-60, Quaternium-61, Quaternium-72, Quaternium-78, Quaternium-80, Quaternium-81,
Quaternium-81, Quaternium-82, Quaternium-83 and Quaternium-84. It has been found out
that Quaternium-80 is the best suitable one among the Quaterniums.
[0039] It has further been found out that especially those of cationic cellulose type polymers
known as Polymer JR type from Amerchol such as Polyquaternium 10 or cationic guar
gum known with trade name Jaguar from Rhône-Poulenc and chemically for example Guar
hydroxypropyl trimonium chloride, are preferred ones. Furthermore, chitosan and chitin
can also be included in the compositions as cationic natural polymers. In this context
reference is also made to the cationic polymers disclosed in DE 25 21 960, 28 11 010,
30 44 738 and 32 17 059, as well as to the products described in EP-A 337 354 on pages
3 to 7. It is also possible to use mixtures of various cationic polymers.
[0040] Composition can comprise an organopolysiloxane wherein at least one silicium atom
is linked to an alkylene group having a hetero-atom, in particular a nitrogen atom,
with a poly-(N-acyl alkyleneimine) units of the formula

wherein n is a number from 1 to 5 and R
15 is hydrogen, a C
1-C
12-alkyl or cycloalkyl, aralkyl or aryl group.
[0041] Preferred organopolysiloxane polymers are those of the type disclosed in EP-A 640
643, in particular optionally quaternized aminoalkyl, in particular aminopropyl dimethyl
polysiloxane/polyethyl oxazoline copolymers of the formula

wherein m and n each are numbers from 20 to 10,000, in particular 50 to 7,000, especially
100 to 5,000, x is a number between 1 and 5, preferably 3, and y is a number from
5 to 30, R
16 is a C
1-C
12-alkyl or aryl group, in particular a methyl, ethyl or benzyl group, and Y- is an
anion.
[0042] Especially suited are the organopolysiloxanes disclosed under the terms A-1, A-2
and A-3 on pages 12 to 13 of EP-A 640 643. The proportion of graft copolymers in the
hair colouring compositions according to the invention ranges from 0.05 % to 5 %,
preferably 0.1 % to 2.5 %, in particular 0.5 % to 1.5 % by weight, calculated to the
total composition.
[0043] Composition according to the present invention can contain organic solvents as penetration
enhancers and also as a solubilzers. Examples of such organic solvents are benzyloxy
ethanol, benzyl alcohol, phenoxy ethanol, phenoxy isopropanol, methyl phenoxy ethanol,
benzyl glycerol, N-benzyl formide, N-methyl pyrrolidone, N-ethyl pyrrolidone, cinnamyl
alcohol, phenethyl alcohol, p-methyl benzyl alcohol, butyl cellosolve, methyl carbitol,
ethyl carbitol, propyl carbitol, butyl carbitol, diethyleneglycol, diethyl ether and
dipropyleneglycol diethyl ether. Typically the concentration of those solvents can
be in the range from 0.5% to 25%, preferably 0.5 - 20% by weight and more preferably
0.5 - 15% by weight, calculated to the total composition.
[0044] Urea is as well preferred as penetration enhancer.
[0045] Permanent shaping compositions according to the invention can contain thickening
agents, especially in the case a gel type of preparation is preferred. These are,
for example, the various cellulose derivatives such as hydroxyalkyl celluloses, e.g.
hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, natural
polysaccharides such as xanthan gum; guar gum and the alkoxylation products thereof
in amounts from 0.1 - 5 %, preferably 0.1 - 3% and most preferably 0.1 - 2% by weight
calculated to the total composition and depending on the desired consistency thereof.
[0046] Another compound may be used in the composition is of ceramide type of compounds
according to general formula

where R
19 and R
20 are independent from each other alkyl- or. alkenyl group mit 10 to 22 carbon atoms,
R
21 is methyl, ethyl, n-propyl or isopropyl group and n is a number between 1 to 6, preferably
2 or 3. The concentration of ceramide type of compound in colouring compositions of
the present invention can be in the range of 0.01 to 2 and especially 0.01 to 1% by
weight calculated to the total composition.
[0047] The tubes or pouches or bottles can be emptied with very low level of remains in
the packaging. The emptying is achieved at most not les than 98% of its content by
weight.
[0048] Filling of the aqueous composition into tube or pouch for obtaining product comprising
at least one reducing agent for permanent shaping hair is carried out in a process
in which the compositions is filled into the tube or pouch with an extendable filling
nozzle entering into pouch or tube in order to secure the long lifetime of the content
(reducing agent comprising composition for permanent shaping hair) - long-term stability.
[0049] The following examples are used to illustrate the invention, but not limit it
Example 1
|
% by weight |
Ammonium thiogylcolate |
9.5 |
Ammonium hydroxide (25%) |
6.6 |
Ammonium carbonate |
1.0 |
Cremophore RH 60* |
1.5 |
C12-C16 alkyl polyglucoside |
1.5 |
Fragrance |
q.s |
Water |
to 100 |
* Ethoxylated hydrogenated castor oil
[0050] The composition of example 1 was filled into the tube as described above. The product
was stable over the period of 12 weeks (period tested) at 40°C and at room temperature.
No instability is observed in terms of perming performance on hair, which was shown
in a comparative permanent shaping test on hair switches, where the permanent shaping
was carried out with a product as above aged and a freshly prepared composition. In
the perming process, as an oxidation agent 2.3% by weight hydrogen peroxide comprising
oxidizing agent is used.
[0051] In another test the same product was filled into a packaging with a volume of 500
ml according to the invention and in a bottle without containing the silicone valve,
meaning that when the cap is opened the content is directly in contact with air. Both
products were stored at room temperature and their content was emptied every week
by removing 50 ml. With the removed composition perming test was carried out as described
above. Comparison was also made with a freshly prepared composition. The evaluation
was carried out by a hair dresser according to following scale.
1 no permanent shaping at all (no curls observed)
2 slight permanent shaping (slight waves)
3 permanent shaping (waves)
4 good permanent shaping
5 very good permanent shaping
[0052] The results are presented in Table I.
Table I: Results of permanent shaping test of the products stored in different packaging
as described above and a freshly prepared permanent shaping composition.
Storage |
Example 1 stored in according to (see above) |
Period (weeks) |
Invention |
Comparative |
Fresh composition |
1 |
5 |
5 |
5 |
2 |
5 |
4 |
5 |
3 |
4 |
3 |
5 |
4 |
5 |
3 |
5 |
6 |
4 |
1 |
5 |
[0053] From the above results it is clear that the composition stored in a packaging according
to invention shows very good perming performance and therefore without loss of its
thiogylcolic acid content, whereas the composition stored in a bottle with a cap without
silicone valve did not show any permanent shaping effect after storing 6 weeks at
room temperature indicating that the reducing agent thioglycolic acid is not stable
under those conditions. Thus, the product of the invention has a longer shelf life
than that of comparative product.
[0054] Similar results are obtained with the following examples as well.
Example 2
[0055]
|
% by weight |
Ammonium thiogylcolate |
5.0 |
Cystein |
2.5 |
Ammonium hydroxide (25%) |
3.2 |
Cremophore RH 60* |
1.5 |
Oleyl polyglucoside |
0.5 |
Fragrance |
q.s |
Water |
to 100 |
*Ethoxylated hydrogenated castor oil |
[0056] The preparation and filling and perming tests were carried out as above. No instability
was observed.
Example 3
[0057]
|
% by weight |
Thiolactic acid |
12.5 |
Ammonium hydroxide (25%) |
9.0 |
Ammonium bicarbonate (25%) |
5.0 |
Urea |
4.0 |
Polyquatenium-6 |
0.5 |
Cocobetaine |
0.8 |
Fragrance |
q.s |
Water |
to 100 |
[0058] The preparation and filling and perming tests were carried out as above. No instability
was observed.