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.
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.
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.
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.
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
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.
With the term permanent shaping throughout the description and as well with the claims, the reference is made to perming and straightening processes.
The inventors have surprisingly found out that the use of a twist cap (A) on a tube (7) or on a pouch packaging component (8) or on 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
Accordingly, the 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 on a pouch packaging component (8) or on 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 infigures 1 and2 Figure 4 presents schematically a pouch confectioned with a cap (circled) as shown infigures 1 and2
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.
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.
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.
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.
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.
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.
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 C10-C18-alkyl sulfates, and in particular the respective ether sulfates, for example, C12-C14-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.
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.
Suitable surfactants of the carboxylate type are alkyl polyether carboxylic acids and the salts thereof of the formula
R1 - (C2H4O)n- O - CH2COOX,
wherein R1 is a C8-C20-alkyl group, preferably a C12-C14-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
Such products have been known for some time and are on the market, for example, under the trade name "AKYPO® " and "AKYPO-SOFT® ".
Also useful are C8-C20-acyl isethionates, alone or in admixture with other anionic surfactants, as well as sulfofatty acids and the esters thereof.
An overview of the anionic surfactants suiutable for compositions of the present invention can furthermore be found in the monography of
Further suitable anionic surfactants are also C8-C22-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-C12-C18-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.
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
R2-O-(R3O)n-Zx,
wherein R2 is an alkyl group with 8 to 18 carbon atoms, R3 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.
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.
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 "PluronicsR", as well as fatty alcohol ethoxylates.
Such amineoxides are state of the art, for example C12-C18- alkyl dimethyl amineoxides such as lauryl dimethyl amineoxide, C12-C18- alkyl amidopropyl or -ethyl amineoxides, C12-C18 -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® ".
Further nonionic surfactants useful in the compositions according to invention are C10-C22-fafty alcohol ethoxylates. Especially suited are C10-C22-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.
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.
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.
In detail, it is possible to use betaines of the structure
sulfobetaines of the structure
and amidoalkyl betaines of the structure
Permanent shaping compositions of the present invention can comprise additionally one or more cationic surfactants, especially as conditioner, presented with the general formula
R11 CO NH (CH2)n
where R11 is saturated or unsaturated, branched or non-branched alkyl chain with 7-21 C atoms and n has value of 1 - 4,
or
R12 CO O (CH2)n
where R12 is saturated or unsaturated, branched or non-branched alkyl chain with 7-21 C atoms and n has value of 1 - 4, and
R8 is H or unsaturated or saturated, branched or non-branched alkyl chain with 1 - 4 C atoms or
R11 CO NH (CH2)n
or
R12 CO O (CH2)n
where R11, R12 and n are same as above.
R9 and R10 are H or lower alkyl chain with 1 to 4 carbon atoms, and X is anion such as chloride, bromide, methosulfate.
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.
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.
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
R13 CO (O CH2 CH2)n OH
R13 CO (O CH2 CH2)n O OC R14
where R13 and R14 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.
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.
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.
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
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
Preferred organopolysiloxane polymers are those of the type disclosed in
Especially suited are the organopolysiloxanes disclosed under the terms A-1, A-2 and A-3 on pages 12 to 13 of
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.
Urea is as well preferred as penetration enhancer.
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.
Another compound may be used in the composition is of ceramide type of compounds according to general formula
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.
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.
The following examples are used to illustrate the invention, but not limit it
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.
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
The results are presented in Table I.
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.
Similar results are obtained with the following examples as well.
The preparation and filling and perming tests were carried out as above. No instability was observed.
The preparation and filling and perming tests were carried out as above. No instability was observed.