Patent Description:
The compositions of the invention are prepared in a cosmetically acceptable medium and the cosmetic treatment method of the keratin substrate provides for the application step on said keratin substrate of a composition as defined below. By means of a single application of at least one of the compositions of the invention, placed in contact with frizzy, curly or wavy keratin fibers (such as hair), it is possible to obtain smooth keratin fibers, with reduced water absorption capacity and greater tensile strength compared to untreated fibers.

It is known that the hair of the human species is composed of a mass of microfibrils composed in turn of amino acidic chains linked together in a different way according to the genetic heritage possessed by the individual.

This category of proteins has a high content of sulfur amino acids (especially cystine and cysteine) as well as significant quantities of acidic amino acids (especially aspartic acid and glutamic acid) and basic amino acids (especially lysine, histidine and arginine).

In \<CIT> the chemical-physical characteristics of both the "natural" keratin fibers and those that have suffered damage from the application of cosmetic treatments known to the current state of the art (for instance: bleaching, permanent waving, dyeing, straightening or chemical stretching. (bleaching, waving, dyeing, straightening or stretching) are well described.

The fibers subjected to this type of treatment tend to take on a dull, frizzy appearance over time with poor tensile strength (they break easily).

An improvement in hair straightening procedures is described in patents <CIT> and <CIT> which relate to a method for modifying the appearance of keratin fibers through the use of particular operating conditions in the presence of glyoxylic acid to obtain, in a semi-permanent way, the modification of said keratin fibers by transforming them from curved or curly into smooth fibers.

Still in the context of improving the appearance of hair, document <CIT> describes the use of compositions based on phenolic compounds and polyamines to allow the protection of a keratin substrate from high energy (UV) sun rays. The composition can be applied indifferently on the hair and on the skin.

<CIT> discloses cosmetic compositions comprising a thickener in combination with fluorinated polymers in order to coat the keratin fibers of the eyelashes increasing their volume, with a lengthening and separating effect. The composition is applied as it is on the eyelashes and eyebrows.

<CIT> describes a hair smoothing composition essentially consisting of at least one derivative of glyoxylic acid formed by the reaction of glyoxylic acid with at least one alpha, beta or gamma amino acid.

<CIT> claims a method of producing copolymers based on perfluoroalkylethyl (meta) acrylates polymerized with alkyl (meta) acrylates for the manufacture of copolymers intended to be used as waterproofing against water and/or oils in natural or synthetic fabrics such as: cotton, cellulose, wool, silk, polyamide as well as on paper and leather.

The need is now felt to improve the procedures for applying glyoxylic acid and make the hair smoothing process faster and more efficient, as well as less stressful for the hair, compared to what is described in <CIT> and <CIT>. In this patent is in fact described that the hair on which the glyoxylic acid is applied is dried and subjected to straightening at a temperature of <NUM> ± <NUM> without prior rinsing aimed at reducing the amount of substances deposited on the hair during the application of the compositions object of that invention.

Also known (patent application <CIT>) is a method of fast smoothing/straightening of the hair in which an aqueous cosmetic composition is applied to the hair comprising glyoxylic acid, lactic acid, an amino-modified polyether-silicone copolymer (INCI name: PEG-<NUM>/PPG-<NUM> Methylaminopropyl/Hydroxypropyl Dimethicone Copolymer). The cosmetic composition is applied to the keratin fibers for <NUM> minutes; after which, without performing a rinsing process, a second composition based on fatty alcohols and cationic conditioning agents is applied for <NUM> minutes; and finally rinse and dry the hair, which is then smoothed with the plate.

However, this method does not allow to persistently smooth/stretch and/or reduce the volume of the hair as the composition applied is not able to modify the keratin fibers and is completely washed away after the first wash. These adverse effects were tested in the comparison tests enclosed to this description in the "Examples" section.

Therefore, the present invention aims to develop a composition that allows to obtain a rapid smoothing/stretching of the hair, associated with a reduction in the volume of the hair, effects that are obtained in an efficient and persistent way while limiting the degradation of the hair. Surprisingly, it has been possible to verify that the smoothing/stretching effects persist even after numerous washings without the need for repeated applications of the composition after each wash.

It has now been surprisingly found that the hair on which glyoxylic acid has been applied can be rinsed to remove excess acid and then directly straightened. This allows the hair to return to a pH similar to the physiological one, before straightening at high temperature, thus minimizing stress on the hair.

This simplification is obtained with the composition of the invention which comprises the combination of glyoxylic acid, or other carboxylic acid of similar properties, with an alkoxylated polyamine and with a fluorinated polymer, as described below.

The invention therefore relates to a composition comprising:.

The composition of the invention may further comprise one or more of the ingredients commonly used in the cosmetic industry.

The substances commonly used in the manufacture of cosmetic products are to be understood as those listed in the <NPL>.

These are classified into categories comprising, but not limited to, the following categories: anti-caking agent, antifoam, antimicrobial, antioxidant, antistatic, astringent, binder, whitening, buffering, swelling, chelating, cleansing, cosmetic dye, denaturing, deodorant, detangling, emollient, emulsifier, emulsion stabilizer, film-forming, flavoring, foaming, gelling, hair conditioning, hair fixative, hair waving or smoothing, moistening, hydrotropic, masking, moisturizing, oxidizing, pearlescent, perfuming, plasticizing, preservative, propellant, reducing, re-greasing, refreshing, soluble smoothing, soothing stabilizer, surfactant, tonic, UV filter, viscosity control substances.

The pH of the composition is between <NUM> and <NUM>.

The invention also relates to the method of application of said composition on the keratin fibers of the human species.

Further purposes and advantages will become evident from the following detailed description of the invention.

In the context of this description, the terms "caucasian" type hair and "european" type hair are to be considered synonyms.

According to a preferred - but not limiting - embodiment, the present invention relates to a mixture of organic substances, dispersed in a cosmetically acceptable medium, and at least one method of applying the same mixture to the keratin fibers.

The composition according to the invention comprises:.

The composition further comprises one or more of the ingredients commonly used in the cosmetic industry.

The composition of the invention is an aqueous composition with a pH between <NUM> and <NUM>.

The concentration of each ingredient (a), (b) or (c) is in the range <NUM>-<NUM>% with respect to the overall composition, the rest being water or an aqueous solution applicable on the hair and containing one or more cosmetically acceptable components.

The composition can be used as such on the hair as an aqueous solution or it can be formulated as a cream or gel according to the knowledge of the cosmetic technique, as for instance described in <CIT>.

The individual components of the composition are detailed as follows:.

The following fluorosilicones belong to these families:.

<NUM>) - Acrylic and/or methacrylic polymers with non-fluorinated backbone and pendant perfluorinated alkyl groups selected from:.

Substances described for their chemical, physical and toxicological properties in the "<NPL> of substances for cosmetic use and in Commission Decision (EU) <NUM>/<NUM> of <NUM> April <NUM> (<NPL>).

Preferred non-limiting examples of suitable alkoxylated polyamines comprise amino molecules, which have at least two primary nitrogen atoms, meaning by this term that at least two primary amino functional groups are present in each molecule, and comprise, but are not limited to, substances corresponding to the following standard formulas:.

Examples of the alkoxylated polyamines for use in the present invention comprise, for instance, diamine compounds belonging to the Jeffamine series, such as the Jeffamine® D and Jeffamine® ED series, JEFFAMINE EDR148 and JEFFAMINE EDR, JEFFAMINE D230, JEFFAMINE D400, JEFFAMINE D2000, JEFFAMINE D4000, JEFFAMINE HK-<NUM>, JEFFAMINE ED600, JEFFAMINE ED900 and JEFFAMINE ED2003 available from Huntsman Corporation, Salt Lake City, Utah USA. <NUM>) - alkoxylated polyamines corresponding to the formula (W6):.

NH<NUM>(CH<NUM>)x∘(OCH<NUM>CH<NUM>O)y∘(CH<NUM>)z∘NH<NUM>     Formula (W6).

where x° and z° are integers between <NUM> and <NUM> and y° is an integer between <NUM> and <NUM>.

Examples of substances belonging to these families are the following:.

The composition of the invention is a ready-to-use mixture comprising substances (a), (b) and (c) dissolved or dispersed in a cosmetically acceptable aqueous medium having a pH between <NUM> and <NUM>.

The concentration of each ingredient (a), (b) or (c) is in the range <NUM>-<NUM>% with respect to the overall composition, the rest being water or a cosmetically acceptable medium (e.g. cream or gel) applicable on the hair.

The term "cosmetically acceptable medium" means the set of substances of common use in the cosmetic art listed in the<NPL>), classified as: anti-caking agent, anti-dandruff, anti-foam, antimicrobial, antioxidant, antistatic, astringent, binder, whitening, buffering, swelling, chelating, cleansing, cosmetic dyeing, denaturing, detangling, emollient, emulsifying, emulsion stabilizer, film-forming, flavoring, foaming, gelling, conditioning, fixative, hair waving or smoothing, moistening, hydrotropic, masking, moisturizing, mattifying, oxidizing, pearlescent, perfuming, plasticizing, solvent, preservative, smoothing, stabilizing, soothing, surfactant, UV filter, viscosity control substances.

The compositions of the invention can be formulated in liquid or semi-liquid, fluid or creamy form, such as: solutions, suspensions, lotions, creams.

The compositions of the invention are applied to the hair with a method that comprises the following basic steps:.

The process of the invention has shown that the keratin fibers after treatment are smooth, even after repeated washes (more than <NUM>), tend to absorb less water in washes and tend to have greater resistance to breakage of the fibers themselves than hair treated with techniques or mixtures commonly used in the cosmetic art. Step (III), which involves the elimination of the excess amount of product compared to that which the single hair can absorb, by means of rinsing with water has proved to be very important in terms of performance as it allows to have a hair at the end of the treatment less damaged (stressed) with consequent improvement of both its appearance and its physical-mechanical characteristics (the hair is more resistant to breakage).

Some experiments were performed to verify the better performance of the mixture object of the invention compared to mixtures already known in the state of the art. In particular, comparisons were made between the mixtures having the best performances described in the patent documents <CIT> and <CIT> and the mixtures object of the present invention with the aim of highlighting the surprising effects achieved with this composition.

The following examples are provided to illustrate the invention.

Tests were carried out on some of the mixtures of substances belonging to the families of organic substances described in points (a), (b), (c), always used in mixture with each other and dispersed or dissolved in a cosmetically acceptable medium by comparing them with similar mixtures of substances covered by patent documents <CIT> and <CIT>. The various components used in the comparative tests are illustrated below:.

The compositions of the invention were compared with the best compositions based on glyoxylic acid dissolved in a cosmetically acceptable medium as described in <CIT> with the aim of comparing the results obtainable from the composition object of the present invention with respect to the "state of the art" in hair smoothing described in patent <CIT>.

For all the tests and in all the tables the evaluations were conducted according to the following scheme:.

Comparison of the reduction of the curly aspect, of the waterproofing effect and of the tensile strength of "afro" and "caucasian" (also known as "european") type hair, obtainable on the same using the different types of mixtures object of the present invention, with respect to mixtures covered by patent <CIT>.

The compositions listed in Tables 1A and 1B were prepared: both tables show the details of the results obtained in curves reduction (smoothing) with mixtures containing glyoxylic acid, PPG-<NUM> bis-(<NUM>-aminopropyl) ether, bis-aminopropyl diglycol, C<NUM>-<NUM> alkyl PEG-<NUM> methacrylate/perfluoro-hexylethyl methacrylate copolymer and perfluorononylethyl carboxydecyl PEG-<NUM> dimethicone on hair type "AFRO" NATURAL CURLY (Tab. 1A) and on hair of "CAUCASIAN" (also called "european") NATURAL CURLY type (Tab.

The mixtures were applied to clean and dry hair with an exposure time of about <NUM> minutes.

Subsequently, the hair treated with the mixtures of the present invention were rinsed with warm water for about <NUM> minutes in order to eliminate the excess of substances present in the composition.

The hair treated with the invention object of the patent <CIT> (as described in tables 1A and 1B) have not been rinsed with water.

Then all hair was dried with a hairdryer at a temperature of about <NUM> until it was dried according to common use in cosmetics.

Once all the hair samples had dried, they were subjected to plating with a special tool in common use ("flat iron") at a temperature of about <NUM>.

Then the hair was subjected to six shampoos applying the common way of use (shampoo application, contact for <NUM> minutes, rinsing with warm water for <NUM> minutes, blow-drying) and evaluation of the results as described in table <NUM>.

Tables 1A and 1B show that the advantages that the mixtures of the present invention allow to bring to the current technique in the field of smoothing of keratin fibers with respect to the mixtures described in <CIT> are evident.

The mixtures described in <CIT>, when used according to the method described there, allow to obtain only the smoothing of the hair.

On the contrary, the mixtures of the present invention allow to obtain, in addition to smoothing, a significant reduction in the quantity of water that the hair can absorb and a greater tensile strenght.

Basically, the hair, with a single application becomes: smooth, waterproof and more resistant to breaking by traction.

Furthermore, the tests show that optimal results are achieved only with the combination of the three components (a), (b) and (c), otherwise the tests are not satisfactory.

Comparison of the reduction of the frizzy appearance, of the waterproofing effect and of the tensile strength of "afro" and "caucasian" (also known as "european") type hair, obtainable on the same using the different types of mixtures object of the present invention, with respect to mixtures covered by <CIT>.

The compositions listed in Tables 2A and 2B were prepared. Both tables show the details of the results obtained in volume reduction (frizz) with mixtures containing maleic acid, bis-aminopropyl diglycol and acrylates/perfluorohexylethyl methacrylate copolymer.

Tables 2A and 2B show how the advantages that the mixtures of the present invention allow to bring to the current technique in terms of reducing the frizz effect of keratin fibers are evident compared to the mixtures described in <CIT>.

The compositions listed in Tables 3A and 3B were prepared. Both tables show the details of the results obtained in curves reduction (smoothing).

Tables 3A and 3B show how the advantages that the mixtures of the present invention allow to bring to the current technique in terms of reducing the frizz effect of keratin fibers are evident compared to the mixtures described in <CIT>.

Comparison of the reduction of the frizzy appearance, of the waterproofing effect and of the tensile strength of "afro" and "caucasian" (also known as "european") type hair, obtainable on the same using the different types of mixtures object of the present invention, with respect to mixtures covered by patent <CIT>.

The compositions listed in Tables 4A and 4B were prepared. Both tables show the details of the results obtained in volume reduction (frizz).

Tables 4A and 4B show how the advantages that the mixtures of the present invention allow to bring to the current technique in terms of reducing the frizz effect of keratin fibers are evident compared to the mixtures described in <CIT>.

Furthermore, the tests show that optimal results are achieved only with the combination of the three components (a), (b) and (c), otherwise the tests are not satisfactory.

Similarly, to Examples <NUM>-<NUM>, tests were carried out with the compositions of the invention in comparison with the tests shown in the example on pages <NUM> and <NUM> of the patent application <CIT>. The results are shown in Tables <NUM>-<NUM> and there it is highlighted how the performances obtainable with the object of the present invention are much higher than those of the example presented in the patent application <CIT>.

With the aim of demonstrating the total difference between the performances obtainable with the object of the present invention with respect to the example reported on pages <NUM>/<NUM> of application <CIT>, tests were organized in parallel between the mixtures object of the invention and the relative methods of application and the mixtures and methods of use described in the aforementioned application.

From the tests performed on "afro" and "european" (also known as "caucasian") hair, total absence of performance similar to that obtainable with the object of the invention was found.

In particular, the various mixtures object of the invention show the ability to smooth the curly hair fiber in a way lasting over time (even <NUM> shampoos), to make it less permeable to water (a property that can also be found after <NUM> shampoos) and the property to make the hair fiber more resistant to traction (even after <NUM> shampoos). The same kind of results are obtained in the case of reducing the "frizz" effect.

Conversely, the mixtures described in the example on pages <NUM> and <NUM> of application <CIT>, applied in the manner mentioned in the same application both on curly hair (with the intention of making it smooth) and on "frizzy" hair (with the intent to reduce its volume) show the inability of the formulations described to give the hair fibers the properties found with the mixtures relating to the present invention. In other words, there is no smoothing effect after <NUM> shampoos, no kind of waterproofing and no increase in the tensile strength of the fiber.

It would seem that these are substances intended to be used for the modeling (finish) of the hair fibers in the final phase of the cosmetic procedure without modifying the hair fiber with the consequence that the characteristics given to the fibers are lost at the first wash.

Always referring to the known art, in the patent document <CIT> a copolymer is mentioned which has the commercial name of "SILSOFT A+" whose macromolecule is composed of an alternation of silicone hydrophobic blocks and polyether blocks, as per Scheme <NUM>
<CHM>
PO = polypropylene oxide; EO = polyethylene oxide.

As shown in scheme <NUM>, Silsoft A+ is a very different macromolecule from those of the present invention.

First of all because there are two (<NUM>) different types of monomers (an amino-silicone polymer block and a mixed polyethylene + polypropylene glycol polymer block) joined together via the amino silicone nitrogen atom.

Differently from the alkoxylated polyamines of the present invention, in Silsoft A+ there are no primary amino groups (-NH<NUM>) which, as is known, have a much higher reactivity than the tertiary amino groups towards the amino acid residues present in the hair fibers.

The essence of the present invention lies precisely in having found the right combination of three molecules already known, and used individually or in association with other molecules different from those of the invention, for the treatment of keratin fibers.

Claim 1:
A cosmetic composition for the treatment of keratin fibers comprising:
(a) at least one carboxylic acid having a number of carbon atoms lower than <NUM> selected from the saturated and unsaturated aliphatic carboxylic acids, their salts and mixtures thereof;
(b) at least one fluorinated polymer selected from perfluoro-acrylic or perfluoro-silicone polymers, and mixtures thereof;
(c) at least one alkoxylated polyamine and mixtures thereof;
(d) at least one component selected from water and a cosmetically acceptable aqueous solution
the composition having a pH between <NUM> and <NUM>.