Patent Description:
According to IUPAC, the International Union of Pure and Applied Chemistry, green chemistry means "the invention, design and use of chemicals and processes for reducing or eliminating the use and the production of hazardous substances". The main objectives of green chemistry include: preventing the production of waste, rather than treating it after it has been produced; minimising the toxicity of the chemicals used; and using renewable raw materials wherever possible.

Quaternary ammonium salts are widely used as cationic surfactants for fabric softeners, anti-electrostatic agents, corrosion inhibitors, hair conditioners, dispersants, germicides, biocides.

Among these quaternary ammonium salts, cetrimonium chloride or behentrimonium chloride are known and are mainly used as cationic surfactants in cosmetic and/or household products. Other types of quaternary ammonium salts acting as cationic surfactants and biocides are the polymers of quaternary ammonium salts such as, for example, silicone cocoamido quat or silicone dimeramido quat.

The products potentially containing quaternary ammonium salts as cationic surfactants are usually used on a daily and/or high frequency basis by consumers. In addition, they come into direct contact with the consumer's skin layer and/or are sometimes inhaled in the form of vapours.

Cationic surfactants, which include quaternary ammonium salts, are one of the most important categories of products used in hair products. These products are characterized by a so-called "substantivity", i.e., the ability to reside on hair, resisting washing in water: this property is linked to the ionic features of the hair which, having an isoelectric point of approximately <NUM>, is superficially characterized by a net negative charge, under physiological pH conditions. Neutralization of the surface charges of hair by cationic surfactants is one of the mechanisms of action through which these products are believed to have an "antistatic" action on the hair and to reduce the so-called "fly away" effect. Moreover, cationic surfactants are known to improve the tone of hair, "swelling" it, a phenomenon related to the aforesaid substantivity. For these reasons, cationic surfactants are among the most commonly used products in the formulation of shampoos and conditioners or other conditioning products.

Another group of ingredients highly used in hair products is that of vegetable oils, desirable for the protective action on hair: it is believed in particular that the use of oils for hair care is beneficial to increase the softness thereof; fill the gaps between cuticles, compacting them and avoiding the penetration of potentially harmful substances; improve the shine thereof; reduce the friction and the forces involved during combing, thus increasing stem resistance to breakage.

Moreover, in a "green" cosmetic scenario which uses products of vegetable origin, the presence of vegetable oils in cosmetic products for hair is now expected and requested by the consumer.

<CIT> describes a quaternary ammonium salt having a formula characterised by a chain comprising an alkylated polyethylene glycol derivative, whose counter anion X is a halogen.

<CIT> describes a quaternary ammonium salt with a chain including an acylated polyethylene glycol derivative. In this case, the counter anions permitted for neutralisation of the salt are chosen from: acetate, citrate, tartrate, halogen, SO<NUM><NUM>-, MeSO<NUM>-; EtSO<NUM>-. The product is included in a cosmetic composition intended for cleansing and care of the skin of the body or face; lips; eyebrows; eyelashes; nails and hair; or, in a composition for hair styling, hair colouring.

<CIT> describes a quaternary ammonium salt with a chain comprising an alkyl derivative of polyethylene glycol having an alkane group. The product is in chloride form and is intended for cosmetic use for conditioning hair, skin or textile fibres.

<CIT> describes a salt having a central quaternary ammonium group, substituted with two chains comprising a polyethylene glycol derivative. The counter anion is in this case chosen from C2-C22 fatty acids, C4-C44 dimerised fatty acids, glutamic acid, tri-acids (such as citric acid). The product is included in a personal care formulation that may be intended for cleansing, hair conditioning, skin conditioning, hair styling, dandruff treatment, hair growth promotion and the like.

<NPL>) describes a quaternary ammonium salt based on a quaternized glycine derivative with two methyl groups and a hexadecyl group, esterified with a glycerol derivative.

<CIT> describes a quaternary ammonium salt based on a quaternised glycine derivative with two methyl groups and a hexadecyl group, esterified with a glycerol derivative. The product, in the form of chloride, is intended for cleaning fabrics from stains.

The site https://www. de/en/databases/fiedler/generalstatements/surfactants. html (XP055877187) describes various surfactants, including those in the form of sulphates and sulphonates. The latter can be used with other emulsifiers, also for cosmetic purposes.

Colorimetric labelling test (<NPL>); <NPL>)) show that the rinsing resistance of monofunctional cations is lost or less evident when the cationic surfactant has a relatively short carbon chain (number of carbon atoms of about <NUM>). A greater length of the carbon chain leads to a better substantivity of the surfactant, desirable for the reasons set out above. This effect is thought to be due to the fact that, in addition to electrostatic bonds, Van der Waals forces also come into play, which bind the surfactant to keratin in the presence of an aqueous phase.

As explained above, the combination of cationic surfactants and vegetable oils in hair care products is absolutely common in the cosmetics field. However, due to their hydrophobicity, vegetable oils paradoxically perform an opposite action to that of cationic surfactants, reducing or nullifying the swelling effect on hair.

In fact, when vegetable oils penetrate hair, they reduce the amount of water absorbed by the same, leading to a "deflation" of the hair and sometimes to dryness.

The Applicant has developed a restructuring agent for hair (or a hair restructuring association) which solves the technical problems of the prior art. The restructuring agent of the invention comprises or alternatively consists of:.

A further subject matter of the present invention are cosmetic formulations comprising the restructuring association of the invention, as a hair restructuring and/or conditioning agent.

The association of the invention ensures considerable benefits on hair:.

Compared to the products of the prior art, the Applicant considers that the association of the invention is particularly advantageous since it allows to combine vegetable oils and cationic surfactants, improving the effectiveness thereof and preventing the two ingredients from nullifying each other's effects.

Although not bound by any theory, the Applicant believes that the effective coexistence of the cationic surfactant and the sulpho-derivative of vegetable fatty acids derives from the sulpho-derivation of the latter. In fact, it is hypothesized that the sulpho-derivative of fatty acids maintains the typical lubricating properties thereof, creating a protective film on hair which facilitates and improves the substantivity of the cationic surfactant despite the length of the carbon chain; the Applicant believes that such an effect is probably due to electrostatic or ionic interactions, as well as to a fraction of hydrophobic interactions, between the lipid film of the sulpho-derivative of the fatty acid and the cationic surfactant.

A further hypothesis which, according to the Applicant, could justify the restructuring effectiveness of the association is that, by virtue of the ionic nature of the compounds present in the association, the latter interacts with the saline bridges of the hair, maintaining the protein structure which constitutes it unaltered.

The microfibrils of hair have subunits called protofilaments, each containing sections of alpha-helical proteins arranged in a helical formation. The alpha-helix of proteins is maintained in this helical formation, characterising hair, by various chemical forces, including hydrogen bonds, disulphide bridges, Van der Waal forces and ionic forces.

The alteration of one or more of these chemical forces can cause a change in the shape of hair: during the ironing processes, for example, the aforementioned forces are broken, altering the structure of the helix and "stretching" it, leading to the final result of straighter and smoother hair.

The association of the invention, exhibiting restructuring properties for hair, can be useful both for repairing hair damaged by periodic and continuous invasive thermal or chemical treatments; and in combination with oxidizing agents, bleaching agents or hair dyes, to facilitate the restoration of the alpha-helical structure of the keratin; and in combination with heat treatments of hair to support the styling or setting thereof.

Furthermore, the association of the invention has the following technical advantages:.

For the purposes of the present invention, "restructuring" means an agent capable of forming ionic bonds with hair, restoring the alpha-helix structure of the proteins constituting the hair.

In view of its properties, the association of the invention can be, in addition or alternatively, defined as "conditioning" since it improves the ability to comb hair, reducing the static thereof.

It should also be noted that both components of the association have cleaning/surfactant power. In this sense, the association of the invention can also be generically defined as a "detergent".

For the quaternary ammonium salt of formula (I), the substituent R<NUM> is hydrogen.

Depending on whether the substituents R<NUM> and R<NUM> are equal to hydrogen (-H) or to the radical R<NUM> (formula II), the value of m may change accordingly.

In general, with reference to the counteranion X-, m represents the number of molecules of the counteranion contained in the salt of formula (I). Preferably, m is a number such that it guarantees the neutrality of the molecule of the salt of formula (I). In particular, m is an integer number comprised between <NUM> and <NUM>, preferably comprised between <NUM> and <NUM>, preferably comprised between <NUM> and <NUM>, preferably comprised between <NUM> and <NUM>, preferably equal to <NUM> or <NUM> or <NUM> or <NUM> or <NUM> or <NUM> or <NUM>.

According to a preferred embodiment, the salt of formula (I) comprises, at most, a number of quaternary ammonium groups equal to <NUM>, regardless of the value of n. In other words, the quaternary ammonium molecule and its counteranion X- are preferably with each other in a stoichiometric ratio of <NUM>:<NUM> or alternatively equal to <NUM>:<NUM> or alternatively equal to <NUM>:<NUM>, regardless of the value of n.

According to a particularly preferred embodiment, the salt of formula (I) comprises, at most, a number of quaternary ammonium groups equal to <NUM>, regardless of the value of n. In other words, the quaternary ammonium molecule and its counteranion X- are preferably with each other in a stoichiometric ratio of <NUM>:<NUM> or alternatively equal to <NUM>:<NUM>, regardless of the value of n.

Table <NUM> below shows the structural formulas of the different preferred embodiments of the salt of formula (I), for each substituent R<NUM> not in accordance with the invention, for which R<NUM> is hydrogen.

R<NUM> is hydrogen; in other words, the preferred embodiment of the salt of formula (I) is (IA).

For the embodiment indicated in table <NUM>, (IA), the substituents R<NUM>, R<NUM>, R<NUM> are methyl.

The substituents R<NUM>, R<NUM> and R<NUM> of the salt of formula (I) are the same as each other and are methyl.

The substituents R<NUM>, R<NUM> and R<NUM> of the salt of formula (I) are the same as each other and consist of the linear substituent methyl.

The substituents R<NUM>, R<NUM> and R<NUM> of the salt of formula (IA) are the same as each other and consist of the linear substituent methyl.

It should be noted that the considerations made above with reference to the substituents R<NUM>, R<NUM>, R<NUM> apply to both the quaternary ammonium group of the salt of formula (I) and to the radical R<NUM>.

For the embodiment indicated in Table <NUM> (IA), the counteranion mX- is selected from the group of carboxylic acids (in the form of carboxylate ions) consisting of:.

It should be noted that fatty acids are saturated or unsaturated aliphatic monocarboxylic acids with a carbon number of ≥ <NUM> and ≤ <NUM>, preferably ≥ <NUM> and ≤ <NUM>.

For the purposes of the present invention, keto acids are carboxylic acids which contain a ketone residue and are involved in different biological processes, such as the formation process of ketone bodies or glycolysis.

For the embodiment (IA) of the quaternary ammonium salt of the invention, the counteranion X- is preferably chosen from the group of carboxylic acids (in the form of carboxylate ions) consisting of: formic acid, acetic acid, lactic acid, acrylic acid, adipic acid, aldaric acid, oxalic acid, phthalic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, tartaric acid, glutaric acid, pimelic acid, maleic acid, malic acid, fumaric acid, suberic acid, citric acid, isocitric acid, butyric acid, oleic acid, palmitic acid, stearic acid, glutamic acid, aspartic acid, acetoacetic acid, pyruvic acid, levulinic acid, benzoic acid, salicylic acid, cinnamic acid, caffeic acid.

According to a preferred embodiment, the counteranion X- is acetate or malate (from malic acid).

Polyglycerol-n means a polymer consisting of a number n of glycerol base-structural units; it should be noted that the polyglycerols commonly available on the market are mixtures of polyglycerols, comprising <NUM>% or more of the polyglycerol of interest where about <NUM>% of the mixture consists of one or more of its different homologs, i.e., polyglycerols with a number n of repetitive units lower or higher than the one considered.

In particular, a polyglycerol-n in which n ≤ <NUM> can be synthesized by green experimental methods, starting from natural plant glycerin, following the Cosmos and NaTrue standards.

In contrast, a polyglycerol-n in which n > <NUM> is normally obtained with experimental methods known to those skilled in the art involving the use of synthetic (nonvegetable) glycerin.

According to a preferred embodiment of the quaternary ammonium salt of formula (I), n is comprised between <NUM> and <NUM>, preferably comprised between <NUM> and <NUM>, preferably equal to <NUM>, <NUM>, <NUM> or <NUM>.

In solution (or mixture), the quaternary ammonium salt of formula (I) is preferably electrically neutral. For the purposes of the present invention, electrically neutral means a molecular structure that contains an equal number of positive charges and of negative charges.

The quaternary ammonium salt of formula (I) can be advantageously obtained with the use of reactions known in the state of the art: by way of example, <FIG> shows the synthesis diagram of the quaternary ammonium salt of formula (IA), regardless of the type of counteranion mX-, starting from the acidification reaction of the trimethylglycine (reaction I, <FIG>), and subsequent organic acid esterification reaction catalyzed with the polyglycerol-n reagent (reaction II, <FIG>). Thereby, the desired quaternary ammonium salt product of formula (IA) and water are obtained.

It should be noted that, advantageously, water constitutes the only secondary product of the quaternary ammonium salt synthesis reaction of formula (I); in this sense, there is no formation and/or potential release into the environment of other compounds or chemical derivatives.

As for the quaternary ammonium salt of formula (IA), the synthesis reaction of the quaternary ammonium salt of formula (I) can be carried out starting from amino acid derivatives, characterized by an α-carbon quaternary amino group (N-R<NUM>, R<NUM>, R<NUM>), regardless of the type of counteranion X-.

Advantageously, the starting amino acid derivative (N-R<NUM>, R<NUM>, R<NUM>), the polyglycerol-n and the organic acid used in said chemical reactions are in turn obtained, as far as possible, with green synthesis methods according to the Cosmos and NaTrue standards and Regulation (EC) <NUM>/<NUM>, thus contributing to the sustainability of the final product. The Applicant hereinafter describes particularly preferred embodiments of the salt of formula (I).

According to a preferred embodiment of the salt of formula (I), preferably of the salt of formula (IA), the substituents R<NUM> and R<NUM> are equal to the radical R<NUM> (formula II) and equal to each other.

According to this embodiment, the substituent R<NUM> of R<NUM> is hydrogen.

R<NUM> of R<NUM> is hydrogen; for the substituents R<NUM>, R<NUM>, R<NUM>, the above considerations apply.

According to a particularly preferred embodiment of this first embodiment, the substituents R<NUM>, R<NUM> and R<NUM> of R<NUM> are equal to each other and consist of the linear methyl substituent.

According to this preferred embodiment, the salt of formula (I), preferably of formula (IA), is characterised by a plurality of positive charges on the corresponding quaternary nitrogen atoms N.

Still preferably, the salt of formula (I), preferably of formula (IA), is characterised by a maximum of <NUM> quaternary ammonium groups and thus by three positive charges on the corresponding quaternary nitrogen atoms N, irrespective of the value of n.

According to this preferred embodiment, the value of m may preferably be equal to <NUM> or <NUM> or <NUM>. Still preferably, the positive charges of the quaternary nitrogen atoms are neutralised under the following conditions:.

Still preferably, when the substituent R<NUM> is equal to R<NUM> and m is equal to <NUM>, the two counteranions X- neutralising the two positive charges of the nitrogen atoms of the salt of formula (I), preferably of formula (IA), may consist of the same carboxylic acid (same entity) or of two carboxylic acids of different nature (different entity).

According to this first embodiment of the salt of formula (I), the most preferred form of carrying out the invention is the salt of formula (IA5), wherein the substituents R<NUM> and R<NUM> are equal to the radical R<NUM>, R<NUM> is hydrogen, the substituents R<NUM>, R<NUM> and R<NUM> are methyl groups. The number of quaternary ammonium groups is equal to <NUM>, regardless of the n value; m is equal to <NUM> and the counteranion X- is the citrate ion or m is equal to <NUM> and the counteranion X- is the acetate ion:
<CHM>.

According to this embodiment of structure formula (IA5), n is equal to <NUM>, <NUM>, <NUM>, or <NUM>, more preferably <NUM>.

According to a preferred embodiment of the salt of formula (I), preferably of the salt of formula (IA), the substituent R<NUM> is hydrogen, the substituent R<NUM> is equal to the radical R<NUM>, characterised by the following structure of formula (II):
<CHM>.

According to a particularly preferred embodiment mode of the present embodiment, the substituents R<NUM>, R<NUM> and R<NUM> of R<NUM> are equal to each other and consist of the linear methyl substituent.

According to this preferred embodiment, the salt of formula (I), preferably of formula (IA), is characterised by a double positive charge on the corresponding quaternary nitrogen atoms N.

According to this preferred embodiment, the value of m may preferably be equal to <NUM> or <NUM>. Still preferably, the positive charges of the quaternary nitrogen atoms are neutralised under the following conditions:.

According to this second embodiment of the salt of formula (I), one of the most preferred form of carrying out the invention is the salt of formula (IA3), wherein the substituent R<NUM> is equal to the radical R<NUM>, R<NUM> is hydrogen, R<NUM> is hydrogen, the substituents R<NUM>, R<NUM> and R<NUM> are methyl groups, wherein m is equal to <NUM> and the counteranion X- is acetate:
<CHM>.

Preferably n is equal to <NUM>, <NUM>, <NUM> or <NUM>, more preferably <NUM>.

According to an alternative embodiment of the salt of Formula IA3, m is equal to <NUM> and X- is the monoionised malate ion or the monoionised tartrate ion.

According to this second embodiment of the salt of formula (I), another preferred form of carrying out the invention is the salt of formula (IA4), wherein the substituent R<NUM> is equal to the radical R<NUM>, R<NUM> is hydrogen, R<NUM> is hydrogen, the substituents R<NUM>, R<NUM> and R<NUM> are methyl groups, wherein m is equal to <NUM> and the counteranion X- is the malate ion or the tartrate ion:
<CHM>.

According to the salt of formula (IA4), n is equal to <NUM>, <NUM>, <NUM>, or <NUM>, more preferably <NUM>.

According to a preferred embodiment of the salt of formula (I), preferably of the salt of formula (IA), the substituent R<NUM> is equal to hydrogen H and the substituent R<NUM> is hydrogen.

In this preferred embodiment, the salt of formula (I), preferably the salt of formula (IA), is characterised by a single positive charge on the quaternary nitrogen N.

According to this preferred embodiment, the value of m is preferably equal to <NUM>. Still preferably, in this first preferred embodiment, the positive charge of the quaternary nitrogen is neutralised by the counteranion mX-, which satisfies the following conditions.

It should be noted that, preferably, the degree of ionisation of the pluriprotic carboxylic acid is influenced by the pH conditions of the chemical environment in which the salt of formula (I) is placed, preferably the salt of formula (IA), or to those of the process at which the quaternisation thereof takes place. In fact, although the quaternisation reaction carried out under acid catalysis is advantageous because it uses the carboxylic acid destined to neutralise the quaternary N, the same reaction can also be carried out under alkaline catalysis.

The Applicant hereinafter describes particularly preferred embodiments of the salt of formula (IA).

According to this third embodiment of the salt of formula (I), a preferred form of carrying out the invention is the salt of formula (IA1), wherein the substituents R<NUM> and R<NUM> are both hydrogen, m is equal to <NUM>, the substituent R<NUM> is hydrogen, the substituents R<NUM>, R<NUM> and R<NUM> are methyl:
<CHM>.

According to this first preferred embodiment, the counteranion X- is acetate. The acetate counteranion is particularly advantageous because it gives the quaternary ammonium salt of formula (I) a pleasant fruity smell.

According to another way of carrying out the third embodiment of the salt of formula (I), the substituents R<NUM> and R<NUM> are both hydrogen, m is equal to <NUM>, the substituent R<NUM> is hydrogen, the substituents R<NUM>, R<NUM> and R<NUM> are methyl and the counteranion X- is malate, as in the following formula (IA2):
<CHM>.

Preferably n is equal to <NUM>, <NUM>, <NUM> or <NUM>, more preferably n is <NUM>.

The Applicant points out that the malate ion as depicted in formula (IA2) is for illustrative purposes only and not limiting the purposes of the invention.

For the purposes of the present invention, the malate is preferably the dicarboxylate ion of the natural enantiomer of the malic acid, namely the L-form (or <NUM>-hydroxy-<NUM>,<NUM>-butanedioic acid), which is the one biologically active.

According to this second embodiment, the quaternary ammonium salt of formula (IA2) may be preferably Polyglyceryl-<NUM> Betainate Malate (INCI name).

The association according to the invention preferably comprises at least one sulpho-derivative of vegetable fatty acids.

For the aim of the present invention, the expression "sulpho-derivative of vegetable fatty acids" means a sulphate derivative and/or sulphonated derivative of one or more vegetable fatty acids.

Preferably, the sulpho-derivative of vegetable fatty acids consists of a sulphate derivative or a sulphonate derivative of a vegetable fatty acid; alternatively, the sulpho-derivative of vegetable fatty acids comprises a sulphate derivative and/or a sulphonate derivative of one or more vegetable fatty acids.

According to a preferred embodiment, the sulpho-derivative of vegetable fatty acids is a sulphate and/or sulphonate derivative of one or more vegetable fatty acids selected from the group consisting of: capronic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoceric acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, linoleic acid, linolenic acid and ricinoleic acid.

For the purposes of the present invention, vegetable fatty acid means a natural fatty acid which is obtained from or is obtainable from or is comprised in a vegetable oil. According to a preferred embodiment, the vegetable fatty acid is in the form of a vegetable oil. Natural vegetable oils suitable for the purposes of the invention are preferably selected from the group consisting of: peanut oil, behen oil, coconut oil, cotton oil, jojoba oil, sunflower oil, linseed oil, corn oil, sweet almond oil, palm oil, olive oil, castor oil, sesame oil and soybean oil. It should be noted that plant oils are known to contain mixtures of fatty acids in which one fatty acid is predominant over the others (<NUM>-<NUM>% by weight).

Techniques for making sulphate derivatives and/or sulphonate derivatives of vegetable fatty acids are known to those skilled in the art.

Those skilled in the art will understand that, depending on the synthetic methods used for the sulphation or sulphonation reactions and depending on the structure of a vegetable fatty acid considered, it is possible to obtain different sulphated (sulphation) and/or sulphonated (sulphonation) chemicals in mixture within the same process or synthetic method ("<NPL>).

For example, a synthetic sulphation method preferably involves the use of sulphuric acid (or chlorosulphonic acid) and subsequent neutralization of the reaction product with ammonia or sodium hydroxide or other methods known to those skilled in the art and/or available in the literature (<NPL>).

A synthetic sulphonation method preferably includes the use of fuming sulphuric acid (oleum - H<NUM>SO<NUM>·xSO<NUM>), sulphur dioxide - sulfuric anhydride (sulphur trioxide, liquid or gas - SO<NUM>) or other methods known to those skilled in the art and/or available in the literature (<NPL>)).

Preferably, the counteranion of the sulpho-derivative of the vegetable fatty acid is a monovalent cation, preferably it is sodium.

According to an alternative embodiment, the sulpho-derivative of plant fatty acids is a mixture of sulphate derivatives and sulphonate derivatives of ricinoleic acid (castor oil).

Preferably, the sulpho-derivative of vegetable fatty acids is a sulphate derivative of ricinoleic acid. The sulphate derivative of ricinoleic acid, obtained by the sulphation methods indicated above, is preferably the sulphoricinoleate with molecular formula C<NUM>H<NUM>O<NUM>S and/or related constitutional (or structural) isomers.

According to a preferred embodiment, the sulpho-derivative of vegetable fatty acids is.

According to this first embodiment, the sulphate derivative is sulphated castor oil.

According to another alternative embodiment of the invention the sulpho-derivative of vegetable fatty acids is preferably a sulphonate derivative of ricinoleic acid, obtainable by the synthetic methods described above; preferably said sulphonate derivative is the sulphonate of ricinoleic acid with molecular formula C<NUM>H<NUM>O<NUM>S and/or constitutional (or structural) isomers thereof.

Preferably, the sulphonate of ricinoleic acid is the sulphonate (IUPAC name: sodium (Z,12R)-<NUM>-hydroxy-<NUM>-sulphonatooctadec-<NUM>-enoate) of formula (IIIB2).

According to this second embodiment, the sulphate derivative is sulphonated castor oil.

The Applicant describes below different preferred embodiments of the hair restructuring association of the invention (c1)-(c5).

According to a preferred embodiment, the hair restructuring association comprises or consists of the salt of formula (IA1) and at least one sulpho-derivative of vegetable fatty acids, the latter being sulphated castor oil (formula IIIB1) and/or sulphonated castor oil (formula IIIB2).

According to a preferred embodiment, the hair restructuring association comprises or consists of the salt of formula (IA2) and at least one sulpho-derivative of vegetable fatty acids, the latter being sulphated castor oil (formula IIIB1) and/or sulphonated castor oil (formula IIIB2).

According to a preferred embodiment, the hair restructuring association comprises or consists of the salt of formula (IA3) and at least one sulpho-derivative of vegetable fatty acids, the latter being sulphated castor oil (formula IIIB1) and/or sulphonated castor oil (formula IIIB2).

According to a preferred embodiment, the hair restructuring association comprises or consists of the salt of formula (IA4) and at least one sulpho-derivative of vegetable fatty acids, the latter being sulphated castor oil (formula IIIg1) and/or sulphonated castor oil (formula IIIB2).

According to a preferred embodiment, the hair restructuring association comprises or consists of the fifth preferred embodiment of the salt of formula (IA5) and at least one sulpho-derivative of vegetable fatty acids, the latter being sulphated castor oil (formula IIIB1) and/or sulphonated castor oil (formula IIIB2).

The restructuring association according to the invention, as already mentioned, in addition to performing a hair repair function, also performs other technical/cosmetic functions.

In particular, the restructuring association of the invention is preferably used in cosmetic formulations also as a cleaning agent (surfactant), and/or as a wetting agent, and/or as a conditioning/softening agent, and/or as an emulsifying agent, and/or as an antistatic agent.

A further object of the present invention is a cosmetic formulation comprising the association of the quaternary ammonium salt of formula (I) and the sulpho-derivative of vegetable fatty acids, in combination with excipients and/or diluents suitable for the purpose.

Excipients and/or diluents suitable for the formulation of cosmetic formulations are for example selected from: water; cationic surfactants; anionic surfactants; amphoteric surfactants; conditioners; active ingredients, such as for example proteins, amino acids, osmoprotectants, vitamins; anti-dandruff agents; thickeners; viscosifying agents; filming agents, emulsifiers; antioxidants; chelators; pigments for hair dye; buffering agents for pH regulation; natural extracts; fragrances; perfumes; essential oils; humectants.

In the cosmetic formulation of the claims, the salt of formula (I) is preferably in a concentration comprised between about <NUM>% and <NUM>% (w/w), preferably between <NUM>% and <NUM>%, preferably between about <NUM>% and <NUM>% (w/w), preferably between about <NUM>% and <NUM>% (w/w), preferably equal to about <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% (w/w) by weight on the total weight of the formulation.

Preferably, the salt content of formula (I) in a cosmetic formulation is related to the sulpho-derivative content; preferably, the salt of formula (I) is formulated in amounts not exceeding <NUM>% by weight of the sulpho-derivative, preferably comprised between <NUM>% and <NUM>% by weight of the sulpho-derivative, preferably comprised between <NUM>% and <NUM>% by weight of the sulpho-derivative, preferably comprised between <NUM>% and <NUM>% by weight of the sulpho-derivative, preferably comprised between <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% by weight of the sulpho-derivative.

It should be noted that the cosmetic formulation comprising the association of the invention can contain the salt of formula (I) as the sole cationic surfactant or it can be in combination with other cationic surfactants.

When used in combination with other cationic surfactants (e.g., polymeric cationic surfactants) and/or non-ionic surfactants, at the above concentrations, the salt of formula (I) enables to reduce the content of other polymeric cationic surfactants.

Cationic surfactants usable in combination with the association of the invention, are for example selected from the group consisting of: cetrimonium chloride (or CTAC), behentrimonium chloride (or BTAC), stearamidopropyl dimethylamine (or SAPDMA) and guar hydroxypropylthrimethylammonium chloride (or GHPTAC), Dioleylethyl Hydroxyethylmonium Methosulphate (Tetranil CO-<NUM>) and Behenoyl PG-Trimonium Chloride (Quartamine BTC-<NUM>).

Preferably, the sulpho-derivative of the vegetable fatty acid is in a concentration comprised between <NUM>% and <NUM>% (w/w) by weight on the total weight of the cosmetic formulation, preferably comprised between <NUM>% and <NUM>% (w/w), preferably between <NUM>% and <NUM>% (w/w), preferably between <NUM>% and <NUM>% (w/w), preferably equal to <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% (w/w).

It should be noted that the cosmetic formulation comprising the association of the invention can contain the sulpho-derivative as the sole anionic surfactant or it can be in combination with other anionic surfactants.

Examples of anionic surfactants that can be used in combination with the association of the invention are sulphate surfactants, including, for example, alkyl sulphates (e.g., INCI: Sodium Lauryl Solfate or Sodium Dodecyl sulfate); Alkyletheresulphates (e.g., INCI: Sodium Laureth Solfate).

The cosmetic formulation preferably has a pH greater than <NUM> and less than <NUM>; preferably the cosmetic formulation has a pH between <NUM> and <NUM>, preferably between <NUM> and <NUM>.

Without wishing to be bound by any theory, the Applicant considers that the pH influences the conditioning capacities of a cationic system; in this sense, at the pH values indicated above, the cosmetic formulation showed better conditioning capacities (the hair was more easily combed than at other pH values of the formulation).

The pH of the cosmetic formulation can be adjusted by including one or more buffering agents in the formulation; an average person skilled in the art, based on his general knowledge, would be able to select one or more suitable buffering agents for the purpose without any difficulty, choosing from those known in the state of the art.

The cosmetic formulation is preferably in the form of a hair cleansing product, a hair conditioning product.

When in the form of a hair cleansing product, the cosmetic formulation is preferably in the form of a shampoo, shampoo conditioner (<NUM> in <NUM>).

When in the form of a hair conditioning product, the cosmetic formulation is in the form of a conditioner or oil not oil conditioner for hair.

According to a preferred embodiment, the cosmetic formulation in the form of a detergent or hair conditioner comprises the restructuring combination in a concentration comprised between about <NUM>% and <NUM>% (w/w), preferably between about <NUM>% and <NUM>%, preferably between about <NUM>% and <NUM>%, preferably between about <NUM>% and <NUM>%, preferably equal to <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% by weight on the total weight of the cosmetic formulation.

According to a preferred embodiment, the cosmetic formulation is in the form of a hair conditioning product and preferably comprises a fatty alcohol with a number of carbon atoms comprised between <NUM> and <NUM>, preferably comprised between <NUM> and <NUM>.

Preferably, the fatty alcohol contained in the formulation is selected from the group consisting of cetyl alcohol, stearyl alcohol or combination of the foregoing (cetyl stearyl alcohol). According to a preferred embodiment, the amount of alcohol is comprised between <NUM>% and <NUM>% by weight with respect to the amount of salt of formula (I).

The association with fatty alcohol advantageously promotes the ability to comb hair, reducing the force required for the hair styling operation with a greater smoothness of the comb with each passage.

Another object of the present invention is a cosmetic method for restructuring hair comprising at least the steps of:.

More preferably, the composition comprising the quaternary ammonium salt of formula (I) not in association with the sulpho-derivative of vegetable fatty acids is prepared according to <CIT>, the text of which is incorporated herewith by reference.

It is noted that the composition comprising or consisting of the hair restructuting association of the invention can be a leave-in composition or a rinse-off composition; the composition comprising the quaternary ammonium salt of formula (I) not in association with the sulpho-derivative of vegetable fatty acids can be a rinse-off composition or a leave-in composition.

The Applicant reports examples below for illustrative and non-limiting purposes of cosmetic use of the restructuring association according to the invention.

For the following examples <NUM>-<NUM>, "Blank" means untreated hair strands; "Benchmark" is the compound bis-aminopropyl diglycol dimaleate.

The substance/active tested against the Benchmark is the restructuring association of the invention, in the specific embodiment including Polyglyceryl-<NUM> Betainate Malate and Sulfated Castor Oil. In the foregoing, the Benchmark and the active are also generally referred to as "products".

Materials: The products were tested in aqueous solution (<NUM>% active, <NUM>% water).

Method: <NUM> strands of hair were used, addressing <NUM> of them to the group "Blank", <NUM> of them to the group "Benchmark" and <NUM> of them to group "Hair restructuring association of the invention". Each strand weighed <NUM>. Measurements were performed using a dynamometer following the DIASTRON procedure. Values are expressed in MPa.

The strands are immersed, firstly, in the aqueous solution for <NUM> minutes (pH unchanged compared to the natural ones of the products) and, secondly, for <NUM> minutes in a rinse off conditioner formulation including Polyglyceryl-<NUM> Betainate Acetate, Polyglyceryl-<NUM> Oleate, Cetearyl Alcohol, Aqua and <NUM>% of the active tested. The strands are rinsed, dried and then the measurements are taken.

The graph of <FIG> shows that the addition of the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, restores strength to damaged hair due to aggressive treatments and bleaching.

Method: tested on <NUM> samples each (each strand weighed <NUM>) with a dynamometer following the DIASTRON procedure. Values expressed in MPa. The strands are firstly immersed for <NUM> minutes in an aqueous solution including <NUM>% active, <NUM>% water (pH unchanged compared to the natural ones of the products); and secondly, for <NUM> minutes in a rinse off conditioner formulation including Polyglyceryl-<NUM> Betainate Acetate, Polyglyceryl-<NUM> Oleate, Cetearyl Alcohol, Aqua and <NUM>% active tested. It is rinsed, dried and then the measurements are taken.

Tests show an increase in breaking strength even after a single application, highlighting the restructuring properties of the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil.

All samples (hair strands) have been combed for <NUM> times and broken hairs have been weighted (with <NUM> accuracy, METTLER TOLEDO EXCELLENCE analytical scale). Reference is made to <FIG>.

The efficacy of the treatment with hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, seems to be almost double respect to the benchmark treatment.

Reference is made to <FIG>, <FIG>, <FIG> and <FIG>. The keratin structure of the hair reflects its health. The more raised and jagged the scales, the less healthy and shiny the hair is.

As shown in the figures mentioned above, hair treated with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, shows a better alignment of the scales of the cuticle more than hair treated with BENCHMARK, thus being able to boast a greater restructuring effect on the hair.

The sample comprising the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, shows the probable presence of a film covering the surface of the hair, as highlighted by the red arrows (<FIG>).

Method: tested on <NUM> samples each (each strand weighed <NUM>) with a dynamometer following the DIASTRON procedure. Values expressed in MPa. The products were tested in aqueous solution (<NUM>% active, <NUM>% water). The strands are immersed in solution for <NUM> minutes (pH unchanged compared to the natural ones of the products) and then <NUM> minutes in a rinse off conditioner formulation including Polyglyceryl-<NUM> Betainate Acetate, Polyglyceryl-<NUM> Oleate, Cetearyl Alcohol, Aqua and <NUM>% active tested. It is rinsed, dried and then the measurements are taken.

<FIG> shows the concentrations of the main non-metallic elements in the bleached hair tested: carbon (C), oxygen (O), nitrogen (N) and sulfur (S). In particular, the concentration of sulfur was taken into consideration in light of its presence in the form of sulfur amino acids in the keratin of the hair. Data collected showed no significant variation between the samples: no treatment, including the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, modifies the composition of the non-metallic elements present in the hair. The hair is not denaturalized.

The <FIG> and <FIG> show the normalized concentrations of calcium, copper, magnesium, sodium and potassium in the bleached hair tested. In the detail, in the same figures, it is possible to note the decrease in the sodium and potassium content in the samples treated with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, and BENCHMARK. This decrease, based on previous analyses of natural and bleached hair strands, can be attributed, hypothetically, to the residual presence of salts resulting from the use of sodium and potassium persulfates employed as bleaching agents. The presence of potassium was detected only in the BLANK sample, the sample treated with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, is the one showing the lowest sodium content.

SEM/EDX investigations on <NUM> hair strands bleached twice and treated with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, complexed with copper ions showed that the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, is able to restore the original structure and compactness of the hair. The hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, was used <NUM>% complexed with copper nitrate in solution, then in <NUM>% water and <NUM>% of a solution including the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil.

SAMPLES DESCRIPTION: n. <NUM> hair samples in the form of strands identified as follows:.

All samples have been previously bleached twice.

Rinse off conditioner formulation: water, citric acid, phenoxyethanol, Greenquat® BT emulsion (see examples above), panthenol, ethylhexylglycerin, sodium polyphosphate.

Reference is made to <FIG>. The untreated sample, like all samples, have been previously bleached twice in order to explore the effect of the cosmetic treatments on heavily damaged cuticles. In fact, as visible in figures, some hairs are completely deprived of the cuticle and, when present, the scales are very open and irregular.

Reference is made to <FIG>. The sample have been treated with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil alone and the effect of the treatment is clearly visible in the figures mentioned above. Observing the images, the differences between sample (left) treated with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, and the untreated one (right) are clear. Furthermore, the beneficial effect of the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, is proved by a greater compactness of the scales and a greater adherence to the hair shaft.

Aqueous Cu solution - Reference is made to <FIG>. Very damaged by the bleaching, even in the internal part of the shaft, no benefit from the treatment with a simple aqueous solution of a copper salt - Cu(NO<NUM>)<NUM>.

Hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, ONLY - Reference is made to <FIG>. The hair seems to regained a partial compactness. the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil + CONDITIONER (see examples above) - reference is made to <FIG>. The hair seems to regained its original compactness.

Copper treated samples have also been analyzed by EDX spectroscopy, in order to verify the penetration of Copper ions inside the structure of the hair. The EDX spectra, recorded on the hair sections, showed the presence of copper, both on the surface and in the internal part of the hairs.

In particular, the copper ions complexed by the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, (Samples <NUM> and <NUM>) seem to be more concentreated in the hair respect to the use of a simple aqueous solution of a copper salt - Cu(NO<NUM>)<NUM> (Sample <NUM>). Copper instead is clearly absent in Sample <NUM> (untreated sample). This result may indicate that the treatments with the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, and the hair restructuring association of the invention, comprising in this case Polyglyceryl-<NUM> Betainate Malate and Sulphated Castor Oil, and the RINSE OFF CONDITIONER (see examples above) are able to penetrate the structure of the hair as shown by the effective transport of copper ions.

Claim 1:
Hair restructuring association comprising or alternatively consisting of
(a) a quaternary ammonium salt of formula (I), and
<CHM>
(b) at least one sulpho-derivative of vegetable fatty acids, said sulpho-derivative comprising or consisting of a sulphate derivative and/or a sulphonate derivative of one or more vegetable fatty acids
wherein
R<NUM>, R<NUM> are independently chosen between hydrogen and a radical R<NUM>, wherein the radical R<NUM> consists of the following structure of formula (II)
<CHM>
R<NUM> is hydrogen,
R<NUM>, R<NUM>, R<NUM> are the same as each other and consist of the linear substituent methyl,
the counteranion mX- is chosen from the group consisting of: formic acid, acetic acid, lactic acid, unsaturated monocarboxylic acids, adipic acid, aldaric acid, oxalic acid, phthalic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, tartaric acid, glutaric acid, pimelic acid, maleic acid, malic acid, fumaric acid and suberic acid, isocitric acid, citric acid, fatty acids, acidic amino acids, keto acids and aromatic carboxylic acids,
m is an integer number comprised between <NUM> and <NUM>,
n is comprised between <NUM> and <NUM>.