Cosmetic compositions, application of such compositions, application of aminosilicone, method of treating creatine materials and method of enhancing preservation of conditioning effects produced by a cosmetic composition

(21) Application number: 357038 ^{(51) Int.Cl.}

A61K 8/898 (2006.01) A61K 8/92 (2006.01) A61Q 5/12 (2006.01) (22) Date of notification: 08.11.2002

Patent Office of the Republic of Poland

<td colspan="2">₍₅₄₎ A cosmetic composition for washing and caring for keratin substances,⁽⁵⁴⁾ its application and treatment of keratin substances</td>

<td></td><td>(73) The right holder of the patent:</td>

<td>(30) Priority: 2001-11-08, FR, 0114476 2001-11-08, FR, 0114477</td><td>LOREAL, Paris, FR (72) Inventor (s): JONATHAN GAWTREY, Boulogne, FR</td>

<td>(43) Application was announced:</td><td>SERGE RESTLE, Saint-Prix, FR</td>

<td>May 19, 2003 BUP 10/03</td><td>SANDRINE DECOSTER, Saint Gratien, FR PASCALE LAZZERI, Levallois Perret, FR</td>

<td>(45) The grant of the patent was announced:</td><td></td>

<td>May 31, 2012 WUP 05/12</td><td>(74) Representative: item. stalemate. Jolanta Mitura</td>

PL 211 335 B1

Description of the invention

The present invention relates to a cosmetic composition for cleaning and caring for keratin substances, comprising in a cosmetically acceptable medium at least one specific aminosilicone and at least one conditioning agent. The invention also relates to the use of the composition and the method of treating keratin substances.

It is known that hair that has been subjected to a varying degree of weathering (damaged and / or weakened) or mechanical or chemical treatments such as dyeing, discoloration and / or permanent waving is often difficult to comb and style and does not have softness.

It has already been recommended, in compositions for washing or caring for keratin substances such as hair, to use conditioning agents, especially cationic polymers or silicones, to facilitate detangling and to give them softness and elasticity. However, the beneficial effects mentioned above in the case of dry hair are also accompanied by cosmetic effects, which are judged to be undesirable, namely pod hair (lack of lightness), lack of smoothness (hair patchy from root to tip).

Moreover, the use of aminosilicones for this purpose has various disadvantages. Due to their strong affinity with the hair, some of these silicones, when used frequently, will become sorely deposited on the hair and cause undesirable effects such as unpleasant-to-touch sensation, static, rough hair and sticking to the styling. . These disadvantages are exacerbated in the case of fine hair, which lacks energy and volume.

EP 0890355 discloses a composition for use on hair for lightening it comprising (a) a guanidinium salt (b) an alkalizing agent other than a guanidinium salt and (c) silicone and conditioning agents. The composition damages the hair to a small extent and causes minimal irritation to the scalp.

EP 1138317 discloses a hair dye fixer containing a compound capable of complexing with an acid dye, a hair dye using this fixative, and a method of dyeing the hair resulting in extended color durability with minimal scalp irritation.

US-A-4601902 discloses conditioning compositions which contain an aminosilicone with at least one aminoethyliminopropyl group to improve the appearance, softness and styling of the hair.

It has turned out, however, that the present cosmetic compositions containing conditioning agents are not entirely satisfactory.

The applicant has found that the combination of a particular amino silicone with conditioning agents overcomes the above-mentioned disadvantages of the known compositions.

After thorough research in this area. The Applicant has surprisingly found that a composition containing at least one aminosilicone as defined below and at least one conditioning agent allows the reduction or even elimination of disadvantages such as lack of shine, smoothness and softness of the hair, while maintaining other beneficial cosmetic properties associated with the compositions. containing silicone.

This combination gives improved cosmetic properties (lightness, detangling, volume, smoothness and shine), and the effects are long-lasting and long-lasting.

The applicant has now found that the maintenance of cosmetic properties (especially conditioning effects) is improved due to the presence of a specific amino silicone.

Moreover, when applied to the skin, the compositions according to the invention, in particular in the form of a lather or shower gel, improve skin softness.

The compositions according to the invention promote the deposition of the conditioning agents on keratin substances.

Thus, the cosmetic composition for cleaning and caring for keratin substances according to the invention is characterized in that it comprises in a cosmetically acceptable medium at least one conditioning agent and at least one aminosilicone selected from the aminosilicones of formula (1):

PL 211 335 B1

<img file="PL211335B1_D0001.tif" />

wherein:

- m and n are numbers whose sum (n + m) is in the range from 50 to 250,

- n is from 49 to 249, and - m is from 1 to 10,

- R1, R2, R3, the same or different, represent a C1-C4 hydroxy or alkoxy group, at least one of the R1 to R3 groups being an alkoxy group, or of formula (2):

<img file="PL211335B1_D0002.tif" />

wherein:

- p and q are numbers whose sum (p + q) ranges from 50 to 350,

- p is from 49 to 349, a

- q is a number from 1 to 10,

- R1, R2, different, represent a C1-C4 hydroxy or alkoxy group and at least one of the R1 and R2 groups is an alkoxy group, with the

- Conditioning agents are selected from the group consisting of synthetic oils, mineral oils, vegetable oils, fluoro oils or perfluorine oils, natural or synthetic waxes, ceramides, carboxylic acid esters, silicones other than silicones of formula (1) or ( 2), anionic polymers, non-ionic polymers, cationic polymers and amphoteric polymers, cationic proteins, cationic protein hydrolysates and cationic surfactants, as well as mixtures of these various compounds; and

- the concentration of the conditioning agent is in the range of 0.01-10% by weight with respect to the total weight of the composition;

- the concentration of the aminosilicone (s) of formula (1) or (2) is in the range of 0.1-15% by weight relative to the total weight of the composition.

The novel composition according to the invention is useful for conditioning keratin substances, improving their lightness, softness, shine and / or ease of combing and to facilitate the styling of keratin substances. In addition, the maintenance of the conditioning effects of the compositions is improved upon shampooing.

The various objects of the invention will be described in detail below. All meanings and definitions of compounds used in the present invention, given below, are valid for all subjects of the invention.

PL 211 335 B1

According to the invention, the term "keratin substances" means hair, eyelashes, eyebrows, skin, nails, mucous membranes or the scalp, in particular hair.

The amino silicones of the invention are selected from the amino silicones of the above formulas (1) or (2).

In formula (1), preferably:

- m and n are numbers whose sum (n + m) ranges from 100 to 200,

- n is a number in the range of 125 to 175 and m is a number in the range of 1 to 5;

Preferably the alkoxy group is a methoxy group.

In the aminosilicones of formula (1), the molar ratio of the hydroxyl group to the alkoxy group is preferably in the range from 0.2: 1 to 0.4: 1, more preferably from 0.25: 1 to 0.35: 1, and most preferably is equal to 0 , 3: 1.

The amino silicone of formula (1) has a weight average molecular weight preferably in the range from 2,000 to 1,000,000, more preferably from 3,500 to 200,000.

In formula (2), preferably:

- p and q are numbers whose sum (p + q) ranges from 150 to 250,

- p is from 159 to 239 and q is from 1 to 5;

A preferred alkoxy group is methoxy.

In the aminosilicones of formula (2), the molar ratio of the hydroxyl group to the alkoxy group is preferably in the range from 1: 0.8 to 1: 1.1, more preferably from 1: 0.9 to 1: 1, and most preferably is equal to 1: 0. , 95.

The amino silicone of formula (2) has a weight average molecular weight preferably in the range from 2,000 to 200,000, more preferably from 5,000 to 100,000, and most preferably from 10,000 to 50,000.

The weight average molecular weight of these amino silicones is measured by gel permeation chromatography (GPC) at room temperature with a polystyrene standard. Styragel columns are used.

THF is used as eluent and the flow rate is 1 ml / min. 200 μ of a 0.5% by weight solution of silicone in THF is injected. For detection, refractometry and UV rays are used.

Commercial products corresponding to these silicones of the formulas (1) or (2) may contain in their compositions one or more other aminosilicones whose structure differs from that shown in formulas (1) and (2).

The product containing amino silicones of formula (1) is sold by the company Wacker under the name Belsil® ADM 652.

The product containing amino silicones of formula (2) is sold by the company Wacker under the name Fluid WR 1300®.

When these amino silicones are used, a particularly preferred embodiment includes using them in the form of an oil-in-water emulsion which may contain one or more surfactants. They can be of any nature, but are preferably cationic and / or non-ionic.

The numeric average size of the silicone particles in the emulsion is generally from 3 to 500 nm.

Preferably, the average particle size of the aminosilicone microemulsion of formula (2) ranges from 5 to 60 nm (inclusive), more preferably from 10 to 50 nm (inclusive).

According to the invention, aminosilicone microemulsions of formula (2) sold under the name Finish CT 96 E® or SLM 28020® by the company Wacker can be used.

Preferably, said aminosilicone is selected such that the angle of contact with water of a hair treated with a composition containing 2% (active substance) of the described silicone according to the invention ranges from 90 to 180 ° (inclusive), preferably from 90 to 130 ° (inclusive).

To measure the contact angle, the aminosilicone is preferably dissolved or dispersed in an aminosilicone solvent or an aminosilicone emulsion (especially hexamethyldisiloxane or water depending on the hydrophilicity of the silicone).

Preferably, a composition containing one or more aminosilicones of formula (1) or (2) is such that the angle of contact with water of the hair treated with the composition ranges from 90 to 180 ° (inclusive), and preferably from 90 to 130 ° (inclusive). ).

The contact angle measurement is performed by immersing the hair in distilled water and evaluating the force exerted by the water on the hair during immersion in distilled water and during removal. The forces measured in this way are directly related to the contact angle θ between the water and the hair surface. A hair is considered to be hydrophilic when the angle θ is in the range 0 to 90 ° and hydrophobic when the angle is in the range of 90 to 180 °.

PL 211 335 B1

The test is carried out on strands of natural hair that have been discolored under the same conditions and then washed.

Each 1 g lock is placed in a crystallization dish 75 mm in diameter, then evenly coated with 5 ml of the test compound. The lock is left for 15 minutes at room temperature, then rinsed for 30 seconds. The squeezed lock is left in the open air until it is completely dry.

For each evaluation, 10 hairs subjected to the same treatment are analyzed. Each sample, attached to a precision microbalance, is immersed in a vessel filled with distilled water. This DCA ("Dynamic Contact Angle Analyzer") scale from Cahn Instruments measures the force (F) exerted by the water on the hair.

At the same time, the circumference of the hair (P) is measured by observing it under a microscope.

The average wettability force on 10 hairs and the cross-section of the tested hair made it possible to obtain the contact angle between the hair and water, according to the formula:

F = P * Πv * cosθ where F is the wetting force expressed in Newtons, P is the hair circumference in meters, Γίν is the liquid / water vapor interfacial tension in J / m²and θ is the contact angle.

The product SLM 28020® from Wacker, at a 12% concentration in water (i.e. 2% aminosilicone), gives a contact angle of 93 ° according to the test indicated above.

The product Belsil ADM 652 ex Wacker, at a 2% concentration in hexamethyldisiloxane (i.e. 2% aminosilicon), gives a contact angle of 111 ° in the test described above.

The amino silicone (s) of formula (1) or (2) is used in an amount ranging from 0.01 to 15% by weight based on the total weight of the composition. Preferably the amount is in the range of 0.1 to 15% by weight, more preferably 0.5 to 10% by weight.

In the context of the present invention, the term "conditioning agent" means any agent whose function is to improve the cosmetic properties of keratin substances such as hair, in particular smoothness, softness, easy to comb and electrostatic properties.

Conditioning agents may be water soluble or insoluble.

Conditioning agents as defined above are selected from the group consisting of synthetic oils, such as polyolefins, mineral oils, vegetable oils, fluorinated oils or perfluorinated oils, natural or synthetic waxes, ceramides, carboxylic acid esters, silicones other than those of formula ( 1) or (2), anionic, non-ionic, cationic and amphoteric polymers, cationic proteins, cationic protein hydrolysates and cationic surfactants, commonly used in cosmetic or dermatological compositions, as well as mixtures of these various compounds.

The insoluble conditioning agents may be solid, liquid or pasty at room temperature (25 ° C) and atmospheric pressure, and may especially be in the form of oils, waxes or resins.

The insoluble conditioning agents are especially dispersed in the particulate compositions typically having a number average size ranging from 2 nanometers to 100 microns, and preferably from 30 nanometers to 20 microns (measured with a granulometer).

Insoluble conditioning agents are insoluble in water at a concentration greater than or equal to 0.1 wt%. at 25 ° C; ie, that under these conditions they do not form a macroscopically isotropic clear solution.

As synthetic oils, mention may be made, in particular, of polyolefins, in particular poly-alpha-olefins, and in particular:

- of the hydrogenated or non-hydrogenated polybutene type, preferably hydrogenated or non-hydrogenated polyisobutene.

Preference is given to using isobutylene oligomers with a molecular weight below 1,000 and mixtures thereof with polyisobutylene with a molecular weight above 1,000, and preferably ranging from

1000 up to 15,000.

As an example of poly-α-olefins that can be used in the present invention, mention may be made specifically of the products sold under the name Permethyl® 99 A, 101 A, 102 A, 104 A (n = 16) and 106 A (n = 38) by Presperse Inc. or alternatively products sold under the name Arlamol® HD (n = 3) by the company ICI (n is the degree of polymerization),

- of the hydrogenated or non-hydrogenated polydecene type.

Such products are, for example, sold under the names Ethylflo® by the company Ethyl Corp and Arlamol® PAO by the company ICI.

Animal and vegetable oils are preferably selected from the group consisting of sunflower oil, corn oil, soybean oil, avocado oil, jojoba oil, pumpkin oil, grape seed oil, sesame oil, hazelnut oil, fish oil, glycerol tricaprocaprylate or animal or vegetable oils of formula R9COOR10, where R9 is a higher fatty acid residue having from 7 to 29 carbon atoms, and R10 is a linear or branched hydrocarbon chain having from 3 to 30 carbon atoms, especially alkyl or alkenyl, for example purceline oil or liquid jojoba wax.

Natural or synthetic essential oils such as eucalyptus, lavender, vetiver, cubeb, lemon, sandalwood, rose, chamomile, charcoal, nutmeg, cinnamon, hyssop, caraway, orange, geranium, juniper, and bergamot oils can also be used.

Waxes are natural (animal or vegetable) or synthetic substances that are solid at room temperature (20 ° -25 ° C). They are water-insoluble, oil-soluble and can form a water-repellent coating.

For a definition of waxes, see PD Dorgan, Drug and Cosmetic Industry, December 1983, pp. 30-33.

The wax (s) is (are) selected in particular from Carnauba wax, Candelila wax, Alpha wax, paraffin wax, ozoketite, vegetable waxes such as olive tree wax, rice wax, hydrogenated jojoba wax or pure flower waxes such as such as essential waxes, from black currant flowers sold by the company Bertin (France), animal waxes such as beeswax, modified beeswax (cerabelin); Other waxes or waxy starting materials that can be used in the invention are especially marine waxes, such as the product sold by Sophim under the symbol M82, and polyethylene and polyolefin waxes in general.

According to the invention, compounds of the ceramide type are, in particular, natural or synthetic ceramides and / or glycoceramides and / or pseudoceramides and / or neoceramides. Ceramide compounds are described, for example, in the patent applications DE 4424530, DE 4424533, DE 4402929, DE 4420736, WO 95/23807, WO 94/07844, EP-A-0 646572, WO 95 / 16-665, FR-2673179, EP-A-0227994, WO 94/07844, WO 94/24097 and WO 94/10131, the contents of which are hereby incorporated by reference.

Particularly preferred ceramide compounds include, for example:

2-N-linoleoylaminoctadecane-1,3-diol,

2-N-oleoylaminoctadecane-1,3-diol,

2-N-palmitoylaminoctadecane-1,3-diol,

2-N-stearoylaminoctadecane-1,3-diol,

2-N-behenoylaminoctadecane-1,3-diol,

2-N- [2-hydroxypalmitoyl] aminooctadecane-1,3-diol,

2-N-stearoylaminoctadecane-1,3,4-triol, especially N-stearoylphytosphingosine,

Cetyl acid 2-N-palmitoylaminohexadecane-1,3-diol, bis (N-hydroxyethyl-N-cetyl) malonamide, N- (2-hydroxyethyl) -N- (3-cetyloxy-2-hydroxypropyl) amide. N-docosanoyl-N-methyl-D-glucamine, or mixtures of these compounds.

Fluorinated oils are, for example, perfluoropolyethers described in particular in patent application EP-A-486 135 and fluorocarbon compounds described in particular in patent application WO 93/11103.

The term "hydrofluorocarbon compounds" denotes compounds whose chemical structure includes a carbon skeleton in which some hydrogen atoms have been replaced with fluorine atoms.

The fluorinated oils may also be fluorocarbons, such as fluoroamines, for example perfluorotributylamine, fluorocarbons, for example perfluorodecahydronaphthalene, fluorinated esters and ethers.

Perfluoropolyethers are sold, for example, under the trade names Fomblin by the company Montefluos and Krytox by the company Du Pont.

Fluorocarbon compounds also include fluorine-containing fatty acid esters, such as the product sold under the name Nofable FO by the company Nippon Oil.

PL 211 335 B1

The fatty alcohols may be selected from linear or branched C8-C22 fatty alcohols, optionally oxyalkylated with 1-15 moles of alkylene oxide or polyglycerolated with 1-6 moles of glycerol. The alkylene oxide is preferably ethylene oxide and / or propylene oxide.

The carboxylic acid esters are especially esters of mono-, di-, tri- or tetra carboxylic acids.

The monocarboxylic acid esters are especially the monoesters of linear or branched, saturated or unsaturated C1-C26 aliphatic acids and linear or branched C1-C26 saturated or unsaturated aliphatic alcohols. The total number of carbon atoms in these esters is greater than or equal to 10.

Among the monoesters, there can be mentioned dihydroabietyl behenate, octyldodecyl behenate, isocetyl behenate, cetyl lactate, C12-C15 alkyl lactate, isostearyl lactate, lauryl lactate, linoleyl lactate, oleyl lactate, octoethyl octanoate, cearyl iso ethyl octanoate decyl, isocetyl isostearate, isocetyl laurate, isocetyl stearate, isodecyl octoate, isodecyl oleate, isononyl isononanoate, isostearyl palmitate, methylacetyl ricinoleate, myristyl stearate, octyl isononanoate, 2-ethylhexyl isononate, octyl palmitate, octyl pelargonate, octyl stearate, octyldodecyl erucanate, oleyl erucanate, ethyl and isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl palmitate, octyl myropyristyl palmitate butyl, cetyl myristate or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate, dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Esters of C4-C22 di- or tricarboxylic acids and C1-C22 alcohols and esters of mono-, di- or tri-carboxylic acids and C2-C26 alcohols of di-, tri-, tetra- or pentahydroxy alcohols can also be used.

May be mentioned diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, diisostearyl maleate, dioctyl undecylenate glyceryl stearate oktylododecylostearoilu, monoricinoleate, pentaerythritol tetraizononanian pentaerythritol tetraizopelargonian pentaerythritol tetraizostearynian pentaerythritol tetraoktanian pentaerythritol propylene glycol dicaprylate and caproate, tridecyl erucanate, Triisopropyl Citrate, Triisostearyl Citrate, Glycerol Trimactate, Glycerol Trioctanoate, Trioctyldodecyl Citrate, Trioleyl Citrate.

Of the esters mentioned above, preference is given to: ethyl and isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl myristate, butyl myristate, cetyl myristate, or 2-octyldodutinate, butearyl, butearybutinyl, iso-styl stearate myristate. dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate and cetyl octanoate.

Silicones other than those represented by the formula (1) or (2) that can be used in the invention are, in particular, polyorganosiloxanes, which are insoluble in the composition and can be in the form of oils, waxes, resins or gums.

Polyorganosiloxanes are described in detail in Walter Noll "Chemistry and Technology of Silicones" (1968) Academic Press. These silicones can be volatile or non-volatile.

Volatile silicones are selected from compounds with a boiling point of 60-260 ° C and in particular from:

(i) cyclic compounds containing 3-7 and preferably 4-5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold especially under the name "Volatile Silicone 7207" sold by Union Carbide or "Silbione 70045 V 2" by Rhodia Chimie, decamethylcyclopentasiloxane sold especially under the name "Volatile Silicone 7158" sold by Union Carbide or "Silbione 70045 V 5" Sold by Rhodia Chimie, and mixtures thereof.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type such as "Volatile Silicone FZ 3109" sold by Union Carbide having the chemical formula:

<img file="PL211335B1_D0003.tif" />

PL 211 335 B1

Mixtures of cyclic silicones with organosilicon compounds may also be mentioned, such as a mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and a mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis (2,2,2 ', 2', 3,3'-hexatrimethylsilyloxy) ) neopentane;

(ii) linear volatile silicones containing 2-9 silicon atoms with a viscosity less than or equal to 5 * 10^-6m²/ s at 25 ° C. An example is decamethyltetrasiloxane sold especially under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in an article published in Cosmetics and toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd &amp; Byers "Volatile Silicone Fluids for Cosmetics".

Non-volatile silicones are particularly preferably used, in particular polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, organofunctional modified polyorganosiloxanes.

More specifically, these silicones are selected from polyalkyloxanes, including mainly polydimethylsiloxanes having trimethylsilyl end groups having a viscosity ranging from 5 * 10^-6 up to 2.5 m²/ s, at a temperature of 25 ° C, preferably 1 * 10^-5 - 1 m²/ s.

The viscosity of the silicones is measured, for example, at 25 ° C according to ASTM 445 Annex C.

Among these polyalkylsiloxanes, the following commercial products can be mentioned, but are not limited to:

Silbione® oils of series 47 and 70,047 or Mirasil® oils marketed by Rhodia Chimie, such as for example 70,047V 500,000 oil;

- Mirasil series oils marketed by Rhodia Chimie;

- 200 series oils from Dow Corning, such as especially DC200 with a viscosity of 60,000 cSt (mm²/ s);

- Viscasil® oils from General Electric and some oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes having dimethylsilanol end groups (Dimethiconol in the CTFA dictionary), such as the oils of the 48 series from Rhodia Chimie.

In this category of polyalkylsiloxanes, mention may also be made of the products sold under the names Abil® Wax 9800 and 9801 by Goldschmidt which are poly (C1-C20) alkylsiloxanes.

The polyalkylarylsiloxanes are selected in particular from linear and / or branched polydimethylmethylphenylsiloxanes and polydimethyldiphenylsiloxanes with a viscosity of 1 * 10^-5 up to 5 * 10^-6 m²/ s at 25 ° C.

Among these polyalkylarylsiloxanes, there may be mentioned, for example, the products sold under the following names: Silbione oils series 70 641 from Rhodia Chimie;

Rhodorsil oils series 70 633 and 763 from Rhodia Chimie;

Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

PK series silicones from Bayer, such as the PK 20 product; PN and PH series silicones from Bayer, such as the product PN 1000 and PH 1000;

some General Electric SF series oils, such as SF 1023, SF 1154, SF 1250, SF 1265.

The silicone rubbers which can be used according to the invention are, in particular, polydiorganosiloxanes with a high number average molecular weight in the range of 200,000-10,000,000, used individually or as a mixture in a solvent. The solvent may be selected from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecanes, or mixtures thereof.

The following products can in particular be mentioned: polydimethylsiloxane, polydimethylsiloxane / methylvinylsiloxane, polydimethylsiloxane / diphenylsiloxane.

polydimethylsiloxane / phenylmethylsiloxane, polydimethylsiloxane / diphenylsiloxane / methylvinylsiloxane

Products which can be used in particular according to the invention are mixtures such as:

- mixtures formed from end-chain hydroxylated polydimethylsiloxane, referred to in CTFA as dimethiconol, and from cyclic polydimethylsiloxane, referred to in CTFA as cyclomethicone, such as product Q2 1401 sold by Dow Corning;

PL 211 335 B1

mixtures made of polydimethylsiloxane rubber with cyclic silicone, such as the product SF 1214 Silicone Fluid from General Electric; this product is a dimethicone SF 30 gum, with a number average molecular weight of 500,000, dissolved in SF 1202 Silicone Fluic oil corresponding to decamethylcyclopentasiloxane;

mixtures of two PDMS with different viscosities, in particular a PDMS gum and a PDMS oil, such as the product SF 1236 from General Electric. This product is a mixture of SE 30 rubber as defined above with a viscosity of 20 m²/ s and SF 96 oil with a viscosity of 5 * 10^-6 m²/ s. The product preferably comprises 15% SE 30 gum and 85% SF 96.

The organopolysiloxane resins which can be used according to the invention are cross-linked siloxane systems having the following units R2SiO2 / 2, R3SiO1 / 2, RSiO3 / 2 and SiO4 / 2, wherein R is a hydrocarbon group containing 1-16 carbon atoms or a phenyl group. Among these products, those in which R is a C1-C4 lower alkyl group, especially a methyl group, or a phenyl group are particularly preferred.

Among these resins, mention may be made of the product sold under the name Dow Corning 593 or the products under the names Silicone Fluid SS 4230 and SS 4267 from General Electric which are dimethyl / trimethylsiloxane structured silicones.

Mention may also be made of the trimethyl siloxysilicate resins sold under the names X22-4914, X21-5034 and X21-5037 by the company Shin Etsu.

The organo-modified silicones that can be used in the present invention are those defined above and contain in their structure one or more organic functional groups linked via a hydrocarbon group.

Among these modified silicones other than those represented by formula (1) or (2), mention may be made of polyorganosiloxanes containing:

polyethyleneoxy and / or polypropyleneoxy groups optionally containing C6-C24 alkyl groups such as the products known as dimethicone copolyol sold by Dow Corning under the name DC 1248 and a C12 alkylmethicone copolyol sold by Dow Corning under the name Q2 5200;

- substituted or unsubstituted amino groups such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the name Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning; substituted amino groups are especially C1-C4 aminoalkyl groups;

- thiol groups such as the products sold under the names GP 72 A and GP 71 from Genesee;

alkoxylated groups such as the product sold under the name Silicone Copolymer F-755 by the company SWS Silicones and Abil Wax 2428, 2434 and 2440 by the company Goldschmidt;

- hydroxylated groups such as the hydroxyalkyl functional polyorganosiloxanes described in French patent application FR-A-85/16334;

- acyloxyalkyl groups such as, for example, the polyorganosiloxanes described in US Patent No. 4,957,732;

anionic groups of the carboxylic type, such as for example in the products described in EP 186 507 from Chisso Corporation or in the alkyl carboxylic type, such as in the products X-22-3701E from Shin-Etsu; 2-hydroxyalkyl sulfonate; 2-hydroxyalkyl thiosulfate, such as those sold by Goldschmidt under the names Abil S201 and Abil S255;

- hydroxyacylamino groups such as the polyorganosiloxanes described in patent application EP 342 834; for example, the product Q2-8413 from Dow Corning may be mentioned.

According to the invention, it is also possible to use silicones containing a polysiloxane part and a part consisting of an organic non-silicone chain, one of the two parts constituting the polymer backbone, the other being grafted onto this backbone. Such polymers are described, for example, in EP-A-412 704, EP-A-412 707, EP-A-640 105, EP-A-582 152, WO 95/00578 and WO 93/23009 and in US patents 4 693 935, 4 728 571 and 4 972 037. These polymers are preferably anionic polymers or nonionic polymers.

Such polymers are, for example, copolymers obtainable by radical polymerization starting from a monomer mixture consisting of:

a) 50-90% by weight of tert-butyl acrylate,

b) 0-40% by weight of acrylic acid,

c) 5-40% by weight of silicone macromer of formula (3)

PL 211 335 B1

<img file="PL211335B1_D0004.tif" />

where v is a number in the range of 5 to 700;

wherein the percentages by weight are based on the total weight of monomers.

Other examples of graft silicone polymers are especially polydimethylsiloxanes (PDMS) onto which they are grafted via a thiopropylene type linking chain unit, mixed units of poly (meth) acrylic acid type polymer and polydimethylsiloxanes (PDMS) onto which they are grafted via a linking chain unit of the type thiopropylene, polyisobutyl (meth) acrylate type polymer units.

According to the invention, all silicones can be used in the form of an emulsion, nanoemulsion or microemulsion.

According to the invention, particularly preferred silicones are:

- non-volatile silicones selected from the family of polyalkylsiloxanes containing trimethylsilyl end groups, such as oils with a viscosity of 0.2-2.5 m²/ s at 25 ° C, such as the oils of the DC200 series from Dow Corning, especially those with a viscosity of 60,000 cSt, the oils of the Silbione 70047 and 47 series, especially the oil 70,047V 500,000, sold by Rhodia Chimie, polyalkylsiloxanes containing dimethylsilanol end groups, such such as dimethiconols or polyalkylaryl siloxanes such as Silbione 70641 V 200 oil sold by Rhodia Chimie;

a polyorganosiloxane resin sold under the name Dow Corning 593;

- polysiloxanes containing amine groups, such as amodimethicones other than of formula (1) or trimethylsilylamodimethicones.

Conditioning agents which are listed below are generally water-soluble, in particular anionic, non-ionic, cationic, amphoteric polymers, cationic proteins, cationic protein hydrolysates and cationic surfactants, as well as mixtures of these various compounds.

Usually used as anionic polymers are polymers containing groups derived from carboxylic, sulfonic or phosphoric acid, and preferably having a weight average molecular weight in the range of about 500 to 5,000,000, as determined for example by gel permeation chromatography.

The anionic polymers may be selected from the group consisting of:

1) Polymers containing carboxyl units derived from monomers which are unsaturated mono or dicarboxylic acids of formula (4):

^R'\ / (Α, νΟΟΟΗ

Γ-C 'formula (4) ^R3 where n is an integer from 0 to 10, A1 is a methylene group, optionally attached to the carbon atom of the unsaturated group or to the adjacent methylene group when n is greater than 1, through a heteroatom such as oxygen or sulfur R1 is hydrogen or a phenyl or benzyl group, R2 is a hydrogen atom or a lower alkyl group or a carboxyl group, R3 is a hydrogen atom, a lower alkyl group or a -CH2-COOH group, a phenyl or a benzyl group.

In the above formula, the lower alkyl group is preferably a group having 1 to 4 carbon atoms, especially a methyl or ethyl group.

Particularly preferred anionic film-forming polymers containing carboxyl groups include:

A) Homo- or copolymers of acrylic or methacrylic acid or their salts, in particular the products sold under the names Versicol E or K by the company Ciba and Ultrahold by the company BASF. Acrylic acid and acrylamide copolymers sold as the sodium salt under the names Reten 421, 423 or 425 by Hercules; sodium salts of polyhydroxycarboxylic acids.

<img file="PL211335B1_D0005.tif" />

PL 211 335 B1

B) Copolymers of acrylic or methacrylic acid with a monoethylene monomer such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally cross-linked.

Such polymers are described in French Patent No. 1,222,944 and German Patent Application 2,330,956; copolymers of this type, optionally containing N-alkylated and / or hydroxyalkylated acrylamide units in the chain, as described in Luxembourg Patent Applications Nos. 75370 and 75371 or sold under the name Quadramer by the company American Cyanamid. Mention may also be made of copolymers of acrylic acid and C1-C4 alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and C1-C20 alkyl methacrylate, for example lauryl methacrylate, such as the product sold by ISP under the name Acrylidone LM and methacrylic acid / ethyl acrylate / acrylate terpolymers tert-butyl, such as the product sold under the name Luvimer 100 P by BASF.

C) Crotonic acid-derived copolymers, such as copolymers containing in the chain units of vinyl acetate or propionate, and optionally other monomers, such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain, containing a at least 5 carbon atoms, which polymers may optionally be grafted and cross-linked, or alternatively, an allyl or methallyl ester of an α- or β-cyclic carboxylic acid. Such polymers are described, inter alia, in French Patent Nos. 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products falling within this class include resins 28-29-30 , 26-13-14 and 28-13-10 sold by National Starch.

D) Copolymers derived from C4-C8 monounsaturated carboxylic acids or anhydrides selected from the group consisting of:

- copolymers comprising (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) at least one monomer selected from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, functional groups the anhydrides of these copolymers are optionally monoesterified or monoamidated. Such polymers are described in US Patent Nos. 2,047,398, 2,723,248 and 2,102,113 in GB Patent 839,805, and are in particular polymers sold under the names Gantrez AN or ES by the company ISP.

- copolymers including (i) one or more anhydrides: maleic, citraconic or itaconic and (ii) one or more monomers selected from allyl or methallyl esters optionally having one or more acrylamide, methacrylamide, α-olefin, methacrylic or acrylic esters, acrylic or methacrylic acid or vinylpyrrolidone groups in the chain, the functional the anhydride groups of these copolymers are optionally monoesterified or monoamidated. Such polymers are described, for example, in French patents

350 384 and 2,357,241 by the Applicant.

E) Polyacrylamides containing carboxylate groups.

2) Polymers containing sulfonate groups, which are polymers containing vinylsulfone, styrene sulfone, naphthalenesulfone or acrylamidoalkylsulfone units.

These polymers can be selected especially from the group consisting of:

polyvinyl sulfonic acid salts with a weight average molecular weight in the range of about 1000 to 100,000, and copolymers with an unsaturated comonomer such as acrylic or methacrylic acid and their esters, acrylamide or its derivatives, vinyl ethers and vinylpyrrolidone;

polystyrene sulfonic acid sodium salts, with a weight average molecular weight of about 500,000 and about 100,000, which are sold under the names Flexan 500 and Flexan 130, respectively, by National Starch. These compounds are described in French patent 2 198 719;

the salts of polyacrylamide sulfonic acid mentioned in US patent 4,128,631, in particular polyacrylamidoethylpropanesulfonic acid sold under the name Cosmedia Polymer HSP by the company Cognis.

According to the invention, the anionic film-forming polymers are preferably selected from acrylic acid copolymers such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer sold under the name Ultrahold Strong by BASF; copolymers derived from crotonic acid, such as vinyl acetate / vinyl tert-butylbenzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by National Starch; polymers derived from maleic acid or anhydride,

PL 211 335 B1 of fumaric or itaconic acid with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives and acrylic acid and its esters, such as methyl vinyl ether / monoesterified maleic anhydride copolymer, sold under the name Gantrez ES 425 by ISP, acid copolymers methacrylic acid and methyl methacrylate sold under the name Eudragit L by the company Rohm Pharma, a copolymer of methacrylic acid and ethyl acrylate, marketed under the name Luvimer MAEX or MAE by BASF and a vinyl acetate / crotonic acid copolymer sold under the name Luviset CA 66 by BASF and a polyethylene glycol grafted vinyl acetate / crotonic acid copolymer under the name Aristoflex A from BASF.

The anionic film-forming polymers that are most preferred are selected from the following: methyl vinyl ether / monoesterified maleic anhydride copolymer, sold under the name Gantrez ES 425 by ISP, acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer, sold under the name Ultrahold Strong by BASF, methacrylic acid and methyl methacrylate copolymers, sold under the name Eudragit L by Rohm Pharma, vinyl acetate / vinyl tert-butylbenzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers, sold under the name Resin 28-29-30 by National Starch, a copolymer of methacrylic acid and ethyl acrylate sold under the name Luvimer MAEX or MAE by BASF and a vinylpyrrolidone / acrylic acid / lauryl methacrylate terpolymer sold under the name Acrylidone LM by the company ISP.

The amphoteric polymers used in the present invention may be selected from polymers having K and M units distributed statistically along the polymer chain, where K is a unit derived from a monomer containing at least one basic nitrogen atom and M is a unit derived from an acidic monomer containing one or more carboxyl or sulfo groups or alternatively K and M may be derived from zwitterionic monomers, carboxybetaines or sulfobetaines;

K and M may also be a cationic polymer chain containing primary, secondary, tertiary or quaternary amine groups, wherein at least one of the amine groups is substituted with a carboxyl or sulfo group linked by a hydrocarbon group, or alternatively K and M form part of a polymer chain containing the unit ethylene-α, β-dicarboxylic acid, wherein one of the carboxyl groups has been prepared for the purpose of reacting with a polyamine containing one or more primary or secondary amine groups.

Particularly preferred amphoteric polymers as defined above are selected from the following polymers:

(1) Polymers prepared by copolymerizing a monomer derived from a vinyl compound with a carboxyl group, such as especially acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as especially methacrylate and dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylamide and acrylamide. These compounds are described in US Patent No. 3,836,537. Mention may also be made of the sodium acrylate / acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyguart KE 3033 by the company Cognis.

The vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and the above vinyl compound are sold under the names MERQUAT 28 0, MERQUAT 2 95 and MERQUAT Plus 3330 by the company Nalco.

(2) Polymers containing units derived from:

a) at least one monomer selected from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,

b) at least one acid comonomer containing one or more reactive carboxyl groups, and

c) at least one basic comonomer such as acrylic and methacrylic acid esters containing primary, secondary, tertiary or quaternary amine substituents and the product of dimethylaminoethyl methacrylate quaternization with dimethyl sulfate or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are particularly preferred according to the invention contain from 2 to 12 carbon atoms in the alkyl groups, namely N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N- decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides.

PL 211 335 B1

The acid comonomers are selected specifically from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids, as well as alkyl monoesters containing from 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Particularly used are copolymers appearing in the CTFA dictionary (4th Ed., 1991) under the designation octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, such as those sold under the name Amphomer or Lovocryl 47 by the company National Starch.

(3) Cross-linked and partially or fully alkylated polyaminoamides derived from polyaminoamides of general formula (5):

<img file="PL211335B1_D0006.tif" />

in which R4 is a divalent group derived from a saturated dicarboxylic acid, an aliphatic mono-or dicarboxylic acid containing an ethylene double bond, from esters of these acids and a lower alkanol of 1-6 carbon atoms or from a group obtained by addition of any of said acids with bis a (primary) or bis (secondary) amine; Z is a bis-primary, mono-or bis-secondary polyalkylene polyamine group, and is preferably:

a) in an amount of 60 to 100 mol%, a group of formula (6):

-NH — f-iCHJ - NH-l · - -,_Customs and Jp in formula 6) where x = 2, p = 2 or 3, or alternatively x = 3 and p = 2, this group being derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine;

b) from 0 to 40 mol%, a group of the above formula (6) where x = 2, p = 1, and which is derived from ethylenediamine, or a group of the formula which is derived from piperazine:

/-\

-NN \ _ /

c) in an amount from 0 to 20 mol% a group -NH- (CH2) 6-NH- which is derived from hexamethylenediamine, these polyaminoamines being cross-linked by addition of one difunctional cross-linking agent selected from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives , with 0.025 to 0.35 moles of crosslinker per amino group of the polyaminoamide and alkylated with acrylic acid, chloroacetic acid, or alkane sultone or their salts.

The saturated carboxylic acids are preferably selected from acids with 6-10 carbon atoms, such as adipic acid, trimethyl-2,2,4-adipic and trimethyl-2,4,4-adipic, terephthalic, acids containing an ethylene double bond, as in for example acrylic, methacrylic, itaconic acid.

The alkane sultones used in the alkylation are preferably propane sultone or butane sultone; salts of the alkylating agents are preferably sodium or potassium salts.

(4) Polymers containing zwitterionic units of formula (7):

<img file="PL211335B1_D0007.tif" />

wherein R5 is an unsaturated polymerizable group such as acrylate, methacrylate, acrylamide or methacrylamide group, y and z are an integer from 1 to 3, R6 and R7 are hydrogen, methyl, ethyl or propyl, R8 and R9 are hydrogen or an alkyl group such that the sum of the carbon atoms in R8 and R9 does not exceed 10.

Polymers containing such units may also contain units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate, or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.

By way of example, mention may be made of a butyl methacrylate / dimethyl carboxymethyl ammonioethyl methacrylate copolymer such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

(5) Chitosan derived polymers containing monomer units according to the following formulas (8), (9) and (10).

<img file="PL211335B1_D0008.tif" />

unit (8) is present in an amount ranging from 0 to 30%, unit (9) in an amount ranging from 5 to 50%, and unit (10) in an amount ranging from 30 to 90%, it should be understood that in the unit (10) R10 represents a group of the following formula:

R₁₂ R_n

1¹² 1¹³^RnC - (O)_q-CH - wherein q is 0 or 1;

if q = 0, R11, R12 and R13, same or different, represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamino residue or a dialkylamino residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted with one or more groups amino, hydroxy, carboxyl, alkylthio or sulfonate, an alkylthio residue in which the alkyl group contains an amino residue, at least one of the R11 groups R12 and R13 in this case are hydrogen;

or, when q = 1, each of R11, R12 and R13 is hydrogen, as well as the salts formed by these compounds with bases or acids.

(6) Polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "Evalsan" by the company Jan Dekker.

(7) Polymers according to general formula (11), such as those described in French Patent No. 1,400,366.

<img file="PL211335B1_D0009.tif" />

where R14 is hydrogen, CH3O, CH3CH2O or phenyl, R15 is hydrogen or a lower alkyl group such as methyl, ethyl, R16 is hydrogen or a lower alkyl group such as methyl, ethyl, R17 is a lower alkyl group such as methyl , ethyl or a group corresponding to the formula: -R18-N (R16) 2,

R18 represents -CH2-CH2-, -CH2-CH2-CH2- or -CH2-CH (CH3) -,

R16 has the meaning as mentioned above,

As well as the higher homologues of these groups containing up to 6 carbon atoms, r has the meaning that the molecular weight is in the range from 500 to 6,000,000, preferably from 1,000 to 1,000,000.

(8) -DXDX- amphoteric polymers selected from the group consisting of:

a) Polymers prepared by the action of chloroacetic acid or sodium chloroacetate on compounds containing at least one unit of formula (12):

-DXDX- (formula 12) where D is a group of the following formula / - \

-Ν Ν \ _ / and X represents the symbol E or E 'which, same or different, represent a divalent group which is a straight chain or branched alkylene group containing up to 7 carbon atoms in the main chain, unsubstituted or substituted by hydroxyl groups and which may also contain oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; wherein oxygen, nitrogen and sulfur atoms are present as ether, thioether, sulfoxide, sulfone, sulfonium, alkylamino or alkenylamino, hydroxyl, benzylamino, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane groups;

b) Polymers of formula (13):

-DXDX- (formula 13) where D is a group of the following formula:

/ \

-Ν Ν \ _ / a X stands for the symbol E or E 'and at least once E'; E is as indicated above and E 'is a divalent group which is a straight chain or branched alkylene group containing up to 7 carbon atoms in the backbone unsubstituted or substituted by one or more hydroxyl groups and which may contain one or more nitrogen atoms. the nitrogen atom being substituted with an alkyl chain optionally interrupted by an oxygen atom and containing necessarily one or more carboxyl or one or more hydroxyl functional groups and betainized by reaction with chloroacetic acid or sodium chloroacetate.

(9) (C1-C5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semi-amination with N, N-dialkylaminoalkylamine, such as N, N-dimethylaminopropylamine or by semi-esterification with N, N-dialkanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.

The amphoteric polymers that are particularly preferred according to the invention belong to the family (1).

The nonionic polymers that can be used according to the invention are selected, for example, from the group consisting of:

- vinylpyrrolidone homopolymers;

- copolymers of vinylpyrrolidone and vinyl acetate;

polyalkyloxazolines, such as the polyethyloxazolines sold by Dow Chemical under the names Peox 50,000, Peox 200,000 and Peox 500,000;

vinyl acetate homopolymers, such as the product sold by the company Hoechst under the name Appretan EM or the product sold under the name Rhodopas A 012 by the company Rhodia Chimie;

- copolymers of vinyl acetate and acrylic ester, such as the product sold under the name Rhodopas AD 310 by the company Rhodia Chimie;

vinyl acetate ethylene copolymers, such as the product sold under the name Appretan TV by the company Hoechst;

- copolymers of vinyl acetate and maleic ester, for example dibutyl maleate, such as the product sold under the name Appretan MB Extra by the company Hoechst;

PL 211 335 B1

- copolymers of polyethylene and maleic anhydride;

alkyl acrylate homopolymers and alkyl methacrylate homopolymers, such as the product sold under the name Micropearl RQ 750 by the company Matsumoto or the product sold under the name Luhydran A 848 S by the company BASF;

- acrylic ester copolymers, such as, for example,

- copolymers of alkyl acrylates and alkyl methacrylates, such as the products sold under the names Primal AC-261 K and Eudragit NE 30 D by Rohm &amp; Haas, under the names Acronal 601, Luhydran LR 8833 or 8845 by BASF or under the names Appretan N 9213 or N 9212 by Hoechst;

- copolymers of acrylonitrile and a non-ionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of products sold under the names Nipol LX 531 B by the company Nippon Zeon or under the name CJ 0601 B by the company Rohm &amp; Haas;

- polyurethanes, such as the products sold under the names Acrysol RM 1020 or Acrysol RM 2020 by Rohm &amp; Haas and the products Uraflex XP 401 UZ and Uraflex XP 402 UZ by DSM Resins;

- alkyl acrylate urethane copolymers, such as the product sold by the company National Starch;

polyamides, such as the product sold under the name Estapor LO 11 by the company Rhodia Chimie;

- unmodified or chemically modified non-ionic guar gums.

Unmodified nonionic guar gums are, for example, those sold under the name VIDOGUM® GH 175 by the company UNIPECTINE and under the name JAGUAR C by the company MEYHALL.

The nonionic modified guar gums are preferably modified with C1-C6 hydroxyalkyl groups. Examples include hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

Guar gums are well known in the art and can for example be prepared by reacting suitable alkene oxides such as, for example, propylene oxides with guar gum to obtain hydroxypropyl modified guar gum.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120, JAGUAR DC 293 and JAGUAR HP 105 by the company MEYHALL or under the trade name GALACTASOL 4H4FD2 by the company AQUALON.

Alkyl groups in nonionic polymers contain 1-6 carbon atoms, unless otherwise stated.

Functionalized or non-functionalized polyurethanes can also be used as polymers.

Particularly preferred polyurethanes for use in the present invention are described in EP 0751162, EP 0637600, FR 2743297 and EP 0648485 owned by the Applicant, as well as EP 0656021 or WO 94/03510 from BASF and EP 0619111 from National Starch.

Conditioning agents of the cationic polymer type that can be used in accordance with the invention can be selected from agents known to date as cosmetic agents for improving the cosmetic properties of hair treated with detergent compositions, i.e. in particular those described in EP-A-0 337 354 and in French applications patents 2270846, 2383660, 2598611, 2470596 and 2,519,863.

For the purposes of the present invention, the expression "cationic polymer" means any polymer that contains cationic groups and / or groups that are capable of being ionized into cationic groups.

Preferably the cationic polymers are selected from polymers which contain units with primary, secondary, tertiary and / or quaternary amine groups which may either form part of the polymer backbone or may be a side substituent directly linked to the main chain.

The cationic polymers used typically have a number average molecular weight in the range of about 500 to 5 * 10⁶and preferably ranging from about 10³ up to about 3 * 10⁶.

Among the cationic polymers, mention may be made, in particular, of those of the polyamine, polyaminoamide type and quaternary ammonium polymers. These are famous products.

Polymers of the polyamine, polyaminoamide type and quaternary ammonium polymers used in the invention which can be particularly emphasized are described in French patents Nos. 2,505,348 or 2,542,997.

PL 211 335 B1

Among the above polymers, the following can be mentioned:

(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and containing at least one of the following units of the formulas (14), (15), (16) or (17):

<img file="PL211335B1_D0010.tif" />

in which

R1 and R2, the same or different, represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group;

R3, the same or different, represent a hydrogen atom or a CH3 group;

A, same or different, represents a linear or branched alkyl group containing 1-6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group containing 1-4 carbon atoms;

R4, R5, R6, the same or different, represent an alkyl group having 1-18 carbon atoms or a benzyl group, preferably an alkyl group having 1-6 carbon atoms;

X is an anion derived from an inorganic or organic acid such as a methosulfate or a halide anion such as chloride or bromide.

The copolymers of family (1) may also contain one or more units derived from comonomers that may be selected from the family of acrylamides, methacrylamides, diacetoneacrylamides, acrylamides and methacrylamides substituted on nitrogen with lower (C1-C4) alkyl groups, acrylic or methacrylic acids, or their esters, vinyl lactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among these copolymers from the family (1) the following can be mentioned:

- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide, such as those sold under the name HERCOFLOC by the company HERCULES,

- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, described for example in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA,

PL 211 335 B1

- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETEN by the company HERCULES,

- quaternary or non-quaternary vinylpyrrolidone / acrylate or dialkylaminoalkyl methacrylate copolymers, such as the products sold under the name "GAFQUAT" by ISP, such as, for example, "GAFQUAT® 734" or "GAFQUAT® 755" or also the products known as "COPOLYMER 845, 958 and 937 ". These polymers are described in more detail in French patents 2077143 and 2393573,

- dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX® VC 713 by the company ISP,

vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymers specifically sold under the name STYLEZE CC 10 by the company ISP, and vinylpyrrolidone / dimethylaminopropyl methacrylamide quaternary copolymers, such as the product sold under the name "GAFQUAT® HS 100" by the company ISP.

(2) Cationic polysaccharides, especially cationic celluloses and cationic galactomannan gums. As cationic polysaccharides, particularly mention may be made of cellulose ether derivatives containing quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

The cellulose ether derivatives containing quaternary ammonium groups as described in French Patent 1492597, in particular polymers sold under the name "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the Amerchol company. These polymers are also defined in the CTFA dictionary as quaternary ammonium derivatives of hydroxyethyl cellulose reacted with a trimethylammonium substituted epoxy compound.

Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses such as e.g.

Commercial products corresponding to this definition are especially those sold under the names "Celquat® L 200" and "Celquat® H 100" by the company National Starch.

Cationic galactomannan gums are described in more detail in US patents US 3,589,578 and US 4,031,307 such as guar gums containing cationic trialkylammonium groups. For example, guar gums modified with salt (e.g. chloride) of 2,3-epoxypropyltrimethylammonium are used.

Such products are sold in particular under the trade names Jaguar® C13 S, Jaguar® C 15, Jaguar® C 17 or Jaguar® C 162 by the company Meyhall.

(3) Polymers composed of piperazinyl units and divalent alkylene or hydroxyalkylene groups containing straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen or an aromatic or heterocyclic ring, as well as oxidation and / or quaternization products of these polymers. These polymers are described in particular in French patents 2162025 and 228061.

(4) Water-soluble polyaminoamides prepared especially by polycondensation of an acid compound with a polyamine; said polyaminoamides may be cross-linked with epihalohydrin, diepoxide, dianhydride, unsaturated dianhydride, bis-unsaturated derivative, bis-halohydrin, bis-azetidinium, bis-haloacyldiamine, bis-alkyl halide or alternatively a difunctional reaction oligomer with the reaction oligomer bis-halohydrin, bis-azetidinium, bis-haloacyl diamine, bis-alkyl halide, epihalohydrin, diepoxide or a bis-unsaturated derivative, wherein the crosslinker is used in an amount ranging from 0.025 to 0.35 moles per amino group in the polyaminoamide. Such polyaminoamides may be alkylated or, if they contain one or more tertiary amine groups, they may be quaternized. Such polymers are described in French Patent Nos. 2,252,840 and 2,368,508.

(5) Polyaminoamide derivatives prepared by the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. By way of example, mention may be made of the adipic acid / dialkylaminohydroxyalkyldialkylene triamine polymers in which the alkyl group contains from 1 to 4 carbon atoms and is preferably methyl, ethyl or propyl. Such polymers are described in French Patent No. 1,583,363.

PL 211 335 B1

Among these derivatives, mention may be made in particular of the polymers adipic acid / dimethylaminohydroxypropyl / diethylenetriamine sold under the name "Cartaretine F, F4 or F8" by the company

Sandoz.

(6) Polymers prepared by the reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of polyalkylene polyamine to dicarboxylic acid ranges from 0.8: 1 to 1.4: 1. The resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups in the polyaminoamide ranging from 0.5: 1 to 1.8: 1. Such polymers are described in US patents 3,227,615 and US 2,961,347.

Polymers of this type are especially sold under the name "Hercosett® 57" by the company Hercules Inc. or also under the name "PD 170" or "Delsette® 101" by Hercules in the case of an adipic acid / epoxypropyl / diethylenetriamine copolymer.

(7) Alkyl diallylamine or dialkyldiallylammonium cyclopolymers, such as homopolymers or copolymers having as their main chain constituent units of formula (18) or (19):

- (CH₂kJCH_withk • CR

C (r₁₂) -CH₂(CH₂) k formula (18)) ch₂ ch₂

N + _Y_

WITH \ ^Y / V

-fCR0t - CR "

AND ^xCR

C {R,_?) -CH₂CH pattern (19)

Where putty is 0 or 1 and the sum of k + t is 1;

R12 represents a hydrogen atom or a methyl group;

R10 and R11 independently represent an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amido (C1-C4) alkyl group, or

R10 and R11, together with the nitrogen atom to which they are bonded, may be heterocyclic groups such as piperidyl or morpholinyl,

Y^- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. Such polymers are described in French Patent No. 2080759 and in Supplementary Certificate No. 2190406.

R10 and R11 are preferably independently an alkyl group having 1 to 4 carbon atoms.

Among the polymers described above, mention may be made in particular of the dimethyldiallylammonium chloride homopolymer sold under the name "Merquat® 100" by the company Nalco (and its low weight average molecular weight homologues) and the copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "Merquat® 550".

(8) A quaternary diammonium polymer containing repeating units of formula (20): R_1S

Ν -'- Α .- 'Ν · * »- B. pattern (20)

Μ- ^^χWherein R13, R14, R15 and R16, identical or different, represent aliphatic, alicyclic or araliphatic groups containing from 1 to 20 carbon atoms or lower hydroxyalkyl aliphatic groups or alternatively

R13, R14, R15 and R16 together or separately form with the nitrogen atoms to which they are bonded, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively.

R13, R14, R15 and R16 represent a linear or branched C1-C6 alkyl group, substituted nitrile, ester, acyl or amide group or a -CO-O-R17-D or -CO-NH- R17-D group, wherein R17 is an alkylene group and D is a quaternary ammonium group;

PL 211 335 B1

A1 and B1 are polymethylene groups containing from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked or incorporated into the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amine, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X^- is an anion derived from an inorganic or organic acid;

A1, R13 and R15 together with the two nitrogen atoms to which they are attached can form a piperazine ring;

and furthermore, when A1 is a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene group,

B1 may also be (CH2) n-CO-D-OC- (CH2) n-, where n is in the range 1-100, preferably 1-50, and D is:

a) a glycol residue of the formula -OZO, wherein Z is a linear or branched hydrocarbon group or a group of one of the following formulas:

- (CH2-CH2-O) x-CH2-CH2- [CH2-CH (CH3) -O] y-CH2-CH (CH3) where x and y represent an integer from 1 to 4 which represents the specific and only degree of polymerization or any number from 1 to 4 representing the average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) the rest of the bis-primary diamine of the formula:

-NH-Y-NH-, wherein Y is a linear or branched hydrocarbon group or a divalent group -CH2-CH2-SS-CH2-CH2-;

d) a ureylene group of the formula -NH-CO-NH-.

Preferably X^- is an anion such as chloride or bromide. Such polymers typically have a number average molecular weight in the range 1,000-100,000.

Polymers of this type are described in particular in French patents Nos. 2320330, 2270846, 2316271, 2336434 and 2413907 and in US patents 2273780, 2375853, 2388614, 2454547,

3206462, 2261002, 2271378, 3874870, 4001432, 3929990, 3966904, 4005193, 4025617, 4025627, 4025653, 4026945 and 4027020.

In particular, polymers which consist of repeating units of formula (21) can be used:

^R1 ^R3

<img file="PL211335B1_D0011.tif" />

wherein R1, R2, R3 and R4, identical or different, represent an alkyl or hydroxyalkyl group containing about 1-4 carbon atoms, n and p are integers ranging from about 2 to 20, and X^- denotes an anion derived from an inorganic or organic acid.

One compound of formula (21) that is particularly preferred is one in which R1, R2, R3 and R4 are methyl group n = 3, p = 6, and X = Cl, which according to the CTFA nomenclature is known as hexadimethrin chloride.

(9) Quaternary ammonium polymers containing units of formula (22):

l "|" - N + - (CH₂)_r-NH-CO- (CH₇) -CO-NH- (CHJ -N + -A—

X- I ^zqs | ^Rand g formula (22) R. ¹⁸ X- ^2t wherein:

R18, R19, R20 and R21, identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or -CH group₂-CH2 (OCH₂CH2) pOH,

In which p is 0 or an integer from 1 to 6, provided that R18, R19, R20 and R21 are not simultaneously a hydrogen atom, ris, identical or different, represent an integer from 1 to 6, q is 0 or an integer from 1 to 34, X^- is an anion such as a halide anion, A is a divalent group and is preferably -CH2-CH2-O-CH2-CH2-.

Such compounds are described in particular in the patent application EP-A-122 324.

Among these polymers, mention may be made of the products "Mirapol® A 15", "Mirapol® AD1", "Mirapol® AZ1" and "Mirapol® 175" sold by the company Miranol.

(10) Quaternary polymers of vinylpyrrolidone and vinylimidazole, such as for example the products sold under the name Luviquat® FC 905, FC 550 and FC 370 by BASF (11) Polyamines such as Polyguart® H sold by the company Cognis, listed in the CTFA dictionary under the name "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE".

(12) Cross-linked polymers of methacryloyloxy (C1-C4) alkyltri (C1-C4) alkylammonium salt, such as polymers made by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide with dimethylaminoethyl methacrylate then homopolymerized with methylaminoethyl chlorimated or copolymerized with methylaminoethyl quaternization, cross-linking with a compound containing olefinic unsaturation, especially methylenebisacrylamide. In particular, a cross-linked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of the copolymer in mineral oil may be used. This dispersion is sold under the name "Salcare® SC 92" by the company Ciba. Cross-linked methacryloyloxyethyltrimethylammonium chloride homopolymer in the form of dispersions containing about 50% by weight of the homopolymer in mineral oil or liquid ester may also be used. These dispersions are sold under the names "Salcare® SC 95" and "Salcare® SC 96" by the company Ciba.

Other cationic polymers that can be used in the present invention are cationic proteins or hydrolysates of cationic proteins, polyalkylenimines, especially polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.

Of all the cationic polymers that can be used in the context of the present invention, quaternary cellulose ether derivatives are preferably used, such as those sold under the name "JR 400" by Amerchol, cationic cyclopolymers, especially dimethyl diallylammonium chloride homopolymers or copolymers sold under the name "Merquat". ® 100 "," Merquat® 550 "and" Merquat® S "by Nalco, vinylpyrrolidone and vinylimidazole quaternary polymers, and mixtures thereof.

Cationic proteins or protein hydrolysates are, in particular, chemically modified polypeptides containing quaternary ammonium groups either at the end of the chain or grafted onto it. Their molecular weights may be in the range, for example, from 1,500 to 10,000, and especially about 2,000 to 5,000. Among these compounds, mention may be made in particular of

collagen hydrolysates containing triethylammonium groups, such as the products sold under the name Quat-Pro E by the company Maybrook and referred to in the CTFA dictionary as "Triethonium Hydrolyzed Collagen Ethosulphate";

- collagen hydrolysates containing triethylammonium and trimethylstearylammonium groups, such as the products sold under the name Quat-Pro S by the company Maybrook and referred to in the CTFA dictionary as "Steartrimonium Hydrolyzed Collagen";

animal protein hydrolysates containing trimethylbenzylammonium groups, such as the products sold under the name Crotein® BTA by the company Croda and referred to in the CTFA dictionary as "Benzyltrimonium hydrolyzed animal protein";

- protein hydrolysates containing, linked to the polypeptide chain, quaternary ammonium groups containing at least one alkyl group with 1-18 carbon atoms.

Among these protein hydrolysates, the following can be mentioned:

- Croquat® L in which the quaternary ammonium groups contain a C12 alkyl group;

- Croquat® M, in which the quaternary ammonium groups contain a C10-C18 alkyl group;

- Croquat® S, in which the quaternary ammonium groups contain a C18 alkyl group;

- Crotein Q, in which the quaternary ammonium groups contain at least one alkyl group with 1-18 carbon atoms.

These different products are sold by the Croda company.

PL 211 335 B1

Other quaternary proteins or hydrolysates are, for example, represented by the formula (23):

CH,

NH-A χθ _{W2ór (23)} pattern (23)

CH where X^- is an anion of an organic or inorganic acid, A is a protein residue derived from protein hydrolysates, especially collagen, R5 is a lipophilic group with up to 30 carbon atoms, and R6 is an alkylene group with 1-6 carbon atoms. Mention may be made, for example, of the products sold by Inolex under the name Lexein® QX 3000, referred to in the CTFA dictionary as "Cocotrimonium Collagen Hydrolysate".

Mention may also be made of quaternized vegetable proteins such as wheat, corn or soybean proteins. Quaternary wheat proteins marketed by Croda under the names Hydrotriticum WQ or QM are designated in the CTFA dictionary as "Cocodimonium Hydrolysed Wheat Protein"; Hydrotriticum QL, referred to in the CTFA dictionary as "Lauridimonium Hydrolysed Wheat Protein"; or Hydrotriticum QS, referred to in the CTFA dictionary as "Steardimonium Hydrolysed Wheat Protein".

Cationic surfactants are especially selected from quaternary ammonium salts, quaternary ammonium salts of imidazoline, quaternary diammonium salts and quaternary ammonium salts containing at least one ester functional group.

Cationic surfactants can be selected from the following:

A) quaternary ammonium salts of general formula (24):

X formula (24) where X^- is an anion selected from the group consisting of halide anions (chlorides, bromides or iodides) or (C2-C6) alkyl sulfates, more particularly methyl sulfate, phosphates, alkyl or alkylarylsulfonates, anions derived from an organic acid such as acetate or lactate;

i) the groups R1 to R3, which may be the same or different, represent linear or branched aliphatic groups having 1-4 carbon atoms or aromatic groups such as aryl or alkylaryl. The aliphatic groups may contain heteroatoms such as, in particular, oxygen, nitrogen, sulfur or halogens.

Aliphatic groups are selected from alkyl, alkoxy, and alkylamide groups.

R4 is a linear or branched alkyl group having 16 to 30 carbon atoms.

The cationic surfactant is preferably a behenyltrimethylammonium salt (e.g. chloride).

ii) the groups R1 and R2, which may be the same or different, represent a linear or branched aliphatic group having 1-4 carbon atoms or an aromatic group such as aryl or alkylaryl. Aliphatic groups may contain heteroatoms such as oxygen, nitrogen, sulfur, or halogens. Aliphatic groups are selected from alkyl, alkoxy, alkylamido, and hydroxyalkyl groups having from about 1 to 4 carbon atoms.

R3 and R4, the same or different, represent a linear or branched alkyl group having 12-30 carbon atoms and at least one ester or amide function.

R3 and R4 are selected, especially, from (C12-C22) alkylamido (C2-C6) alkyl and (C12-C22) alkylacetate groups.

The cationic surfactant is preferably a stearamidopropyl dimethyl (myristyl acetate) ammonium salt (e.g. chloride);

PL 211 335 B1

B) imidazolinium quaternary ammonium salts such as, for example, of formula (25):

<img file="PL211335B1_D0012.tif" />

wherein R5 is alkenyl or alkyl containing from 8 to 30 carbon atoms, for example tallow fatty acid derivatives,

R6 represents a hydrogen atom, a C1-C4 alkyl group, or an alkenyl or alkyl group having 8-30 carbon atoms,

R7 is a C1-C4 alkyl group,

R8 is hydrogen or a C1-C4 alkyl group and X is an anion selected from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates or alkylarylsulfonates.

Preferably R5 and R6 are a mixture of alkenyl or alkyl groups having from 12 to 21 carbon atoms, such as, for example, tallow fatty acid derivatives,

R7 is methyl, and

R8 is hydrogen.

Such products are, for example, Quaternium-27 (CTFA 1997) or Quaternium-83 (CTFA 1997), sold under the names Rewoquat® W75, W90, W75PG and W75HPG by Witco,

B) quaternary diammonium salts of formula (26):

GR₁₂

And n

R_s N (CH₂)₃- NO₁₄^R11 ^Ri3

2X formula (26) wherein R9 is an aliphatic group having from about 16 to 30 carbon atoms;

R10, R11, R12, R13 and R14, identical or different, are selected from hydrogen and alkyl groups containing an alkyl group of 1-4 carbon atoms, X is an anion selected from the group consisting of halides, acetates, phosphates, nitrates and methyl sulfates. Such quaternary diammonium salts include especially propano (tallow alkyl) diammonium dichloride;

D) quaternary ammonium salts containing at least one ester functional group, of formula (27):

<img file="PL211335B1_D0013.tif" />

&lt;

<img file="PL211335B1_D0014.tif" />

wherein R15 is selected from C1-C6 alkyl and C1-C6 hydroxyalkyl or dihydroxyalkyl groups;

R16 is selected from:

- groups

ABOUT

II

Ri-Γθ- linear or branched, saturated or unsaturated C1-C22 hydrocarbon groups R20,

- a hydrogen atom;

PL 211 335 B1

R18 is selected from:

- groups

ABOUT

II

FŁ ^ -C—

- linear or branched C1-C6 saturated or unsaturated hydrocarbon groups R22,

- a hydrogen atom;

R17, R19 and R21, same or different, are selected from linear or branched, saturated or unsaturated C7-C21 hydrocarbon groups;

n, pir, same or different represent integers in the range of 2-6; y is an integer ranging from 1-10;

x and z, which are the same or different, represent integers in the range of 0-10;

X^- is a simple or complex organic or inorganic anion;

with the proviso that the sum of x + y + z is 1 to 15, and when x = 0 then R16 is R20, and when z = 0 then R18 is R22.

Particularly the ammonium salts of the formula 27 in which

R15 is a methyl or ethyl group; x and y are equal to 1; z is equal to 0 or 1; n, pir are equal to 2;

R16 is selected from:

-groups

ABOUT

II

Rig-C -

- methyl, ethyl or C14-C22 hydrocarbyl groups

- a hydrogen atom;

R17, R19 and R21, same or different, are selected from linear or branched, saturated or unsaturated C7-C21 hydrocarbon groups;

R₁₈means a group

ABOUT

AT

Rff C- or a hydrogen atom.

Such compounds are sold, for example, under the names Dehyguart® by the Cognis company, Noxamium® by the Ceca company and Rewoquat® WE 18 by the Rewo-Witco company.

Preferred quaternary ammonium salts are stearamidopropyl dimethyl ammonium chloride (myristyl acetate) sold under the name Ceraphyl® 70 by Van Dyk and Quaternium-27 or Quaternium-83 sold by Witco.

Cationic surfactants are classified as soluble conditioning agents, but depending on their chemical structure, some cationic surfactants may be water-insoluble.

According to the invention, the surfactant (or agents) comprises from 0.001% to 10% by weight, preferably 0.1% to 3% by weight of the total weight of the final composition.

According to one particularly preferred embodiment, the compositions according to the invention contain at least one cationic polymer and / or at least one silicone.

The compositions according to the invention preferably also contain at least one surfactant, usually in an amount of about 0.1% - 60% by weight, preferably 3% - 40%, even more preferably 5% - 30%, based on the total weight of the composition.

Such surfactant may be selected from anionic, amphoteric, nonionic and cationic agents or mixtures thereof.

The following surfactants are particularly suitable for practicing the present invention:

(i) Anionic surfactants

The nature of these agents is not essential in the context of the present invention.

PL 211 335 B1

As an example of anionic surfactants that can be used alone or as mixtures in the context of the present invention, there may be mentioned, in particular (non-limiting list) salts (especially alkali salts, namely sodium, ammonium salts, amine salts, amino alcohol salts or magnesium salts). the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; alkylsulfonates, alkylphosphates, alkylsulfonates, alkylarylsulfonates, α-olefinsulfonates, paraffin sulfonates; alkylsulfosuccinates, alkylethersulfosuccinates, alkylsulfosuccinates; alkylsulfosuccinates; alkylsulfoacetates; alkyl ether phosphates; acylsarcosinates; acyl isethionates and N-acyl taurates, the alkyl or acyl group of all these compounds preferably having from 8 to 24 carbon atoms, and the aryl group is preferably phenyl or benzyl. Among the anionic surfactants which may also be used, mention may be made of fatty acid salts such as oleic, ricinoleic, palmitic, stearic, coconut oil acids or hydrogenated coconut oil acids; acyl lactates in which the acyl group contains from 8 to 20 carbon atoms. Weak anionic surfactants such as alkyl-D-galactoside uronic acids and their salts, polyoxyalkylenated (C6-C24) alkylethercarboxylic acids, polyoxyalkylenated (C6-C24) alkylaryl ether carboxylic acids, polyoxyalkylenated (C6-amino and C24) alkylcarboxylic acids can also be used. salts, especially those containing from 2 to 50 ethylene oxide groups, and mixtures thereof.

Among the anionic surfactants, the salts of the alkyl sulphates and the alkyl ether sulphates and mixtures thereof are preferably used according to the invention.

(ii) Non-ionic surfactants:

Nonionic surfactants are also well known compounds (see in particular the "Handbook of Surfactants" by MR PORTER, Blackie &amp; Son edition (Glasgow and London), 1991, pp. 116-178). The nature of these agents is not essential in the context of the present invention. Thus, they may be selected from (non-limiting list) polyethoxylated, polypropoxylated or polyglycerated alcohols, polyethoxylated, polypropoxylated or polyglycerated alpha-diols, polyethoxylated, polypropoxylated or polyglycerated alkyl phenols or polyoxyethylene, polypropoxylated or polyglycerated fatty acids, having a fatty chain of for example 8-18 carbon atoms and a number of ethylene oxide or propylene oxide groups ranging from 2 to 50 and a number of glycerol groups ranging from 2 to 30. Mention may also be made of copolymers of ethylene and propylene oxide, condensates of ethylene and propylene oxide with fatty alcohols; polyethoxylated fatty amides containing preferably from 2 to 30 moles of ethylene oxide, polyglycerated fatty amides containing on average from 1 to 5 glycerol groups, especially from 1.5 to 4; polyethoxylated fatty amines preferably containing from 2 to 30 moles of ethylene oxide; ethoxylated sorbitan fatty acid esters containing from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkyl polyglycosides, N-alkylglucamine derivatives, amine oxides such as (C10-C14) alkylamine oxides or N-acylaminopropylmorpholine oxides. Among the nonionic surfactants, alkyl polyglucosides are particularly preferred in the context of the present invention.

(iii) Amphoteric surfactants:

Amphoteric surfactants, the nature of which is not essential in the context of the present invention, may be particularly (non-limiting) aliphatic secondary or tertiary amine derivatives in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms and contains at least one solubility-enhancing anionic group (e.g. carboxyl, sulfonate, sulfate, phosphate, phosphono); mention may also be made of (C8-C20) alkylbetaines, sulfobetaines, (C8-C20) alkylamido (C1-C6) alkylbetaines or (C8-C20) alkylamido (C1-C6) alkylsulfobetaines.

Among the amine derivatives, mention may be made of the products sold under the name MIRANOL, such as those described in US patents 2,528,378 and US 2,781,354, with the formulas:

R2-CONHCH2CH2-N⁺(R3) (R4) (CH2COO^-) wherein:

R2 is the alkyl group of R2-COOH, present in the hydrolyzed coconut oil, a heptyl, nonyl or undecyl group, R₃ is a β-hydroxyethyl group, R₄ represents a carboxymethyl group; and

R2 '-CONHCH2CH2-N (B) (C)

PL 211 335 B1 in which:

B is -CH2CH2OX ', C is - (CH2) z-Y' where z = 1 or 2,

X 'represents the group -CH2CH2-COOH or a hydrogen atom,

Y 'is -COOH or the group -CH2-CHOH-SO3H,

R2 'represents an alkyl group of R9-COOH present in coconut oil or hydrolyzed linseed oil, an alkyl group, especially a C7, C9, C11 or C13, a C17alkyl group and its iso or unsaturated C17 form.

These compounds are listed in the CTFA Dictionary, 5th Edition, 1993, as disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium lauramphodipropionate, disodium caprylamphodipropion amphodipropionamphionamphionamphionamphionamphionate.

As an example, mention may be made of the cocoamphodiacetate sold under the name Mirand® C2M by the company Rhodia Chimie.

(iv) Cationic surfactants:

Cationic surfactants may be selected from the group consisting of:

A) quaternary ammonium salts of general formula (24):

+

X pattern (24)

<img file="PL211335B1_D0015.tif" />

in which X^- is an anion selected from the group of halides (chlorides, bromides or iodides) or (C2-C6) alkyl sulphates, especially methyl sulphate, phosphates, alkyl or alkylarylsulphonates, anions derived from an organic acid such as acetate or lactate, and

i) the groups R1 to R3, same or different, represent a linear or branched aliphatic group having 1-4 carbon atoms or an aromatic group such as aryl or alkylaryl. The aliphatic groups may contain heteroatoms such as, in particular, oxygen, nitrogen, sulfur or halogens.

The aliphatic groups are selected from alkyl, alkoxy, and alkylamide groups.

R4 is a linear or branched alkyl group having 16-30 carbon atoms.

The cationic surfactant is preferably a behenylotrimethylammonium salt (e.g. chloride).

ii) the groups R1 and R2, the same or different, represent a linear or branched aliphatic group having 1-4 carbon atoms or an aromatic group such as aryl or alkylaryl. The aliphatic groups may contain heteroatoms such as, in particular, oxygen, nitrogen, sulfur or halogens.

The aliphatic groups are selected from alkyl, alkoxy, alkylamido, and hydroxyalkyl groups having about 1-4 carbon atoms;

R3 and R4, the same or different, represent a linear or branched alkyl group having 12-30 carbon atoms and at least one ester or amide function.

R3 and R4 are especially selected from (C12-C22) alkylamido (C2-C6) alkyl and (C12-C22) alkylacetate groups.

A preferred cationic surfactant is a salt (e.g. chloride) of stearamidopropyl dimethyl (myristyl acetate) ammonium;

B) imidazolinium quaternary ammonium salts such as, for example, of formula (25):

“R 1 ⁺

Ϊ⁶ CH₂-CH₂~ M (R_S.) -CG-R_s^x formula (25) &amp; lt; / R &amp; lt; 5 &amp; gt; in which R5 is an alkenyl or alkyl group containing 8-30 carbon atoms, for example derivatives of tallow fatty acids,

R6 represents a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group having 8-30 carbon atoms,

R7 is a C1-C4 alkyl group,

PL 211 335 B1

R8 represents a hydrogen atom or a C1-C4 alkyl group and X is an anion selected from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates or alkylarylsulfonates.

Preferably R5 and R6 are a mixture of alkenyl or alkyl groups having 12-21 carbon atoms, such as, for example, tallow fatty acid derivatives,

R7 is methyl and R8 is hydrogen.

Such a product is, for example, Quaternium-27 (CTFA 1997) or Quaternium-83 (CTFA 1997) which are sold under the names Rewoquat® W75, W90, W75PG and W75HPG by the Witco company;

C) quaternary diammonium salts of formula (26):

<img file="PL211335B1_D0016.tif" />

wherein R9 is an aliphatic group having about 16-30 carbon atoms,

R10, R11, R12, R13 and R14, the same or different, are selected from hydrogen and alkyl groups having 1-4 carbon atoms, and

X is an anion selected from the group consisting of halides, acetates, phosphates, nitrates and methyl sulfates.

Such: quaternary diammonium salts especially include propano (tallow alkyl) diammonium dichloride;

C) quaternary ammonium salts with at least one ester functional group, of formula (27):

<img file="PL211335B1_D0017.tif" />

wherein

R15 is selected from C1-C4 alkyl and C1-C6 hydroxyalkyl or dihydroxyalkyl groups;

R16 is selected from:

groups

ABOUT

II ^Ri-linear or branched, C1-C22 saturated or unsaturated hydrocarbon groups R20, hydrogen;

R18 is selected from:

Linear or branched, C1-C6 saturated or unsaturated hydrocarbon groups R22, hydrogen;

R17, R19 and R21, same or different, are selected from linear or branched, saturated or unsaturated C7-C21 hydrocarbon groups;

n, pir, same or different are integers 2-6; y is an integer from 1-10; x and z, equal or different, are integers 0-10;

X^- is a simple or complex organic or inorganic anion;

Provided that the sum of x + y + z ranges 1-15, and when x = 0 then R16 is R20, and when z = 0 then R18 is R22.

Especially the ammonium salts of formula 27, in which

R15 is methyl or ethyl; x and y = 1; z = 0 or 1; n, pir are equal to 2; R16 is selected from: group

ABOUT

II

Rljg-C -

- methyl, ethyl or C14-C22 hydrocarbyl groups; a hydrogen atom;

R17, R19 and R21, same or different, are selected from linear or branched, saturated or unsaturated C7-C21 hydrocarbon groups;

R₁₈means a group

ABOUT

II ^R2T^C.~ or a hydrogen atom.

Such compounds are sold, e.g. under the names Dehyquart® by the Cognis company, Stepenquat® by the Stepan company, Noxamium® by the Ceca company and Rewoquat® WE 18 by the Rewo-Witco company.

Preferred quaternary ammonium salts are behenylotrimethylammonium chloride and also stearamidopropyl dimethyl chloride (myristyl acetate) ammonium, sold under the name Ceraphyl® 70 by Van Dyk and Quaternium-27 or Quaternium-83 from Witco.

The anionic surfactants used are preferably sodium (C12-C14) alkyl sulphates, triethanolamine or ammonium, (C12-C14) sodium, triethanolamine or ammonium alkyl ether sulphates, ethoxylated with 2.2 moles of ethylene oxide, sodium cocoyl isethionate and α- (C₁₂-C₁₆) sodium olefin sulfonate and mixtures thereof with:

an amphoteric surfactant such as the amine derivatives known as disodium cocoamphodipropionate or sodium cocoamphopropionate, especially sold by Rhodia Chimie under the trade name Miranol® C2M CONC as an aqueous solution containing 38% active substance or under the trade name Miranol® C32; or

an amphoteric surfactant such as alkylbetaines, especially cocobetaines sold under the name Dehyton® AB 30 in the form of an aqueous solution containing 32% active substance by the company Cognis or (C8-C20) alkylamido (C1-C6) alkylbetaines, especially Tegobetaine® F50, sold by the company Goldschmidt.

The composition according to the invention may also contain at least one additive selected from the group consisting of thickeners, anti-dandruff or anti-seborrhoeic agents, fragrances, pearlescent agents, hydroxy acids, electrolytes, preservatives, silicone or non-silicone sunscreens, vitamins, provitamins such as panthenol, anionic or non-ionic polymers, proteins, protein hydrolysates, 18-methylejicosanic acid, as well as mixtures of these various compounds, and any additive normally used in the field of cosmetics that does not alter the cosmetic properties of the compositions according to the invention.

These additives are present in the composition according to the invention in amounts in the range of 0-20% by weight, based on the total weight of the composition. One skilled in the art can easily determine the exact amount of each additive depending on its nature and function.

The compositions according to the invention can in particular be used for washing or caring for keratin substances such as hair, skin, eyelashes, eyebrows, nails, lips, scalp and especially hair.

The compositions according to the invention are cleansing compositions such as shampoos, shower gels and foaming baths. In this embodiment of the invention, the compositions contain at least one cleansing base, usually an aqueous one.

The surfactant or surfactants forming the cleansing base may be selected either alone or in mixtures from the group of anionic, amphoteric and nonionic surfactants such as those described above.

The quantitative and qualitative composition of the washing base is such that it is sufficient to impart a satisfactory foaming and washing power to the final composition.

PL 211 335 B1

The inventive washing base may constitute 4-50% by weight, preferably 6-35% by weight, even more preferably 8-25% by weight of the total weight of the final composition.

The cosmetic compositions according to the invention are useful for the care of keratinous substances, such as skin or hair, by applying a cosmetic composition as defined above to the keratinous substances, followed by optional rinsing with water.

The use of the compositions according to the invention enables the styling, treatment, care, washing or make-up removal of skin, hair or any other keratin substance.

The compositions of the invention may also be in the form of a shampooed, rinse-off or no-rinse-on composition, a permanent waving, straightening, staining or decolorizing composition, or in the form of a rinse-off composition, to be applied before or after dyeing, decolorizing, perm or for straightening the hair or for application between two permanent waving or straightening steps.

When the composition is in the form of a rinse-off conditioner, it preferably contains a cationic surfactant whose concentration is usually in the range 0.1-10 wt%, preferably 0.5-5 wt% based on the total weight of the composition.

The compositions according to the invention may also take the form of cleansing compositions for the skin, in particular bath or shower solutions or gels or make-up removal products.

The compositions according to the invention may be in the form of aqueous or hydroalcoholic lotions for the care of the skin and / or hair.

The compositions according to the invention may also take the form of a gel, milk, cream, emulsion, thickened lotion or foam, and may be applied to the skin, nails, eyelashes, lips, and in particular to the hair.

The compositions can be packaged in a variety of ways, particularly nebulizers, pump-dispensing bottles, or aerosol containers, so that the composition can be applied as a spray or as a foam. Such forms of packaging are desirable, for example, in order to obtain a hair care spray, varnish or mousse.

Throughout the description and claims, the percentages shown are percentages by weight.

The invention will be illustrated in more detail by the following examples which should not be construed as limiting.

In the examples, SA represents the active ingredient.

Example 1

A shampoo was prepared with the following composition

<td>Composition</td><td>Cord)</td>

<td>Sodium lauryl ether sulfate (70/30 C12 / C14) with 2.2 moles of ethylene oxide, containing 70% SA</td><td> 7</td>

<td>Kokoilobetaine</td><td> 2,5</td>

<td>Ethylene glycol distearate</td><td> 1,5</td>

<td>A polydimethylsiloxane of formula (2) sold by the company Wacker under the name SLM 28020</td><td> 1,5</td>

<td>Polydimethylsiloxane, 60,000 cSt (DC200-60000 cSt from Dow Corning)</td><td> 1</td>

<td>Hydroxyethylcellulose quaternised with 2,3-epoxypropyltrimethylammonium chloride, sold under the name Ucare Polymer JR-400 by Amerchol</td><td> 0,4</td>

<td>An acrylic polymer in the form of an emulsion sold under the name Aqua SF1 by Noveon</td><td> 0,8</td>

<td>Preservatives (supplemental amount)</td><td></td>

<td>PH regulators</td><td>to pH 5.0</td>

<td>Demineralized water (make-up quantity)</td><td> 100</td>

Hair washed with this shampoo has been soft and smooth for a long time.

Identical results are obtained by replacing 1.5 g of polydimethylsiloxane of formula (2) as SA for 1 g of polydimethylsiloxane of formula (1) sold by the company Wacker under the name Belsil ADM 652.

PL 211 335 B1

Example 2

A rinse-off conditioner was prepared with the following composition

<td>Cetyl alcohol</td><td>3.7 g</td>

<td>Myristyl alcohol</td><td>0.4 g</td>

<td>Hydroxyethylcellulose (Natrosol 250 HHR from Aqualon)</td><td>0.25 g</td>

<td>A mixture of myristate / palmitate / myristyl / cetyl / stearyl stearate (Blanc de Baleine Vegetal from Laserson)</td><td>0.8 g</td>

<td>Cetyltrimethylammonium chloride as an aqueous solution containing 25% SA (Dehyquart® A OR from Cognis)</td><td>2.5 g (0.62g SA)</td>

<td>Behenylotrimethylammonium chloride as a water / isopropanol solution containing 80% SA (Genamin KDM-F from Clariant)</td><td>0.6 g (0.48g SA)</td>

<td>A polydimethylsiloxane of formula (2) sold by the company Wacker under the name SLM 28020</td><td>5 g (0.85g SA)</td>

<td>Dipalmitoylethylhydroxyethylmethylammonium methosulfate / cetyl alcohol / stearyl alcohol (70/30 w / w) (Dehyquart® F 30 from Cognis)</td><td>1 g</td>

<td>Citric acid in quantity</td><td>to pH 3.5 + 0.5</td>

<td>Fragrances, preservatives</td><td>Qs</td>

<td>Deionized water (make-up quantity)</td><td>100 g</td>

The hair on which this composition was applied remained soft and smooth for a long time. Example 3

A rinse-off conditioner was prepared with the following composition

<td>Ethyltrimethylammonium methacrylate homopolymer as a cross-linked inverse emulsion (Salcare SC 96 from Ciba)</td><td>0.5 g</td>

<td>Maize starch hydroxypropylphosphate</td><td>3 g</td>

<td>Hydrogenated Castor Oil Ethoxylated (40 EO)</td><td>0.5 g</td>

<td>A polydimethylsiloxane of formula (2) sold by the company Wacker under the name SLM 28020</td><td>2 g</td>

<td>Fragrances</td><td>Qs</td>

<td>Preservatives</td><td>Qs</td>

<td>Demineralized water (make-up quantity)</td><td>100 g</td>

The hair on which this composition was applied remained soft and smooth for a long time. Example 4

A rinse-off conditioner was prepared with the following composition

<td>SMDI / polyethylene glycol polymer with end decyl groups (Aculyn 4 4 from Rohm &amp; Haas)</td><td>1 g</td>

<td>Ethyltrimethylammonium methacrylate homopolymer as a cross-linked inverse emulsion (Salcare SC 96 from Ciba)</td><td>0.2 g</td>

<td>Hydrogenated Castor Oil Ethoxylated (40 EO)</td><td>0.5 g</td>

<td>A polydimethylsiloxane of formula (2) sold by the company Wacker under the name SLM 28020</td><td>2 g</td>

<td>Fragrances</td><td>qs</td>

<td>Preservatives</td><td>qs</td>

<td>Demineralized water (make-up quantity)</td><td>100 g</td>

PL 211 335 B1

The hair on which this composition was applied remained soft and smooth for a long time.

Example 5

A no-rinse spray foam care foam was prepared from 95 g of Example 3 and 5 g of isobutane / propane / butane propellant (56/24/20) under the name Propel 45 from Repsol. The hair to which the foam was applied remained soft and smooth for a long time.