FR3152981A1 - Process for preparing a cosmetic composition comprising a powdery phase and a film-forming polymer solubilized in a volatile solvent; pigment formulation. - Google Patents

Abstract

Process for preparing a cosmetic composition comprising a powder phase and a film-forming polymer solubilized in a volatile solvent; pigment formulation. The present invention relates to a process for preparing a composition, in particular for coating keratin materials, more particularly for making up and/or caring for keratin materials, such as the skin, in particular comprising a physiologically acceptable medium and containing at least: a) a powder phase, and b) at least one volatile solvent, c) at least one film-forming polymer in the state solubilized in said volatile solvent, comprising at least one step of grinding said film-forming polymer in the solid state with at least a portion of the powder phase.

Description

Process for preparing a cosmetic composition comprising a powder phase and a film-forming polymer solubilized in a volatile solvent; pigment formulation.

The present invention aims to propose, for the field of skincare and/or makeup of keratinous materials and in particular of skin, a new process for preparing a composition comprising a powder phase and at least one film-forming polymer solubilized in at least one volatile solvent.

Cosmetic compositions, such as foundations, are commonly used to provide aesthetic color to the skin, but also to enhance uneven skin tone by concealing blemishes and discoloration, reducing the appearance of surface imperfections like pores and wrinkles, and masking blemishes and acne scars. In this regard, coverage, color, and a natural finish are the main properties sought. To achieve this effect, the compositions generally contain a powdered phase comprising particulate colorants and possibly fillers.

For some years now, consumers have been looking for compositions that provide good hold of the skincare and/or makeup effect over time in order to avoid having to reapply the composition too often.

One of the solutions proposed by the state of the art for achieving good adhesion is the use of at least one film-forming polymer. This allows the composition, once applied, to form a more cohesive, adhesive, and tenacious film on the substrate after drying. In this case, the film-forming polymer can be directly dissolved in a volatile solvent under agitation during the manufacturing of the skincare and/or makeup composition. This preparation method has the drawback of requiring a significant amount of time for the complete dissolution of the film-forming polymer. Another solution consists of using the film-forming polymer in a form that has been previously dissolved in a volatile solvent to carry the polymer. This preparation method is more restrictive because it either involves additional preparation time or makes it difficult to find a film-forming polymer in a pre-dissolved form that is suitable for the composition and commercially available from polymer suppliers and manufacturers. In this case, there is also the added constraint of finding a volatile solvent suitable for the composition. This may require ordering and testing different references of film-forming polymers previously solubilized in different solvents depending on the compositions manufactured.

Therefore, there remains a need to find a new process for preparing a skincare and/or makeup composition of keratinous materials comprising a powdered phase and at least one film-forming polymer solubilized in at least one volatile solvent which does not present the disadvantages or constraints mentioned previously.

The applicant was surprised to discover that this objective was achieved with a process for preparing a composition, in particular for coating keratinous materials, more specifically for making up and/or caring for keratinous materials, such as skin, including a physiologically acceptable medium and containing at least:
a) a powdery phase, and
b) at least one volatile solvent,
(c) at least one film-forming polymer in solubilized state in said volatile solvent, comprising at least one step of grinding said film-forming polymer in solid state with at least a portion of the powder phase, including particulate colouring materials present in the composition.

This discovery is the basis of the invention.

The present invention therefore relates to a method for preparing a composition, in particular for coating keratinous materials, more particularly for making up and/or caring for keratinous materials, such as skin, in particular comprising a physiologically acceptable medium and containing at least:
a) a powdery phase, and
b) at least one volatile solvent,
(c) at least one film-forming polymer in solubilized state in said volatile solvent, comprising at least one step of grinding said film-forming polymer in solid state with at least a portion of the powder phase, including particulate colouring materials present in the composition.

Another object of the invention relates to a composition that can be obtained by said preparation process.

According to a particular embodiment, the invention also relates to the process of manufacturing a composition as defined above containing at least one or more particulate coloring material(s), comprising at least the following steps:
a) preparation of a particulate colorant formulation comprising said particulate colorant(s) and at least one film-forming polymer in solid form by grinding said film-forming polymer with part or all of the particulate colorant(s); and
b) mixing of said volatile solvent with the particulate colouring formulation thus obtained.

Another object of the invention also relates to a particulate colour formulation that can be obtained by step a) of the process as defined above.

Another object of the invention also relates to a care and/or makeup composition of keratinous materials comprising at least the particulate coloring formulation as defined above.

The invention also relates to a method of coating keratinous materials, more particularly of caring for and/or making up keratinous materials, such as skin, characterized in that it comprises the application on keratinous materials of a composition as defined above.

Definitions

In the context of the present invention, "keratinous material" means in particular the skin (body, face, eye contour, cheeks, eyelids), lips and/or keratinous fibers such as eyelashes and eyebrows.

By "physiologically acceptable" we mean compatible with the skin, lips and/or keratin fibers such as eyelashes and eyebrows, which has a pleasant color, smell and feel and does not generate unacceptable discomforts (tingling, pulling) likely to deter the consumer from using this composition.

Powdered phase

A composition according to the invention preferably has a powder phase content greater than or equal to 5% by weight, in particular greater than or equal to 10% by weight, and more particularly ranging from 12 to 40% by weight, relative to the total weight of the composition.

The powder phase preferably comprises at least one filler and/or and at least one particulate colouring material.

Charges

By "fillers," we mean colorless or white, solid particles of all shapes, which are insoluble and dispersed throughout the composition. Whether mineral or organic in nature, they contribute to the makeup's softness, matte finish, and uniformity.

The filler or fillers used in the composition of the invention is (are) chosen from mineral fillers, organic fillers and mixtures thereof.

The charge or charges used in the composition of the invention is (are) present in the composition of the invention, preferably, at a content ranging from 0 to 15% by weight, more preferably from 1 to 10% by weight relative to the total weight of the composition.

The filler or fillers used in the composition of the invention is (are) present, preferably, at a content ranging from 0 to 50% by weight, more preferably from 10 to 40% by weight relative to the total weight of the powdered phase.

Among the mineral fillers that can be used in the compositions according to the invention, we can mention talcs, natural micas, synthetic micas such as fluorphlogopite, silica, magnesium and aluminum silicates, kaolin, bentone, calcium carbonate and magnesium hydrogen carbonate, hydroxyapatite, boron nitride, hollow silica microspheres (Silice Beads from Maprecos), silica-based fillers such as Aerosil 200®, Aerosil 300®; Sunsphere H-33®, Sunsphere H-51® marketed by Asahi Glass; Chemicelen® marketed by Asahi Chemical; silica and titanium dioxide composites, such as the TSG® series marketed by Nippon Sheet Glass, perlite powders, and mixtures thereof.

Among the organic fillers that can be used in the compositions according to the invention are polyamide powders (Nylon® Orgasol from Atochem), poly-β-alanine and polyethylene powders, polytetrafluoroethylene powders (Teflon®), lauroyl-lysine, starches such as native corn starches with the INCI name: ZEA MAYS (CORN) STARCH, modified starches such as aluminium starch octenylsuccinate (DRY FLO), metallic soaps derived from carboxylic organic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate, Polypore® L 200 (Chemdal Corporation), silicone resin microbeads (Tospearl® from Toshiba, for example), spherical powders organopolysiloxane elastomer with INCI name: DIMETHICONE/VINYL DIMETHICONE CROSSPOLYMER (DOWSIL TREFIL)
E-506 S SILICONE POWDER®, DOWSIL 9506 POWDER® from DOW CORNING CHEMICAL), polyurethane powders, in particular, cross-linked polyurethane powders comprising a copolymer, said copolymer comprising trimethylol hexyllactone, such as the hexamethylene diisocyanate/trimethylol hexyllactone polymer, marketed under the name PLASTIC POWDER D-400® or PLASTIC POWDER D-800® by TOSHIKI, carnauba microwaxes, such as that marketed under the name MicroCare 350® by MICRO POWDERS, synthetic wax microwaxes, such as that marketed under the name MicroEase 114S® by MICRO POWDERS, microwaxes consisting of a mixture of carnauba wax and polyethylene wax, such as those marketed under the names Micro Care 300® and 310® by MICRO POWDERS, microwaxes made from a mixture of carnauba wax and synthetic wax, such as that marketed under the name Micro Care 325® by MICRO POWDERS, polyethylene microwaxes, such as those marketed under the names Micropoly 200®, 220®, 220L® and 250S® by MICRO POWDERS; fibers of synthetic or natural, mineral or organic origin. They can be short or long, single or arranged, for example braided, hollow or solid. Their shape can be any shape, including circular or polygonal cross-section (square, hexagonal or octagonal) depending on the specific application. In particular, their ends are blunt and/or polished to prevent injury. The fibers have a length ranging from 1 µm to 10 mm, preferably from 0.1 mm to 5 mm and better from 0.3 mm to 3 mm. Their cross-section may be contained within a circle of diameter ranging from 2 nm to 500 µm, preferably from 100 nm to 100 µm and better from 1 µm to 50 µm; and their mixtures.

Particulate coloring matter

The particulate colouring material(s) according to the invention is (are), preferably, chosen from pigments, mother-of-pearl, reflective particles and mixtures thereof.

A composition according to the invention may comprise a content of particulate colouring material(s) preferably ranging from 5 to 90% by weight, and preferably ranging from 10 to 70% by weight relative to the total weight of the composition.

The powdered phase of the composition according to the invention may comprise a content of particulate colouring matter(s) preferably ranging from 5 to 100% by weight, and preferably ranging from 10 to 75% by weight relative to the total weight of the powdered phase.

Pigments

By "pigments," we mean particles of any shape, white or colored, mineral or organic, insoluble in the physiological environment.

Pigments can be white or colored, mineral and/or organic.

Examples of mineral pigments include titanium dioxide, zirconium or cerium oxides, zinc oxides, iron oxides (black, yellow or red), chromium oxides, manganese violet, blue, pink or ultramarine violet, chromium hydrate and ferric blue, bismuth oxychloride, and metallic powders such as aluminum powder and copper powder.

According to a particular embodiment of the invention, the mineral pigment comprises at least one lipophilic or hydrophobic coating.

According to a particular embodiment of the invention, the pigments can be coated according to the invention by at least one compound selected from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; silicone surfactants such as organopolysiloxanes, alkylalkoxysilanes such as triethoxycaprylylsilane; fluorinated surfactants such as perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups; Fluoro-silicone surfactants such as perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialcoxysilanes; and mixtures thereof.

According to a particular method, the pigments can be coated according to the invention with an N-acylated amino acid or one of its salts which may include an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

The amino acid can be, for example, lysine, glutamic acid, or alanine. The salts of these compounds can be aluminum, magnesium, calcium, zirconium, zinc, sodium, or potassium salts. Thus, according to a particularly preferred embodiment, the pigments can be coated with an N-acylated amino acid derivative, which can be, in particular, a glutamic acid derivative and/or one of its salts, and more specifically a stearoyl glutamate, such as aluminum stearoyl glutamate. Examples of pigments treated with aluminum stearoyl glutamate include titanium dioxide pigments and black, red, and yellow iron oxide pigments sold under the trade name NAI® by MIYOSHI KASEI.

According to a particular method, the pigments can be coated according to the invention with isopropyl titanium triisostearate. Examples of pigments treated with isopropyl titanium triisostearate (ITT) include those sold under the trade names BWBO-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BWYO-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate) and BWRO-I2® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by KOBO.

Organic pigments can be chosen from the materials below and their mixtures:
- cochineal carmine
- organic pigments of azo, anthraquinone, indigoid, xanthenic, pyrenic, quinoline, triphenylmethane, and fluorane dyes.

Among the organic pigments, we can notably mention the D&C certified pigments known by the following names: D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6.

The chemical materials corresponding to each of the organic coloring materials mentioned above are listed in the book "International Cosmetic Ingredient Dictionary and Handbook", Edition 1997, pages 371 to 386 and 524 to 528, published by "The Cosmetic, Toiletry, and Fragrance Association".

More specifically, the pigments will be chosen from titanium dioxides, iron oxides (black, yellow or red), and their mixtures; said pigments possibly including at least one lipophilic or hydrophobic coating.

Mother-of-pearl

By "mother-of-pearl," we mean colored particles of any shape, iridescent or not, notably produced by certain mollusks in their shells or synthesized, and which exhibit a color effect through optical interference.

Examples of pearlescent pigments include titanium mica coated with iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, and pearlescent pigments based on bismuth oxychloride. They can also consist of mica particles on the surface of which at least two successive layers of metallic oxides and/or organic colorants are superimposed.

Mother-of-pearl can more specifically possess a yellow, pink, red, bronze, orange, brown, green, blue, purple and/or copper color or reflection.

As an illustration of the mother-of-pearl that can be introduced into the composition, we can mention gold-colored mother-of-pearl, notably marketed by the company ENGELHARD under the name Brillant Gold 212G® (Timica), Gold 222C® (Cloisonne), Sparkle Gold® (Timica), Gold 4504® (Chromalite) and Monarch Gold 233X® (Cloisonne); bronze mother-of-pearl, notably marketed by the company MERCK under the name Bronze Fine® (17384) (Colorona) and Bronze® (17353) (Colorona) and by the company ENGELHARD under the name Super Bronze® (Cloisonne); orange mother-of-pearl, notably marketed by ENGELHARD under the names Orange 363C® (Cloisonne) and Orange MCR 101® (Cosmica) and by MERCK under the names Passion Orange® (Colorona) and Matte Orange® (17449) (Microna); brown mother-of-pearl, notably marketed by ENGELHARD under the names Nu-antique Copper 340XB® (Cloisonne) and Brown CL4509® (Chromalite); copper-tinted mother-of-pearl, notably marketed by ENGELHARD under the name Copper 340A® (Timica); red-tinted mother-of-pearl, notably marketed by MERCK under the name Sienna Fine® (17386) (Colorona); yellow-tinted mother-of-pearl, notably marketed by ENGELHARD under the name Yellow® (4502) (Chromalite); red mother-of-pearl with a gold sheen, notably marketed by the company ENGELHARD under the name Sunstone G012® (Gemtone); pink mother-of-pearl, notably marketed by the company ENGELHARD under the name Tan opale G005® (Gemtone); black mother-of-pearl with a gold sheen, notably marketed by the company ENGELHARD under the name Nu Antique Bronze 240 AB® (Timica); blue mother-of-pearl, notably marketed by the company MERCK under the name Matte Blue® (17433) (Microna); white mother-of-pearl with a silver sheen, notably marketed by the company MERCK under the name Xirona Silver®; and orange-pink-green-gold mother-of-pearl, notably marketed by the company MERCK under the name Indian Summer® (Xirona), and their mixtures.

As another example of nacre, we can also mention particles containing a borosilicate substrate coated with titanium oxide.

Glass substrate particles coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

Finally, as examples of mother-of-pearl, we can also mention polyethylene terephthalate glitter, in particular that marketed by Meadowbrook Inventions under the name Silver 1P 0.004X0.004® (silver glitter).

A composition according to the invention may include a nacre content preferably ranging from 1 to 50% by weight, more preferably ranging from 1 to 30% by weight relative to the total weight of the composition.

Reflective particles

The term "reflective particles" refers to particles whose size, structure (particularly the thickness of their constituent layer(s), physical and chemical composition, and surface condition) allow them to reflect incident light. This reflection can, where applicable, be intense enough to create visible highlights on the surface of the composition or mixture when applied to the makeup base—that is, brighter points that contrast with their surroundings, appearing to shine.

Reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them, and more specifically to optimize this effect in terms of color rendering. They can, in particular, possess a yellow, pink, red, bronze, orange, brown, gold, and/or copper color or reflection.

These particles can have various shapes, including platelet-shaped or globular, particularly spherical.

Reflective particles, regardless of their shape, may or may not have a multilayer structure and, in the case of a multilayer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

When reflective particles do not have a multilayer structure, they can be composed, for example, of metal oxides, including titanium or iron oxides obtained by synthesis.

When reflective particles have a multilayer structure, they may, for example, comprise a natural or synthetic substrate, including a synthetic substrate at least partially coated by at least one layer of a reflective material, such as at least one metal or metallic material. The substrate may be monomaterial, multimaterial, organic, and/or inorganic.

More specifically, it can be chosen from among glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, including aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being exhaustive.

The reflective material may include a layer of metal or a metallic material.

Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

As another example of reflective particles with a mineral substrate coated with a layer of metal, we can also mention particles with a borosilicate substrate coated with silver.

Silver-coated glass substrate particles in the form of wafers are sold under the name MICROGLASS METASHINE REFSX 2025 PS® by TOYAL. Nickel/chromium/molybdenum alloy-coated glass substrate particles are sold under the names CRYSTAL STAR GF 550® and GF 2525® by the same company.

Particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium may also be used, said substrate being coated with at least one layer of at least one metallic oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

An example is the aluminium, bronze or copper powders coated with _SiO2 marketed under the name VISIONAIRE® by the company ECKART.

According to a particular embodiment of the invention, the particulate coloring material(s) is/are chosen from
- titanium dioxides (CI: 77891) such as the commercial product HOMBITAN FF PHARMA® sold by the company VENATOR;
- yellow iron oxides (CI: 77492), red iron oxides (CI: 77491), black iron oxides (CI: 77499), and their mixtures such as the commercial products sold under the name SUNPURO® by the company SUN;
- mother-of-pearl such as, for example, those based on mica covered with titanium dioxide and/or iron oxide, like the product sold under the trade name TIMIRON PEARL SHEEN MP 30® by the company MERCK; those based on mica, barium sulfate and titanium dioxide, like the product sold under the trade name RONAFLAIR LOW LUSTER PIGMENT® by the company MERCK;
- bismuth oxychloride as the product sold under the trade name RONAFLAIR LF 2000® by the company MERCK;
- their mixtures.

More specifically, the particulate colouring material(s) will be chosen from pigments, and more specifically from titanium dioxide, iron oxides (black, yellow or red), and their mixtures; said pigments possibly including at least one lipophilic or hydrophobic coating agent.

Film-forming polymer

The composition of the invention comprises at least one film-forming polymer solubilized in at least one volatile solvent; said composition being obtained by a preparation process comprising at least one step of grinding said film-forming polymer in the solid state with at least a part of the powdered phase, in particular the particulate coloring materials present in the composition.

For the purposes of this invention, "polymer" means a compound consisting of the repetition of one or more motifs (these motifs being derived from compounds called monomers). This motif or these motifs are repeated at least twice and preferably at least three times.

By "film-forming" polymer, we mean a polymer capable of forming, either alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, particularly on keratinous materials, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that said film can be isolated and handled in isolation, for example when said film is made by pouring onto a non-stick surface such as a Teflon or silicone surface.

By "polymer solubilized in at least one volatile solvent", we mean the state of the polymer at room temperature (25°C) and atmospheric pressure (760 mm Hg or 10 ⁵ Pa); the latter being present in the composition of the invention in a fluid form in the solubilized state in at least one volatile solvent, in particular in at least one volatile organic solvent, and more particularly in at least one volatile oil.

By "polymer in solid state" is meant the state of the polymer at room temperature (25°C) and atmospheric pressure (760 mm Hg or 10 ⁵ Pa); it not being present in the composition of the invention in a fluid form in a solubilized state in an organic solvent, in particular a volatile organic solvent.

Preferably, a composition according to the invention comprises from 5% to 60% by weight, more preferably from 10% to 50% by weight, more particularly from 20% to 40% by weight of active film-forming polymer(s) in solubilized form relative to the total weight of the composition.

Film-forming polymers according to the invention are preferably chosen from hydrophobic film-forming polymers.

For the purposes of this invention, the term "hydrophobic film-forming polymer" refers to a film-forming polymer that has no affinity for water and, as such, is not suitable for formulation in its solute state in an aqueous medium. In particular, a hydrophobic polymer is defined as a polymer having a solubility in water at 25 °C of less than 1% by weight.

In particular, the hydrophobic film-forming polymer is a polymer chosen from the group comprising film-forming polymers soluble in an organic solvent medium, especially liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and will form a single homogeneous phase when incorporated into the medium.

According to a particular embodiment of the invention, the hydrophobic film-forming polymer(s) is/are selected from
- a silicone resin;
- a copolymer comprising carboxylate groups and polydimethylsiloxane groups;
- a vinyl polymer comprising at least one carbosiloxane dendrimer-derived motif;
- a sequenced ethylenic copolymer;
- a polysaccharide grafted with organosiloxane groups;
- a polysaccharide ether;
- a norbornene polymer grafted with organosiloxane groups;
- their mixtures.

Silicone resins

More generally, the term "resin" refers to a compound with a three-dimensional structure. "Silicone resins" are also called "silicon resins" or "siloxane resins".

The nomenclature for silicone resins (also called siloxane resins or silicone resins) is known as "MDTQ", the resin being described according to the different siloxane monomeric units it comprises, each of the letters "MDTQ" characterizing a type of unit.

The letter "M" represents the Monofunctional unit with the formula _{R1R2R3SiO1 / 2} , the silicon atom being bonded _to a single oxygen atom in the polymer comprising this unit.

The letter "D" signifies a Difunctional Unit _{R1 R2} SiO2 _/2 in which the silicon atom is bonded to two oxygen atoms.

The letter "T" represents a Trifunctional unit R ₁ Si _3/2 .

Such resins are described for example in "Encyclopedia of Polymer Science and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or even US 5,082,706, US 5,319,040, US 5,302,685 and US 4,935,484.

In the motifs M, D, T defined previously, R, namely R ₁ , R ₂ and R ₃ , represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

Finally, the letter "Q" signifies a Tetrafunctional SiO _4/2 unit in which the silicon atom is bonded to four oxygen atoms which are themselves bonded to the rest of the polymer.

Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the R radical, the length of the polymer chain, the degree of branching and the size of the dangling chains.

Examples of silicone resins that can be used in the compositions according to the invention include silicone resins of type MQ, type T or type MQT.

MQ Resins:

As an example of MQ type silicone resins, we can cite alkylsiloxysilicates of formula [(R ₁ ) ₃ SiO _1/2 ] _x (SiO _4/2 ) _y (MQ units) in which x and y are integers from 50 to 80, and such that the R ₁ group represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

As an example of MQ silicone resins, we will cite those with the INCI name Trimethylsiloxysilicate such as those marketed under the reference SR1000® by the company General Electric and under the reference BELSIL TMS 803® by the company Wacker.

T Resins:

As an example of T-type silicone resins, we can cite polysilsesquioxanes of formula (RSiO _3/2 ) _x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

Preferably, polymethylsilsesquioxane resins can be used in which R represents a methyl group, such as those marketed by the Wacker company under the reference Resin MK® such as Belsil PMS MK®: a polymer comprising repeating _{CH3SiO3 /2} units (T units), which may also include up to 1% by weight of ( _CH3 ) _{2SiO2/ 2} units (D units) and having an average molecular weight of about 10000 g/mol.

MQT Resins:

As examples of resins containing MQT patterns, those cited in US document 5,110,890 are known.

A preferred form of MQT-type resins is MQT-propyl resin (also called MQTPr). Such resins usable in the compositions according to the invention include those described and prepared in application WO 2005/075542.

MQ-T-propyl resin preferably comprises the following units:
(i) (R1 ₃ SiO _1/2 ) _a
(ii) (R2 ₂ SiO _2/2 ) _b
(iii) (R3SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d
with R1, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group,
a, b, c and d being mole fractions,
a being between 0.05 and 0.5,
b being between zero and 0.3,
Since c is greater than zero,
d being between 0.05 and 0.6
a + b + c + d = 1,
provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

Preferably, siloxane resin comprises the following units:
(i) (R1 ₃ SiO _1/2 ) _a
(ii) (R ₃ SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d
with R1 and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, R1 preferably being a methyl group and R3 preferably being a propyl group,
a being between 0.05 and 0.5, preferably between 0.15 and 0.4,
c being greater than zero, preferably between 0.15 and 0.4,
d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or even between 0.2 and 0.55,
a + b + c + d = 1, and a, b, c and d are mole fractions,
provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

The siloxane resins usable according to the invention can be obtained by a process comprising the reaction of
A) an MQ resin comprising at least 80 mole percent of (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d units
R1 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
a and d being greater than zero,
the a/d ratio being between 0.5 and 1.5; and of
B) a propyl T resin comprising at least 80 mole percent of ( _{R3SiO3 /2} ) _c units,
R3 represents an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
Since c is greater than zero,
provided that at least 40% by mole of the R3 groups are propyl groups,
where the mass ratio A/B is between 95:5 and 15:85, preferably the mass ratio A/B is 30:70.

Advantageously, the A/B mass ratio is between 95:5 and 15:85. Preferably, the A/B ratio is less than or equal to 70:30. These preferred ratios have been shown to allow comfortable deposition.

Preferably, the composition according to the invention comprises, as a silicone resin, at least one MQ type resin, more particularly of the Trimethylsiloxysilicate type, such as those marketed under the reference SR1000® by Momentive Performance Materials and under the reference TMS 803® by Wacker.

Copolymers containing carboxylate groups and polydimethylsiloxane groups

For the purposes of this application, "copolymer comprising carboxylate groups and polydimethylsiloxane groups" means a copolymer obtained from (a) one or more carboxylic monomers (acid or ester), and (b) one or more polydimethylsiloxane (PDMS) chains.

In this application, the term “carboxylic monomer” means both carboxylic acid monomers and carboxylic acid ester monomers.

Thus, the monomer (a) can be chosen for example from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, their esters and mixtures of these monomers.

Examples of esters include the following monomers: acrylate, methacrylate, maleate, fumarate, itaconoate and/or crotonoate.

According to a preferred embodiment of the invention, the monomers in the form of esters are more particularly chosen from linear or branched alkyl acrylates and methacrylates, preferably in C1-C24 and better in C1-C22, the alkyl radical being preferably chosen from methyl, ethyl, stearyl, butyl, ethyl-2-hexyl radicals, and mixtures thereof.

Thus, according to a particular embodiment of the invention, the copolymer comprises as carboxylate groups, at least one group selected from acrylic acid, methacrylic acid, methyl, ethyl, stearyl, butyl, ethyl-2-hexyl acrylates or methacrylates, and mixtures thereof.

In this application, "polydimethylsiloxanes" (also called organopolysiloxanes or, in abbreviation, PDMS) means, in accordance with general acceptance, any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of principal motifs in which silicon atoms are linked together by oxygen atoms (siloxane bond ºSi-O-Siº), comprising trimethyl radicals directly linked via a carbon atom to said silicon atoms. The PDMS chains that can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one end of the chain; that is to say, the PDMS may, for example, have a polymerizable radical group on both ends of the chain or have a polymerizable radical group on one end of the chain and a trimethylsilyl terminal group on the other end of the chain. The polymerizable radical group may, in particular, be an acrylic or methacrylic group, especially a _CH₂ =CR₁-COO-R₂ group.
where R1 represents a hydrogen or a methyl group and R2 represents
-CH ₂ -, -(CH ₂ ) _n - with n = 3, 5, 8 or 10, -CH ₂ –CH(CH ₃ )–CH ₂ - , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -,
-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ –.

The copolymers used in the composition of the invention are generally obtained according to the usual methods of polymerization and grafting, for example by radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one or both ends of the chain) and (B) of at least one carboxylic monomer, as described for example in documents US-A-5,061,481 and US-A-5,219,560.

The copolymers obtained generally have a molecular weight ranging from 3000 to 200000, and preferably from 5000 to 100,000.

Examples of copolymers that can be used in the composition of the invention include polydimethylsiloxane grafted acrylic acid and stearyl acrylate copolymers, polydimethylsiloxane grafted stearyl methacrylate copolymers, polydimethylsiloxane grafted acrylic acid and stearyl methacrylate copolymers, and polydimethylsiloxane grafted methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate copolymers.

One example of a copolymer that can be used in the composition of the invention is the copolymer with the INCI name ACRYLATES/ETHYLHEXYL ACRYLATE/DIMETHICONE METHACRYLATE, such as the commercial product
KP-561® sold by SHIN ETSU.

Vinyl polymers grafted with a carbosiloxane dendrimer

The vinyl polymer has a backbone and at least one side chain, which includes a carbosiloxane dendrimer-derived motif exhibiting a carbosiloxane dendrimer structure.

The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure possessing branched groups having high molecular weights, said structure having high regularity in the radial direction from the linkage to the backbone. Such carbosiloxane dendrimer structures are described as a highly branched siloxane-silylalkylene copolymer in Japanese patent application filed with the Kokai Public Examination Office 9-171154.

A vinyl polymer according to the invention may contain motifs derived from carbosiloxane dendrimers which can be represented by the following general formula (I):
[Chem 1]

(I)
in which:
- R ¹ represents an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms;
- ^Xi represents a silylalkyl group which, when i = 1, is represented by formula (II):

Or
[Chem 4]

in which:
^R4 represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and
R ⁵ represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, with methylene and propylene groups being preferred; and
organic groups containing a styryl group with the formula:
[Chem 5]

in which:
R ⁶ represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, the methyl group being preferred;
R ⁷ represents an alkyl group of 1 to 10 carbon atoms;
R ⁸ represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred;
b is an integer from 0 to 4; and
c is either 0 or 1, so if c is 0, -(R8)c- represents a bond.

In one embodiment, ^R1 may represent an aryl group having from 5 to 10 carbon atoms or an alkyl group having from 1 to 10 carbon atoms. The alkyl group may preferably be represented by a methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl, or cyclohexyl group. The aryl group may preferably be represented by a phenyl or naphthyl group. Methyl and phenyl groups are particularly preferred, with the methyl group being preferred above all.

In one embodiment, ^R2 represents an alkylene group having from 2 to 10 carbon atoms, in particular a linear alkylene group, such as an ethylene, propylene, butylene, or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1-methylpentylene, or 1,4-dimethylbutylene group. The ethylene, methylethylene, hexylene, 1-methylpentylene, and 1,4-dimethylbutylene groups are preferred.

According to one embodiment, ^R3 is selected from the methyl, ethyl, propyl, butyl and isopropyl groups.

In formula (II), i indicates the number of generations and thus corresponds to the number of repetitions of the silylalkyl group.

For example, when the number of generations is equal to one, the carbosiloxane dendrimer can be represented by the following general formula:
[Chem 6]

in which Y, ^R1 , ^R2 and ^R3 are as defined above, ^R12 represents a hydrogen atom or is identical to ^R1 ; a1 is identical to ^a1 . Preferably, the total average number of ^OR3 groups in a molecule is in the range of 0 to 7.

When the number of generations is equal to 2, the carbosiloxane dendrimer can be represented by the following general formula:
[Chem 7]

in which Y, ^R1 , ^R2 , ^R3 , and ^R12 are the same as defined above; ^a1 and ^a2 represent the ^a1 of the indicated generation. Preferably, the total average number of ^OR3 groups in a molecule is in the range of 0 to 25.

In the case where the number of generations is equal to 3, the carbosiloxane dendrimer is represented by the following general formula:
[Chem 8]

in which Y, ^R1 , ^R2 , ^R3 , and ^R12 are the same as defined above; ^a1 , ^a2 , and ^a3 represent the ^a1 of the indicated generation. Preferably, the total average number of ^OR3 groups in a molecule is in the range of 0 to 79.

A vinyl polymer having at least one carbosiloxane dendrimer-derived motif possesses a side chain containing a carbosiloxane dendrimer structure, and can be obtained from the polymerization:
(A) from 0 to 99.9 parts by weight of a vinyl monomer; and
(B) of 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing a radically polymerizable organic group, represented by the general formula (I) as defined above.

The vinyl-type monomer that is component (A) in the vinyl polymer having at least one carbosiloxane dendrimer-derived motif is a vinyl-type monomer that contains a radical-polymerizable vinyl group. There are no particular limitations with respect to such a monomer.

The following are examples of this vinyl-like monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower analog alkyl methacrylate; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a higher analog methacrylate; vinyl acetate, vinyl propionate, or a lower analogous fatty acid vinyl ester; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher analogous fatty acid ester; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide, or analogous vinyl-type monomers containing amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or analogous vinyl-type monomers containing hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or analogous vinyl-type monomers containing a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, or an analogous vinyl-type monomer with ether bonds; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or an analogous silicone compound possessing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid; an unsaturated monomer polymerizable with radicals possessing a sulfonic acid group such as a styrene sulfonic acid group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and an ester of methacrylic acid of an alcohol possessing a tertiary amine group such as an ester of methacrylic acid and diethylamine.

Multifunctional vinyl-type monomers can also be used.

The following represent examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris-(2-hydroxyethyl)isocyanurate dimethacrylate, tris-(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups having divinylbenzene groups on both ends, or analogous silicone compounds having unsaturated groups.

A carbosiloxane dendrimer, which is component (B), can be represented by formula (I) as defined above.

The following represent preferred examples of group Y of formula (I): an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group, and a 5-hexenyl group.

A carbosiloxane dendrimer according to the present invention can be represented by the following average structure formulas:

Thus, according to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:

in which:
Y, ^R1 , ^R2 and ^R3 are as defined in formulas (I) and (II) above;
^a1 , ^a2 and ^a3 meet the definition of ^a1 according to formula (II); and
R ¹² is H, an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms.

According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulas:

The vinyl polymer comprising the carbosiloxane dendrimer according to the invention can be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154.

For example, it can be produced by subjecting to a hydrosilylation reaction an organosilicon compound which contains a hydrogen atom bonded to a silicon atom, represented by the following general formula (IV):
[Chem 9]

(IV)
where R ¹ being as defined above in formula (I),
and an organosilicon compound that contains an alkenyl group.

In the formula above, the organosilicon compound can be represented by 3-methacryloxypropyltris-(dimethylsiloxy)silane, 3-acryloxypropyltris-(dimethylsiloxy)silane, and 4-vinylphenyltris-(dimethylsiloxy)silane. The organosilicon compound containing an alkenyl group can be represented by vinyl tris-(trimethylsiloxy)silane, vinyl tris-(dimethylphenylsiloxy)silane, and 5-hexenyltris-(trimethylsiloxy)silane.

The hydrosilylation reaction is carried out in the presence of chloroplatinic acid, a vinylsiloxane and platinum complex, or an analogous transition metal catalyst.

A vinyl polymer having at least one carbosiloxane dendrimer-derived motif can be chosen from polymers such that the motif of a carbosiloxane dendrimer-derived motif is a carbosiloxane dendritic structure represented by the following formula (III):
[Chem 10]

(III)
in which Z is a divalent organic group, "p" is 0 or 1, ^R1 is as defined above in formula (IV) and ^Xi is a silylalkyl group represented by formula (II) as defined above.

In a vinyl polymer having at least one carbosiloxane dendrimer-derived motif, the polymerization ratio between components (A) and (B), in terms of the weight ratio between (A) and (B), is in the range of 0/100 to 99.9/0.1, or even 0.1/99.9 to 99.9/0.1, and preferably in the range of 1/99 to 99/1. A ratio between components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B).

A vinyl polymer having at least one carbosiloxane dendrimer-derived motif can be obtained by copolymerizing components (A) and (B), or by polymerizing component (B) alone.

Polymerization can be radical polymerization or ionic polymerization, however radical polymerization is preferred.

Polymerization can be achieved by causing a reaction between components (A) and (B) in a solution for a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50°C to 150°C.

A suitable solvent for this purpose is hexane, octane, decane, cyclohexane, or a similar aliphatic hydrocarbon; benzene, toluene, xylene, or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, or ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-isobutyl ketone, or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, or similar esters; methanol, ethanol, isopropanol, butanol, or similar alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, or an organosiloxane oligomer analogue.

A radical initiator can be any compound known in the art for classical radical polymerization reactions. Specific examples of such radical initiators are 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), or analogous azobis-like compounds; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, or an analogous organic peroxide. These radical initiators can be used alone or in combination with two or more. Radical initiators can be used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of components (A) and (B). A chain transfer agent may be added. The chain transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane possessing a mercaptopropyl group or an analogous mercapto-type compound; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane, or an analogous halogenated compound.

In the manufacture of vinyl-type polymer, after polymerization, the residual vinyl monomer that has not reacted can be removed under vacuum heating conditions.

To facilitate the preparation of raw materials for cosmetic products, the number-average molecular weight of the vinyl polymer containing a carbosiloxane dendrimer can be chosen from the range of 3,000 to 2,000,000, preferably from 5,000 to 800,000. It can be a liquid, gum, paste, solid, powder, or any other form. Preferred forms are solutions, obtained by diluting a dispersion or powder in solvents.

A suitable vinyl polymer for the invention may also be one of the polymers described in the examples of application EP 0 963 751.

According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer can be obtained from the polymerization:
- from 0 to 99.9 parts by weight of one or more acrylate or methacrylate monomer(s); and
- from 100 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy] carbosiloxane dendrimer
silylpropyl.

Monomers (A1) and (B1) correspond respectively to particular monomers (A) and (B).

According to one embodiment, a vinyl polymer having at least one carbosiloxane dendrimer-derived motif may comprise a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy]silylpropyl carbosiloxane dendrimer-derived motif corresponding to one of the following formulas:

According to a preferred mode, a vinyl polymer having at least one carbosiloxane dendrimer-derived motif used in the invention comprises at least one butyl acrylate monomer.

According to one embodiment, a vinyl polymer may further comprise at least one fluorinated organic group. A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO 03/045337.

Vinyl polymers grafted with at least one carbosiloxane dendrimer-derived motif that may be particularly suitable for the present invention are those with INCI name: ACRYLATES/POLYTRIMETHYLSILOXYMETHACRYLATE and corresponding to the polymer in the solid state of the commercial products DOWSIL FA 4002 ID SILICONE ACRYLATE® and DOWSIL FA 4004 ID SILICONE ACRYLATE® sold by Dow Corning.

Sequenced ethylenic copolymers

According to a preferred embodiment, the sequenced ethylenic copolymer (also called a sequenced ethylenic polymer) according to the invention comprises at least one first sequence having a glass transition temperature (Tg) greater than or equal to 40°C and being derived wholly or partly from one or more first monomers, such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40°C, and at least one second sequence having a glass transition temperature less than or equal to 20°C and being derived wholly or partly from one or more second monomers, such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20°C, said first sequence and said second sequence being linked together by a statistical intermediate segment comprising at least one of said first monomers constituting the first sequence and at least one of said second monomers constituting the second sequence, and said sequenced copolymer having a polydispersity index I greater than 2.

The sequenced polymer used according to the invention thus comprises at least a first sequence and at least a second sequence.

By "at least" a sequence, we mean one or more sequences.

By "sequenced" polymer, we mean a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences.

By "ethylenic" polymer, we mean a polymer obtained by polymerization of monomers comprising an ethylenic unsaturation.

The sequenced ethylenic polymer used according to the invention is prepared exclusively from monofunctional monomers.

This means that the sequenced ethylenic polymer used according to the present invention does not contain multifunctional monomers, which break the linearity of a polymer to obtain a branched or even cross-linked polymer, depending on the proportion of multifunctional monomer. The polymer used according to the invention also does not contain macromonomers (by "macromomomer" is meant a monofunctional monomer having a pendant group of polymeric nature, and preferably having a molecular mass greater than 500 g/mol, or a polymer having a polymerizable (or ethylenic unsaturation) terminal group on one of its ends), which are used in the preparation of a grafted polymer.

It is specified that in what precedes and follows the terms "first" and "second" sequences in no way condition the order of said sequences (or blocks) in the structure of the polymer.

The first and second sequences of the polymer used in the invention can advantageously be incompatible with each other.

By "sequences incompatible with each other", it is understood that the mixture formed by a polymer corresponding to the first sequence and by a polymer corresponding to the second sequence is not miscible in the polymerization solvent, which is the major component by weight of the sequenced polymer, at room temperature (25°C) and atmospheric pressure ( ^10⁵ Pa), for a content of the mixture of said polymers greater than or equal to 5% by weight, relative to the total weight of the mixture of said polymers and said polymerization solvent, it being understood that:
(i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that
ii) each of the polymers corresponding to the first and second sequences has an average molecular mass (by weight or number) equal to that of the sequenced polymer +/- 15%.

In the case of a mixture of polymerization solvents, assuming two or more solvents are present in identical mass proportions, said polymer mixture is immiscible in at least one of them.

Of course, in the case of polymerization carried out in a single solvent, the latter is the major solvent.

The polymer sequenced according to the invention comprises at least a first sequence and at least a second sequence linked together by an intermediate segment comprising at least one monomer constituting the first sequence and at least one monomer constituting the second sequence. The intermediate segment (also called the intermediate sequence) has a glass transition temperature Tg between the glass transition temperatures of the first and second sequences.

The intermediate segment is a sequence comprising at least one monomer constituting the first sequence and at least one monomer constituting the second sequence of the polymer allows to "compatibilize" these sequences.

Advantageously, the intermediate segment comprising at least one monomer constituting the first sequence and at least one monomer constituting the second sequence of the polymer is a statistical polymer.

Preferably, the intermediate sequence is essentially derived from monomers constituting the first and second sequences.

By "essentially", we mean at least 85%, preferably at least 90%, better 95% and even better 100%.

By "ethylenic" polymer, we mean a polymer obtained by polymerization of monomers comprising an ethylenic unsaturation.

Preferably, the polymer according to the invention does not include silicon atoms in its skeleton.

By "skeleton" we mean the main chain of the polymer, as opposed to the dangling side chains.

Preferably, the polymer according to the invention is not water-soluble, that is to say, the polymer is not soluble in water or in a mixture of water and lower linear or branched monoalcohols having 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without modification of pH, at an active matter content of at least 1% by weight, at room temperature (25°C).

Preferably, the polymer according to the invention is not an elastomer.

By "non-elastomeric polymer" we mean a polymer which, when subjected to a stress intended to stretch it (for example, 30% relative to its initial length), does not return to a length substantially identical to its initial length when the stress ceases.

The polydispersity index of the polymer of the invention is greater than 2.

Advantageously, the sequenced polymer used in the compositions according to the invention has a polydispersity index I greater than 2, for example from 2 to 9, preferably greater than or equal to 2.5, for example from 2.5 to 8, and better greater than or equal to 2.8 and in particular, from 2.8 to 6.

The polydispersity index I of the polymer is equal to the ratio of the average mass by weight Mw to the average mass by number Mn.

The average molar masses by weight (Mw) and by number (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

The average mass by weight (Mw) of the polymer according to the invention is preferably less than or equal to 300,000 g/mol, it ranges for example from 35,000 to 200,000 g/mol, and better from 45,000 to 150,000 g/mol.

The number average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70,000 g/mol, it ranges for example from 10,000 to 60,000 g/mol, and better from 12,000 to 50,000 g/mol.

Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example from 2 to 9, preferably greater than or equal to 2.5, for example from 2.5 to 8, and better greater than or equal to 2.8 and in particular, from 2.8 to 6.

First sequence with a Tg greater than or equal to 40°C

The sequence having a Tg greater than or equal to 40°C has, for example, a Tg ranging from 40 to 150°C, preferably greater than or equal to 50°C, ranging for example from 50°C to 120°C, and better greater than or equal to 60°C, ranging for example from 60°C to 120°C.

The glass transition temperatures indicated for the first and second sequences can be theoretical Tgs determined from the theoretical Tgs of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3rd ed, 1989, John Wiley, according to the following relationship, known as Fox's Law:
[Math 2]
1/Tg = Σ (ωi / Tgi),
i being the mass fraction of monomer i in the considered sequence and Tgi being the glass transition temperature of the homopolymer of monomer i.

Unless otherwise stated, the Tg values indicated for the first and second sequences in this application are theoretical Tg values.

The difference between the glass transition temperatures of the first and second sequences is generally greater than 10°C, preferably greater than 20°C, and better than 30°C.

The sequence having a Tg greater than or equal to 40°C can be a homopolymer or a copolymer.

The sequence having a Tg greater than or equal to 40°C may be derived in whole or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40°C. This sequence may also be called a "rigid sequence".

In the case where this sequence is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40°C. This first sequence can be a homopolymer, consisting of a single type of monomer (whose corresponding homopolymer Tg is greater than or equal to 40°C).

If the first sequence is a copolymer, it may be derived entirely or partially from one or more monomers, the nature and concentration of which are chosen so that the Tg of the resulting copolymer is greater than or equal to 40°C. The copolymer may, for example, comprise:
- monomers such that homopolymers prepared from these monomers have Tg values greater than or equal to 40°C, for example a Tg ranging from 40°C to 150°C, preferably greater than or equal to 50°C, for example ranging from 50°C to 120°C
- monomers which are such that the homopolymers prepared from these monomers have Tgs less than 40°C, chosen from monomers having a Tg between 20°C and 40°C and/or monomers having a Tg less than or equal to 20°C, for example a Tg ranging from -100°C to 20°C, preferably less than 15°C, in particular ranging from -80°C to 15°C and better less than 10°C, for example ranging from -50°C to 0°C, as described below.

The first monomers whose homopolymers have a glass transition temperature greater than or equal to 40°C are preferably chosen from the following monomers, also called principal monomers:
- methacrylates with the formula _CH2 =C( _CH3 ) _-COOR1
in which R ₁ represents an unsubstituted alkyl group, linear or branched, containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R ₁ represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl, such as isobornyl methacrylate,
- acrylates with the formula _CH2 =CH- _COOR2
in which R ₂ represents a C4 to C12 cycloalkyl group such as an isobornyl group or a tert-butyl group,
- (meth)acrylamides with the formula:
[Chem 11]

Or
_R7 and _R8, whether identical or different, each represent a hydrogen atom or a linear or branched C1-C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl group; or _R7 represents H and _R8 represents a 1,1-dimethyl-3-oxobutyl group.
R' denotes H or methyl.

Examples of monomers include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide, and their mixtures.

The first sequence is advantageously obtained from at least one acrylate monomer of formula _CH₂ =CH- _COOR₂ and at least one methacrylate monomer of formula _CH₂ =C( _CH₃ ) _-COOR₂, wherein _R₂ represents a C4-C12 cycloalkyl group, preferably a C8-C12 cycloalkyl, such as isobornyl. The monomers and their proportions are preferably chosen such that the glass transition temperature of the first sequence is greater than or equal to 40°C.

According to one implementation method, the first sequence is obtained from:
i) of at least one acrylate monomer of formula _CH2 =CH- _COOR2 in which _R2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl,
ii) and at least one methacrylate monomer of formula _CH2 =C( _CH3 ) _-COOR'2 in which _R'2 represents a C4-C12 cycloalkyl group, preferably a C8-C12 cycloalkyl group, such as isobornyl.

According to one embodiment, the first sequence is obtained from at least one acrylate monomer of formula _CH2 =CH- _COOR2 in which _R2 represents a C8-C12 cycloalkyl group, such as isobornyl, and at least one methacrylate monomer of formula _CH2 =C( _CH3 ) _-COOR'2 in which _R'2 represents a C8-C12 cycloalkyl group, such as isobornyl.

Preferably, _R2 and _R'2 represent an isobornyl group, independently or simultaneously.

Preferably, the sequenced copolymer comprises 50 to 80 wt% of isobornyl methacrylate/acrylate, 10 to 30 wt% of isobutyl acrylate and 2 to 10 wt% of acrylic acid.

The first sequence can be obtained exclusively from said acrylate monomer and said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are preferably in mass propositions between 30:70 and 70:30, preferably between 40:60 and 60:40, especially in the order of 50:50.

The proportion of the first sequence advantageously ranges from 20 to 90% by weight of the polymer, better from 30 to 80% and even better from 60 to 80%.

According to one implementation method, the first sequence is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

Second sequence of glass transition temperature below 20°C.

The second sequence advantageously has a glass transition temperature Tg less than or equal to 20°C, for example a Tg ranging from -100°C to 20°C, preferably less than or equal to 15°C, in particular ranging from -80°C to 15°C and better less than or equal to 10°C, for example ranging from -100°C to 10°C, in particular ranging from -30°C to 10°C.

The second sequence is derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20°C.

This sequence can also be called a "flexible sequence".

The monomer having a Tg less than or equal to 20°C (called the second monomer) is preferably chosen from the following monomers:
- acrylates of formula _CH2 = _CHCOOR3 , with _R3 representing an unsubstituted alkyl group at C1 to C12, linear or branched, with the exception of the tert-butyl group, in which one or more heteroatoms chosen from O, N, S, may be intercalated
- methacrylates of formula CH ₂ =C(CH ₃ )-COOR ₄ , with R ₄ representing an unsubstituted alkyl group at C6 to C12 linear or branched, in which is (are) possibly intercalated one or more heteroatoms chosen from O, N and S;
- vinyl esters of formula R ₅ -CO-O-CH =CH ₂ where R ₅ represents a linear or branched C4 to C12 alkyl group;
- vinyl alcohol ethers and C4 to C12 alcohol ethers,
- C4 to C12 N-alkyl acrylamides, such as N-octylacrylamide,

- and their mixtures.

Preferred monomers with a Tg of less than or equal to 20°C are isobutyl acrylate, ethyl-2-hexyl acrylate, or mixtures thereof in any proportion.

Each of the first and second sequences can contain, in a minority proportion, at least one monomer constituting the other sequence.

Thus the first sequence can contain at least one monomer that constitutes the second sequence and vice versa.

Each of the first and/or second sequences may include, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned previously.

The nature and quantity of this or these additional monomers are chosen so that the sequence in which they are found has the desired glass transition temperature.

This additional monomer is chosen, for example, from:
- monomers with ethylenic unsaturation(s) comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and salts thereof,
- methacrylates of the formula _CH2 =C( _CH3 ) _-COOR6 in which _R6 represents a linear or branched alkyl group, containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents selected from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate,
- methacrylates of formula CH ₂ =C(CH ₃ )-COOR ₉ , R ₉ representing a linear or branched C6 to C12 alkyl group, in which one or more heteroatoms chosen from O, N and S are possibly intercalated, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I, F);
- acrylates of formula _CH2 = _CHCOOR10 , _R10 representing a linear or branched C1-C12 alkyl group substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or _R10 represents a C1-C12-O-POE (polyoxyethylene) alkyl with 5-10 repetition of the oxyethylene motif, for example methoxy-POE, or R8 represents a polyoxyethylenated group comprising 5-10 ethylene oxide motifs.

In particular, the first sequence may include, as an additional monomer:
- (Metha)acrylic acid, preferably acrylic acid,
- tert-butyl acrylate
- methacrylates of formula _CH2 =C( _CH3 ) _-COOR1 in which _R1 represents an unsubstituted alkyl group, linear or branched, containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobuty group,
- (meth)acrylamides with the formula:

Or
_R7 and _R8, whether identical or different, each represent a hydrogen atom or a linear or branched C1-C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl group; or _R7 represents H and _R8 represents a 1,1-dimethyl-3-oxobutyl group.
R' denotes H or methyl.

Examples of (meth)acrylamide monomers include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide and their mixtures.

The additional monomer can represent 0.5 to 30% by weight of the polymer. According to one embodiment, the polymer of the invention does not contain any additional monomer.

Preferably, the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first sequence and isobutyl acrylate and acrylic acid monomers in the second sequence.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportions in the first sequence and isobutyl acrylate and acrylic acid monomers in the second sequence.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportions in the first sequence, and isobutyl acrylate and acrylic acid monomers in the second sequence, the first sequence representing 70% by weight of the polymer.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equal weight proportions in the first sequence, and isobutyl acrylate and acrylic acid monomers in the second sequence. Preferably, the sequence with a Tg value above 40°C represents 70% by weight of the polymer, and the acrylic acid represents 5% by weight of the polymer.

According to one embodiment, the first sequence does not include any additional monomer.

In a preferred embodiment, the second sequence comprises acrylic acid as an additional monomer. In particular, the second sequence is advantageously obtained from an acrylic acid monomer and at least one other monomer having a Tg less than or equal to 20°C.

According to a preferred embodiment, the composition according to the invention comprises at least one copolymer comprising at least one acrylate monomer of formula _CH2 =CH- _COOR2 in which _R2 represents a C8-C12 cycloalkyl group and/or at least one methacrylate monomer of formula _CH2 =C( _CH3 ) _-COOR'2 in which _R'2 represents a C8-C12 cycloalkyl group, at least one second acrylate monomer of formula _CH2 = _CHCOOR3 , in which _R3 represents an unsubstituted C1-C12 alkyl group, linear or branched, except for the tert-butyl group, and at least one acrylic acid monomer.

Preferably, the copolymer used in the compositions according to the invention is obtained from at least one isobornyl methacrylate monomer, at least one isobornyl acrylate monomer, at least one isobutyl acrylate monomer and at least one acrylic acid monomer, in particular is chosen from the polymers with INCI name ACRYLIC ACID/ISOBUTYL ACRYLATE/ISOBORNYL ACRYLATE COPOLYMER in their solid form such as those of the commercial products MEXOMER PAS® and MEXOMER PAZ® manufactured and sold by the company NOVEAL.

Advantageously, the copolymer used in the invention comprises 50 to 80% by weight of methacrylate/isobornyl acrylate mixture, 10 to 30% by weight of isobutyl acrylate and 2 to 10% by weight of acrylic acid.

The sequenced copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and in particular 2 to 15% by weight, for example 3 to 15% by weight, in particular 4 to 15% by weight, or even 4 to 10% by weight of acrylic acid monomers, relative to the total weight of said copolymer.

The constituent monomers of the second sequence and their proportions are chosen such that the glass transition temperature of the second sequence is less than or equal to 20°C.

Intermediate segment

The intermediate segment (also called the intermediate sequence) links the first and second sequences of the polymer used according to the present invention. The intermediate segment results from the polymerization:
i) of the first monomer(s), and possibly of the additional monomer(s), remaining available after their polymerization at a conversion rate of a maximum of 90% to form the first sequence,
ii) and the second monomer(s), and possibly the additional monomer(s), added to the reaction mixture.

The formation of the second sequence is initiated when the first monomers no longer react or are incorporated into the polymer chain either because they are all consumed or because their reactivity no longer allows them to be.

Thus the intermediate segment includes the first available monomers, resulting from a conversion rate of these first monomers less than or equal to 90%, when the second monomer(s) are introduced during polymer synthesis.

The intermediate segment of the sequenced polymer is a statistical polymer (also called a statistical sequence). That is, it comprises a statistical distribution of the first monomer(s) and the second monomer(s), as well as any additional monomer(s) that may be present.

Thus, the intermediate segment is a statistical sequence, as are the first and second sequences if they are not homopolymers (that is, if they are both formed from at least two different monomers).

Copolymer preparation process:

The ethylenic copolymer sequenced according to the invention is prepared by free radical polymerization, according to well-known techniques of this type of polymerization.

Free radical polymerization is carried out in the presence of an initiator whose nature is adapted, in a known manner, according to the desired polymerization temperature and the polymerization solvent. In particular, the initiator can be chosen from among peroxide initiators, redox couples, or other radical polymerization initiators known to those skilled in the art.

In particular, examples of peroxide-functioning initiators include:
a) peroxyesters, such as tert-butyl peroxyacetate, tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate (Akzo Nobel's Trigonox 21S®), 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Akzo Nobel's Trigonox 141®);
b) peroxydicarbonates, such as di-isopropylperoxydicarbonate;
c) peroxyketones, such as methyl ethyl ketone peroxide;
d) hydroperoxides, such as hydrogen peroxide ( _H2O2 ), tert _- butyl hydroperoxide;
e) diacyl peroxides, such as acetyl peroxide, benzoyl peroxide;
f) dialkyl peroxides, such as di-tert-butyl peroxide;
g) inorganic peroxides, such as potassium _{peroxodisulfate} ( _{K2S2O8 )} ;

As an example of an initiator in the form of a redox couple, we can cite the potassium thiosulfate + potassium peroxodisulfate couple.

In a preferred embodiment, the initiator is selected from organic peroxides comprising 8 to 30 carbon atoms. Preferably, the initiator used is 2,5-Bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, marketed under the reference Trigonox® 141 by Akzo Nobel.

The sequenced copolymer used according to the invention is prepared by free radical polymerization and not by controlled or living polymerization. In particular, the polymerization of the sequenced ethylenic copolymer is carried out in the absence of controlling agents, and in particular in the absence of controlling agents conventionally used in living or controlled polymerization processes such as nitroxides, alkoxyamines, dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates, copper-based catalysts, for example.

Sequenced copolymers such as those described above are notably described in patent applications EP-A-1411069 and EP-A-1882709.

The synthetic solvent used for the polymerization of the film-forming copolymer is generally chosen from volatile oils with a flash point below 80°C, such as isododecane for example.

Polysaccharides grafted with organosiloxane groups

Among the polysaccharides grafted with organosiloxane groups, we can mention the polysaccharides obtained by reaction
a) of a polysaccharide with
b) an organopolysiloxane comprising an isocyanate group of the following formula (1):
[Chem 12]

in which ^R1 , ^R2 , ^R3 and ^R4 independently represent a radical chosen from an alkyl group having from 1 to 8 carbon atoms, a fluoroalkyl group having from 1 to 8 carbon atoms and an aryl group having from 6 to 12 carbon atoms; n is an integer from 1 to 10 and a is an integer from 0 to 3; and
(c) an organic compound comprising an isocyanate group of the following formula (2):
[Chem 13]

in which R ⁵ represents an alkyl group having from 3 to 30 carbon atoms, an aryl group having from 6 to 12 carbon atoms or an aralkyl group having from 6 to 30 carbon atoms or a group of the following formula (3):
[Chem 14]

in which R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms; R ⁷ is an alkyl group having 1 to 30 carbon atoms; X denotes a -NHCONH or NHCOO- group.

The polysaccharide is preferably chosen from pullulans, celluloses, chitins, chitosans, starches, mannans, hyaluronic acid, and their forms modified by alkylation, acylation, cationization, or the addition of a polyoxyalkylated chain. More specifically, it is chosen from a pullulan or a cellulose, particularly hydroxypropylcellulose.

The organopolysiloxane comprising an isocyanate group of formula (1) is preferably chosen from the compound of the following formula:
[Chem 15]

The organic compound comprising an isocyanate group of formula (2) is preferably chosen from stearyl isocyanate or a compound of structure

These polysaccharides grafted with organosiloxane groups and their synthesis are described in patents EP2647366B1, KR10-1666267B1 and application WO2023/068123.

Among the polysaccharides grafted with organosiloxane groups, the polymer with INCI name TRIMETHYLSILOXYSILYLCARBAMOYL PULLULANE will be used in solid form such as that in the product sold under the trade name TSPL-30-ID® or the product TSPL-30-D5® by the company Shin Etsu.

Polysaccharide ethers

By "polysaccharide ether" we mean an alkyl polysaccharide whose alkyl group comprises from 1 to 30, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms.

Preferably, the alkyl polysaccharides according to the invention are derivatives of cellulose, pullulan or guar or mixtures thereof.

According to a particular embodiment, the alkyl polysaccharide(s) are chosen from alkylcelluloses whose alkyl group, linear or branched, comprises from 1 to 20 carbon atoms, in particular from 2 to 15 carbon atoms.

Alkylcellulose is an alkyl ether of cellulose comprising a chain made up of β-anhydroglucose units linked together by acetal bonds. Each anhydroglucose unit has three replaceable hydroxyl groups, all or part of which can react according to the following reaction:
Cell-OM + R-Hal Cell-OR + MHal
with Hal representing a halogen such as Cl, M representing a cationic counter ion such as alkali metal Na+ or K+, or alkaline earth metal, preferably an alkali metal such as Na, Cell representing a polysaccharide radical such as cellulose, R representing a linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 2 to 3 carbon atoms such as methyl or ethyl, and MHal the generated salt such as sodium chloride.

[0067] Advantageously, the compound(s) E are chosen from ethylcellulose, propylcellulose and mixtures thereof, preferably ethylcellulose.

The ethylcellulose polymers used in a cosmetic composition according to the invention are preferably polymers having a degree of substitution in ethoxy groups, ranging from 2.5 to 2.6 per anhydroglucose unit, in other words comprising an ethoxy group content ranging from 44% to 50%.

The average molar mass of ethylcellulose is preferably chosen so that the viscosity of a 5 wt% solution in an 80/20 (toluene/ethanol) mixture at 25°C is from 4 to 300 mPa.s, preferably from 5 to 200 mPa.s, for example from 5 to 150 mPa.s. (ASTM D 914 standard).

The ethylcellulose used in the composition according to the invention is more particularly in powder form.

For example, it is marketed under the trade names ETHOCEL Standard® by Dow Chemicals, including ETHOCEL Standard 7 FP Premium® and ETHOCEL Standard 100 FP Premium®. Other commercially available products, such as those marketed by Ashland, Inc., under the names Aqualon Ethylcellulose® type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable for carrying out the invention.

According to another particular embodiment, the polysaccharide ether(s) are selected from alkylguars, i.e., guar gums modified by the substitution of a hydroxyl hydrogen by a linear or branched alkyl group, comprising from 1 to 20 carbon atoms, in particular from 2 to 10 carbon atoms, preferably from 2 to 3 carbon atoms, such as 2 carbon atoms. Advantageously, the alkyl polysaccharide is ethyl guar. Ethyl guar is notably known by the INCI name: C1-5 ALKYL GALACTOMANNAN, as in the commercial products ASI D-5783 MODIFIED POLYSACCHARIDE ETHYL GUAR® and N HANCE AG 200 sold by ASHLAND, and the commercial product LANCO-GEL CP 5® sold by LANGER.

According to another particular embodiment, the polysaccharide ether(s) are chosen from alkylpullulanes such as myristoyl pullulan, such as the commercial product MYRISTOYL PULLULAN® sold by the company KATAKURA CHIKKARIN.

Norbornene polymers grafted with organosiloxane groups

Among the norbornene polymers grafted with organosiloxane groups, we can mention norbornene resins modified by a linear, branched or monocyclic organosiloxane such as described in patent JP4475413B2.

They correspond to the following formula:
[Chem 16]

where ^R1 to ^R16 , identical or different, represent a hydrogen atom, a monovalent hydrocarbon group, substituted or unsubstituted, having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, an organooxycarbonyl group having 2 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cyanose group, an amide group, an imide group or
a (SiR ¹⁹ ) ₃ group where R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an organooxy group having 1 to 10 carbon atoms, an amide group, an imide group or
an O(SiR ²⁰ ₂ O) _p SiR ²⁰ ₃ group where R ²⁰ is a monovalent hydrocarbon group, substituted or unsubstituted, having 1 to 10 carbon atoms, and p is an integer from 0 to 20; the acid anhydride groups may be identical or different from each other, and any two of the groups R ¹ to R ¹⁶ may form an acid anhydride group;
R ¹⁷ is a hydrogen atom or a monovalent hydrocarbon group having from 1 to 10 carbon atoms;
R ¹⁸ is a simple connection;
X is the formula: -(SiR ²¹ ₂ O) _q SiR ²¹ ₃ -Si(OSiR ²² ₃ ) _r R ²⁰ _3-r where R ²⁰ is a monovalent hydrocarbon group, substituted or unsubstituted, having from 1 to 10 carbons, and R ²¹ are monovalent hydrocarbon groups, substituted or unsubstituted, having from 1 to 20 carbons, which may be identical or different from each other, and R ²² is R ²¹ or a group (OSiR ²¹ ₂ ) _s R ²¹ where s is an integer from 0 to 20,
q is an integer from 1 to 100,
r is 2 or 3, and t is an integer from 0 to 10
m is 0.1 or 2;
n is an integer from 10 to 1,000,000.

Among these polymers, we can mention in particular the one with INCI name: NORBORNENE/TRIS(TRIMETHYLSILOXY) SILYLNORBORNENE in solid state such as that in the commercial product NBN-30-ID® sold by SHIN ETSU.

Volatile solvent

The composition of the invention comprises at least one volatile solvent in which said film-forming polymer is solubilized.

For the purposes of this invention, "volatile solvent" means any liquid chemical compound capable of solubilizing the film-forming polymer and capable of evaporating upon contact with the skin in less than one hour at room temperature and atmospheric pressure. The volatile solvent is a volatile cosmetic compound, liquid at room temperature, having, in particular, a non-zero vapor pressure, and, more specifically, a vapor pressure ranging from 2.66 to 40,000 Pa, and more particularly from 2.66 Pa to 13,000 Pa.

The volatile solvent(s) is/are present in the composition of the invention in a total quantity sufficient to solubilize the film-forming polymer(s) present in said composition.

According to a preferred form, the composition of the invention comprises the volatile solvent(s) in a content ranging from 10 to 70% by weight, more preferably ranging from 20 to 50% by weight relative to the total weight of the composition.

Volatile oils

According to a particular embodiment of the invention, the volatile solvent(s) is/are organic, and more particularly is/are chosen from among volatile oils.

Oil is defined as any fatty substance in liquid form at room temperature (20-25 °C) and atmospheric pressure (760 mm Hg).

For the purposes of this invention, "volatile oil" means any oil capable of evaporating upon contact with the skin in less than one hour at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa, and more particularly ranging from 2.66 Pa to 1300 Pa.

The volatile oil or oils can be chosen from hydrocarbon oils, silicone oils, and mixtures thereof.

For the purposes of the present invention, "silicone oil" means an oil formed from a silicon-oxygen chain -Si-O-Si-O-Si-O in which organic groups attach to the silicon atoms.

For the purposes of the present invention, "hydrocarbon oil" means an oil comprising at least carbon atoms and hydrogen atoms and possibly also oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.

a) Volatile hydrocarbon oils

The volatile hydrocarbon oils usable in the compositions (A) according to the invention can be chosen from among the C8-C16 branched alkanes.

Examples include C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopar® or Permetyl®.

C8-C16 branched esters such as isohexyl neopentanoate can also be mentioned. Other volatile hydrocarbon oils, such as petroleum distillates, particularly those sold under the name Shell Solt® by the Shell company, can also be used.

The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the volatile linear alkanes comprising from 6 to 14 carbon atoms.

As an example of linear alkanes suitable for the invention, mention may be made of the alkanes described in Cognis patent applications WO 2007/068371 or WO2008/155059 (mixtures of distinct alkanes differing by at least one carbon atom). These alkanes are obtained from fatty alcohols, themselves obtained from coconut or palm oil.

Examples of linear C6-C14 alkanes suitable for the invention include n-hexane (C6); n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), and mixtures thereof.

Examples include n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references PARAFOL 12 97® and PARAFOL 14 97® respectively, as well as their mixtures.

In another embodiment, a mixture of n-dodecane and n-tetradecane is used. In particular, the dodecane/tetradecane mixture in the weight ratio 85/15, marketed by BIOSYNTHIS under the reference VEGELIGHT 1214®, can be used.

According to yet another embodiment, a mixture of volatile linear alkanes in C9-C12 is used, with the INCI name: C9-12 ALKANE, such as the product marketed by the company BIOSYNTHIS under the reference VEGELIGHT SILK®.

According to yet another embodiment, a mixture of n-undecane (C11) and n-tridecane (C13) is used, such as those obtained in examples 1 and 2 of application WO2008/155059 from Cognis and such as that sold under the trade name CETIOL ULTIMATE® by BASF.

b) Volatile silicone oils

Volatile silicone oils can also be used, such as volatile linear or cyclic silicone oils, particularly those with a viscosity ≤ 5 centistokes (5 ^mm² /s), and having, in particular, 2 to 10 silicon atoms, preferably 2 to 7 silicon atoms. These silicones may optionally contain alkyl or alkoxy groups having 1 to 10 carbon atoms. Examples of volatile silicone oils usable in the invention include octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

According to a particularly preferred embodiment, the volatile solvent is a volatile hydrocarbon oil selected from among the C8-C16 branched alkanes, and more particularly is isododecane.

Pharmaceutical forms

The skincare and/or makeup compositions according to the invention can be chosen from gels, creams, milks, lotions.

The skincare and/or makeup compositions according to the invention may be anhydrous or aqueous formulations. They may be liquid or solid, such as hot-poured products or loose or pressed powders.

The term "anhydrous" means that the composition contains less than 5% by weight of water relative to the total weight of the composition, or even less than 1% by weight, or even free of water, the water not being added during the preparation of the composition, but corresponding to the residual water provided by the ingredients in the form of a mixture.

The skincare and/or makeup compositions according to the invention can be chosen from aqueous dispersions, oily compositions, or multi-phase compositions such as emulsions like oil-in-water emulsions, water-in-oil emulsions, bi- or tri-phase compositions in particular bi-phase gels also called gel/gel such as those described in patents EP2958540B1, EP2958541B1, EP3185958B1.

. Suitable skincare and/or makeup compositions according to the invention may contain one or more compounds that are well known to those skilled in the art and generally present in foundations.

The skincare and/or makeup compositions according to the invention may, in addition to additives commonly used in skincare and/or makeup products, include:
- active ingredients such as moisturizers like hydroxyethylurea, vitamins, for example vitamins A, E, C, B3, adenosine, hyaluronic acid and its salts;
- ceramides;
- UV filters;
- water-soluble dyes, fat-soluble dyes;
- hydrophilic gelling agents;
- lipophilic gelling agents;
- the charges;
- perfumes
- the conservatives
- and their mixtures.

Such compositions are prepared in particular according to the general knowledge of the expert.

According to a particular method, the composition according to the invention is a skin care product, in particular a sun product, a product for oily skin, a product for dry skin, an anti-aging product.

According to a particular mode, the composition according to the invention is a face makeup product such as a foundation; an eye makeup product such as an eyeshadow; a cheek makeup product such as a blush; a lip makeup product such as lipsticks; a product for eyelash or eyebrow makeup such as mascaras, eyeliners.

Obviously, a person skilled in the art will adapt the nature of the compounds in the composition using their general common knowledge to prepare a composition that can be used in the context of the invention.

For high viscosity compositions, such as thick creams, the viscosity, measured at 25°C and under atmospheric pressure, is greater than or equal to 4.5 Pa.s at a shear rate of 200 s ^-1 and less than or equal to 50 Pa.s (using a Brookfield Rheomat RM 180® viscometer equipped with a No. 4 spindle, the measurement being carried out after 10 minutes of spindle rotation in order to stabilize the rotation speed and viscosity).

For more fluid compositions, the viscosity can be less than 4.5 Pa.s, for example between 1 mPa.s (or 1 cps) and 4.5 Pa.s at a rate (tariff) at a shear rate of 200 s ^-1 (using a Brookfield Rheomat RM 180® viscometer equipped with a No. 4 spindle, the measurement being carried out after 10 minutes of spindle rotation in order to stabilize the rotation speed and viscosity).

Manufacturing process

Another object of the invention relates to a method for manufacturing a skincare and/or makeup composition as defined above, comprising at least one step of grinding said film-forming polymer with at least part of the powdered phase, in particular the particulate coloring materials present in the composition.

According to a particular embodiment, the invention also relates to the process of manufacturing a composition as defined above containing at least one or more particulate coloring material(s), comprising at least the following steps:
a) preparation of a particulate colorant formulation comprising said particulate colorant(s) and at least one film-forming polymer in solid form by grinding said film-forming polymer with part or all of the particulate colorant(s); and
b) mixing of said volatile solvent with the particulate colouring formulation thus obtained.

Step b) of mixing can be carried out at room temperature (25°C) and atmospheric pressure with a planetary mixer of the Hauschild Speedmixer® type for a time preferably ranging from 5 to 15 minutes.

Another object of the invention also relates to a particulate colour formulation that can be obtained by step a) of the process as defined above.

Another object of the invention also relates to a care and/or makeup composition of keratinous materials comprising at least the particulate coloring formulation as defined above.

The colouring material(s) may be chosen from those described above, and in particular are chosen from pigments, and more particularly are chosen from titanium dioxides, iron oxides (black, yellow or red), and their mixtures; said pigments possibly comprising at least one lipophilic or hydrophobic coating.

Another object of the invention also relates to a care and/or makeup composition of keratinous materials as defined above comprising at least one particulate coloring formulation as defined above.

The powdered phase, the film-forming polymer, and any additional ingredients are mixed dry, in proportions according to the invention, and then part or all of the powdered phase and the film-forming polymer are subjected to a dry milling step. Among the various dry milling processes, micronizing mills using friction, collision, or a combination thereof for powders can be used, allowing for very fine grinding qualities.
(D50 < 10µm), such as air jet (or inert gas), pin, or knife mills.

The term "mill-micronizer" according to the invention refers to a mill that refines particles to sizes on the order of a few microns, or even on the order of a micron, or even smaller. Commercial examples of mills for dry grinding include the CHRISPRO Jet Mill® air jet mill, manufactured by MICRO-45 MACINAZIONE S.A. (Italy), the HOSOKAWA® pin mill supplied by ALPINE A. G. (Germany), and the IKA® M20 type knife mill, marketed by IKA Werke GmbH & Co. KG (Germany).

In particular, air jet, pin, or knife mills can be used; more preferably, a pin or knife mill will be used, preferably a pin mill.

According to a particular embodiment of the invention, the particulate colour formulation that can be obtained according to this preparation process of the invention has a particle size profile with a D50 ranging from 1 to 15µm, and preferably from 1 to 10 µm.

Particle size analysis of the colour formulation is generally carried out by simple dispersion of said particles in a liquid dispersant and is measured at 25°C for example with a laser particle size analyzer, according to the supplier's recommendations.

Together

In another aspect, the invention also relates to a cosmetic set comprising:
(i) a container delimiting one or more compartments(d), said container being closed by a closing element; and
ii) a makeup and/or skincare composition according to the invention arranged inside said compartment(s).

The container can, for example, be in the form of a pot or a box.

The closure element may be in the form of a lid or a tear-off cap. In particular, this closure element may include a mounted cap that can be moved by translation or pivoting relative to the container holding the makeup and/or skincare composition(s).

It is understood that within the framework of the present invention the weight percentages given for a compound or a family of compounds are always expressed in weight relative to the total weight of the composition.

Throughout the application, the expression "includes a" or "comprises a" should be understood as meaning "containing at least one" or "comprising at least one", unless otherwise specified.

It is understood that the following examples are provided for illustrative purposes only and are in no way limiting the scope of protection conferred by this application.

Examples

Example 1 of a pigment preparation according to the invention

The following composition was prepared according to the following procedure.

Ingredients Example 1 (invention) Pigments
Titanium dioxide coated with aluminum stearoyl glutamate (68.5%)
Yellow iron oxide coated with aluminum stearoyl glutamate (25%)
Red iron oxide coated with aluminum stearoyl glutamate (5%)
Black iron oxide coated with aluminum stearoyl glutamate (1.5%)
70 Resin
solid-state trimethyl siloxysilicate 30 Preparation protocol for example 1 of pigment preparation:

The solid trimethylsiloxysilicate resin and pigments were pre-mixed with a spatula, then 50 grams of the mixture were ground for 15 seconds using an IKA M20® knife mill, marketed by IKA Werke GmbH & Co. KG (Germany). The lid was then opened, and the edges, lid, and grinding chamber were scraped with a brush to check for any clumping (powder stuck to the walls). The mixture was then ground for another 15 seconds.

Example 2 (invention) and example 2a (not part of the invention) of foundation

The following compositions were prepared according to the following operating procedures.

Ingredients Example 2 (invention) Pigment preparation of example 1 comprising 15% by weight of active ingredient Trimethyl Siloxysilicate 50 Isododecane 50

Ingredients Example 2a
(excluding invention) Pigments
Titanium dioxide coated with aluminum stearoyl glutamate (68.5%)
Yellow iron oxide coated with aluminum stearoyl glutamate (25%)
Red iron oxide coated with aluminum stearoyl glutamate (5%)
Black iron oxide coated with aluminum stearoyl glutamate (1.5%)
35 Resin
solid-state trimethyl siloxysilicate 15 Isododecane 50 Protocol for preparing example 2 (invention) and example 2a (non-invention):

The ingredients are placed in a stainless steel bowl and then mixed with a spatula for 10 seconds. The results are shown in the following table:

Assessment Example 2 (invention) Example 2a
(excluding invention) Composition appearance Homogeneous mixture. No aggregate formation. Formation of resin aggregate stuck to the spatula.

It has been observed that example 2 according to the invention using a pigment formulation obtained according to the process according to the invention makes it possible to obtain a homogeneous foundation unlike example 2a outside the invention obtained according to another preparation process.

Claims (26)

A process for preparing a composition, in particular for coating keratinous materials, more particularly for making up and/or caring for keratinous materials, such as skin, in particular comprising a physiologically acceptable medium and containing at least:
a) a powdery phase, and
b) at least one volatile solvent,
(c) at least one film-forming polymer in solubilized state in said volatile solvent, comprising at least one step of grinding said film-forming polymer in solid state with at least a portion of the powder phase of the composition. A process according to claim 1, wherein the composition has a powder phase content greater than or equal to 5% by weight, in particular greater than or equal to 10% by weight, and more particularly ranging from 12 to 40% by weight, relative to the total weight of the composition. A process according to claim 1 or 2, wherein the powdered phase of the composition comprises at least one filler and/or and at least one particulate coloring matter. A method according to claim 3, wherein the filler or fillers is (are) present at a content of 0 to 15% by weight, more preferably 1 to 10% by weight relative to the total weight of the composition. A process according to claim 3 or 4, wherein the filler or fillers is (are) present at a content ranging from 0 to 50% by weight, more preferably from 10 to 40% by weight relative to the total weight of the powdered phase. A process according to claim 3, wherein the content of particulate colouring matter(s) varies from 5 to 90% by weight, and preferably from 10 to 70% by weight relative to the total weight of the composition. A process according to claim 3, wherein the powdered phase comprises a content of particulate colouring material(s) preferably ranging from 5 to 100% by weight, and preferably ranging from 10 to 75% by weight relative to the total weight of the powdered phase. A process according to any one of claims 3, 6 and 7, wherein the particulate colouring material(s) is/are selected from pigments, mother-of-pearl, reflective particles and mixtures thereof, and more particularly selected from titanium dioxide, iron oxides and mixtures thereof; said pigments optionally comprising at least one lipophilic or hydrophobic coating. A process according to any one of the preceding claims, wherein the composition comprises from 5 to 60% by weight, more preferably from 10 to 50% by weight, more particularly from 20 to 40% by weight of film-forming polymer(s) active material in solubilized form relative to the total weight of the composition. A process according to any one of the preceding claims, wherein the film-forming polymer(s) is/are hydrophobic, in particular liposoluble. A method according to any one of the preceding claims, wherein the hydrophobic film-forming polymer(s) is/are selected from
- a silicone resin;
- a copolymer comprising carboxylate groups and polydimethylsiloxane groups;
- a vinyl polymer comprising at least one carbosiloxane dendrimer-derived motif;
- a sequenced ethylenic copolymer;
- a polysaccharide grafted with organosiloxane groups;
- a polysaccharide ether;
- a norbornene polymer grafted with organosiloxane groups;
- their mixtures. A process according to claim 11, wherein the silicone resin is Trimethylsiloxysilicate. A process according to claim 11, wherein the copolymer comprising carboxylate groups and polydimethylsiloxane groups is selected from those with INCI name ACRYLATES/ETHYLHEXYL ACRYLATE/DIMETHICONE METHACRYLATE in the solid state. . Process according to claim 11, wherein the vinyl polymer comprising at least one carbosiloxane dendrimer-derived motif is selected from that of INCI name ACRYLATES/POLYTRIMETHYLSILOXYMETHACRYLATE in the solid state. A process according to claim 11, wherein the sequenced ethylenic copolymer is obtained from at least one isobornyl methacrylate monomer, at least one isobornyl acrylate monomer, at least one isobutyl acrylate monomer and at least one acrylic acid monomer, in particular is selected from the polymers with INCI name ACRYLIC ACID/ISOBUTYL ACRYLATE/ISOBORNYL ACRYLATE COPOLYMER POLYTRIMETHYLSILOXYMETHACRYLATE in the solid state. Process according to claim 11, wherein the polysaccharide grafted with organosiloxane groups is that of INCI name: TRIMETHYLSILOXYSILYLCARBAMOYL PULLULANE in solid state. Composition according to claim 16, wherein the polysaccharide ether is selected from Ethyl Cellulose, Ethyl Guar and Myristoyl Pullulane. The process according to claim 11, wherein the norbornene polymer grafted with organosiloxane groups is that of INCI name: NORBORNENE/TRIS(TRIMETHYLSILOXY) SILYLNORBORNENE in the solid state. A process according to any one of the preceding claims, wherein the volatile solvent(s) is/are organic, in particular selected from volatile oils, and more particularly selected from volatile hydrocarbon oils, volatile silicone oils and mixtures thereof. A method according to any one of the preceding claims, wherein the composition of the invention comprises the volatile solvent(s) in a content ranging from 10 to 70% by weight, more preferably ranging from 20 to 50% by weight relative to the total weight of the composition. A method for manufacturing a composition according to any one of claims 3, 6 to 20, wherein the powdered phase contains at least one or more particulate colorant(s), comprising at least the following steps:
a) preparation of a particulate colorant formulation comprising said particulate colorant(s) and at least one film-forming polymer in solid form by grinding said film-forming polymer with part or all of the particulate colorant(s); and
b) mixing of said volatile solvent with the particulate colouring formulation thus obtained. Composition that can be obtained by the process according to any one of claims 1 to 21. Particulate colour formulation that can be obtained according to step a) of the process according to claim 21. Skincare and/or makeup composition, comprising at least one particulate colouring formulation according to claim 23. Cosmetic set including:
(i) a container delimiting one or more compartments(d), said container being closed by a closing element; and
ii) a composition as defined in any one of claims 1 to 22 and 24 arranged inside said compartment(s). A method for coating keratinous materials, more particularly for makeup and/or care of keratinous materials, such as skin, characterized in that it comprises the application to keratinous materials of a composition according to any one of claims 1 to 24.