JP4907989B2 - Care and / or makeup cosmetic composition structured with silicone polymer - Google Patents

Description

  The present invention contains a liquid fatty phase comprising at least one oil structured with a specific polymer, is easy to apply, is sufficient, is particularly colored, glossy and does not bleed Care and / or makeup cosmetic composition for skin, including human hair and / or lips, provided in particular in the form of a molded makeup product, especially as a makeup stick or dome, such as a lipstick that provides adhesion About.

  Cosmetic cosmetic compositions are for example for the treatment of wrinkles, for moisturizing the skin and lips, for the protection of skin, lips and body surface growth parts from UV rays, for the treatment of acne and / or self-tanning agents A composition comprising at least one active compound to act as.

  The present invention more particularly relates to cosmetic and dermatological compositions such as makeup products that are easy to apply, provide abundant adhesion and exhibit not only retention but also properties such as color transfer and stability. About.

  In cosmetic products it is common to find a structured, gelled and / or hardened liquid fatty phase. The composition cures particularly in the case of molded solid compositions such as perfume and lipsticks, eye shadows, concealer products and foundations. This structuring is achieved using waxes or fillers. Unfortunately, this wax and filler tends to matte the composition, which is not always desirable, especially for lipsticks or eye shadows.

  The term liquid fatty phase, also called oil, is a coating that is liquid at room temperature (25 ° C) and atmospheric pressure (760mmHg) composed of one or more fatty substances that are compatible with each other at room temperature. It should be understood as meaning the fat phase to do.

  The expression structured liquid phase is to be understood as meaning a hardened or gelled liquid fatty phase.

  The expression cured liquid fatty phase is to be understood as meaning that for application, this cured phase does not flow under its own weight when the silicone polyamide is added thereto.

  The expression gelled liquid phase for application should be understood to mean that the addition of silicone polyamide to this fatty phase increases the viscosity of this phase.

  The structuring of the liquid fatty phase suppresses the exudation from its solid composition and, moreover, adheres to the skin or lips and then bleeds this phase into the wrinkles and fine lines required especially in lipsticks or eye shadows Can be suppressed. The expression blur is understood to mean that the composition attached to the skin or lips protrudes from its initial contour.

  Gloss is primarily related to the nature of the liquid fatty phase. Thus, to increase the gloss of the lipstick, it is possible to reduce the amount of wax and filler in the composition, but in that case the bleed of the liquid fatty phase is increased. In other words, the amount of wax and filler required to produce a suitably hard stick is an obstacle to adhesion gloss.

  The document EP-A-1068856 [1] describes a solid cosmetic composition free of waxes containing a polymer-structured liquid fatty phase, wherein the fatty phase is mainly non-silicone oil.

  The document WO-A-01 / 97758 [2] describes a polyamide resin-based cosmetic composition comprising a structurant selected from esters and amides of N-acylamino acids and mixtures thereof. The composition also comprises unsaturated and saturated fatty alcohols, fatty and / or aromatic carboxylic esters, ethoxylated and / or propoxylated alcohols and acids, silicones, mineral oils and branched hydrocarbons; preferably fatty acid esters, Including a solvent for the polyamide resin, which may be selected from fatty alcohols, mineral oils, branched hydrocarbons and mixtures thereof.

  By using a silicone oil-based fatty phase, if the oil is slightly volatile or non-volatile, long-term retention, i.e., good color retention over time (no change, no color loss) And, if the silicone oil is volatile, a non-transferable composition that does not form a deposit on a support such as glass, cup, fiber or tobacco, placed in contact with the makeup coating It is now possible to get

  At present, the use of silicone oils in cosmetics gels these media and is accompanied by a small number of molecules that can result in a composition that exists in a solid form, for example, lipstick or molded foundation. Limited by. The use of cosmetic compositions in which the fatty phase is mostly siliconized causes problems in most cases with compatibility with materials normally used in cosmetics.

  Literature US-A-5874 069 [3], US-A-5919441 [4], US-A-6051216 [5], WO-A-02 / 17870 [6], and WO-A-02 / 17871 [7] ], WO-A-99 / 06473 [12], US-A-6353076 [13] by polysiloxane-based and polyamide-based wax or by a polymer containing a siloxane group and a group capable of hydrogen interaction Cosmetic compositions such as deodorant sticks or gels containing a gelled silicone oil phase have been prepared.

  In WO-A-02 / 17870 [6], it is considered to add another structuring agent to the composition, but the amount added does not lose the transparency of the product in the case of hydroxystearic acid. In order to do so, it must be in a small amount, for example less than 0.5%.

  WO-A-02 / 17871 [7] includes a second structurant with a silicone polymer in an amount corresponding to 0.5 to 2% by weight of the composition, a non-silicone organic compound, a volatile silicone and optionally another It is similarly contemplated to use a solvent system containing silicone.

  The document EP-A-1177784 [8] is structured, for example, with an organic compound having an amide group and optionally with a small proportion of one or more polymeric or non-polymeric second structuring agents. Deodorant compositions comprising a liquid phase containing a volatile silicone and optionally a non-volatile silicone and / or a non-silicone hydrophobic organic liquid are described by way of example. This document lists, among the second structuring agents, polymers having groups that exhibit siloxane groups and hydrogen interactions without giving examples or results for compositions using these polymers.

  Sticks obtained by simply structuring the liquid fatty phase with just one or more gelled silicone polymers do not exhibit sufficient mechanical resistance to shear, especially during application of the stick to the lips and / or skin. Cause the destruction of the stick.

  By incorporating a polymer such as silicone polyamide (PASi) in a compatible fatty medium, it is common to obtain a solid makeup system that does not require the use of a wax, especially a conventional structuring agent of the wax type. It is clear from the above that it is possible to obtain highly or even fully siliconized systems that are difficult.

  However, application of the formulation thus obtained could prove difficult and it was not possible to obtain a sufficient amount of adhesion to allow makeup.

Application and adhesion are even less satisfactory due to the high degree of condensation required to obtain a solid system of sufficient hardness.
EP-A-1068856 WO-A-01 / 97758 US-A-5874 069 US-A-5919441 US-A-6051216 WO-A-02 / 17870 WO-A-02 / 17871 WO-A-99 / 06473 US-A-6353076 EP-A-1177784 US-A-5981680 US-A-5969172

  The object of the present invention is just to provide a care or makeup composition for the skin and / or lips which makes it possible to overcome the disadvantages and solve the problems mentioned above. In particular, it is an object of the present invention to provide a composition that is easy to apply and in any event results in a greater abundant adhesion, ie abundant mass, than with prior art compositions. A richer attachment of the material gives a more “make-up effect”, particularly in the case of pigmented colored compositions, the attachment with a darker color allows for the makeup of the lips, for example.

  Surprisingly, the Applicant has determined that by using certain polymers in combination with one or more compositions capable of lowering the enthalpy and optionally melting temperature of these polymers. In the absence or small amount of water, it is possible to structure a liquid fatty phase, for example in the form of a makeup or care product, which is easy to apply due to the excellent slipperiness of the silicone oil system, in particular during its application And this use has been found to result in greater abundant adhesion, ie, abundant mass, than with prior art compositions anyway. More abundant adhesion of the composition gives more “make-up effect”, especially in the case of pigmented colored compositions, due to the adherence having a darker color, for example lip makeup, in prior art compositions Makeup is possible that was not satisfactorily possible or even impossible at all.

  Equally surprisingly, it has further been found that the compositions of the present invention comprising the combinations referred to above exhibit this property, which is improved both for the product before application and for adhesion when gloss is desired. In addition, the compositions of the present invention comprising the combinations mentioned above provide a non-smearing coating or adhesion, which has properties of enhanced retention and possibly non-color transfer, Not sticky.

  The combination of these specific compounds with one or more compounds capable of lowering their melting enthalpy ΔH and optionally their melting temperature mp is sufficient and further improved to enable makeup It is possible to obtain gels, in particular solid gels, with excellent mechanical strength and acceptable rheology to enable the deposition of rich masses with gloss.

  A cosmetic composition for makeup or care comprising a combination of a specific polymer according to the present invention and a specific compound that is a compound capable of lowering or decreasing the enthalpy ΔH and optionally the melting temperature mp of the polymer, It is not described in the technology.

  The effects obtained thanks to this combination of a specific polymer and a specific compound which can lower the melting enthalpy of the polymer and possibly reduce the melting point, in particular the ease of application, the mass attached, As well as surprising improvements in adhesion and product gloss do not appear in the prior art literature.

  The present invention avoids sunshine in the form of sticks for the skin, face or lips, not only for lip makeup products such as lipsticks, lip pencils and lip glosses, but also for scalp and skin care products including lips. Cleansing products, especially in the form of sticks, such as products, or lip balms, makeup products for both facial and body skin, foundation moldings as sticks or in dishes, concealer products and temporary tattoo products And also for makeup products for eyes, especially pencil-shaped eyeliners, and cakes for mascara, especially keratin fibers (eyelashes, eyebrows, hair).

More precisely, the subject of the present invention is
A makeup cosmetic composition comprising a liquid continuous fatty phase structured by at least one structured polymer having a weight average molecular weight in the range of 500 to 500,000,
The polymer comprises at least one portion, the portion comprising:
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least two groups capable of establishing hydrogen interactions selected from: urea groups, urethane groups, thiourea groups, oxamide groups, guanidino groups and biguanidino groups, and combinations thereof;
Including
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C., the liquid fatty phase being capable of reducing the enthalpy of melting of the structured polymer Containing two compounds
The composition comprises at least one pigment; and
The composition wherein the liquid fatty phase, the structured polymer and the compound capable of reducing the enthalpy of melting of the structured polymer form a physiologically acceptable medium.

  According to the present invention, the expression “structured polymer” is generally understood to mean a polymer that allows the composition to be hardened or gelled by forming hydrogen bonds.

  The composition of the invention can be provided in the form of a paste, a solid or a more or less viscous cream. It can be a simple or multiple, especially oil-in-water or water-in-oil, water-in-oil-in-water or oil-in-water-in-oil emulsion, or a hard or soft gel with an oily continuous phase. Simple or multiple emulsions can include an aqueous or oily continuous phase optionally containing dispersed lipid vesicles. In particular, it is provided as a stick or in the form of a molded article in a dish, more particularly an oily, in particular anhydrous hard gel, in particular in the form of an anhydrous stick. More particularly, it is provided in the form of a translucent or opaque hard gel (depending on whether it contains pigments) and the liquid fatty phase forms a continuous phase. The water contained in the anhydrous composition is less than 10% water, for example less than 5% by weight, preferably less than 2% by weight.

  The structuring of the liquid lipid phase can be adjusted depending on the structured polymer used and the enthalpy and optionally the nature of the compound capable of lowering the melting temperature, the stiff structure having excellent mechanical strength. It can be obtained in the form of a baton, stick or dome that already has a glossy appearance. These batons are particularly colored with abundant mass after easy application, especially when they are colored, and do not bleed, especially with glossy adhesion with excellent color retention over time. Make it possible to get. The composition can include one or more structured polymers and one or more compounds that reduce the melting enthalpy and optionally the melting temperature of those polymers.

  Advantageously, the composition according to the invention is a composition for the lips, more preferably a lipstick composition, especially in the form of a stick.

Liquid fatty phase The liquid fatty phase according to the invention generally comprises at least one oil selected from hydrocarbons, silicones and fluorinated oils.

  Oil is a non-aqueous compound that is immiscible with water.

  The liquid fatty phase can comprise at least one volatile oil.

  For the purposes of the present invention, volatile oils advantageously have a flash point (measured by the method) of preferably 35 to 135 ° C. or no flash point. The flash point is the temperature at which the vapor generated by the fuel ignites upon contact with a flame, spark or heat source.

  Volatile oils are advantageously in the range of 0.01 mm to 300 mmHg (1.33 Pa to 40,000 Pa), better in the range of 0.05 to 190 mmHg (6.65 Pa to 25330 Pa) at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). Having a vapor pressure of

  According to the present invention, the volatile oil is linear, branched or having a flash point above 40 ° C., preferably above the softening point of the gelling system, and / or a viscosity below 8 cSt. It can be selected from cyclic silicone oils, for example linear, branched or cyclic polydimethylsiloxane (PDMS) having 3 to 7 silicon atoms.

  Examples of volatile oils include the compounds shown in Table 1 below.

  The composition can contain a non-volatile silicone oil.

  The silicone oils of the present invention advantageously have a viscosity selected from a range ranging from 5 to 800,000 cSt, preferably from 10 to 500,000 cSt and better still from 10 to 5000 cSt at 25 ° C.

  Nonvolatile silicone oils include polydimethylsiloxane, polyalkylmethylsiloxane, dimethicone copolyol, alkylmethicone copolyol, cetyl dimethicone, silicone with alkyl glyceryl ether groups, silicone with side chain amine groups, and dilauroyltrimethylolpropane siloxy. It can be silicate. The alkyl groups of these oils have in particular 2 to 24 carbon atoms.

  Nonvolatile silicone oils that can be used in the present invention are in particular non-volatile polydimethylsiloxanes (PDMS) that are liquid at room temperature; pendant and / or silicone chains each having 2 to 24 carbon atoms. Polydimethylsiloxane containing a terminal group, alkyl group, alkoxy group or phenyl group; phenyl-trimethylone, phenyldimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenyldimethicone, diphenylmethyldiphenyltrisiloxane, 2-phenylated silicone Phenylethyltrimethylsiloxysilicate; one or more pendant or having 1 to 12 carbon atoms at the end of the chain, wherein all or some of the hydrogen atoms are replaced by fluorine atoms Fluorinated series having It can be ricone, dimethiconol and mixtures thereof.

  That is, the volatile silicone oil can be selected, for example, from the group consisting of the compounds shown in Table 1, heptamethyloctyltrisiloxane, dodecamethylpentasiloxane, and mixtures thereof.

  Volatile silicone oils are also fluorinated silicone oils such as silicones with alkyl and perfluoroalkyl groups, silicones with oxyethylenated / oxypropylenated (EO / PP) side groups and perfluorinated groups, perfluorinated. Selected from the group comprising: silicones having open side groups and glycerolated side groups, perfluoroalkylmethylphenyl silicones, and these oils have a vapor pressure of 0.02 mmHg or more.

Volatile non-silicone oils may be selected from the group comprising hydrocarbons, such as hydrocarbon oils and isododecane and isohexadecane, C ₈ -C ₁₆ isoparaffins, volatile esters and ethers such as isohexyl or isodecyl neopentanoate.

  Volatile oils are also selected from perfluoroalkanes such as perfluoropolyethers, perfluorodecalin, perfluorodamantane, esters (monoesters, diesters and triesters) of perfluoroalkyl phosphates and fluorinated oils such as fluorinated ester oils. be able to.

  Examples of volatile non-silicone oils that can be used in the present invention include the compounds in Table 2 below.

  The liquid fatty phase is advantageously less than 1000 cSt, better still at least 30% by weight with a viscosity less than 100 cSt, even better because the silicone polymer used in the present invention is soluble in low viscosity silicone oils. Advantageously, it contains at least 40% by weight of silicone oil. It can also contain other non-silicone oils or mixtures of non-silicone oils.

  If the fatty phase comprises a volatile oil, it advantageously represents 3 to 89.4%, better 5 to 60%, for example 5 to 10% of the total weight of the composition.

The liquid fatty phase can also contain other non-silicone oils such as:
Fatty acids may have various chain lengths, the latter being linear or branched, saturated or unsaturated hydrocarbons consisting of esters of fatty acids and glycerol Vegetable oils of triglycerides content; these oils are especially wheat germ, corn, sunflower, karate, castor, sweet almond, macadamia, apricot, soy, rapeseed, cottonseed, lucerne, poppy seed, pumpkin seed , Sesame, cucumber, avocado, hazelnut, grape seed or blackcurrant seed, oat evening primrose, millet, barley, quinoa, olive, rye, safflower, cinnamon, passionflower and muskrose oil; or sold by Stealrineries Dubois Or Miglyol 810, 812 by Dynamite Nobel And caprylic / capric triglycerides such as those sold under the name 818;
Formula R _a COOR _b (wherein R _a + R _b is ≧ 10, R _a is 1 to 40, better still a linear or branched chain containing 7 to 19 carbon atoms. A synthetic oil or ester of a branched higher fatty acid, wherein R _b represents a branched hydrocarbon chain containing 1 to 40, better 7 to 19 carbon atoms), for example purcellin (purcellin) oil (Ketosuteariru octanoate), isononyl isononanoate, benzoate C ₁₂ -C ₁₅ alcohol, isopropyl myristate, 2-ethylhexyl palmitate, octanoic acid esters of alcohols or polyalcohols, decanoic acid ester or ricinoleic acid Esters, hydroxylated esters such as isostearyl lactate or diisostearyl malate and esters of pentaerythritol;
Synthetic ethers having 10 to 40 carbon atoms;
-Fatty acids such as linoleic acid or linolenic acid; and-Polar oils such as mixtures thereof.

  The liquid fatty phase also contains paraffin volatile oils (isoparaffin, isododecane, etc.) or paraffin non-volatile oils and their derivatives, hydrogenated polyisobutenes such as petrolatum, polydecene, parleam, squalane and their Non-polar oils such as linear or branched hydrocarbons or fluorocarbons originating from synthetic or minerals that are volatile or non-volatile, such as mixtures, can be included.

Thus, the present invention can be practiced with various fatty phases, for example:
1) a fatty phase consisting of a mixture of oils comprising at least one non-volatile silicone oil and at least one volatile silicone oil;
2) a fatty phase consisting of a mixture of oils comprising at least one non-volatile silicone oil and at least one non-silicone volatile oil;
3) a fatty phase consisting of an oil mixture comprising at least one non-volatile silicone oil, at least one volatile silicone oil and at least one volatile non-silicone oil;
4) a fatty phase consisting of a mixture of oils comprising at least one volatile silicone oil, one non-volatile non-silicone oil and optionally at least one volatile non-silicone oil; and
5) Fat phase consisting exclusively of volatile silicone oil.

  In the case of 1), 2) and 3), the mixture can also contain non-volatile non-silicone oils. Of course, it should be understood that, in all cases, according to the present invention, the fatty phase contains compounds capable of reducing the enthalpy of melting of the structured polymer.

  In general, the liquid fatty phase represents 5 to 99% of the total weight of the composition, and even better 20 to 75%.

Structured Silicone Polymer The structured polymer of the composition is solid at room temperature (25 ° C.) and atmospheric pressure (760 mmHg) and is soluble in the liquid fatty phase at temperatures from 25 to 250 ° C.

  The expression polymer is to be understood as meaning, for the purposes of the present invention, a compound having at least 2 repeating parts, preferably at least 3 repeating parts, and better still 10 repeating parts.

  In the compositions according to the invention, the structured silicone polymer generally represents 0.5 to 80%, preferably 2 to 60%, better 5 to 40% of the total weight of the composition.

  Moreover, the proportion of the mass of the polymer of structured polymer / oil, for example silicone oil and other oils, is preferably 0.1 to 50%.

  Polymers used as structuring agents in the compositions of the present invention are described in documents US-A-5874069 [3], US-A-5919441 [4], US-A-6051216 [5] and US-A-5981680. Polyorganosiloxane type polymers such as those described in [11].

According to the invention, the polymers used as structuring agents can belong to the following two groups:
1) at least two groups capable of establishing hydrogen interactions (these two groups occupy space in the polymer chain); and / or
2) A polyorganosiloxane containing at least two groups capable of establishing hydrogen interactions (these two groups occupy space in a grafted or branched state).

  A polymer containing two groups capable of establishing hydrogen interactions in the polymer chain has the formula:

Including at least one part corresponding to
In the above formula,
1) R ¹ , R ² , R ³ and R ⁴ can be the same or different;
Linear, branched or cyclic, saturated or unsaturated C ₁ to C ₄₀ hydrocarbon-based groups, with one or more oxygen, sulfur and / or nitrogen atoms in their chain A group which may contain and may be partially or wholly substituted by fluorine atoms,
A C ₆ to C ₁₀ aryl group optionally substituted by one or more C ₁ to C ₄ alkyl groups,
A polyorganosiloxane chain which may contain one or more oxygen, sulfur and / or nitrogen atoms,
Represents a group selected from;
2) The radicals X can be the same or different and can contain one or more oxygen and / or nitrogen atoms in the chain, linear or branched C ₁ to C ₃₀ Represents an alkylenediyl group;
3) Y is a saturated or unsaturated C ₁ to C ₅₀ linear or branched divalent alkylene group, arylene group, cycloalkylene group, alkylarylene group or arylalkylene group, Or containing multiple oxygen, sulfur and / or nitrogen atoms and / or the following atoms or groups of atoms as substituents (fluorine, hydroxyl, C ₃ to C ₈ cycloalkyl, C ₁ to C ₄₀ Alkyl, C ₅ to C ₁₀ aryl, phenyl optionally substituted by 1 to 3 C ₁ to C ₃ alkyl groups, C ₁ to C ₃ hydroxyalkyl and C ₁ to C ₆ aminoalkyl) Or a group that may have one of
4) Y is the formula:

Represents a group corresponding to
In the above formula,
T is linear or branched, saturated or unsaturated, optionally substituted by a polyorganosiloxane chain and optionally containing one or more atoms selected from O, N and S Represents a C ₃ to C ₂₄ trivalent or tetravalent hydrocarbon-based group, or T represents a trivalent atom selected from N, P and Al;
R ⁵ represents one or more ester groups, amide groups, urethane groups, thiocarbamate groups, urea groups, thiourea groups and / or sulfonamido groups that may be bonded to other chains of the polymer. Represents a linear or branched C ₁ to C ₅₀ alkyl group or polyorganosiloxane chain which may contain,
5) The radicals G can be the same or different,

A divalent group selected from (R ⁶ represents at least 50% of the polymer radical R ⁶ represents a hydrogen atom and at least two of the polymer radicals G:

Represents a hydrogen atom or a linear or branched C ₁ to C ₂₀ alkyl group under the condition that it is a group other than
6) n is an integer in the range of 2 to 500, preferably 2 to 200, m is an integer in the range of 1 to 1000, preferably 1 to 700, better still 6 to 200 It is.

According to the present invention, 80% of the polymer groups R ¹ , R ² , R ³ and R ⁴ are preferably selected from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups.

According to the present invention, Y can represent a variety of divalent groups, and optionally includes one or two free valences that establish bonds with other portions of the polymer or copolymer.
Preferably Y is
a) a linear C ₁ to C ₂₀ and preferably a C ₁ to C ₁₀ alkylene group,
b) a C ₃₀ to C ₅₆ branched alkylene group which may contain ring and unconjugated unsaturation,
c) C ₅ ~C ₆ cycloalkylene group,
d) a phenylene group optionally substituted by one or more C ₁ to C ₄₀ alkylene groups,
e) a C ₁ to C ₂₀ alkylene group containing 1 to 5 amide groups,
f) from C ₁ containing one or more substituents selected from a hydroxyl group, a C ₃ to C ₈ cycloalkane group, a C ₁ to C ₃ hydroxyalkyl group and a C ₁ to C ₆ alkylamine group An alkylene group of C ₂₀ , and
g) Formula:

(Wherein R ¹ , R ² , R ³ , R ⁴ , T and m are the same as defined above)
A polyorganosiloxane chain, and
h) Formula:

Represents a group selected from a polyorganosiloxane chain.

  The second group of polyorganosiloxanes has the formula (II):

Including at least one portion corresponding to
In the above formula,
R ¹ and R ³ can be the same or different and are the same as defined above for formula (I);
R ⁷ represents the same group as defined above for R ¹ and R ³ or is of formula -XGR ^{9 wherein} X and G are as defined above for formula (I) Represents a group that is the same as defined, and R ⁹ is selected from O, S and N optionally substituted by a hydrogen atom, or one or more fluorine atoms and / or one or more hydroxyl groups A linear, branched or cyclic, saturated or unsaturated C ₁ to C ₅₀ hydrocarbon-based group, optionally containing one or more atoms in the chain, or one or more Represents a phenyl group optionally substituted by a C ₁ to C ₄ alkyl group,
R ⁸ represents a group of formula -XGR ⁹ where X, G and R ⁹ are the same as defined above;
M ₁ is an integer in the range 1 to 998,
M ₂ is an integer ranging from 2 to 500.

  According to the invention, the polymer used as a gelling agent can be a homopolymer, ie a polymer comprising several identical moieties, in particular a moiety of formula (I) or formula (II).

According to the invention, a polymer consisting of a copolymer comprising several different parts of formula (I), i.e. at least one of the groups R ¹ , R ² , R ³ , R ⁴ , X, G, Y, m and n is It is also possible to use different polymers in one of the parts. The copolymer is also formed from several parts of formula (II), wherein at least one of the groups R ¹ , R ³ , R ⁷ , R ⁸ , m ₁ and m ₂ is different in at least one of the parts. It may be.

  A copolymer comprising at least one part of formula (I) and at least one part of formula (II), wherein the part of formula (I) and the part of formula (II) are optionally identical or different from each other. It is also possible to use it.

  According to one variant of the invention, ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups, urea groups, urethane groups, thiourea groups, oxamide groups, guanidino groups and biguanidino groups, and their It is also possible to use a copolymer further comprising at least one hydrocarbon-based moiety comprising two groups capable of establishing hydrogen interactions selected from the combination.

  These copolymers are block copolymers or graft copolymers.

  According to a first embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of the formulas —C (O) NH— and —HN—C (O) —.

  In this case, the gelling agent is of formula (III) or (IV):

A polymer comprising at least one portion of
In the above formula, R ¹ , R ² , R ³ , R ⁴ , X, Y, m and n are the same as defined above.

The above part is
The following reaction mechanism:

By a condensation reaction between an α, ω-carboxylic acid end and a silicone containing one or more diamines,
Or the following reaction mechanism:
CH ₂ = CH-X ¹ -COOH + H ₂ NY-NH ₂ → CH ₂ = CH-X ¹ -CO-NH-Y-NH-CO-X ¹ -CH = CH ₂
Reaction of two molecules of α-unsaturated carboxylic acid with diamine followed by the following mechanism:

(Where X ^1- (CH ₂ ) _2- corresponds to X as defined above, and Y, R ¹ , R ² , R ³ , R ⁴ , and m are the same as defined above. Or by addition of siloxane to ethylenic unsaturation,
Or the following reaction mechanism for silicones containing α, ω-NH ₂ termini and diacids of formula HOOC-Y-COOH:

Can be obtained either by reaction with

In these polyamides of formula (III) or (IV), m is preferably in the range 1 to 700, more preferably 15 to 500, even better in the range 10 to 100, n is in particular 1 to 500, Preferably from 1 to 100, better still in the range of 4 to 25,
X is a linear or branched alkylene chain, preferably containing 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms,
Y is linear or branched containing 1 to 40 carbon atoms, in particular 1 to 20 carbon atoms, better still 2 to 6 carbon atoms, in particular 6 carbon atoms Or optionally alkylene containing rings and / or unsaturation.

In formulas (III) and (IV), the alkylene group corresponding to X or Y optionally has at least one of the following elements in its alkylene moiety:
1) 1 to 5 amide groups, urea groups or carbamate groups,
2) C ₅ or a cycloalkyl group C _6, and
3) a phenylene group optionally substituted by 1 to 3 identical or different C ₁ to C ₃ alkyl groups,
Can be contained.

In formulas (III) and (IV), the alkylene group is also
・ Hydroxyl group,
A C ₃ to C ₈ cycloalkyl group,
1 to 3 C ₁ to C ₄₀ alkyl groups,
A phenyl group optionally substituted by 1 to 3 C ₁ to C ₃ alkyl groups,
A C ₁ to C ₃ hydroxyalkyl group, and a C ₁ to C ₆ aminoalkyl group optionally substituted by at least one moiety.

  In these formulas (III) and (IV), Y is also

Wherein R ⁵ represents a polyorganosiloxane chain, and T represents the formula:

Represents the group of
Where a, b and c are independently integers ranging from 1 to 10 and R ¹⁰ is defined as a hydrogen atom or as defined for R ¹ , R ² , R ³ and R ⁴ It is the same group.

In the formulas (III) and (IV), R ¹ , R ² , R ³ and R ⁴ are independently a linear or branched C ₁ to C ₄₀ alkyl group (preferably a CH ₃ group). C ₂ H ₅ group, nC ₃ H ₇ group or isopropyl group), a polyorganosiloxane chain or a phenyl group optionally substituted by 1 to 3 methyl or ethyl groups.

  As already seen, the polymer may comprise the same or different moieties of formula (III) or (IV).

  The polymer is therefore a polyamide containing several parts of formula (III) or (IV) of different lengths, i.e. the formula:

Wherein X, Y, n and R ¹ to R ⁴ have the meanings indicated above, and m ₁ and m ₂ are different from 1 to 1000. And p is an integer in the range of 2 to 300.

  In this formula, the moiety can be in the form of a block copolymer, or a random or alternating copolymer. In this copolymer, the portions may not only differ in length but also in chemical structure, and can contain, for example, different groups Y. In this case, the copolymer has the formula:

In which R ¹ to R ⁴ , X, Y, m ₁ , m ₂ , n and p have the meanings indicated above and Y ¹ is different from Y Selected from the groups defined for Y. As before, the various portions can be structured to form block copolymers, or either random or alternating copolymers.

  In this first embodiment of the invention, the structurant can also consist of a graft copolymer. For example, polyamides containing silicone units may be grafted and optionally crosslinked by silicone chains containing amide groups. The polymer can be synthesized with a trifunctional amine.

  In this case, the copolymer has at least one formula:

Part of
In which X ¹ and X ² are the same or different and have the meaning given for X in formula (I), and n is the same as defined in formula (I). , Y and T are the same as defined in formula (I), R ¹¹ to R ¹⁸ are groups selected from the same groups as R ¹ to R ^4, and m ₁ and m ₂ are 1 P is an integer in the range of 2 to 500.

In formula (VII):
P is in the range 1 to 25, better 1 to 7,
R ¹¹ to R ¹⁸ are methyl groups,
・ T is the following formula:

Wherein R ¹⁹ is a hydrogen atom or a group selected from the groups defined for R ¹ to R ⁴ and R ²⁰ , R ²¹ and R ²² are independently A linear or branched alkylene group, more preferably a formula having R ²⁰ , R ²¹ and R ²² especially representing —CH ₂ —CH ₂ —:

Corresponding to
M ₁ and m ₂ are in the range 15 to 500, better 15 to 45;
X ¹ and X ² represent-(CH ₂ ) _10-
· Y is, -CH ₂ - preferably represents a.

  These polyamides containing grafted silicone moieties of formula (VII) can be copolymerized with polyamide-silicones of formula (II) to form block copolymers, alternating copolymers or random copolymers. The weight percentage of grafted silicone moiety (VII) in the copolymer can range from 0.5% to 30% by weight.

  According to the invention, as already seen, the siloxane units are in the main chain or backbone of the polymer, but they can also be present in the graft or pendant chain. In the main chain, the siloxane units are in the form of segments as described above. In the pendant chain or graft chain, the siloxane units may appear individually or in segments.

According to the present invention, preferred siloxane-based polyamides are:
A polyamide of the formula (III) in which m is 15 to 50,
A polyamide of the formula (III) in which m is 30 to 500,
A mixture of two or more polyamides, wherein at least one polyamide has a value of m in the range 15 to 50 and at least one polyamide has a value of m in the range 30 to 50,
M ₁ selected within the range of 15 to 50 and m ₂ selected within the range of 30 to 500, the proportion corresponding to m ₁ being 1% to 99% by weight of the total weight of the polyamide, and a polymer of formula (V) in which the proportion corresponding to m ₂ is 1% to 99% by weight of the total weight of the polyamide,
1) 80% to 99% by weight of polyamide, where n is equal to 2 to 10, in particular 3 to 6, and
2) 1% to 20% by weight of polyamide where n is in the range 30 to 500, in particular 30 to 100
A mixture of polyamides of the formula (III) in combination with
1) 1% to 20% by weight of polyamide with n equal to 2 to 10, in particular 3 to 6;
2) 80% to 99% by weight of the polyamide where n is in the range 30 to 500, in particular 30 to 100
A mixture of polyamides of the formula (III) in combination with
A polyamide corresponding to formula (VI), wherein at least ^one of the groups Y and Y ¹ contains at least one hydroxyl substituent,
A polyamide of formula (III) synthesized by at least a part of an activated diacid (diacid chloride, dianhydride or diester) instead of a diacid,
A polyamide of the formula (III) in which X represents-(CH ₂ ) _3- or-(CH ₂ ) _10- ,
The polyamide is selected from the group consisting of monofunctional amines, monofunctional acids, monofunctional alcohols, including fatty acids, fatty alcohols and fatty amines, such as octylamine, octanol, stearic acid and stearyl alcohol, etc. Polyamide of formula (III) with functional chain ends.

According to the invention, the end of the polymer chain is
A C ₁ to C ₅₀ alkyl ester group by introducing a C ₁ to C ₅₀ monoalcohol during the synthesis,
A C ₁ to C ₅₀ alkylamide group by using a monoacid as the terminating group if the silicone is α, ω-diamined, or a monoamine if the silicone is an α, ω-dicarboxylic acid. finish.

  According to a variant of one embodiment of the invention, it is possible to use a copolymer of silicone polyamide and hydrocarbon-based polyamide, i.e. a copolymer comprising a moiety of formula (III) or (IV) and a hydrocarbon-based polyamide part. Is possible. In this case, the polyamide-silicone moiety can be arranged at the end of the hydrocarbon-based polyamide.

  Polyamide-based structuring agents containing silicone can be produced by silylamidation of polyamides based on fatty acid dimers. This can be achieved by reacting the free acid sites existing as end sites in the polyamide with oligosiloxane-monoamine and / or oligosiloxane-diamine (amidation reaction), or alternatively with oligosiloxane alcohol or oligosiloxane diol. (Esterification reaction). The esterification reaction requires the presence of an acid catalyst as is known in the art. The polyamide containing free acid sites used for its amidation or esterification reaction should have a relatively high number of acid end groups (e.g. polyamides with a high acid number, e.g. 15 to 20). .

  1 to 300, more specifically 2 to 50, and even better 2, 6, 9.5, 12, 13.5, 23 or 31 for the amidation of free acid sites in hydrocarbon polyamides Siloxane diamines having siloxane groups can be used for reaction with hydrocarbon-based polyamides based on fatty acid dimers. Siloxane diamines containing 13.5 siloxane groups are preferred and best results are obtained with siloxane diamines containing 13.5 siloxane groups and polyamides containing a high number of carboxylic acid end groups.

  The reaction can be carried out in xylene to extract the water formed from the solution by azeotropic distillation or at higher temperatures (about 180 to 200 ° C.) without solvent. In general, the amidation effect and reaction rate decrease with increasing siloxane diamine, ie, with a large number of siloxane groups. Free amine sites can be blocked after the initial amidation reaction of diaminosiloxanes by reacting them with either an organic acid such as siloxane acid or benzoic acid.

  For the esterification of the free acid sites of the polyamide, this can be carried out in boiling xylene with about 1% by weight of paratoluenesulfonic acid as catalyst relative to the total weight of the reactants.

  These reactions performed at the carboxylic acid end groups of the polyamide cause the incorporation of silicone moieties only at the ends of the polymer chain.

  It is also possible to use polyamides containing free amine groups and to prepare polyamide-silicone copolymers by amidation reaction with siloxanes containing acid groups.

  Adjusting a structurant based on a copolymer between a hydrocarbon-based polyamide and a silicone polyamide is a high temperature (eg, 200 to 300 ° C.) that undergoes an amide group transfer such that the ethylenediamine component of the original polyamide is replaced by an oligosiloxane diamine. It is also possible, for example, by transamidation of polyamides having ethylenediamine moieties with oligosiloxane-α, ω-diamines.

  The copolymer of hydrocarbon-based polyamide and polyamide-silicone can also be a graft copolymer comprising a hydrocarbon-based polyamide backbone with pendant oligosiloxane groups.

This is for example:
By hydrosilylation of unsaturated bonds in polyamides based on fatty acid dimers,
・ By silylation of amide group of polyamide, or ・ Silylation of unsaturated polyamide using oxidation, that is, hydroxyl group that reacts with siloxane carboxylic acid or siloxane alcohol by oxidizing unsaturated group to alcohol or diol Can be obtained. The olefinic part of the unsaturated polyamide is also. It can be epoxidized and the epoxy group can then be reacted with a siloxane amine or siloxane alcohol.

  According to a second embodiment of the invention, the structuring agent consists of a homopolymer or copolymer containing urethane groups or urea groups.

  As before, the polymer can include a polyorganosiloxane moiety containing two or more urethane and / or urea groups in the backbone of the polymer or in side chains or as pendant groups.

  The polymer comprising at least two urethane groups and / or urea groups in the backbone has the formula:

Including at least one part corresponding to
In which R ¹ , R ² , R ³ , R ⁴ , X, Y, m and n have the meaning given above for formula (I) and U is

Represents —O— or —NH— so as to correspond to a urethane group or a urea group.

In this formula (VIII), Y is a linear or branched C ₁ to C ₄₀ alkylene group optionally substituted by a C ₁ to C ₁₅ alkyl group or a C ₅ to C ₁₀ aryl group. It can be. Preferably, the group — (CH ₂ ) ₆ — is used.

Y is also a C ₁ to C ₁₅ alkyl group or a C ₅ to C ₁₂ alicyclic or aromatic group optionally substituted by a C ₅ to C ₁₀ aryl group, such as isophorone diisocyanate. Represents a group selected from the derived groups methylene-4,4-biscyclohexyl, 2,4- and 2,6-tolylene, 1,5-naphthylene, p-phenylene and 4,4'-biphenylenemethane be able to. In general, Y preferably represents a linear or branched C ₁ to C ₄₀ alkylene group or a C ₄ to C ₁₂ cycloalkylene group.

  Y may also represent a polyurethane block or a polyurea block corresponding to the condensation of several diisocyanate molecules with one or more diol or diamine type binder molecules. In this case, Y contains several urethane or urea groups in the alkylene chain.

  It has the formula:

Wherein B ¹ is a group selected from the groups given for Y above, U is —O— or —NH—, and B ² is
A linear or branched C ₁ to C ₄₀ alkylene group,
An alkyl substituent, for example 1 to 3 methyl or ethyl groups, or an alkylene substituent, for example a C ₅ to C ₁₂ cycloalkylene group optionally having a diol group cyclohexanedimethanol,
A phenylene group optionally having a C ₁ to C ₃ alkyl substituent, and

(Wherein T is one or more hydrocarbon-based trivalent groups optionally containing heteroatoms such as oxygen, sulfur and nitrogen, and R ⁵ is a polyorganosiloxane chain or straight chain Or a branched C ₁ to C ₅₀ alkyl chain).

  T is for example:

(w is an integer ranging from 1 to 10 and R ⁵ is a polyorganosiloxane chain).

When Y is a linear or branched C ₁ to C ₄₀ alkylene group, — (CH ₂ ) ₂ — and — (CH ₂ ) ₆ — are preferred.

  In the formula given above for Y, d is an integer from 0 to 5, preferably from 0 to 3, more preferably equal to 1 or 2.

Preferably, B ² is a linear or branched C ₁ to C ₄₀ alkylene group, especially — (CH ₂ ) ₂ — or — (CH ₂ ) ₆ — or a group:

(R ⁵ is a polyorganosiloxane chain).

  As before, the polymer making up the structuring agent may be formed from silicone urethane and / or silicone urea moieties of different lengths and / or configurations and may be a block or random copolymer.

  According to the invention, the silicone can also contain urethane groups and / or urea groups as side branches rather than in the backbone.

  In this case, the polymer has at least one formula:

Wherein R ¹ , R ² , R ³ , m ₁ and m ₂ have the meaning given above for formula (I),
U represents O or NH;
R ²³ represents a C ₁ to C ₄₀ alkylene group optionally containing one or more heteroatoms selected from O and N, or a phenylene group,
R ²⁴ is optionally substituted by a linear, branched or cyclic, saturated or unsaturated C ₁ to C ₅₀ alkyl group, and 1 to 3 C ₁ to C ₃ alkyl groups Selected from the phenyl group.

  The polymer comprising at least one moiety of formula (X) contains siloxane units and urea or urethane groups, which can be used as structuring agents in the compositions of the present invention.

  Siloxane polymers may have a single urea group or urethane group per branch, or may contain branches containing two urea groups or urethane groups, or alternatively, Can contain a mixture of branches containing one urea group or urethane group and branches containing two urea groups or urethane groups.

  They can be obtained from branched polysiloxanes containing one or two amino groups per branch by reacting these polysiloxanes with monoisocyanates.

  Examples of this type of starting polymer containing amino and diamino branches include the following formula:

Can be mentioned.

  In these formulas, the symbol “/” indicates that the segments can be of different lengths and in random order, R preferably contains 1 to 6 carbon atoms, and better still Represents a linear aliphatic group having 1 to 3 carbon atoms.

  The polymer containing branches contains a siloxane polymer containing at least 3 amino groups per polymer molecule, containing only one monofunctional group (e.g. acid, isocyanate or isothiocyanate) A monofunctional group can be formed by reacting with a compound that reacts with one of the amino groups to form a group capable of establishing hydrogen interactions. The amino groups can be on these side chains extending from the main chain of the siloxane polymer such that groups capable of establishing hydrogen interactions are formed on the side chains, or alternatively The amino group can be at the end of the main chain such that the group capable of hydrogen interaction is the end group of the polymer.

  Methods for forming polymers containing siloxane moieties and groups capable of establishing hydrogen interactions include reaction of siloxane diamine and diisocyanate in a silicone solvent to provide a gel directly. be able to. The reaction can be carried out in a silicone fluid and the resulting product is dissolved in the silicone fluid at an elevated temperature and the temperature of the system is then reduced to form a gel.

  A preferred polymer for incorporation into the composition according to the invention is a siloxane-urea copolymer which is linear and contains urea groups in the polymer backbone as groups capable of establishing hydrogen interactions.

  As an illustration of a polysiloxane terminated with 4 urea groups, the formula:

In the above formula, Ph is a phenyl group, and n is a number from 0 to 300, in particular from 0 to 100, for example 50.

  This polymer has the following polysiloxanes containing amino groups:

Can be obtained by reacting with phenyl isocyanate.

  A polymer of formula (VIII) containing urea groups or urethane groups in the chain of the silicone polymer has the formula:

Where m, R ¹ , R ² , R ³ , R ⁴ and X are the same as defined for formula (I), α, ω-NH ₂ or —OH end groups A silicone containing, diisocyanate OCN-Y-NCO (Y has the meaning given by formula (I)) and optionally formula H ₂ NB ² -NH ₂ or HO-B ² -OH. Can be obtained by reaction with a diol or diamine binder where B ² is the same as defined in formula (IX).

  According to the stoichiometric ratio between the two reactants, diisocyanate and binder, Y may have the formula (IX) where d is equal to 0 or d is equal to 1 to 5. it can.

  As in the case of the polyamide silicones of formula (II) or (III), in the present invention polyurethane or polyurea silicones containing parts of different lengths and structures, in particular parts having different lengths depending on the number of silicone parts, It is possible to use. In this case, the copolymer is for example of the formula:

Wherein R ¹ , R ² , R ³ , R ⁴ , X, Y and U are the same as defined for formula (VIII) and m ₁ , m ₂ , N and p are the same as defined for formula (V).

  Branched polyurethanes or polyurea silicones can also be substituted for the diisocyanate OCN-Y-NCO with the formula:

The triisocyanate can be used.

  Polyurethane or polyurea silicones containing branches containing organosiloxane chains with groups capable of establishing hydrogen interactions are thus obtained. The polymer can be, for example, the formula:

Wherein X ¹ and X ² are the same or different and have the meanings given for X in formula (I), and n is the formula (I ) And Y and T are the same as defined in formula (I), and R ¹¹ to R ¹⁸ are groups selected from the same groups as R ¹ to R ⁴ , M ₁ and m ₂ are numbers in the range of 1 to 1000, and p is an integer in the range of 2 to 500.

  As with the polyamide, this copolymer can also contain unbranched polyurethane silicone moieties.

In this second embodiment of the invention, preferred silicone-based polyureas and polyurethanes are:
A polymer of formula (VIII), wherein m is 15 to 50,
A polymer of formula (VIII), wherein m is from 30 to 500,
A mixture of two or more polymers, wherein at least one polymer has a value of m in the range of 15 to 50 and at least one polymer has a value of m in the range of 30 to 50;
M ₁ selected within the range of 15 to 50 and m ₂ selected within the range of 30 to 500, the proportion corresponding to m ₁ being 1% to 99% by weight of the total weight of the polymer, and a polymer of formula (XII) in which the proportion corresponding to m ₂ is 1% to 99% by weight of the total weight of the polymer;
1) 1% to 20% by weight of a polymer, where n is equal to 2 to 10, in particular 3 to 6;
2) 80% to 99% of polymers where n is in the range 30 to 500, especially 30 to 100
A mixture of polymers of formula (VIII) in combination with
A copolymer comprising two moieties of the formula (VIII), wherein at least one of the groups Y contains at least one hydroxyl substituent,
A polymer of formula (VIII) synthesized by at least a portion of an activated diacid (diacid chloride, dianhydride or diester) instead of a diacid,
A polymer of the formula (VIII) in which X represents-(CH ₂ ) _3- or-(CH ₂ ) _10- ; and the polymer is a fatty acid, fatty alcohol and fatty amine, such as octylamine, octanol, stearic acid And a polymer of the formula (VIII) having a monofunctional chain end selected from the group consisting of monofunctional amines, monofunctional acids, monofunctional alcohols, including stearyl alcohol and the like.

  As in the case of polyamides, a polyurethane or polyurea silicone and a hydrocarbon-based polyurethane or polyurea copolymer is reacted with a non-silicone α, ω-bifunctional block, such as a polyester, It can be used in the present invention by carrying out in the presence of polyether or polyolefin.

  As has already been seen, the gelling agent consisting of the homopolymer or copolymer of the present invention comprises a siloxane moiety in the main chain of the polymer and either in the main chain of the polymer or at its end, or in the side chain or branch of the main chain. Either can contain groups capable of establishing hydrogen interactions. This is the following five arrays:

Where the solid line is the backbone of the siloxane polymer and the square represents a group capable of establishing hydrogen interactions.

  In the case of (1), a group capable of establishing hydrogen interaction is arranged at the end of the main chain. In the case of (2), two groups capable of establishing hydrogen interaction are arranged at each end of the main chain.

  In the case of (3), the group capable of establishing hydrogen interaction is arranged in the repeating part in the main chain.

  In the case of (4) and (5), these are the first of the parts where the group capable of establishing hydrogen interactions copolymerizes with the part that does not contain groups capable of establishing hydrogen interactions. It is arranged on a branch of one set of main chains. The values of n, x and y thus indicate that the polymer has desirable properties in terms of agents for gelling the fatty phase based on silicone oil.

  According to the present invention, the structuring of the liquid fatty phase containing at least one silicone oil reduces the melting temperature and enthalpy of melting of one or more of the polymers mentioned above and of these or these polymers. Can be obtained with the help of a combination with one or more possible compounds.

  Examples of polymers that can be used include silicone polyamides obtained according to Examples 1 to 3 of document US-A-5981680.

  The polymers and copolymers used in the composition according to the invention advantageously have a softening point of from 65 ° C to 190 ° C. Preferably they have a softening point in the range from 70 to 130 ° C, better still from 80 ° C to 105 ° C. This softening point is lower than that of known structured polymers, thereby facilitating the use of the polymer, allowing the use of volatile oils and inhibiting the degradation of the liquid fatty phase.

  They have good solubility in silicone oil and produce macroscopically uniform compositions. Preferably they have an average molecular weight of 500 to 200,000, for example 1000 to 100,000, preferably 2000 to 200,000.

Compounds that can lower the melting enthalpy and optionally the melting temperature of the structured polymer The compounds according to the invention lower, lower or lower the melting enthalpy (ΔH) and optionally the melting temperature (mp) of the structured polymer One or more compounds that can be made, preferably capable of lowering the melting enthalpy (ΔH) and melting temperature (mp). This or these compounds can facilitate application of the compositions and improve the adhesion obtained with these compositions. That is, this adhesion is more abundant than that obtained under the same conditions with compositions that do not contain these compounds. Said compounds can lower or lower or lower the melting enthalpy and optionally the melting temperature of the fatty phase structured polymer.

  The expression lowering the enthalpy of melting means that once a polymer comes into contact with this or these compounds, it has a lower enthalpy than that it exhibits in its pure state, expressed in relation to the mass of the polymer present. Should be understood to mean

  The enthalpy of melting is a so-called output compensated calorimetric technique that applies a temperature increase of 2 ° C. per minute using a differential scanning calorimetry, for example, a calorimeter sold under the name MDSC 2920 by TA Inst. Measured by differential scanning calorimetry.

  The enthalpy of melting corresponds to the lower surface of the resulting temperature recording curve.

  The temperature record is a power compensated differential calorimetric enthalpy curve, which represents the amount of heat given by the units of time plotted on the y-axis as a function of temperature on the x-axis.

  The reduction in melting enthalpy (ΔH) depends on the amount of the above compounds in the composition. This amount is sufficient to cause a decrease in melting enthalpy (ΔH), which is generally at least 3 J / g of pure polymer, preferably at least 4 J / g of pure polymer, more preferably 5-10 J / g.

  All effects described above are observed when the compound is included in such amounts. In other words, by incorporating a sufficient amount of these compounds that are potentially capable of causing a decrease in the enthalpy of melting, it is virtually possible at first to make them have a potential effect.

  In addition, the compounds can also generally lower the melting temperature (m.p.) of the structured polymer.

  The expression melting temperature, lowering the melting point is understood to mean that the polymer once in contact with this or these compounds has a lower melting temperature than it exhibits in the pure state.

  Melting temperature, melting point is applied according to the present invention by a differential scanning calorimetry, for example, using a calorimeter sold under the name MDSC 2920 by the company TA Inst. With a temperature increase of 2 ° C. per minute. This corresponds to the melting point measured by a so-called output compensation calorimetric technique (differential scanning calorimetry). What is considered the melting point is the point corresponding to the temperature of the most endothermic peak of the temperature record obtained. The temperature record was defined above.

  To determine the value of the melting temperature reduction caused by a compound capable of lowering the melting point contained in the composition of the present invention, the melting temperature of the pure polymer is first measured by the above method, then Solubilize the polymer with one or more compounds capable of lowering or decreasing the melting temperature above the previously determined mp, and for the mixture of the polymer and compound, under the same conditions, in the same manner Measure the melting point.

  The decrease in melting temperature depends on the amount of the above compounds in the composition. This amount must be sufficient to cause a true decrease or decrease in the melting temperature of the polymer. This reduction or this reduction is generally at least 3 ° C, preferably at least 4 ° C, more preferably 5-20 ° C.

  In addition, compounds capable of lowering the melting temperature and melting enthalpy are advantageously compounds that result in a composition that is macroscopically uniform and / or soluble or dispersible in the fatty phase of the composition. It is.

  A macroscopically uniform composition is one that is observed as a single phase with the naked eye at room temperature (between 20 ° C. and 25 ° C.).

  Compounds capable of reducing the enthalpy of melting of the structured polymer are preferably soluble in the fatty phase of the composition. That is, the compound is distributed in the fatty phase in the form of individual molecules.

  Compounds capable of reducing the melting enthalpy of the structured polymer are preferably dispersible in the fatty phase of the composition. That is, the compound is uniformly distributed in the fatty phase in the form of a mass of molecules having a size that cannot be perceived by the naked eye.

  These properties can be explained by the fact that these compounds are “compatible” with the structured polymer, and optionally with other compounds of the composition.

  Preferably, compounds capable of reducing the enthalpy of melting of the polymer also reduce the melting temperature.

  More preferably, these compounds lower the melting temperature and result in a visually uniform composition.

  In other words, preferably, the particular compound used in the composition of the present invention simultaneously satisfies the three conditions associated with lower melting temperature, lower melting enthalpy and formation of a visually uniform composition. Must.

  The compound capable of causing the melting enthalpy and optionally the melting temperature of the structured polymer to be reduced is a hydrocarbon containing at least one functional group containing a free electron doublet capable of interacting with the hydrogen bonds of the polymer And / or selected from silicone compounds. This functional group is selected, for example, from hydroxyl (alcohol), carboxyl, amino, primary, secondary and tertiary amines, urea and urethane, ethers and esters.

  Preferred functional groups are those of alcohols, so that the compounds capable of causing the melting enthalpy of the structured polymer and possibly a decrease in melting temperature are preferably polyols such as monoalcohols, diols and triols, As well as polyol ethers.

  In particular, the enthalpy of melting and optionally the compound capable of causing a decrease in melting temperature can be selected from silicone diols.

  Suitable silicone diols are specifically described in document US-A-5969172, which can be used as a reference for that description, and are sold by the company GENERAL ELECTRIC.

The compounds of this document have the following formula:
M _a M ' _b D _c D' _{d Te} T ' _f Q _g
Corresponding to
Subscripts a, c, d, e, f and g are zero or positive integers, provided that the sum of subscripts b, d and f is 1 or greater,
M is the formula:
R ^I ₃ SiO _1/2
Have
Each R ′ independently represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms;
M 'is the formula:
R ^II _3-h R ^III _h SiO _1/2
Have
Each R ^II is independently a monovalent hydrocarbon group having 1 to 40 carbon atoms, and R ^III is H ₂ (OH) CCH (OH) CH ₂ OCH ₂ CH ₂ CH ₂ -and (HOCH ₂ ) ₂ C (CH ₂ CH ₃ ) CH ₂ OCH ₂ CH ₂ CH _2- , a monovalent hydrocarbon group selected from the group consisting of (subscript h is 1, 2 or 3) And
D is the formula:
R ^IV ₂ SiO _2/2
Have
Each R ^IV is independently a monovalent hydrocarbon group having 1 to 40 carbon atoms;
D 'is the formula:
R ^V _2-i R ^VI _i SiO _2/2
Have
Each R ^IV is independently a monovalent hydrocarbon group having 1 to 40 carbon atoms, and R ^V is H ₂ (OH) CCH (OH) CH ₂ OCH ₂ CH ₂ CH ₂ -and (HOCH ₂ ) ₂ C (CH ₂ CH ₃ ) CH ₂ OCH ₂ CH ₂ CH _2- , a monovalent hydrocarbon group selected from the group consisting of (subscript i is 1 or 2) Yes,
T is the formula:
R ^VII SiO _3/2
Have
Each R ^VII is independently a monovalent hydrocarbon group having 1 to 40 carbon atoms;
T 'is the formula:
R ^VIII SiO _3/2
Have
R ^VIII is selected from the group consisting of H ₂ (OH) CCH (OH) CH ₂ OCH ₂ CH ₂ CH ₂ -and (HOCH ₂ ) ₂ C (CH ₂ CH ₃ ) CH ₂ OCH ₂ CH ₂ CH _2- And Q has the formula SiO _4/2 .

  Preferred compounds are those shown in Table 3 below.

In Table 3, 1,3-diols, the functional group i.e. R ^III, R ^V or R ^VIII is a group _{(HOCH 2) 2 C (CH} 2 CH 3) CH 2 OCH 2 CH 2 CH 2 -, i.e. trimethylol It means that a monoallyl ether propane (TMPMAE), 1,2-diol functional group is _{H 2 (OH) CCH (OH} ) CH 2 OCH 2 CH 2 CH 2 -, i.e. derived from monoallyl glycerol It means that it is a group.

In Table 3, further preferred compounds are M′D ₃ M ′, M′D _7,5 M ′, M′D ₁₀ M ′ and M′D ₂₅ M ′.

  Compounds that can cause melting enthalpies and, in some cases, a reduction in melting temperature, also have an alkyl group of 1 to 4 carbon atoms and an alkylene group of 1 to 4 carbon atoms. Oxyalkylenated polydi (alkyl) siloxane type having, preferably, the polydi (alkyl) siloxane alkyl group is a methyl group, the oxyalkylene group is an oxypropylene group and / or an oxyethylene group, It can also be selected from compounds in which the compound is PDMS oxypropylene and / or PDMS oxyethylene.

  This type of compound is known under the name dimethicone polyol or copolyol (PDMS-EO-PO), among which polydimethylsiloxaneoxyethylene (manufactured by DEGUSSA sold under the designation ABIL B 8873) 7 / 9EO) Oxypropylene (10 / 14PO), or known under the INCI name PEG / PPG-17 / 18 dimethicone and sold by DOW CORNING under the product name "Q2-5220 resin modifier" Examples thereof include polydimethylsiloxaneoxyethylene (200E) and oxypropylene (200P).

Other compounds that can cause the melting enthalpy of the polymer, and optionally lowering of the melting point, are monoalkyl ethers of polyalkylene (1-4 carbon atoms) glycols, such as polypropylene glycol, or of the formula:
H- [OCH (CH ₃ ) CH ₂ ] _n O- (CH ₂ ) ₁₃ -CH ₃
A polyalkylene glycol monoalkyl ether such as polypropylene glycol monomyristyl ether wherein n is 2 to 200.

  Another group of compounds capable of causing the enthalpy of melting of the structured polymer and optionally lowering the melting temperature is from linear or branched aliphatic monoalcohols having more than 8 carbon atoms, for example from 12 Of the 26 carbon atoms, 2-butyloctanol, 2-hexyldecanol, 2-undecyldecanol, 2-undecylpentadecanol, oleyl alcohol, etc., the preferred alcohol is octyldodecanol.

  A compound capable of causing the enthalpy of fusion and optionally lowering of the melting temperature of one or more polymers is a single compound, or alternatively, each of any group of compounds defined above or It is possible to include some of these compounds that can be selected from the group.

  The content of one or more compounds that can cause the enthalpy of melting of the polymer and optionally the melting temperature is generally 5 to 25% by weight, preferably 10 to 20% by weight.

  This amount is sufficient, as defined above, and makes it possible to obtain a decrease in the enthalpy of polymer melting and / or the melting temperature of the polymer, generally at least 3 J / g and at least 3 ° C., respectively.

  It is not known in the art to use, in cosmetic compositions, compounds that reduce the melting enthalpy and optionally the melting temperature of polymers such as PASi. The combination of such compounds with certain polymers according to the invention is not described or suggested in the prior art. In light of the prior art, the above combination is a surprising improvement in properties, in particular the ease of application of cosmetic compositions containing this combination and in some cases the gloss, as well as the particular mass of adhesion obtained from cosmetic compositions containing this combination. And there was nothing that could come to mind that in some cases also improved gloss.

  The melting enthalpy of the polymer and optionally the compound that lowers the melting temperature, and the amount of structured polymer may be selected according to the desired hardness of the composition and the specific application expected to be due to the desired stability. it can. Each amount of (at least one) structured polymer and melting enthalpy and optionally a compound that lowers the melting point can be a disintegrable solid that does not flow under the influence of its own weight. .

  According to one embodiment of the invention corresponding to a stick, the composition preferably has a hardness in the range of 20 to 2000 gf, better 20 to 900 gf, in particular 20 to 600 gf, for example 150 to 450 gf. . This hardness should be measured in particular by a probe that penetrates the composition with the aid of a texture analyzer (e.g. TA-TXT2i from Rheo) equipped with an ebonite cylinder with a height of 25 mm and a diameter of 8 mm. Can do. The hardness is measured at 20 ° C. at the center of 5 samples of the composition. A cylinder is introduced into each sample of the composition at a preceding speed of 2 mm / second, followed by a speed of 0.5 mm / second, and finally at a subsequent speed of 2 mm / second, for a total displacement of 1 mm. The recorded hardness value is the maximum peak value. The measurement error is ± 50 gf.

  The hardness is also measured at 20 ° C using an Indelco-Chatillon DFGHS 2 tensile tester that cuts a 12.7 mm diameter lipstick tube and moves at a speed of 100 mm / min. It can also be measured by the “cheese wire” method, which is essential. It is expressed as the shear force (expressed in grams-force) required to cut the stick under these conditions. According to this method, the hardness of the composition in the form of a stick according to the invention is 30 to 300 gf, preferably 30 to 250 gf, for example 30 to 200 gf, better 30 when the stick diameter is equal to 12.7 mm. To 120gf.

  The hardness of the composition may be even lower as long as the composition is self-supporting and can easily disintegrate to form a satisfactory adhesion to the skin and lips. Thanks to the presence of the polymer melting enthalpy and possibly the temperature-decreasing compound in the composition according to the invention, in any case easy application and a sufficient amount of satisfactory adhesion are obtained.

  In addition, at these hardness values, the compositions of the present invention exhibit excellent impact strength.

  In general, the mass ratio of the silicone polymer / the enthalpy of melting of the polymer and optionally the compound capable of lowering the melting temperature is generally in the range of 0.1 to 50, preferably 0.5 to 25, better 1 to 15. is there.

  The structured silicone polymer preferably represents 5 to 30% by weight of the composition.

Other Additives The compositions of the present invention may also comprise any material normally used in the field under consideration, especially fillers, polyols or fatty phase soluble dyes, antioxidants, essential oils, preservatives, perfumes, Fat-soluble polymers, especially hydrocarbon-based fat-soluble polymers such as polyalkylenes or poly (vinyl laurate), liquid fatty phase structuring agents, waxes, gums, resins, surfactants such as trioleyl phosphate such as water, emollients, Additional cosmetic or dermatological actives such as humectants, vitamins, liquid lanolin, essential fatty acids, lipophilic sunscreens or polyol-soluble sunscreens, and mixtures thereof may also be included. The composition according to the invention can also contain ionic and / or non-ionic type lipid vesicles. These materials other than water should be present in the composition in the range of 0% to 20%, preferably 0.01% to 20%, better still 0.1% to 10% of the total weight of the composition by conventional methods. Can do.

  If the composition contains an aqueous phase, it is a single-layer or multi-layer emulsion, this aqueous phase can represent 0.1% to 70% of the total weight of the composition, in particular 0.5% to 40%. %, Even better is 1% to 20%. The aqueous phase can contain any water-miscible compound such as polyol, and may be gelled with a suitable gelling agent in some cases.

  It goes without saying that those skilled in the art are advised to use optimum additional materials and / or so that the advantageous properties of the composition according to the invention are not adversely affected or substantially unaffected by the contemplated addition. Care will be taken to select that amount.

  The compositions of the present invention may specifically contain one or more waxes, such as polyethylene wax, but avoid the use of wax if it is desired to obtain a product that is glossy or even transparent. In general, the amount of wax does not exceed 20% and preferably 10% of the total weight of the composition, which corresponds to, for example, 3% to 5%. In the absence of wax or in the presence of small amounts of wax, the compositions according to the invention all exhibit the advantageous properties described above.

  The composition according to the invention is in the form of an optionally colored care composition for keratinous substances, such as skin, lips and / or body surface growth parts, in the form of sticks or domes, or in the form of molded articles, avoiding sunlight. Or it may be in the form of a care composition, in particular in the form of a make-up removal product. It is especially as a care base for skin, body surface growth or lips (lip balm to protect lips from cold and / or sunlight and / or wind, or care cream for skin, nails or hair) Can be used.

  The composition of the invention can be provided in the form of a particularly soft transparent gel or transparent stick.

  The compositions of the present invention may also have a foundation, blusher, face powder, eye shadow, concealer product, eyeliner or body makeup product optionally having care or treatment properties; optionally having care or treatment properties, for example Lip makeup such as lipsticks, lip gloss or pencils; body surface growth parts such as eyelashes in the form of nails or especially mascara cakes, or makeup in the form of pencils especially for eyebrows and hair.

  In particular, the composition according to the invention may be a cosmetic product containing cosmetic active substances such as essential oils, vitamins, humectants, sunscreens and ceramides.

  In the case of a makeup composition, the hydrophobic or hydrophilic solid particles can constitute a pigment for making up the skin, lips and / or body surface growth parts.

  Needless to say, the compositions of the invention must be cosmetically or dermatologically acceptable. That is, it must be a non-toxic, physiologically acceptable medium that can be applied to human skin, body surface growth or lips. For the purposes of the present invention, the expression “cosmetically acceptable” means a composition with a pleasant appearance, smell and feel.

  Furthermore, the makeup or care composition according to the present invention is a non-volatile oil (silicone oil or non-silicone oil) and / or pasty or viscous at least 10% by weight in order to obtain a product that is comfortable and does not cause tension. It must contain a thick product.

  The expression pasty product is to be understood as meaning a viscous fatty substance containing a liquid part and a solid part. For the purposes of the present invention, the expression “pasty fatty substance” means a melting point in the range of 20 to 55 ° C., preferably in the range of 25 to 45 ° C., and / or 240 revolutions per minute for a 60 Hz power supply, or 50 Hz. Measured using a Contraves TV or Rheomat 180 viscometer with a spindle rotating at 200 rev / min for an electrical power supply, or alternatively observed on a 40 ° C flat cone spindle on a Haake Rs75 rheometer Means a fatty substance having a viscosity in the range of 0.1 to 40 Pa (1 to 400 poise), preferably 0.5 to 25 Pa, measured at 40 ° C. measured by flow in the Newtonian region.

  A person skilled in the art can select a spindle for measuring the viscosity so that the viscosity of the pasty formulation tested can be measured based on his general knowledge.

  The melting point values are consistent with the maximum endothermic melting peak measured by the “differential scanning calorimetry” method with the present invention and, as already indicated above, with a temperature increase of 20 ° C./min.

  Examples of pasty products that can be used in the present invention include lanolin and lanolin having a viscosity of 18 to 21 Pa, preferably 19 to 20.5 Pa, and / or a melting point of 30 to 55 ° C., preferably 30 to 40 ° C. Derivatives such as acetylated lanolin or oxypropylenated lanolin or isopropyl lanolate, and mixtures thereof may be mentioned. Esters of fatty acids or fatty alcohols, especially those containing 20 to 65 carbon atoms (melting point of about 20 to 35 ° C. and / or viscosity in the range of 0.1 to 40 Pa at 40 ° C.), eg triisostearyl citrate Or cetyl citrate, arachidyl propionate, vinyl polylaurate, cholesterol esters, eg triglycerides of plant origin such as hydrogenated vegetable oils, viscous polyesters such as poly (12-hydroxystearic acid) and mixtures thereof are also used can do. Examples of plant-derived triglycerides that can be used include hydrogenated castor oil derivatives such as “THIXINR” manufactured by Rheox.

  Polydimethylsiloxane (PDMS) containing, for example, stearyl dimethicone containing an alkyl or alkoxy type pendant chain containing 8 to 24 carbon atoms and having a melting point of 20-55 ° C., for example 20-40 ° C., especially Dow Mention may also be made of silicone-based pasty fatty substances such as those sold under the trade names DC2503 and DC25514 by Corning and mixtures thereof.

  The pasty fatty substance may be present in a proportion of 0 to 60% by weight, preferably in a proportion of 0.1 to 45% by weight, even more preferably in a proportion of 2 to 30% by weight, relative to the total weight of the composition. it can.

  According to the present invention, the composition generally further comprises solid particles selected from fillers and pigments (including pearlescent pigments) and mixtures thereof.

  The expression pigment is understood to mean any solid particles that are insoluble in the composition and contribute to give and / or modify the color and / or iridescent appearance.

  The pigment is white or colored, inorganic and / or organic and may or may not be coated. The inorganic pigment can be selected from, for example, zinc oxide, iron oxide, titanium oxide and mixtures thereof. Among inorganic pigments, mention may be made, for example, of optionally surface-treated titanium oxide or zinc oxide, and iron oxide or chromium oxide, manganese violet, ultramarine, chromium hydrate and iron blue. Among the organic pigments, mention may be made of lacquers based on carbon black, D & C type pigments, carmine, barium, strontium, calcium or aluminum. The pigment may represent 0.1 to 50%, preferably 0.5 to 40%, better still 2 to 30% of the total weight of the composition.

  According to the present invention, the composition may further contain a colorant selected from lipophilic dyes, hydrophilic dyes and mixtures thereof.

  This colorant is generally present in an amount of 0.01 to 50%, preferably 5 to 30% of the total weight of the composition, if present. It should be noted that the coloring effect can also be provided by the pigments (and pearlescent pigments) already mentioned above in connection with the solid particles.

  The fat-soluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, Quinoline Yellow and Annat.

  Hydrophobic dyes are in particular beet juice and methylene blue. Soluble dyes can represent 0% to 20% of the composition weight, better 0.1% to 6% (if present).

  The composition according to the invention can be prepared by known methods commonly used in the cosmetic or dermatological field. It heats the polymer to at least its softening point and adds to it any waxes and / or pasty formulations, oils, polymers melting enthalpy and optionally compounds that lower the melting temperature, and then the whole clear solution Can be produced by a process consisting of mixing until is obtained. Colorants and / or solid particles and additives are then added with stirring. The resulting homogeneous mixture can then be cast into a suitable mold, such as a lipstick mold, or directly into a packaging article, particularly a case or dish.

The subject of the present invention is also a structured makeup solid composition for the skin, lips and / or body surface growth part, which is sufficient for application to the skin, lips and / or body surface growth part An amount of at least one pigment,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof A liquid continuous fatty phase structured by at least one polymer (homopolymer or copolymer) having a weight average molecular weight in the range of 500 to 500000 containing
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C .;
The liquid fatty phase comprises at least one compound capable of lowering the melting enthalpy and optionally the melting temperature of the structured polymer;
The composition is optionally provided in solid form, the pigment, the liquid fatty phase, the enthalpy of melting of the structured polymer and optionally the compound capable of lowering the melting temperature, and the structured polymer Forms a physiologically acceptable medium.

  This makeup composition is preferably self-supporting.

The subject of the present invention is also a structured lipstick composition, which comprises an amount of at least one pigment sufficient to be applied to the lips,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof A liquid continuous fatty phase structured by at least one polymer (homopolymer or copolymer) having a weight average molecular weight in the range of 500 to 500000 containing
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C .;
The liquid fatty phase comprises at least one compound capable of lowering the melting enthalpy and optionally the melting temperature of the structured polymer, and the enthalpy of melting of the pigment, the fatty phase, the polymer and the structured polymer. And optionally the compound capable of lowering the melting temperature forms a physiologically acceptable medium.

  The present invention relates to a method of cosmetic care, makeup or treatment comprising applying a cosmetic composition according to the present invention to human keratin materials.

The subject of the invention also has a weight average molecular weight in the range of 500 to 500,000 in a sufficient amount to produce a cosmetic composition containing a continuous liquid fatty phase or a physiologically acceptable composition. At least one polymer (homopolymer or copolymer), wherein the polymer is
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one such moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof Contains
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C .;
The liquid fatty phase optionally consists of a silicone oil having a flash point of 40 ° C. or higher partly and completely, one compound capable of lowering the melting enthalpy and possibly the melting temperature of the structured polymer Including
The composition is provided in the form of a self-supporting solid having a hardness in the range of 20 to 2000 gf, preferably 20 to 900 gf and better still 20 to 600 gf.

The subject of the invention is also the use of a continuous liquid fatty phase which is essentially structured by a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight average molecular weight in the range of 500 to 500,000. (The polymer is)
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one such moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof Contains
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C .;
The liquid fatty phase optionally comprises a silicone oil having a flash point of 40 ° C. or higher partially or completely, and a compound capable of lowering the melting enthalpy and optionally the melting temperature of the polymer Included in the composition or to produce a physiologically acceptable composition that is easy to apply and / or provides abundant mass adhesion.

The subject of the invention also has a weight average molecular weight in the range of 500 to 500,000,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups Containing at least one said moiety comprising at least two groups capable of establishing a hydrogen interaction selected from a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group Use of a sufficient amount of at least one polymer (homopolymer or copolymer),
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C.
Easy application and / or rich mass deposition in cosmetic compositions or containing at least one compound capable of lowering the enthalpy and optionally melting temperature of the liquid continuous fatty phase and the polymer Use of the composition to structure a free-standing solid to produce a physiologically acceptable composition.

The subject of the invention also has a weight average molecular weight in the range of 500 to 500,000 of a continuous fatty phase which is basically structured,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof In combination with a sufficient amount of at least one polymer (homopolymer or copolymer) containing
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C.
The liquid fatty phase optionally consists of a volatile oil having a flash point of 40 ° C. or higher, in the cosmetic composition or for producing a physiologically acceptable composition. At least one compound capable of lowering the melting enthalpy and optionally the melting temperature, to facilitate the application of the composition and / or optionally to increase its gloss and adhesion of the composition Contains as an active substance for.

The present invention further has a weight average molecular weight in the range of 500 to 500,000,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof The use of a continuous liquid fatty phase optionally structured by a sufficient amount of at least one structured polymer (homopolymer or copolymer) containing
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C.
The liquid fatty phase optionally consists of partially or completely volatile oils, and in the cosmetic composition or to produce a physiologically acceptable composition, the melting enthalpy and optionally the melting of the polymer. At least one compound capable of lowering temperature is included as an agent to increase the mass of deposition of the composition.

  Due to the advantageous features of these uses, the composition has a hardness of 20 to 2000 gf, preferably 20 to 900 gf and better still 20 to 600 gf.

The present invention also relates to a cosmetic method for facilitating application of a cosmetic composition containing a liquid fatty phase, wherein the fatty phase has a weight average molecular weight in the range of 500 to 500,000. ,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof A sufficient amount of at least one polymer (homopolymer or copolymer) containing
Structuring the fatty phase with a polymer that is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C.
And at least one compound capable of lowering the enthalpy of melting of the polymer and optionally the melting temperature into the composition.

The present invention also relates to a cosmetic method for increasing the mass of adhesion of a cosmetic composition containing a liquid fatty phase, wherein the fatty phase has a weight average molecular weight in the range of 500 to 500,000. ,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof A sufficient amount of at least one polymer (homopolymer or copolymer) containing
Structuring the fatty phase with a polymer that is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C.
And at least one compound capable of lowering the enthalpy of melting of the polymer and optionally the melting temperature into the composition.

The present invention finally has a weight average molecular weight in the range of 500 to 500,000,
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least one said moiety comprising at least two groups capable of establishing hydrogen interactions selected from: a urea group, a urethane group, a thiourea group, an oxamide group, a guanidino group and a biguanidino group, and combinations thereof At least one polymer (homopolymer or copolymer) containing
Said composition in a cosmetic or physiologically acceptable composition comprising a continuous liquid aliphatic phase which is solid at room temperature and structured with a polymer which is soluble in the liquid fatty phase at a temperature of 25 to 250 ° C. The use of a sufficient amount of the compound capable of reducing the melting enthalpy and optionally the melting temperature of the polymer so as to facilitate the application of the polymer and to increase the mass of deposition of the composition.

  The makeup formulation, which illustrates the present invention by way of illustration and not limitation, is described in more detail in the following examples. Amounts are given as mass%. The compounds are indicated mainly by the CTFA (“International Cosmetic Ingredient Dictionary”) name.

(Example 1: Comparison)
In this example not in accordance with the present invention, a lip and facial makeup formulation was prepared solely with silicones of silicone polyamide as the structurant and phenylated silicone as the oil.

  The formulation was then pigmented and cast into pots.

  The composition of the prepared formulation is shown below.

  The silicone polymer is melted at 110 ° C. and mixed with a portion of the oil to obtain a liquid mixture. In parallel, the pigment is ground in the remaining oil. Finally, the pigmented ground product is mixed at 110 ° C. with a mixture of oil and gelling agent.

  The sticking obtained on the hand by the stick is fine and uneven.

  In short, the formulation prepared in this comparative example is hard and difficult to apply, with very little color sticking in between.

(Example 2)
In this example according to the invention, the composition is the same as that of claim 1 except that the compound according to the invention, which reduces the melting temperature of the polymer by 20% by weight, ie octadodecanol, is added to the formulation.

  The composition of the formulation is shown below.

  The silicone polymer is melted at 110 ° C. and mixed with a portion of silicone oil and octadodecanol to obtain a liquid mixture. In parallel, the pigment is ground in the remaining oil. Finally, the pigmented ground product is mixed at 110 ° C. with a mixture of oil and gelling agent.

  The 12.7mm stick obtained after removal from the mold has a smooth, uniform and glossy appearance at room temperature.

  The adhesion obtained under the same conditions as in Example 1 is richer than that of Example 1.

  The adhesion is shiny.

  In conclusion, thanks to the presence of octadodecanol, the formulations according to the invention are easy to apply and the adhesion has a darker color, for example enabling lip makeup. Moreover, the improvement in product and adhesion gloss is significant.

Claims (40)

A balm, lipstick or eye shadow composition comprising a liquid continuous fatty phase structured by at least one structured polymer having a weight average molecular weight in the range of 500 to 500,000,
The polymer comprises at least one portion, the portion comprising:
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups At least two groups capable of establishing hydrogen interactions selected from: urea groups, urethane groups, thiourea groups, oxamide groups, guanidino groups and biguanidino groups, and combinations thereof;
Including
The polymer is solid at room temperature and is soluble in the liquid fatty phase at a temperature of 25 to 250 ° C., the liquid fatty phase comprising 2-butyloctanol, 2-hexyldecanol, 2-undecyldecanol, 2 -Containing at least one linear or branched aliphatic monoalcohol having 12 to 26 carbon atoms selected from undecylpentadecanol, oleyl alcohol, and octyldodecanol,
The composition comprises at least one pigment; and
A composition wherein the liquid fatty phase, the structured polymer and monoalcohol form a physiologically acceptable medium.   The composition according to claim 1, wherein the liquid fatty phase comprises at least one hydrocarbon oil.   The composition according to claim 1 or 2, wherein the liquid fatty phase comprises at least one silicone oil.   4. A composition according to any one of the preceding claims, wherein the liquid fatty phase comprises at least one volatile oil having a flash point in the range of 35 to 135 ° C.   A composition according to any one of the preceding claims, wherein the liquid fatty phase comprises at least one volatile oil having a vapor pressure in the range of 0.01 to 300 mmHg at 25 ° C. Volatile oil, isododecane, isohexadecane, C ₈ -C ₁₆ isoparaffins, composition according to claim 4 or 5 selected from isohexyl neopentanoate and isodecyl neopentanoate.   Volatile oil contains the following compounds: isododecane, octyltrimethicone, hexyltrimethicone, decamethylcyclopentasiloxane D5, octamethylcyclotetrasiloxane D4, dodecamethylcyclohexasiloxane D6, heptamethyloctyltrisiloxane, decamethyltetrasiloxane , Dodecamethylpentasiloxane, 1.5cSt (25 ° C) polydimethylsiloxane, 2cSt (25 ° C) polydimethyl-siloxane, 3cSt (25 ° C) polydimethylsiloxane, 5cSt (25 ° C) polydimethylsiloxane, and 6. A composition according to claim 4 or 5 selected from the group consisting of:   6. Composition according to claim 4 or 5, wherein the volatile oil is selected from perfluoropolyethers, perfluoroalkanes, perfluoroadamantanes, esters of perfluoroalkyl phosphates and fluorinated ester oils.   The composition according to any one of claims 1 to 8, wherein the liquid fatty phase comprises a non-volatile silicone oil.   10. A composition according to any one of claims 2 to 9, wherein the liquid fatty phase comprises at least 30% by weight of silicone oil.   The composition according to claim 4 or 5, wherein the volatile oil represents 3 to 89.4% of the total weight of the composition. The structured polymer has the formula:

Including at least one part corresponding to
In the above formula,
1) R ¹ , R ² , R ³ and R ⁴ can be the same or different;
Linear, branched or cyclic, saturated or unsaturated C ₁ to C ₄₀ hydrocarbon-based groups containing one or more oxygen, sulfur and / or nitrogen atoms in their chain And a group that may be partially or wholly substituted by fluorine atoms,
A C ₆ to C ₁₀ aryl group optionally substituted by one or more C ₁ to C ₄ alkyl groups,
Represents a group selected from a polyorganosiloxane chain which may contain one or more oxygen, sulfur and / or nitrogen atoms;
2) The radicals X can be the same or different and can contain one or more oxygen and / or nitrogen atoms in the chain, linear or branched C ₁ to C ₃₀ Represents an alkylenediyl group;
3) Y is a saturated or unsaturated C ₁ to C ₅₀ linear or branched divalent alkylene group, arylene group, cycloalkylene group, alkylarylene group or arylalkylene group, one or May contain a plurality of oxygen, sulfur and / or nitrogen atoms and / or the following atoms or groups of atoms as substituents (fluorine, hydroxyl, C ₃ to C ₈ cycloalkyl, C ₁ to C ₄₀ Alkyl, C ₅ to C ₁₀ aryl, phenyl optionally substituted by 1 to 3 C ₁ to C ₃ alkyl groups, C ₁ to C ₃ hydroxyalkyl and C ₁ to C ₆ aminoalkyl ) Which may have one of
4) Y is the formula:

Represents a group corresponding to
In the above formula,
T is linear or branched, saturated or unsaturated, optionally substituted by a polyorganosiloxane chain and optionally containing one or more atoms selected from O, N and S Represents a C ₃ to C ₂₄ trivalent or tetravalent hydrocarbon-based group, or T represents a trivalent atom selected from N, P and Al;
R ⁵ includes one or more ester groups, amide groups, urethane groups, thiocarbamate groups, urea groups, thiourea groups, and / or sulfonamide groups that may be bonded to other chains of the polymer. Represents a linear or branched C ₁ to C ₅₀ alkyl group or polyorganosiloxane chain which may be
5) The radicals G can be the same or different,

A divalent group selected from (R ⁶ represents at least 50% of the polymer radical R ⁶ represents a hydrogen atom and at least two of the polymer radicals G:

Represents a hydrogen atom or a linear or branched C ₁ to C ₂₀ alkyl group under the condition that it is a group other than
6) The composition according to any one of claims 1 to 11, wherein n is an integer in the range of 2 to 500, and m is an integer in the range of 1 to 1000. Y is
a) a linear C ₁ to C ₂₀ alkylene group,
b) a C ₃₀ to C ₅₆ branched alkylene group which may contain ring and unconjugated unsaturation,
c) C ₅ ~C ₆ cycloalkylene group,
d) a phenylene group optionally substituted by one or more C ₁ to C ₄₀ alkylene groups,
e) a C ₁ to C ₂₀ alkylene group containing 1 to 5 amide groups,
f) from C ₁ containing one or more substituents selected from a hydroxyl group, a C ₃ to C ₈ cycloalkane group, a C ₁ to C ₃ hydroxyalkyl group and a C ₁ to C ₆ alkylamine group An alkylene group of C ₂₀ , and
g) Formula:

(Wherein R ¹ , R ² , R ³ , R ⁴ , T and m are the same as defined above)
13. The composition of claim 12, which represents a group selected from: The structured polymer has the formula (II):

Including at least one portion corresponding to
In the above formula,
R ¹ and R ³ can be the same or different and are the same as defined above for formula (I) of claim 12,
R ⁷ represents the same group as defined above for R ¹ and R ³ or is of formula -XGR ⁹ , wherein X and G are for formula (I) of claim 12 Represents a group that is the same as defined above, and R ⁹ is optionally substituted by a hydrogen atom, or one or more fluorine atoms and / or one or more hydroxyl groups A linear, branched or cyclic, saturated or unsaturated C ₁ to C ₅₀ hydrocarbon-based group, optionally containing one or more atoms selected from N in the chain, or one Or represents a phenyl group optionally substituted by a plurality of C ₁ to C ₄ alkyl groups,
R ⁸ represents a group of formula -XGR ⁹ where X, G and R ⁹ are the same as defined above;
m ₁ is an integer ranging from 1 to 998;
The composition according to any one of claims 1 to 11, wherein m ₂ is an integer in the range of 2 to 500. The polymer is of formula (III) or (IV):

Including at least one part of
13. The composition according to claim 12, wherein R ¹ , R ² , R ³ , R ⁴ , X, Y, m and n are the same as defined in claim 12. X and / or Y represents an alkylene group, the alkylene part of which at least one of the following elements:
1) 1 to 5 amide groups, urea groups or carbamate groups,
2) C ₅ or a cycloalkyl group C _6, and
3) a phenylene group optionally substituted by 1 to 3 identical or different C ₁ to C ₃ alkyl groups,
And / or hydroxyl groups,
A C ₃ to C ₈ cycloalkyl group,
1 to 3 C ₁ to C ₄₀ alkyl groups,
A phenyl group optionally substituted by 1 to 3 C ₁ to C ₃ alkyl groups,
Hydroxyalkyl group from C ₁ C _3, and
A composition according to any one of claims 12 to 15 in which at least one element from C ₁ is selected from the group consisting of aminoalkyl groups C ₆ are substituted. Y is

Wherein R ⁵ represents a polyorganosiloxane chain, and T represents the formula:

Represents the group of
Wherein a, b and c are each independently an integer ranging from 1 to 10, and R ¹⁰ is a hydrogen atom or R ¹ , R ² , R ³ and R ^{4 in} claim 12 16. A composition according to any one of claims 12 to 15 which is the same group as defined. R ¹ , R ² , R ³ and R ⁴ are each independently a linear or branched C ₁ to C ₄₀ alkyl group, a polyorganosiloxane chain or 1 to 3 methyl or ethyl groups 16. A composition according to any one of claims 12 to 15 which represents an optionally substituted phenyl group. The structured polymer has at least one formula:

Part of
In which X ¹ and X ² are the same or different and have the meanings given for X in claim 12, n, Y and T are the same as defined in claim 12. R ¹¹ to R ¹⁸ is a group selected from the same groups as R ¹ to R ⁴ in claim 12, m ₁ and m ₂ are numbers in the range 1 to 1000, and p is 12. The composition according to any one of claims 1 to 11, which is an integer in the range of 2 to 500. p is in the range 1 to 25;
R ¹¹ to R ¹⁸ are methyl groups,
T is the following formula:

Wherein R ¹⁹ is a hydrogen atom or a group selected from the groups defined for R ¹ to R ⁴ and R ²⁰ , R ²¹ and R ²² are independently A formula that is a linear or branched alkylene group:

Corresponding to
m ₁ and m ₂ are in the range of 15 to 500;
X ¹ and X ² represent-(CH ₂ ) _10-
Y is, -CH ₂ - composition of claim 19 which represents the. The structured polymer has the following formula:

Including at least one part corresponding to
In which R ¹ , R ² , R ³ , R ⁴ , X, Y, m and n have the meaning given above for formula (I) in claim 12 and U is , -O- or -NH-, or
Y represents a group selected from a C ₅ to C ₁₂ alicyclic or aromatic group optionally substituted by a C ₁ to C ₁₅ alkyl group or a C ₅ to C ₁₀ aryl group, or Y Represents a linear or branched C ₁ to C ₄₀ alkylene group or a C ₄ to C ₁₂ cycloalkylene group, or
Y represents a polyurethane block or polyurea block corresponding to the condensation of several diisocyanate molecules with one or more diol or diamine type binder molecules;
formula:

Wherein d is an integer from 0 to 5, B ¹ is a group selected from the groups given above for Y, and U is —O— or —NH—. And B ² is
A linear or branched C ₁ to C ₄₀ alkylene group,
A C ₅ to C ₁₂ cycloalkylene group optionally having an alkyl or alkylene substituent,
A phenylene group optionally having a C ₁ to C ₃ alkyl substituent, and the formula:

Wherein T is a hydrocarbon-based trivalent group optionally containing one or more heteroatoms including oxygen, sulfur and nitrogen, and R ⁵ is a polyorganosiloxane chain or straight chain 12. The composition according to any one of claims 1 to 11, which is selected from the group of: a straight or branched C ₁ to C ₅₀ alkyl chain. The structured polymer has at least one formula:

Wherein R ¹ , R ² , R ³ , m ₁ and m ₂ have the meaning given to formula (I) in claim 12;
U represents O or NH;
R ²³ represents a C ₁ to C ₄₀ alkylene group optionally containing one or more heteroatoms selected from O and N, or a phenylene group,
R ²⁴ is a linear, branched or cyclic, saturated or unsaturated C ₁ to C ₅₀ alkyl group, and phenyl optionally substituted by 1 to 3 C ₁ to C ₃ alkyl groups 12. A composition according to any one of claims 1 to 11 selected from the group. The polymer used in the structured system has at least one formula:

Wherein X ¹ and X ² are the same or different and have the meanings given for X in claim 12, n, Y and T are defined in claim 12. R ¹¹ to R ¹⁸ are groups selected from the same groups as R ¹ to R ⁴ in claim 12, and m ₁ and m ₂ are in the range of 1 to 1000. 12. The composition according to any one of claims 1 to 11, wherein the composition is a number and p is an integer ranging from 2 to 500.   The structuring system is selected from ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups, urea groups, urethane groups, thiourea groups, oxamide groups, guanidino groups and biguanidino groups, and combinations thereof. 24. A composition according to any one of claims 12 to 23, further comprising a hydrocarbon-based moiety comprising two groups capable of establishing a hydrogen interaction.   25. The composition of claim 24, wherein the copolymer is a block copolymer or a graft copolymer.   26. A composition according to any one of the preceding claims, wherein the polymer represents 0.5 to 80% of the total weight of the composition.   27. The composition of claim 26, wherein the polymer represents 5 to 40% of the total weight of the composition.   28. Composition according to any one of claims 1 to 27, wherein the liquid fatty phase represents 5 to 99% of the total weight of the composition.   The composition according to any one of claims 1 to 28, wherein the monoalcohol is octyldodecanol.   30. A composition according to any one of claims 1 to 29, wherein the content of one or more monoalcohols is generally from 5 to 25% by weight.   31. A composition according to any one of the preceding claims, wherein the weight ratio of structured polymer / monoalcohol is in the range of 0.1 to 50.   32. The composition according to any one of claims 1 to 31, further comprising at least one cosmetic active agent or dermatological active agent.   33. The composition of claim 32, wherein the active agent is selected from essential oils, vitamins, humectants, sunscreens, scar-forming agents and ceramides.   34. A composition according to any one of the preceding claims, comprising at least one additive selected from fillers, antioxidants, preservatives and perfumes.   The composition according to claim 1, wherein the pigment is selected from zinc oxide, iron oxide, titanium oxide and mixtures thereof.   36. The composition according to any one of claims 1 to 35, further comprising a dye.   37. A composition according to any one of the preceding claims, provided in the form of a transparent gel or a transparent stick. A structured solid composition for balm, lipstick, or eye shadow, in an amount sufficient for application of said composition to skin, lips and / or body surface growth parts; and
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, and in the chain or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups, urea It is possible to establish hydrogen interactions selected from groups, urethane groups, thiourea groups, oxamide groups, guanidino and biguanidino groups, and combinations thereof provided that at least one group differs from the ester group A liquid continuous fatty phase structured by at least one polymer having a weight average molecular weight in the range of 500 to 500,000 containing at least one said moiety comprising at least two groups
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C .;
The liquid fatty phase has 12 to 26 carbon atoms selected from 2-butyloctanol, 2-hexyldecanol, 2-undecyldecanol, 2-undecylpentadecanol, oleyl alcohol, and octyldodecanol; Comprising at least one linear or branched aliphatic monoalcohol having
A composition wherein the pigment, the liquid fatty phase, the monoalcohol, and the structured polymer form a physiologically acceptable medium.   40. A method of cosmetic makeup for human keratin materials, comprising applying a cosmetic composition according to one of claims 1-38 to keratin materials. Said composition in a perfume oil, lipstick or eye shadow composition comprising a pigment and a liquid continuous fatty phase structured by at least one polymer (homopolymer or copolymer) having a weight average molecular weight in the range of 500 to 500,000 2-butyloctanol, 2-hexyldecanol, 2-undecyldecanol, 2-undecylpentadecanol, oleyl alcohol, to facilitate the application of the product and increase the mass and / or gloss of the composition . And a sufficient amount of at least one linear or branched aliphatic monoalcohol having 12 to 26 carbon atoms selected from octyldodecanol ,
The polymer comprises at least one portion, the portion comprising:
At least one polyorganosiloxane group consisting of 1 to 1000 organosiloxane units, in the chain of the part or in the form of a graft, and ester groups, amide groups, sulfonamido groups, carbamate groups, thiocarbamate groups Establishing hydrogen interactions selected from the group consisting of urea group, urethane group, thiourea group, oxamide group, guanidino group and biguanidino group, and combinations thereof, provided that at least one group is different from the ester group At least two groups,
Including
The polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250 ° C.
Use of the monoalcohol .