Flowable cosmetic compositions having unique rheological properties, polymers adapted to impart said properties and their synthesis

Abstract

A flowable cosmetic composition having unique rheological properties is provided. [Solution] The formulation comprises 0.1 to 50% by weight of a flowable branched polymer obtained by the reaction of components (A) to (C), in which component (A) is a linear polymer having a molecular weight Mw of 5,000 to 50,000 Da and having a reactive functional group X in the chain at a concentration of 0.1 to 50 mmol per 1 g of polymer, and component (B) is a linear polymer having a molecular weight Mw of 10,000 to 100,000 Da and having a terminal reactive functional group X that reacts with the functional group X in an addition or condensation reaction. The component (C) is a linear molecule or oligomer or a mixture thereof having a molecular weight of 50 to 1000 Da and has a reactive functional group Y in the molecule that reacts with the functional group X by an addition or condensation reaction, the molar ratio of the functional groups of the components (B) and (A) is 0.01 to 0.5, the molar ratio of the functional groups of the components (C) and (A) is 0.5 to 1.2, and the functional group X of the component (A) reacts with the functional groups Y of the components (B) and (C).

Description

[Technical field]

[0001] The present invention relates to a series of fluid cosmetic compositions, more precisely to non-solid cosmetic compositions having rheological properties of viscoelastic fluids suitable for producing corresponding fluid cosmetic products having specific rheological properties determined to provide extended application time, comparable film properties, long-lasting properties and non-migratory properties. The present invention also relates to polymers that can be used to impart such specific rheological properties to the cosmetic compositions, as well as to their synthesis. [Background technology]

[0002] In cosmetics, the continuous demand for sophisticated products with precise finishes, unexpected sensory experiences and advanced functionality is the driving force towards the design and conceptualization of novel cosmetic ingredients that can be crucial in creating the above mentioned effects, in particular in achieving the desired sensory changes in the final cosmetic product.

[0003] In particular, the invention described below aims to obtain a cosmetic product that has a unique feel compared to similar products on the market, which is achieved by applying the cosmetic product to the user's body without applying a force perpendicular to the flow direction (herein referred to as normal force or F). N Such forces resist thinning of the formulation between the applicator and the application surface (such as between a finger and facial skin in the case of foundation) and impart unique properties to the formulation that are evaluated.

[0004] To better understand this concept, consider naturally occurring lubricating fluids that arise from biopolymer solutions. These biopolymers, synthesized by tissues, allow secretions to be thickened and stiff: for example, mucins are glycoproteins present in mucus secretions of the respiratory and digestive tracts, which have lubricating and protective functions. The main properties of such physiological fluids are their viscous and "stringy" properties. From a rheological point of view, mucus has the so-called Weissenberg effect, which means that a fluid rotated by a stirrer rises along the rod of the stirrer itself (the "rod-rising" effect). This behavior is quite common in the case of highly branched hydrocolloid solutions, for example concentrated solutions of xanthan gum, which are highly viscous, elastic and stringy, and which exhibit the Weissenberg effect. The film and lubricating effects are due to the fact that when such a fluid is placed under the action of a direct shear force along a certain direction (for example, between two surfaces in relative motion), a force perpendicular to such direction (normal force, F) that separates the two surfaces in relative motion is generated. N ) is obtained by the fact that

[0005] Although liposoluble polymers with the above hydrocolloid properties are rare, silicone fluids are widely used in cosmetic compositions, as shown for example in US Pat. No. 5,399,633, which provides the use of alkyl-silicone elastomers, and in US Pat. No. 5,499,663, which provides the use of silicone reagents (e.g., organopolysiloxanes) in the presence of a fluid carrier that strongly characterizes the properties of the material. Depending on the molecular weight and the degree of crosslinking, different cosmetic performances and applications are obtained.

[0006] Consider now that a cosmetic composition containing a lubricating fluid is subjected to controlled flow, for example by being sandwiched between two parallel flat surfaces that are subjected to a relative rotational motion. Due to such rotational motion, the flowable cosmetic composition generates a force that separates the two surfaces from each other, which force is perpendicular to the surfaces themselves and is expressed as F N (expressed in Newtons) over the area of ​​material being shed (mm 2 (expressed as N / mm 2)

[0007] The generated F N is proportional to the shear rate and has a maximum value (F N,MAX ), after which it shows an increasing trend. N decreases.

[0008] The shear rate to be considered is 0.1 s -1 ~1000s -1 , which corresponds to the shear rate for topical application of cosmetics. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent Application Publication No. 1010715 [Patent Document 2] US Patent Application Publication No. 2012 / 156148 Summary of the Invention [Problem to be solved by the invention]

[0010] Provided are flowable cosmetic compositions having unique rheological properties, polymers adapted to impart said properties, and methods for synthesizing the same. [Means for solving the problem]

[0011] In order to achieve the above object, the present invention provides a fluid cosmetic composition comprising a formulation containing 0.1 to 50% by weight of at least one fluid branched polymer obtained by a reaction of the following components (A), (B) and (C), wherein the component (A) is a linear polymer having a molecular weight Mw of 5,000 Da to 50,000 Da (expressed in polystyrene equivalent) and having a reactive functional group X in the chain at a concentration of 0.1 to 50 mmol per 1 g of polymer, and the component (B) is a linear polymer having a molecular weight Mw of 10,000 Da to 100,000 Da (expressed in polystyrene equivalent) and having an adduct or a terminal reactive functional group Y capable of reacting with the functional group X in an addition or condensation reaction, the component (C) is a linear molecule or oligomer (or a mixture thereof) having a molecular weight of 50 Da to 1000 Da and having a reactive functional group Y in the molecule capable of reacting with the functional group X in an addition or condensation reaction, the molar ratio of the functional groups of the component (B) and the component (A) is 0.01 to 0.5, the molar ratio of the functional groups of the component (C) and the component (A) is 0.5 to 1.2, and the reactive group X of the component (A) is capable of reacting with the reactive site Y of the component (B) and the component (C). Effect of the Invention

[0012] Starting from the above mentioned principles, the present invention provides a fluid cosmetic composition, which has lubricious sensory properties as a function of the fact that it makes it possible to maintain a thickness of material between surfaces under relative motion during application (e.g. hand / face or applicator / lips) by opposing a force that is applied perpendicular to the user's body during use.

[0013] The application time or "play time" during which the cosmetic product can be applied and shaped is very long, the melting sensation (the ability of the product to melt and become uniform on the skin) occurs, and the lack of fading makes the cosmetic product highly compatible with the skin. Furthermore, the elasticity of the flowable composition used gives the product considerable film properties, without the unpleasant dryness and stiffness that accompanies the drying of the most commonly used film formers. The formation of a homogeneous and comfortable film is reflected in the highly desirable properties of the formulation's long-lasting ("long-wear") and non-migratory ("non-transferable") properties.

[0014] This behavior was achieved by incorporating a flowable branched polymer with strong elastic and lubricating properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] More precisely, according to the present invention, contrary to the teachings of Patent Documents 1 and 2, a fluid cosmetic composition has been obtained, characterized in that it has a formulation containing 0.1 to 50% by weight of at least one fluid branched polymer obtained by reaction of the following components (A), (B) and (C):

[0016] In this fluid cosmetic composition, the component (A) is a linear polymer having a molecular weight Mw of 5,000 Da to 50,000 Da (expressed in polystyrene equivalent) and having a reactive functional group X in the chain at a concentration of 0.1 to 50 mmol per 1 g of polymer, said component (B) being a linear polymer having a molecular weight Mw of 10,000 Da to 100,000 Da (expressed in polystyrene equivalents) and having a terminal reactive functional group Y of a type capable of reacting with functional group X in an addition or condensation reaction; The component (C) is a linear molecule or oligomer (or a mixture thereof) having a molecular weight of 50 Da to 1000 Da and having a reactive functional group Y in the molecule capable of reacting with a functional group X in an addition or condensation reaction; The molar ratio of the functional groups of the component (B) and the component (A) is 0.01 to 0.5 (mol Y B / mol X A ) and The molar ratio of the functional groups of the component (C) and the component (A) is 0.5 to 1.2 (mol Y C / mol X A ) and The reactive group X of the component (A) can react with the reactive site Y of the component (B) and the component (C).

[0017] The flowable branched polymer has the properties of a viscoelastic fluid with shear thinning behavior, and is thinned at 0.1 s at 20° C. between two flat plates with a diameter of 50 mm and a distance of 1 mm. -1 and 1000s -1 When rotated between shear rates of 3000 Pa, the maximum normal pressure (P N,MAX ) corresponding to a maximum normal force (F N,MAX ) can be generated.

[0018] Such branched polymers appear as viscous fluids at temperatures between 10°C and 70°C, and their viscosity decreases when subjected to shear forces ("shear thinning"); thus, such branched polymers are materials that, as they spread, reduce their viscosity parallel to the flow while at the same time generating a "cushion" effect perpendicular to the flow, resulting in unique lubricating properties.

[0019] Said components (A) and (B) can be selected from the major polymer systems used in cosmetics, such as silicones, polysaccharides, polyesters, polyethers, polyurethanes, as non-limiting examples.

[0020] The reactive functional groups X and Y can be conveniently selected from complementary reactive groups such as, but not limited to, Si-H, carboxyl, vinyl, hydroxyl, alkoxy (-O-CH3, -O-CH2CH3, -O-CH(CH3)2), amine, isocyanate, and the like.

[0021] One class of such mobile branched polymers is represented by the branched alkyl dimethicones.

[0022] In this branched polymer, the component (A) is preferably selected from polymethylhydrosiloxanes, the structural formula of which is as follows:

[0023] [ka] (where x>2; R is H or CH3)

[0024] In this branched polymer, the component (B) is preferably selected from linear polydimethylsiloxanes having terminal vinyl groups, and has the following structural formula:

[0025] [ka] (Here, n is specified so that the molecular weight Mw of the polymer is 10,000 Da to 100,000 Da).

[0026] In this branched polymer, said component (C) is preferably selected from α-olefins having the general formula CH2=CH-R, where R is an alkyl group containing from 6 to 50 carbon atoms.

[0027] Such branched polymers can be advantageously synthesized by a hydrosilylation reaction in which polymethylhydrosiloxane (A) is simultaneously reacted with vinyl-terminated polydimethylsiloxane (B) and an α-olefin (C) in the presence of a hydrosilylation catalyst (Karstedt catalyst).

[0028] Another class of such mobile branched polymers is represented by branched cellulose derivatives. In these branched polymers, the component (A) is preferably selected from cellulose derivatives, in particular ethyl cellulose, and can be selected from commercially available ethyl cellulose grades that ensure the presence of the appropriate number of hydroxyl groups in the structure. In these branched polymers, the component (B) is preferably selected from linear polyesters with terminal isocyanate groups. In these branched polymers, the component (C) is preferably selected from aliphatic monoisocyanates of the general formula O=C=NR, where R is an alkyl group containing 6 to 50 carbon atoms.

[0029] Such flowable branched polymers can be advantageously synthesized by reacting the hydroxyl of ethyl cellulose (A) with a linear polyester having terminal isocyanate groups (B) and an aliphatic monoisocyanate (C) simultaneously in the presence of a Zn-based catalyst.

[0030] A further class of such mobile branched polymers is represented by branched polyester derivatives, in which the component (A) is preferably selected from polyglycerol or polyglycerol esters, which ensure the presence of an appropriate number of hydroxyl groups in the structure. In which the component (B) is preferably selected from linear polyesters with terminal acid groups. In which the component (C) is preferably selected from aliphatic monoacids with alkyl groups containing 6 to 50 carbon atoms.

[0031] Such branched polymers can be advantageously synthesized by esterification reaction in which polyglycerol (A) is reacted simultaneously with a linear polyester diacid (B) and an aliphatic monoacid (C) in the presence of a Sn-based catalyst.

[0032] The mobile branched polymers of the present invention were unexpectedly obtained by synthesizing components (A), (B) and (C) in a single step. This ingenuity in the synthesis step and the careful selection of the molar ratio of the reactive groups of components (A), (B) and (C) are crucial aspects for the formation of mobile branched polymers with the above-mentioned rheological properties.

[0033] The use of raw materials with the described rheological behavior, such as those according to the present invention, in the formulation gives the formulation itself special properties that cannot be obtained by using conventional raw materials.In particular, the formulation obtained in this way has a long application time or "play time" and optimal wear resistance (high "long wear" and "long lasting").The rheological properties of the raw materials are inherited by the various flowable formulations described in the present invention.

[0034] Some example formulations of flowable cosmetic compositions having unique rheological properties according to the present invention are given below. EXAMPLES

[0035] The cosmetic products of the present invention, such as lip fluid, foundation, concealer, primer (Examples 1, 2, 3, 4, 5, 6 and 7), have a very special feel due to the advanced rheological properties of the materials contained therein.

[0036] Such rheological properties make the cosmetic compositions very special. The lip liquor (Example 1) is very comfortable on application and over time with a "non-transfer" effect, because the material (Sample II) forms a soft but wear-resistant thin film. The same rheological properties are maintained by the formulation with Sample V of the non-silicone lip liquor (Example 6). Unlike normal "non-transfer" cosmetic compositions, the described ones do not dry out the lips when applied and do not cause an annoying tightening effect. The fluid cosmetic compositions for the face (Examples 2, 3, 4, 5 and 7) are very comfortable on application and over time, giving a "non-transfer" effect and flexibility, due to the presence of the described ingredients (Sample I, Sample II, Sample III, Sample IV and Sample VI).

[0037] Raw materials used Sample I : A highly elastic liquid with unique properties that, when applied for a long period of time, gives a unique sensory effect. Its elasticity and soothing properties make the cosmetic composition very comfortable, soft and long-lasting on the skin.

[0038] [Table 1]

[0039] Sample II : An elastic liquid that, despite its fluidity, has a unique and very controlled sensory profile. It adheres very well and creates a thin, long-lasting film that is comfortable over time.

[0040] [Table 2]

[0041] Sample III : A high molecular weight branched alkyl silicone. The silicone properties give the material a soft feel, while the waxy (alkyl) properties give it a creamy, melty feel when applied. It can be used in all product categories and gives a pleasant creaminess.

[0042] [Table 3]

[0043] Sample IV : Fluid raw material (60°C). Partially cross-linked alkyl silicone functionalized with waxy chains. Has the function of modifying the rheology of medium to high viscosity silicone oils and fluid alkyl silicones. Viscosity-adjusted cosmetic oils are elastic and impart shine and creaminess upon application.

[0044] [Table 4]

[0045] Sample V : Branched ethyl cellulose that has fluid elasticity at temperatures below 60°C through branching and alkyl functionalization of solid raw materials at room temperature. It has the ability to modify the rheology of low polarity oils and esters.

[0046] [Table 5]

[0047] Sample VI : A partially crosslinked polyester functionalized with alkyl chains. It has the ability to modify the rheology of medium to high polarity oils and esters. This cosmetic oil is elastic and imparts shine and creaminess upon application.

[0048] [Table 6]

[0049] [Table 7]

[0050] [Table 8]

[0051] [Table 9]

[0052] [Table 10]

[0053] [Table 11]

[0054] [Table 12]

[0055]

Table 13

[0056]

Table 14

Claims

1. 1. A flowable cosmetic composition, characterized in that it has a formulation containing 0.1 to 50% by weight of at least one flowable branched polymer obtained by reaction of the following components (A), (B) and (C): said component (A) is a linear polymer having a molecular weight Mw of 5,000 Da to 50,000 Da (expressed in polystyrene equivalent) and having reactive functional groups X in the chain at a concentration of 0.1 to 50 mmol per gram of polymer; said component (B) being a linear polymer having a molecular weight Mw of 10,000 Da to 100,000 Da (expressed in polystyrene equivalents) and having a terminal reactive functional group Y of a type capable of reacting with functional group X in an addition or condensation reaction; The component (C) is a linear molecule or oligomer or a mixture thereof having a molecular weight of 50 Da to 1000 Da, and has a reactive functional group Y in the molecule capable of reacting with the functional group X in an addition or condensation reaction; The mobile branched polymer is a branched alkyl dimethicone comprising: Said component (A) is selected from polymethylhydrosiloxanes having the following structural formula: 【Chemistry 1】 (wherein x>2; y≧0; R is H or CH 3 ). Said component (B) is selected from linear polydimethylsiloxanes having terminal vinyl groups having the following structural formula: 【Chemistry 2】 (where n is specified so that the molecular weight Mw of the polymer is 10,000 Da to 100,000 Da). said component (C) being selected from α-olefins having the general formula CH 2 ═CH—R, where R is an alkyl group containing from 6 to 50 carbon atoms; the molar ratio of the functional groups of the component (B) and the component (A) is 0.01 to 0.5; the molar ratio of the functional groups of the component (C) and the component (A) is 0.5 to 1.2; the reactive group X of the component (A) is capable of reacting with the reactive site Y of the component (B) and the component (C); A flowable cosmetic composition, wherein the reaction is a simultaneous hydrosilylation reaction in the presence of a hydrosilylation catalyst.

2. 2. The fluid cosmetic composition according to claim 1, characterized in that the components (A) and (B) are polymers selected from the polymer series used in cosmetics, in particular silicones, polyesters, polyurethanes.

3. The reactive functional groups X and Y are complementary reactive groups, particularly Si-H, carboxyl, vinyl, hydroxyl, alkoxy (-O-CH 3 , —O—CH 2 CH 3 , —O—CH(CH 3 ) 2 3. The fluid cosmetic composition according to claim 1, characterized in that the compound is selected from the group consisting of aryl, arylalkyl, arylalkylphenyl ...

4. 3. The fluid cosmetic composition according to claim 1, which is a lip fluid.

5. 3. The fluid cosmetic composition according to claim 1, which is a foundation.

6. 3. The fluid cosmetic composition according to claim 1, which is a lip concealer.

7. 3. The fluid cosmetic composition according to claim 1, which is a primer.

8. 1. A flowable branched polymer for a flowable cosmetic composition, characterized in that it is the result of a reaction between the following components (A), (B) and (C): said component (A) is a linear polymer having a molecular weight Mw of 5,000 Da to 50,000 Da (expressed in polystyrene equivalent) and having reactive functional groups X in the chain at a concentration of 0.1 to 50 mmol per gram of polymer; said component (B) being a linear polymer having a molecular weight Mw of 10,000 Da to 100,000 Da (expressed in polystyrene equivalents) and having a terminal reactive functional group Y of a type capable of reacting with functional group X in an addition or condensation reaction; Component (C) is a linear molecule or oligomer or a mixture thereof having a molecular weight of 50 Da to 1000 Da, and has a reactive functional group Y in the molecule capable of reacting with the functional group X in an addition or condensation reaction; The mobile branched polymer is a branched alkyl dimethicone comprising: Said component (A) is selected from polymethylhydrosiloxanes having the following structural formula: 【Chemistry 3】 (wherein x>2; y≧0; R is H or CH 3 ). Said component (B) is selected from linear polydimethylsiloxanes having terminal vinyl groups having the following structural formula: 【Chemistry 4】 (where n is specified so that the molecular weight Mw of the polymer is 10,000 Da to 100,000 Da). said component (C) being selected from α-olefins having the general formula CH 2 ═CH—R, where R is an alkyl group containing from 6 to 50 carbon atoms; the molar ratio of the functional groups of the components (B) and (A) is 0.01 to 0.5; the molar ratio of the functional groups of the components (C) and (A) is 0.5 to 1.2; the reactive group X of component (A) is capable of reacting with the reactive moiety Y of components (B) and (C); The flowable branched polymer is characterized in that the reaction is a simultaneous hydrosilylation reaction in the presence of a hydrosilylation catalyst.

9. 9. The mobile branched polymer according to claim 8, characterized in that the components (A) and (B) are polymers selected from the polymer series used in cosmetics, in particular silicones, polyesters, polyurethanes.

10. The reactive functional groups X and Y are complementary reactive groups, particularly Si-H, carboxyl, vinyl, hydroxyl, alkoxy (-O-CH 3 , —O—CH 2 CH 3 , —O—CH(CH 3 ) 2 9. The mobile branched polymer according to claim 8, characterized in that the mobile branched polymer is selected from the group consisting of amines and isocyanates.

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