FR3112949A1 - WATER-IN-OIL EMULSIONS CONTAINING LATEX AND SILOXYSILICATE RESIN - Google Patents

Abstract

Water-in-oil emulsions containing latex and siloxysilicate resin Disclosed herein are water-in-oil (w/o) emulsion compositions for hair, eyelashes and/or eyebrows including at least one latex-containing polymer containing at least one styrene group and at least one siloxysilicate, as well as methods of preparing and using such emulsions. Preferably, the composition is a composition for eyelashes, for example a mascara composition additionally including at least one colorant.

Description

WATER-IN-OIL EMULSIONS CONTAINING LATEX AND SILOXYSILICATE RESIN

Field of invention

The present invention relates to water-in-oil (w/o) emulsions (compositions) comprising at least one polymer comprising latex comprising at least one styrene group and at least one siloxysilicate resin. The compositions have beneficial cosmetic properties including good (good) or improved wear, sebum resistance and/or water resistance properties. Significantly, the compositions also have good or improved removal properties.

Discussion of context

Mascara compositions are commonly used to enhance the appearance of eyelashes. Conventional mascara compositions generally use waxes to form crystal lattice structures to enhance curl, volume, length, thickness, and/or color of eyelashes. However, conventional mascara compositions including waxes tend to become less resistant to oil and/or sebum, causing smudging, flaking, and/or color transfer after being worn for a period of time.

Mascaras are in particular prepared on the basis of two types of formulations: aqueous mascaras qualified as cream mascaras, in the form of a dispersion of waxes in water, and anhydrous or low water content mascaras, qualified as water-resistant mascaras (qualified as “water repellent”), in the form of dispersions of waxes in organic solvents.

Aqueous mascaras mainly contain a surfactant system, for example based on triethanolamine stearate, which makes it possible to obtain a stable dispersion of agglomerated wax particles in an aqueous phase. This system plays an important role in obtaining such a dispersion, in particular at the interface in the interactions between wax particles.

However, the mascaras described above have the disadvantages, among other things, of being dry, of having poor flexibility and/or of having poor consistency. Also, consumers find it difficult to remove such mascaras from the eyelashes.

Document WO 2019/122102 relates to a direct emulsion for use on lips containing at least 10% silicone resin.

Document WO 2014/046883 relates to a cosmetic composition of powder in suspension containing particles coated with a binder composition, a silicone gel composition, and the evaporation residue of an alcohol-based composition and a process for preparing the composition.

Document WO 2010/149493 relates to a composition for making up and/or caring for keratinous materials, comprising at least one fatty phase, at least one silicone resin and at least one styrene/acrylate copolymer.

Document WO 2014/143757 relates to compositions containing a silicone resin emulsion containing 0.5% by weight to 95% by weight of a silicone resin or a pressure-sensitive adhesive (AAC), 0.1 to 90% by weight of an ethylene oxide/propylene oxide block copolymer, and a sufficient amount of water to total 100 percent by weight.

US 10,441,527 is directed to fluid compositions containing multiple components, the first of which may include a copolymer which is a cross-linked siloxane (e.g. a cross-linked aminosiloxane), a silicone polyether copolymer (e.g. a silicone polyether copolymer (AB )n), and/or a saccharide siloxane copolymer, and the second of which may include an organopolysiloxane resin and/or an acrylate copolymer.

Document FR 2968983 relates to fluid anhydrous compositions containing at least one organopolysiloxane elastomer powder coated with a silicone resin; at least one first organopolysiloxane elastomer vehicle in a first oil; at least one wax; at least one organic lacquer; and at least a second oil.

Document US 2006/0078578 relates to film-forming compositions containing a dispersed non-quaternary montmorillonite mineral and a film-forming component.

There is a need to develop a cosmetic composition, in particular for making up the eyelashes, making it possible to obtain a product that wears well, is resistant to water and to sebum, which is preferably easy to remove after use.

The present invention relates to water-in-oil (w/o) emulsion compositions for hair, eyelashes and/or eyebrows comprising at least one polymer comprising latex comprising at least one styrene group, wherein the composition comprises from about 2% to about 6% by weight based on the total weight of the composition of the polymer comprising at least one styrene group, and at least one siloxysilicate resin. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

The present invention relates to water-in-oil (w/o) emulsion compositions for hair, eyelashes and/or eyebrows comprising at least one polymer comprising latex comprising at least one styrene group, in which the composition comprises from about 2% to about 6% by weight based on the total weight of the composition of the polymer comprising at least one styrene group, at least one siloxysilicate resin, and at least one wax. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

The present invention also relates to methods for treating, caring for and/or making up the hair, the eyelashes, and/or the eyebrows by applying the compositions of the present invention to the hair, the eyelashes, and/or the eyebrows in an amount sufficient to treat, care for and/or make up hair, eyelashes and/or eyebrows. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

The present invention also relates to methods of improving the removal properties (from hair, eyebrows and/or eyelashes) of a water-in-oil (w/o) emulsion composition comprising at least one siloxysilicate resin , and optionally at least one wax, by adding at least one polymer comprising latex comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight relative to the total weight of the composition polymer comprising at least one styrene group to the composition. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

The present invention also relates to processes for preparing a water-in-oil (w/o) emulsion composition for hair, eyelashes and/or eyebrows comprising the combination of at least one polymer comprising latex comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight based on the total weight of the composition of the polymer comprising at least one styrene group to the composition, at least one siloxysilicate resin, and optionally at least a wax, to form the composition. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

Detailed description of the invention

As used herein, the term "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

Other than in the working examples, and unless otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions must be understood as being modified in all cases by the term "approximately", meaning to the nearest 10% the number indicated.

"Film former" or "film former" as used herein means a polymer or resin which leaves a film on the substrate to which it is applied, for example, after a solvent accompanying the film former has evaporated, absorbed into and/or dissipated onto the substrate.

"Transfer resistance" as used herein refers to the quality displayed by compositions which are not easily removed by contact with another material, such as, for example, an article of clothing or skin, for example. “Smudge resistance” is a type of “transfer resistance” – in the context of mascara compositions, smudges appear when the eyelashes come into contact with the skin around the eye area and the mascara transfers to the eye area. the skin in contact. Transfer resistance can be evaluated by any method known in the art for evaluating it. For example, the resistance to transfer of a composition can be evaluated by a test which can involve the application of the composition to human keratinous material such as hair, eyelashes or eyebrows followed by rubbing a material, by example, a sheet of paper, against the hair, eyelashes or eyebrows after expiration of a certain time after application, such as 2 minutes after application. Similarly, the transfer resistance of a composition can be assessed by the amount of product transferred from a wearer to any other substrate, such as transfer from an individual's hair, eyelashes or eyebrows to an article of clothing. or the skin after expiration of a certain time after applying the composition to the hair, eyelashes or eyebrows. The amount of composition transferred to the substrate (eg, collar, skin, or paper) can then be assessed and compared. For example, a composition may be transfer resistant if a major portion of the product is left on the hair, eyelashes or eyebrows of the wearer. Additionally, the amount transferred can be compared to that transferred by other compositions, such as commercially available compositions. In a preferred embodiment of the present invention, little or no composition is transferred to the substrate from the hair, eyelashes or eyebrows.

"Long-wearing" compositions as used herein refer to compositions where the color remains the same or substantially the same as when applied, as seen with the naked eye, after an extended period of time. Long-wear properties can be evaluated by any method known in the art for evaluating such properties. For example, long-term wear can be evaluated by a test involving applying a composition to human hair, eyelashes or eyebrows and evaluating the color of the composition after an extended period of time. For example, the color of a composition can be evaluated immediately after application to hair, eyelashes or eyebrows and these characteristics can then be re-evaluated and compared after a certain time. Additionally, these characteristics can be evaluated against other compositions, such as commercially available compositions.

"Water repellent" as used herein refers to the ability to repel water and permanence with respect to water. Water repellency properties can be evaluated by any method known in the art for evaluating such properties. For example, a mascara composition can be applied to false eyelashes, which can then be placed in water for a period of time, such as, for example, 20 minutes. When the pre-set time expires, the false eyelashes can be removed from the water and passed over a material, such as, for example, a sheet of paper. The extent of residue left on the material can then be assessed and compared to other compositions, such as, for example, commercially available compositions. For example, a composition can be water repellent if a major part of the product is left on the wearer, for example, the eyelashes. In a preferred embodiment of the present invention, little or no composition is transferred from the wearer.

"Substituted" as used herein means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulfonate groups, thiosulfate groups, siloxane groups , and polysiloxane groups. The substituent(s) may further be substituted.

"Volatile", as used herein, means having a flash point of less than about 100°C.

"Non-volatile", as used herein, means having a flash point of greater than about 100°C.

"Removal properties", as used herein, refers to the removal of the compositions from hair, eyebrows and/or eyelashes. “Easy removal properties” for a removal process refers to processes that are not time consuming and/or do not substantially damage hair, eyebrows and/or eyelashes. Stripping properties can be assessed, for example, by comparing the stripping ability of a composition using a stripping solvent (e.g., a water-based composition containing a soap/surfactant in an oil-based composition) with the ability to remove other compositions (including commercial compositions) using the same solvent. For example, the compositions under evaluation can be applied to hair, eyebrows and/or eyelashes (real or artificial), and allowed to dry for a designated period of time (eg, 15 minutes). Then, the number of passes it takes to completely remove the composition from the hair, eyebrows and/or eyelashes using a removal solvent and a cotton swab can be counted and compared to other compositions.

The compositions and methods of the present invention may include, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any optional ingredients, components, or limitations described herein or otherwise useful. For example, the film-forming component of the emulsion composition may "consist essentially of" or "consist of" a polymer comprising latex(es) comprising at least one styrene group and siloxysilicate resin(s).

The "film-forming component" of the emulsion composition of the present invention comprises at least one polymer comprising latex comprising at least one styrene group and at least one siloxysilicate resin. It may also optionally contain one or more additional film-forming agents. Preferably, the film-forming component contains a major part (more than 50% by weight) of polymer comprising at least one styrene group and a siloxysilicate resin, preferably more than 60% by weight, preferably more than 70% by weight, preferably more than 80% by weight, preferably more than 90% by weight, and may contain up to 100% by weight of these film formers, all percentages being based on the total weight of the two types of film formers per relative to the total weight of the film-forming component. All ranges and subranges within the percentages specified above are included herein such as, for example, 10% to 100% by weight, 25% to 90% by weight, 50% to 85% by weight, etc.

The "film-forming component" of the emulsion composition of the present invention preferably comprises from 1% to 15% by weight based on the total weight of the composition, preferably 2% to 10% by weight based on the total weight of the composition , and preferably from 3% to 8% by weight based on the total weight of the composition, including all ranges and subranges included.

In the sense of the emulsion compositions and components of the present invention which "consist essentially of" the identified ingredients, the "basic and novel properties" of such compositions and components are elimination properties.

In the sense of the methods of the present invention aimed at improving removal properties of an emulsion composition which "consists essentially of" the identified ingredients, the "basic and innovative property" of such methods is the improvement of the properties elimination of a composition.

As indicated above, the compositions of the present invention comprise "latex", which is a colloidal dispersion of polymer particles in an aqueous liquid phase. The “latex” is generally obtained by polymerization or copolymerization in suspension or emulsion of monomers according to processes which are well known to those skilled in the art. Such monomers can be chosen in particular from styrene, butadiene, acrylonitrile, chloroprene, vinyl acetate, urethanes, isoprene, isobutylene, and acrylic or methacrylic acid, maleic acid, crotonic acid or itaconic acid or their esters or amides.

Polymer comprising latex comprising at least one styrene group

In accordance with the present invention, water-in-oil emulsion compositions comprising at least one polymer comprising latex comprising at least one styrene group, wherein the composition comprises from about 2% to about 6% by weight of the weight total polymer composition comprising at least one styrene group, are provided. According to preferred embodiments, the latex is an aqueous dispersion of styrene/acrylate copolymer.

In particular, the latex preferably comprises a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one C ₁ to C ₁₈ alkyl (meth)acrylate monomer, preferably C ₁ to C ₁₂ alkyl (meth)acrylate, and preferably a C ₁ to C ₁₀ alkyl (meth)acrylate. The C ₁ to C ₁₈ alkyl (meth)acrylate monomer is preferably chosen from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, hexyl acrylate , octyl acrylate, 2-ethylhexyl acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate. As the styrene monomer which can be used in the invention, examples which may be mentioned include styrene and α-methylstyrene.

According to preferred embodiments, the polymer comprising at least one styrene group is at least one high molecular mass polymer comprising at least one styrene group. As used herein, "high molecular weight" means a weight average molecular weight of greater than 100,000 Da, preferably greater than 120,000 Da, preferably greater than 135,000 Da, and preferably greater than 150,000 Da, including all included ranges and sub-ranges such as, for example, 100,000 Da – 500,000 Da, 120,000 Da to 600,000 Da, 150,000 Da to 200,000 Da, etc.

Any styrene acrylate copolymer or derivative thereof may be suitable for use in the compositions of the present invention. The polymer comprising latex comprising at least one styrene group preferably has a glass transition temperature (Tg) ranging from about -15°C to about 90°C, such as from about 0°C to about 50°C, such as about 5°C to about 25°C, such as about 10°C to about 20°C, inclusive of all ranges and subranges included. For example, a copolymer comprising (1) styrene and ammonium acrylates, (2) acrylates, and/or (3) acrylic groups is suitable. A particularly preferred copolymer is styrene/acrylates/ammonium methacrylate copolymer or styrene acrylic copolymer, commercial examples of which include SYNTRAN 5620 and SYNTRAN 5760 (with or without paraben), from Interpolymer Corporation; JONCRYL 77, by BASF Performance Chemicals; and RHOPLEX P376, from Dow Chemical Company.

Preferably, the polymer comprising latex comprising at least one styrene group is present in the compositions of the present invention in an amount ranging from about 5% to about 15%, more preferably from about 5% to about 12% , and preferably from about 5% to about 8%, by weight, based on the total weight of the composition, including all ranges and subranges included. The polymer comprising latex comprising at least one styrene group comprises (1) a polymer comprising at least one styrene group; and (2) a liquid phase carrier for the polymer.

According to preferred embodiments, the polymer comprising at least one styrene group is present in an amount ranging from approximately 2% to approximately 6%, preferably from approximately 2.25% to approximately 5.5%, and preferably from about 2.5% to about 5%, by weight, based on the total weight of the composition, including all ranges and subranges included.

Surprisingly, it has been found that water-in-oil (w/o) emulsion compositions comprising at least one siloxysilicate resin, and optionally at least one wax, containing the polymer comprising at least one styrene group in amounts to both below and above the identified concentration range have inferior removal properties compared to such emulsions containing the polymer comprising at least one styrene group in amounts within the identified concentration range. Also surprisingly, it was found that such an increase in removability properties in the identified concentration range is generally independent of the amount of siloxysilicate resin present in the emulsions.

Siloxysilicate resin

According to the present invention, compositions comprising at least one siloxysilicate resin are provided. Siloxysilicate resins generally have the formula:

[(R) ₃ SiO] _x (SiO _4/2 ) _y

where R is an alkyl group preferably comprising 1 to 8 carbon atoms. A non-limiting example of a siloxysilicate in accordance with the present invention is trimethylsiloxysilicate, which can be represented by the following formula:

[(CH ₃ ) ₃ SiO] _x (SiO _4/2 ) _y .

In the above formulas, x and y preferably vary between numbers such as, 10 and 150, 25 and 125, 35 and 100, and 50 to 80, for example.

Preferred siloxysilicate resins are commercially available from General Electric, Dow Corning, Wacker, Milliken, Siltech, Grant Industries, Momentive and Shin-Etsu Silicones under the trade name Resin MQ®.

The at least one siloxysilicate resin is preferably present in the compositions of the present invention in an amount of less than 15% by weight, preferably less than 10% by weight, inclusive of all ranges and sub-ranges included such that, for example, 1% to 15% by weight, 3% to 12% by weight, 1% to 10% by weight, 3% to 8% by weight, etc., all weights being based on the weight of the composition in its entirety.

Although not wishing to make any theory, in general, compositions comprising at least one polymer comprising latex comprising at least one styrene group and at least one siloxysilicate resin have good or improved removal properties while maintaining beneficial cosmetic properties including good (good) or improved wear, sebum resistance and/or water resistance properties. Since both the latex and the siloxysilicate resin are expected to increase the long wear properties of a composition, it can be expected that an increase in concentrations of both in a composition results in a corresponding increase in the difficulty of elimination. However, contrary to this expectation, it was surprisingly found that at concentrations of about 2% to about 6%, such amounts of polymer comprising at least one styrene group did improve the removal properties of compositions, including in mascara compositions containing low levels of wax, whereas concentration levels either side of this range resulted in emulsions having inferior removal properties.

According to particularly preferred embodiments, the combined amount of siloxysilicate resin and polymer comprising at least one styrene group present is from about 5% to 25% by weight, preferably from about 7.5% to about 20% , preferably from about 10% to about 15% by weight based on the total weight of the composition, including all ranges and subranges included within these ranges. Also, the weight ratio of siloxysilicate resin to polymer having at least one styrene group present is preferably from 1:1 to about 5:1, preferably from about 2:1 to about 4:1.

Water

According to the present invention, compositions comprising water are provided. The compositions of the present invention comprise sufficient water to form a water-in-oil emulsion, preferably from about 5% to about 80% water, more preferably from about 10% to about 50% water. water, and more preferably from about 15% to about 30% water by weight based on the total weight of the composition, including all ranges and subranges included.

Oil

According to the present invention, compositions comprising at least one oil are proposed. The compositions of the present invention comprise sufficient oil to form a water-in-oil emulsion, preferably from about 5% to about 80% oil, more preferably from about 10% to about 50% oil. oil, and more preferably from about 15% to about 30% oil by weight based on the total weight of the composition, inclusive of all ranges and subranges included.

Suitable oils include volatile and/or non-volatile oils. Such oils can be any acceptable oil including, but not limited to, silicone oils and/or hydrocarbon oils.

According to some embodiments, the oil carrier comprises one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature of less than or equal to 6 cSt and comprising 2 to 7 silicon atoms, these silicones being optionally substituted by alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that can be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof. Other volatile oils that can be used include KF 96A with a viscosity of 6cSt, a commercial product from Shin Etsu with a flash point of 94°C. Preferably, the volatile silicone oils have a flash point of at least 40°C.

Non-limiting examples of volatile silicone oils are listed in Table 1 below.

Compound Flash point
(°C) Viscosity
(cSt) Octyltrimethicone
Hexyltrimethicone
Decamethylcyclopentasiloxane
(cyclopentasiloxane or D5)
Octamethylcyclotetrasiloxane
(cyclotetadimethylsiloxane or D4)
Dodecamethylcyclohexasiloxane (D6)
Decamethyltetrasiloxane(L4)
KF-96 A from Shin Etsu
PDMS (polydimethylsiloxane) DC 200 (1.5cSt) from Dow Corning
PDMS DC 200 (2cSt) from Dow Corning 93
79
72

55

93
63
94
56

87 1.2
1.2
4.2

2.5

7
1.7
6
1.5

2

Additionally, a volatile linear silicone oil can be employed in the present invention. Suitable volatile linear silicone oils include those described in U.S. Patent No. 6,338,839 and WO03/042221. In one embodiment, the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, the decamethyltetrasiloxane is further combined with another solvent which is more volatile than the decamethyltetrasiloxane.

According to other embodiments, the oil carrier comprises one or more non-silicone volatile oils and can be chosen from volatile hydrocarbon oils, volatile esters and volatile ethers. Examples of such volatile non-silicone oils include, but are not limited to, volatile hydrocarbon oils of 8 to 16 carbon atoms and mixtures thereof and in particular branched C ₈ to C ₁₆ alkanes such as isoalkanes in C ₈ to C ₁₆ (also known as isoparaffins), isododecane, isodecane, and for example, the oils sold under the trade names of Isopar or Permethyl. Preferably, the volatile non-silicone oils have a flash point of at least 40°C.

Non-limiting examples of volatile non-volatile silicone oils are given in Table 2 below.

Compound Flash point (°C) Isododecane
Propylene glycol n-butyl ether
Ethyl 3-ethoxypropionate
Propylene glycol methyl ether acetate
Isopar L (isoparaffin C ₁₁ to C ₁₃ )
Isopar H (isoparaffin C ₁₁ to C ₁₂ ) 43
60
58
46
62
56

The volatility of solvents/oils can be determined using the evaporation rate as specified in U.S. Patent No. 6,338,839.

According to other embodiments of the present invention, the oil carrier comprises at least one non-volatile oil. Examples of non-volatile oils that can be used in the present invention include, but are not limited to, polar oils such as:

- hydrocarbon-based vegetable oils with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids of which may have various chain lengths, these chains possibly being linear or branched, and saturated or unsaturated ; these oils are in particular wheat germ oil, corn oil, sunflower oil, shea butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy seed oil, pumpkin oil, sesame seed oil , pumpkin seed oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant seed oil, evening primrose oil, millet oil , barley oil, quinoa oil, olive oil, rye oil, safflower oil, bancoul oil, passion flower oil, or rosehip oil; or caprylic/capric acid triglycerides, for example those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

- synthetic oils or esters of formula R ₅ COOR ₆ in which R ₅ represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including 7 to 19 carbon atoms, and R ₆ represents a chain based on a branched hydrocarbon containing 1 to 40 carbon atoms, of which 3 to 20 carbon atoms, with R ₆ + R ₇ ≥ 10, such as, for example, Purcellin's oil (cetostearyl octanoate), isononanoate isononyl, C ₁₂ to C ₁₅ alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters, for example isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

- synthetic ethers containing 10 to 40 carbon atoms;

- C ₈ to C ₂₆ fatty alcohols, for example oleyl alcohol, cetyl alcohol, stearyl alcohol, and cetearyl alcohol; And

- their mixtures.

Further, examples of non-volatile oils that can be used in the present invention include, but are not limited to, non-polar oils such as branched and unbranched hydrocarbons and hydrocarbon waxes including polyolefins, particularly petroleum jelly (petrolatum), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene , polybutene, mineral oil, pentahydrosqualene, and mixtures thereof.

The compositions of the present invention may optionally further comprise any additive usually used in the field(s) considered. For example, waxes, dispersants, antioxidants, sunscreens, preservatives, perfumes, fibers, fillers, neutralizing agents, cosmetic and dermatological active agents such as, for example, emollients, moisturizers, vitamins, essential fatty acids, surfactants, elastomers of silicone, pasty compounds, viscosifiers, eg, fat-soluble/fat-dispersible polymers, additional film-forming agents, colorants, and mixtures thereof can be added. A non-exhaustive listing of such ingredients can be found in US Patent Application Publication Nos. 2004/0170586 and 2009/0142289. Additional examples of suitable additional components can be found in the other references. Still other examples of such additional ingredients can be found in The International Cosmetic Ingredient Dictionary and Handbook ( ^9th ed. 2002).

According to preferred embodiments of the present invention, compositions further comprising at least one wax are provided.

“Wax” means a lipophilic compound, solid at room temperature (25°C), with a reversible solid/liquid state change, having a melting point greater than or equal to 30°C.

The waxes used in accordance with the present invention can be any wax and are not particularly limited. The waxes can be hydrocarbon, fluorinated and/or silicone, and be of vegetable, mineral, animal and/or synthetic origin.

Suitable examples of waxes include, but are not limited to, carnauba wax, candelilla wax, BIS-PEG-12 DIMETHICONE CANDELILLATE wax such as, for example, Siliconyl Candelilla Wax marketed by the company KOSTER KEUNEN, hydrogenated jojoba such as for example that marketed by the company DESERT WHALE, hydrogenated palm oil such as that marketed by the company SIO, rice bran wax, sumac wax, ceresin waxes, laurel wax , Chinese insect wax, lacquer wax, hydrogenated olive oil such as Waxolive from SOLIANCE, waxes obtained by hydrogenation of olive oil esterified with fatty alcohols with a C ₁₂ chain at C ₁₈ such as those sold by the company SOPHIM under the trade names Phytowax Olive 12L44, 14L48, 16L55 and 18L57, the waxes obtained by hydrogenation of castor oil esterified with cetyl or behenyl alcohol such as for example those which are sold s under the names Phytowax Ricin 16 L 64 and Phytowax Ricin 22 L 73 by the company SOPHIM, hydrogenated camelina wax, ouricury wax, lignite wax, ozokerite waxes such as for example Wax SP 1020 P marketed by the company Strahl & Pitsch, microcrystalline waxes such as for example those sold under the trade name Microwax HW by the company PARAMELT, triglycerides of lauric, palmitic, cetyl and stearic acid (INCI name: hydrogenated coco glycerides) such as for example those sold under the trade name Softisan 100 by the company SASOL, polymethylene waxes such as for example those sold under the trade name Cirebelle 303 by the company SASOL, polyethylene waxes such as for example those sold under the trade names Performalene 400 polyethylene, Performalene 655 polyethylene and Performalene 500-L polyethylene by the company New Phase Technologies, alcohol-polyethylene waxes such as for example the one marketed under the name Performacol 425 Alcohol by the company BARECO, the 95/5 ethylene/acrylic acid copolymer sold under the trade name AC 540 wax by the company Honeywell, hydroxyoctacosanyl hydroxystearate such as by example that sold under the trade name Elfacos C 26 by the company AKZO, octacosanyl stearate such as for example that sold under the name Kester Wax K 82H by the company KOSTER KEUNEN, stearyl stearate such as for example that sold under the name Liponate SS by the company LIPO CHEMICALS, pentaerythritol distearate such as for example that marketed under the name Cutina PES by the company COGNIS, the mixture of dibehenyl adipate, dioctadecyl adipate and di-eicosanyl adipate (INCI name C ₁₈ -C ₂₂ dialkyl adipate), the mixture of dilauryl adipate and ditetradecyl adipate (INCI name: C ₁₂ to C ₁₄ dialkyl adipate), the mixture of dioctadecyl sebacate, didocosyl sebacate and dieicosyl (INCI name: C ₁₈ -C ₂₂ dialkyl sebacate) and the mixture of dioctadecyl octadecanedioate, didocosyl octanedioate and dieicosyl octanedioate (INCI name: C ₁₈ -C ₂₂ dialkyl octanedioate) such as for example those marketed by the company COGNIS, pentaerythrityl tetrastearate such as for example Liponate PS-4 from the company Lipo Chemicals, tetracontanyl stearate such as for example Kester Wax K76H from the company KOSTER KEUNEN, stearyl benzoate such as for example Finsolv 116 from the company FINETEX, behenyl fumarate such as for example Marrix 222 from AKZO BERNEL, di-(trimethylol-1,1,1-propane) tetrastearate such as for example that offered under the name "HEST 2T-4S by the company HETERENE, didotriacontanyl distearate such as, for example, Kester Wax K82D from the company KOSTER KEUNEN, polyethylene glycol montanate with 4 ethylene oxide units (PEG-4) such as, for example, that which is sold under the common name ercial Clariant Licowax KST1, hexanediol disalicylate such as for example Betawax RX-13750 marketed by the company CP Hall, dipentaerythritol hexastearate such as for example that which is sold under the trade name Hest 2P-6S by the company HETERENE , ditrimethylolpropane tetrabehenate such as for example that which is sold under the trade name Hest 2T-4B by the company HETERENE, jojoba esters such as for example that which is sold under the trade name Floraester HIP by the company FLORATECH, the mixtures of saturated linear carboxylic acid hydrocarbons (C ₂₀ to C ₄₀ ) (INCI name: C ₂₀ -C ₄₀ acid polyethylene) such as for example Performacid 350 acid from the company NEW PHASE TECHNOLOGIES, a synthetic wax of the Fischer type -Tropsch such as that marketed under the name Rosswax 100 by the company ROSS, cetyl alcohol, stearyl alcohol, behenyl alcohol, dioctadecyl carbonate such as for example Cutina KE 3737, polyb sucrose ehenate such as, for example, Crodaderm B from the company CRODA, and mixtures thereof, may in particular be cited. Such waxes are also described in US Patent Application Publication No. 2009/0142289.

Waxes of vegetable origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumac wax, waxes obtained by hydrogenation of olive oil esterified with fatty alcohols with a C ₁₂ chain at C ₁₈ sold by the company SOPHIM in the Phytowax range (12L44, 14L48, 16L55 and 18L57), rice bran wax, cetyl, stearyl and behenyl alcohols, laurel wax and ouricury wax are preferably used.

If present, the wax(es) is (are) preferably present in an amount of at least 5% by weight, preferably about 5 to about 35% by weight, preferably from about 7.5 to about 30% by weight, and preferably from about 10 to about 25% by weight based on the total weight of the composition, including all ranges and under -beaches included.

According to preferred embodiments, the compositions of the present invention comprise at least one polyorganosiloxane copolymer. The polyorganosiloxane copolymer useful herein is preferably a polymer (homopolymer or copolymer) having at least one moiety which contains: at least one polyorganosiloxane group consisting of 1 to about 1000 polyorganosiloxane units in the chain of the moiety or as a graft, and at least two groups capable of establishing hydrogen interactions. Non-limiting examples of polyorganosiloxane copolymers are disclosed, for example, in U.S. Patent No. 8,945,525.

Additional polyorganosiloxane copolymers which may be used in the long wear lip compositions of the present invention include those described in US 5,874,069, US 5,919,441, US 6,051,216, and US 5,981,680.

A preferred polyorganosiloxane copolymer for use in the present invention contains at least one moiety selected from formula (III):

and the formula (IV)

in which :

(a) R ¹ , R ² , R ³ and R ⁴ are the same or different and can be selected from the group consisting of methyl, ethyl, propyl, isopropyl, a siloxane chain, and phenyl;

(b) X is straight or branched chain alkylene having 1 to 30 carbons;

(c) Y is selected from the group consisting of straight or branched chain alkylenes having 1 to 40 carbons;

(d) m is a number between 1 and 700;

(e) n is a number between 1 and 500.

Particularly preferred polyorganosiloxane copolymers useful herein are commercially available from Dow Corning under the tradenames DC 8178® and DC 8179®, which are known under the INCI designation Nylon-611/Dimethicone Copolymer.

If present, the polyorganosiloxane copolymer is preferably present in the compositions of the present invention in an amount ranging from about 1% to about 35% by weight, preferably from about 5% to about 25% by weight, and preferably from about 7% to about 15% by weight, inclusive of all ranges and subranges, all weights being based on the weight of the composition as a whole.

Suitable fillers and/or viscosity increasing agents include silicate clays such as, for example, silicate clays containing at least one cation which may be selected from calcium, magnesium, aluminum, sodium, potassium, and lithium cations, and their mixtures. Non-limiting examples of such products include smectite clays such as montmorillonites, hectorites, bentonites, beidellites, saponites, vermiculites, stevensite, and chlorites. Preferred clays are synthetic silicate clays, most preferably lithium magnesium sodium silicate, commercially available from Rockwood under the trade name Laponite®. Other preferred examples of silicate clays which can be used in the present invention are selected from lithium magnesium silicate, calcium sodium aluminum silicate, calcium magnesium silicate, sodium magnesium silicate, calcium aluminum, magnesium aluminum silicate, sodium potassium aluminum silicate, and sodium silver aluminum silicate.

If present, the filler and/or viscosity enhancing agent is preferably present in the compositions of the present invention in an amount of 0.1% to 10% by weight , preferably in an amount of 0.5% to 7%, preferably in an amount of 1% to 5% by weight, based on the total weight of the composition.

According to preferred embodiments of the present invention, the compositions may further comprise a desired agent. The desired agent can be, for example, any colorant (pigment, dye, etc.), fiber or any additional film-forming agent known in the art.

Acceptable colorants include pigments, dyes, such as oil-soluble dyes, pearlescent pigments, and pearlescent agents.

Dyes Representative fat-soluble oils that can be used in accordance with the present invention include Sudan Red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, Annatto, and quinoline.

Representative pearlescent pigments include white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and pearlescent pigments based on bismuth oxychloride.

Representative pigments include white, colored, inorganic, organic, polymeric, non-polymeric, coated and uncoated pigments. Representative examples of inorganic pigments include titanium dioxide, optionally surface treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, hydrated chromium, and ferric blue. Representative examples of organic pigments include carbon black, D & C type pigments, and lakes based on cochineal carmine, barium.

Suitable fibers include, but are not limited to, fibers which provide an improved elongation effect. "Fiber" should be taken to mean an object of length L and diameter D such that L is much larger than D, D being the diameter of the circle in which the cross-section of the fiber is inscribed. In particular, the L/D ratio (or form factor) is chosen in the range going from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150. The fibers which can be used in the composition of the invention may be fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or structured, for example, braided, hollow or solid. They can be of any shape and in particular of circular or polygonal cross-section (square, hexagonal or octagonal) depending on the specific application envisaged. In particular, their ends are blunted and/or polished to avoid injury. They can be rigid or non-rigid fibers. They can be of synthetic or natural origin, mineral or organic. They can be surface treated or not, coated or not, and colored or not.

If present, the desired agent is preferably present in the compositions of the present invention in an amount of 0.1% to 30% by weight, preferably in an amount of 0.5% to 25%, of preferably in an amount of 1% to 20% by weight, based on the total weight of the composition.

According to other preferred embodiments, methods of treating, caring for and/or enhancing the appearance of the hair, eyebrows or eyelashes by applying the compositions of the present invention to the hair, eyebrows or eyelashes in an amount sufficient to treat, caring for and/or strengthening the appearance of the hair, eyebrows or eyelashes are offered. In accordance with these preceding preferred embodiments, the compositions of the present invention are applied topically to the desired area of the hair, eyebrows or eyelashes in an amount sufficient to treat, care for and/or enhance the appearance of the hair, eyebrows or eyelashes. The compositions may be applied to the desired area as needed, preferably once or twice daily, more preferably once daily and then preferably allowed to dry before subjecting to contact such as with clothing or other objects (eg. example, a topcoat). Preferably, the composition is allowed to dry for about 1 minute or less, more preferably for about 45 seconds or less. The composition is preferably applied to the desired area which is dry or has been dried before application, or to which a base has been previously applied.

According to a preferred embodiment of the present invention, compositions having improved cosmetic properties such as, for example, an increased removal capacity from the hair, eyebrows or eyelashes to which they have been applied are provided. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

According to a preferred embodiment of the present invention, methods of improving the removal properties (from hair, eyebrows and/or eyelashes) of a water-in-oil (w/o) emulsion composition comprising at least one siloxysilicate resin, and optionally at least one wax, by adding at least one polymer comprising latex comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight based to the total weight of the composition of the polymer comprising at least one styrene group to the emulsion composition, resulting in enhanced removal properties of the emulsion composition, are provided. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

According to a preferred embodiment of the present invention, methods for preparing a water-in-oil (w/o) emulsion composition for hair, eyelashes and/or eyebrows comprising the combination of at least one polymer comprising latex comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight based on the total weight of the composition of the polymer comprising at least one styrene group and at least one siloxysilicate resin, and optionally at least one wax, to form the emulsion composition are provided. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, etcetera used in the specification and the claims are to be understood as being modified in all cases by the term "about". Accordingly, unless otherwise indicated, the numerical parameters specified in the following specification and appended claims are approximations which may vary depending on the desired properties which the present invention seeks to achieve.

Although the numerical ranges and parameters specifying the broad scope of the invention are approximations, the numerical values specified in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without thereby limiting its scope. Percentages are given on a weight basis.

Examples

Example 1 - Typical mascara composition

Total %100.00 Phase Chemical name % w/w AT Surfactants 5 AT Raincoats 15 AT Oils 25 AT Conservatives 1 AT Dyes – Iron oxides 8 AT Water QS AT Polyol 2 AT Trimethylsiloxysilicate 8 AT clays 3 B Styrene/Acrylates/Ammonium Methacrylate Copolymer 4

Typical procedure for preparing compositions of the present invention

In a metal container A, all phase A materials were added and heated to 90°C.

When metal container A was at 90°C, they were homogenized for 30 minutes at 2000 rpm.

After the mixture was uniform and cooled to 45°C, B was added later, and mixed for 10 min.

The batch was cooled to 30°C.

Example 2 – Determination of elimination properties

Water-in-oil emulsions were prepared containing the same basic ingredients but varying amounts of (1) styrene/acrylates/ammonium methacrylate copolymer containing latex (ranging from 0% to 10%); (2) MQ resin in combination with nylon 611/dimethicone (ranging from 0% to 16.7%); and (3) waxes (ranging from 17% to 25.5%) and their removal properties were tested as follows:

Compositions were applied to artificial eyelashes and allowed to dry at room temperature. Once dried, the compositions were subjected to contact with removal solvent (makeup remover) using a cotton pad until the composition was completely removed from the eyelashes. The number of passes it took to completely remove the compositions from the eyelashes were counted and recorded, with 4 = easy removal; 5 = good elimination; 6 = bad elimination; and 7 = difficult elimination.

Compositions containing an MQ resin, and optionally at least one wax, containing from about 2% to about 6% styrene/acrylates/ammonium methacrylate copolymer have been found to possess easy or good removal properties, while that compositions containing the copolymer in amounts outside the range of 2% to 6% possessed poor or difficult removal properties. It was also found that the removal properties were generally not affected by the amount of MQ resin present in the compositions.

Claims (10)

A water-in-oil emulsion composition comprising (a) water, (b) at least one oil, (c) at least one polymer comprising latex comprising at least one styrene group, wherein the composition comprises about 2% to about 6% by weight based on the total weight of the composition of the polymer comprising at least one styrene group, and (d) at least one siloxysilicate resin. Composition according to Claim 1, in which the polymer comprising at least one styrene group is a copolymer comprising (1) styrene and ammonium acrylates, (2) acrylates, and/or (3) acrylic groups. Composition according to any one of the preceding claims, in which the polymer comprising at least one styrene group is a copolymer of styrene/acrylates/ammonium methacrylate. A composition according to any preceding claim, wherein the siloxysilicate resin is a trimethylsiloxysilicate resin. A composition according to any preceding claim, further comprising at least one wax in an amount from about 10% to about 25% by weight of the total weight of the composition. A composition according to claim 1, further comprising at least one silicate clay. A composition according to any preceding claim, wherein the siloxysilicate resin is present in an amount of from about 1% to about 10% by weight of the total weight of the composition. A composition according to any preceding claim, wherein the weight ratio of siloxysilicate resin to polymer comprising at least one styrene group ranges from about 2:1 to about 4:1. Composition according to any one of the preceding claims, in the form of a mascara. A composition according to any preceding claim, further comprising a colorant.