FR3108256A1 - REACTIVE TWO-STEP LIP SYSTEM - Google Patents

Abstract

Two-Step Reactive Lip System Disclosed is a two-step cosmetic, as used on the lips, wherein the basecoat includes a surface stabilized dispersion of copolymer particles, and the topcoat includes amine silicone and a viscous silicone, the viscous silicone having a viscosity of at least 100,000 centistokes when measured at a concentration by weight of 100% and using a rotational viscometer at 25 ° C. Figure: none

Description

TWO-STEP REACTIVE LIP SYSTEM

Field of invention

The present invention relates to cosmetic compositions, and in particular to two-step cosmetics, wherein the base coat includes a surface-stabilized dispersion of copolymer particles and a styrenic block copolymer, and the topcoat includes an amino silicone and a viscous silicone. .

Context

Cosmetic products such as lip glosses and other lip cosmetics are expected to have good wear and transfer resistance properties, while being non-sticky and having a glossy finish. However, this combination of characteristics is a challenge to meet, especially for products that are also intended to make lips appear fuller and/or plumper on application. Accordingly, a cosmetic product which can provide this combination of characteristics is useful and desirable.

Short summary

A first aspect of the present disclosure is a two-step reactive lip system, comprising a base coat and a top coat. The base coat is applied to the lips first, and the top coat is then applied over the base coat. The basecoat includes at least two components: a styrenic block copolymer and a dispersion of surface-stabilized copolymer particles with one or more stabilizers in a non-aqueous medium containing at least one hydrocarbon-based oil, wherein the copolymer is a C ₁ to C ₄ alkyl (meth)acrylate and maleic anhydride. The topcoat includes an amine silicone and a viscous silicone, the viscous silicone has a viscosity of at least 100,000 centistokes when measured at 100% concentration by weight and using a rotational viscometer at 25°C.

Optionally, the copolymer particles and stabilizers contain between about 10% and about 30% by weight of the one or more stabilizers, between about 50% and about 89.99% by weight of the C ₁ -C alkyl (meth)acrylate ₄ , and between about 0.01% and about 25% maleic anhydride. Optionally, the copolymer particles are present in the dispersion in an amount between about 20% and about 60% by weight of the total dispersion.

The copolymer may optionally contain between 80% and 99.99% by weight of the C ₁ to C ₄ alkyl (meth)acrylate and between 0.01% and 20% by weight of the maleic anhydride.

The one or more stabilizers may include a cycloalkyl (C ₃ -C ₁₂ ) (meth)acrylate polymer, the cycloalkyl (C ₃ -C ₁₂ ) (meth)acrylate polymer being a (meth)acrylate homopolymer cycloalkyl (C ₃ to C ₁₂ ) or a random copolymer of cycloalkyl (meth) acrylate (C ₃ to C ₁₂ ) and alkyl (meth) acrylate C ₁ to C ₄ present in a weight ratio (C ₃ -C ₁₂ )cycloalkyl (meth)acrylate/C ₁ -C ₄ alkyl (meth)acrylate greater than 4. In some systems, the one or more stabilizers include isobornyl acrylate . In some systems, only one stabilizer is used.

Optionally, the hydrocarbon oil which forms part of the non-aqueous medium within which the surface-stabilized copolymer particles are dispersed contains between 10 and 18 carbons, such as n-decane, isodecane, isodecane, n-tetradecane, or isohexadecane.

The basecoat may also contain other materials, such as at least one pigment, which may be present in the basecoat in an amount between 0.5% and 40% by weight.

With the topcoat, the amino silicone may optionally be present in a total amount between 0.5% and 40% by weight in the topcoat composition.

Optionally, the viscous silicone is a dimethiconol. Optionally, the viscous silicone is present in a total amount between about 0.1% and about 50% by weight in the topcoat composition.

A second aspect of the present disclosure is a method for imparting long wear in lip cosmetics. The process involves the application of a basecoat, then the application of a topcoat to the basecoat. The base coat is applied to the lips first, and the top coat is then applied over the base coat. The basecoat includes a dispersion of surface-stabilized copolymer particles with one or more stabilizers in a non-aqueous medium containing at least one hydrocarbon-based oil, wherein the copolymer is a C1-4 alkyl (meth)acrylate₁to C₄and maleic anhydride. The top coat includes an amino silicone and a viscous silicone, viscous silicone has a viscosity of at least about 100,000 centistokes when measured at 100% concentration by weight and using a rotational viscometer at 25°C.

Optionally, the styrenic block copolymer is a tri-block copolymer of styrene and ethylene/butylene. The styrenic block copolymer can be present in the basecoat in an amount between about 1% and about 20% by weight in the basecoat composition.

Optionally, the copolymer particles and the stabilizers contain between about 10% and about 30% by weight of the one or more stabilizers, between about 50% and about 89.99% by weight of the C ₁ to C ₄ , and between about 0.01% and about 25% of maleic anhydride. Optionally, the copolymer particles are present in the dispersion in an amount between about 20% and about 60% by weight of the total dispersion.

The copolymer may optionally contain between 80% and 99.99% by weight of the C ₁ to C ₄ alkyl (meth)acrylate and between 0.01% and 20% by weight of the maleic anhydride.

The one or more stabilizers may include a cycloalkyl (C ₃ -C ₁₂ ) (meth)acrylate polymer, the cycloalkyl (C ₃ -C ₁₂ ) (meth)acrylate polymer being a (meth)acrylate homopolymer cycloalkyl (C ₃ to C ₁₂ ) or a random copolymer of cycloalkyl (meth) acrylate (C ₃ to C ₁₂ ) and alkyl (meth) acrylate C ₁ to C ₄ present in a weight ratio (C ₃ -C ₁₂ )cycloalkyl (meth)acrylate/C ₁ -C ₄ alkyl (meth)acrylate greater than 4. In some systems, the one or more stabilizers include isobornyl acrylate . In some systems, only one stabilizer is used.

Optionally, the hydrocarbon oil which forms part of the non-aqueous medium in which the surface-stabilized copolymer particles are dispersed contains between 10 and 18 carbons, such as n-decane, isodecane, isododecane, n-tetradecane , or isohexadecane.

The basecoat may also contain other materials, such as at least one pigment, which may be present in the basecoat in an amount between 0.5% and 40% by weight.

With the topcoat, the amino silicone may optionally be present in a total amount between 0.5% and 40% by weight in the topcoat composition.

Optionally, the viscous silicone is a dimethiconol. Optionally, the viscous silicone is present in a total amount between 0.1% and 50% by weight in the topcoat composition.

As used herein, items such as " a " and " an " when used in a claim are understood to mean one or more of what is claimed or described.

As used herein, the term " about [ a number ] " is intended to include values rounded to the appropriate significant digit. Thus, "about 1" would be understood to include values between 0.5 and 1.5, while "about 1.0" would be understood to include values between 0.95 and 1.05.

As used here, the expression “ alkyl radical ” is a saturated C ₁ to C ₈ hydrocarbon group, linear or branched, in particular C ₁ to C ₆ , preferably C ₁ to C ₄ such as methyl, ethyl, isopropyl, and t-butyl.

As used herein, an " alkylene radical " is a divalent C ₁ to C ₈ saturated hydrocarbon group, linear or branched, in particular C ₁ to C ₆ , preferably C ₁ to C ₄ such as methylene, ethylene , or propylene;

As used here, the term “anhydrous” dispersion or composition refers to a dispersion or composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular devoid of water. If necessary, such small amounts of water can in particular be introduced by ingredients of the composition which can contain residual amounts.

As used herein, an " aryl radical " is a cyclic hydrocarbon based radical , aromatic unsaturated, comprising from 6 to 12 carbon atoms, mono or bicyclic, fused or not, preferably the aryl group comprises 1 ring and with 6 carbon atoms such as phenyl.

As used herein, the term " aryloxy radical " means an aryl-oxy radical, i.e., aryl-O- with aryl as defined above, preferably phenoxy.

As used herein, the expression “ aryl alkoxy ( C ₁ to C ₄ ) radical ” means an aryl-alkyl (C ₁ to C ₄ ) -O radical, preferably benzoxy.

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

As used herein, the term " between [ two numbers ] " is intended to include both of these numbers. For example, "x is between 1 and 2" is intended to cover 1 ≤ x ≤ 2. The term "x is between about 1 and about 2" would be intended to cover 0.95 ≤ x ≤ 2.05.

As used herein, the expression "cyclic radical " means a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms such as cyclohexyl or phenyl.

As used herein, the expression " cycloalkyl radical e " means a saturated cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms. carbon, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl radical potentially being substituted by one or more alkyl groups (C ₁ to C ₄ ) such as methyl, preferably the cycloalkyl radical is an isobornyl group.

As used herein, the expression “ ethylenic copolymer ” means a polymer resulting from the polymerization of two monomers: monomer a) (C ₁ to C ₄ ) alkyl acrylate (C ₁ to C ₄ alkyl ) and monomer b) of ethylenically unsaturated anhydride compound.

As used herein, the expression “ ethylenically unsaturated anhydride compound ” means a carboxylic acid anhydride compound comprising at least one ethylenic unsaturation –(R _a )C=C(R _b )–, –C(R _a )= C(R _b )–R _c or >C=C(R _a )–R _b , with R _a , R _b , and R _c , which may be the same or different, representing a hydrogen atom or an alkyl group ( C ₁ to C ₄ ) such as methyl, preferably hydrogen. In particular, the ethylenically unsaturated anhydride compound is a cyclic compound, which is preferably 5 or 6 membered, and comprising ethylenic unsaturation.

As used herein, the term " hydrocarbon oil " means an oil consisting essentially of, or consisting of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and containing no silicon or fluorine atoms. It may contain hydroxy, ester, ether, carboxylic acid, amine and/or amide groups.

As used herein, the terms " include ", " include " and " including " are intended to be non-limiting.

As used herein, the term "non- polymeric compound " refers to a compound that is not obtained directly via a monomer polymerization reaction.

As used herein, the term " oil " means a fatty substance which is liquid at room temperature (25°C) and atmospheric pressure.

As used herein, the term " non-volatile oil " refers to an oil with a vapor pressure of less than 0.13 Pa.

As used herein, the expression " silicone oil " means an oil comprising at least one silicon atom and in particular at least one Si-O group.

As used herein, the term " volatile oil " refers to an oil (or non-aqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ^-3 to 300 mmHg), preferably ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mmHg) and preferably ranging from 1.3 Pa to 1,300 Pa (0.01 to 10 mmHg) .

A first aspect of the present disclosure relates to the two compositions of a two-step reactive lip system, a base coat and a top coat. The base coat is applied to the lips first and then the top coat is applied over the base coat.

Embodiments of the disclosed basecoat are a dispersion of surface-stabilized copolymer particles with one or more stabilizers in a non-aqueous medium containing at least one hydrocarbon-based oil, wherein the copolymer is a (meth)acrylate C ₁ to C ₄ alkyl and maleic anhydride. Embodiments of the disclosed topcoat should contain an amine silicone and a viscous silicone, the viscous silicone has a viscosity of at least 100,000 centistokes when measured at 100% weight concentration and at using a rotational viscometer at 25°C. Each of these three elements will be described below in more detail.

Dispersion of surface-stabilized copolymer particles with one or more stabilizers

The dispersion of surface-stabilized copolymer particles comprises at least three components: (I) particles of at least one surface-stabilized copolymer with (II) at least one stabilizer in a preferably anhydrous medium, further containing (III) at least one hydrocarbon-based oil. Additionally, the disclosed dispersions contain particles, which are generally spherical, of at least one surface-stabilized polymer, in a non-aqueous medium.

The dispersion may be present in the basecoat in an amount between about 10% and about 70% by weight in the basecoat composition, and preferably between about 30% and about 50% by weight.

(I) Copolymer particles

The particle(s) of the dispersion is (are) constituted by one or more ethylenic copolymer(s) of (IA)alkyl (C ₁ to C ₄ )alkyl acrylate (in C ₁ to C ₄ ) and (IB) an ethylenically unsaturated anhydride compound.

According to a preferred embodiment, the copolymer constituting the copolymer particles is an acrylate copolymer:

(IA) of formula H ₂ C=C(R)-C(O)-O-R' with R representing a hydrogen atom or an alkyl group (C ₁ to C ₄ ) such as methyl, and R' representing a (C ₁ to C ₄ ) alkyl group such as methyl or ethyl, preferably a C ₁ to C ₄ alkyl (meth)acrylate; And

(IB) of an ethylenically unsaturated anhydride monomer.

Preferably, the copolymer particles are a polymer of C ₁ to C ₄ alkyl (meth)acrylate and an ethylenically unsaturated anhydride monomer. More preferably, the copolymer particles are a copolymer of C ₁ -C ₄ alkyl (meth)acrylate and maleic anhydride.

The monomers (IA) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) n-butyl acrylate and tert-butyl (meth)acrylate.

A C ₁ to C ₄ alkyl acrylate monomer is advantageously used. Preferably, (IA) is chosen from methyl acrylate and ethyl acrylate.

The polymer of the particles also comprises an ethylenically unsaturated anhydride monomer b).

Preferably, the ethylenically unsaturated anhydride compound(s) (IB) are chosen from derivatives of maleic anhydride (IB1) and itaconic anhydride (IB2):

formulas (IB1) and (IB2) in which R _a , R _b and R _c , which may be identical or different, represent a hydrogen atom or an alkyl group (C ₁ to C ₄ ); preferably, R _a , R _b , and R _c represent a hydrogen atom.

More preferentially, the ethylenically unsaturated anhydride monomer is of formula (Ib) and even more preferentially maleic anhydride.

According to a preferred embodiment, the polymer(s) of the particles comprise (comprise) or consist (consist) essentially of, from 80 to 99.99% by weight of monomer (IA) and from 0.01 to 20 % by weight of monomer (IB), based on the total weight of the polymer.

In certain embodiments, the copolymer of the particles can be: a methyl acrylate/maleic anhydride copolymer, an ethyl acrylate/maleic anhydride copolymer, or a methyl acrylate/ethyl acrylate/ maleic anhydride.

Advantageously, the copolymer particles are composed of an uncrosslinked polymer.

The copolymer particles preferably have a number average molecular weight ranging from 2,000 to 10,000,000.

The copolymer particles preferably have a number-average size ranging from 5 to 500 nm, in particular ranging from 10 to 400 nm and even better, ranging from 20 to 300 nm.

The copolymer particles may be present in the dispersion in an amount ranging from 20% to 60% by weight based on the total weight of the dispersion of surface-stabilized copolymer particles, in particular between 21% and 58.5% by weight based to the total weight of the dispersion of surface-stabilized copolymer particles, preferably ranging from 30% to 50% by weight relative to the total weight of the dispersion of surface-stabilized copolymer particles, and more preferably ranging from 36% to 42% by weight based on the total weight of the dispersion of surface-stabilized copolymer particles.

The copolymer particles may be present in the basecoat in an amount between about 2% and about 42% by weight in the basecoat composition, and preferably between about 6% and about 30% by weight, and so even more preferably between about 10% and about 21% by weight.

The C ₁ -C ₄ alkyl (meth)acrylate may be present in the basecoat in an amount between about 1.6% and about 42% by weight in the basecoat composition, and preferably between about 4.8% and about 30% by weight, and even more preferably between about 8% and about 21% by weight.

The maleic anhydride may be present in the basecoat in an amount between about 0.02% and about 8.4% by weight in the basecoat composition, and preferably between about 0.06% and about 6% by weight, and even more preferably between about 0.1% and about 4.2% by weight.

(II) One or more stabilizers

One or more stabilizers can be used. Preferably, only one type of stabilizer is used.

The stabilizers consist of ethylenic polymers chosen from (IIC) polymers of alkyl (C ₁ to C ₆ ) cycloalkyl acrylate (C ₃ to C ₁₂ ) monomers; and (IID) alkyl (C ₁ to C ₆ ) cycloalkyl (C ₃ to C ₁₂ ) acrylate and alkyl (C ₁ to C ₄ ) alkyl acrylate (C ₁ to C ₄ ).

According to a preferred embodiment of the invention, the stabilizers consist of ethylenic polymers chosen from

(IIC) polymers of monomers of formula H ₂ C=C(R)-C(O)-O-R'', R representing a hydrogen atom or an alkyl group (C ₁ to C ₄ ) such as methyl, and R'' representing a cycloalkyl group (C ₅ to C ₁₀ ) such as norbornyl or isobornyl, preferably isobornyl; And

(IID) copolymers of H ₂ C=C(R)-C(O)-O-R' and of H ₂ C=C(R)-C(O)-O-R'', R, R' and R'' being as previously defined.

In preferred embodiments, the stabilizer is an isobornyl (meth)acrylate polymer chosen from: (i) an isobornyl (meth)acrylate homopolymer and/or (ii) random copolymers of (meth)acrylate isobornyl and C ₁ to C ₄ alkyl (meth)acrylate which are preferably present in a weight ratio of isobornyl (meth)acrylate/C ₁ to C ₄ alkyl (meth)acrylate of more than 4. Advantageously, this weight ratio is from 4.5 to 19. For random copolymers, the defined weight ratio makes it possible to obtain a polymer dispersion which is stable, in particular after storage for seven days at room temperature.

In preferred embodiments, the stabilizer is: (i) an isobornyl acrylate homopolymer; (ii) a random copolymer of isobornyl acrylate/methyl acrylate; (iii) a random copolymer of isobornyl acrylate/ethyl acrylate; or (iv) a random copolymer of isobornyl acrylate/methyl acrylate/ethyl acrylate according to the weight ratio described above.

Advantageously, the sum of stabilizer(s) + copolymer particles comprises from 10% to 50% by weight of copolymers (IID) and from 50 to 90% by weight of polymers (IIC), based on the total weight of the sum of stabilizer (s) + copolymer particles.

Preferably, the sum of stabilizer(s)+copolymer particle(s) present in the dispersion comprises from 15% to 30% by weight of copolymers (IID) and from 70% to 85% by weight of polymers (IIC ), relative to the total weight of the sum of stabilizer(s)+copolymer particle(s).

In some embodiments, the surface stabilized copolymer particles comprise between about 10% and about 30% by weight of the one or more stabilizers, between about 50% and about 89.99% by weight of the alkyl (meth)acrylate C ₁ to C ₄ , and between about 0.01% and about 25% maleic anhydride.

The stabilizer may be present in the basecoat in an amount between about 0.2% and about 18% by weight in the basecoat composition, and preferably between about 0.6% and about 13% by weight, and even more preferably between about 1% and about 9% by weight.

(III) Hydrocarbon base oil

The dispersion comprises one or more identical or different, preferably identical, hydrocarbon-based oils. Hydrocarbon base oil can be volatile or non-volatile. According to a preferred embodiment, the hydrocarbon-based oil(s) is (are) volatile or is (are) a mixture of different volatile oils, more preferably chosen from isododecane and octyldodecanol. According to another particular embodiment, the hydrocarbon-based oil(s) is (are) a mixture of a volatile oil and a non-volatile oil.

The hydrocarbon-based oil can optionally be chosen from:

(i) hydrocarbon-based oils containing 8 to 14 carbon atoms, and in particular branched C ₈ to C ₁₄ alkanes, for example C ₈ to C ₁₄ isoalkanes of petroleum origin (also known as name of isoparaffins), for example isododecane (also known under the name of 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the trade names Isopar or Permethyl;

(ii) linear alkanes, for example n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also their mixtures, the mixture undecane-tridecane, the mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ) obtained in examples 1 and 2 of patent application WO 2008/155 059 in the name of the company Cognis, and mixtures thereof ;

(iii) short chain esters (containing 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate;

(iv) hydrocarbon-based oils of vegetable origin such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths varying from C ₄ to C ₂₄ , these chains being optionally linear or branched, and saturated or unsaturated; these oils are in particular heptanoic or octanoic acid triglycerides, or alternatively wheat germ oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppyseed oil, pumpkin seed oil, sesame oil, pumpkin seed oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, bancoul oil, passionflower oil and rosehip oil; shea butter; or otherwise caprylic/capric acid triglycerides, for example those sold by the company Stéarineries Dubois or those sold under the names Miglyol ^810® , ^812® and ^818® by the company Dynamit Nobel;

(v) synthetic ethers containing 10 to 40 carbon atoms;

(vi) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof;

(vii) synthetic esters such as oils of formula R ₁ C(O)-OR ₂ in which R ₁ represents a linear or branched fatty acid residue comprising from 1 to 40 carbon atoms and R ₂ represents a chain with hydrocarbon base, in particular branched, containing from 1 to 40 carbon atoms, provided that R ₁ + R ₂ ≥ 10, for example purcellin oil (cetostearyl octanoate), isopropyl myristate, palmitate isopropyl, C ₁₂ -C ₁₅ alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alkyl or polyalkyl heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters; and or

(viii) fatty alcohols which are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing 12 to 26 carbon atoms, e.g. octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol.

The dispersion may also include a silicone oil, in addition to the hydrocarbon-based oil. If a silicone oil is present in the dispersion, it is preferably in an amount which does not exceed 10% by weight based on the weight of the dispersion, more particularly in an amount of less than 5% and more preferably 2%. Silicone oil can be volatile or non-volatile.

Volatile silicone oils can include, but are not limited to, volatile linear or cyclic silicone oils, especially those with a viscosity of ≤ 8 centistokes (cSt) (8 × 10 ^-6 m ² /s), and especially containing 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms. Some embodiments use dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof .

Nonvolatile silicone oils can include, but are not limited to, linear or cyclic nonvolatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes including alkyl, alkoxy and/or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for example phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates and pentaphenyl silicone oils.

In certain embodiments, the dispersion comprises a hydrocarbon-based oil in an amount ranging from 60 to 100% by weight of the total weight of the oils present in the composition, and a silicon oil in an amount ranging from 0 to 40 % by weight of the total weight of the oils present in the composition. According to a preferred embodiment of the invention, the composition contains as oil only a hydrocarbon-based oil.

Advantageously, the hydrocarbon-based oils of the invention are apolar, that is to say, formed only of carbon and hydrogen atoms.

In certain embodiments, the hydrocarbon-based oils are preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, which are in particular volatile, more particularly the apolar oils, described above.

In certain embodiments, the hydrocarbon-based oils are preferably chosen from hydrocarbon-based oils containing from 10 to 18 carbon atoms, which are in particular volatile, more particularly the apolar oils, described previously.

Preferably, the hydrocarbon-based oil(s) of the invention is (are) isododecane.

According to another embodiment, the hydrocarbon-based oil(s) is (are) a mixture of non-volatile and volatile oils; preferably the mixture includes isododecane as the volatile oil. In particular, in the mixture, the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.

Process for preparing the dispersion

A non-limiting example of preparation of the dispersion is as follows. The polymerization is carried out in “dispersion”, ie, by precipitation of the polymer in the course of formation, with protection of the particles formed with one or more stabilizers, preferably a stabilizer.

In a first step, the stabilizers are prepared by mixing the constituent monomer(s) of the stabilizing polymers (IIC) or (IID) (mentioned above) with a free radical initiator, in a known solvent. as the synthesis solvent, and by polymerization of these monomers.

In a second step, the constituent monomers of the copolymer particles are added to the stabilizing polymer formed in the previous step and a polymerization of these added monomers is carried out in the presence of the free radical initiator.

When the non-aqueous medium is a non-volatile hydrocarbon-based oil, the polymerization can be carried out in an apolar organic solvent (synthetic solvent), followed by the addition of the non-volatile hydrocarbon-based oil (which should be miscible with said synthesis solvent) and selective elimination by distillation of the synthesis solvent.

Dye(ies) and/or pigment(s) may be added during the first step. According to another variant, the dye(s) and/or the pigment(s) are added during the second stage or after the second stage.

A synthetic solvent which is such that the monomers of the stabilizing polymer and the free radical initiator are soluble therein, and the polymer particles obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen.

In particular, the synthesis solvent which is apolar and organic is chosen, preferably it is chosen from alkanes such as heptane or cyclohexane.

When the non-aqueous medium is a volatile hydrocarbon-based oil, the polymerization can be carried out directly in said oil, which also acts as a synthetic solvent. The monomers should be soluble therein, as should the free radical initiator, and the resulting copolymer particles should be insoluble therein.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5% to 45% by weight. The total amount of monomers can be present in the solvent before the start of the reaction, or part of the monomers can be added gradually as the polymerization reaction proceeds.

The polymerization is preferably carried out in the presence of one or more free radical initiators, in particular of the type such as:

(i) peroxide, in particular chosen from tert-butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; Or

(ii) azo, in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2'-azobis(2-amidinopropane) dihydrochloride.

The polymerization is preferably carried out at a temperature ranging from 70° C. to 110° C. and at atmospheric pressure.

The copolymer particles are surface stabilized, when they are formed during polymerization, by means of the stabilizer. The stabilization can be carried out by any known means, and in particular by direct addition of the stabilizer, during the polymerization. The stabilizer is preferably also present in the mixture before polymerization of the monomers of the copolymer. However, it is also possible to add it continuously, in particular when the monomers of the copolymer are also added continuously. It is possible to use from 10% to 30% by weight and preferably from 15% to 25% by weight of the stabilizer(s) relative to the total weight of the monomers used (stabilizers (II)) + copolymer particles (I) ).

The dispersion advantageously comprises from 30% to 65% by weight of solids relative to the total weight of said dispersion and preferably from 40% to 60% by weight relative to the total weight of said dispersion.

The dispersion may comprise a quantity of particles of copolymer (I)+stabilizers (II) ranging from 1% to 50% by weight, preferably ranging from 2% to 30% by weight, relative to the total weight of the dispersion.

According to a preferred embodiment of the invention, the dispersion according to the invention is an anhydrous composition.

According to another embodiment of the present patent application, the dispersion is an inverse emulsion, i.e., of the water-in-oil (W/O) type. In this case, the composition comprises one or more surfactants, which are preferably nonionic.

Amino silicone

The topcoat preferably comprises an amino silicone. In preferred embodiments, the silicone amine is present in an amount between 0.5% and 40% by weight in the topcoat composition.

In certain embodiments, the amino silicone compounds used in the process of the invention are preferably chosen from amino alkoxysilanes, such as those of formula (IV1):

R' ₁ -Si(OR' ₂ ) _z (R' ₃ ) _x (IV1)

where R' ₁ is a linear or branched, saturated or unsaturated, cyclic or acyclic C ₁ to C ₁₀ hydrocarbon-based chain substituted by one or more groups chosen from the groups:

(i) NH ₂ primary amine or N(H)R secondary amine, R representing an alkyl group (C ₁ to C ₄ ),

(ii) aryl or aryloxy substituted by amino or (C ₁ to C ₄ )alkylamino or by amino C ₁ to C ₄ alkyl, and

(iii) aldehyde –C(O)-H, carboxy –C(O)-OH, amide –C(O)-NH ₂ or urea –NH-C(O)-NH ₂ ; R' ₁ is optionally interrupted in its hydrocarbon-based chain by one or more heteroatoms (in particular O, S, NH), a carbonyl group (CO), or one of their combinations, such as ester –C( O)-O-, or amide -C(O)-NH-, R' ₁ being linked directly to the silicon atom via a carbon atom,

R' ₂ and R' ₃ which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms, z denotes an integer ranging from 1 to 3, and x denotes an integer ranging from 0 to 2 , with z + x = 3.

Preferably, R′ ₂ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably, R′ ₂ represents a linear alkyl group, comprising from 1 to 4 carbon atoms.

Preferably, R′ ₂ represents an ethyl group.

Preferably, R′ ₃ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably, R′ ₃ represents a linear alkyl group, comprising from 1 to 4 carbon atoms.

Preferably, R′ ₃ represents a methyl or ethyl group.

Preferably, R′ ₁ is an acyclic chain.

Preferably, R' ₁ is a linear or branched, saturated or unsaturated C ₁ to C ₆ hydrocarbon-based chain substituted by an amine group NH ₂ or N(H)R, R representing a C ₁ to C ₆ , C ₃ to C ₆ cycloalkyl, or C ₆ aromatic.

Preferably, R′ ₁ is a chain based on a saturated linear C ₁ to C ₆ hydrocarbon substituted by an amine group NH ₂ .

More preferentially, R′ ₁ is a chain based on a saturated linear C ₂ to C ₄ hydrocarbon substituted by an amine group NH ₂ .

Preferably, R′ ₁ is a saturated linear C ₁ to C ₆ hydrocarbon-based chain substituted by an NH ₂ amine group.

R' ₂ represents an alkyl group comprising from 1 to 4 carbon atoms,

R′ ₃ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably, z is equal to 3.

Preferably, the amino alkoxysilane of formula (IV1) is chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane and N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane.

More preferably, the amino alkoxysilane (IV1) is selected from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane.

Even more preferably, the amino alkoxysilane (IV1) is 3-aminopropyltriethoxysilane (APTES).

The silicone polymers can also be polydialkyl (C ₁ to C ₄ )siloxanes, in particular polydimethylsiloxanes, comprising amine groups at the chain end or on side chains are in particular amino alkyl groups (C ₁ to C ₆ ) terminals or side such as aminopropyl, more particularly those of formula (IV2) or (IV3) or (IV4):

(IV2)

where R ^a and R ^b , which may be identical or different, preferably identical, represent an alkyl group (C ₁ to C ₄ ) such as methyl, alkoxy (C ₁ to C ₄ ) such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, arylalkyl (C ₁ to C ₄ ) such as benzyl, or arylalkoxy (C ₁ to C ₄ ) such as benzoxy, preferably alkyl (C ₁ to C ₄ ) such as methyl, R ^c and R' ^c , which may be identical or different, preferably identical, represent a hydrogen atom, an alkyl group (C ₁ to C ₄ ), an amino alkyl group (C ₁ to C ₄ ) or alkyl (C ₁ to C ₄ ) amino (C ₁ to C ₄ ) alkyl, preferably a hydrogen atom or an amino (C ₁ to C ₄ ) alkyl group such as aminoethyl; X represents a covalent bond, an oxygen atom, preferably a covalent bond; ALK and ALK', which may be identical or different, preferably identical, represent an alkylene group (C ₁ to C ₆ ), preferably alkylene (C ₁ to C ₄ ) such as propylene; n representing an integer greater than 2 and more particularly the value of n is such that the mass-average molecular mass of the silicone is between 500 and 55,000;

preferentially, the polydialkyl (C ₁ to C ₄ )siloxanes of formula (IV2) are of formula (IV′2) or (IV′′2) below:

(IV'2)

(IV''2)

formula (IV2) in which the value of n is such that the weight-average molecular mass of the silicone is between 500 and 55,000. As an example of aminosilicone (IV2) or (IV'2), mention may be made of those sold under the names DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32 and DMS-A35 by the company Gelest. For the formula (IV''2), R ^c , R' ^c , ALK, ALK', and n are as defined above for (IVb). Preferably, ALK and ALK' are identical and represent an alkylene group (in C ₁ to C ₄ ) such as propylene, R ^c and R ^'c are identical and represent an alkyl amino group (in C ₁ to C ₄ ) such as aminoethyl;

in particular, dimethoxysilyl ethylenediaminopropyl dimethicone (RN: 71750-80-6), under the trade name GP-RA-157, sold by Genesee Polymers can be used;

(IV3)

where R ^a , R ^b , and R ^d , which may be identical or different, preferably identical, represent an alkyl group (in C ₁ to C ₄ ) such as methyl, alkoxy (in C ₁ to C ₄ ) such as methoxy , aryl such as phenyl, aryloxy such as phenoxy, arylalkyl (C ₁ to C ₄ ) such as benzyl, or arylalkoxy (C ₁ to C ₄ ) such as benzoxy, preferably alkyl (C ₁ to C ₄ ) such as than methyl, R ^d can also represent an alkyl group (in C ₁ to C ₆ ) substituted by an alkyl group (in C ₁ to C ₄ ) amino or amino, R ^c represents a hydrogen atom or an alkyl group (in C ₁ to C ₄ ), preferably a hydrogen atom; ALK represents an alkyl group (C ₁ to C ₆ ), preferably alkylene (C ₁ to C ₄ ) such as propylene; n and m, which may be identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the mass-average molecular mass of the silicone is between 1,000 and 55,000. (C ₁ to C ₄ )siloxanes of formula (IV3) correspond to formula (IV′3) below:

(IV'3)

where the values of n and m are such that the weight average molecular weight of the silicone is between 1,000 and 55,000. As examples of silicone (IV3), mention may be made of those sold under the names AMS-132, AMS- 152, AMS-162, AMS-163, AMS-191 and AMS-1203 by the company Gelest;

(IV4)

where R ^a and R ^b , which may be identical or different, preferably identical, represent an alkyl group (C ₁ to C ₄ ) such as methyl, alkoxy (C ₁ to C ₄ ) such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, arylalkyl (C ₁ to C ₄ ) such as benzyl, or arylalkoxy (C ₁ to C ₄ ) such as benzoxy, preferably alkyl (C ₁ to C ₄ ) such as methyl, and R ^d represents an alkyl (C ₁ to C ₆ ) group optionally substituted by an alkyl (C ₁ to C ₄ ) amino or amino group, preferably alkyl (C ₁ to C ₄ ), such as isobutyl, tert -butyl or n -butyl, R ^c represents a hydrogen atom or an alkyl group (C ₁ to C ₄ ), preferably a hydrogen atom; ALK represents an alkylene group (C ₁ to C ₆ ), preferably alkylene (C ₁ to C ₄ ) such as propylene, n representing an integer greater than 2 and more particularly the value of n is such that the molecular mass average mass of silicone is between 500 and 5,000; and preferably, the polydialkyl (C ₁ to C ₄ ) siloxanes of formula (IV4) correspond to the formula (IV′4) below:

H ₂ NCH ₂ CH ₂ CH ₂ -Si(CH ₃ ) ₂ -O-[Si(CH ₃ ) ₂ -O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (IV'4)

where the value of n is such that the weight average molecular weight of the silicone is between 500 and 3000. As examples of silicones (IV4), mention may be made of the products sold under the names MCR-A11 and MCR-A12 by the Gelest company.

The amino silicone can also include amodimethicones of formula (IV5):

(IV5)

where R ^a and R ^b , which may be identical or different, preferably identical, represent an alkyl group (C ₁ to C ₄ ) such as methyl, alkoxy (C ₁ to C ₄ ) such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, arylalkyl (C ₁ to C ₄ ) such as benzyl, or arylalkoxy (C ₁ to C ₄ ) such as benzoxy, preferably alkyl (C ₁ to C ₄ ) such as methyl,

R ^c represents a hydrogen atom or an alkyl group (C ₁ to C ₄ ), preferably a hydrogen atom;

R ^e represents a hydroxyl, alkoxy (C ₁ to C ₄ ), amino or alkyl (C ₁ to C ₄ ) amino group,

R ^f represents an alkyl group (in C ₁ to C ₄ ) such as methyl, alkoxy (in C ₁ to C ₄ ) such as methoxy, a hydroxyl group or -O–(SiR ₂ ) _x -R', R representing a alkyl group (C ₁ to C ₄ ) or alkoxy (C ₁ to C ₄ ) and R' representing an alkoxy group (C ₁ to C ₄ ) or hydroxyl; preferably, R ^f represents an alkyl (C ₁ to C ₄ ), alkoxy (C ₁ to C ₄ ) or -O–(SiR ₂ ) _x -R' group, R representing an alkyl group (C ₁ to C ₄ ) such as methyl and R′ a hydroxyl or alkoxy group (C ₁ to C ₄ ) such as methoxy;

R^grepresents a hydrogen atom or an alkyl group (C₁To VS₆)

ALK and ALK', which may be the same or different, represent an alkylene group (C₁To VS₆), preferably alkylene (C₁To VS₄) such as ethylene or propylene; n and m, which may be the same or different, represent an integer greater than 2, p and x are integers greater than or equal to 0; preferably, p is between 2 and 20 and more particularly the values of m, n, p and x are such that the weight-average molecular weight of the silicone is between 2,000 and 700,000, preferably between 5,000 and 500,000; and preferably, the amodimethicones of formula (IV5) are of formula (IV'5) or (IV''5) below:

(IV'5)

where ALK represents an alkylene group (C ₁ to C ₆ ), preferably ethylene, ALK' represents an alkylene group (C ₁ to C ₆ ), preferably propylene, and m, n and p which may be the same or different , represent an integer greater than 2, m, n and p being such that the mass average molecular mass of the compound is between approximately 5,000 and 500,000; preferably, p represents an integer between 8 and 20;

(IV''5)

where R ^a and R ^b , which may be identical or different, preferably identical, represent an alkyl group (C ₁ to C ₄ ) such as methyl, alkoxy (C ₁ to C ₄ ) such as methoxy, preferably alkyl (C ₁ to C ₄ ) such as methyl, R ^c represents a hydrogen atom or an alkyl group (C ₁ to C ₄ ), preferably a hydrogen atom; R ^f represents an alkyl group (C ₁ to C ₄ ) such as methyl, alkoxy (C ₁ to C ₄ ) such as methoxy, or -O–(SiR ₂ ) _x -R', R representing an alkyl group ( C ₁ to C ₄ ) such as methyl and R′ a hydroxyl or alkoxy group (C ₁ to C ₄ ) such as methoxy; R ^g represents a hydrogen atom or an alkyl group (C ₁ to C ₆ ), ALK represents an alkylene group (C ₁ to C ₆ ), preferably ethylene, ALK' represents an alkylene group (C ₁ to C ₆ ), preferably propylene, n and m, which may be identical or different, representing an integer greater than 2, x is an integer greater than or equal to 0; preferably, the values of m, n and x are such that the weight-average molecular weight of the silicone is between 2,000 and 700,000, preferably between 5,000 and 500,000;

even more particularly, (IV''5) is represented by the formula (IV'''5)

(IV'''5)

where R ^f , R ^g , ALK, ALK', m, n are as defined for (IV''5). The amodimethicones and trimethylsiloxy amodimethicones belonging to the formula (IV''5) and the formula above are, for example, the amodimethicones and trimethylsiloxy amodimethicones of the ADM type sold by the company Wacker-Belsil®.

Mention may also be made of polydimethylsiloxanes carrying aminoethylaminopropyl groups, carrying a methoxy and/or hydroxyl function and α-ω silanols in the form of a 60% cationic aqueous emulsion (supplier's reference: Emulsion Xiameter MEM-8299 by Dow Corning or supplier reference: Belsil ADM 4000 E by Wacker).

The amino silicone can be a polydimethylsiloxane bearing an aminoethyl iminopropyl group, in the form of a stored nonionic 15% microemulsion (supplier reference: Belsil ADM Log 1).

Preferred embodiments use polydialkyl (C ₁ to C ₄ ) siloxanes comprising primary amine groups at the chain end and/or on side chains.

In preferred embodiments, the amino silicone includes diamines or triamines. When the topcoat is applied, the diamines or triamines can then react with different maleic anhydride groups, allowing a rapid crosslinking reaction to occur at normal temperatures for lipstick application (e.g., about room temperature, or about body temperature).

Viscous Silicone

Viscous silicone has a viscosity of at least about 100,000 centistokes (cSt) when measured at 100% concentration by weight and using a rotational viscometer at 25°C.

Procedure

Viscosity can be measured with a rotational viscometer such as a Brookfield Synchro-lectric viscometer or a Wells-Brookfield Cone and Plane viscometer using a method similar to ASTM D 1084 Method B or ASTIM D 4287 (for cone and plane). The temperature is maintained at 25°C and a suitable viscometer is used such as a Brookfield Synchro-lectric viscometer or a Wells-Brookfield Cone and Plane viscometer, Brookfield Engineering Laboratories, Stoughton, MA.

A container of sufficient diameter to avoid wall effects is filled with the sample to a level such that the pin can be immersed, and that air is not trapped in the sample. We select the spindle and the speed. The shaft should be centered in the bottle and the fluid level should be at the mark on the shaft. Level the viscometer. Depress the clutch and start the engine. Release the clutch and allow the dial to rotate until the motor stabilizes at a fixed point in the dial unless otherwise specified. Using the dial reading and the factor given for the model, spindle and speed used, calculate the viscosity.

If specified by the manufacturer, to calculate viscosity from "dial" readings on the viscometer (e.g., % torque), multiply by the factor listed based on spindle size and spindle speed: Viscosity (Cp) = (dial reading)*(factor). To convert to centistokes, Viscosity (cSt) = viscosity (cP) / sample density (g/cm ³ ).

The viscous silicone can be present in a total amount between 0.1% and about 50% by weight in the topcoat composition, and preferably in an amount between 5% and 30% by weight.

Viscous silicones may include, but are not limited to, silicone gums (INCI name: dimethiconol) alone or mixed with a silicone oil, such as the product marketed by Dow Corning under the name Dow Corning 1501 Fluid, which is a mixture of dimethiconol and cyclopentasiloxane in the ratio 14.7/85.3 (dimethiconol); silicone elastomers (including thermoplastic silicone elastomers) such as those marketed under the names KSG by the company Shin-Etsu; silicone waxes; and their combinations.

In one embodiment, the viscous silicones include co-emulsifiers, such as, but not limited to, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone (and) PEG-9 . The co-emulsifiers facilitate the stability of the composition. In another embodiment, the oily phase can also include cosmetically acceptable additives or adjuvants as well as cosmetic or dermatological active agents.

The basecoat and/or topcoat may also contain other ingredients, such as colorants, additional hydrocarbon-based oils, additional silicone oils, styrenic block copolymer, etc.

In some embodiments, the basecoat and/or topcoat may contain between 0% and 50% by weight of hydrocarbon-based oils or additional silicone oils in a given composition (basecoat and/or topcoat). In some embodiments, the basecoat and/or topcoat may preferably contain no additional hydrocarbon-based oils or silicone oils. In some embodiments, the basecoat and/or topcoat may preferably contain between 20% and 30% by weight hydrocarbon-based oils or additional silicone oils. In some embodiments, the additional hydrocarbon-based oil is isododecane.

Dyes

According to certain embodiments of the present application, the base layer can also use at least one colorant. In some embodiments, the colorant is a pigment, a beading agent, or a combination thereof. The combined colorants should be present in the basecoat in a total amount less than or equal to 40% by weight in the basecoat, preferably less than or equal to 30% by weight, more preferably less than or equal to 20% by weight, and even more preferably less than or equal to 15% by weight, and most preferably less than or equal to 10% by weight. In some embodiments, the combined colorants are present in the basecoat in a total amount greater than or equal to 0.001% by weight, and preferably greater than or equal to 0.5% by weight. In preferred embodiments, the combined colorants are present in the basecoat in a total amount between 0.5% and 40% by weight. In other embodiments, the combined colorants are present in the basecoat in a total amount between 0.001% and 40% by weight. In still other embodiments, the combined colorants are present in the basecoat in a total amount between 1% and 30%. In some embodiments, the combined colorants are present in the basecoat in a total amount between 5% and 30%. In some embodiments, one or more of the colorants are pigments.

In preferred embodiments, the second composition does not contain any colorant.

Suitable colorants include, but are not limited to, lipophilic dyes, pigments and beading agents, and mixtures thereof. Any colorant typically found in lipstick compositions can be used.

Suitable examples of 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 and quinoline yellow.

Suitable pigments can be white or colored, inorganic and/or organic, and coated or uncoated. Mention may be made, for example, of inorganic pigments such as titanium dioxide, optionally surface-treated, zirconium or cerium oxides and iron or chromium oxides, manganese violet, ultramarine blue, hydrate chrome and ferric blue. Mention may also be made, among the organic pigments, of carbon black, pigments of the D & C type and lakes based on cochineal flesh or based on barium, strontium, calcium or aluminum, such as D&C Red No. 10, 11, 12, and 13, D&C Red No. 7, D&C Red No. 5 and 6, and D&D Red No. 34, as well as lacquers such as D&C Yellow Lake No. 5 and D&C Red Lake No. 2.

Suitable pearlescent pigments may also be included, and may be selected from, for example, white pearlescent pigments, such as mica coated with titanium oxide or bismuth oxychloride, colored pearlescent pigments, such as mica coated titanium oxide with iron oxides, mica coated with titanium oxide with in particular ferric blue or chromium oxide, or mica coated with titanium oxide with an organic pigment of the aforementioned type, and pearlescent pigments based on bismuth oxychloride.

Color additives, such as natural extracts, may also be suitable in various embodiments. One such example is spirulina platensis extract, although other extracts may also be appropriate.

In preferred embodiments, the colorant(s) is/are present in a total amount between 0.5% and 40% by weight in the basecoat composition. In more preferred embodiments, the colorant(s) is/are present in a total amount between 1% and 30% by weight. In even more preferred embodiments, the colorant(s) is/are present in a total amount between 5% and 30% by weight. In some embodiments, one or more of the colorants is (are) pigment(s).

Styrenic Block Copolymer

The first component in the base layer is at least one styrenic block copolymer.

Suitable examples of styrenic block copolymers include the Kraton™ class of rubbers (Shell Chemical Company) or similar thermoplastic elastomers. Kraton™ rubbers are thermoplastic elastomers in which the polymer chains comprise a di-blocked, tri-blocked, multi-blocked or radial or star-blocked configuration or many mixtures thereof. Kraton™ tri-block rubbers have polystyrene (hard) segments on each end of a rubber (soft) segment, while Kraton™ di-block rubbers have a polystyrene (hard) segment attached to a rubber segment ( soft). The Kraton™ radial or star configuration can be a four-pointed or other multi-pointed star made of rubber with a polystyrene segment attached to each end of a rubber segment. The configuration of each of the Kraton™ rubbers forms separate polystyrene and rubber domains.

Each Kraton™ rubber molecule is believed to comprise sequenced segments of styrene monomer units and rubber monomer and/or co-monomer units. The most common structure for Kraton™ tri-block copolymer is the linear A-B-A block type styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/propylene-styrene, or styrene-ethylene/butylene-styrene.

The Kraton™ diblock is preferably the AB block type such as styrene-ethylene/propylene, styrene-ethylene/butylene, styrene-butadiene, or styrene-isoprene. The Kraton™ rubber configuration is well known in the art and any block copolymer elastomer of similar configuration is within the scope of the disclosure. Other block copolymers are sold under the trade name Septon (which stands for elastomers known as SEEPS, sold by Kurary, Co., Ltd) and those sold by Exxon Dow under the trade name Vector™.

Other thermoplastic elastomers useful in the present invention include block copolymer elastomers comprising styrene-butylene/ethylene-styrene (tri-block) copolymer (sometimes referred to as styrene-ethylene-butylene tri-block copolymer), of ethylene/propylene-styrene (radial or star sequence) or a mixture of the two. (Some manufacturers refer to block copolymers as hydrogenated block copolymers, eg, hydrogenated styrene-butylene/ethylene-styrene copolymer (tri-block)). A hydrogenated styrene/butadiene copolymer (Kraton G1657), commercially available from Kraton Polymers, can also be used.

Preferably, the at least one styrenic block copolymer is present in an amount ranging from approximately 1% to approximately 20% by weight of active material relative to the total weight of the base layer, preferably from approximately 5% to about 20%, more preferably about 7% to about 20%, and more preferably about 9% to about 20% by weight based on the total weight of the basecoat composition. In certain embodiments, the at least one styrenic block copolymer is present in an amount ranging from about 2% to about 15% by weight of active material relative to the total weight of the basecoat composition.

The styrenic block copolymer can be present in the basecoat in an amount between about 1% and about 20% by weight in the basecoat composition.

Example 1

Referring to the compositions listed in Tables 1 and 2, all ingredients were combined and mixed at room temperature until homogeneous. The basecoat and topcoat were then transferred to a desired container.

Table 1 – Base coat formulations disclosed

Matter Form. 1
% w/w Form. 2
% w/w Copolymer dispersion
(50% in isododecane) 15 to 25% 25 to 35% Styrenic Block Copolymer
(30% in isohexadecane) 40 to 60% 15 to 35% Isododecane 30-70% 30-70% Dyes (Pigments)
(40% in isododecane) 0.5 to 40% 0.5 to 40%

Painting 2 – Top coat formulas disclosed

Matter Form. 3
% w/w Amino silicone 0.5 to 40% Viscous silicones 0 to 99.5% Isododecane 0 to 99.5%

Ratings

The results of evaluation of the combination basecoats and topcoats are summarized in Table 3. The formulations were evaluated based on their testing for adhesion (ASTM tape resistance), and solvent resistance (ASTM tape resistance). olive oil, acetic acid (vinegar), and artificial saliva), compared to a standard commercial product.

Adhesion tests. A film of a sample was applied to a black byko-chart Black Scrub Panels P121-10N #5015 using a 1 mil spatula applicator. The films were allowed to dry at 35°C and 60% RH for 15 to 30 minutes, after which a 3 mil spatula dab of a topcoat formulation was applied to the basecoat, and then dried. allowed to dry overnight at 35°C at 60% RH. Adhesion tests were carried out on one end of the fingerboard with a spatula. A piece of ASTM standard grid tape (Intertape 51596) was placed over the sample and removed at a 180° angle. A rating scale was used to estimate the degree of sample shrinkage. For example, a rating scale such as a 1 to 3 scale can be used to estimate the degree of sample shrinkage from the substrate on the tape, where 1 is essentially no (very good) shrinkage, 2 is a some shrinkage (good), and 3 is essentially complete shrinkage (bad).

Solvent resistance. The unused portion of the samples used for the adhesion tests was then used to evaluate the solvent resistance. To assess the samples, two drops of olive oil, then two drops of artificial saliva, and two drops of 2% acetic acid were placed on 6 different sections of the film. Let stand 10 minutes. Fold a Kimwipe into a square for each drip area. Gently wipe the drop 15 times. Observe how much product wipes off on the wipe and how/if product moves on the byko-chart substrate. As a result of abrasion, the shrinkage/loss of sample on the film and the paper towel is estimated. The same grading scale described above was used to estimate the degree of sample shrinkage.

Viewable volume. The ability of the samples to provide any increase in plumpness to the lips was visually assessed. A rating scale was used to assess the plumpness of the lips before application. After application of the base coat and the top coat, the plumpness of the lips was again visually estimated.

Table 3 – Summary of assessments

Assessment 1+3 2+3 Olive oil resistance Good Good Resistance to acetic acid Very good Very good Resistance to artificial saliva Very good Very good Resistance to ASTM standard adhesive tape Very good Very good

Example not ° 2

Referring to the compositions listed in Tables 4 and 5, all ingredients were combined and mixed at room temperature until homogeneous. The basecoat and topcoat were then transferred to a desired container.

Painting 4 – Base coat formula

Matter A-Base
% w/w Copolymer dispersion
(50% in isododecane) 10 to 70% Pigments
(30% in isododecane) 1.5 to 50% Isododecane 10 to 50%

Painting 5 – Top coat formulas

Matter Finish A
% w/w Finish B
% w/w Finish C
% w/w Amino silicone 0.5 to 40% 0.5 to 40% - Viscous Silicone
(15% solids content in isododecane)

60-99.5% 80-99% Isododecane 60-99.5% - 1 to 20%

Ratings

The basecoat and topcoat evaluation results are summarized in Table 6. The formulations were evaluated based on their gloss values, adhesion tests (ASTM standard tape resistance) as described above, solvent resistance (resistance to olive oil, acetic acid (vinegar), and artificial saliva) as described above, gloss, gloss retention, compared to a product standard trade.

Topcoats containing the viscous silicone in conjunction with the amino silicone show an amazing improvement in topcoat holdout and gloss holdout. For example, the top coat containing the viscous silicone and the amino silicone (base A finish B) retains its integrity and longevity of gloss more than the same sample made without incorporation of the amino silicone in the top coat (base A finish C) . Comparing base A finish C to base A finish B, resistance in the presence of olive oil, artificial saliva and acetic acid is maintained in both cases, but the gloss and longevity values of gloss is enhanced when the amino silicone is incorporated into the topcoat with the high molecular weight silicone.

Shine. The gloss of the film is first analyzed using a gloss meter (BYK: micro-TRI-gloss) at an angle of 20° and 60°. The higher the value, the glossier the film.

Gloss retention: after the solvent resistance test, the gloss retention of the integrity of the film (in particular of the topcoat) was visually assessed. The shrinkage of the topcoat on wiping is visually estimated. Samples were estimated immediately post-wipe and 24 hours later. For samples with poor gloss retention, the gloss was reduced and the topcoat appeared broken. Good gloss retention showed no film breakage and a gloss profile equivalent to the rest of the unbroken film.

Painting 6 – Summary of evaluations

Abrasion base layer Top coat Oil Saliva Acetic acid Adhesion Shine Gloss retention AT AT 1.125 1 1 1.1 8 Finish coat retained AT B 1 1 1 1.06 61.2 Finish coat retained AT VS 1 1 1 1.04 47.2 Finish coat removed

Example 3

Referring to the compositions listed in Tables 4 and 5, all ingredients were combined and mixed at room temperature until homogeneous. The basecoat and topcoat were then transferred to a desired container.

Table 7 - Base Coat Formula

Matter E-based
% w/w Copolymer dispersion
(50% in isododecane) 10 to 70% Pigments
(30% in isododecane) 10 to 40% Styrenic Block Copolymer
(26.7% in isododecane) 10 to 40%

Table 8 - Top Coat Formulas

Matter Finish B
% w/w Finish C
% w/w Amino silicone 0.5 to 40% - Viscous Silicone
(15% solids content in isododecane) 60-99.5% 60-99.5% Isododecane - 0.5 to 40%

Ratings

The basecoat and topcoat evaluation results are summarized in Table 9. The formulations were evaluated as described above based on their gloss values, adhesion tests (resistance to ASTM adhesive tape), solvent resistance (resistance to olive oil, acetic acid (vinegar) and artificial saliva), gloss and gloss retention.

As can be seen, especially in comparison with the evaluations in Table 6, the addition of a styrenic block copolymer significantly increases the gloss, without impacting the gloss retention. As mentioned above, the addition of the amino silicone also significantly increases gloss, while improving gloss retention.

Table 9 – Summary of evaluations

Abrasion base layer Top coat Oil Saliva Acetic acid Adhesion Shine Gloss retention E B 1 1.06 1.06 1 64.2 Finish coat retained E VS 1 1 1 1 56 Finish coat removed

One of skill in the art will recognize or be able to establish using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Claims (10)

Two-step reactive lip system including:
a basecoat composition which comprises a dispersion of surface-stabilized copolymer particles with one or more stabilizers in a non-aqueous medium containing at least one hydrocarbon-based oil, the copolymer being a (meth)acrylate C ₁ -C ₄ alkyl and maleic anhydride; And
a topcoat composition that includes at least one viscous silicone and an amino silicone, wherein the viscous silicone has a viscosity of at least 100,000 centistokes when measured at 100% weight concentration and at using a rotational viscometer at 25°C. A two-step reactive lip system according to claim 1, wherein the copolymer particles surface-stabilized with one or more stabilizers comprise:
between about 10% and about 30% by weight of one or more stabilizers,
between about 50% and about 89.99% by weight of the C ₁ to C ₄ alkyl (meth)acrylate, and
between about 0.01% and about 25% maleic anhydride. A two-step reactive lip system according to claim 1, wherein the copolymer particles are present in an amount between about 20% and about 60% by weight in the dispersion. A two-step reactive lip system according to claim 1, wherein the copolymer comprises between about 80% and about c89.99% by weight of the C ₁ -C ₄ alkyl (meth)acrylate, and between about 0.01 % and about 20% maleic anhydride. A two-step reactive lip system according to claim 1, wherein the hydrocarbon oil contains between 10 and 18 carbons. A two-step reactive lip system according to claim 1, wherein the hydrocarbon oil is isodecane, isododecane, isohexadecane, n-dodecane, or n-tetradecane. A two-step reactive lip system according to claim 1, wherein the dispersion is present in the base composition in an amount between about 5% and about 75% by weight. A two-step reactive lip system according to claim 1, wherein the viscous silicone is dimethiconol. A two-step reactive lip system according to claim 1, wherein the one or more stabilizers comprise a cycloalkyl (C 3 -C 12 ) (meth)acrylate polymer, the cycloalkyl (C ₃ -C ₁₂ ) (meth)acrylate polymer ₃ to C ₁₂ ) being a homopolymer of (meth)acrylate of cycloalkyl (in C ₃ to C ₁₂ ) or a random copolymer of (meth)acrylate of cycloalkyl (in C ₃ to C ₁₂ ) and of (meth)acrylate of C ₁ to C ₄ alkyl present in a weight ratio (C ₃ to C ₁₂ cycloalkyl (meth)acrylate)/C ₁ to C ₄ alkyl (meth)acrylate of more than 4. A two-step reactive lip system according to claim 1, wherein the one or more stabilizers are isobornyl acrylate.