HK1124629B

HK1124629B - Use of thermoplastic elastomers in a composition and compositions thereof

Info

Publication number: HK1124629B
Application number: HK09101507.5A
Authority: HK
Inventors: J．C．布拉姆斯; P.迈特拉; 郑涛; D．A．宾德
Original assignee: 雅芳产品公司
Priority date: 2005-12-21
Filing date: 2006-12-14
Publication date: 2013-08-02

Description

Use of thermoplastic elastomers in one or more compositions thereof

Technical Field

The present invention relates generally to compositions for forming films on surfaces and uses thereof.

Background

Cosmetic, personal care and pharmaceutical compositions comprising a film-forming polymer intended for application to biological surfaces to improve adhesion, long-lasting effect and protect skin and nails and a colorant intended for application to skin and nails are commercially available. Cosmetic preparations comprising polymers such as thermoplastic elastomers as film formers which are easily removable with soap and water are exemplified in U.S.2004/0223933A1 and EP 144068033A 1. The specific examples given in this case comprise polymers wherein at least one block of the polymer is water-soluble or hydrophilic and is charged. While this art discusses the use of thermoplastic elastomers in cosmetic formulations that impart desirable film-forming properties, thermoplastic elastomer copolymers are generally insoluble or less soluble in aqueous or alcoholic solvents and, therefore, are generally considered unsuitable for use in polymeric cosmetic compositions.

US 6824881B 2 describes a process for preparing thermoplastic siloxane block copolymers.

U.S.2003/147819a1 and EP1329483a2 discuss the use of cosmetic base pigments in cosmetic and resin compositions. Among the numerous other polymers, thermoplastic elastomer resins are cited in these applications, indeed in these applications, in the case where they are used as solid resins in which pigments can be dispersed.

Thermoplastic elastomers are generally used in areas where the switching properties of solid melt are of less importance, such as footwear, wire insulation, adhesives, and the like. More specifically, thermoplastic elastomers are typically used in applications where the polymer is heated above the melting temperature of the high melting region of the polymer. This makes the polymer liquid. As the polymer cools, the high melting regions form crosslinks, creating a physically rather than chemically crosslinked network. These network structures form swellable elastomeric structures that can be broken down and reformed when temperature is changed. Other elastomeric structures may generally be formed by chemical crosslinking through, for example, condensation or free radical chain transfer mechanisms. These structures with chemical cross-linking are not reversibly formed. Although thermoplastic elastomers generally rely on the use of higher heat, as suggested by the prior art, their application to cosmetic and skin care products is not obvious and inadequate.

U.S.5,800,816; 5,911,974; 6,036,947, respectively; 6,274,152, respectively; 6,071,503, respectively; 6,139,823, respectively; and 6,340,466 describes the use of a silicone resin, MQ resin in combination with one or more of a non-volatile or volatile silicone, a non-volatile oil, a silicone fluid, a silicone gum, a silicone wax, a cyclomethicone, or a Guerbet ester.

For compositions to function satisfactorily, they must exhibit many desirable performance parameters. The known compositions provide films on biological substrates and have desired performance parameters. Desirable characteristics of the film-forming composition include: good application, producing a uniform film with the desired gloss or sheen, good adhesion, a degree of flexibility, good film strength to avoid film cracking and flaking, preferably without irritation on the skin, hair and/or nails to which the film-forming composition is applied.

Despite the advances made in film forming processes and compositions, there remains a need in the art for film forming compositions that provide durable, transfer resistant, comfortable, highly flexible, tack-free, and water-resistant films.

Thus, there is a need for a method and composition for providing a film on a biological substrate that is durable, flexible, water and oil resistant, abrasion resistant, and transfer resistant for delivery of actives, colorants, and the like.

Furthermore, it is an object of the present invention to provide cosmetic, personal care and pharmaceutical compositions comprising the compositions, wherein the compositions can form durable, flexible, water and oil resistant, abrasion resistant and transfer resistant films for delivering actives, colorants and the like.

Brief description of the invention

In accordance with the above objects and other objects detailed herein, the deficiencies associated with the prior art are overcome by the present invention which, in one embodiment, provides a composition comprising at least a thermoplastic elastomer, a tackifying resin, and a volatile solvent, the composition forming a physically cross-linked film on a biological substrate.

In one embodiment, the compositions of the present invention comprise a charge-neutral hydrophobic thermoplastic elastomer, a tackifying resin or mixture thereof, and a volatile solvent or mixture thereof, which forms a physically cross-linked film upon dissipation of the solvent and is water-insoluble when applied to a biological surface such as keratinous tissue. The biological surface may be any surface to which cosmetics, personal care products, and pharmaceutical compositions are typically applied, including but not limited to skin, lips, hair, nails, and the like. Compositions for application to keratinous surfaces cause the formation of physical crosslinks upon evaporation or dissipation of the volatile solvent or mixture thereof. The resulting film is durable, flexible, water and oil resistant, abrasion resistant, and transfer resistant.

One embodiment of the present invention provides a method of imparting flexibility, water resistance, oil resistance, abrasion resistance, and transfer resistance to keratinous tissue comprising: applying the composition of the present invention to keratinous tissue; activating the composition by techniques known to those skilled in the art, such as, but not limited to, heating, physical rubbing, and changing the pH level; allowing the volatile solvent or mixture thereof to dissipate; a physically cross-linked film is formed on the keratinous tissue. Compositions for topical application to keratinous tissue form a durable, flexible, water and oil resistant, abrasion resistant, and transfer resistant film when applied to the keratinous tissue.

Another embodiment provides a method of forming a film on a keratinous surface comprising contacting the surface with a composition of the present invention. The composition comprises a charge-neutral hydrophobic thermoplastic elastomer, a tackifying resin or mixture thereof, and a volatile solvent or mixture thereof, wherein the thermoplastic elastomer film former comprises a hard domain and an elastomer domain. When the composition is applied to a keratinous surface, the volatile solvent or mixture thereof is dissipated by activating the composition by heat, physical abrasion, and changing the pH level, and the resulting film is physically crosslinked and is durable, flexible, water and oil resistant, abrasion resistant, and transfer resistant.

These and other aspects of the present invention will become apparent to those skilled in the art upon reading the following detailed description of the invention, including the illustrative embodiments and examples.

Detailed Description

The present invention relates to a composition comprising a thermoplastic elastomer film former, a tackifying resin or mixture thereof and a volatile solvent or mixture thereof for delivering active ingredients, colorants, and the like by topically applying the composition to a biological matrix or surface. The composition may be a single phase organic composition, a water-in-oil emulsion or an oil-in-water emulsion, having a viscosity ranging from free-floating to semi-solid and preferably water-insoluble. The composition can be topically applied to keratinous tissue, including, but not limited to, hair, skin, and nails, to form a durable or long-lasting, flexible, water-resistant, oil-resistant, abrasion-resistant, and generally transfer-resistant film on the keratinous tissue. Non-limiting examples of such topical compositions include cosmetics, hair cosmetics, pharmaceutical products, insect repellents, and sun products.

Desirable properties of films formed from the composition include: good application, producing a uniform film with a desired gloss or sheen, short drying times, good adhesion, a degree of flexibility, good film strength to avoid film cracking or peeling, preferably without irritation on the skin, hair and/or nails or other keratinous surfaces to which the film-forming composition is applied.

One embodiment of the present invention includes a composition comprising a thermoplastic elastomer that is particularly useful as a film former in combination with a tackifying resin or mixture thereof and a volatile solvent or mixture thereof. The thermoplastic elastomer in the composition of the present invention is electrically neutral and hydrophobic. While natural and synthetic polymers and mixtures thereof have been used as film formers in cosmetic compositions, charge-neutral hydrophobic thermoplastic elastomers are particularly beneficial in forming flexible, water and oil resistant, abrasion and transfer resistant, shrink resistant, non-tacky and comfortable films. The thermoplastic elastomer film former is present in the composition in an amount of about 0.1 wt.% to about 90 wt.%, preferably 0.5 wt.% to about 70 wt.%, more preferably about 0.7 wt.% to 30 wt.%, based on the total weight of the composition. The thermoplastic elastomer in the composition of the present invention may be compounded with organic molecules such as dyes, uv absorbers and drugs or actives for delivery to the keratinous surface to which the composition is applied to form a coherent continuous film.

Generally, thermoplastic elastomers are multiphase compositions in which at least one phase contains a material that is hard at room temperature but becomes liquid or softer upon heating, i.e., a hard phase or domain. The other phase of the thermoplastic elastomer contains a material that is softer at room temperature and more rubber-like, i.e., the elastomeric phase or region. The thermoplastic elastomer may be a block copolymer. The block copolymers of the present invention may be any form of diblock, triblock, and multiblock copolymers. The topical compositions preferably contain a thermoplastic elastomer of an A-B-A tri-block copolymer. For example, the block copolymers contain hard domains or blocks A (higher T) in the form of A-B diblock copolymers_gBlock(s) and a soft elastomeric region or block B (lower T)_ga-B-a tri-block copolymer, such as poly (styrene-B-elastomer-B-styrene), styrene-isobutylene-styrene (SIBS), styrene-siloxane-styrene, multi-block copolymer structure (a-B) n, and having (a-B)_nx(wherein x represents n functional linkages) structure. The thermoplastic elastomer is preferably an A-B diblock copolymer, an A-B-A triblock copolymer, (A-B)_nMulti-block copolymers and mixtures thereof. More specifically, non-limiting thermoplastic elastomers include polyurethane/elastomer block copolymers, polyester/elastomer block copolymers, polyamide/elastomer block copolymers, polyetherimide/polysiloxane block copolymers, and any combination thereof.

In a preferred embodiment, the thermoplastic elastomer is a linear a-B-a triblock type, such as, but not limited to, styrene-butadiene-styrene, styrene-isoprene-styrene, or styrene-ethylenebutylene-styrene. More preferably, the thermoplastic elastomer used as a film former in the composition of the present invention is styrene isobutylene styrene (SIBS).

The film-forming thermoplastic elastomers used according to the invention have a range of glass transition temperatures (T)_g) This results in the creation of a soft and elastic film. The glass transition temperature is the point at which the polymer or fragment thereof transitions from a solid brittle state to a rubbery liquid state. Those skilled in the art will appreciate that T for various polymers_gThis concept can be understood and identified by reference to the glass transition points described in the general knowledge and references used (see, Polymer Handbook, eds. J. Brandrup et al, 2 Volumes Set, Fourth Edition, John Wiley and sons, Inc., June 2003; Introduction to Polymer Science and technology, eds. H.S. Kaufman and J.J.Falcetta, John Wiley and sons, Inc., 1977) to understand this concept and to identify specific combinations of hard and elastomeric phases useful in the present invention.

In a further embodiment, any charge neutral, non-polar hydrophobic thermoplastic elastomer may be used in the composition as a film former, wherein one phase, preferably the hard phase, has a glass transition temperature (T @)_g) Is about 40 ℃ or greater, preferably about 50 ℃ or greater, still more preferably about 60 ℃, and the T of another phase, preferably the elastomeric phase_gLess than about 25 deg.C, preferably about 10 deg.C or less, more preferably about 0 deg.C or less. A further embodiment includes thermoplastic elastomers wherein T of the two phases_gThe difference is about 15 ℃. Preferably about 30 c, more preferably about 50 c. These properties enable the composition to be water and oil resistant and to be used as a means of delivering active ingredients such as, but not limited to, colorants, UV absorbers, insecticides, and drugs in the form of a non-tacky, flexible and comfortable film.

In addition to the glass transition temperature, the solubility parameter provides a number of methods for predicting the interaction between substances such as liquids and polymers. They can be used to determine the suitability of a mixture of a polymer for a particular use and a solvent for a particular purpose of formulation. A further embodiment of the present invention relates to the solubility parameter between two phases or zones of the thermoplastic elastomer and/or between each phase and the volatile solvent or mixture thereof. The person skilled in The art will understand that The Solubility parameter between The thermoplastic elastomer phase and The solvent or mixture thereof can be determined by reference to The general knowledge and The references used to form The composition of The invention (see, for example, Allan F.M. Barton, Handbook of solvent parameters and Other copolymer parameters, Second Edition, CRC Press, Boca raten, Florida, 1991; Handen, Charles M., "The Three Dimensional solvent parameters-Key compositions impurities: I.solvent plastics, Polymers, and resins," Journal of Paint Technology, Vol.39, No.505, 1967; Handen, Charles M., "The Three Dimensional solvent parameters, dye Polymers, and resins," Journal of Paint Technology, nucleotide No.511, Journal of solvent parameters, Journal of Paint II, Journal of Paint III, Journal of Paint II, pH 7. The name of Paint systems, pH 7. The invention is incorporated by reference, pH 7, Journal of plastics, pH I.M. 7. The invention is incorporated by reference.

In a further embodiment particularly suitable for achieving particularly good properties of the composition, the difference in solubility parameter between the rigid phase and the elastomeric phase of the thermoplastic elastomer is at least 0.5(cal/cc)^1/2. In another embodiment of the composition, the at least one volatile solvent has a solubility parameter of about 0.2(cal/cc) of the thermoplastic elastomer, preferably the rigid phase of the thermoplastic elastomer^1/2And (4) the following steps. In a further composition, at least one of the volatile solvents has a solubility parameter in the thermoplastic elastomer, preferably in the elastomer phase, of about 0.2(cal/cc)^1/2And (4) the following steps.

Similar to increasing the temperature of the thermoplastic elastomer, dissolving the thermoplastic elastomer in a volatile solvent or mixture thereof results in a decrease in strength or disruption of physical crosslinking. While not being bound by theory, it is believed that when the solvent in the composition evaporates, the composition is essentially "dry" and restores its original integrity by forming physical crosslinks. The thermoplastic elastomers of the present invention generally form a network structure by physical crosslinking that can be broken and recovered; whereas chemical crosslinks formed by other non-thermoplastic elastomeric polymers cannot be reversibly formed.

More specifically, a method of applying a thermoplastic elastomer as a film former in a composition has the advantage of a higher T_gAnd lower T_gThe difference in free energy density of dissolution between the melted zones. Another advantage of the composition of the present invention is that no separate structurant is required. In particular, a solvent system that is compatible with the solvent energy of the middle block copolymer (e.g., elastomer domains) and incompatible with the terminal block copolymer (e.g., hard domains) provides the primary film former and structurant. Therefore, the addition of a structuring agent is not necessary. Preferential selective dissolution of higher T by exposing thermoplastic elastomeric polymers to solvents_gCan temporarily disrupt the crosslinked gel structure in a volatile solvent or mixture thereof in the melt zone. This state can be maintained in the product article during storage, wherein the thermoplastic elastomer film former composition is a low viscosity, free-flowing material. When applied to, for example, skin, evaporation of the volatile solvent that disrupts the physical crosslinks results in the physical crosslinks and reformation of the desired film structure. Due to higher T_gThe melting temperature of the melted region is significantly higher than the body temperature and the only mechanism that can damage the membrane is selective dissolution. The chemicals most likely to damage the product film on the exposed skin are either highly hydrophobic (i.e., vegetable oils) or hydrophilic (i.e., water). These membranes are resistant to damage by amphiphilic substances such as fatty acids and surfactants because they rely on a reduction in surface energy and are composed of molecules containing a combination of high and low hydrophilic components.

Volatile solvents produce films that exhibit excellent water, oil and abrasion resistance and can be used, for example, on nails, for example, as nail polishes. The volatile nonpolar solvent may be linear, cyclic, or branched and has a boiling point at normal atmospheric pressure of less than about 250 deg.C, preferably less than about 200 deg.C, and more preferably less than about 175 deg.C. The composition may be a single phase organic composition, a water-in-oil emulsion or an oil-in-water emulsion, having a viscosity ranging from a free-flowing liquid to a semi-solid gel-like form. Preferred compositions are water insoluble. The volatile nonpolar solvent included in the composition of the present invention may be, for example, an organic solvent based on hydrocarbons, esters, silicones, or amides. The solvents or combinations thereof are preferably those that promote temporary disruption of physical crosslinks in the composition. While not wishing to be bound by any theory, it is believed that as the volatile solvent or mixture thereof evaporates or dissipates, the physical crosslinks of the thermoplastic elastomer, which were temporarily broken, recover, forming a film when in contact with keratinous tissue. The film, by itself or in combination with other components of the composition, provides unique characteristics to the compositions of the present invention.

The preferred solvent depends on the particular thermoplastic elastomer used in the present invention. The solvent may be used in combination with one or more other solvents conventionally used in compositions known in the art. The particular solvent may be selected and is considered to be compatible with the film-forming thermoplastic elastomer present in the composition in an amount that promotes temporary disruption of the physical crosslinks of the thermoplastic elastomer and allows the physical crosslinks to reform when the volatile solvent or mixture thereof evaporates. Typically, the topical compositions of the present invention contain, in addition to the thermoplastic elastomer film former and the tackifying resin, an acceptable volatile solvent or mixture of volatile solvents that enables the composition to maintain its gel, liquid or semi-solid form.

In one embodiment relating to the solvent portion of the thermoplastic elastomer composition, the composition must contain a volatile solvent or mixture thereof that is compatible with the elastomer region when the thermoplastic elastomer concentration is low, e.g., less than or equal to about 5 weight percent in the composition. The composition may optionally further comprise a combination of one or more non-volatile solvents. In addition, the composition may optionally also contain a solvent or mixture thereof compatible with the hard domains.

However, when the concentration of thermoplastic elastomer is high, for example greater than or equal to about 5 wt% in the composition, the composition must contain a volatile solvent or mixture thereof that is compatible with the hard domains. The composition may optionally contain a softening-compatible volatile or non-volatile solvent or combination thereof.

The amount of solvent, including solvent mixture, as noted above, must be such as to ensure that the product has an acceptable viscosity (i.e., is easy to use without running) depending on the nature of the solvent and the nature and amount of other ingredients, such as, in particular, thermoplastic elastomers and other film-forming ingredients, plasticizers, thickeners, solids, and the like. The amount of volatile solvent can be readily determined by routine experimentation. Generally, however, the amount of solvent suitable for the purposes of the present invention falls within the range of from about 1% to about 90% by weight of the composition, preferably from about 5% to about 80% by weight of the composition, and more preferably from about 10% to about 70% by weight of the composition.

Non-limiting examples of volatile solvents for use in the compositions described herein include aliphatic, olefinic and aromatic hydrocarbons, chlorinated hydrocarbons, ketones, acetates, ethers, chloroform, alcohols, esters, silicones, and combinations thereof. These solvents are volatile, wherein the solvents evaporate rapidly when the composition is applied to keratinous tissue, such as, but not limited to, skin, lips, hair, and nails.

One skilled in the art will appreciate that the solvent and dissolution conditions can be adjusted to produce a composition having the desired characteristics. The skilled artisan will further appreciate that depending on many parameters such as thermoplastic elastomer, solvent and other ingredients and conditions, the solubility parameter and glass transition temperature T can be approximated by formulations known in the art_g。

One of ordinary skill in the art will be able to determine the solubility parameters and select solvents depending on the block copolymer selected for the application of interest. More information on the solvent for the solubility parameters useful in processing a particular block copolymer can be obtained from various manufacturers of block copolymers. Additional discussion of the concept of polymer solubility parameters exists in: encyclopedia of Polymer Science and Technology, Vol.3, Interscience, New York (1965) and Encyclopedia of Chemical Technology, Supp.Vol., Interscience, New York (1971), the contents of which are incorporated herein by reference.

In another embodiment, tackifying resins can be used to modify the viscosity and elasticity of the composition, which can affect the properties of the composition by achieving optimal tack/adhesion and cohesion properties that are critical to long-term use characteristics. Advantageously, the tackifying resin may be selected to provide residual tackiness to the thermoplastic elastomer composition. The compositions of the invention described herein typically comprise a resin or a mixture of tackifying resins.

Further embodiments of the invention include a composition comprising a thermoplastic elastomer, a solvent or mixture thereof, and a tackifying resin or mixture thereof, wherein the tackifying resin is a silicone resin, for example, the composition may comprise a tackifying resin, which may be a silicone resin or a non-silicone resin, or a mixture of tackifying resins comprising a silicone resin, or a mixture of a silicone resin and a non-silicone resin. In another embodiment, the composition may contain a silicone-based thermoplastic elastomer, a solvent or mixture thereof, and a tackifying resin or mixture thereof, wherein the tackifying resin is a silicone resin or a non-silicone resin.

The silicone resin in the thermoplastic elastomer film-forming composition provides additional transfer resistance without compromising the comfort of the composition of the present invention, wherein the composition is durable, flexible, water and oil resistant, abrasion resistant and transfer resistant for delivery of actives, colorants and the like. More specifically, the use of the triblock copolymer, silicone resin and volatile solvent in a composition, such as a cosmetic composition, provides certain characteristics, including long-term durability and transfer resistance, while maintaining a comfortable, flexible consistency. For example, compositions containing a thermoplastic elastomer, a silicone resin, and a volatile solvent produce compositions with enhanced resistance to water and oil transfer without losing comfort on the skin and alcohol. Non-limiting examples of Silicone resinsExamples include MQ, MT, T, and combinations thereof. MQ resin has the general formula M_xQ_yWherein M is R₁R₂R₃SiO_1/2(ii) a Q is SiO_4/2；R₁、R₂And R₃Each independently or together being C_1-30Straight or branched chain alkyl or phenyl or fluoroalkyl or amino or combinations thereof. The ratio of M to Q (x to y) ranges from about 0.7 to about 2. MT resins of the formula M_xT_yWherein M is R₁R₂R₃SiO_1/2(ii) a And T is RSiO_3/2Wherein R, R₁、R₂And R₃But are not limited to alkyl, phenyl, alkylphenyl, fluoroalkyl, amino, and combinations thereof. The ratio of M to T (x to y) ranges from about 0.7 to about 3, preferably the ratio of M to T is from about 0.7 to about 3. Another silicone resin is a silicone resin having the formula RSiO_3/2Wherein R is alkyl, phenyl, alkenyl, alkylphenyl, amino, fluoroalkyl, or alkyl phosphate.

Without being bound by theory, due to their specific functional groups, the silicone resin forms a three-dimensional (3-D) cage or ladder structure that can move to or self-assemble in the elastomeric or hard domains in the A-B-A triblock copolymer composition. For example, in a composition containing a SIBS thermoplastic elastomer and a silicone tackifying resin of MQ or T resin where the functional groups are phenyl groups, the 3-D structure can be observed to self-assemble along the hard domains. In another example, a functional group that is an alkyl or branched alkyl group causes the resin to migrate into the elastomer mid-block region. In another example, fluorine or perfluoroalkyl groups are selected as functional groups of the silicone resin, which results in the formation of phase separated domains, providing additional oil and/or water resistance. In addition, other desirable characteristics include a high level of gloss, which is provided by alkyl-, phenyl-, or amino-modified MQ or T resins. Without being bound by theory, the T of the silicone resin can be varied by using a combination of these resins_gTo further modify the morphology of the film to produce a comfortable, durable, transfer resistant, highly flexible, tack-free, and water-resistant composition.

A further embodiment of the present invention is directed to a composition comprising a tackifying resin selected as described below wherein the tackifying resin is present in an amount of from about 0.1% to about 50%, preferably from about 3% to about 40%, more preferably from about 5 to 30% by weight of the total composition or a mixture of tackifying resins in a ratio of 1: 10, preferably in a ratio of 1: 5.

One of ordinary skill in the art will appreciate that the residual tack of the composition can be adjusted at room temperature and at normal atmospheric pressure by selecting the appropriate tackifying resin or mixtures thereof. T of resin_gAnd compatibility are the primary factors controlling the adhesion characteristics of the polymer/resin combination. T is_gIn relation to the softening point, the T of the tackifying resin is known to the formulator for formulation purposes_gThe value is more useful than knowing the value of the softening point. For example, the correct T is used in polymers_gThe tackifying resin and the correct resin concentration may provide the desired characteristics. Preferred tackifying resins or mixtures thereof have a softening point of from about 5 ℃ to about 250 ℃, more preferably from about 30 ℃ to about 200 ℃. In contrast, T of the preferred tackifying resins_gAbout-60 c and about 200 c, preferably about-40 c and about 170 c, and most preferably about-30 c to about 150 c.

In one embodiment, the solubility parameter of at least one of the tackifying resins is about 1(cal/cc) of the respective elastomeric phase of the thermoplastic elastomer in the composition^1/2Within, preferably about 0.5(cal/cc)^1/2More preferably about 0.2(cal/cc)^1/2Within. In another embodiment, at least one of the tackifying resins has a solubility parameter in the composition of about 1(cal/cc) of each of the hard phases of the thermoplastic elastomer^1/2Within, preferably about 0.5(cal/cc)^1/2More preferably about 0.2(cal/cc)^1/2Within.

The transfer resistance and durability enhancement can be achieved by the addition of a second tackifying resin, such as a silicone resin. T of the second resin_gPreferred ranges of (a) are from about-60 ℃ to about 250 ℃, more preferably from about-40 ℃ to about 200 ℃. However, it is preferably whenThese parameters are used when the tackifying resin is a silicone resin. Except for T of the second tackifying resin_gIn addition, its solubility parameter is also important in the compositions of the present invention. Preferably, the difference in solubility parameter between the thermoplastic elastomer and the second tackifying resin should be at least about 1(cal/cc)^1/2Or greater, more preferably at least about 1.5(cal/cc)^1/2Or larger.

Non-limiting examples of suitable tackifying resins may include any natural or modified rosin or mixtures thereof, for example, gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; glycerol and pentaerythritol esters of natural or modified rosins such as, for example, pale, glycerol esters of wood rosin, glycerol esters of hydrogenated rosin, glycerol esters of polymerized rosin, pentaerythritol esters of hydrogenated rosin, and phenol-modified pentaerythritol esters of rosin; copolymers and terpolymers of natural terpenes such as styrene/terpene and alpha methyl styrene/terpene; polyterpene resins, or those produced from hydrocarbons of terpenes, such as, for example, bicyclic monoterpene known as pinene, hydrogenated polyterpene resins; phenol-modified terpene resins and hydrogenated derivatives thereof, such as bicyclic terpenes; aliphatic petroleum hydrocarbons; hydrogenated aliphatic petroleum hydrocarbon resins; aliphatic petroleum hydrocarbon resins and hydrogenated derivatives thereof; and aliphatic/aromatic or cycloaliphatic aromatic copolymers and hydrogenated derivatives thereof.

Other non-limiting examples of preferred tackifying resins include rosin esters, rosin salt esters, hydrocarbon resins obtained by oligomerization of the C5 and C9 fractions of petroleum, such as Wingtack10 and Wingtack85(Sartomer comp.inc.; Exton, PA), aliphatic resins, terpene-phenol resins, polyterpenes (e.g. Sylvagum)TR 90；ArizonaChemical；Jacksonville，FL)Aromatic resins, synthetic C5 resins, mixtures of synthetic C5-C9 resins, coumarone-indene resins, copolymers of alpha-methylstyrene and vinyltoluene, and silicone resins, such as, but not limited to, MQ resins (e.g., SR1000 from GESilicones; waterford, NY), MT resins and T resins (Dow Corning)2-2078 Fluid from Dow Corning corp; midland, MI) and mixtures thereof.

In a preferred embodiment of the present invention, the composition of the present invention is directed to a composition comprising a charge-neutral hydrophobic thermoplastic elastomer film former, a tackifying resin or mixture thereof, and a volatile solvent or mixture thereof, which overcomes these disadvantages and produces a film having characteristics such as good adhesion, stability, flexibility, abrasion resistance, non-tackiness, good retention, transfer resistance, abrasion resistance, and short migration time. The compositions of the present invention provide physically crosslinked films on keratinous surfaces when the volatile solvent or mixture thereof evaporates at a rate that preferably allows the formation of a continuous film without the disadvantages described above, having the desired performance parameters.

The compositions of the present invention can be used in a wide variety of cosmetic, personal care and pharmaceutical formulations comprising an effective amount of a thermoplastic elastomer, a tackifying resin or mixture thereof and a volatile solvent or mixture thereof, which is necessary to obtain the desired properties. Depending on the application and the degree of durability, flexibility, applicability, abrasion resistance, uniformity, gloss or sheen, adhesion, water and oil resistance, transfer resistance, and abrasion resistance, preferably without irritation, the skilled artisan will be able to determine the effective amounts and types of thermoplastic elastomer film formers, tackifying resins or mixtures thereof, and volatile solvents or mixtures thereof desired. Depending on the application, one skilled in the art will also be able to determine the amount and type of thermoplastic film former, tackifying resin or mixture thereof, and volatile solvent or mixture thereof, as well as other ingredients necessary to achieve a stable cosmetic or pharmaceutical product. The stable cosmetic or pharmaceutical product is one of the sufficient stability that the cosmetic or pharmaceutical product can be efficiently produced commercially.

In another embodiment, the compositions of the present invention may be used to maintain or adhere to surfaces, topical coatings and functionalized ingredients. Actives or functionalized ingredients may include colorants, pigments, ultraviolet filters, moisturizers, fragrances, insecticides, pharmaceuticals, and other actives or functionalized ingredients known in the cosmetic or pharmaceutical arts.

A further embodiment of the present invention relates to a composition, preferably a topical liquid, gel, foam, cream, lotion or semisolid, which is a cosmetic, personal care product, pharmaceutical or pharmaceutical formulation, insect repellent or sun product, wherein the composition comprises at least a thermoplastic elastomer film former, a tackifying resin or mixture thereof and a volatile solvent or mixture thereof. The composition is water-resistant, oil-resistant, abrasion or rub-resistant and transfer-resistant, flexible, tack-free, glossy, durable, provides a moisture barrier, and is capable of binding and/or delivering one or more active ingredients, such as, but not limited to, colorants, dyes, ultraviolet absorbers, moisturizers, biologically active agents, insecticides/pesticides, and organic or inorganic active agents. For example, the compositions of the present invention are sweat and water resistant, including resistant to treated swimming pool water, fresh water, and seawater. The composition is also dirt resistant and will not fall off. The compositions may be used in a wide variety of products such as, but not limited to, sun care, skin care, color cosmetics, mascara, hair products (shampoos, conditioners, hairsprays, mousses, and dyes/colorants), mascara, nail polish, lip gloss clear, foundation, eye make-up, skin care, personal hygiene, and for the delivery of drugs or actives for topical use.

The present invention relates to a composition, in particular a cosmetic composition, having transfer resistance, long-term use and water resistance. The composition comprises a thermoplastic elastomer, in particular a di-block, tri-block or multi-block copolymer, a tackifying resin or a mixture thereof and a volatile solvent or a mixture thereof, and also to cosmetics and pharmaceuticals comprising the composition.

Many cosmetic compositions, including pigmented cosmetics such as foundations, concealers, mascaras, lipsticks and other make-up products, insect repellents and sunscreen lotions, produce a soft oily film that is very easy to rub off or transfer. Thus, the composition can be at least partially deposited by contact on certain objects, such as glass, cups, clothing or objects of the skin. When deposited, the composition leaves a mark on the object. This result is not optimal and needs to be repeated regularly using the composition.

Although some transfer-resistant cosmetic compositions are known in the art, most of these compositions still need improvement. These cosmetic compositions with high transfer resistance known in the art generally comprise fatty substances, volatile oils, in particular volatile silicone oils and/or volatile hydrocarbon oils. Moreover, these non-transferable compositions are mostly sticky; the use and spreadability of the composition is therefore not ideal for cosmetic products.

In addition to transfer resistance, the composition must remain stable. Film formers commonly used in the art are mixed with solvents to function as thickeners. However, if the solvent in these thickeners migrates out of the gel matrix, the resulting formulation can be problematic, resulting in instability of the formulation. Thus, there remains a need for a transfer resistant, stable composition that also has desirable characteristics such as, but not limited to, ease of use, comfort, flexibility, durability, lack of tackiness during and after use, abrasion resistance, oil resistance, and water resistance.

The compositions of the present invention provide excellent transfer resistance, durability, long-term use, and water resistance in a wide range of applications. Such applications include, but are not limited to, pigmented cosmetics including foundations, concealers, mascaras, eyeliners, eye shadows, lipsticks, lip glosses, blushes; nail polish; hair sprays, gels and mousses, sun blocks, moisturizing lotions, lotions containing active ingredients and fragrances. The product of the invention is particularly useful in any cosmetic, personal care or pharmaceutical application involving the creation of a flexible film that adheres tightly to keratinous surfaces.

In a preferred embodiment, the thermoplastic elastomer film former of the present invention is water insoluble. Can be treated at room temperature to provide good adhesion to the skin and no stickiness. It is also preferred that the thermoplastic elastomer film former be compatible with the other ingredients of the composition.

The compositions of the present invention may also be effective in providing water resistance. The composition can therefore minimize the wash-off of active or functionalized ingredients, which is particularly useful in sun products and mascaras. The composition may also retard skin dehydration by forming a closed film and reducing transepidermal water loss, particularly in moisturizers.

In one embodiment, the composition may create a membrane barrier between the skin and the environment, wherein the membrane comprises active and/or functional ingredients. The film formed from the composition may enhance the activity of the functionalized ingredients, such as SPF and UV light protection and/or humidity and environmental protection.

In another embodiment, the compositions of the present invention may also include other additives commonly used in the art, such as antioxidants, fragrances, essential oils, stabilizers, cosmetic actives, moisturizers, vitamins, essential fatty acids, lipophilic sunscreens, lipid soluble polymers, especially hydrocarbon polymers such as polyolefins and polyacrylates, for improving smoothness or spreadability, water and oil resistance, transfer resistance, or other cosmetic or pharmaceutical properties desired by those skilled in the art. Non-limiting examples of optional added ingredients include: softeners, thickeners such as clays or organoclays, silicates, cellulose derivatives, plasticizers, gels, oils, waxes, preservatives, solvents, surfactants; hectorite; synthetic polymers such as acrylic polymers or conjunct polymers of the polyurethane type; glues, especially xanthan gum; a spreading agent; a dispersant; preservatives, especially water-soluble preservatives; defoaming agents; a humectant; an anti-ultraviolet agent; a fragrance; a filler; a cosmetic or pharmaceutical active agent; a moisturizing agent; vitamins and their derivatives; and biological substances and derivatives thereof. If the softness and elasticity of the composition are still further enhanced, plasticizers which are generally used for incorporation into cosmetic materials may also be added. Suitable materials may include low and high molecular weight plasticizers, which may optionally be used, dissolved or dissolved in a co-solvent.

Suspending and thickening agents typically include waxes, silicone gums, clays, fumed silicone gums, fatty acid soaps, and various hydrocarbon gels, as well as other ingredients that are incorporated into the formulation that remain on the surface of the keratinous tissue. Non-limiting examples of such ingredients, e.g., emollients, that may preferably be used in The compositions of The present invention include glycerin, propylene glycol, cyclomethicone, dimethicone and emollients and other similar ingredients disclosed in The International Cosmetic dictionary and Handbook volumes.1 and 2.eds. wenninger, j.a. and g.n.mcewen, Cosmetic, Toiletry, and Fragrance Association, Washington DC, 2000, which are incorporated herein by reference.

For dyed or pigmented products, the ratio of thermoplastic film former, tackifying resin, volatile solvent, and other ingredients may be adjusted to maximize the adherence, water, oil, and transfer resistance of the keratinous substrate or surface. An important consideration is the ratio between the amount of pigment and film former. It is to be understood that pigment means inorganic or organic, white or various colored particles. Colorants that may be used in The practice of The present invention may include pigments, lakes, and dyes, which are well known in The art and disclosed in The Cosmetic Ingredient Handbook, First Edition, j.m. nikitaikis et al, Cosmetic, Toiletry, and Fragrance Association, Washington DC, 1988, The contents of which are incorporated herein by reference.

Non-limiting examples of organic pigments include FD&C dye, D&C dyes, including D&C Red, Nos.2, 5, 6, 7, 10, 11, 12, 13, 30 and 34, D&C Yellow No.5, Blue No.1, Violet No. 2. Exemplary inorganic pigments include, but are not limited to, metal oxides and metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum oxide, aluminum hydroxide, iron oxide (alpha-Fe)₂O₃、y-Fe₂O₃、Fe₃O₄FeO), red iron oxide, yellow iron oxide, black iron oxide, iron hydroxide, titanium dioxide, titanium suboxide, zirconium oxide, chromium hydroxide, manganese oxide, cobalt oxide, cerium oxide, nickel oxide and zinc oxide and composite oxides and composite hydroxides such as iron titanate, cobalt titanate and cobalt aluminate. Other suitable colorants include ultramarine blue (i.e., sodium aluminum silicate containing sulfur), prussian blue, manganese violet, bismuth oxychloride, talc, mica, sericite, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium aluminum silicate, silica, titanated mica, iron oxide titanated mica, bismuth oxychloride, and any other pigment or treated pigment known in the cosmetic art.

Fillers and nacres may also be added to the formulation to modify the texture and matte/gloss appearance of the composition. It is understood that fillers refer to lamellar or non-lamellar, inorganic or synthetic, colorless or white particles. It is understood that nacres refer to shiny particles produced or synthesized, in particular, from the shells of certain mollusks. Pearling agents that may be used in the practice of the present invention include mica, iron oxide, titanium dioxide, and any other pearling agent known in the cosmetic art.

While some of these materials may include an oily feel and enhance spreadability, as observed in some ester or organic sunscreens, all of the compositions of the present invention maintain their desirable characteristics: transfer resistance, abrasion resistance, water and oil resistance, durability, flexibility, applicability, abrasion resistance, uniformity, gloss or sheen, dry time, tackiness, preferably without irritation. The person skilled in the art will of course take care to select the optimum other compounds and/or their amounts so that the advantageous properties of the composition according to the invention are not, or not substantially, impaired by the additional substances of interest. However, in embodiments where these materials are added to the formulations of the present invention to enhance the spreadability and softening properties of the product, it is preferred that the materials be present in sufficiently low concentrations that the formulation retains its desired properties. The skilled person may select these ingredients in different ways to prepare a composition having the desired properties, such as consistency or texture. The thermoplastic elastomer film former, other ingredients, and their concentrations may also be adjusted to alter the desired properties.

The techniques and compositions of the present invention can be used in a wide variety of products, including but not limited to: lipsticks, lip glosses, mascaras, foundations, sunscreens, insect repellents, nail polishes, and skin care products such as face masks, sunscreens, and insect repellents. In particular, the compositions of the present invention may comprise cosmetic formulations. One embodiment of the present invention relates to cosmetic foundations, wherein the formulation of the cosmetic foundation may contain, in addition to the composition of the present invention, other thickeners and emollients in amounts to provide coverage and achieve other desirable characteristics.

Another embodiment of the present invention is a mascara that uses the composition of the present invention and produces enhanced stability and adhesion to keratinous surfaces such as eyelashes. Mascara using the composition of the present invention may also provide greater wear resistance, improved water resistance, and improved cosmetic properties.

A further embodiment of the invention comprises a lotion, such as a sun lotion or a sun milk. Lotions using the compositions of the present invention may provide enhanced transfer and water resistance. Lotions using the composition may also provide greater abrasion resistance.

Another embodiment of the present invention includes an eyeliner product. Eyeliners using the compositions of the present invention can provide enhanced stability and adhesion to eyelid tissue. Eyeliners using the compositions of the present invention may also provide greater water resistance and improved cosmetic properties.

Another embodiment is a lip cosmetic composition using the composition of the present invention, which provides a uniform film having a shiny texture and maintaining a comfortable feel throughout the day of use. Preferred lip cosmetics are non-tacky or sticky, and while not transferring, moving or staining, are durable, soft, elastic, flexible, and comfortable on the skin.

The person skilled in the art will be able to select and manufacture the packaging and application device according to any embodiment of the invention, according to their general knowledge, and to adapt it according to the characteristics of the composition to be packaged. Furthermore, in particular, the type of device to be used is related to the consistency of the composition, in particular its viscosity; it may depend on the nature of the components present in the composition, for example the presence of volatile compounds.

In a further embodiment, a method of imparting durability, flexibility, oil resistance, water resistance, abrasion resistance, and transfer resistance to keratinous tissue comprising: applying to keratinous tissue such as, but not limited to, skin, hair and nails, a composition of the present invention comprising at least a charge-neutral hydrophobic thermoplastic elastomer film former, a tackifying resin, or a mixture thereof, and a volatile solvent, or a mixture thereof; activating the topical composition by heat, physical friction or pH; allowing the volatile solvent to dissipate; and forming physical crosslinks in an amount effective to deliver durability, flexibility, oil resistance, water resistance, abrasion resistance, and transfer resistance through a film-forming transmission when the composition is applied to keratinous tissue.

All patents, patent applications, published PCT applications and articles, books, references, reference manuals, and abstracts cited herein are hereby incorporated by reference in their entirety to more fully describe the state of the art to which the invention pertains.

As various changes could be made in the above-described subject matter without departing from the scope and spirit of the invention, it is intended that all subject matter contained in the above description or defined in the appended claims be interpreted as illustrative and explanatory only. Many modifications and variations of the present invention are possible in light of the above teachings.

Examples

The following examples are presented to further describe and explain embodiments within the scope of the present invention. These examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.

Example 1

Lip composition prototype

Table 1 provides a lip composition prototype formulation based on a thermoplastic elastomer composition. Briefly, the lip composition was prepared by stirring and heating at 105 ℃ for 15 minutes until homogeneous, 7% of ethylene-isobutylene-styrene (SIBS) in isododecane. The mixture was stirred while slowly cooling to about 25 ℃. The resulting soft gel structure is then used to prepare prototypes by adding other ingredients commonly used in cosmetic formulations.

The finished SIBS softgel was mixed with 7% by weight of isododecane and heated to about 60 ℃, then the pigment and sylvagum were added until homogeneous. The mixture was then slowly cooled to room temperature with constant stirring.

Table 1: prototype formulation

Example 2

Transfer resistance of lip compositions

The transfer resistance of the Lip composition as described in example 1 was checked using a variation of the transfer resistance protocol of U.S. Pat. No. 6,074,654 and compared to commercially available Lip stain products Lipfine (Procter & Gamble; Cincinatti, OH) and Lip polish (Maybelline; New York, NY), the contents of which are incorporated herein by reference. The protocol used is described below.

Transfer resistance test method

The method is used to determine the water and oil transfer and adhesion resistance properties of cosmetic films. This experiment can predict the ability of a cosmetic film to resist color transfer to objects in contact with the skin. These objects include clothing, handkerchiefs or tissues, napkins and utensils such as comforters, glasses and tablecloths, and oily fingers or certain objects such as oily food.

The film formed by the cosmetic composition exhibits a degree of transfer resistance which is directly proportional to the hardness and solvent resistance of the film. Hardness and solvent resistance can be expressed as a function of the stain and rub tests described below. When conducting this experiment, standard safety measures should be observed.

Equipment:

a glass sheet;

collagen sausage-like packaging such as Nippi casting grade F;

a constant humidity chamber adjusted to 95% relative humidity;

a multi-purpose knife;

a ruler;

a single-sided tape;

double-sided adhesive tape;

25 micron thick tank settling bars;

white styrofoam dinner plates such as Amoco selections Plastic DLTableware；

A 1.5 inch diameter annular metal perforator;

1kg weight;

a vegetable oil;

a cosmetic applicator with a brush at the end; and

lint-free wipers, e.g. KimwipesEX-L。

The method comprises the following steps:

(1) a 3 x 4 inch layered collagen sausage-like package was prepared by imbibing water in a 90% relative humidity chamber for at least 24 hours.

(2) The collagen layer was removed to ambient conditions and immediately wrapped around the glass plate only. The collagen layer was attached to the glass with tape. The collagen surface should be flat without wrinkles.

(3) The collagen-coated glass sheets were allowed to equilibrate for 24 hours at ambient conditions.

(4) A thin (1 mil), uniform film of cosmetic formulation was applied to the collagen surface.

(5) The cosmetic sample on collagen was kept at ambient conditions for 1 hour.

(6) Three drops of vegetable oil were placed on the right side of the membrane using a pipette. Using another pipette, three drops of water were placed on the left side of the membrane.

(7) The oil and water sections were separated and gently brushed with a cosmetic brush applicator to evenly distribute the oil and water over the membrane surface.

(8) The oil and water remained on the membrane for 15 minutes.

(9) Excess oil and water were carefully wiped off the membrane surface using a lint-free wiper, using as little pressure as possible during this step.

(10) Two disks were cut from a clean white styrofoam dinner plate with a 1.5 inch diameter circular metal punch. The surface and edges of each disc should be flat and smooth.

(11) The discs of step (10) were each firmly attached to the bottom surface of a 1kg weight with double-sided tape.

(12) The cosmetic sample was applied to the collagen surface of step (5) and the weight was placed on top of the cosmetic sample such that disc #1 was in contact with the oil cut side of the membrane and disc #2 was in contact with the water cut side of the membrane. It is important to carefully place the weight so that excessive force other than 1kg cannot be used.

(13) The top of the 1kg weight was grasped and the disk was carefully rotated 360 degrees while maintaining a 1kg force on the film. The weight is not lifted or pressed during the rotation to the weight. The entire 360 degree rotation is completed in a time interval of 3 to 5 seconds.

(14) The weight was raised straight away from the film surface and the disc was carefully removed from the weight to avoid damaging the disc.

(15) Color transfer on each disc was based on visual identification of the disc when compared to commercial products as positive and negative benchmarks. The positive control used was lipdefinition (prime) and the negative control used was Lip polish product.

(16) The criteria in the "star rating system" for determining the degree of transfer are explained in table 2.

Table 2: criteria used as transfer rating Scale

Standard of merit	Scale
		Less than negative control	*
Equal to or slightly better than the negative control	**
		Between negative and positive controls	***
Approximately equal to the positive control	****
		Better than positive control	*****

The results of the water and oil transfer resistance described above show that the transparent lip gloss formulation of example 1 comprising a thermoplastic elastomer shows equal to or better than positive (lipdefinition)_TMPrime coat) water resistance of the control. However, with respect to oil transfer resistance, the Lip gloss formulation of example 1 was indeed less than, equal to, or slightly better than the negative (Lip Polish) control. Remarkably, less pigment was transferred to the styrofoam disks from the formulation of example 1 than the control in the water resistance test. Some formulations provide oil transfer resistance over a negative control, which is the minimum satisfactory benchmark for oil transfer resistance. The results were quantified according to the star rating system shown in table 3 below.

Table 3: in vitro evaluation of clear highlighting lipstick prototype

Prototype formula number	Transfer resistance (oil)	Transfer resistance (water)
			8442-45-I	*	*****
8442-45-II	*	*****
			8442-45-III	*	****
8442-45-IV	**	****
			8442-45-V	**	*****

Example 3

The flexibility of the lip gloss formulation of example 1 was examined using a variation of the flexibility protocol of U.S.6,074,654, the contents of which are incorporated herein by reference. The flexibility of the cosmetic film is important for the durability (durability) and comfort of the cosmetic film.

Flexibility was determined by the rubber tensile test. This experiment can predict the ability of the color film to resist flaking or peeling, a type of indication of failure after use by skin movement during normal movement. The flexible rubber tensile test is based on the determination of weight loss before and after rubber tensile.

Equipment:

ansell Industrial technician uses a separate glove (12 "long, 17 mil) USDA acceptable #390, 9;

an inclined eye shadow brush by Avon Products, Inc.

Analytical balance (4 decimal places); and

a ruler.

The method comprises the following steps:

(1) a1 inch wide strip was cut from the wrist area of the glove, avoiding the rib-like structure and thumb.

(2) A1 x 1 inch area was drawn in the center of the smooth surface of the tape, avoiding the raised numbers.

(3) Weighing the rubber band and recording the weight; hereinafter referred to as a.

(4) The initial weight of the cosmetic for the tape was determined to produce a dry film weight of 20 mg. This can be determined by dividing 20mg by the weight percent of non-volatile materials present in the cosmetic. For example, 40mg of a cosmetic containing 50% non-volatile matter must be used to obtain a 20mg dry film.

(5) A clean eye shadow brush was used to apply the amount of cosmetic determined in step (4) in balance to the 1 x 1 inch area of the band marked in step (2).

(6) The combined weight of rubber band and applied cosmetic was weighed. The weight of the wet film containing the rubber tape was designated as B.

(7) And (4) placing the sample on the rubber belt of the step (6) under the ambient room condition for 24 hours. Optimal test conditions to reliably correlate the test with the physical properties of the composition require a dried film. Drying means evaporating at least 90% of the volatile carrier in the cosmetic composition.

(8) The combined weight of rubber band a and cosmetic film used was weighed; hereinafter referred to as C. The weight of the dried film, D, (D ═ C-a) was determined by subtracting C from a. The weight should be 20. + -.2 mg.

(9) The rubber tape was gently stretched to change the marked film length from 1.00 inch to 1.75 inches.

(10) When a loose film sheet on the rubber tape is observed, the film sheet is removed from the rubber tape by wiping strongly with a clean eye shadow brush on the film surface: 10 rubs in the vertical direction and 10 rubs in the horizontal direction.

(11) The rubber band is carefully restored to approximately its original shape.

(12) Recording the weight of the rubber band (with the remaining cosmetic); the procedure is as follows.

(13) The flexibility of the films was rated based on percent weight loss ("PWL") using the "star rating system" as follows table 4:

table 4: criteria used as rating in flexibility tests

The weight loss percentage of the cosmetic film was calculated using the following equation:

percentage loss of weight (PWL) ═ 1- (E-a)/(C-a) ] × 100%

For some very flexible films, the weight loss percentage is negligible. Thus, in some cases, the PWL value may become negative (weight gain) due to some dust transferred by the brush.

Steps (1) to (12) were repeated 3 times for each cosmetic formulation tested. Determining an average of the three PWL values; hereinafter referred to as the average percent weight loss ("APWL"). Lower APWL values correspond to flexible films having the desired balance of film adhesion and adhesion.

To test for statistical differences between samples, at least 20 replicates per sample were performed. If there is a statistical difference between the samples, a student's T-test is performed for evaluation. The results of the flexibility test of the lip gloss formulations of example 1 were quantified according to the star rating system shown in table 5 below.

The results of the flexibility test as described above indicate that the lip gloss formulation of example 1 comprising a thermoplastic elastomer exhibits excellent flexibility.

Table 5: in vitro evaluation of clear highlighting lipstick prototype

Prototype formula number	Flexibility
		8442-45-I	*****
8442-45-II	*****
		8442-45-III	*****
8442-45-IV	*****
		8442-45-V	****

Example 4

Thermoplastic elastomer composition

As shown in tables 6 and 7, other examples of thermoplastic elastomers gelled with a solvent (isododecane) that selectively dissolves the low melting region of the polymer were prepared with other ingredients. Generally, the solvent that dissolves the high melting region should be 1.0(cal/cc) of the high melting region^1/2And (4) the following steps. In this example, the high melting region is one having a solubility parameter in the range of 8.9 to 9.0(cal/cc)^1/2Internal styrene (ref: Cosmet.&Toiletries, 103: 47-69, 1988). The low melting polyisobutylene has a solubility parameter of 7.9-8.0(Polymer handbook 4)^thed.j.brandrup, e.h.immergut, e.a.grulked eds., j.wiley and sons inc.ny, 1999, pp 704).

Table 6: thermoplastic elastomer composition

Composition (I)	A	B	C	D
					TiO₂	3％	3％	3％	3％
Red 7 calcium lake	0.2％	0.2％	0.2％	0.2％
					Talc-14	4.8％	4.8％	4.8％	4.8％
Red iron oxide 34-2045	1.5％	1.5％	1.5％	1.5％
					Cosmetic red iron oxide	1.5％	1.5％	1.5％	1.5％
SIBS	10％	10％	10％	15％
					WingTack-10	0％	5％	10％	10％
WingTack-85	0％	5％	10％	15％
					Isododecane	79％	69％	59％	49％
In all	100％	100％	100％	100％

Table 7: thermoplastic elastomer composition

Composition (I)	E	F	G	H
					TiO₂	3％	3％	3％	3％
Red 7 calcium lake	0.2％	0.2％	0.2％	0.2％
					Talc-14	4.8％	4.8％	4.8％	4.8％
Red iron oxide 34-2045	1.5％	1.5％	1.5％	1.5％
					Cosmetic red iron oxide	1.5％	1.5％	1.5％	1.5％
SIBS	10％	10％	10％	10％
					WingTack-10	0％	5％	10％	10％
WingTack-85	0％	5％	10％	15％
					Acetic acid butyl ester	5％	10％	15％	20％
Isododecane	74％	59％	44％	34％
					In all	100％	100％	100％	100％

Example 5

Thermoplastic elastomer composition containing silicone resin

As shown in tables 8 and 9, compositions containing mixtures of SIBS thermoplastic elastomers and tackifying resins, including silicone resins, were prepared with the other ingredients. These formulations contain SIBS as thermoplastic elastomer, isododecane as solvent, and a tackifying resin mixture: non-silicone resin, SylvasumTR 90 and Koboguard 5400, and silicone resin, GESR1000(MQ resin) and Dow Corning2-2078 Fluid (T resin).

Table 8: thermoplastic elastomer composition containing silicone resin

Table 9: thermoplastic elastomer composition containing silicone resin

Example 6

Transfer resistance of thermoplastic elastomer compositions containing silicone resins

The transfer resistance of the thermoplastic elastomer composition containing a silicone resin as described in example 5 was examined and tested as described in example 2. The results are based on the criteria shown in table 2. The results of water and oil transfer resistance of the thermoplastic elastomer compositions containing the silicone resins are shown in Table 10. Most of these formulations showed resistance to water transfer. Formulations containing silicone resins as one of the tackifying resins may be added to improve oil transfer resistance.

Table 10: in vitro evaluation of thermoplastic elastomer compositions containing Silicone resins

Prototype formula number	Transfer resistance (oil)	Transfer resistance (water)
			SIBS-MQ3	**	****
SIBS-MQ6	**	*****
			SIBS III+MQ	**	***
SIBS V+MQ	*****	*

All patents, patent applications, published articles, abstracts, books, reference manuals, and abstracts cited herein are hereby incorporated by reference in their entirety to more fully describe the state of the art to which the invention pertains.

It should be understood that the above description is only illustrative of the present invention. Numerous alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances which fall within the scope of the appended claims.

Claims

1. A composition, comprising: a charge-neutral hydrophobic thermoplastic elastomer film former, a tackifying resin, or a mixture thereof, and a volatile solvent, or a mixture thereof, wherein the thermoplastic elastomer film former comprises hard domains and elastomer domains, wherein the composition is water-insoluble, wherein the thermoplastic elastomer film former is physically crosslinked when the volatile solvent, or mixture thereof, dissipates; and wherein the tackifying resin or mixture thereof comprises a second tackifying resin, the second tackifying resin being a silicone resin, the silicone resin being an MQ resin, an MT resin or a T resin.

2. The composition of claim 1, wherein the thermoplastic elastomer film former is a block copolymer.

3. The composition of claim 2, wherein the block copolymer has at least two blocks.

4. The composition of claim 2, wherein the block copolymer has at least three blocks.

5. The composition of claim 1 wherein the thermoplastic elastomer film former is an a-B-a tri-block copolymer.

6. The composition of claim 5 wherein the A-B-A tri-block copolymer is styrene-isobutylene-styrene.

7. The composition of claim 1, wherein T of the hard domain_gGreater than or equal to 40 ℃, T of the elastomer zone_gLess than 25 ℃.

8. The composition of claim 1, wherein T of the hard domain_gGreater than 50 ℃, T of the elastomer zone_gLess than 10 ℃.

9. The composition of claim 1, wherein T of the hard domain_gT in the elastomer zone at 60 ℃ or higher_gLess than 0 ℃.

10. The composition of claim 1, wherein T of the hard domain and the elastomer domain_gThe difference is 50 ℃.

11. The composition of claim 1, wherein the difference in solubility parameters of the hard domain and the elastomer domain is at least 0.5(cal/cc)^1/2。

12. The composition of claim 1, wherein the charge-neutral hydrophobic thermoplastic elastomer film former is present in an amount of 0.1 wt% to 90 wt%, based on the total weight of the composition.

13. The composition of claim 1, wherein the charge-neutral hydrophobic thermoplastic elastomer film former is a polyurethane/elastomer block copolymer, a polyester/elastomer block copolymer, a polyamide/elastomer block copolymer, a polyetherimide/polysiloxane block copolymer, a styrene copolymer, or any combination thereof.

14. The composition of claim 13, wherein the styrenic copolymer is a poly (styrene-b-elastomer-b-styrene) block copolymer, or a styrene-siloxane-styrene block copolymer.

15. The composition of claim 1, wherein the tackifying resin has a softening point of from 5 ℃ to 250 ℃.

16. The composition of claim 1, wherein the T of the tackifying resin_gIs-60 ℃ to 200 ℃.

17. The composition of claim 1, wherein the solubility parameter of at least one tackifying resin is 0.2(cal/cc) per elastomer domain^1/2Within.

18. The composition of claim 1, wherein the solubility parameter of at least one of the tackifying resins is 0.2(cal/cc) per hard domain^1/2Within.

19. The composition of claim 1, wherein the tackifying resin is rosin, modified rosin, terpene, polyterpene, hydrocarbon resin obtained by oligomerization of the C5 to C9 fraction of petroleum, coumarone-indene resin, a copolymer of alpha-methylstyrene and vinyltoluene, or any combination thereof.

20. The composition of claim 1, wherein the T of the second tackifying resin_gIs from-60 ℃ to 250 ℃.

21. The composition of claim 1, wherein the second tackifying resin has a solubility parameter of 1(cal/cc)^1/2Or larger.

22. The composition of claim 1, wherein at least one of the volatile solvents has a boiling point of less than 250 ℃ at atmospheric pressure.

23. The composition of claim 1, wherein the volatile solvent or mixture thereof selectively solvates each of the hard and elastomer regions of the thermoplastic elastomer.

24. The composition of claim 1, wherein at least one of the volatile solvents has a solubility parameter in each elastomer zone of 0.2(cal/cc)^1/2Within.

25. The composition of claim 1, wherein at least one of the volatile solvents has a solubility parameter in each of the hard domains of 0.2(cal/cc)^1/2Within.

26. The composition of claim 1, wherein the charge-neutral hydrophobic thermoplastic elastomer film former is less than or equal to 5 weight percent of the total weight of the composition, and the volatile solvent or mixture thereof is compatible with the elastomer region.

27. The composition of claim 1, wherein the charge-neutral hydrophobic thermoplastic elastomer film former is greater than or equal to 5 weight percent of the total weight of the composition, and the volatile solvent or mixture thereof is compatible with the hard domain.

28. The composition of claim 1, wherein the volatile solvent is an aliphatic hydrocarbon, an olefinic hydrocarbon, an aromatic hydrocarbon, a chlorinated hydrocarbon, a ketone, an ether, an alcohol, an ester, a siloxane, or a combination thereof.

29. The composition of claim 28, wherein the chlorinated hydrocarbon is chloroform and the ester is an acetate ester.

30. The composition of claim 1, wherein the composition is a cosmetic, pharmaceutical, insect repellent, or sunscreen.

31. The composition of claim 30, wherein the cosmetic is nail polish, a lip gloss product, a lip gloss, a foundation, an eye cosmetic, a skin care product, or a personal hygiene product.

32. The composition of claim 31, wherein the cosmetic for the eye is a mascara.

33. The composition of claim 1, further comprising an ingredient, wherein the ingredient is a colorant, sunscreen, moisturizer, bioactive agent, insecticide, or organic or inorganic active agent.

34. The composition of claim 1, wherein the composition is a liquid, gel, foam, cream, or semi-solid.

35. The composition of claim 1, wherein the composition is a lotion.

36. The composition of claim 1, wherein the composition is durable, flexible, water and oil resistant, abrasion resistant, and transfer resistant.

37. A method of delivering durability, comfort, flexibility, water resistance, oil resistance, abrasion resistance, and transfer resistance to keratinous tissue comprising:

a) applying the composition of claim 1 to keratinous tissue;

b) dissipating the volatile solvent or mixture thereof; and

c) a physically cross-linked film is formed,

thereby imparting flexibility, water resistance, oil resistance, abrasion resistance, and transfer resistance when the composition is applied to keratinous tissue.

38. A method of forming a film on a keratinous surface comprising:

a) contacting the surface with the composition of claim 1;

b) allowing the volatile solvent or mixture thereof to dissipate from the composition; and

c) forming physical crosslinks in the thermoplastic elastomer film former;

thereby forming a film on the keratinous surface wherein the film is flexible, water resistant, oil resistant, abrasion resistant, and transfer resistant.