HK1235010B - Topical composition for skin - Google Patents

Description

Skin external use composition

Technical Field

The present application relates to a skin external application composition, a cosmetic composition, or a mascara composition.

Background Art

Functional polymers are sometimes required in the preparation of cosmetics or pharmaceuticals. For example, cosmetics (e.g., mascara) or other cosmetics or pharmaceuticals applied to the skin may require polymers that are resistant to solvents of varying properties (e.g., sweat, tears, and sebum). Patent Documents 1 and 2 describe polymers suitable for the preparation of cosmetics.

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Publication No. 2000-119140

Patent Document 2: Japanese Patent Publication No. 2003-055136

Summary of the Invention

Problems to be solved by the invention

The present application provides a composition for external use on the skin, a cosmetic composition, or a mascara composition. A primary object of the present application is to provide a composition for external use on the skin, a cosmetic composition, or a mascara composition comprising a functional polymer that exhibits low solubility in polar and non-polar solvents, prevents diffusion into these solvents, and is suitable for film formation.

Technical solutions to the problem

The skin topical composition of the present application may contain a polymer described below. The skin topical composition may be formulated into a cosmetic composition, such as a mascara composition. In this case, the composition may be formulated with a medium or base acceptable in cosmetics or dermatology.

The dosage form of the skin external application composition, cosmetic material composition or mascara composition of the present application is not particularly limited and can be formed into a variety of dosage forms according to the purpose. For example, the above dosage form can be appropriately selected from powders, gels, ointments, creams or solutions. For example, the above skin external application composition can be prepared into dosage forms such as softening lotions, nourishing lotions, nourishing creams, massage creams, essences, foams, facial masks, lotions, foundation creams, makeup bases, gels, lotions, soaps, liquid detergents, shower gels, sunscreens, sunscreen oils, spray-type solutions, ointments, pastes or sprays.

In one example, the above-mentioned skin external application composition can be applied to hair-producing areas where sebum and sweat are produced simultaneously, such as eyebrows, hair, or underarms, and other skin areas that require both water resistance and oil resistance. As an example, a mascara composition can be mentioned, but it is not limited to this.

For example, the mascara composition may contain a polymer described below as a film-forming agent. In this case, the polymer can prevent the mascara composition from spreading due to tears or sweat, and can also prevent makeup from spreading due to sebum.

Next, the polymer contained in the above-mentioned external skin preparation composition, cosmetic composition, or mascara composition will be described.

As described later, the polymer of the present application may exhibit low solubility in both polar and non-polar solvents or have a glass transition temperature within a predetermined range, and may have all of the above characteristics in some cases.

The polymer of the present application may exhibit low solubility in polar solvents and non-polar solvents. In the present application, the term non-polar solvent refers to a solvent having a dielectric constant (dielectric constant) at 25°C in the range of about 1 to 3, about 1.5 to 2.5, or about 1.5 to 2, and the term polar solvent may refer to a solvent having a dielectric constant (dielectric constant) at 25°C in the range of about 75 to 85 or about 75 to 80. As a representative example of the above-mentioned non-polar solvent, hexane (dielectric constant (25°C): about 1.89) can be cited, and as a representative example of the above-mentioned polar solvent, water (dielectric constant (25°C): about 78.54) can be cited, but are not limited thereto. In the field of chemistry, the dielectric constant is known for each solvent.

In one example, the solubility of the polymer in the polar solvent may be less than 10 or less than 5. In one example, the solubility of the polymer in the non-polar solvent may be less than 10 or less than 5. The solubility indicates that the lower the value is, the better the resistance of the polymer to the solvent is, so there is no particular restriction on its lower limit. In the present application, the solubility in a specific solvent indicates the number of grams (g) of the polymer that can be dissolved in 100g of the solvent to the maximum extent. In addition, unless otherwise specified, the solubility in the present application indicates the solubility measured at room temperature. In the present application, the term normal temperature refers to the temperature in the natural state without being heated or cooled, for example, it can be a temperature in the range of about 10°C to 30°C, about 15°C to 30°C or about 20°C to 30°C, or a temperature of about 25°C.

The polymer may exhibit suitable solubility in solvents intermediate between the polar and non-polar solvents. For example, the polymer may have a solubility of 15 or greater, or approximately 15 to 50, in solvents having a dielectric constant at 25°C ranging from 4 to 15, 5 to 15, 5 to 10, or 5 to 8. Examples of such solvents include, but are not limited to, ethyl acetate (dielectric constant (25°C): approximately 6.02).

The glass transition temperature of the polymer of the present application may be 10°C or more. In another example, the glass transition temperature may be 15°C or more, 20°C or more, 25°C or more, or 30°C or more. The glass transition temperature of the polymer may be about 110°C or less, about 100°C or less, 90°C or less, 80°C or less, 70°C or less, 60°C or less, or 55°C or less. In the present application, the glass transition temperature is a theoretical value obtained from the monomer composition of the polymer by the so-called Fox equation. The glass transition temperature as described above may be useful, for example, in the case where the above-mentioned polymer is used as a film-forming agent. Within the range of the above-mentioned glass transition temperature, the above-mentioned polymer can be used to effectively form a coating without stickiness or breakage, etc.

A polymer having the above-mentioned characteristics can be prepared by, for example, adjusting the types and ratios of monomers forming the polymer.

For example, the polymer may include a first monomer unit having a homopolymer solubility parameter of less than 10 (cal/cm ³ ) ^1/2 and a second monomer unit having a homopolymer solubility parameter of 10 (cal/cm ³ ) ^1/2 or more.

In the present application, the solubility parameter refers to the solubility parameter of a homopolymer obtained by polymerizing the corresponding monomer, thereby understanding the degree of hydrophilicity and hydrophobicity of the monomer. There is no particular limitation on the method for determining the solubility parameter, and methods known in the art can be used. For example, the above parameter can be calculated or determined using the so-called HSP (Hansen solubility parameter) method known in the art. In the above, in another embodiment, the solubility parameter of the homopolymer of the first monomer can be in the range of about 5 (cal/cm ³ ) ^1/2 to 9.5 (cal/cm ³ ) ^1/2 or 7 (cal/cm ³ ) ^1/2 to 9 (cal/cm ³ ) ^1/2 . In the above, the solubility parameter of the second monomer can be, in another example, in the range of 10 (cal/cm ³ ) ^1/2 to 15 (cal/cm ³ ) ^1/2 or 10 (cal/cm ³ ) ^1/2 to 13 (cal/cm ³ ) ^1/2 . Suitable use of monomers having solubility parameters in the above ranges can form polymers exhibiting the aforementioned properties.

In the present application, a polymerized unit of any monomer or compound means a form in which the monomer or compound is contained in a polymer as a monomer unit through a polymerization reaction.

As the first monomer, a variety of monomers can be selected as long as they have the above-mentioned solubility parameters. Examples of monomers that can be used as the first monomer include alkyl (meth)acrylates and aromatic (meth)acrylates. In this application, the term (meth)acrylate can refer to either acrylate or methacrylate.

Examples of the alkyl group contained in the alkyl (meth)acrylate include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 8 to 20 carbon atoms, or 10 to 20 carbon atoms. These alkyl groups may be substituted with one or more substituents. Examples of such monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isobornyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, and dodecyl (meth)acrylate.

Examples of the aromatic (meth)acrylate include aryl (meth)acrylates and arylalkyl (meth)acrylates. In the above examples, the aryl group or the aryl group of the arylalkyl group may be, for example, an aryl group having 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Furthermore, the alkyl group of the arylalkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. In the above examples, the alkyl group may be linear, branched, or cyclic, and the alkyl or aryl group may be substituted with one or more substituents.

Examples of the aryl group or arylalkyl group include, but are not limited to, a phenyl group, a phenethyl group, a phenylpropyl group, and a naphthyl group.

As the first monomer, for example, a compound represented by the following Chemical Formula 1 can be exemplified.

[Chemical Formula 1]

In Chemical Formula 1, Q may be hydrogen or an alkyl group, and B may be a linear or branched alkyl group or an alicyclic hydrocarbon group having 4 or more carbon atoms, or an aromatic substituent such as the above-mentioned aryl group or arylalkyl group.

In Chemical Formula 1, examples of the alkyl group present in Q include an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may be substituted with any one or more substituents.

In Chemical Formula 1, B can be a linear or branched alkyl group having 4 or more carbon atoms, 7 or more carbon atoms, or 9 or more carbon atoms. Compounds containing relatively long-chain alkyl groups are referred to as hydrophobic compounds. There is no particular upper limit on the number of carbon atoms in the linear or branched alkyl group; for example, the alkyl group can have 20 or fewer carbon atoms.

In other embodiments, B in Chemical Formula 1 may be an alicyclic hydrocarbon group, such as an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms. Examples of such hydrocarbon groups include alicyclic alkyl groups having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms, such as cyclohexyl or isobornyl. Compounds having alicyclic hydrocarbon groups are also referred to as relatively hydrophobic compounds.

In the present application, examples of substituents that can be arbitrarily substituted on the alkyl, alkylene, or aromatic substituents in the above Chemical Formula 1 or the later-described Chemical Formula 2 or 3 include, but are not limited to, halogen groups such as chlorine or fluorine; epoxy groups such as glycidyl, epoxyalkyl, glycidoxyalkyl, or alicyclic epoxy groups; acryloyl, methacryloyl, isocyanate, mercapto, alkyl, alkenyl, alkynyl, or aryl groups.

Taking the physical properties of the target polymer into consideration, appropriate types can be selected from the monomers described above and used.

As the second monomer, a monomer selected from monomers known to have the aforementioned solubility parameters can also be used.

For example, as the second monomer, a compound represented by the following Chemical Formula 2 or 3 may be used.

[Chemical Formula 2]

In Chemical Formula 2, Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen or an alkyl group, and m is any number;

[Chemical Formula 3]

In Chemical Formula 3, Q is hydrogen or an alkyl group, A and U are each independently an alkylene group, and X is a hydroxyl group or a cyano group.

In Chemical Formulas 2 and 3, examples of the alkylene group include an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. These alkylene groups may be linear, branched, or cyclic. These alkylene groups may be optionally substituted with one or more substituents.

In Chemical Formulas 2 and 3, examples of the alkyl groups present in Q and Z include those having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. These alkyl groups may be linear, branched, or cyclic. Furthermore, these alkyl groups may be optionally substituted with one or more substituents.

In Chemical Formulas 2 and 3, m and n are arbitrary numbers, for example, each independently within the range of 1 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 16, or 1 to 12.

In one example, as the second monomer, a compound in which Q in the above chemical formula 2 is hydrogen or an alkyl group with 1 to 4 carbon atoms, U is an alkylene group with 1 to 4 carbon atoms, Z is hydrogen or an alkyl group with 1 to 4 carbon atoms, and m is approximately 1 to 30 can be used, but is not limited thereto.

The polymer can be prepared by polymerizing the first monomer and the second monomer at an appropriate ratio.

For example, the polymer may comprise 50 to 99.9 parts by weight of a first monomer unit and 0.1 to 20 parts by weight of a second monomer unit. In the above, in another example, the first monomer unit may be present in 60 to 99.9 parts by weight, 70 to 99.9 parts by weight, or 80 to 99.9 parts by weight. In addition, the second monomer unit may be included in 5 to 20 parts by weight or 7 to 20 parts by weight. In this application, unless otherwise specified, the unit weight part may represent the weight ratio between the components. In addition, in the above, the weight ratio of the monomer units may represent the weight ratio of the monomers used in the preparation of the polymer. Thus, for example, the polymer comprising 50 to 99.9 parts by weight of a first monomer unit and 0.1 to 20 parts by weight of a second monomer unit may represent the case where the polymer is formed by polymerizing a monomer mixture containing the first monomer and the second monomer in a weight ratio of 50 to 99.9:0.1 to 20 (first monomer: second monomer). If the weight ratio of the second monomer in the polymer is less than 0.1 parts by weight or the weight ratio of the first monomer is greater than 99.9 parts by weight, resistance to oily solvents or sebum may be insufficient. If the weight ratio of the second monomer is greater than 20 parts by weight or the weight ratio of the first monomer is less than 50 parts by weight, the polymer may not be formed due to phase separation, or resistance to polar solvents or resistance to sweat, tears, etc. may be insufficient.

In another example, the polymer may contain 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, or 80% or more of the polymerized units of the first monomer, based on weight. The ratio of the polymerized units of the first monomer, based on weight, may be 99% or less, 98% or less, 97% or less, 96% or less, 95% or less, 94% or less, 93% or less, 92% or less, 91% or less, or 90% or less. In such a state, the polymer may contain the polymerized units of the second monomer at a ratio of 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, or about 8 parts by weight or less, per 100 parts by weight of the polymerized units of the first monomer. The second monomeric polymerized units may be included in the polymer at a ratio of approximately 0.1 parts by weight or greater, 0.15 parts by weight or greater, 0.2 parts by weight or greater, or 5 parts by weight or greater, relative to 100 parts by weight of the first monomeric polymerized units. These ratios ensure resistance to oily solvents or sebum, and also effectively ensure resistance to polar solvents or resistance to sweat, tears, and the like.

In addition to the aforementioned first monomer and second monomer, the polymer may further contain other additional monomers.

For example, the polymer may include a silicon-containing compound, such as the compound represented by the following chemical formula 5, as a polymer unit. The compound represented by the following chemical formula 5 can form siloxane bonds within the polymer, which improves the polymer's cohesiveness and contributes to improved water resistance and oil resistance.

[Chemical Formula 5]

In Chemical Formula 5, R1 to R6 are each independently hydrogen, hydroxyl, alkyl, alkoxy, alkenyl, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy, or (meth)acryloyloxyalkyl, and at least one is alkenyl, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy, or (meth)acryloyloxyalkyl.

In addition, in Chemical Formula 5, n is a number within the range of 0 to 20.

In Chemical Formula 5, examples of the alkyl group or alkoxy group include linear, branched, or cyclic alkyl groups or alkoxy groups having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, which may be arbitrarily substituted with one or more substituents.

In Chemical Formula 5, examples of the alkenyl group include linear, branched, or cyclic alkenyl groups having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, which may be arbitrarily substituted with one or more substituents.

In Chemical Formula 5, at least one of R1 to R6 is a polymerizable functional group such as an alkenyl group, a (meth)acryloyl group, a (meth)acryloylalkyl group, a (meth)acryloyloxy group, or a (meth)acryloyloxyalkyl group. Through this functional group, the compound can be included as a polymerized unit in the polymer. The polymerizable functional group is typically a (meth)acryloylalkyl group or a (meth)acryloyloxyalkyl group. As described above, the alkyl group can be a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

In Chemical Formula 5, at least one, two or more, or three of R1 to R6 may be an alkoxy group.

In one example, the compound of Chemical Formula 5 may be the following: In Chemical Formula 5, n is 0, R1, R3, R5, and R6 are each independently hydrogen, an alkyl group, an alkoxy group, a (meth)acryloylalkyl group, or a (meth)acryloyloxyalkyl group, and at least one, two or more, or three of R1, R3, R5, and R6 are alkoxy groups, and at least one of R1, R3, R5, and R6 is a (meth)acryloylalkyl group or a (meth)acryloyloxyalkyl group. In this case, the alkyl group may be an alkyl group having 1 to 8 carbon atoms, and the alkoxy group may be an alkoxy group having 1 to 8 carbon atoms.

In another example, the compound of Chemical Formula 5 may be the following: In the above Chemical Formula 5, n is 1 or greater, R1 to R6 are each independently hydrogen, an alkyl group, an alkoxy group, a (meth)acryloylalkyl group, or a (meth)acryloyloxyalkyl group, and at least one of R1 to R6 is a (meth)acryloylalkyl group or a (meth)acryloyloxyalkyl group. In this case, among R1 to R6, the functional group other than a (meth)acryloylalkyl group or a (meth)acryloyloxyalkyl group may be an alkyl group. In the above, the alkyl group may be an alkyl group having 1 to 8 carbon atoms, and the alkoxy group may be an alkoxy group having 1 to 8 carbon atoms.

The polymer may include 50 to 99.9 parts by weight of polymerized units of the first monomer, 0.1 to 20 parts by weight of polymerized units of the second monomer, and 0.1 to 10 parts by weight of polymerized units of the compound of Chemical Formula 5. If the ratio of polymerized units of the compound of Chemical Formula 5 is too low, the effects of adding the compound, such as imparting gloss to the film or preventing diffusion, may be weak. If the ratio is too high, the polymer may exhibit properties unsuitable for film formation.

In another example, the polymer may contain 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, or 80% or more of the first monomer polymerized units, based on weight. The ratio of the first monomer polymerized units, based on weight, may be 99% or less, 98% or less, 97% or less, 96% or less, 95% or less, 94% or less, 93% or less, 92% or less, 91% or less, or 90% or less. In the above state, the polymer may contain polymerized units of the compound of Chemical Formula 5 at a ratio of 20 parts by weight or less, 15 parts by weight or less, 13 parts by weight or less, 10 parts by weight or less, or about 8 parts by weight or less, relative to 100 parts by weight of the first monomer polymerized units. The polymerized units of the compound of Chemical Formula 5 may be included in the polymer at a ratio of about 0.1 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, about 0.5 parts by weight or more, or about 1 part by weight or more, relative to 100 parts by weight of the polymerized units of the first monomer. These ratios ensure resistance to oily solvents or sebum, and effectively ensure resistance to polar solvents or resistance to sweat, tears, and the like.

In addition to the polymerized units of the first and second monomers, the polymer may further include polymerized units of a vinyl monomer. Such a vinyl monomer can effectively polymerize the hydrophilic and hydrophobic monomers without phase separation during polymerization.

The vinyl monomer can be selected and used without particular limitation as long as it can exhibit the above-mentioned functions.

Examples of such monomers include amide monomers such as N-acrylamide compounds, ester monomers such as vinyl ester compounds, and ether monomers such as vinyl ether compounds.

For example, as the vinyl monomer, a compound represented by the following Chemical Formula 6 may be used.

[Chemical Formula 6]

In Chemical Formula 6, X is a nitrogen atom or an oxygen atom, Y is a carbonyl group or a single bond, R1 and R3 are each independently hydrogen or an alkyl group, or R1 and R3 are linked together to form an alkylene group, and R2 is an alkenyl group (wherein, when X is an oxygen atom, R1 is not present).

In Chemical Formula 6, when Y is a single bond, no other atoms exist in the portion represented by Y, and a structure in which R3 and X are directly linked can be realized.

In Chemical Formula 6, R2 can be, for example, a linear, branched, or cyclic alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, and can be substituted or unsubstituted. Typically, the alkenyl group can be a vinyl group or an allyl group.

In Chemical Formula 6, R1 and R3 are each independently hydrogen or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or may be linked together to form an alkylene group having 1 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 8 carbon atoms. In the above, when R1 and R3 form an alkylene group, the compound of Chemical Formula 6 may be a cyclic compound.

As the vinyl monomer, for example, a compound in which X in the above Chemical Formula 6 is a nitrogen atom, Y is a carbonyl group, R1 and R3 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, and R2 is an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 8 carbon atoms; or a compound in which X in the above Chemical Formula 6 is a nitrogen atom, Y is a carbonyl group, R1 and R3 are linked to form an alkylene group having 3 to 12 carbon atoms, and R2 is an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 8 carbon atoms can be used. Examples of such compounds include, but are not limited to, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, and N-vinyl-N-methylacetamide.

Alternatively, the following compounds may be used as vinyl monomers: In the above Chemical Formula 6, X is an oxygen atom, Y is a single bond or a carbonyl group, R3 is an alkyl group having 1 to 20 carbon atoms, and R2 is an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 8 carbon atoms. Examples of such compounds include, but are not limited to, vinyl acetate, vinyl decanoate, vinyl neononanoate, and vinyl valerate.

The polymer may comprise 50 to 99.9 parts by weight of polymerized units of the first monomer, 0.1 to 20 parts by weight of polymerized units of the second monomer, and 1 to 30 parts by weight of polymerized units of the vinyl monomer. By adjusting the ratio of the vinyl monomer to the above-mentioned range, a polymer having target physical properties can be easily prepared without phase separation.

In another example, the polymer may contain 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, or 80% or more of the polymerized units of the first monomer, based on weight. The ratio of the polymerized units of the first monomer may be 99% or less, 98% or less, 97% or less, 96% or less, 95% or less, 94% or less, 93% or less, 92% or less, 91% or less, or 90% or less, based on weight. In the above state, the polymer may contain polymerized units of the vinyl monomer at a ratio of 60 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, about 40 parts by weight or less, about 30 parts by weight or less, about 25 parts by weight or less, about 20 parts by weight or less, or about 15 parts by weight per 100 parts by weight of the polymerized units of the first monomer. The polymerized units of the vinyl monomer may be included in the polymer at a ratio of about 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, about 2 parts by weight or more, or about 4 parts by weight or more relative to 100 parts by weight of the polymerized units of the first monomer. By adjusting the ratio of the vinyl monomer to the aforementioned range, a polymer having desired physical properties can be easily prepared without phase separation.

The polymer can be prepared using the first monomer and the second monomer in a known polymerization method. In one example, the polymer can be prepared by a solution polymerization method using a solvent (e.g., an organic solvent), such as a free radical solution polymerization method. For example, when the polymer is used for applications such as cosmetics that contact the human body, a solvent that is harmless to the human body can be selected as a solvent during the polymerization process. Examples of such solvents include, but are not limited to, isododecane, isoparaffins, and isohexadecane.

In one example, the preparation of the polymer described above is basically carried out in the presence of the first monomer and the second monomer, and may also be carried out in the presence of the vinyl monomer. This polymerization can be carried out by so-called solution polymerization.

That is, the preparation method of the present application may include a process of subjecting a monomer mixture comprising the first monomer, the second monomer, and the vinyl monomer to solution polymerization in a solvent.

In the above, the specific types of the first monomer and the second monomer or the vinyl monomer contained in the monomer mixture are as described above. In addition, if necessary, the monomer mixture may also contain other monomers such as the compound of Chemical Formula 5. Such monomers can be reacted in the presence of a suitable free radical initiator, and the specific type of initiator used in this case is not particularly limited.

In addition, the ratio of each monomer mentioned above can also be partially applied in the same manner as the ratio of each polymerized unit mentioned above, for example.

The polymerization can be carried out using an organic solvent, for example, a solvent having a dielectric constant (25° C.) in the range of 1 to 3. By using such a solvent, uniform mixing of the first and second monomer mixtures with the vinyl monomer can be achieved, thereby efficiently forming the target polymer, increasing the polymerization rate, and improving productivity.

The specific type of the above-mentioned solvent is not particularly limited. For example, liquid paraffin, specifically liquid paraffin having 8 to 14 carbon atoms such as isodedecane, can be used.

The above-mentioned preparation method can be carried out according to a conventional solution polymerization method, except for the aforementioned matters, such as the use of the above-mentioned monomer mixture. As mentioned above, the above-mentioned monomer mixture contains a first monomer and a second monomer, which are likely to undergo phase separation, but the presence of the vinyl monomer allows efficient polymerization to form a polymer.

In the present application, the polymer may have a weight average molecular weight (Mw) in the range of 10,000 to 500,000. In the present application, the weight average molecular weight may be, for example, a conversion value to standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight may refer to the weight average molecular weight unless otherwise specified. The molecular weight (Mw) as described above may be useful, for example, when the polymer is used as a film-forming agent. Within the range of the above molecular weight (Mw), the polymer can be used to effectively form a film without agglomeration, etc.

Such polymers can be used, for example, as film formers. They can form uniform films (films) by coating, exhibit high stability even when applied to skin, and are resistant to both polar and non-polar solvents, demonstrating excellent resistance to a variety of solvents, including sweat, tears, and sebum.

Therefore, these polymers are suitable for use in the preparation of film-forming agents or cosmetic compositions. These film-forming agents or cosmetic compositions can be used to prepare a variety of cosmetics, including facial masks, makeup products such as mascara for use on the corners of the mouth and eyes, nail polish for use on fingernails and toenails, lipstick, eye shadow, hairspray, and eyeliner. Furthermore, due to the aforementioned properties, these polymers and film-forming agents can also be used in pharmaceuticals. Examples of pharmaceutical applications include thin adhesive plasters and transdermal absorption preparations.

The ratio of the polymer in the skin external application composition, cosmetic composition, or mascara composition is not particularly limited and can be selected in consideration of the intended use, etc. For example, the polymer can be contained in the skin external application composition, cosmetic composition, or mascara composition at a ratio ranging from approximately 1% to 20% by weight.

The above-mentioned skin external preparation composition, cosmetic material composition or mascara composition may also contain other active ingredients according to the purpose. As additional active ingredients, not only cosmetic ingredients such as whitening or anti-ultraviolet rays can be exemplified, but also medicinal ingredients, physiologically active ingredients or pharmacologically active ingredients can be exemplified. As such active ingredients, examples include: local anesthetic ingredients (lidocaine, dibucaine hydrochloride, dibucaine, benzocaine, etc.), analgesic ingredients (salicylic acid derivatives such as methyl salicylate, indomethacin, piroxicam, ketoprofen, felbinac, etc.), anti-inflammatory ingredients (glycyrrhizic acid, glycyrrhizic acid dipotassium salts; glycyrrhetic acid, stearyl glycyrrhetinate, butylbenzyl hydroxy acid, benzyl nicotinate, hydrocortisone, hydrocortisone butyrate, hydrocortisone acetate, prednisone valerate acetate (prednisone valerate acetate, etc.) valeroacetate), prednisone acetate, prednisone, dexamethasone, dexamethasone acetate, dimethyl isopropyl azulene picroprofen, arnica extract, scutellaria baicalensis extract, cattail extract, chamomile extract, calamine, licorice extract, guaiac oil, gardenia extract, gentian extract, black tea extract, tocopherol, tocopheryl acetate, comfrey extract, perilla extract, peony extract, sage extract, swertia japonica extract, morus alba bark extract, pyridoxine hydrochloride, peach leaf extract, cornflower extract, saxifrage extract, mugwort extract, Roman chamomile extract, etc.), antihistamine ingredients (chlorpheniramine maleate, diphenhydramine, diphenhydramine hydrochloride, diphenhydramine salicylate, etc.), local irritant ingredients (ammonia, l-menthol, dl-camphor hor), peppermint oil, benzyl nicotinate, valyl nonylamide, etc.), antipruritic ingredients (crotamiton, etc.), antiseptic or bactericidal ingredients (acrinol, chlorhexidine gluconate, chlorhexidine hydrochloride, benzalkonium chloride, benzethonium chloride, povidone iodine, iodoform, iodine, potassium iodide, mercurochrome, cresol, triclosan, phenol, isopropyl cresol, thymol, sodium salicylate, undecylenic acid, photosensitizer, hinokitiol, phenoxyethanol, chlorobutanol, quaternary ammonium salt 73, zinc pyrithione, parabens, eucalyptus extract, raprosin rosemary, etc.), antifungal ingredients (clotrimazole, clotrimazole acetate, miconazole acetate, econazole acetate, bifonazole, oxoconazole acetate, sulconazole acetate, neticonazole hydrochloride, bifonazole and tioconazole, omoconazole acetate, etc. imidazole antifungal agents; terbinafine, terbinafine hydrochloride and allylamine antifungals such as naftifine; benzylamine antifungals such as butenafine; allylamine antifungals such as apomorphine hydrochloride; thiocarbamic acid antifungals such as tolnaftate and tolcylcerate; nitropyrrolidone, isazolam, ciclopirox, etc.) tissue repair ingredients (allantoin, heparin analogs, vitamin A palmitate, vitamin D2, retinyl acetate, retinol, vitamin A oil, panthenol, etc.), astringent ingredients (zinc oxide, acanthopanax senticosus extract, aluminum chloride, yellow cucurbit extract and its salts, citric acid, birch extract, tea extract, hops extract, horse chestnut extract, etc.), dead skin toughening ingredients (urea, glycerin, concentrated glycerin, potassium hydroxide, salicylic acid, sulfur, colloidal sulfur, resorcinol, glycolic acid, lactic acid, sodium sulfate, etc.), moisturizing ingredients (butylene glycol, sodium pyrrolidone carboxylate, propylene glycol , sodium salt of nucleic acid, angelica dahurica leaf extract, aspartic acid, alanine, arginine, sodium alginate, marshmallow extract, aloe vera extract, oyster extract, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed conchiolin, hydrolyzed eggshell membrane, hydrolyzed egg white, hydrolyzed silk, brown algae extract, quince extract, blackberry bush extract, xylitol, keto acid, cucumber extract, quince seed extract, glycine, glycerin, glucose, cape aloe extract, cystine, cysteine, mallow extract, serine, sorbitol, trehalulose, sodium lactate, sodium hyaluronate, placenta extract, loofah extract, reduced maltose, mannitol, lily extract, lactoferrin, lysine, apple extract, royal jelly extract, etc.), emollient ingredients (almond oil, avocado oil, olive oil, oleic acid, Atlantic bream oil (orange) roughyoil), cocoa butter, carrot extract, squalene, ceramide, evening primrose oil, grape seed oil, jojoba oil, macadamia nut oil, mineral oil, mink oil, eucalyptus oil, rosehip oil, petrolatum, etc.), whitening ingredients (ascorbic acid, ascorbic acid derivatives, arbutin, retinol (recinol), ellagic acid, glutathione, kojic acid, rosehip extract, kiwi extract, etc.), UV protection ingredients (para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, para-dimethylaminobenzoate The present invention also includes, but is not limited to, herbal extract ingredients, vitamins, amino acids or minerals, etc., including, but not limited to, amyl formate, 2-ethylhexyl p-dimethylaminobenzoate, tert-butyl methoxydibenzoylmethane, oxybenzones, octyl triazone, octyl salicylate, ethyl diisopropyl cinnamate, methyl diisopropyl cinnamate, cinnamon ether ester, dimethoxycinnamic acid glyceryl caprylate, octyl dimethoxybenzylidene dioxoimidazolidine propionate, tea extract, drometrizole, isopropyl p-methoxycinnamate, homosalate, octyl methoxycinnamate, etc.

The above-mentioned external skin preparation composition, cosmetic composition, or mascara composition may contain other solvents, solvents, additives, etc. depending on the application.

In the above, examples of the solvent or solvent component include alcohols (e.g., polyethylene glycol), ethers (in addition to ethyl ether, glycol ethers (cellosolves such as methyl cellosolve; dialkylene glycol alkyl ethers such as diethylene glycol diethyl ether), nitriles (acetonitrile), ketones (acetone), and esters (carboxylic acid alkyl esters such as ethyl acetate).

Examples of additives include, but are not limited to, plasticizers, wetting agents, defoaming agents, colorants, preservatives, fragrances, flavorings, pigments, and thickeners, and also include common ingredients used in quasi-drugs, pharmaceuticals, and cosmetics, such as powdered bases or carriers (binders, disintegrants, excipients, and lubricants), oily bases or carriers (animal and vegetable oils, petrolatum, paraffin oil, silicone oil, higher fatty acid esters or higher fatty acids), aqueous bases or carriers (gel bases such as xanthan gum), preservatives, chelating agents, antioxidants, fresheners, stabilizers, fluidizers, emulsifiers, thickeners, buffers, dispersants, adsorbents, moisturizers, wetting agents, desiccants, antistatic agents, and other resins (polyamide resins, olefin resins such as hydrogenated polybutene, etc.).

There are no particular limitations on the method for preparing the above-mentioned external skin preparation composition, cosmetic composition, mascara composition, etc. using the above-mentioned components or, if necessary, adding other known components, and a known method can be used.

Effects of the Invention

BRIEF DESCRIPTION OF THE DRAWINGS

The present application provides a composition for external use on skin, a cosmetic composition, or a mascara composition that utilizes a functional polymer suitable for film formation, exhibiting low solubility in polar and non-polar solvents, low diffusion properties in these solvents. Compositions utilizing such polymers exhibit resistance to various solvents, such as sebum, sweat, and tears, thereby effectively maintaining the long-lasting application of makeup.

DETAILED DESCRIPTION

Hereinafter, the present application will be specifically described with reference to Examples and Comparative Examples, but the scope of the present application is not limited to the following Examples.

In the following Examples and Comparative Examples, various physical properties were evaluated in the following manner.

1. Solubility determination of polymers

The polymer solution prepared in the embodiment or comparative example is kept at a temperature of about 150°C for about 60 minutes to evaporate the solvent. 1g of the polymer from which the solvent is evaporated is extracted. 1g of the extracted polymer is placed in 5g of a solvent (hexane, ethyl acetate, acetone or water), stirred at room temperature for 30 minutes, and then the insoluble residual polymer is removed. The transparent solution from which the residual polymer has been removed is fractionated and dried at 150°C for 30 minutes to remove the solvent. The solid content is calculated by comparing the mass of the residual polymer in the solution from which the solvent has been removed. The concentration of the polymer dissolved in the solvent is determined by the solid content, and the measured amount is converted into a value relative to 100g of solvent to determine the solubility. In the case where the solution is not transparent even after removing the residual polymer, the above process is performed after the solution is passed through a filter (0.45μm, NYLON) to obtain a transparent solution.

＜Solubility Evaluation Criteria＞

A: When the solubility is 15 or more

B: Solubility greater than 10 and less than 15

C: When the solubility is greater than 5 and less than 10

D: When the solubility is 5 or less

2. Molecular Weight Determination

The weight average molecular weight (Mw) and molecular weight distribution (PDI) were measured using GPC under the following conditions, and the measurement results were converted using standard polystyrene of an Agilent system to prepare a calibration curve.

<Measurement conditions>

Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

Column: Connected with 2 PL Mixed B

Column temperature: 40°C

Eluent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Concentration: ~1 mg/mL (inject 100 μL)

3. Calculation of glass transition temperature

The glass transition temperature (Tg) was calculated from the monomer composition using the following numerical formula.

<Numerical formula>

1/Tg＝ΣWn/Tn

In the above numerical formula, Wn is the weight fraction of each monomer in the polymer, Tn is the glass transition temperature displayed when the monomer forms a homopolymer of the polymer, and the right side of the above numerical formula is the weight fraction of the monomer used divided by the glass transition temperature displayed when the monomer forms a homopolymer of the polymer (Wn/Tn), calculated for each monomer, and the result of summing all the calculated values.

4. Sebum diffusion test

The polymer prepared in each preparation example was dissolved in isododecane as a solvent at a concentration of approximately 10% by weight. Ceresine, synthetic wax, and microcrystalline wax were dissolved at concentrations of 7%, 6%, and 8% by weight, respectively, at approximately 90°C to prepare Composition A. Propylene carbonate and disteardimonium hectorite were then added to Composition A at concentrations of 8% and 2% by weight, respectively, and uniformly dispersed for 20 minutes to prepare Composition B. Iron oxide (CI 77499) was then added to the mixture at a concentration of 6% by weight. An appropriate amount of preservative was then added, the mixture was dispersed for 30 minutes, and then slowly cooled to approximately 28°C to prepare a mascara formulation.

The sebum diffusion test using the prepared mascara formulation was conducted in both in vitro and in vivo tests, as detailed below.

In vitro tests

The mascara formulation was applied to a glass sheet (glass plate) at a thickness of 30 μm and then completely dried at room temperature. After drying, 0.1 g of water and sebum were added dropwise to the mascara. After 20 minutes, a cotton pad was placed on the mascara and moved back and forth 30 times with a force of 200 gf. The degree of seepage from the cotton pad was compared and evaluated according to the following criteria.

＜Evaluation Criteria＞

The degree of bleeding from the cotton pad was compared on a scale of 0 to 5, with a value of 5 being given for a case where the mascara did not bleed from the cotton pad at all, and a value of 3 being given for a control (reference) using the polymer of Comparative Example 1 below. The grade that was excellent compared to the control was numerically expressed to the first decimal place as a relative comparison between the samples.

In vivo testing:

Six hours after applying the prepared mascara formulation to the eyelashes of the subjects, images were taken for comparison and evaluation based on the following criteria.

＜Evaluation Criteria＞

After 6 hours, an image was taken and the diffusion area was analyzed and expressed as a numerical value. In the image analysis, the diffusion area was expressed as a numerical value in pixel units.

5. Water resistance test

The mascara formulation prepared above was applied to a glass sheet (glass plate) at a thickness of 30 μm and then completely dried at room temperature. The dried sample was then immersed in water at room temperature for approximately 30 minutes, removed, and water resistance was evaluated according to the following criteria based on the mass loss rate (=100×(1-B/A), unit: %), where A is the total mass of the glass sheet coated with the mascara formulation, and B is the total mass of the glass sheet measured after immersion in water, removal, and dehumidification.

＜Evaluation Criteria＞

A: When the mass reduction rate is 5% or less

B: Mass reduction rate greater than 5%

6.NMR evaluation method

0.1 g of the polymer solution prepared in the Examples or Comparative Examples was extracted and dissolved in 1 mL of the following NMR solvent. 1H-NMR was measured using the following analyzer according to the manufacturer's manual to confirm the composition and conversion rate of the polymer. For example, in the presence of unpolymerized monomer, a -H peak originating from =CH2 at the end of the double bond was observed in the H-NMR spectrum at approximately 5.7 ppm to 6.4 ppm. The composition of the resulting polymer can be confirmed by the area of the -H peak originating from each polymer structure.

<Measurement conditions>

Analytical instruments: 500 MHz NMR (Varian Unity Inova 500), 1H-NMR

Concentration: 10 to 20 mg/mL, solvent: CDCl3-d3 (deuterated chloroform)

Temperature: 25℃

Example 1

As shown in Table 1 below, a monomer mixture was prepared by mixing EHMA (2-ethylhexyl methacrylate), IBOMA (isobornyl methacrylate), and EOEOEA (ethoxyethoxyethyl acrylate) at a weight ratio of 25:60:15 (EHMA:IBOMA:EOEOEA). This monomer mixture was added to isododecane as a solvent to a total monomer concentration of approximately 35% by weight. Subsequently, the mixture was sparged with nitrogen for approximately 30 minutes at room temperature while stirring to remove dissolved oxygen. The deoxygenated reaction mixture was heated to approximately 70°C and sparged with nitrogen for approximately 40 minutes. When the temperature reached 70°C, an appropriate amount of a thermal initiator (V-65, Wako Chemicals) was added and dissolved in the isododecane solvent, and a polymerization reaction was carried out. After the reaction was allowed to proceed for about 24 hours, the temperature was lowered to room temperature to terminate the reaction and obtain a polymer solution.

Examples 2 to 10 and Comparative Examples 1 and 2

A polymer solution was obtained in the same manner as in Example 1 except that the types and ratios of the monomers in the monomer mixture were changed as shown in Tables 1 and 2 below.

Table 1

Table 2

1. NMR evaluation

NMR evaluation of the polymer of Example 1 revealed almost no 1H peaks derived from the double bond terminals of the monomers, confirming effective polymerization. Furthermore, a -CH- peak adjacent to -COO- of EHMA and IBOMA forming the polymer, as well as a peak derived from -OCH2CH2O- of EOEOEA, were observed in the 5.0 ppm to 3.5 ppm region, with an area value of 9. Furthermore, peaks derived from -CH2- and -CH3 at the meta position of the side chain were observed in the 2.5 ppm to 1.3 ppm region, with an area value of 36. The 1H peak derived from -CH2CH- or -CH2CH2 in the polymer main chain was observed in the 1.3 ppm to 0.5 ppm region, with an area value of 55.

The polymer of Example 2 was also evaluated by NMR in the same manner. As a result of the evaluation, almost no 1H peak of =CH2 from the double bond terminal was confirmed, which confirmed that polymerization was carried out effectively. In addition, the -CH- peak adjacent to -COO- of EHA and CHMA forming the polymer and the peak of -OCH2CH2O from EOEOEA were confirmed to have an area value of 10 in the region of 4.8ppm to 3.4ppm. In addition, a peak with an area value of about 3 was confirmed in the region of 2.5ppm to 2.0ppm from -CH2- adjacent to -COO- of EHA forming the polymer, and a peak with an area value of 57 was confirmed in the region of 2.0ppm to 1.5ppm from -CH2- of the side chain and -CH3 at the meta position. In addition, the 1H area value confirmed from -CH2CH- or -CH2CH2- of the polymer main chain was about 29 in the region of 1.5ppm to 0.5ppm.

In the case of the polymer of Example 3, almost no 1H peaks were observed for =CH2 at the double bond terminals. Furthermore, the -CH2- and -CH- peaks adjacent to -COO- of LMA and IBOMA, which form the polymer, and the -OCH2CH2-O and -OCH3 peaks derived from PEGMA appeared in the 4.7-3.3 ppm region, with an area value of 17. Furthermore, the peaks derived from -CH2- and -CH3 at the meta position of the side chains had an area value of 72 in the 2.0-1.5 ppm region, and the 1H peak derived from -CH2CH- in the polymer backbone had an area value of 11 in the approximately 1.5-0.5 ppm region.

In the NMR measurements of the polymer of Example 4, almost no 1H peaks were observed for =CH2 at the double bond terminals. Furthermore, the -CH2- and -CH- peaks adjacent to -COO- in LMA and IBOMA, which form the polymer, and the -OCH2CH2O- peak from EOEOEA appeared in the 4.7 ppm to 3.3 ppm region, with peak areas of 9. Furthermore, peaks with an area of 36 were observed in the 2.0 ppm to 1.5 ppm region from -CH2- and -CH3 at the meta position of the side chains, and a 1H peak with an area of 55 was observed from -CH2CH- or -CH2CH2- in the polymer main chain in the 1.5 ppm to 0.5 ppm region.

NMR analysis of the polymer in Example 5 revealed virtually no 1H peaks originating from the double bond terminals, indicating efficient polymerization. Furthermore, -CH2- and -CH- peaks adjacent to -COO- of the polymer-forming monomers LMA, IBOMA, and KBE-503, the -OCH2CH2O- peak derived from EOEOEA, and the SiO(CH2-)3 peak derived from KBE-503 were observed in the 4.7 to 3.3 ppm region, with an area value of 10. Peaks from the -CH2- and meta-positions of the side chains were observed in the 2.0 to 1.5 ppm region, with an area value of 35. Furthermore, 1H peaks from -CH2CH- or -CH2CH2- in the polymer backbone were observed in the 1.5 to 0.5 ppm region, with an area value of 55.

In Example 6, NMR analysis revealed that almost no 1H peaks were observed for =CH2 at the double bond terminals. A peak for -CH- adjacent to -COO- in EHMA, IBOMA, and KBM-503, the polymer-forming compounds, a peak for -OCH2CH2O- in EOEOEA, and a peak for -Si-O(CH3)3 in KBM-503 were observed in the 5.0-3.5 ppm region, with an area value of 9. Furthermore, peaks with an area value of 36 were observed in the 2.5-1.3 ppm region from -CH2- and -CH3 at the meta position in the side chains, and a 1H peak with an area value of 55 was observed in the 1.3-0.5 ppm region from -CH2CH- or -CH2CH2- in the polymer backbone.

Analysis of the polymer in Example 7 using the 1H-NMR evaluation method revealed virtually no 1H peaks originating from the terminal =CH2 double bonds. The -CH2- and -CH- peaks adjacent to -COO- of LMA, IBOMA, and KBE-503, the -OCH2CH2O- peak of EOEOEA, and the -SiO(CH2-)3 peak derived from KBE-503 were observed in the 4.7-3.3 ppm region, with an area value of 11. Peaks with an area value of 35 were observed in the 2.0-1.5 ppm region from the -CH2- and meta-positions of the side chains, and 55 from the 1H area value of -CH2CH- or -CH2CH2- in the polymer backbone, from 1.5-0.5 ppm.

NMR analysis of the polymer in Example 8 revealed no 1H peaks derived from the =CH2 residue at the double bond terminals, confirming efficient polymerization. Furthermore, peaks of -CH2- and -CH- adjacent to -COO- residues of LMA and IBOMA constituting the polymer, as well as peaks derived from -OCH2CH2-O and -OCH3 residues of PEGMA, were observed in the 5.0 to 2.8 ppm region, with an area value of 14. Furthermore, a -COO-CH3 peak of VA was observed, as well as peaks derived from -CH2- and -CH3 residues in the side chains in the meta position, with an area value of 35 in the 2.0 to 1.5 ppm region. 1H peaks derived from -CH2CH- and -CH2CH2- residues in the polymer backbone had an area value of 51 in the 1.5 to 0.5 ppm region.

In the case of the polymer of Example 9, almost no 1H peaks were observed for =CH2 at the double bond terminals. The -CH- peaks adjacent to -COO- of EHMA and IBOMA, the -OCH2CH2-O and -OCH3 peaks of PEGMA, and the -NCH2- peak derived from NVP appeared in the 5.0 ppm to 2.8 ppm region, with a peak area value of 9. Furthermore, peaks with an area value of 37 were observed in the 2.5 ppm to 1.5 ppm region from -CH2- and -CH3 at the meta position of the side chain, and the 1H area value of 54 was observed from -CH2CH- and -CH2CH2- in the polymer main chain in the 1.5 ppm to 0.5 ppm region.

In the case of Example 10, no 1H peak originating from =CH2 at the double bond terminal was observed. However, the -CH- peak adjacent to -COO- of EHMA and IBOMA constituting the polymer, the -OCH2CH2-O and -OCH3 peaks of PEGMA, and the -NCH2- peak originating from NVP were confirmed in the 5.0 ppm to 2.8 ppm region with an area value of 11. Furthermore, peaks with an area value of 37 were confirmed in the 2.5 ppm to 1.5 ppm region from -CH2- and -CH3 at the meta position of the side chain, and the 1H peaks from -CH2CH- and -CH2CH2- in the polymer main chain had an area value of 52 in the 1.5-0.5 ppm region.

2. Physical property evaluation

The results of measuring the physical properties of each polymer in Examples and Comparative Examples are summarized and described in Tables 3 and 4 below.

Table 3

Table 4

The above results confirm that the polymer used in the present application has low solubility in polar and non-polar solvents and is a polymer suitable for film formation having low diffusion properties in these solvents. Therefore, it can be confirmed that the polymer exhibits resistance to various solvents such as sebum, sweat, and tears, thereby providing a skin external application composition, cosmetic material composition, or mascara composition that can effectively maintain the durability of makeup, etc.

Claims (14)

1. A topical skin composition comprising a polymer, said polymer comprising a first monomer polymerization unit having a homopolymer solubility parameter of less than 10.0 (cal/ ^cm³ ) ^¹/² , a second monomer polymerization unit having a homopolymer solubility parameter of 10.0 (cal/ ^cm³ ) ^¹/² or greater, and a polymerization unit of a compound of chemical formula 5 below, wherein said polymer has a room temperature solubility of less than 10 in nonpolar solvents with a dielectric constant in the range of 1 to 3 at 25°C, and a room temperature solubility of less than 10 in polar solvents with a dielectric constant in the range of 75 to 85 at 25°C. The nonpolar solvent is hexane, and the polar solvent is water or acetone. The polymer comprises 70 to 99.9 parts by weight of the first monomer polymerization unit, 5 to 20 parts by weight of the second monomer polymerization unit, and 0.1 to 10 parts by weight of the polymerization unit of the compound of chemical formula 5 below. The first monomer is a compound represented by chemical formula 1 below, and the second monomer is a compound represented by chemical formula 2 or 3 below. Chemical formula 5 In the chemical formula 5, R1 to R6 are each independently hydrogen, hydroxyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, at least one of which is alkenyl, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, n is a number in the range of 0 to 20, the alkyl group in the (meth)acryloylalkyl group is an alkyl group with 1 to 4 carbon atoms, and the alkyl group in the (meth)acryloyloxyalkyl group is an alkyl group with 1 to 4 carbon atoms; Chemical Formula 1 In the chemical formula 1, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, and B is an alkyl group having 7 to 20 carbon atoms or an alicyclic hydrocarbon group having 6 to 18 carbon atoms. Chemical formula 2 In the chemical formula 2, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and m is a number in the range of 1 to 12. Chemical formula 3 In the chemical formula 3, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, A and U are each independently an alkylene group having 1 to 4 carbon atoms, X is a hydroxyl group, and n is a number in the range of 1 to 12. 2. A topical skin composition comprising a polymer, said polymer comprising a first monomer polymerization unit having a homopolymer solubility parameter of less than 10.0 (cal/ ^cm³ ) ^¹/² , a second monomer polymerization unit having a homopolymer solubility parameter of 10.0 (cal/ ^cm³ ) ^¹/² or greater, and polymerization units of a compound of formula 5 below, said polymer having a glass transition temperature in the range of 10°C to 110°C. The polymer comprises 70 to 99.9 parts by weight of the first monomer polymerization unit, 5 to 20 parts by weight of the second monomer polymerization unit, and 0.1 to 10 parts by weight of the polymerization unit of the compound of chemical formula 5 below. The first monomer is a compound represented by chemical formula 1 below, and the second monomer is a compound represented by chemical formula 2 or 3 below. Chemical formula 5 In the chemical formula 5, R1 to R6 are each independently hydrogen, hydroxyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, at least one of which is alkenyl, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, n is a number in the range of 0 to 20, the alkyl group in the (meth)acryloylalkyl group is an alkyl group with 1 to 4 carbon atoms, and the alkyl group in the (meth)acryloyloxyalkyl group is an alkyl group with 1 to 4 carbon atoms; Chemical Formula 1 In the chemical formula 1, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, and B is an alkyl group having 7 to 20 carbon atoms or an alicyclic hydrocarbon group having 6 to 18 carbon atoms. Chemical formula 2 In the chemical formula 2, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and m is a number in the range of 1 to 12. Chemical formula 3 In the chemical formula 3, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, A and U are each independently an alkylene group having 1 to 4 carbon atoms, X is a hydroxyl group, and n is a number in the range of 1 to 12. 3. The topical skin composition according to claim 1, wherein the polymer has a room temperature solubility of 5 or less in solvents with a dielectric constant in the range of 1 to 3 at 25°C. 4. The topical skin composition according to claim 1, wherein the polymer has a solubility of less than 5 at room temperature in a solvent with a dielectric constant in the range of 75 to 85 at 25°C. 5. The topical skin composition according to claim 1, wherein the polymer has a solubility of 15 or more at room temperature in a solvent with a dielectric constant in the range of 4 to 15 at 25°C. 6. The topical skin composition according to claim 1, wherein the solubility parameter of the homopolymer of the first monomer is in the range of 5 (cal/cm ³ ) ^1/2 to 9.5 (cal/cm ³ ) ^1/2 . 7. The topical skin composition according to claim 1, wherein the solubility parameter of the homopolymer of the first monomer is in the range of 7 (cal/cm ³ ) ^1/2 to 9 (cal/cm ³ ) ^1/2 . 8. The topical skin composition according to claim 1, wherein the first monomer is an alkyl (meth)acrylate. 9. The topical skin composition according to claim 1, wherein in the chemical formula 1, Q is hydrogen or methyl. 10. The topical skin composition according to claim 1, wherein the solubility parameter of the homopolymer of the second monomer is in the range of 10.0 (cal/ ^cm3 ) ^1/2 to 15.0 (cal/ ^cm3 ) ^1/2 . 11. The topical skin composition according to claim 1, wherein the solubility parameter of the homopolymer of the second monomer is in the range of 10.0 (cal/ ^cm3 ) ^1/2 to 13.0 (cal/ ^cm3 ) ^1/2 . 12. The topical skin composition according to claim 1 or 2, wherein the polymer further comprises a polymerization unit of a vinyl monomer. 13. A cosmetic material composition comprising a polymer, said polymer comprising a first monomer polymerization unit having a homopolymer solubility parameter of less than 10.0 (cal/ ^cm³ ) ^¹/² , a second monomer polymerization unit having a homopolymer solubility parameter of 10.0 (cal/ ^cm³ ) ^¹/² or greater, and a polymerization unit of a compound of chemical formula 5 below, wherein said polymer has a room temperature solubility of less than 10 in nonpolar solvents with a dielectric constant in the range of 1 to 3 at 25°C, and a room temperature solubility of less than 10 in polar solvents with a dielectric constant in the range of 75 to 85 at 25°C. The nonpolar solvent is hexane, and the polar solvent is water or acetone. The polymer comprises 70 to 99.9 parts by weight of the first monomer polymerization unit, 5 to 20 parts by weight of the second monomer polymerization unit, and 0.1 to 10 parts by weight of the polymerization unit of the compound of chemical formula 5 below. The first monomer is a compound represented by chemical formula 1 below, and the second monomer is a compound represented by chemical formula 2 or 3 below. Chemical formula 5 In the chemical formula 5, R1 to R6 are each independently hydrogen, hydroxyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, at least one of which is alkenyl, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, n is a number in the range of 0 to 20, the alkyl group in the (meth)acryloylalkyl group is an alkyl group with 1 to 4 carbon atoms, and the alkyl group in the (meth)acryloyloxyalkyl group is an alkyl group with 1 to 4 carbon atoms; Chemical Formula 1 In the chemical formula 1, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, and B is an alkyl group having 7 to 20 carbon atoms or an alicyclic hydrocarbon group having 6 to 18 carbon atoms. Chemical formula 2 In the chemical formula 2, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and m is a number in the range of 1 to 12. Chemical formula 3 In the chemical formula 3, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, A and U are each independently an alkylene group having 1 to 4 carbon atoms, X is a hydroxyl group, and n is a number in the range of 1 to 12. 14. A mascara composition comprising a polymer, said polymer comprising a first monomer polymerization unit having a homopolymer solubility parameter of less than 10.0 (cal/ ^cm³ ) ^¹/² , a second monomer polymerization unit having a homopolymer solubility parameter of 10.0 (cal/ ^cm³ ) ^¹/² or greater, and a polymerization unit of a compound of chemical formula 5 below, wherein said polymer has a room temperature solubility of less than 10 in nonpolar solvents with a dielectric constant in the range of 1 to 3 at 25°C, and a room temperature solubility of less than 10 in polar solvents with a dielectric constant in the range of 75 to 85 at 25°C. The nonpolar solvent is hexane, and the polar solvent is water or acetone. The polymer comprises 70 to 99.9 parts by weight of the first monomer polymerization unit, 5 to 20 parts by weight of the second monomer polymerization unit, and 0.1 to 10 parts by weight of the polymerization unit of the compound of chemical formula 5 below. The first monomer is a compound represented by chemical formula 1 below, and the second monomer is a compound represented by chemical formula 2 or 3 below. Chemical formula 5 In the chemical formula 5, R1 to R6 are each independently hydrogen, hydroxyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, at least one of which is alkenyl, (meth)acryloyl, (meth)acryloylalkyl, (meth)acryloyloxy or (meth)acryloyloxyalkyl, n is a number in the range of 0 to 20, the alkyl group in the (meth)acryloylalkyl group is an alkyl group with 1 to 4 carbon atoms, and the alkyl group in the (meth)acryloyloxyalkyl group is an alkyl group with 1 to 4 carbon atoms; Chemical Formula 1 In the chemical formula 1, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, and B is an alkyl group having 7 to 20 carbon atoms or an alicyclic hydrocarbon group having 6 to 18 carbon atoms. Chemical formula 2 In the chemical formula 2, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and m is a number in the range of 1 to 12. Chemical formula 3 In the chemical formula 3, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, A and U are each independently an alkylene group having 1 to 4 carbon atoms, X is a hydroxyl group, and n is a number in the range of 1 to 12.