KR101773679B1

KR101773679B1 - Skin external preparation composition

Info

Publication number: KR101773679B1
Application number: KR1020150179266A
Authority: KR
Inventors: 채해석; 최기환; 김경섭; 김수정; 윤정애; 윤성수; 홍상현
Original assignee: 주식회사 엘지생활건강
Priority date: 2014-12-15
Filing date: 2015-12-15
Publication date: 2017-08-31
Also published as: KR20160072813A

Abstract

The present application relates to a skin external composition composition, a cosmetic composition or a mascara composition. The present application can provide a composition for external application for skin, a cosmetic composition or a mascara composition to which a functional polymer having low solubility for polar and non-polar solvents and having a low bleeding characteristic for the solvent is applied. The composition to which the polymer is applied may exhibit resistance to various solvents such as sebum, perspiration and tears, so that the sustainability of make-up and the like can be effectively maintained.

Description

[0001] SKIN EXTERNAL PREPARATION COMPOSITION [0002]

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

Functional polymers may be required for the production of cosmetics or pharmaceuticals. For example, cosmetics such as mascara or other cosmetics or medicines applied to the skin may require a polymer having resistance to solvents having different properties such as sweat, tears and sebum. Patent Documents 1 and 2 disclose polymers to be applied to the production of cosmetics.

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-119140 Patent Document 2: JP-A 2003-055136

The present application provides a skin external composition composition, a cosmetic composition or a mascara composition. The present application is directed to providing a skin external composition composition, a cosmetic composition or a mascara composition comprising a functional polymer which exhibits a low solubility in polar and nonpolar solvents and is suitable for film formation in which bleeding against the solvent can be prevented, The purpose.

The composition for external application for skin of the present application may contain a polymer described later. The composition for external application for skin may be formulated into a cosmetic composition such as, for example, a mascara composition. In such a case, the composition may be formulated containing a cosmetically or dermatologically acceptable medium or base.

The formulation of the external skin application composition, cosmetic composition or mascara composition of the present application is not particularly limited and may be formed into various formulations depending on the purpose. For example, the formulation may be appropriately selected from a powder, a gel, an ointment, a cream, or a liquid. For example, the composition for external application for skin may be used as a softening agent, a nutritional lotion, a nutritional cream, a massage cream, an essence, a foam, a pack, a milky lotion, a foundation, a makeup base, a gel, a lotion, Sunflower oil, spray liquid, ointment, patch, spray, and the like.

In one example, the composition for external application for skin may be applied to a skin area where both water resistance and oil resistance are required, such as a hair growth area where sebum and sweat occur at the same time, for example, eyebrows, hair or armpits. But is not limited thereto.

For example, the mascara composition may include a polymer as described below as a film-forming agent. In this case, the mascara composition is prevented from being spread by the polymer due to tears or sweat, and smear of makeup by sebum can be prevented.

Hereinafter, the polymer contained in the composition for external application for skin, the cosmetic composition or the mascara composition will be described.

The polymer of the present application shows a low solubility in a polar solvent and a non-polar solvent. The term nonpolar solvent in the present application means a solvent having a dielectric constant at 25 DEG 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 means a solvent having a dielectric constant at 25 DEG C May be understood to mean a solvent having a dielectric constant in the range of about 75 to about 85 or about 75 to about 80. A typical example of the non-polar solvent is hexane (dielectric constant (25 캜): about 1.89). A typical example of the polar solvent is water (dielectric constant (25 캜): about 78.54) But is not limited to. Dielectric constants are known for each solvent in the chemical field.

In one example, the polymer may have a solubility in the polar solvent of 10 or less or 5 or less. In one example, the solubility of the polymer in the nonpolar solvent may be 10 or less or 5 or less. The lower limit of the solubility means that the polymer is more resistant to the solvent, the lower limit of the solubility is not particularly limited. In the present application, the solubility in a specific solvent means the number of grams (g) of the polymer capable of being dissolved to the maximum of 100 g of the solvent. In addition, unless otherwise specified, the solubility in the present application means the solubility measured at ambient temperature. In the present application, the term ambient temperature is a natural, non-warming or non-warming temperature, for example, a temperature within the range of about 10 ° C to 30 ° C, about 15 ° C to 30 ° C, or about 20 ° C to 30 ° C, Lt; / RTI >

The polymer may exhibit an appropriate solubility for a solvent in an intermediate stage of the polar and non-polar solvent. For example, the polymer may have a solubility in a solvent having a dielectric constant at 25 占 폚 in the range of 4 to 15, 5 to 15, 5 to 10, or 5 to 8, Lt; / RTI > Examples of such solvents include, but are not limited to, ethyl acetate (dielectric constant (25 캜): about 6.02).

The polymer having the above characteristics can be prepared, for example, by controlling the kind and proportion of the monomer forming the polymer.

For example, the polymer of the second monomer is greater than the solubility parameter of a single polymer 10 (cal / cm ^3), the solubility parameter of the polymeric unit and a single polymer of a first monomer 10 of less than ^1/2 (cal / cm3) ^1/2 Of polymerized units.

In this application, the solubility parameter refers to the solubility parameter of a homopolymer prepared by polymerizing the monomer, whereby the degree of hydrophilicity and hydrophobicity of the monomer can be determined. The manner of obtaining the solubility parameter is not particularly limited and may be in accordance with a method known in the art. For example, the parameter may be calculated or obtained according to a method known in the art as a so-called Hansen solubility parameter (HSP). The solubility parameter of a single polymer of the first monomer in the above is 5 In another example (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 . Further, the solubility parameter of the second monomer in the above is different from the example 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 . It is possible to form a polymer exhibiting the above-mentioned characteristics by appropriately applying a monomer having a solubility parameter in this range.

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

As the first monomer, various types of monomers can be selected and used as long as they have the above solubility parameter. As the monomer which can be used as the first monomer, alkyl (meth) acrylate or aromatic (meth) acrylate can be exemplified. The term (meth) acrylate in the present application may mean acrylate or methacrylate.

Examples of the alkyl group in the alkyl (meth) acrylate include linear, branched or cyclic alkyl groups of 1 to 20 carbon atoms, 4 to 20 carbon atoms, 8 to 20 carbon atoms, or 10 to 20 carbon atoms, The alkyl group may optionally be substituted by one or more substituents. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (Meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate or lauryl (meth) acrylate.

As the aromatic (meth) acrylate, aryl (meth) acrylate or arylalkyl (meth) acrylate can be exemplified. The aryl group of the aryl or arylalkyl in the above may be, for example, an aryl group having 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. The alkyl group of the arylalkyl 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. The alkyl group may be linear, branched or cyclic, and the alkyl or aryl group may be optionally substituted by one or more substituents.

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

As the first monomer, for example, a compound represented by the following formula (1) can be exemplified.

[Chemical Formula 1]

In the general formula (1), Q is hydrogen or an alkyl group, B is a linear or branched alkyl group having 4 or more carbon atoms or an alicyclic hydrocarbon group, or an aromatic substituent such as an aryl group or an arylalkyl group.

Examples of the alkyl group present in Q in the formula (1) 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 and 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic. The alkyl group may be optionally substituted with one or more substituents.

In formula (1), B may be a linear or branched alkyl group having 4 or more carbon atoms, 7 or more carbon atoms, or 9 or more carbon atoms. Such a compound containing a relatively long alkyl group is known as a hydrophobic compound. The upper limit of the number of carbon atoms of the linear or branched alkyl group is not particularly limited. For example, the alkyl group may be an alkyl group having 20 or less carbon atoms.

In another embodiment, B may be an alicyclic hydrocarbon group, for example, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms, and examples of such hydrocarbon groups include cyclohexyl group or iso And an alicyclic alkyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms, such as boronyl group, and the like. Compounds having an alicyclic hydrocarbon group are also known as relatively hydrophobic compounds.

Examples of the substituent which may optionally be substituted in the alkyl group, alkylene group or aromatic substituent in the formula 1 or the formula 2 or 3 to be described later include a halogen such as chlorine or fluorine, a glycidyl group, an epoxy alkyl group, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group or an alicyclic epoxy group, acryloyl group, methacryloyl group, isocyanate group,

Among such monomers, a suitable kind may be selected and used in consideration of the physical properties of the desired polymer.

As the second monomer, a monomer selected from monomers known to have the above-described solubility parameter can be used.

For example, as the second monomer, a compound represented by the following formula (2) or (3) may be used.

(2)

Q is hydrogen or an alkyl group, U is an alkylene group, Z is a hydrogen or an alkyl group, and m is an arbitrary number.

(3)

In 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.

Examples of the alkylene group in the formulas (2) and (3) 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 and 1 to 4 carbon atoms. The alkylene group may be linear, branched or cyclic. The alkylene group may optionally be substituted with one or more substituents.

Examples of the alkyl group present in Q and Z in formulas (2) and (3) 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 and 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

In the general formulas (2) and (3), m and n are arbitrary numbers, for example, each independently is 1 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, To 30, from 1 to 20, from 1 to 16, or from 1 to 12.

In one embodiment, 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 May be used in an amount of about 1 to 30, but the present invention is not limited thereto.

The polymer may be prepared by polymerizing the first and second monomers in an appropriate ratio.

For example, the polymer may include 50 to 99.9 parts by weight of the first monomeric polymerization unit and 0.1 to 20 parts by weight of the second monomeric polymerization unit. In another embodiment, the first monomeric polymerization unit may be present in an amount of 60 to 99.9 parts by weight, 70 to 99.9 parts by weight, or 80 to 99.9 parts by weight in another example. The second monomer polymerization unit may be contained in an amount of 5 to 20 parts by weight or 7 to 20 parts by weight. Unless otherwise specified, the unit weight portion in the present application may mean a weight ratio between the respective components. In addition, the weight ratio of the monomer polymerization unit may be a weight ratio of the monomer used in the production of the polymer. Therefore, for example, when the polymer comprises 50 to 99.9 parts by weight of the first monomer polymerization unit and 0.1 to 20 parts by weight of the second monomer polymerization unit, the first monomer and the second monomer are mixed in a weight of 50 to 99.9: 0.1 to 20 May mean that the polymer mixture is formed by polymerizing the monomer mixture comprising the monomer (first monomer: second monomer). If the weight ratio of the second monomer in the polymer is less than 0.1 part by weight or the weight ratio of the first monomer is more than 99.9 parts by weight, resistance to oil solvent or endodiffic resistance may not be sufficient, and the weight ratio of the second monomer If 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 the like, resistance to polar solvents, or resistance to perspiration or tears may not be sufficient.

In another example, the polymer may comprise at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, or at least 80% by weight of the polymerized units of the first monomer. Wherein the ratio of the first monomeric polymerization units is 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% % &Lt; / RTI > In the above state, the polymer may be such that the polymerization unit of the second monomer is 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 15 parts by weight or less, 10 parts by weight or less, or about 8 parts by weight or less. The polymerization unit of the second monomer may be contained in an amount of about 0.1 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, or 5 parts by weight or more based on 100 parts by weight of the polymerized units of the first monomer. Resistance to a polar solvent, resistance to perspiration or tears can be effectively ensured while securing the resistance to oil-based solvents and the resistance to an oil-based solvent at the above ratios.

The polymer may include additional monomers for imparting other functions besides the first and second monomers described above, for example, for controlling the glass transition temperature and the like.

The polymer may be prepared by a known polymerization method using the first and second monomers. In one example, the polymer may be prepared by a solution polymerization method using a solvent, for example, an organic solvent, for example, a radical solution polymerization method. For example, when the polymer is applied to a use in contact with the human body such as cosmetics, a solvent which is friendly to the human body can be selected and used in the polymerization process. Examples of such solvents include, but are not limited to, isododecane, isoparaffin, or isohexadecane.

In the present application, the polymer may have a weight average molecular weight (Mw) in the range of 10,000 to 500,000. The weight average molecular weight in the present application may be, for example, a conversion value relative to standard polystyrene measured using GPC (Gel Permeation Chromatograph), and unless otherwise specified, the term molecular weight may refer to a weight average molecular weight have. The molecular weight (Mw) as described above may be useful, for example, when the polymer is applied as a film-forming agent. It is possible to efficiently form a coating film without aggregation or the like by using the polymer in the molecular weight (Mw) range.

In the present application, the polymer may have a glass transition temperature in the range of 10 占 폚 to 70 占 폚. In the present application, the glass transition temperature is a theoretical value obtained from the monomer composition of the polymer through the so-called Fox equation. Such a glass transition temperature may be useful, for example, when the polymer is applied as a film forming agent. The polymer can be used in the range of the glass transition temperature to enable the formation of a film efficiently without tackiness or cracking.

Such a polymer may be used, for example, as a film former. Such a polymer can form a uniform film (coating) by application or the like, exhibits high stability even when it is applied to skin or the like, exhibits resistance to both polar and non-polar solvents and can be used in various solvents such as sweat, It is possible to exhibit excellent resistance to the above.

Accordingly, the polymer can be used in the manufacture of various cosmetics including nail polish, lipstick, eye shadow, styling agent for hair, eye liner, etc. that can be applied to makeup of mascara and the like applied to the cosmetic pack, And can be applied to the production of film formers or compositions for cosmetics. In addition, the polymer or film forming agent can be applied to medicines by the above-mentioned characteristics. Examples of medicinal uses include bandages and transdermal absorption preparations.

The proportion of the polymer in the external preparation for skin, the cosmetic composition or the mascara composition is not particularly limited and may be selected in consideration of the application and the like. For example, the polymer may be included in the skin topical composition, cosmetic composition or mascara composition at a ratio within a range of about 1% to 20% by weight.

The external preparation for skin, the cosmetic composition or the mascara composition may further contain other active ingredients depending on the use. Examples of the additional effective ingredient include not only cosmetic ingredients such as whitening and ultraviolet ray shielding but also active ingredients, physiologically active ingredients, and pharmacologically active ingredients. Examples of such effective components include local anesthetic components (lidocaine, dibucaine hydrochloride, dibucaine, ethyl benzoate), analgesic components (salicylic acid derivatives such as methyl salicylate, indomethacin, piroxycam, ketoprofen, Etc.), antiinflammatory components (glycyrrhetinic acid, glycyrrhizinic acid salts such as dipotassium glycyrrhizinate, glycyrrhetinic acid, stearyl glycyrrhetinate, bepsiamark, benzyl nicotinate, hydrocortisone, hydrocortisone, Dicamethasone, dexamethasone acetate, dimethylisopropyl azelene propionate, alnica extract, golden extract, toad extract, chamomile extract, carrageenan, acaric acid hydrocortisone, valproic acid acetic acid prednizone, Ginseng extract, licorice extract, guaiazulene, gardenia extract, gentian extract, black tea extract, tocopherol, tocopheryl acetate, carrot extract, (Antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants, , Ammonia, l-menthol dl-can pool, peppermint oil, nicotinic acid benzyl, nonylic acid waniramide and the like), zinnia ingredient (crotonic acid (Iodine), iodide, potassium iodide, merbromin, oxyder, cresol, tricholinic acid, etc.), antiseptic or disinfecting components (acinol, chlorhexidine gluconate, chlorhexidine hydrochloride, benzalkonium chloride, benzethionium chloride, povidone iodide, , Phenol, isopropylmethylphenol, thymol, sodium salicylate, undecylenic acid, photosensor, hinokitiol, phenoxyethanol, chlorobutanol, quaternium 73, chinpyrithione, paraoxybenzoic acid esters, eucalyptus extract, resorcinol rosemary extract, etc.), antifungal compounds (such as clotrimazoacetate, crotriamazoate, myconazole acetate, eicosanol acetate, Imidazole antifungal agents such as oxycodone acetate, oxaconazole acetate, sorconosuric acid hydrochloride, Nechikonajor hydrochloride, biponazole and thioconazole, and acomoxanthorrhic acid, allyl amines such as terbinafine, terbinafine hydrochloride and naftifine Benzylamine-based antifungal agents such as amine-based antifungal agents and butenaphin, allylamine-based antifungal agents such as amorphous hydrochloride, thiocarbamate-based antifungal agents such as tranafate and tricylate, pyrrolitrin, Vitamin A 2 palmitate, vitamin D2, retinol acetate, retinol, vitamin A oil, panthenol, etc.), convergent components (acid, Glycerin, concentrated glycerin, potassium hydroxide, salicylic acid, salicylic acid, glycerin, glycerin, glycerin, glycerin, glycerin, (Butylene glycol, sodium pyrrolidonecarboxylate, propylene glycol, sodium ribonucleic acid, myrtle extract, asuragic acid, alanine, arginine alginate Hydrolyzed collagen, hydrolyzed collagen, hydrolyzed egg shell, hydrolyzed egg white, hydrolyzed silk, algae extract, chrysanthemum extract, kiwi extract Kiss, xylitol, chitosan, cucumber extract, kuinsseedekisu, glycine, glycerin, glucose, caprolaoe extract, cystin, cysteine, A lotion, an extract of lycopene, an extract of lychee, an apple extract, a royal jelly extract, etc.) were added to a molybdate solution Ingredients (almond oil, avocado oil, olive oil, oleic acid, orange raffia oil, cacao oil, carrot acid, squalane, ceramide, evening primrose oil, grape seed oil, jojoba oil, macadamia nut oil, mineral oil, mink oil, eucalyptus oil, Oil, and lanolin), whitening components (ascorbic acid, ascorbic acid derivatives, arbutin, lecithin, eragic acid, glutathione, kojic acid, age cane kiss, kiwi extract, etc.) Ethyl ester of p-aminobenzoic acid, amyl alcohol of paradimethylaminobenzoic acid, Ethylhexyl alcohol ester of terpara dimethylamino benzoic acid, t-butylmethoxydibenzoylmethane, oxybenzyne, octyltriazone, octyl salicylate, ethyl diisopropylpropionate, methyl diisopropylpropionate, synokisite, dimethoxy Octyl methoxycinnamate, octyl methoxycinnamate, etc.), herbal extract components (such as glyceryl octanoate, glyceryl octanoate, dimethoxybenzylidene dioxoimidazolidinone octylate, chestnut extract, drometrizol, paramethoxycarboxylic acid isopropyl, , Vitamins, amino acids, or minerals. However, the present invention is not limited thereto.

The external preparation for skin, cosmetic composition or mascara composition may contain other solvent, solvent or additive depending on the use.

Examples of the solvent or solvent component may include, but are not limited to, alcohols (e.g., polyethylene glycol), ethers (such as diethyl ether and the like, glycol ethers such as methyl cellosolve, etc.) (Acetonitrile, etc.), ketones (acetone, etc.) or esters (e.g., carboxylic acid alkyl esters such as ethyl acetate, etc.) ) Can be exemplified.

Examples of the additives include publicly known components such as a plasticizer, a wetting agent, a defoaming agent, a colorant, a preservative, a fragrance, a flavoring agent, a pigment or a thickener as well as an ingredient for use in quasi-drugs, medicines or cosmetics such as a powdery base or carrier (Base oil, wax, petroleum jelly, paraffin oil, silicone oil, higher fatty acid ester or higher fatty acid), aqueous base or carrier (gel base such as xanthan gum, etc.) Etc.), a preservative, a chelating agent, an antioxidant, a coolant, a stabilizer, a fluidizing agent, an emulsifier, a tackifier, a buffering agent, a dispersant, an adsorbent, a humectant, a humectant, a desiccant, Olefin resins such as polybutene), and the like, but the present invention is not limited thereto.

The method for manufacturing the external preparation for skin, the cosmetic composition or the mascara composition using the above-mentioned components or, if necessary, further other known components is not particularly limited and a known method can be applied.

The present application can provide a composition for external application for skin, a cosmetic composition or a mascara composition to which a functional polymer having low solubility for polar and non-polar solvents and having a low bleeding characteristic for the solvent is applied. The composition to which the polymer is applied may exhibit resistance to various solvents such as sebum, perspiration and tears, so that the sustainability of make-up and the like can be effectively maintained.

The present application will be described in detail by way of 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, physical properties were evaluated in the following manner.

1. Measurement of solubility of polymer

The polymer solution prepared in the example or the comparative example is kept at a temperature of about 150 캜 for about 60 minutes to volatilize the solvent. Collect 1 g of the volatilized polymer. 1 g of the collected polymer is added to 5 g of a solvent (hexane, ethyl acetate, acetone or water), stirred at room temperature for 30 minutes, and then the undissolved residual polymer is removed. The transparent solution from which the residual polymer has been removed is collected and dried at 150 ° C for 30 minutes to remove the solvent. The solids content is calculated by comparing the mass of the remaining polymer in the solvent-free solution. The solubility is determined by measuring the concentration of the polymer dissolved in the solvent through the solid content and converting the measured amount into the value for 100 g of the solvent. If the solution is not transparent after removal of the residual polymer, the solution is passed through a filter (0.45 탆 NYLON) to obtain a clear solution, followed by the above procedure.

A: Solubility of 15 or more

B: Solubility of more than 10, less than 15

C: Solubility of more than 5, less than 10

D: Solubility of 5 or less

2. Molecular weight measurement

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

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

Column: Two PL Mixed B connections

Column temperature: 40 ° C

Eluent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

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

3. Estimation of glass transition temperature

The glass transition temperature (Tg) was calculated by the following formula according to the monomer composition.

1 / Tg =? Wn / Tn

In the above formula, Wn is the weight fraction of each monomer in the polymer, Tn is the glass transition temperature that occurs when the monomer forms a homopolymer, and the right side of the formula indicates the weight fraction of the monomer used to form the homopolymer (Wn / Tn) divided by the glass transition temperature in the case where the glass transition temperature (Tg) was measured for each monomer.

4. sebum blurring test

The polymer prepared in each Preparation Example was dissolved in isododecane as a solvent at a concentration of about 10% by weight, ceresine, synthetic wax and microcrystalline wax were dissolved in 7 wt% %, 6 wt% and 8 wt%, respectively, at a temperature of about 90 캜 to prepare a composition A. Subsequently, propylene carbonate and distearmonium hectorite were added to the composition A at a concentration of 8 wt% and 2 wt%, respectively, and the mixture was uniformly dispersed for 20 minutes to prepare a composition B. Subsequently, iron oxide (CI 77499) is added at a concentration of 6% by weight, preservatives are added in an appropriate amount, dispersed for 30 minutes, and slowly cooled to about 28 캜 to prepare a mascara formulation .

The sebum blurring test using the manufactured mascara formulation was carried out in an in-vitro test and an in-vivo test, and the details are as follows.

In-vitro testing

The mascara formulation is applied to a slide glass (glass plate) to a thickness of 30 탆, and is then completely dried at room temperature. After drying, 0.1 g of water and 0.1 g of sebum were each dropped on the mascara, left for 20 minutes, put on a cotton pad, and reciprocated 30 times at a force of 200 gf. .

When a comparison was made on a scale within the range of 0 to 5 according to the degree of the appearance on the cotton wool, the case where no mascara was observed on the cotton wool was designated as 5, and the case where the polymer of Comparative Example 1 was applied was referred to as a reference. , And the superior level to the control group was quantified to the first decimal place by a relative comparison between the samples.

In-vivo testing:

The prepared mascara formulations were applied to the subject's eyelashes, and images were taken after 6 hours, and compared and evaluated according to the following criteria.

After 6 hours, images are taken and the blurring area is analyzed by image analysis. The area of blur at the time of image analysis is expressed in units of pixels.

5. Water resistance test

The dried mascara formulations were applied to a slide glass (glass plate) to a thickness of 30 탆 and dried thoroughly at room temperature. The dried sample was immersed in water at room temperature for about 30 minutes and then taken out to obtain a mass reduction rate (= B is the total mass of the slide glass coated with the mascara formulation, and B is the total mass of the slide glass measured after removing the water after being immersed in water, The water resistance is evaluated according to the standard.

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

B: If the mass reduction rate exceeds 5%

6. NMR Evaluation Method

0.1 g of the polymer solution prepared in the Example or Comparative Example was taken out and dissolved in 1 mL of the following NMR solvent. 1 H-NMR was measured using the following analytical instrument according to the manufacturer's manual, You can see the conversion rate. For example, in the presence of an unpolymerized monomer, a -H peak derived from = CH2 of the double bond end in the < 1 > H-NMR spectrum is confirmed at about 5.7 ppm to 6.4 ppm, and -H The area of the peak can be used to identify the constituents of the polymer.

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

Concentration: 10 to 20 mg / mL, solvent: CDCl3-d3

Temperature: 25 ℃

Example 1.

As shown in Table 1, a monomer mixture prepared by mixing EHMA (ethylhexyl methacrylate), IBOMA (isobornyl methacrylate) and EOEOEA (ethoxyethoxyethyl acrylate) in a weight ratio of 25:60:15 (EHMA: IBOMA: EOEOEA) To the isododecane was added so that the concentration of the entire monomer was about 35% by weight, and then dissolved oxygen was bubbled through the flask with nitrogen for about 30 minutes at room temperature with stirring. The oxygen-depleted reaction mixture was further subjected to nitrogen bubbling for about 40 minutes while raising the temperature to about 70 ° C. When the temperature was increased to 70 ° C., a proper amount of a thermal initiator (V-65, Wako Chemicals) was dissolved in isododecane, which was a solvent, and the polymerization reaction was allowed to proceed. After the reaction was continued for about 24 hours, the temperature was lowered to room temperature to terminate, and a polymer solution was obtained.

Examples 2 to 4 and Comparative Examples 1 and 2

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

Example Comparative Example One 2 3 4 One 2 Polymer A B C D E F EHA 15 LMA 20 15 EHMA 30 CHMA 75 IBOMA 60 74 75 EOEOEA 10 10 10 PEGMA 6 TMSS 100 PVP 100 Content Unit: g
EHA: ethyl hexyl acrylate (single polymer solubility parameter: 8.4 (cal / cm ³ ) ^1/2 )
LMA: lauryl methacrylate (single polymer solubility parameter: 8.2 (cal / cm ³ ) ^1/2 )
EHMA: ethylhexyl methacrylate (single polymer solubility parameter: 8.3 (cal / cm ³ ) ^1/2 )
CHMA: cyclohexyl methacrylate (single polymer solubility parameter: 7.9 (cal / cm ³ ) ^1/2 )
IBOMA: isobornyl methacrylate (single polymer solubility parameter: 8.1 (cal / cm ³ ) ^1/2 )
EOEOEA: ethoxyethoxy ethylacrylate (single polymer solubility parameter: 10.6 (cal / cm ³ ) ^1/2 )
PEGMA: polyethyleneglycol monoethyl ether methacrylate (mole number of ethylene oxide unit: 9 moles, solubility parameter of single polymer: 10.8 (cal / cm ³ ) ^1/2 )
TMSS: trimethylsiloxysilicate (single polymer solubility parameter: 7.5 (cal / cm ³ ) ^1/2 ) (Trimethyl siloxysilicate: Dow Corning MQ-1600 Resin)
PVP: polyvinyl pyrrolidone (single polymer solubility parameter: 11 (cal / cm ³ ) ^1/2 , Aldrich K30)
Mw: Weight average molecular weight (x 10000)
Tg: glass transition temperature (unit: ° C)

1. NMR Evaluation

As a result of NMR analysis for the polymer of Example 1, it was confirmed that 1H peak originating from ═CH _{2 at} the double bond end of the monomer was hardly confirmed, confirming effective polymerization. Further, peaks derived from EHMA formed of polymer and -CH ₂ -chain adjacent to -COO- and -OCH ₂ CH ₂ O- of EOEOEA were observed in the range of 5.0 ppm to 3.5 ppm, where the area value of the peak was 9. Also, a peak derived from -CH ₂ - in the side chain and -CH ₃ derived from the meta position was identified as a peak in the area value 36 in the range of 2.5 ppm to 1.3 ppm, and -CH ₂ CH- or -CH The peak of 1 H found from ₂ CH ₂ - was found to have an area of 55 in the 1.3 ppm to 0.5 ppm region.

The NMR of the polymer of Example 2 was also evaluated. As a result of the evaluation, 1H peak derived from ═CH _{2 at the} double bond end was hardly confirmed and it was confirmed that the polymerization was efficiently performed. Also, the peaks derived from the EHA formed of the polymer and the -COO-adjacent -CH-peak of CHMA and -OCH ₂ CH ₂ O- of EOEOEA were confirmed to have an area value of 10 in the region of 4.8 ppm to 3.4 ppm. Also adjacent -CH ₂ EHA of -COO- formed of polymer-area from the value was about third of the peak found at 2.5 ppm to 2.0 ppm region, the side chain -CH ₂ - -CH ₃ from the origin in the meta-position 2.0 a peak of an area value of 57 was confirmed in the range of ppm to 1.5 ppm. Further, the 1H area value determined from -CH ₂ CH- or -CH ₂ CH ₂ - derived from the main chain of the polymer was about 29 at 1.5 ppm to 0.5 ppm.

Also in the case of the polymer of Example 3, 1H peak derived from ═CH _{2 at the} double bond end was hardly recognized. In addition, a peak derived from the -COO-adjacent -CH ₂ - and -CH- peaks of LMA and IBOMA formed of the polymer and -OCH ₂ CH ₂ -O and -OCH ₃ of PEGMA appeared in the region of 4.7 ppm to 3.3 ppm And the area value of the peak was 17. In addition, the side chain of the -CH ₂ - is -CH ₃ peak from the origin at the meta position was identified at 2.0 ppm to 1.5 ppm region to the area value of 72, 1H is checked by a -CH ₂ CH- derived from the polymer backbone The area value of the peak was 11 in the range of about 1.5 ppm to 0.5 ppm.

As a result of NMR measurement on the polymer of Example 4, 1H 1H derived from = CH2 of the double bond end was hardly observed. In addition, the peaks derived from the -COO-adjacent -CH ₂ - and -CH- peaks of LMA and IBOMA formed of the polymer and -OCH ₂ CH ₂ O- of EOEOEA appear in the range of 4.7 ppm to 3.3 ppm, 9. Also, peaks of an area value of 36 in the range of 2.0 ppm to 1.5 ppm from -CH ₃ derived from -CH ₂ - in the side chain and -CH ₃ derived from the meta-position were confirmed, and -CH ₂ CH- or -CH ₂ CH ₂ - The confirmed 1H area value was 55 at 1.5 ppm to 0.5 ppm.

2. Property evaluation

The results of measuring the physical properties of the polymers of Examples and Comparative Examples are summarized in Table 2 below.

Example Comparative Example One 2 3 4 One 2 Polymer A B C D E F for
year
Degree
Hexane D C D D A D Ethyl acetate A A A A A D Acetone C D D D A D water D D D D D A sebum
Smear In vitro 4.1 4.0 3.8 4.0 3.0 3.3 In vivo 2300 3100 3200 3000 4500 3800 Water resistance test A A A A A B Weight average molecular weight 35 million 300,000 20 million 20 million Glass transition temperature (캜) 34 31 38 42

From the above results, it can be seen that the polymer used in the present application exhibits low solubility in polar and non-polar solvents and is suitable for film formation having low bleeding characteristics with respect to the solvent, A cosmetic composition or a mascara composition can be provided which can exhibit resistance to various solvents and can maintain the durability of make-up and the like effectively.

Claims

The solubility parameter of a single polymer 10.0 (cal / cm ³⁾ ^1/2 is less than the first solubility parameter of the monomer polymerized units from 50 to 99.9 parts by weight of a single polymer 10.0 (cal / cm ³⁾ ^1/2 or more second monomer polymerized units 0.1 to 20 parts by weight of a solvent having a dielectric constant (25 캜) within a range of 1 to 3 and a solubility at room temperature of 10 or less and a dielectric constant (25 캜) Wherein the solubility of the polymer is 5 or less.

The composition for external application for skin according to claim 1, wherein the polymer has a solubility at room temperature of 5 or less for a solvent having a dielectric constant (25 캜) within a range of 1 to 3.

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The composition for external application for skin according to claim 1, wherein the polymer has a solubility at room temperature of not less than 15 for a solvent having a dielectric constant (25 DEG C) within a range of 4 to 15. [

The composition of claim 1, wherein the first monomer has a solubility parameter of the single polymer within a range of 5 (cal / cm ³ ) ^1/2 to 9.5 (cal / cm ³ ) ^1/2 .

The composition according to claim 1, wherein the first monomer has a solubility parameter of the single polymer within a range of 7 (cal / cm ³ ) ^1/2 to 9 (cal / cm ³ ) ^1/2 .

The composition of claim 1, wherein the first monomer is an alkyl (meth) acrylate or an aromatic (meth) acrylate.

The external preparation for skin according to claim 1, wherein the first monomer is a compound represented by the following formula (1):
[Chemical Formula 1]

In Formula (1), Q is hydrogen or an alkyl group, and B is a linear or branched alkyl group having 4 or more carbon atoms, an alicyclic hydrocarbon group or an aromatic substituent group.

9. The composition for external application for skin according to claim 8, wherein the aromatic substituent is an aryl group or an arylalkyl group.

The composition for external application for skin according to claim 8, wherein Q in the formula (1) is hydrogen or a methyl group, and B is an alkyl group having 7 or more carbon atoms or an alicyclic hydrocarbon group having 6 to 18 carbon atoms.

The composition of claim 1, wherein the second monomer has a solubility parameter of the single polymer within a range of 10.0 (cal / cm ³ ) ^1/2 to 15.0 (cal / cm ³ ) ^1/2 .

The composition of claim 1, wherein the second monomer has a solubility parameter of the single polymer within a range of 10.0 (cal / cm ³ ) ^1/2 to 13.0 (cal / cm ³ ) ^1/2 .

The external preparation for skin according to claim 1, wherein the second monomer is a compound represented by the following formula (2) or (3):
(2)

Q is hydrogen or an alkyl group, U is an alkylene group, Z is a hydrogen or an alkyl group, and m is an arbitrary number.
(3)

In Formula (3), Q is hydrogen or an alkyl group, A and U are each independently an alkylene group, X is a hydroxyl group or a cyano group, and n is an arbitrary number.

And Q is 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, m is an integer from 1 to 30, Of the total amount of the composition.

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The composition for external application for skin according to claim 1, wherein the polymer comprises 70 to 99.9 parts by weight of the first monomer polymerization unit and 5 to 20 parts by weight of the second monomer polymerization unit.

The solubility parameter of a single polymer 10.0 (cal / cm ³⁾ ^1/2 is less than the first solubility parameter of the monomer polymerized units from 50 to 99.9 parts by weight of a single polymer 10.0 (cal / cm ³⁾ ^1/2 or more second monomer polymerized units 0.1 to 20 parts by weight of a solvent having a dielectric constant (25 캜) within a range of 1 to 3 and a solubility at room temperature of 10 or less and a dielectric constant (25 캜) Wherein the solubility in the mascara composition is 5 or less.