KR100642624B1 - Perfluoroalkyl phenylalkyl polysiloxane and cosmetic composition comprising the same - Google Patents

Abstract

Provided are perfluoro alkyl (phenyl alkyl) polysiloxanes and cosmetic compositions comprising the same.

Perfluoroalkyl (phenyl alkyl) polysiloxane according to the present invention is excellent in water resistance and oil resistance, and excellent compatibility, there is no odor is suitable for use in the cosmetic composition, the cosmetic composition comprising the same spreads smoothly when used And skin adhesion is good, does not adhere to coffee mugs and clothes, and excellent makeup persistence.

Perfluoroalkyl (phenyl alkyl) polysiloxanes, dimethicone, cosmetic compositions

Description

Perfluoroalkyl (phenylalkyl) polysiloxane and cosmetic composition comprising the same}

The present invention relates to a cosmetic composition, and more particularly, to a perfluoro alkyl (phenyl alkyl) polysiloxane and a cosmetic composition containing the same, having excellent water resistance, oil resistance and skin adhesion.

Cosmetic composition generally means a composition which protects the skin and imparts aesthetics by applying it to the human body, especially the face. A lotion or cream that protects and nourishes the skin has the function of preventing oil loss in the skin by forming an oil film, but a problem of inferior makeup effect is caused by water or sweat. In addition, in the case of foundation or lipstick which makes the face look healthy and beautiful, makeup products are not only erased by sebum sweat, but in the case of mascara and lipstick, the color, cover effect, gloss, etc. A problem arises.

Accordingly, in order to solve the above problems, conventionally, a method of increasing the water resistance by forming a film of wax or oil and a method of increasing the water resistance and oil resistance by silicone oil or silicone resin have been used. As such, the oil component used in the cosmetic composition should be free of odors, should not change color with time, and have good texture when applied to the skin.

Japanese Patent Laid-Open No. 6-199630 discloses a cosmetic composition comprising polydimethyl siloxane (dimethicone), cyclic silicone oil, and wax, but has a problem in that oil resistance is insufficient and cosmetic persistence is poor.

In order to overcome this, Japanese Patent Application Laid-Open No. 7-17831 discloses a cosmetic composition comprising a polymer having a perfluoroalkyl group, but since these have very strong hydrophobicity, they are insoluble in most solvents and are the basic components of the cosmetic composition. Its compatibility with the bad had many restrictions.

Meanwhile, Korean Patent Laid-Open Publication No. 1998-63318 discloses a lipstick composition containing fluorine-modified methylphenylpolysiloxane, but since the phenyl group is directly substituted in the main chain of the polysiloxane, the phenyl group is recessed in the polymer chain, thereby improving compatibility and gloss. In addition to the fall, it is necessary to use a catalyst containing sulfur in the preparation, and since it is almost impossible to remove this component from the final product, there is a problem in using the cosmetic composition because odor remains in the final product.

Accordingly, the first technical problem to be achieved by the present invention is to provide a perfluoroalkyl (phenyl alkyl) polysiloxane which is excellent in water resistance and oil resistance, excellent in compatibility, and free of odors and thus suitable for use in cosmetic compositions.                         

The second technical problem to be achieved by the present invention is to provide a cosmetic composition comprising the perfluoro alkyl (phenyl alkyl) polysiloxane.

The present invention to achieve the first technical problem,

Provided is a perfluoro alkyl (phenyl alkyl) polysiloxane of formula (I).

(Wherein R ₁ is hydrogen, fluorine, chlorine or a linear or branched alkyl group having 1 to 24 carbon atoms;

R ₂ is hydrogen or a linear or branched alkyl group having 3 to 24 carbon atoms;

Rf is a perfluoro alkyl group having 1 to 12 carbon atoms;

g and h are each independently an integer having 2 to 24 carbon atoms;

k, l, m, n are each independently an integer from 1 to 150)

The present invention to achieve the second technical problem,

It provides a cosmetic composition comprising a perfluoro alkyl (phenyl alkyl) polysiloxane of the formula (1).

According to one embodiment of the invention, the perfluoro alkyl (phenyl alkyl) polysiloxane may be included in an amount of 0.1 to 99% by weight based on the total weight of the cosmetic composition.

According to another embodiment of the present invention, the cosmetic composition may be used in the foundation cosmetics, color cosmetics or hair cosmetic formulations.

Hereinafter, the present invention will be described in more detail.

The perfluoroalkyl (phenyl alkyl) polysiloxane according to the present invention forms a soft pill without pulling after skin application by the polysiloxane component, and can form an excellent and comfortable makeup film. In addition, the perfluoro alkyl group and the polysiloxane component are grafted to provide excellent water resistance and oil resistance and a non-sticky feeling.The alkyl group and the phenyl group enhance the compatibility with oil, give gloss and enhance the film strength. It is effective to increase.

Above all, the perfluoroalkyl (phenyl alkyl) polysiloxane according to the present invention is substituted with a phenyl group on the side chain, not the main chain of the polysiloxane, and since there is an alkylene group between the phenyl group and the main chain, the phenyl group can move freely from the main chain, Since the phenyl group is not likely to be recessed inside the polymer chain and is likely to exist outside the chain, compatibility with other oily substances is not only very high, but also has excellent gloss.

Furthermore, the perfluoroalkyl (phenyl alkyl) polysiloxanes according to the invention do not need to use a sulfur-based catalyst at all in their preparation, and therefore are not odorous in the final product and are therefore very suitable for use in cosmetic compositions.

According to an embodiment of the present invention, in the general formula (1), Rf is C1-C12 perfluoro alkyl, and may be linear or branched. For example, trifluoro methyl, pentafluoro enyl, heptafluoro propyl, nonafluoro butyl, tridecafluoro hexyl, etc. are mentioned. When the perfluoroalkyl group is long, the ratio of the fluorine group is increased, and the water resistance and oil resistance are improved, but the solubility or compatibility with other oils is deteriorated, so it is selected in consideration of this.

According to an embodiment of the present invention, in Formula 1, R2 is preferably a stearyl group. When the stearyl group is substituted, the melting point is 28 to 32 ° C., but is present in wax form at room temperature. This is because it can be melted by body temperature and gently adhered to the skin.

The manufacturing method of the said perfluoro alkyl (phenyl alkyl) polysiloxane is as follows.

When the cyclo methyl siloxane oligomer of the formula (2), the cyclo methyl phenylalkyl siloxane oligomer of the formula (3) and the dimethyl polysiloxane of the formula (4) are mixed and subjected to a linear extension reaction in the presence of a catalyst, a compound of the formula (5) can be obtained.

(Wherein a is an integer of 3 to 8)

(In the formula, b is an integer of 3 to 8,

g and R ₁ are as defined above)

(Wherein c is an integer of 1 to 50)

(Wherein d, e, f are each independently an integer of 1 to 150)

Next, after mixing the compounds of the formula (6) and the formula (7) to the compound of the formula (5), and reacted under a noble metal catalyst, it is possible to obtain a perfluoro alkyl (phenyl alkyl) polysiloxane according to the present invention.

(Wherein h is an integer of 2 to 24;

Rf is a perfluoro alkyl group having 1 to 12 carbon atoms)

(Wherein j is an integer of 1 to 22)

On the other hand, the compounding amount of the perfluoroalkyl (phenyl alkyl) polysiloxane according to the present invention varies depending on the type of cosmetic, but may be blended in an amount of 0.1 to 99% by weight, preferably 1 to 60% by weight of the cosmetic composition.

In the present invention, as the component to be combined with the perfluoro alkyl (phenyl alkyl) polysiloxane as a constituent of the cosmetics, there may be mentioned solid wax or oils, oil gelling component and silicone oil, etc. In addition, organic-inorganic powder, pigment , Preservatives, emollients, moisturizers, wetting agents, fragrances, antioxidants, anti-microbials, anti-fungals, antiperspirants, dermabrasions, hormones, enzymes, pharmaceutical compounds, vitamins, salts, electrolytes, alcohols, polyols, UV absorbers, plants Extractants, surfactants and thickening agents may be further included.

In the above, the solid wax or oils are avocado oil, linseed oil, almond oil, bees wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil , Carnauba wax, ceresin, cod liver oil, candelilla, apricot seed oil, spermaceti, montan wax, Japan wax, sugar cane wax, whale wax, hardened oil, wheat germ oil, sesame oil, rice germ oil, Rice bran oil, sugar cane, sandaflower oil, saffloer oil, shea butter, cinnamon oil, cinnamon oil, jojoba wax, shellac wax, soybean oil, green tea oil, thistle oil, evening primrose oil, corn Oil, rapeseed oil, Japanese paulownia oil, bran oil, germ oil, green oil, palm oil, palm kernel oil, castor oil, hardened castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax ), Jojoba oil, macadamia nut oil, mink oil (mink oil), cottonseed oil, cotton lead, wooden wax, lead nuclear oil, montan lead, palm oil, hardened palm oil, tri palm oil fatty acid glycerides, sunny, peanut oil, lanolin, lanolin derivatives, egg oil and the like. The solid wax has a melting point in the range of about 35 to 120 ° C. and is used in compact, stick or cream formulations.

On the other hand, the oil gelling component is used for stabilizing the formulation in anhydrous formulations, such as polyoxyaluminum stearate, aluminum, magnesium hydroxy stearate and the like.

Examples of silicone oils include dimethyl polysiloxane, methylphenyl polysiloxane, methylhydrogen polysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrohydrogencyclotetrasiloxane, stearoxysilicone, and the like. Higher alkoxy modified silicone, higher fatty acid modified silicone, fluorine modified silicone, amino modified silicone, alkyl modified silicone, higher fatty acid ester modified silicone, silicone resin, silicone rubber, silicone resin and the like.

In particular, makeup products are formulated with organic-inorganic powders or pigments, and organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder and polymethylbenzoguanamine powder. , Tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, 12 nylon powder, 6 nylon powder, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea resin, Phenolic resins, fluorine resins, silicon resins, acrylic resins, melamine resins, epoxy resins, polycarbonate resins, microcrystalline fiber powders, starch, lauroyl lysine and the like are used, and the inorganic powders include titanium oxide, zirconium oxide and zinc oxide. Cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc , Mica, kaolin, celite, white mica, synthetic mica, gold mica, red mica, black mica, litia mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, tungstate metal salt, hydroxide Roxiapatite, vermiculite, hygrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, silica and the like can be used.

Examples of the pigment include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, and inorganic yellow pigments such as iron sulfate and loess; Inorganic black pigments such as iron oxide and carbon black; Inorganic purple pigments such as manganese violet and cobalt violet; Inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; Inorganic blue pigments such as royal blue and ultramarine; And lakes tar-based dyes, lakes natural pigments, and composite powders of these powders. Examples of the pearl pigments include titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated mica, argentine, titanium oxide coated colored mica, and the like. , Stainless powder, etc., and as tar tar, 3 red, 104 red, 106 red, 201 red, 202 red, 204 red, 205 red, 220 red, 226 red, 227 red Arc, red 228, red 230, red 401, red 505, yellow 4, yellow 5, yellow 202, yellow 203, yellow 204, yellow 401, blue 1, blue 2, Blue 201, Blue 404, Green 3, Green 201, Green 204, Green 205, Orange 201, Orange 203, Orange 204, Orange 206, Orange 207, etc. As a natural pigment, carminic acid, lacaic acid, carsamine, braziline, crosine, etc. Can be mentioned.

On the other hand, as the preservative, parabens, BHT, BHA and the like can be commonly used.

When the perfluoroalkyl (phenylalkyl) polysiloxane according to the present invention is used in nail enamels or nail care products, the components formulated in conventional cosmetic compositions such as volatile solubilizers, powders, pigments, antioxidants, preservatives, and flavorings may be used. As the volatile dissolving agent, acetone, ethyl acetate, butyl acetate, methyl isobutyl ketone, isopropyl acetate, aromatic hydrocarbon, ethanol, n-butanol, n-isopropanol and the like are used.

The cosmetic composition containing the perfluoroalkyl (phenyl alkyl) polysiloxane according to the present invention is not particularly limited, but may be prepared in the form of a basic cosmetic, a color cosmetic, a hair cosmetic, and the like. It is a composition characterized by formulations such as astringent cosmetics, nourishing cosmetics, nourishing cream, essence, eye cream, etc., and as a color cosmetic, foundation, makeup base, twin cake, face powder, lipstick, lip gloss, lip liner, mascara eyebrow Formulations such as eye shadow, nail enamel, and the like, and hair cosmetics include hair foam, hair cream, and rinse. Moreover, it does not specifically limit about a product form, either, It can apply to liquid form, an emulsion form, cream form, solid form, paste form, gel form, powder form, multilayer form, mousse form, spray form, etc.

Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited only to these examples.

Preliminary Example 1

Perfluoro Alkyl  (Phenyl Alkyl ) Polysiloxane  Produce

1500 ml of 1N hydrochloric acid was added to a 3000 ml glass reactor, and dichloromethyl silane (manufactured by Aldrich) was rapidly added dropwise at a rate of 5 ml per minute through a dropping funnel. At this time, since heat is generated, the hydrolysis reaction was performed while the reactor was immersed in an ice bath. After completion of the dropwise addition, the mixture was stirred for an additional 30 minutes, and after confirming that there was no exotherm, the mixture was warmed up to 30 ° C. and stirred for an additional 30 minutes, and then the hydrochloric acid solution was separated, and 50 ml of normal hexane and 200 ml of pure water were added and mixed vigorously for 30 minutes. It was stirred and washed. The resultant was vacuum distilled to obtain a cyclomethyl siloxane oligomer. On the other hand, dichloromethyl phenylethyl silane (manufactured by United Chemical Technology) was hydrolyzed in the same manner as above to obtain a cyclomethyl phenylethyl siloxane oligomer. 280 g of the cyclomethyl siloxane oligomer thus obtained, 100 g of cyclomethyl phenylethyl siloxane oligomer and 50 g of dimethylpolysiloxane were mixed in a 1000 ml glass reactor, and then catalytically activated calcium montmorillonite powder (GE Toshiba Silicone Co., Ltd.) was added as a catalyst and stirred. The reaction was carried out at 120 ° C. for 24 hours, and then cooled and filtered to obtain 350 g of phenylmethyl polysiloxane. Next, 300 g of the phenylmethyl polysiloxane was mixed into a 3000 ml stainless high pressure reactor containing 300 g of normal hexane, and 300 g of heptadecafluoro-1-decene (manufactured by Aldirch) was added in 10 equal parts, and the platinum catalyst was added. The addition reaction was carried out under. Next, 400 g of 1-octadecene (manufactured by Aldrich Co., Ltd.) was divided into 10 equal parts, mixed at 7 hour intervals, followed by addition reaction under a platinum catalyst, cooled, filtered, and distilled under vacuum to obtain 99% of solid content of perfluoroalkyl (phenyl). Alkyl) 700 g of polysiloxane was obtained. It was a colorless transparent liquid at 40 ° C. with a weight average molecular weight of 25,000, a viscosity of 800 CPS and a softening point of 28 to 32 ° C.

¹ H-NMR (CDCl ₃ ): δ 0.08 (18 H), δ 0.14 to 0.16 (180 H), δ 0.96 (45 H), δ 1.29 to 1.33 (470 H), δ 1.60 to 1.71 (90 H), δ2.09 (45H), δ2.44-2.60 (50H), δ7.08 -7.21 (50H)

Preliminary Example 2

Tridecafluoro-1-octene (manufactured by Aldrich) was used in place of heptadecafluoro-1-decene, and 1-tetradecene was used in place of 1-octadecene, except that 1-octadecene was used. The perfluoro alkyl (phenyl alkyl) polysiloxanes were prepared by the process. The weight average molecular weight of the resultant was 23,000, and the viscosity was 750 CPS.

¹ H-NMR (CDCl ₃ ): δ 0.08 (18 H), δ 0.14 to 0.16 (180 H), δ 0.96 (45 H), δ 1.29 to 1.33 (370 H), δ 1.60 to 1.71 (90 H), δ2.09 (45H), δ2.44-2.60 (50H), δ7.08 -7.21 (50H)

Examples 1-3 and Comparative Examples 1-2

Preparation of the Lipstick Composition

Each component (% by weight) shown in Table 1 below was heated to 85 ° C, mixed, filled into an airtight lipstick container, and then cooled to 5 ° C to obtain a lipstick composition. The perfluoroalkyl (phenyl alkyl) polysiloxane was used as the compound prepared in Preliminary Example 1 below.

ingredient Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 1. Paraffin Wax 5.0 5.0 5.0 5.0 5.0 2. Candelilla Wax 10.0 10.0 10.0 10.0 10.0 3. ceresin 2.0 2.0 2.0 2.0 2.0 4. Octyl Dodecanol 20.0 20.0 20.0 20.0 20.0 5. Castor Oil 6. Perfluoroalkyl (phenylalkyl) polysiloxanes 10.0 15.0 20.0 7. Perfluorononylethyl Dimethicone - - - 15.0 - 8. Perfluorononylethyl Stearyl Diphenyl Dimethicone - - - - 15.0 9. Isopropyl palmitate 5.0 5.0 5.0 5.0 5.0 10. Castor Oil to 100 to 100 to 100 to 100 to 100 11.Squalane 10.0 10.0 10.0 10.0 10.0 12. Titanium Dioxide 5.0 5.0 5.0 5.0 5.0 13. Iron Oxide 5.0 5.0 5.0 5.0 5.0 14. Red 201 A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount 15.Yellow 204 A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount 16. Mica A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount 17. Preservatives (B.H.T) A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount 18. Spices A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount

Test Example 1

On the effects of the lipstick compositions of each of the above Examples and Comparative Examples, 10 panelists were tested for ease of application, fragrance at the time of application, stickiness (after 3 hours after application), and glossiness (after 5 minutes to 3 hours after application). , The transition to a coffee mug or clothing (cosmetic persistence) was tested and the results are shown in Table 2 below. Meanwhile, the evaluation criteria were determined as follows.

◎: All 10 people are good

○: 8 to 9 out of 10 are good

△: 5 to 7 out of 10 are good

×: 3 or less out of 10 are good

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Ease of application ◎ ◎ ◎ △ ○ Fragrance at the time of application ◎ ◎ ◎ ○ × Stickiness ○ ○ ○ △ ○ Luster ◎ ◎ ◎ △ △ Toilet paper ○ ○ ○ △ ○

As can be seen in Table 2, the cosmetic composition according to the present invention is easy to apply, there is no odor is excellent in the scent at the time of application, and the glossiness is excellent because the phenyl group is not recessed in the silicone polymer chain.

Examples 4-6

Manufacture of foundation, eyeliner and mascara

Each component shown in Table 3 was mixed to prepare a foundation, an eyeliner, and a mascara. In the following perfluoroalkyl (phenyl alkyl) polysiloxane was used the compound prepared in Preliminary Example 2.

Example 4 (Foundation) Example 5 (Eye Liner) Example 6 (mascara) 1. Perfluoroalkyl (phenylalkyl) polysiloxanes 7 12 20 2. Sorbitan monopalmitate - 2 2 3. Vinyl Acetate Emulsion - 10 10 4. Propylene Glycol Monolaurate 2 - - 5. Hydrocarbon Solvent (Isopar E) 40 35 25 6. Purified water to 100 to 100 to 100 7. Water-swellable clay minerals One One One 8. Spices A reasonable amount A reasonable amount A reasonable amount 9. Iron Oxide Black - 10 5 10. Pigment Pigment 15 - - 11. Preservative A reasonable amount A reasonable amount A reasonable amount

Test Example 2

      The cosmetic compositions of Examples 4 to 6 were applied to 10 panelists and tested for ease of application, fragrance and water resistance and oil resistance at the time of application, and the results are shown in Table 4 below. The water resistance was applied to the cosmetic composition and showered for 3 minutes, and then visually observed. The oil resistance was sufficiently sweated for 2 hours outdoors on a sunny day, and in the case of foundation, visually observed the state of makeup disappearance, In the case of mascara and eyeliner, the presence or absence of secondary adhesion under the eyelid was determined.

       (Double-circle): All 10 people are good (no blurring, no secondary attachment)

○: 8 to 9 out of 10 are good (no bleeding, no secondary adhesion)

(Triangle | delta): 5-7 of 10 people are favorable (no bleeding property, no secondary adhesion)

X: 3 or less of 10 people are favorable (no blurring, no secondary adhesion)

Example 4 Example 5 Example 6 Ease of application ◎ ◎ ◎ Fragrance at the time of application ◎ ◎ ◎ Water resistance ◎ ◎ ◎ Oil resistance ◎ ○ ○

As described above, the perfluoroalkyl (phenyl alkyl) polysiloxane according to the present invention has excellent water resistance and oil resistance, excellent compatibility, and is suitable for use in cosmetic compositions due to no odor, and a cosmetic comprising the same The composition spreads smoothly during use to provide a good feeling of use and skin adhesion, and does not adhere to coffee mugs or clothes, and has excellent makeup persistence.

Claims (4)

Perfluoro alkyl (phenyl alkyl) polysiloxanes of formula (1)

(One) (Wherein R ₁ is hydrogen, fluorine, chlorine or a linear or branched alkyl group having 1 to 24 carbon atoms; R ₂ is hydrogen or a linear or branched alkyl group having 3 to 24 carbon atoms; Rf is a perfluoro alkyl group having 1 to 12 carbon atoms; g and h are each independently an integer having 2 to 24 carbon atoms; k, l, m, n are each independently an integer from 1 to 150) Cosmetic composition containing a perfluoro alkyl (phenyl alkyl) polysiloxane of the following formula (1).

(One) (Wherein R ₁ is hydrogen, fluorine, chlorine or a linear or branched alkyl group having 1 to 24 carbon atoms; R ₂ is hydrogen or a linear or branched alkyl group having 3 to 24 carbon atoms; Rf is a perfluoro alkyl group having 1 to 12 carbon atoms; g and h are each independently an integer having 2 to 24 carbon atoms; k, l, m, n are each independently an integer from 1 to 150) The cosmetic composition according to claim 2, wherein the perfluoroalkyl (phenyl alkyl) polysiloxane is contained in an amount of 0.1 to 99% by weight based on the total weight of the cosmetic composition. According to claim 2, wherein the cosmetic composition is a cosmetic composition, characterized in that used in the foundation cosmetics, color cosmetics or hair cosmetic formulations.