WO2010114111A1

WO2010114111A1 - Fluorine-modified silicone polymer, surface treated powder and cosmetics comprising powder

Info

Publication number: WO2010114111A1
Application number: PCT/JP2010/056047
Authority: WO
Inventors: Hisashi Mitsuhashi; Kenichi Saitou; Yasuo Itami; Tetsuya Masutani; Peter Cheshire Hupfield; Don Lee Kleyer; Janet M. Smith
Original assignee: Daikin Industries, Ltd.; Dow Corning Corporation
Priority date: 2009-03-30
Filing date: 2010-03-26
Publication date: 2010-10-07

Abstract

A fluorine-modified silicone polymer prepared by reacting (a) an epoxy-modified fluorocompound of the formula (I): wherein Rf is a fluoroalkyl group having 1 to 6 carbon atoms wherein at least one fluorine atom is optionally substituted by a hydrogen atom or a halogen atom, and R¹ is a bivalent organic group, with (b) an amino group-containing siloxane polymer of the formula (II): wherein R², R⁵, R⁶, R⁷ and R⁸ are an unsubstituted or substituted monovalent organic group, R⁴ and R⁹ are an unsubstituted or substituted monovalent organic group or X, in which X is of the formula: NHR¹¹-Y-[NH-Y]_r- (III) R³ and R¹⁰ are an unsubstituted or substituted monovalent organic group or OR¹², where R¹² is a hydrogen atom or unsubstituted or substituted alkyl group, and a and b are from 0 to 200, provided that when a=0, either or both R⁴ and R⁹ = X.

Description

DESCRIPTION

FLUORINE-MODIFIED SILICONE POLYMER, SURFACE TREATED POWDER AND COSMETICS COMPRISING POWDER

CROSS REFERENCE TO RELATED APPLICATIONS

This application has priority from US Application No. 61/164615 filed March 30, 2009, disclosures of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a powder for cosmetics having surface treated with a surface treatment agent for cosmetics which comprises silane compound containing a short chain fluoroalkyl (Rf) group having at most 6 carbon atoms, and the cosmetics comprising the powder. Since the surface treatment agent of the present invention does not include perfluorooctanoic acid (PFOA) analogue structure, the surface treatment agent is excellent in safety. In addition, the surface treatment agent has excellent water resistance, water- and oil-repellency, feeling of use, and dispersibility with other materials.

RELATED ARTS

It is known that it is possible to impart the character that makeup hardly ruins by a sweat and skin fat; by treating a surface of powder with a coating formation agent which is a phosphate ester containing a perfluoroalkyl group (Rf group) having at least 8 carbon atoms, and blending the treated powder into the cosmetic (cf. JP-A-Sho 62-250074, JP-A-Hei

3-246210, and JP-A-Hei 4-330007 and JP-A-Hei 5-86984), or by treating a surface of powder with a coating formation agent consisting of a silane compound containing the perfluoroalkyl group (Rf group) having 8 or less carbon atoms, and blending the powder with the cosmetic (cf. JP-A-Hei 2-218603, JP-A-Hei 6-192594 and JP- A 2001-2524).

However, it is a problematic that these compounds contain perfluorooctanoic acid (PFOA) and a PFOA analogue substance which have bioaccumulation possibility, and the immediate shift to the short chain Rf group-containing fluorocompound having six or less carbon atoms is required. Then, the cosmetics comprising the silane compound having an Rf group (which is a perfluoroalkyl group) having at most 6 carbon atoms are studied variously (cf. JP-A- 2007-238690, JP-A- 2008-37813 and JP-A- 2008-110924).

However, if only the chain length of Rf group is shortened, water resistance and a water- and oil-repellency have been remarkably spoiled as in the fluorosilane compound mentioned above and a sufficient effect preventing from makeup ruin has not been acquired.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a cosmetic powder surface-treated with a compound which does not have a perfluorooctanoic acid (PFOA) analogue structure and imparts excellent water resistance and water- and oil-repellency, and to provide a cosmetic characterized by containing said cosmetic powder.

As the results of intensive studies to solve the above-mentioned problems, the present inventors discovered that a specific fluorine-modified silicone polymer has excellent characteristics of a surface treatment agent for cosmetics.

That is, the surface-treated powder and the cosmetic of the present invention are characterized by using a surface treatment agent which comprises a product compound obtained by reacting the following the compounds (a) and (b).

The present invention provides a fluorine-modified silicone polymer prepared by reacting (a) an epoxy-modified fluorocompound of the formula:

wherein

Rf is a fluoroalkyl group having 1 to 6 carbon atoms wherein at least one fluorine atom is optionally substituted by a hydrogen atom or a halogen atom, and

R¹ is a bivalent organic group,

with (b) an amino group-containing siloxane polymer (usually, a random, alternate or block copolymer) of the formula:

R² X R⁶ R⁸

R³— SiO — (SiO)₃- (SiO)_b — Si — R¹⁰

I I I I (H)

R⁴ R⁵ R⁷ R⁹

wherein

R², R⁵, R⁶, R⁷ and R⁸ are, the same or different, an unsubstituted or substituted monovalent organic group,

R⁴ and R⁹ are, the same or different, an unsubstituted or substituted monovalent organic group or X, in which X is of the formula:

NHR¹¹- Y-[NH- Y]_r (HI)

wherein

R^{1 x} is a hydrogen atom or a monovalent organic group,

Y each is, the same or different, a bivalent organic group, and r is from O to 10,

R³ and R¹⁰ are, the same or different, an unsubstituted or substituted monovalent organic group or -OR¹², where R¹² is a hydrogen atom or unsubstituted or substituted alkyl group,

and a and b are, the same or different, from 0 to 200, for example, from 1 to 100, provided that when a=0, either or both R⁴ and R⁹ = X.

The present invention further provides a surface treated powder treated with the fluorine-modified silicone polymer

The present invention also provides cosmetics comprising the surface treated powder.

In the epoxy- modified fluorocompound (a) of the formula (I), the Rf group is preferably a perfluoroalkyl group. The Rf group has 1 to 6 carbon atoms. Examples of the Rf group include -CF₃, -CF₂CF₃, -CF₂CF₂CF₃, -CF(CF₃)₂, -CF₂CF₂CF₂CF₃, -CF₂CF(CF₃)₂, -C(CFs)₃, -(CF₂)₄CF₃, -(CF₂)₂CF(CF₃)₂, -CF₂C(CF₃),, -CF(CF₃)CF₂CF₂CF₃, -(CF₂)₅CF₃, -(CF₂)₂H, -CF₂CFHCF₃, -(CF^₄H and -(CF₂)6H. The carbon atom number of the Rf group is from 1 to 6, particularly from 4 to 6, especially 6, from the viewpoint of the above-mentioned PFOA and function. The Rf group may be linear or branched, and is preferably a linear fluoroalkyl group.

In the formula (I), R¹ is preferably a bivalent organic group containing at least one linkage selected from the group consisting Of -CH₂-, -0-, -NR¹³-, -S-, -CO₂-, -CONR¹³- and -SO₂NR¹³-, where R¹³ is an alkyl group or a hydrogen atom. The alkyl group for R¹³ may have 1 to 10, for example, 1 to 4 carbon atoms. Examples of the R¹ include -(CHj)_n-, -(CH₂)_nOCH₂-, -(CH₂)_n-CONR¹³- and -(CH₂)_n-SO₂NR¹³- (wherein n is 1 to 10, particularly 1 to 6). R¹ is preferably an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one (for example, 1 to 5, particularly 1) oxygen atom. Preferable examples of R¹ include -CH₂-, -CH₂OCH₂- and -CH₂CH₂OCH₂-, particularly -CH₂-.

In the amino group-containing siloxane polymer (b) of the formula (II), R², R⁵, R⁶, R⁷, and R⁸ each is an unsubstituted or substituted monovalent organic group, and R⁴ and R⁹ are, the same or different, an unsubstituted or substituted monovalent organic group or X, and R³ and R¹⁰ are, the same or different, an unsubstituted or substituted monovalent organic group or -OR¹², where R¹² is a hydrogen atom or unsubstituted or substituted alkyl group generally having 1 to 20 carbon atoms. Examples of the monovalent organic group include a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. The alkyl group and the alkenyl group may have 1 to 20 carbon atoms, the cycloalkyl group may have 4 to 10 carbon atoms, the aryl group may have 6 to 20 carbon atoms, and the aralkyl group may have 7 to 21 carbon atoms. Examples of the monovalent organic group include alkyl groups such as a methyl group, an ethyl group, a propyl group and a butyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; aryl groups such as a phenyl group; aralkyl groups such as a benzyl group; alkenyl groups such as a vinyl group and an allyl group; fluoroalkyl groups such as 3,3,3-trifluoropropyl group. The total of a and b may be 2 to 300, for example, 5 to 100.

X is of the formula:

NHRⁿ-Y-[NH-Y]r (III) wherein

R¹¹ is a hydrogen atom or a monovalent organic group,

Y each is, the same or different, a bivalent organic group, and

Examples of the monovalent organic group for R¹¹ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. The alkyl group and the alkenyl group may have 1 to 20 carbon atoms, the cycloalkyl group may have 4 to 10 carbon atoms, the aryl group may have 6 to 20 carbon atoms, and the aralkyl group may have 7 to 21 carbon atoms. Specific examples of the monovalent organic group include alkyl groups such as a methyl group, an ethyl group, a propyl group and a butyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; aryl groups such as a phenyl group; aralkyl groups such as a benzyl group; alkenyl groups such as a vinyl group and an allyl group; fluoroalkyl groups such as 3,3,3-trifluoropropyl group.

Examples of the bivalent organic group for Y include an alkylene group (preferably having 1 to 10 carbon atoms) interrupted by an oxygen atom. Examples of Y include -(CH₂)_n- where n is 1 to 10, particularly 1 to 6, -CH₂OCH₂-, -CH₂CH₂OCH₂-, -CH₂CH₂O-, -(CH₂CH₂O)S-, -CH₂CH(CH₃) O-, -(CH₂CH(CH₃)OV, -(CH₂CH₂O)s-(CH₂CH(CH₃)OX- where s and t can be individually varied between 1 and 50. Preferable examples of Y are -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -CH₂CH(CH₃)CH₂- and

-(CH₂V-

In the formula (III), r is from 0 to 10, preferably from 0 to 5, more preferably from 1 to

5.

Preferably, the X group in the amino group-containing siloxane polymer (b) of the formula (II) is of the formula:

NHR^u-(CH₂)_p-[NH-(CH₂)_q-(CHR¹¹)_r-(CH₂)_s]_t- (Ilia) wherein

R¹¹ is the same or different, a hydrogen atom, an alkyl having 1 to 20 carbon atoms or a phenyl group, each of p, q, r and s is, the same or different, from 0 to 10, and t is from 0 to 5. More preferably, the X group in the amino group-containing siloxane polymer (b) of the formula (II) is of the formula:

NH₂-(CH₂)_p-[NH-(CH₂)_q-(CHR¹¹)_r-(CH₂)_s]t- (HIb) wherein

R¹¹ is a hydrogen atom, an alkyl having 1 to 20 carbon atoms or a phenyl group, p is from 1 to 10, each of p, q, r and s is, the same or different, from 0 to 10, and t is 1.

In the formula (Ilia) and (HIb), p may be from 2 to 5, each of q, r and s may be from 1 to 5.

When the X group in the amino group-containing siloxane polymer (b) of the formula (II) is of the formula (HIa) or (HIb), particularly the formula (IHb), the epoxy-modified fluorocompound (a) is reacted in the amount of generally 0.5 to 10 mol, preferably 1, 2 or 3 mol, per 1 mol of the X group so that the epoxy-modified fluorocompound (a) is reacted with the amino group-containing siloxane polymer (b).

The amino group-containing siloxane polymer is usually a random copolymer, an alternate copolymer or a block copolymer. In the amino group-containing siloxane polymer, the amount of the X group is 0.01 to 1 mol based on 1 mol of Si atom. Optionally, almost all of Si atoms may be bonded to the X group.

The epoxy-modified fluorocompound (a) and the X group in the amino group-containing silicone polymer (b) are reacted to give the fluorine-modified silicone polymer. A molar ratio of the epoxy-modified fluorocompound (a) to the X group in the amino group-containing silicone polymer (b) subjected to the reaction may be 0.5:1 to 10:1, preferably 1:1 to 5: 1, particularly 3: 1, to give the reaction product having the same ratio of the epoxy-modified fluorocompound (a) to the X group in the amino group-containing silicone polymer (b). A catalyst may be used for the reaction, but the reaction can be conducted without the catalyst. The reaction may be conducted in the absence of a solvent, but the reaction is conducted preferably in the absence of the solvent. Examples of the solvent include toluene, xylene and other non-reactive solvents. The reaction can be conducted at a temperature of from ambient (20⁰C) to 200⁰C for a time adequate to achieve the level of desired conversion. The reaction progress can be easily monitored spectroscopically, e.g. NMR or IR, or by other means, e.g. titration or chromatography.

The resultant fluorine-modified silicone polymer has a C-N linkage which is formed by the reaction between an epoxy ring in the epoxy-modified fluorocompound and an amine group in the amino group-containing siloxane polymer and in which the C atom is derived from the epoxy ring and the N atom is derived from the amine group.

The fluorine-modified silicone polymer, may be used with or without, usually with the solvent to apply said polymer to the powder.

A fluorine-containing silane compound may be mixed with the fluorine-modified silicone polymer, before the fluorine-modified silicone polymer is used for the surface treatment of the powder.

Generally, the fluorine-containing silane compound is of the formula:

Rf-Z-Si(A)₃ (IV)

wherein

Rf is a fluoroalkyl group having 1 to 6 carbon atoms,

Z is an (unsubstituted or substituted) bivalent or higher valency organic group, and

A each is, the same or different, a hydrogen atom, a monovalent organic group or a hydrolyzable group such as alkoxy, halide or amino group, wherein at least one A is the hydrolyzable group.

In the fluorine-containing silane compound of the formula (IV), the Rf group is preferably a perfluoroalkyl group. The Rf group has 1 to 6 carbon atoms. Examples of the Rf group include -CF₃, -CF₂CF₃, -CF₂CF₂CF₃, -CF(CF₃) ₂, -CF₂CF₂CF₂CF₃, -CF₂CF(CF₃),, -C(CFs)₃, -(CF₂)₄CF₃, -(CF₂)₂CF(CF₃)₂, -CF₂C(CF₃)₃, -CF(CF₃)CF₂CF₂CF₃, -(CF₂)₅CF₃, -(CF₂)₂H, -CF₂CFHCF₃, -(CF₂)^ and -(CF₂)₆H. The carbon atom number of the Rf group is from 1 to 6, particularly from 4 to 6, especially 6, from the viewpoint of the above-mentioned PFOA and function. The Rf group may be linear or branched, and is preferably a linear fluoroalkyl group.

The Z group may be an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one (for example, 1 to 5, particularly 1) oxygen atom or nitrogen atom (for example, 1 to 5, particularly 1 to 3). Preferable examples of Z include -(CH₂)₂-, -(CHz)₃-, -(CH₂)₄-, -CH₂CH(CH₃)CH₂O-CH₂-, -CH₂CH₂CH₂O-CH₂-, -CH₂CH(OH)CH2NHCH₂CH₂CH₂-, -CH₂CH(OH)CH₂NHCH₂CH(CH₃)CH₂-,

-(CH₂CH(OH)CH₂)₂NCH₂CH₂CH₂-, -(CH₂CH(OH)CH₂)₂NCH₂CH(CH₃)CH₂-,

-(CH₂CH(OH)CH₂)₂NCH₂CH₂CH₂-, -(CH₂CH(OH)CH₂)₂-

NCH₂CH₂(-CH₂CH(OH)CH₂)NCH₂CH(CH₃)CH₂-, -(CH₂CH(OH)CH₂)₂-

NCH₂CH₂(-CH₂CH(OH)CH₂)NCH₂CH₂CH₂-, -CH₂CH(OH)CH₂NHCH₂CH₂NHCH₂CH(CH₃)CH₂-, -CH₂CH(OH)CH₂NHCH₂CH₂NHCH₂CH₂CH₂-, and -(CH₂)₆-.

In the formula (IV), the A group each is, the same or different, an unsubstituted or substituted monovalent organic group or X. Examples of the monovalent organic group include a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. The alkyl group and the alkenyl group may have 1 to 20 carbon atoms, the cycloalkyl group may have 4 to 10 carbon atoms, the aryl group may have 6 to 20 carbon atoms, and the aralkyl group may have 7 to 21 carbon atoms. Examples of the monovalent organic group include alkyl groups such as a methyl group, an ethyl group, a propyl group and a butyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; aryl groups such as a phenyl group; aralkyl groups such as a benzyl group; alkenyl groups such as a vinyl group and an allyl group; fluoroalkyl groups such as 3,3,3-trifluoropropyl group. At least one A is the hydrolyzable group. All of the Y groups may be the hydrolyzable group. Examples of the hydrolyzable group include a hydrogen atom, an alkoxy group (having 1 to 10 carbon atoms), a halogen atom (such as chlorine, bromine and iodine) and an amino group.

The fluorine-containing silane compound is preferably of the formula:

Rf-Z-Si(OR¹⁴)₃ (IVa)

wherein

Rf is a fluoroalkyl group having 1 to 6 carbon atoms,

Z is an alkylene group having 1 to 10 carbon atoms, and

R¹⁴ each is, the same or different, an alkyl having 1 to 10 carbon atoms or a phenyl group. An amount of the fluorine-containing silane compound is from 0 to 500 parts by weight, preferably from 1 to 200 parts by weight, more preferably from 10 to 100 parts by weight, based on 100 parts by weight of the fluorine- modified silicone polymer.

The present invention provides a mixture of the fluorine-modified silicone polymer with the component (IV) (that is, the fluorine-containing silane compound). The surface treatment agent may comprise the mixture. In the mixture, a weight ratio of the fluorine-modified silicone polymer to the fluorine-containing silane compound may be 99:1 to 1:99, for example, 95:5 to 10:90.

An amount of the fluorine-modified silicone polymer applied to the powder changes depending on a kind, a particle diameter, an oil absorption amount, a water absorption amount and a specific surface area of the powder. The amount of the fluorine-modified silicone polymer to be applied is from 0.05 to 40 parts by weight, preferably from 0.1 to 30 parts by weight, particularly 1 to 25 parts by weight, based on 100 parts by weight of the powder. When the amount is as above-mentioned, the sufficient effects of the fluorine compound can achieved, and performances of the surface-treated powder and effects in the cosmetics caused by surface-treated powder are sufficiently high.

The powder used in the present invention is not restricted so for as the powder is one which is usually used for cosmetics as powder. An average particle size of the powder may be usually 0.01 micrometers to 1 mm. Examples of the powder include an inorganic powder and an organic powder.

Examples of the inorganic powder include boron nitride, sericite, natural mica, calcined mica, synthetic mica, synthetic sericite, alumina, mica, talc, kaolin, bentonite, smectite, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicate, calcium phosphate, silicic acid anhydride, magnesium oxide, barium sulfate, magnesium aluminometasilicate, iron oxide, chrome oxide, titanium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium oxide, chromium hydroxide, iron blue, lapis lazuli, calcium carbonate, magnesium carbonate, calcium phosphate, aluminum hydroxide, barium sulfate, magnesium sulfate, silicic acid, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, silicon carbide, tungstate metal salt, magnesium aluminate, magnesium aluminometasilicate, chlorohydroxy aluminum, clay, zeolite, hydroxyapatite, ceramic powder, aluminum nitride, titanium nitride, silicon nitride, silicon carbide, cobalt titanate, iron titanate, lithium cobalt titanate, aluminate cobalt, inorganic blue pigments, aluminum powder, gold dust, silver dust, iron powder, platinum powder, low order titanium, finely particulate titanium oxide, butterfly-like barium sulfate, petal-like zinc oxide, tetrapod-like zinc oxide, particular zinc oxide, titanium oxide coated mica, titanium oxide coated mica, titanium oxide coated silica, titanium oxide-coated synthetic mica, bismuth oxychlpride, titanium oxide-coated talc, scales foil, titanium oxide coated coloring mica, titanium oxide coated borosilicic acid (sodium/calcium), titanium oxide coated borosilicic acid (calcium/aluminum), colcothar coated mica, colcothar coated mica titanium, colcothar and black iron oxide coated mica titanium, carmine coated mica titanium, carmine iron blue coated mica titanium, stainless steel powder, copper powder, tourmaline powder, mango violet, cobalt violet, glass fibers, carbon fibers, silicon carbide fibers, alumina fibers, beta-wollastonite, zonolite, potassium titanate fibers, aluminum borate fibers, basic magnesium sulfate fibers, and silicon nitride fibers. At least 2 of the above-mentioned powders, such as a composite of powders may be used.

In the present invention, a method of applying the fluorine-modified silicone polymer to the powder used for the cosmetics is not limited and may be a well-known method.

When the surface treatment method is classified roughly, it has a dry process and a wet process. For example, the dry process can be performed by mixing the surface treatment agent (that is, the surface treatment agent) and the powder for a given time in agitators, such as a Henschel mixer, a ball mill, a jet mill, or a grinder. In the wet method, the powder is dispersed in water or a solvent, the surface treatment agent is added with stirring, and then the solvent is evaporated.

Furthermore, the powder to be treated with the surface treatment in the present invention may be treated with at least one of, for example, oxides or oxide hydrate of aluminum, calcium, magnesium, cerium, silicon, zirconium, titanium, zinc, iron, cobalt, manganese, nickel and/or tin in order to improve affinity and adherence with the surface treatment agent.

The surface-treated powder obtained by the present invention does not include perfluorooctanoic acid (PFOA) analogue structure and has the excellent water resistance and water- and oil-repellency. One or more of the surface-treated powders can be blended into the cosmetic. In another aspect of the present invention, a cosmetic excellent in feeling of use, makeup result, and makeup durability is provided by blending the above-mentioned surface-treated powder.

The amount of the surface-treated powder changes depending on the kinds and agent forms of a cosmetic. The powder surface-treated with the fluorine-modified silicone polymer of the present invention can be blended with the cosmetic, in the amount of 0.1 to 99% by weight for example, 1 to 50% by weight, based on the whole cosmetic.

Examples of the cosmetic blended with the surface-treated powder obtained by the present invention include; makeup cosmetics, such as a makeup base, a powder foundation, a facial liquid foundation, an oily foundation, a stick foundation, a presto powder, a face powder, a white powder, a lipstick, a lipstick overcoat, a lip gloss, a concealer, a rouge, an eye shadow, an eyebrow, an eyeliner, a mascara, a water nail enamel, an oily nail enamel, an emulsified type nail enamel, an enamel topcoat and an enamel base coat; skin care cosmetics, such as an emollient cream, a cold cream, a whitening cream, a milky lotion, a liquid cosmetic, a beauty essence, a pack, a carmine lotion, a liquid face wash, a cleansing foam, a facial cleansing cream, a facial washing powder, a makeup cleansing cream, a body gross, a sunscreen, a suntan cream or a lotion; hair cosmetics, such as a hair growth, hair cream, a hair shampoo, a hair rinse, a hair coloring, a hair brushing agent; and deodorant cosmetics, such as a cream-, lotion-, powder- and spray-type deodorant product. A milky lotion, a soap, a bath additive, a perfume, etc. can be also mentioned.

Examples of other component to be incorporated into the cosmetic blended with the surface-treated powder of the present invention include an oily ingredient, an aqueous ingredient, and a surface active agent. If usually used for the cosmetic, there will be no limitation in particular to other components.

Examples of the oily ingredient include; oils and fats, such as a safflower oil, a soybean oil, an evening primrose oil, a grape-seeds oil, a rose hip oil, a kukui nuts oil, an almond oil, a sesame oil, a wheat germ oil, a corn oil, a cotton seed oil, an avocado oil, an olive oil, a camellia oil, a persic oil, a castor oil, peanut oil, hazelnut oil, a macadamia nuts oil, a meadowfoam oil, cacao butter, Shea butter, a tree low, a coconut oil, a palm oil, a palm kernel oil, a beef tallow, a horse fat, a mink oil, a milk fat, an egg yolk oil, a turtle oil and a jojoba oil; waxes, such as a bee wax, a whale wax, lanolin, a carnauba wax, a candelilla wax, and a microcrystalline wax; hydrocarbons, such as liquid paraffin, flow isoparaffin, squalane, squalene, vaseline, paraffin and ceresin; fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linolic acid, undecylenic acid, hydroxystearic acid, and lanolin fatty acid; higher alcohols, such as myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, a jojoba alcohol, batyl alcohol, cholesterol, phytosterol, a lanolin alcohol, and isostearyl alcohol; sterols, such as cholesterol, sitosterol, phytosterol, and lanosterol; esters, such as ethyl oleate, isopropyl myristate, cetyl octanoate, diisostearyl malate, and glyceryl tricaprylate; silicones, such as methylpolysiloxane, methylphenylpolysiloxane, and decamethyl cyclotetrasiloxane; fluorine-containing oils, such as a pefluoropolyether oil, perfluorocarbon, and hydrofluoroether; organic solvents, such as ethyl acetate, butyl acetate, and toluene.

Examples of the aqueous ingredient include; lower alcohols, such as ethanol and isopropanol; sugar alcohols, such as sorbitol, and maltose; water-soluble vegetable polymers, such as gum arabic, gum tragacanth, galactan, carob gum, guar gum, karaya gum, a carrageenan, pectin, agar, quince seed (quince), a starch

(rice, corn, a potato, wheat), an algae colloid and locust bean gum, water-soluble microorganism polymers, such as xanthan gum, dextran, a succinoglucan, and pullulan, water-soluble animal polymers, such as collagen, casein, albumin, and gelatin; water-soluble starch polymers, such as carboxymethyl starch and methylhydroxypropyl starch; water-soluble cellulose polymer, such as methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, cellulose nitrate, cellulose sodium sulfate, carboxymethyl cellulose sodium, crystalline cellulose, and cellulose powder; water-soluble alginic acid polymers, such as sodium alginate, and propyleneglycol alginate ester; water-soluble vinyl polymers, such as polyvinyl methyl ether and carboxyvinyl polymer; water-soluble polyoxyethylene polymers; water-soluble polyoxyethylene polyoxypropylene copolymer-based polymers; water-soluble acrylic polymers, such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide; other water-soluble synthetic polymers, such as polyethyleneimine, and cationic polymer; and water-soluble inorganic polymers, such as bentonite, magnesium aluminum silicate, montmorillonite, beidellite, nontronite, saponite, hectorite, and a silicic acid anhydride.

Moreover, these water soluble polymers include also coat formation agents, such as polyvinyl alcohol and polyvinyl pyrrolidone.

Examples of the surface active agent include; anionic surface active agents, for example, fatty acid soap, such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acid and its salt, a condensate salt of an amino acid and fatty acid, an alkane sulfonic acid salt, an alkene sulfonate salt, a sulfonate salt of fatty acid ester, a sulfonate salt of fatty acid amide, a formalin condensate sulfonate salt, an alkyl sulfate ester salt, a secondary higher alcohol sulfuric ester salt, alkyl and allyl ethereal sulfate ester salt, a sulfate ester salt of fatty acid ester, a sulfate ester salt of fatty acid alky Io 1 amide, a sulfate ester salt of turkey red oil and the like, an alkyl phosphate salt, an ether phosphate salt, an alkyl allyl ether phosphate salt, an amidophosphate salt, an

N-acylamino acid-based activator; cationic surface active agents, for example, amine salt, such as an alkylamine salt, polyamine, and amino alcohol fatty acid derivatives; an alkyl quarternary ammonium salt, an aromatic quarternary ammonium salt, a pyridium salt, and imidazolium salt; nonionic surface active agents, for example, sorbitan fatty acid ester, glycerine fatty acid ester, poly glycerine fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, cane sugar fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerine fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardening castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene/alkyl-comodified organopolysiloxane, polyglycerol -modified organopolysiloxane, alkanolamide, sugar ether, and sugar amide; and amphoteric surface active agents, for example, betaine, an aminocarboxylate salt, an imidazoline derivative.

In addition, various additives such as a pigment dispersion agent, an oil, a surface active agent, an ultraviolet absorber, an antiseptic, an antioxidant, a coating formation agent, a moisturizer, a thickener, a dye, a pigment, various drugs, and perfume which are used for the usual cosmetic can be suitably blended, if these do not spoil the effect of the present invention.

In the present invention, the surface treatment agent contains the fluorine-modified silicone polymer as an active component. In the present invention, the "treatment" means that the active component is adhered to the powder. Usually, the powder is partially or fully coated with the active component. The treatment gives the result that the powder exhibits the water resistance and water- and oil-repellency.

The embodiments disclosed herein are illustrated in greater detail by the examples described below.

Synthesis Examples 1 to 7

30 mole % diaminoethyl-propyl functional polymer:

The amino functional polymer was prepared by equilibration of 328.6g of -((CH₃)RSiO)_x- where R=CH₂CH(CH₃)CH₂NHCH₂CH₂NH₂ (which had been previously prepared by hydrolysis of (CH₃)RS i(OCH₃)₂), 278.9g of Dow Corning 200 fluid, 10 cst. ((CH₃)₃SiO((CH₃)₂SiO)_xSi(CH3)3 ) and 93.1g of Dow Corning 244 fluid ( ((CH3)2SiO)_Cyciics) using KOH as catalyst. A 2 L round bottom 3 necked flask, equipped with a water cooled reflux condenser connected to a bubbler, nitrogen inlet, mechanical stirrer and temperature controller was used. The contents were heated at 15O⁰C overnight before the catalyst was neutralized with acetic acid before filtering through a bed of filter aid on a porous polymeric membrane. The filtrate was then stripped of cyclics on a wiped film evaporator at 1 Torr and 150⁰C. 50 mole % diaminoethyl-propyl functional polymer:

The amino functional polymer was prepared by equilibration of 43Og of -((CH₃)RSiO)_x- where R=CH₂CH(CH₃)CH₂NHCH₂CH₂NH₂ (which had been previously prepared by hydrolysis of (CH₃)RSi(OCH₃)₂), 186g of Dow Corning 200 fluid, 5 cst. ((CH₃)3SiO((CH3)₂SiO)_xSi(CH₃)3 ) and 54.7g of Dow Corning 244 fluid ( ((CH3)₂Si0)_Cyciics) using KOH as catalyst. A 2 L round bottom 3 necked flask, equipped with a water cooled reflux condenser connected to a bubbler, nitrogen inlet, mechanical stirrer and temperature controller was used. The contents were heated at 150⁰C overnight before the catalyst was neutralized with acetic acid before filtering through a bed of filter aid on a porous polymeric membrane. The filtrate was then stripped of cyclics on a wiped film evaporator at 1 Torr and 15O⁰C.

30 mole % aminopropyl functional polymer:

The amino functional polymer was prepared by equilibration of 260.8g of -((CHORSiO)_x- where R=CH₂CH₂CH₂NH₂ (which had been previously prepared by hydrolysis of (CH₃)RSi(OCH₃)₂), 329.3g of Dow Corning 200 fluid, 10 cst. ((CH₃)₃SiO((CH₃)₂SiO)_xSi(CH₃)₃ ) and 109.9g of Dow Corning 244 fluid ( ((CH₃)₂Si0)_Cyciics) using KOH as catalyst. A 2 L round bottom 3 necked flask, equipped with a water cooled reflux condenser connected to a bubbler, nitrogen inlet, mechanical stirrer and temperature controller was used. The contents were heated at 13O⁰C overnight before the catalyst was neutralized with acetic acid before filtering through a bed of filter aid on a porous polymeric membrane. The filtrate was then stripped of cyclics on a wiped film evaporator at 1 Torr and 15O⁰C.

Conversion of amino functional polymers to fluorine-modified silicone polymers: The general procedure was to heat the appropriate amino functional polymer with CH₂(O)CHCH₂(CF₂)₆F at 8O⁰C overnight, followed by vacuum stripping. The apparatus used for the conversion was a 100 mL 3 neck round bottom flask equipped with water cooled reflux condenser connected to a bubbler, nitrogen inlet, stirrer and temperature controller. The following polymers were prepared:

(Note) Me: CH₃ group

Synthesis Example 8

In the same procedure as in synthesis example 1 was repeated expect that CH₂=CHC(O)OCH₂CH₂(CF₂)₆F 59.8g was used instead of CH₂(O)CHCH₂(CF₂)₆F to give comparative polymer 1.

Example 1

In 13 ml Of C₄F₉OC₂H₅ (HFE-7200) at room temperature (2O ⁰C) was dissolved 0.25 g of fluorine-modified silicone polymer 1 prepared in Synthesis Example 1. 10 g of sericite powder (weight ratio of treating agent/powder: 2.5/100) was dispersed into this solution and mixed well at room temperature. The mixture was dried at 8O⁰C for 2 h then heated at 130⁰C for 6 h. The remaining solid was smashed to give the desired surface-treated powder.

Examples 2 to 7

The same procedure as in Example 1 was repeated except that each of polymers 2 to 7 prepared in Synthesis Examples 2 to 7 was used in instead of polymer 1. Example 8

In 13 ml of C₄F₉OC₂H₅ (HFE-7200) were dissolved 0.085 g of a fluorine-modified silane compound C6F₁3(CH₂)₂Si(OC₂H₅)3 and 0.17O g of the fluorine-modified silicone polymer 1 prepared in Synthesis Example 1. A weight ratio of [fluorine-modified silane]/[polymer 1] was 1/2. 10 g of sericite powder was dispersed into this solution and surface-treated according to the same method described in Example 1.

Example 9

The same procedure as in Example 8 was repeated except that the weight ratio of

[fluorine-modified silane]/[polymer 1] was 1/4.

Example 10

The same procedure as in Example 8 was repeated except that the weight ratio of

[fluorine-modified silane]/[polymer 1] was 1/9.

Comparative Example 1

The same procedure as in Example 1 was repeated except that comparative polymer 1 prepared in Synthesis Example 8 was used instead of polymer 1.

Comparative Example 2

The same procedure as in Example 8 was repeated except that comparative polymer 1 prepared in Synthesis Example 8 was used instead of polymer 1.

Comparative Example 3

0.25 g of the fluorine-modified silane compound C₆F₁₃(CH₂)₂Si(OC₂Hs)₃ was dissolved in 13 ml of isopropyl alcohol (IPA) at room temperature. 1O g of sericite powder was dispersed into this solution and surface-treated according to the same method described in Example 1.

(Evaluation Method)

The water and oil repellency of the samples of surface-treated powder obtained in Examples 1 to 10 and Comparative Example 1 to 3 was evaluated. Measurement was conducted in the following manner. A pressed pellet was prepared from the sample powder. Water and squalane contact angles were measured at more than four points on the pellet. Average values for each sample were shown in Table 1. TABLE 1

Example 11

1O g of the mixed powder shown in Table 2 was surface-treated according to the same method described in Example 1 (treated by the fluorine-modified silicone polymer 1 prepared in Synthesis Example 1).

TABLE 2

This surface-treated powder and other components according to Table 3 were mixed well with a Henschel mixer at room temperature, and then press-formed into a cake to give a powdery foundation. TABLE 3

Example 12

Utilizing the surface-treating agents described in Example 8 (the mixture of the fluorine-modified silane compound C₆Fo(CH₂)₂Si(OC₂H₅)₃ and the fluorine-modified silicone polymer 1 prepared in Synthesis Example 1, a weight ratio of [fluorine-modified silane compound]/[polymer I]: 1/2.), powdery foundations were prepared according to the same method described in Example 11.

Comparative Example 4

Utilizing the fluorine-modified silane compounds C₆F₁₃(CH₂)₂Si(OC₂H₅)₃ dissolved in IPA as surface-treating agent, a powdery foundation was prepared according to the same method described in Example 11.

(Evaluation Method)

Twenty panelists evaluated the aesthetic stability (derived from the oil/water repellency) and feeling in use (smoothness, nonstickness etc.) actually using the samples of powdery foundation obtained in Examples 11, 12 and Comparative Example 4. The average results were shown in Table 4.

1 : Very good

2: Good

3 : Average

4: Poor

5: Very poor

TABLE 4

EFFECT OF THE INVENTION

The surface-treated powder of this invention treated with the fluorine-modified silicone polymer or its mixture with the fluorine-modified silane compound has excellent water and oil repellency. Therefore, cosmetic preparations in which the surface-treated powder of this invention is used have good to excellent aesthetic stability and feeling in use. Increasing the content of the fluorine-modified silicone polymer brings better feeling to the foundation.

Claims

1. A fluorine-modified silicone polymer prepared by reacting (a) an epoxy-modified fluorocompound of the formula:

Rf-R^CH-CH_{2 /τx}

\ / ^(I)

O

wherein

R¹ is a bivalent organic group,

with (b) an amino group-containing siloxane polymer of the formula:

R² X R⁶ R⁸

R³— SiO — (SiO)₃- (SiO)_b — Si-R¹⁰

I I I I (H)

R⁴ R⁵ R⁷ R⁹

wherein

R¹ * is a hydrogen atom or a monovalent organic group,

Y each is, the same or different, a bivalent organic group, and

R³ and R¹⁰ are, the same or different, an unsubstituted or substituted monovalent organic group or OR¹², where R¹² is a hydrogen atom or unsubstituted or substituted alkyl group,

and a and b are, the same or different, from 0 to 200, provided that when a=0, either or both R⁴ and R⁹ = X.

2. The fluorine-modified silicone polymer according to claim 1, wherein, in the epoxy-modified fluorocompound (a) of the formula (I),

Rf is a perfluoroalkyl group having 1 to 6 carbon atoms, and

R¹ is a bivalent organic group containing at least one linkage selected from the group consisting Of -CH₂-, -O-, -NR¹³-, -S-, -CO₂-, -CONR¹³- and -SO₂NR¹³-, where R¹³ is an alkyl group or a hydrogen atom.

3. The fluorine-modified silicone polymer according to claim 1, wherein, in the epoxy-modified fluorocompound (a) of the formula (I),

Rf is a linear fluoroalkyl group having 1 to 6 carbon atoms, and R¹ is -CH₂-, -CH₂OCH₂-, or -CH₂CH₂OCH₂-,

4. The fluorine-modified silicone polymer according to claim 3, wherein, in the epoxy-modified fluorocompound (a) of the formula (I),

R¹ is -CH₂-.

5. The fluorine-modified silicone polymer according to claim 1, wherein, the amino group-containing siloxane polymer (b) of the formula (II) has the definitions that R², R⁵, R⁶, R⁷ and R⁸ are, the same or different, an unsubstituted or substituted alkyl or phenyl group, R⁴ and R⁹ are, the same or different, an unsubstituted or substituted alkyl or phenyl group or X, R³ and R¹⁰ are, the same or different, an unsubstituted or substituted alkyl or phenyl group or -OR¹², where R¹² is a hydrogen atom or unsubstituted or substituted alkyl group; and the formula (III) has the definitions that R^{1 1} is a hydrogen atom or an alkyl or phenyl group, Y each is, the same or different, a bivalent organic group, and r is from O to 5.

6. The fluorine-modified silicone polymer according to claim 1, wherein the X group in the amino group-containing siloxane polymer (b) of the formula (II) is of the formula: NHR¹ '-(CH₂)_P-[NH-(CH₂V(CHR¹¹V(CH₂)_S]₁- (Ilia)

wherein

R¹¹ is the same or different, a hydrogen atom, an alkyl having 1 to 20 carbon atoms or a phenyl group, each of p, q, r and s is, the same or different, from 0 to 10, and t is from 0 to 5.

7. The fluorine-modified silicone polymer according to claim 1, wherein the X group in the amino group-containing siloxane polymer (b) of the formula (II) is of the formula:

NH₂-(CH₂)_p-[NH-(CH₂V(CHRⁿV(CH₂)_s]_t- (DIb)

wherein

R¹¹ is a hydrogen atom, an alkyl having 1 to 20 carbon atoms or a phenyl group,

each of p, q, r and s is, the same or different, from 0 to 10, and t is 1.

8. The fluorine-modified silicone polymer according to claim 7, wherein the epoxy- modified fluorocompound (a) is reacted in the amount of 1, 2 or 3 mol, per 1 mol of the X group when the epoxy-modified fluorocompound (a) is reacted with the amino group-containing siloxane polymer (b).

9. The fluorine- modified silicone polymer according to claim 1, wherein the amino group-containing siloxane polymer is a random copolymer, an alternate copolymer or a block copolymer.

10. A mixture of the fluorine-modified silicone polymer according to anyone of claims 1 to 9 and a fluorine-containing silane compound of the formula:

Rf-Z-Si(A)₃ (IV)

wherein Rf is a fluoroalkyl group having 1 to 6 carbon atoms,

Z is an unsubstituted or substituted bivalent organic group, and

A each is, the same or different, a monovalent organic group or a hydrolyzable group such as alkoxy, halide or amino group, wherein at least one A is the hydrolyzable group.

11. A surface treated powder treated with the fluorine-modified silicone polymer according to anyone of claims 1 to 9.

12. The surface treated powder according to claim 11, wherein the powder is treated with a mixture of the fluorine-modified silicone polymer and a fluorine-containing silane compound of the formula:

Rf-Z-Si(A)₃ (IV)

wherein

Rf is a fluoroalkyl group having 1 to 6 carbon atoms,

Z is an unsubstituted or substituted bivalent organic group, and

13. The surface treated powder according to claim 11, wherein the fluorine-containing silane compound is of the formula:

Rf-Z- Si(OR¹⁴)₃ (IVa)

wherein

Rf is a fluoroalkyl group having 1 to 6 carbon atoms,

Z is an alkylene group having 1 to 10 carbon atoms, and

R¹⁴ each is, the same or different, an alkyl having 1 to 10 carbon atoms or a phenyl group.

14. Cosmetics comprising the surface treated powder according to anyone of claims 11 to 13.

15. A mold release agent comprising the fluorine-modified silicone polymer according to anyone of claims 1 to 9 or the mixture according to claim 10.

16. A water and oil-repelling agent comprising the fluorine-modified silicone polymer according to anyone of claims 1 to 9 or the mixture according to claim 10.

17. A stain-proof treatment agent comprising the fluorine-modified silicone polymer according to anyone of claims 1 to 9 or the mixture according to claim 10.

18. A treatment agent for optical use comprising the fluorine-modified silicone polymer according to anyone of claims 1 to 9 or the mixture according to claim 10.

19. Use, as a surface treatment agent for cosmetics, of a fluorine-modified silicone polymer prepared by reacting (a) an epoxy-modified fluorocompound of the formula:

wherein

R¹ is a bivalent organic group,

with (b) an amino group-containing siloxane polymer of the formula:

R² X R⁶ R⁸

R³— SiO — (SiO)₃- (SiO)₆ — Si-R¹⁰

I I I I (H)

R⁴ R⁵ R⁷ R⁹

wherein

R⁴ and R⁹ are, the same or different, an unsubstituted or substituted monovalent organic group or X, in which X is of the formula: NHR . 11 -Y-[NH-Y]_r (III)

wherein

R¹ ' is a hydrogen atom or a monovalent organic group,

Y each is, the same or different, a bivalent organic group, and