WO2005112871A1

WO2005112871A1 - Water-dispersible powder for cosmetic preparation

Info

Publication number: WO2005112871A1
Application number: PCT/JP2005/009079
Authority: WO
Inventors: Kenichi Sakuma; Kazuyuki Miyazawa
Original assignee: Shiseido Company, Ltd.
Priority date: 2004-05-24
Filing date: 2005-05-18
Publication date: 2005-12-01
Also published as: JP2006008661A; JP3852942B2; TW200608998A

Abstract

Disclosed is a water-dispersible powder for cosmetic preparations which is characterized in that a phosphorylcholine group represented by the formula (1) below is directly covalent bonded to the powder surface. Also disclosed is a cosmetic preparation wherein such a water-dispersible powder is blended. Consequently, there can be obtained a cosmetic preparation in which a powder for cosmetic preparations having excellent dispersibility in water is stably blended.

Description

Specification

Underwater dispersible powder for cosmetics

Technical field

The present invention relates to a powder for cosmetics. More specifically, the present invention relates to a cosmetic powder excellent in dispersibility in water, in which a phosphorylcholine group is directly and covalently bonded to a powder surface, and a cosmetic containing the same.

Background art

[0002] A polymer having a phosphorylcholine group has been studied as a biocompatible polymer, and a biocompatible material in which the polymer is coated with various bases has been developed.

[0003] For example, Patent Document 1 discloses that a powder coated with a homo- or copolymer of 2-metacloyloxetyl phosphorylcholine is used as a cosmetic powder to improve moisture retention and skin adhesion. Improved cosmetics are disclosed.

[0004] Patent Documents 2 and 3 disclose a medical material and a separating agent coated with a polymer having a phosphorylcholine group.

[0005] The above-mentioned materials are mainly obtained by reacting an acrylic monomer having a hydroxyl group with 2-chloro-1,3,2-dioxaphosphorane-1-oxide, and further forming a quaternary ammonium with trimethylamine. Is used to synthesize a monomer having a phosphorylcholine structure, and the surface thereof is coated with a polymer obtained by polymerizing the monomer (see Patent Documents 4 and 5 for a method for producing the polymer).

[0006] Patent Document 4 discloses a copolymer of 2-methacryloxyshethyl phosphorylcholine and ester of methacrylic acid, and Patent Document 5 discloses a single polymer of 2-methacryloxyshethyl phosphorylcholine. Coalescence is being manufactured.

[0007] On the other hand, conventionally, when an attempt is made to disperse a pigment in water, in the case of an inorganic pigment such as a metal oxide, pigment particles generally condense in water despite having high hydrophilicity. Settles quickly.

Therefore, in order to further increase the hydrophilicity and improve the dispersion stability, it is better to coat the pigment particle surface with alumina whose isoelectric point is on the alkaline side and silica whose isoelectric point is on the acidic side. The law is generally adopted.

[0008] Further, it is mixed with a powder having good dispersibility in water to form granules, or treated with a surfactant to increase dispersibility in water (Patent Document 6).

On the other hand, titanium dioxide used as a cloudy bath agent is coated with a fatty acid amino acid surfactant or a dispersing nonionic surfactant such as polyethylene glycol and a fatty acid soap. I have. (Patent Documents 7 and 8).

[0009] In addition, since inorganic powders such as carbon black are highly hydrophobic and are not easily dispersed in water, it is extremely difficult to prepare an aqueous dispersion. Therefore, in order to increase the hydrophilicity of carbon black, an attempt to introduce a hydroxyl group or a carboxyl group by an oxidation reaction (Patent Document 9), or an attempt to introduce a hydrophilic functional group such as a hydroxyl group by plasma irradiation (Patent Document 9) 10) has been adopted.

Patent Document 1: JP-A-7-118123

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-279512

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-98676

Patent Document 4: JP-A-9 3132

Patent Document 5: JP-A-10-298240

Patent Document 6: JP-A-7-196435

Patent Document 7: Japanese Patent Publication No. 7-17494

Patent Document 8: JP-A-3-294220

Patent Document 9: JP-A-11-148027

Patent Document 10: JP-A-2000-0444829

Disclosure of the invention

Problems to be solved by the invention

[0011] However, it is difficult to effectively cover the entire surface by a method in which the surface of the powder is modified with a polymer having a phosphorylcholine group while being modified. Further, since the coated polymer is peeled off by powder force, there may be a problem in durability. Furthermore, since the surface of the powder is coated with a polymer, the powder for cosmetics itself has been required, deviating from the purpose of imparting the desired function such as biocompatibility by the phosphorylcholine group. Basic character Quality can be lost.

[0012] Further, the above-mentioned method for improving the dispersibility of a powder is required only for a cosmetic powder that can only be applied in a limited variety of powders, and is stable over time in water. It was not a method to keep the dispersibility of the whole.

[0013] The present invention has been made in view of the above-mentioned problems, and has a phosphorylcholine group directly and covalently bonded to a powder surface to form a cosmetic powder excellent in dispersibility in water, and to blend the same. The purpose of the present invention is to provide an improved cosmetic.

Means for solving the problem

That is, the present invention provides a water-dispersible cosmetic powder characterized in that a phosphorylcholine group represented by the following formula (1) is directly covalently bonded to the powder surface. is there.

[Formula 4]

[0015] The present invention also provides the above-mentioned cosmetic powder, wherein the powder is a powder having a hydroxyl group on the surface.

[0016] Furthermore, the present invention provides a method of introducing an amino group directly into the surface of a powder, and then reacting a compound containing an aldehyde compound obtained by oxidative cleavage of glycerol phosphorylcholine with the amino group. The present invention also provides a method for producing the above cosmetic powder.

Further, the present invention provides a method for introducing an amino group directly into the surface of a powder, and then adding a carboxyl-containing compound obtained by an oxidative cleavage reaction of phosphorylcholine of glycerol to the amino group. It is intended to provide a method for producing the above powder for cosmetics, characterized by reacting.

[0018] Further, the present invention provides the above cosmetic powder, which is obtained by directly reacting a compound represented by the following formula (2) and Z or (3) on the powder surface. It provides a method for producing a body.

(2)

[Formula 6]

(3)

In the formula, m is 2-6, and n is 1-4. X, X and X each independently represent a methoxy group,

one two Three

It is a xy group or a halogen. However, up to two of X, X, X are methyl group, ethyl

one two Three

Group, propyl group, isopropyl group, butyl group and isobutyl group.

Further, the present invention provides a cosmetic comprising the above-mentioned water-dispersible cosmetic powder.

The invention's effect

[0020] The cosmetic powder of the present invention is a powder having an excellent effect of dispersibility in water, and is a powder used exclusively as a compounding material for cosmetics. In particular, it is extremely useful as a highly dispersible powder and as a raw material for cosmetics containing various powders.

[0021] The cosmetic powder of the present invention does not lose the phosphorylcholine group due to peeling of the polymer as compared with a powder having a phosphorylcholine group introduced by being coated with a polymer having a phosphorylcholine group. Has advantages. In addition, since it is not coated with a polymer, it has the advantage that it does not kill any surface characteristics of the powder itself. For example, it is possible to coat the surface with a phosphorylcholine group without filling the three-dimensional microstructure (micropores, etc.) of the powder surface of several nm. Further, the cosmetic powder of the present invention has an effect of preventing adsorption and denaturation by preventing adsorption to powder when there is a compounding material such as protein or lipid to be dispersed in the cosmetic. Also have. According to the production method of the present invention, it is possible to impart a desired arbitrary amount of a phosphorylcholine group to the surface of various cosmetic powders to be blended with the cosmetic by a simple reaction. is there. As a result, a cosmetic modified powder having a desired function by the phosphorylcholine group can be easily provided.

The thus-produced cosmetic powder of the present invention is effectively compounded in various cosmetics. Brief Description of Drawings

FIG. 1 shows the structural formula and NMR ^ vector of Synthesis Example 1.

FIG. 2 shows the structural formula and NMR ^ vector of Synthesis Example 3.

BEST MODE FOR CARRYING OUT THE INVENTION

[0024] In the cosmetic powder of the present invention, the phosphorylcholine group of the formula (1) is directly and covalently bonded to the cosmetic powder surface. Means that the phosphorylcholine group is introduced by coating with a polymer having a phosphorylcholine group.ヽ and!

As long as the phosphorylcholine group of the formula (1) is introduced into the material surface and the functional group by a covalent bond, an arbitrary spacer may be inserted between the functional group and the phosphorylcholine group.

[0025] The powder is not limited as long as it is used for cosmetics! The powder used is not particularly limited.

The powder generally means any object having an average particle diameter of 0.01 to about LOO m. Specific powders include, for example, inorganic powders (e.g., talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, rhombic mica, biotite, permikilite, magnesium carbonate) , Calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcium sulfate), calcium phosphate Organic powder (for example, polyamide resin powder (eg, polyamide resin powder), fluorine apatite, hydroxyapatite, ceramic powder, metal stone (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, cerium oxide, etc.); Nylon powder), polyethylene powder, polymetari Methyl luate powder, benzoguanamine resin powder, polytetrafluoroethylene powder, polymethylsilsesquioxane powder, silicone elastomer powder, cellulose powder, etc.); inorganic white pigments (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigments ( Inorganic brown pigments (eg, 7-iron oxide); inorganic yellow pigments (eg, yellow iron oxide, loess); inorganic black pigments (eg, iron oxide (iron oxide), iron titanate, etc.); , Black iron oxide, lower titanium oxide, etc.); inorganic purple pigments (eg, manganese violet, cobalt violet, etc.); inorganic green pigments (eg, oxidized chromium, chromium hydroxide, cobalt titanate, etc.); Blue pigments (for example, ultramarine, navy blue, etc.); pearl pigments (for example, titanium oxide coated titanium oxide, titanium oxide coated hydroxy chloride) Metal powder pigments (eg, aluminum-powder powder, kappa-powder, etc.); zirconium, norium or aluminum Organic pigments such as lakes (e.g., Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Organic pigments such as Yellow 205, Yellow 401, and Blue 404, Red 3, Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc.); natural pigments (eg, chlorophyll, -Rotin etc.) and the like.

In the present invention, a powder having a hydroxyl group on the surface is preferable. The powders preferably used are silica, talc, carion, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, mica, biotite, lithia mica, permikulite, magnesium carbonate, carbonate Calcium, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcium sulfate (calcium sulfate), calcium phosphate, fluoroapatite, hydroxy Apatite, ceramic powder, pigment powder for cosmetics such as boron nitride, white pigment for cosmetics such as titanium dioxide and zinc oxide, iron oxide (bengara), iron titanate, y iron monoxide, yellow iron oxide, Loess, black iron oxide, carbon black, lower titanium oxide, mango violet, cobalt bar Colored pigments such as violet, oxidized chromium, chromium hydroxide, chromium titanate, ultramarine, navy blue, etc., titanium oxide coated my strength, titanium oxide coated bismuth chloride, titanium oxide Pearl pigments such as Ted talc, colored oxidized titanium coated myriki, and oxysalt lizard bismuth; and metal powder pigments such as aluminum powder and kappa powder.

[0026] "An amino group is directly introduced into the powder surface, and then a compound containing an aldehyde compound obtained by an oxidative cleavage reaction of phosphorylcholine at glycerol is reacted with the amino group. By introducing an amino group directly into the amino group and reacting a compound containing a carboxyl compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine with the amino group to obtain a highly dispersible water-based cosmetic powder. Production method"

For example, it is manufactured by the following steps. If the cosmetic powder already has an amino group on the surface and it is not necessary to introduce any further amino group, step 1 is omitted.

Step 1: An amino group is introduced into any cosmetic powder by a known method or a method to be developed in the future. Amino groups are introduced directly on the powder surface. Direct means that the method of coating with a polymer having an amino group is not included. The amino group is a primary amine or a secondary amine.

Step 2: An aldehyde compound, a hydrate compound, or a carboxy compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine with a powder having an amino group is converted to a carboxy compound by a reduction amination reaction or an amide compound. Thus, phosphorylcholine groups are directly added to the cosmetic powder surface. In the case of using a carboxyl compound obtained by the oxidative cleavage reaction of glycerol phosphorylcholine, the phosphorylcholine group can be directly added to the powder surface of the cosmetic cosmetic powder by hydroxyl group and esterification of the surface. It is.

Known methods (Step 1) for introducing an amino group or a hydroxyl group into these powders include the following.

1. Introduction of amino group by surface reaction in plasma treatment

Amino groups are introduced into the powder surface by low-temperature plasma in a nitrogen gas atmosphere. Specifically, the powder is stored in a plasma reactor, the inside of the reactor is evacuated by a vacuum pump, and nitrogen gas is introduced. Subsequently, amino groups can be introduced into the powder surface by glow discharge. It is also possible to introduce hydroxyl groups on the powder surface by low-temperature plasma in an oxygen gas atmosphere or an oxygen gas or hydrogen gas atmosphere. Specifically, the powder is subjected to a plasma reaction. After the reaction vessel is housed in a vessel and the inside of the reaction vessel is evacuated with a vacuum pump, oxygen gas or oxygen gas or hydrogen gas is introduced. Subsequently, by a glow discharge, it is also possible to mechanically powder the plasma-treated powder capable of introducing hydroxyl groups to the powder surface. The literature on plasma processing is shown below.

1. M. Muller, C. oehr

Plasma aminofunctionalisation of PVDr microfiltration membranes: comparison of the in plasma modifications with a grafting method using ESCA and an

amino— selective fluorescent probe

Surface and Coatings Technology 116--119 (1999) 802--807

2. Lidija Tusek, Mirko Nitschke, Carsten Werner, Karin Stana—Kleinschek, Volker Ribitsch

Surface characterization of NH3 plasma treated polyamide 6 foils

Colloids and Surfaces A: Physicochem.Eng.Aspects 195 (2001) 81-95

3. Fabienne Poncin—Epaillard, Jean-Claude Brosse, Thierry Falher

Reactivity of surface groups formed onto a plasma treated poly (propylene) film Macromol. Chem. Phys. 200. 989-996 (1999)

2. Introduction of amino group by surface modifier

The surface of a hydroxyl group-containing cosmetic powder is treated with a surface modifier such as alkoxysilane, chlorosilane, and silazane having an amino group.

For example, silicon dioxide is treated with 3-aminopropyltrimethoxysilane having a primary amino group to introduce an amino group. Specifically, the silica is immersed in a mixed solution of water and 2-propanol, and after adding 3-aminopropyltrimethoxysilane, the mixture is heated to 100 ° C. and reacted for 6 hours. After cooling to room temperature, the silica is washed with methanol and dried to obtain a silica powder having amino groups introduced directly to the silica surface.

Powders preferably used in the present method include silica, talc, carion, mica, sericite, sericite, phlogopite, synthetic mica, rhodolite, biotite, lithia mica, permichulite, and magnesium carbonate. , Calcium carbonate, aluminum silicate, barium silicate, calcium silicate For cosmetics such as shim, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, boron nitride, etc. Pigment powders, white pigments for cosmetics such as titanium dioxide and zinc oxide, iron oxide (iron oxide), iron titanate, iron monoxide, yellow iron oxide, loess, black iron oxide, carbon black, low-order titanium oxide Tan, Mango Violet, Cobalt Violet, Chromium Oxide, Chromium Hydroxide, Cobalt Titanate, Ultramarine Blue, Navy Blue, etc., Color Pigments, Titanium Oxide Titanium Coated My Strength, Titanium Oxide Coats , Colored oxidized titanium coated my power, bismuth oxychloride Metal pigments such as pearl pigments such as aluminum powder and kappa powder.

Next, a method (Step 2) of introducing a phosphorylcholine group to the surface of the aminated powder will be described below.

The cosmetic powder obtained in step 1 is immersed in methanol, and phosphatidylglyceraldehyde is added, and left at room temperature for 6 hours. Then, sodium cyanoboronate is added at 0 ° C., and the mixture is heated and stirred overnight to add a phosphorylcholine group to the amino group. The cosmetic powder is washed with methanol and then dried to obtain a cosmetic powder having phosphorylcholine groups directly on the surface. As a reaction solvent, other than methanol, a protic solvent such as water, ethanol, or 2-propanol can be used, but the introduction ratio when methanol is used tends to be high.

Alternatively, the cosmetic powder obtained in step 1 may be added to a carboxylic acid salt produced by reacting a carboxyl compound having a phosphorylcholine group with salt salt in acetonitrile for a certain period of time. The mixture is stirred at room temperature for 6 hours to add a phosphorylcholine group to the amino group.

[0031] A scheme of a method of introducing a phosphorylcholine group using 3-aminopropyltrimethoxysilane as a surface modifier is shown below using silica as an example.

Step 1 “Aminopropylidani on silica surface (general method)”

[Formula 7] — Si— OH — Si

OMe

― Si— OH MeO ~ 5j NH ₉ 100. C, 5h

— ⁰ \ Si- 0- _S i ^^ H ₂ o MeOi 2— Propanol + water

-Si—OH </.

— Si

Step 2 “Introduction of phosphorylcholine group (via aldehyde)”

[Formula 8]

Step 2 “Introduction of phosphorylcholine group (via carboxylic acid)”

[Formula 9]

As described above, a cosmetic powder having an amino group is prepared, and the phosphorylcholine is subjected to a reductive amination reaction with an aldehyde compound or a hydrate compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine. According to the method for producing a powder for cosmetics in which the base is directly added to the surface of the powder for cosmetics, the powder for cosmetics of the present invention can be easily obtained and the surface of various powders for cosmetics can be obtained. There is a great advantage that can be modified.

In addition, a cosmetic powder having an amino group is prepared, and the phosphorylcholine group is similarly converted into a cosmetic powder by an amidation reaction with a carboxyl compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine. It is also possible to produce a cosmetic powder directly applied to the surface.

In the above production method, the glycerol is obtained by an oxidative cleavage reaction of phosphorylcholine. The compound containing an aldehyde compound is a compound that causes a known glycerol phosphorylcholine group to undergo an oxidative cleavage by a known method, and is an extremely simple step. For example, the bond is cleaved by acidifying 1,2-diol with periodate or periodate to obtain an aldehyde compound. The reaction is usually performed in water or an organic solvent containing water. The reaction temperature is 0 ° C and room temperature. Aldehydes may form hydrates through equilibrium reactions in water, but do not affect subsequent reactions with amines. An example of a scheme for preparing a monofunctional aldehyde having a phosphorylcholine group is shown below.

[Formula 10]

“Method for producing water-dispersible cosmetic powder by reacting the compound represented by formula (2) directly on the powder surface”

A phosphorylcholine derivative represented by the following formula (4) is dissolved in distilled water. The phosphorylcholine derivative of the following formula (4) is a known compound and can be obtained as a commercial product.

[Formula 11]

(Four)

[0034] An aqueous solution of the compound of formula (4) was cooled in an ice water bath, sodium periodate was added, and the mixture was stirred for 5 hours. The reaction solution is concentrated under reduced pressure and dried under reduced pressure, and a phosphorylcholine derivative having an aldehyde group represented by the following formula (5) is extracted with methanol.

[Formula 12]

(Five)

Next, 0.9 equivalent of 3-aminopropyltrimethoxysilane was added to the methanol solution of the formula (5). To do. After stirring the mixed solution at room temperature for a predetermined time, the mixture is cooled on ice, an appropriate amount of sodium cyanohydroboron is added, and the mixture is returned to room temperature and stirred for 16 hours. During this time, keep flowing dry nitrogen into the reaction vessel. After filtering the precipitate, a methanol solution of the formula (6) is obtained. The methanol solution also contains the compound of the formula (7) as a by-product.

[Formula 13]

(6)

[Formula 14]

(7)

Next, 20 mL of distilled water is added to 20 mL of a methanol solution having a concentration of about 0.3 mmol ZmL containing the compound of the formula (6), and the powder to be modified is added. The mass of the powder must be adjusted according to its specific surface area. For example, in the case of a powder of 100 m ² / g, an appropriate amount of addition is about 10 g. The powder dispersion is refluxed in an oil bath at 80 ° C, and after 5 hours, the powder is filtered, washed with methanol, and dried under reduced pressure at 80 ° C for 3 hours to obtain the highly dispersible water in water of the present invention. A powder for cosmetics is obtained.

“Method for producing water-dispersible cosmetic powder by reacting compound represented by formula (3) directly on powder surface”

[Formula 15]

The aqueous solution of the compound of the formula (4) was cooled in an ice-water bath, and sodium periodate and lutetium trichloride were added thereto, followed by stirring for 3 hours. The reaction solution is filtered, concentrated under reduced pressure, and dried under reduced pressure, and a phosphorylcholine derivative having a carboxyl group represented by the following formula (8) is extracted with methanol.

[Formula 16]

(8)

Next, after adding formula (8) and salt salt to acetonitrile and stirring for a predetermined time, 2 equivalents of triethylamine and 3-aminopropyltrimethoxysilane are added in 0.9 equivalents. This mixed solution is stirred at room temperature for a predetermined time. During this time, dry nitrogen is kept flowing through the reaction vessel. After filtering the precipitate, an acetonitrile solution of formula (7) is obtained.

[Formula 17]

Next, 10 mL of distilled water and 10 mL of methanol are added to 20 mL of an acetonitrile solution containing the formula (7) at a concentration of about 0.3 mmol ZmL, and the powder to be modified is added. The mass of the powder needs to be adjusted according to its specific surface area. For example, in the case of powder of 100 m ² Zg, it is appropriate that the amount of the additive is about 10 g. The powder dispersion is refluxed in an oil bath at 80 ° C, and after 5 hours, the powder is filtered, washed with methanol, and dried under reduced pressure at 80 ° C for 3 hours to obtain the highly dispersible water-in-water cosmetic of the present invention. A feed powder is obtained.

The water-dispersible cosmetic powder of the present invention is blended with any cosmetic. Cosmetic is not limited, but it can be blended especially with ozw emulsified cosmetics, lotions, and other products that have a process of highly dispersing powder in water or products that have a process of highly dispersing powder in the manufacturing process. Like That's right.

The compounding amount is appropriately determined depending on the kind and purpose of the cosmetic, and is not particularly limited, but is usually in the range of about 0.1 to 95% by mass based on the total amount of the cosmetic. Depending on the type of product, for example, 0.1 for powder two-layer lotion: 1% for L0 mass%, O / W emulsified foundation, powder-containing cream, and O / W emulsified sunscreen 50 mass ^_0/0, powdery foundation, the amount of 10 to 95 weight ^_0/0 for a stick foundation sometimes good preferable.

[0039] The cosmetic of the present invention is produced by blending, in addition to the water-in-highly dispersible cosmetic powder, other components usually used in cosmetics. For example, ordinary powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, anionic surfactants, cationic surfactants, amphoteric surfactants, non- Ionic surfactants, humectants, water-soluble polymers, thickeners, filming agents, UV absorbers, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH A regulator, a skin nutritional agent, a vitamin, an antioxidant, an antioxidant aid, a fragrance, water and the like can be appropriately blended as required, and can be produced by a conventional method according to a desired dosage form.

Example

Next, the present invention will be described in more detail based on examples. Note that the present invention is not limited to these examples. Unless otherwise specified, the compounding amount is mass% based on the total amount.

“Synthesis Example 1 Aldehyde Compound Containing Phosphorylcholine Group”

1-a-glycerol phosphorylcholine (450 mg) was dissolved in 15 ml of distilled water and cooled in an ice-water bath. Sodium periodate (750 mg) was added and stirred for 5 hours. The reaction solution was concentrated under reduced pressure and dried under reduced pressure, and the desired product was extracted from methanol. The structure is shown in the following compound (5). FIG. 1 shows the 1H NMR spectrum of the compound of the formula (5).

[Formula 18]

“Synthesis Example 2 Phosphorylcholine Group-Containing Compound of Formula (2)”

A methanol solution containing 7.5 g of the compound of Synthesis Example 1 is dissolved in 30 mL of dehydrated methanol, and the atmosphere in the vessel is replaced with dry nitrogen. Next, 5.4 g of 3-aminopropyltrimethoxysilane was added to a methanol solution of the compound 1. After stirring this mixed solution at room temperature for 5 hours, it was ice-cooled, 2.5 g of sodium cyanohydroborohydride was added, and the mixture was returned to room temperature and stirred for 16 hours. During this time, dry nitrogen was kept flowing through the reaction vessel. The precipitate was filtered to obtain a methanol solution of the target substance, a compound of the following formula (6) {m = 3, n = 2 in formula (2)}.

[Formula 19]

(6)

“Synthesis Example 3 Carboxyl Compound Containing Phosphorylcholine Group”

5 g of 1-a-glycerol phosphorylcholine was dissolved in 70 ml of water-30 ml of acetonitrile. Under ice cooling, 17 g of sodium periodate and 80 mg of ruthenium trichloride were added, and the mixture was stirred overnight. The precipitate was filtered, concentrated under reduced pressure, and extracted with methanol to obtain 3.86 g (yield: 82%) of the target carboxymethyl phosphorylcholine (8). FIG. 2 shows the 1H-NMR of the compound of the formula (8).

[Formula 20]

"Synthesis example 4 Phosphorylcholine group-containing compound of formula (3)"

3.86 g of the carboxymethyl phosphorylcholine compound represented by the chemical formula (8) and 3 g of thiol chloride were added to acetonitrile under ice-cooling, and the mixture was stirred for 30 minutes, and 3.8 g of 3-aminopropyltrimethoxysilane and 3 g of triethylamine were added. Continue flowing dry nitrogen through the reaction vessel The mixture was stirred at room temperature to obtain a solution of the desired compound of formula (7) {acetonitrile of {{formula (3) m = 3, n = 2}}.

[Formula 21]

(7)

“Example 1: Introducing an amino group directly into the powder surface, and then reacting a compound containing an aldehyde compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine with the amino group Production Method for Underwater Highly Dispersible Cosmetic Powder: Two-Step Production Method "

In a 500 mL Erlenmeyer flask, 100 g of ion-exchanged water, 100 g of 2-propanol, and 5 g of 3-aminopropyltrimethoxysilane were added and vortexed.

After adding 10 g of particulate zinc oxide (particle size: 0.02 to 0.05 / zm), the mixture was heated to 80 ° C and boiled under reflux for 5 hours. After cooling to room temperature, the finely divided zinc oxide powder was filtered three times with 100 mL of methanol, washed, and dried under reduced pressure to obtain a finely divided zinc oxide powder into which an aminopropyl group was introduced. The methanol solution containing the ligated compound lg obtained in Synthesis Example 1 was mixed with the obtained finely divided oxidized zinc powder lOglOOml in methanol, and allowed to stand at room temperature for 5 hours. Subsequently, the mixture was cooled in an ice bath, 0.3 g of sodium cyanohydroborate was added, and the mixture was stirred at room temperature. The filter was filtered, washed three times with 100 mL of methanol, and dried under reduced pressure. A) a powder for cosmetics of the present invention comprising a fine particle zinc oxide powder having phosphorylcholine groups directly on the surface thereof.

“Example 2: Method for producing water-dispersible cosmetic powder by reacting compound represented by formula (2) directly on powder surface: one-step production method”

50 mL of distilled water was added to 50 mL of a methanol solution containing about 1 mmol of the compound of the formula (6) produced in Synthesis Example 2, and 10 g of a fine powder of kanji-zinc zinc oxide was added. This powder dispersion solution was refluxed at 80 ° C. for 5 hours to cause a reaction. After the reflux, filtration, washing with methanol (100 mL) three times, and drying, the fine particles having phosphorylcholine groups of the formula (1) of the present invention directly on the surface have a fine particle. The cosmetic powder of the present invention comprising lead powder was obtained.

[0047] "Effect of dispersibility in water 1"

Cosmetic powders of Examples 1 and 2, fine particles not modified with phosphorylcholine group of formula (1) Oxidized zinc powder (Comparative Example 1) Each l.Og was sufficiently dissolved in 99.Og of ion-exchanged water After suspending, they were placed in a sedimentation volume tube and the time required for the sedimentation volume to reach 50% was compared. The results are shown in [Table 1] below.

[Table 1] Cosmetic powder of Example 1: After about 7 days

Cosmetic powder of Example 2: After about 7 days

Cosmetic powder of Comparative Example 1: After about 3 minutes

[0048] Thus, it was found that the powder for cosmetics of the present invention was significantly modified by being directly modified with the phosphorylcholine group of the formula (1), whereby the dispersion stability in water was greatly improved.

In addition, it was also found that the original performance of the particulate zinc oxide (UV protection performance, color tone, etc.) was not impaired.

“Example 3: Introducing an amino group directly to the powder surface, and then reacting a compound containing a carboxyl compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine with the amino group. Production method of water-based highly dispersible cosmetic powder: two-stage production method ''

After adding 10 g of fine particle titanium dioxide (particle size: 0.02 to 0.05 m), the mixture was heated to 80 ° C and boiled under reflux for 5 hours. After cooling to room temperature, the fine titanium dioxide powder was filtered three times with 100 mL of methanol, washed, and dried under reduced pressure to obtain fine titanium dioxide powder into which an aminopropyl group was introduced.

Next, an aminopropyl group-introduced fine-particle diacid titanium powder 10 g, an acetonitrile solution 3 Oml obtained by reacting the i-conjugated product lg obtained in Synthesis Example 3 and 0.7 g of the iodizide zionyl for 1 hour, 0.5 g of triethylamine was mixed and stirred at room temperature for 5 hours. Subsequently, this mixture is The resultant was washed three times with 100 mL of ethanol, and dried under reduced pressure to obtain a cosmetic powder of the present invention comprising fine particle titanium dioxide having a phosphorylcholine group of the formula (1) directly on the surface.

“Example 4: Production method of water-dispersible cosmetic powder by reacting compound represented by formula (7) directly on powder surface: one-step production method”

To 20 mL of an acetonitrile solution containing about 1 mmol of the compound of the formula (7) produced in Synthesis Example 4, 30 mL of methanol and 10 mL of distilled water were added with 10 g of fine powder of fine titanium dioxide powder. This powder dispersion solution was refluxed at 80 ° C. for 5 hours to cause a reaction. After being refluxed, filtered three times with 100 mL of methanol, washed, and dried, the cosmetic powder of the present invention comprising the fine particle titanium dioxide powder having the phosphorylcholine group of the formula (1) of the present invention directly on the surface is obtained. Got.

[0051] "Experiment on the effect of dispersibility in water 2"

Cosmetic powders of Examples 3 and 4, fine particles not modified with phosphorylcholine group of formula (1) Diacid titanium powder (Comparative Example 2) Each l.Og was converted to ion exchanged water of 99.Og After sufficient suspension, they were placed in a sedimentation volume tube and the time required for the sedimentation volume to reach 50% was compared. The results are shown in [Table 2] below.

[Table 2] Cosmetic powder of Example 3: After about 10 days

Cosmetic powder of Example 4: After about 10 days

Cosmetic powder of Comparative Example 2: about 30 minutes later

[0052] Thus, it was found that the cosmetic powder of the present invention was significantly modified in water by greatly improving the dispersion stability in water by directly modifying the powder with the phosphorylcholine group of the formula (1).

In addition, it was also found that the original performance (UV protection performance, color tone, etc.) of the fine particles of titanium dioxide was not impaired.

“Examples 5 to 12”

In the same manner as in Example 1, the powder into which the phosphorylcholine group of the formula (1) was introduced was changed to silica (Example 5), sericite (Example 6), myriki (Example 7), and talc (Example Example 8), changed to kaolin (Example 9), red iron oxide (Example 10), yellow iron oxide (Example 11), black iron oxide (Example 12) Thus, a phosphorylcholine group-modified powder of the formula (1) was produced. It has been found that the phosphorylcholine group of the formula (1) can be directly covalently introduced into the powder surface by any of the production methods of the present invention.

[Examples 13 to 20]

In the same manner as in Example 2, the powder into which the phosphorylcholine group of the formula (1) was introduced was changed to silica (Example 13), sericite (Example 14), myriki (Example 15), and talc (Example 15). A phosphorylcholine group modification reaction was carried out by changing to Example 16), kaolin (Example 17), red iron oxide (Example 18), yellow iron oxide (Example 19), and black iron oxide (Example 20). It has been found that the phosphorylcholine group of the formula (1) can be directly covalently introduced into the powder surface by any of the methods of the present invention.

"Example 21 O / W emulsified foundation"

(Prescription)

1) Phosphorylcholine group-modified acido sericite (Example 6) 17.0

2) Phosphorylcholine group-modified acid oxidizing ability (Example 7) 20.0

3) Phosphorylcholine group-modified zinc oxide (Example 1) 8.0

4) Phosphorylcholine group modified bengara (Example 10) 0.3

5) Phosphorylcholine group-modified yellow iron oxide (Example 11) 1.2

6) Phosphorylcholine group-modified black acid tannin (Example 12) 0.6

7) Spherical polyethylene powder 6.0

8) Squalane 10.0

9) Olive oil 10.0

10) Stearic acid 2.0

11) Glyceryl monostearate 2.0

12) POE (40) Sorbitan monostearate 2.0

13) Glycerin 5.0

14) Triethanolanolamine 0.8

15) pH adjuster 16) Preservative appropriate amount

17) Remaining ion-exchanged water

(Formulation method)

Heat 1) to 12) at 85 ° C (oil phase). Add 13) to 15) to 17) and disperse uniformly (aqueous phase). Add the oil phase to the aqueous phase, stir at 85 ° C for 100 minutes, add 16), stir and cool to 45 ° C.

The shampoo containing the powder modified with the phosphorylcholine group had excellent stability in powder dispersibility with time and excellent usability.

`` Example 22 O / W type emulsified makeup base ''

(Prescription)

1) Ion exchange water balance

2) Glycerin 20.0

3) 1,2-pentanediol 3.0

4) 1,3-butylene glycol 1.0

5) Liquid paraffin 7.5

6) Isostearic acid 0.5

7) Ascorbic acid (whitening agent) 0.2

8) Power pickle extract (whitening agent) 0.1

9) Saxifraga extract (whitening agent) 0.3

10) di 2-ethylhexyl phthalate 0.3

11) Phosphorylcholine group-modified spherical silica (Example 5) 4.0

12) Phosphorylcholine group-modified zinc oxide (Example 1) 5.0

13) Phosphorylcholine group-modified talc (Example 8) 5.0

14) Suitable amount of stabilizer

15) Suitable amount of fragrance

(Formulation method)

Heat and dissolve 5) to 14) at 85 ° C (oil phase). Add 2) to 4) to 1) and disperse uniformly (aqueous phase). Add the oil phase to the aqueous phase, stir at 85 ° C for 100 minutes, add 15), Stir and cool to 45 ° C.

Example 23 Two-Layer Lotion

(Prescription)

1) Glycerin 4.0

2) Polyethylene glycol (molecular weight 1500) 3.0

3) Ethanol (95%) 15.0

4) Camphor 0.1

5) Liquid phenol (95%) 0.3

6) Phosphorylcholine group-modified zinc oxide (Example 2) 2.0

7) Kaolin modified with phosphorylcholine group (Example 17) 2.0

8) Bentonite 1.5

9) Polymethylsilsesquioxane 0.01

10) Neopentyl glycol dicaprate 0.8

11) Fragrance 0.01

12) Trisodium edetate 0.1

13) Remaining purified water

(Formulation method)

6), 7), 8) and 9) were wetted at room temperature and dissolved at room temperature as well.3), 4), 5), 10) and 12) were similarly dissolved at room temperature 1), 2), 11), 13) Uniformly mixed into.

The iDani cosmetic product containing the phosphorylcholine group-modified powder had good re-dispersibility of the powder layer and excellent usability.

Industrial applicability

[0058] The cosmetic powder of the present invention is excellent in water dispersibility, and is therefore preferably used for powder-containing cosmetics having excellent powder dispersion stability.

Claims

Claims [1] A powder for water-dispersible cosmetics, wherein a phosphorylcholine group represented by the following formula (1) is directly and covalently bonded to the powder surface. [Formula 1], ο 一

(1)

[2] The cosmetic powder according to [1], wherein the powder is a powder having a hydroxyl group on a surface.

[3] An amino group is directly introduced into the powder surface, and then a compound containing an aldehyde compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine is reacted with the amino group. A method for producing the powder for cosmetics according to claim 1 or 2.

[4] An amino group is directly introduced into the powder surface, and then a compound containing a carboxyl compound obtained by an oxidative cleavage reaction of glycerol phosphorylcholine is reacted with the amino group. Item 3. The method for producing a cosmetic powder according to Item 1 or 2.

[5] The production of the cosmetic powder according to claim 1 or 2, wherein the powder is obtained by directly reacting a compound represented by the following formula (2) and Z or (3) on the powder surface. Method.

[Formula 2]

(2)

[Formula 3]

(3)

one two Three

Group, propyl group, isopropyl group, butyl group and isobutyl group.

A cosmetic comprising the water-dispersible cosmetic powder according to claim 1 or 2.