JPH08283605A - Modified powder and blended cosmetic - Google Patents

Abstract

PURPOSE: To obtain a modified powder by treating the surface of powder with a specific perfluoroalkyl/polyoxyalkylene modified silicone, providing a cosmetic excellent in sebum resistance, water resistance, durability and touch by blending a cosmetic with the modified powder. CONSTITUTION: This modified powder is obtained by treating powder with a perfluoroalkyl/polyoxyalkylene modified silicone of the formula [(1) is 0-500; (m) and (n) are each 1-500; R<1> is a (substituted) 1-20C alkyl or aryl; R<2> is a 1-10C fluorine-substitute alkyl; R<3> is a polyoxyalkylene of the formula Cp H2p O(C2 H4 O)a (C3 H6 O)a R<-5> (R<5> is H, phosphate group, etc.; (a) and (b) are each 0-100 and a+b is >=1; (p) is 2-6); R<4> is any of R<1> to R<3> ]. For example, powder of a polymer such as nylon powder, an organic pigment, or white pigment, etc., is cited as the power to be subjected to the surface treatment. The surface treatment is preferably carried out by a wet method. The used amount of the compound of the formula is preferably 3-15 pts.wt. based on 100 pts.wt. of the powder. Hexane, etc., are preferable as the organic solvent used by the wet method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a perfluoroalkyl / polyoxyalkylene co-modified which is a kind of silicone hybrid type polymer having an oil-repellent fluorine compound-containing group and a hydrophilic group at the same time in one molecule. By adding a modified powder surface-treated with silicone (hereinafter referred to as FPD-modified silicone) to cosmetics, water and oil repellency,
The present invention relates to a cosmetic material having excellent durability.

More specifically, by utilizing the phenomenon that when the FPD-modified silicone-coated powder retains water, the powder itself becomes adhesive to the skin without losing its water and oil repellency, The present invention relates to cosmetics having excellent sebum resistance, water resistance, and durability.

[0003]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
U.S. Patent No. 632744 and Japanese Patent Publication No. 61-55481.
As described in Japanese Patent Publication No. JP-A-2003-264, the surface of the powder is treated with various fluorine compounds to introduce a fluoroalkyl chain to the surface of the powder to introduce water- and oil-repellent properties into the powder. There is.

Cosmetics using these fluorine-treated powders,
For foundations, for example, by utilizing the fact that powder does not get wet with sebum and sweat, a lasting type foundation that is more durable than makeup has been developed.

Heretofore, in the conventional foundation, the bond between the skin and the powder was often obtained by a physical adhesive force with the binder oil. However, these fluorine-treated powders have a fluorine-based oil agent or a high viscosity. Since they are only compatible with oils, the physical bond was the main bond between the skin and the fluorinated powder when these oils were not used.

[0006] When this physical adhesive force is utilized, the fluorine-treated powder cannot maintain the bond with the skin against a large amount of sweat and sebum generated in the summer and during exercise, and gradually falls off from the skin. There was a problem that the makeup became thin over time.

To solve this problem, Japanese Patent Publication No. 6-10260
As disclosed in Japanese Patent No. 7, there is a report that the problem has been solved by combining a fluorinated powder and a fluorinated oil agent, but in reality, the fluorinated pigment is characterized by having an extremely low surface free energy. In addition, since fluorinated oils also have the same low surface free energy, even if the problem of wetting of fluorinated pigments is solved, it is weak in terms of binding force to the skin and leap the makeup sustainability. It didn't improve.

In view of the above problems, the present inventors have made diligent efforts, and as a result, when the FPD-modified silicone retains water,
It was found that it has the property of thickening or gelling, and that it retains a certain amount of water and has a strong water and oil repellency. , And found that a cosmetic having excellent water resistance and durability can be obtained.

Furthermore, for products such as foundations and eye shadows that do not use water, FPD is applied at the time of application.
The modified silicone works as a part of the oil agent on the powder surface, and acts as a texture modifier during application, but
It has been found that after water is supplied from the skin, it thickens to increase the binding force with the skin, thereby playing a role in improving the durability of makeup.

Further, since the FPD-modified silicone has a polyoxyalkylene chain, a perfluoroalkyl chain, and a siloxane chain in the molecule, surface treatment having an affinity with these constituents, for example, surface hydroxyl groups of untreated powder is used. It has been found that the characteristics of the feel and the durability can be obtained by utilizing the FPD-modified silicone and then subjecting the FPD-modified silicone to the surface treatment after the fluorine compound treatment, the silicone treatment, the amino acid treatment and the like are performed in advance.

JP-A-1-180810 and JP-A-1-180811 disclose a technique of coating powder with a compound having a perfluoroalkyl chain and an oxyalkylene group or a hydroxyl group. . While these compounds have a water-repellent silicone skeleton as a main chain, these compounds have a hydrophilic skeleton such as a polyoxyalkylene group or a polyhydric alcohol as a main chain. Therefore, as described in the publication, this technique aims at obtaining a cosmetic that can be easily removed by a detergent, and has poor durability to sebum components having a surface-active function. Therefore, although the modified powder of the present invention has a similar purpose, it has different performance in terms of product quality.

[0012] To supplement this point, in the examples of the publication, cosmetics containing a wetting agent such as glycerin, which does not last long, are tested as a comparative example. Since it is an evaluation in a test system where the effect of
It is clear that the level of sustainability is inferior to that of the evaluation system of the present invention in which a silicone oil or a fluorine-based oil agent having superior durability is compared.

Therefore, the present invention relates to a modified powder surface-treated with FPD-modified silicone and a cosmetic composition containing the modified powder.

[0014]

That is, claim 1 of the present invention is a modified powder surface-treated with a perfluoroalkyl / polyoxyalkylene co-modified silicone having the structure of Chemical formula 3.

[0015]

Embedded image

(However, l, m, and n are integers, and l =
0-500, m = 1-500, n = 1-500,
R ¹ is the same or different, unsubstituted or substituted C ¹ to C ¹
20 alkyl or aryl groups, R ² has 1 to 1 carbon atoms
10 is a fluorine-substituted alkyl group, R ³ is —C _p H _2p
O a _{(C 2 H 4 O) a} (C 3 H 6 O) a polyoxyalkylene group represented by _b R ^5, R ⁴ is either R ¹ or R ² or R ^3, R ⁵ is hydrogen An atom or an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phosphoric acid group or a sulfuric acid group, a, b and p are integers, and a =
0 to 100, b = 0 to 100, a + b is 1 or more,
p = 2-6. )

According to a second aspect of the present invention, the powder is surface-treated with a compound selected from a silicone compound and a fluorine compound, and then the surface is treated with a perfluoroalkyl / polyoxyalkylene co-modified silicone having a structure of Chemical formula 4. It is the treated modified powder.

[0018]

[Chemical 4]

(However, l, m, and n are integers, and l =
0-500, m = 1-500, n = 1-500,
R ¹ is the same or different, unsubstituted or substituted C ¹ to C ¹
20 alkyl or aryl groups, R ² has 1 to 1 carbon atoms
10 is a fluorine-substituted alkyl group, R ³ is —C _p H _2p
O a _{(C 2 H 4 O) a} (C 3 H 6 O) a polyoxyalkylene group represented by _b R ^5, R ⁴ is either R ¹ or R ² or R ^3, R ⁵ is hydrogen An atom or an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phosphoric acid group or a sulfuric acid group, a, b and p are integers, and a =
0 to 100, b = 0 to 100, a + b is 1 or more,
p = 2-6. )

A third aspect of the present invention is a cosmetic containing the modified powder according to the first and second aspects.

The structure of the present invention will be described in detail below.

The FPD-modified silicone referred to in the present invention is
It is a general term for perfluoroalkyl / polyoxyalkylene co-modified silicones having the structure shown in Chemical Formula 3 above.

As the method for synthesizing the FPD-modified silicone, the method described in JP-A-6-246144 can be used.

The powder referred to in the present invention refers to an inorganic or organic powder conventionally used in cosmetics, and its shape, particle size and crystal form are not limited, but for example, the shape is plate-like, rod-like, needle-like. , Spindle shape, spherical shape, irregular shape, flat shape, phosphorous shape, etc., and the average primary particle diameter is 5n.
Powders in the range of m to 100 μm can be used,
Further, as the crystal type, an amorphous type or the like can be used in addition to the intrinsic crystal type.

As an example of the powder used in the present invention, red 1
04, Red 201, Yellow 4, Blue 1, Black 40
No. 1 dye, yellow No. 4 Al lake, yellow No. 203 Ba
Lakes and other lake pigments, dyes, nylon powder, silk powder, urethane powder, Teflon powder, silicone powder, cellulose powder and other polymers, yellow iron oxide, red iron oxide, black iron oxide, low order titanium oxide, chromium oxide, Carbon black, ultramarine, dark blue, colored pigments such as cerium oxide, white pigments such as zinc oxide and titanium oxide, body pigments such as talc, mica, sericite and kaolin, pearl pigments such as mica titanium, barium sulfate, calcium carbonate, Metal salts such as magnesium carbonate, aluminum silicate and magnesium silicate, inorganic powder such as silica and alumina, metal soap such as zinc stearate, fine titanium oxide, fine zinc oxide, fine iron oxide, alumina treated fine titanium oxide and silica treated Examples thereof include fine particle titanium oxide.

These powders may or may not be surface-treated in advance. As the type of surface treatment, conventionally known surface treatments such as fluorine compound treatment, silicone treatment, pendant treatment, silane coupling agent treatment,
Titanium coupling agent treatment, oil treatment, N-acylated lysine treatment, polycarboxylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, biological extract component treatment, plasma treatment, mechanochemical treatment, etc. Treatment with a silicone compound or a fluorine compound is preferable because it has good compatibility with the modified silicone. Examples of silicone compounds are methylhydrogenpolysiloxane, cyclic methylhydrogenpolysiloxane, dimethylpolysiloxane, alkylalkoxysilanes and terminal modified dimethylpolysiloxane, and examples of fluorine compounds are perfluoroalkylsilanes and perfluoroalkyls. Examples thereof include phosphoric acid esters and salts thereof and metal soaps thereof, Teflon, perfluoroalkylcarboxylic acids and metal soaps thereof.

The surface treatment method used in the present invention includes:
Wet method, dry method, mechanochemical method, etc. can be mentioned,
A wet method is preferable because uniform coating treatment is easy and decomposition products are not generated. It should be noted that when a fluorine compound is treated by a mechanochemical method, for example, a method using a ball mill, hydrogen fluoride may be generated due to the breakage of a perfluoroalkyl chain in rare cases. The wet method referred to in the present invention refers to a method obtained by introducing FPD-modified silicone and powder or pretreated powder into an organic solvent, stirring and mixing to remove the solvent, drying, and optionally pulverizing. Examples of organic solvents include methylene chloride, hexane,
Those having a low surface tension such as toluene are preferable. The dry method is a method of simply mixing the FPD-modified silicone and the powder with stirring. Other examples include spray drying method and fluidized granulation method.
It does not matter if the PD-modified silicone is coated around the powder.

In the surface treatment used in the present invention, FPD
The mixing ratio of the modified silicone and the powder or the pretreated powder varies depending on the oil absorption amount and the specific surface area of the powder, but is 0.
3 to 100 parts is preferable, and more preferably 3 to 15 parts.
Parts by weight. If the amount is less than 0.3 parts, the treatment is not sufficient and 1
If it exceeds 00 parts, the granulation may be violent and the feel may be deteriorated.

When the modified powder of the present invention is blended in a cosmetic composition, the compounding amount varies depending on the dosage form, but the modified powder is preferably 1 to 99 parts by weight per 100 parts by weight of the cosmetic composition. Then, it is preferable that the present modified powder occupies 30% or more of the total powder weight in the cosmetic.

Examples of the cosmetics of the present invention include foundation, white powder, blusher, pressed powder, cheek color, undercover, lipstick, eye shadow, eyeliner, nail color, makeup base and the like.

In the cosmetic of the present invention, in addition to the above-mentioned components, powders, resins, oils, silicone oils, ultraviolet absorbers, surfactants, fragrances, preservatives and bactericides which have been conventionally used in cosmetics. , A moisturizing agent, a solvent, a viscous agent, a physiologically active ingredient and the like can be simultaneously added.

As an example of the powder, according to the above powder example,
Further, the surface treatment may or may not be performed.

Examples of the oil agent are polyhydric alcohols such as glycerin, diglycerin, polyethylene glycol, propylene glycol, and 1,3-butanediol,
Cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, higher alcohols such as octyldodecanol, isostearic acid, undecylenic acid, fatty acids such as oleic acid, myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, Hexyldecyl dimethyloctanoate, glycerin monostearate, diethyl phthalate, ethylene glycol monostearate, esters such as octyl oxystearate, hydrocarbons such as liquid paraffin, vaseline, squalane, lanolin, reduced lanolin, carnauba wax, etc. Oils such as waxes, mink oil, cacao butter, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, olive oil, ethylene / α-olefin / co-oligomer, liquid oil Paraffin, paraffin, and the like.

Examples of other types of oil agents include, for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, alkyl-modified organopolysiloxane, terminal-modified organopolysiloxane,
Fluorine-modified organopolysiloxane, FPD-modified silicone, amodimethicone, amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid, silicone compounds such as silicone RTV rubber, perfluoropolyether, fluorinated pitch, fluorocarbon, fluoroalcohol And other fluorine compounds.

As the surface active agent, for example, anionic surface active agent, cationic surface active agent, nonionic surface active agent, betaine surface active agent can be used.

Examples of organic UV absorbers include 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl paradimethylaminobenzoate, and 2-hydroxy-4.
-Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, p-methoxyhydrocinnamic acid diethanolamine salt, para-aminobenzoic acid (hereinafter abbreviated as PABA), Ethyldihydroxypropyl PABA, glyceryl PABA, homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, octyldimethyl PABA, octyl methoxycinnamate, octyl salicylate, PABA, 2- Phenyl-
Benzimidazole-5-sulfuric acid, triethanolamine salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2,2 '
-Dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, 4- (3,4-dimethoxyphenylmethylene) -2, 5-dioxo-1-imidazolidine propionic acid 2-ethylhexyl etc. are mentioned.

Examples of the solvent include water, lower alcohols such as ethanol and isopropyl alcohol, LPG, dimethyl ether, petroleum ether, N-methylpyrrolidone and the like.

Examples of physiologically active ingredients are anti-inflammatory agents, tyrosinase activity inhibitors, plant extracts, vitamins,
Examples include sulfur and urea.

[0039]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples.

Collapse of the cosmetics used in Examples and Comparative Examples,
Evaluation of the feeling was performed by a method in which 10 panelists, a total of 10 women aged 24 to 33, used the cosmetics prepared in Examples and Comparative Examples, and the results were answered in a questionnaire. The questionnaire shows the percentage of panelists among the evaluators who agreed on the evaluation items. For example, if the score is 100, all the panelists evaluated, and if the score was 50, half of the panelists evaluated that the cosmetics of the example were more difficult to collapse and more difficult to remove than the comparative example.
In this evaluation, the level of sebum resistance and durability was evaluated as the collapse and drop of the cosmetic.

Further, as a severe evaluation of water resistance, a practical test (2 hours) in an indoor pool was conducted, the test site was peeled off with a cellophane tape, and the surface of the cellophane tape was enlarged 30 times, and the water resistance was changed from that state. The level was evaluated. The evaluation results use the same score notation as described above.

Example 1 95 parts of sericite was dispersed in 300 parts of methylene chloride, 5 parts of FPD-modified silicone having the structure shown in Chemical formula 5 was added, and the mixture was further stirred. The methylene chloride was distilled off under reduced pressure while heating to obtain modified sericite, and the obtained powder was pulverized. Similarly, 5% FPD-modified silicone-treated titanium oxide, talc, yellow iron oxide, red iron oxide, and black iron oxide were obtained.

[0043]

Embedded image

Example 2 92 parts of sericite treated with 3% methyl hydrogen polysiloxane was dispersed in 300 parts of methylene chloride, and then
8 parts of FPD-modified silicone having the structure shown in
Stir even better. The methylene chloride was distilled off under reduced pressure while heating to obtain modified sericite, and the obtained powder was pulverized. Similarly, 8% FPD-modified silicone / silicone-treated titanium oxide, talc, yellow iron oxide, red iron oxide, and black iron oxide were obtained.

[0045]

[Chemical 6]

Example 3 96 parts of sericite treated with 5% perfluoroalkyl phosphoric acid ester salt manufactured by Daito Kasei Kogyo Co., Ltd. was added to 30 parts of methylene chloride.
After dispersing in 0 part, 4 parts of FPD-modified silicone having the structure shown in Chemical formula 7 was added, and the mixture was further stirred. The methylene chloride was distilled off under reduced pressure while heating to obtain modified sericite, and the obtained powder was pulverized. Similarly, 4% FPD
Modified silicone / PF treated titanium oxide, talc, yellow iron oxide, red iron oxide, and black iron oxide were obtained.

[0047]

[Chemical 7]

Example 4 Foundation Using the modified powder of Example 1, a foundation was prepared according to the formulation shown in Table 1.

[0049]

[Table 1]

After mixing the powder components with a Henschel mixer, the liquid components were added and further stirred and mixed. Then, after pulverizing with an atomizer, it was punched with a die to obtain a product.

Example 5 Foundation Using the modified powder of Example 2, a foundation was prepared according to the formulation shown in Table 2.

[0052]

[Table 2]

After mixing the powder components with a Henschel mixer, the liquid components were added and further stirred and mixed. Then, after pulverizing with an atomizer, it was punched with a die to obtain a product.

Example 6 Foundation Using the modified powder of Example 3, a foundation was prepared according to the formulation shown in Table 3.

[0055]

[Table 3]

After mixing the powder components with a Henschel mixer, the liquid component was added and further stirred and mixed. Then, after pulverizing with an atomizer, it was punched with a die to obtain a product.

Comparative Example 1 Foundation A foundation was prepared in the same manner except that an untreated powder was used instead of the modified powder used in Example 4.

Comparative Example 2 Foundation A foundation was prepared in the same manner except that 3% methylhydrogenpolysiloxane-treated powder was used instead of the modified powder used in Example 5.

Comparative Example 3 Foundation Instead of the modified powder used in Example 6, 5% of perfluoroalkyl phosphate ester salt manufactured by Daito Kasei Kogyo Co., Ltd.
A foundation was prepared in the same manner except that the treated powder was used.

Using the examples and the comparative examples, evaluations were made on the cosmetics in terms of difficulty in breaking, difficulty in falling, water resistance, and feel. The results are shown in Table 4.

[0061]

[Table 4]

From the comparison between the example and the comparative example, it can be seen that the example is more resistant to collapse of the cosmetic material than the comparative example, is excellent in durability and sebum resistance, and is excellent in touch. In addition, the results of the water resistance test also show that the examples have better water resistance than the comparative examples.

In the comparison between Example 4 and Comparative Example 1, the FPD-modified silicone-treated powder and the untreated powder were compared.
The untreated powder was greatly affected by wetting and collapsed immediately.

In the comparison between Example 5 and Comparative Example 2, the FPD-modified silicone / silicone treated powder and the silicone treated powder were compared. The silicone-treated powder maintained strong water resistance as compared with the untreated powder, but was inferior in durability when compared with the examples.

In the comparison between Example 6 and Comparative Example 3, the FPD-modified silicone / PF-treated powder and the fluorine-treated powder were compared. In this combination, the example is a combination of the modified powder of the present invention and a fluorine-modified silicone, which is a type of fluorine-based oil agent, and the comparative example is a combination of a fluorine-treated powder and a fluorine-modified silicone, It is known that the comparative examples have high levels of water and oil repellency and durability. Also for this combination, the examples showed superior results to the comparative examples for each evaluation item. In particular, a difference was observed in the state of the panelists with O skin (greasy skin) over time.
The low evaluation value was due to the small difference between the panelists' evaluations of D skin (dry skin) and OD skin (mixed skin).

[0066]

From the above, the present invention provides sebum resistance,
It is obvious to provide a cosmetic having excellent water resistance, durability and feel.

Claims (3)

[Claims] 1. A modified powder which is surface-treated with a perfluoroalkyl / polyoxyalkylene co-modified silicone having the structure of Chemical formula 1. Embedded image (However, l, m, and n are integers, and 1 = 0 to 500,
m = 1 to 500, n = ^{1 to} 500, R ¹ is the same or different, unsubstituted or substituted C 1-20 alkyl or aryl group, and R ² is C 1-10 fluorine-substituted alkyl And R ³ is —C _p H _2p O (C ₂ H ₄
O) is _a (C ₃ H ₆ O) a polyoxyalkylene group represented by _b R ^5, R ⁴ is either R ¹ or R ² or R ^3, R ⁵ is a hydrogen atom or 1 to carbon atoms 5 is an alkyl group, an acetyl group, a phosphoric acid group or a sulfuric acid group, a, b and p are integers, and a = 0 to 100,
b = 0 to 100, a + b is 1 or more, and p = 2 to 6. ) 2. A modified powder obtained by surface-treating a powder with a compound selected from a silicone compound and a fluorine compound, and further surface-treating it with a perfluoroalkyl / polyoxyalkylene co-modified silicone having a structure of Chemical formula 2. body. Embedded image (However, l, m, and n are integers, and 1 = 0 to 500,
m = 1 to 500, n = ^{1 to} 500, R ¹ is the same or different, unsubstituted or substituted C 1-20 alkyl or aryl group, and R ² is C 1-10 fluorine-substituted alkyl And R ³ is —C _p H _2p O (C ₂ H ₄
O) is _a (C ₃ H ₆ O) a polyoxyalkylene group represented by _b R ^5, R ⁴ is either R ¹ or R ² or R ^3, R ⁵ is a hydrogen atom or 1 to carbon atoms 5 is an alkyl group, an acetyl group, a phosphoric acid group or a sulfuric acid group, a, b and p are integers, and a = 0 to 100,
b = 0 to 100, a + b is 1 or more, and p = 2 to 6. ) 3. A cosmetic containing the modified powder according to claim 1 or 2.