JPH107805A - Fluoroalkyl phosphate-modified organo (poly) siloxane, its production and cosmetic comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound, excellent in water and oil repellencies and capable of manifesting good compatibility with cosmetics by modifying an organo(poly)siloxane with a specific fluoroalkyl phosphate. SOLUTION: This compound is obtained by modifying at least one Si atom in an organo(poly)siloxane with a phosphoric triester group of formula I R<1> is a 2-20C straight-chain or branched alkylene; R<2> is a 1-20C straight-chain or branched alkylene which may be substituted with hydroxyl; (p) is 0-20; (l) and (x) are each 2-12; (m) and (y) are each 0 or 1; (n) and (z) are each 0-15; (a), (b) and (c) are each the number of groups in the parentheses bonded to P atom; [(a)+(b)+(c)] is 3; (a) is 1 or 2; (b) and (c) are each 0 or 1}. The compound is produced by reacting the organo(poly)siloxane having at least one H bonded to Si atom with a fluoroalkyl phosphate of formula II. Thereby, a cosmetic excellent in good feeling of use and emulsification stability without causing messy makeup due to perspiration or sebum is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluoroalkyl phosphate modified organo (poly) siloxane having excellent water and oil repellency, which is useful as a cosmetic material, a cosmetic material and the like, a process for producing the same, and a process for producing the compound. The present invention relates to a cosmetic that contains and has excellent makeup durability and feeling of use.

[0002]

BACKGROUND OF THE INVENTION Silicone has a high backbone binding energy, heat resistance, acid resistance,
It is known that it has excellent weather resistance and the like, and has low surface tension and has releasability, lubricity, water repellency and the like. Furthermore, since the intermolecular force is small, the main chain is flexible and the gas permeability is high, and since it is physiologically inert, it has characteristics such as low toxicity and low irritation. For these reasons, conventionally, silicones have been used in a wide range of fields such as electricity, electronics, automobiles, machinery, medical care, cosmetics, textiles, paper, pulp, and building materials.

[0003] In particular, in the field of cosmetics and cosmetics,
Conventionally, various water-repellent cosmetics have been used for the purpose of protecting the skin from water and sweat and preventing the makeup from being lost, and as this water-repellent component, silicone oil or silicone resin is used for skin cream, It is incorporated in skin protection cosmetics such as skin lotions and makeup cosmetics.
However, although conventionally used silicone oils and silicone resins have a certain effect on water repellency, they do not have a sufficient effect on oil repellency. Therefore, these cosmetics have a problem that makeup is lost by sebum.

[0004] For this reason, attempts have been made to develop compounds having both excellent water repellency and oil repellency. For example, Japanese Patent Application Laid-Open No. 2-295912 discloses a cosmetic containing a specific fluorine-modified silicone. It is disclosed that it has excellent water resistance and sebum resistance.

However, water- and oil-repellent bases used in cosmetics have (2) excellent emulsion stability in addition to (2) sufficient water and oil repellency against sweat and sebum. ,
(C) It is also required that the viscosity is low and the usability is good, but the fluorine-modified silicone is insufficient in terms of emulsion stability and usability, and the oil repellency has not yet been satisfactory. .

Accordingly, development of a compound which is excellent in water repellency and oil repellency, does not cause makeup loss due to sweat or sebum when blended in cosmetics, gives a good feeling in use, and has excellent emulsion stability. Was desired.

[0007]

Under these circumstances, the present inventors have made intensive studies to solve the above-mentioned problems, and as a result, it has been found that organo (poly) siloxane modified with a specific fluoroalkyl phosphate ester has excellent water repellency.・ It has oil repellency and shows good compatibility with cosmetics.
The present invention has been completed.

That is, in the present invention, at least one silicon atom of the organo (poly) siloxane has the following general formula (1):

[0009]

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[0010] [wherein, R ¹ is a linear or branched alkylene group having 2 to 20 carbon atoms, R ² is a linear or branched alkylene having 1 to 20 carbon atoms which may be substituted with a hydroxyl group Represents a group, p represents a number of 0 to 20, l and x are the same or different, and represent a number of 2 to 12, m and y are the same or different, and represent 0 or 1, n and z are Identical or different, each represents a number from 0 to 15, a, b, and c each represent the number of groups in parentheses bonded to a phosphorus atom;
+ C = 3, a is 1 or 2, and b and c are 0 or 1. ]

[0011] A fluoroalkyl phosphate modified organo (poly) siloxane characterized by being modified with a phosphate triester group represented by the following formula, a process for producing the same, and a cosmetic containing the compound: It is.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1) representing a phosphoric acid triester group for modifying a silicon atom of an organo (poly) siloxane, a linear or branched alkylene having 2 to 20 carbon atoms represented by R ^1. As the group, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene,
Dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group, etc.
Preferably those having 2 to 12 carbon atoms, for example, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene,
Examples include a dodecamethylene group, and particularly, an ethylene, propylene, tetramethylene, hexamethylene, octamethylene, and nonamethylene group, and an ethylene group is more preferable.

In the general formula (1), p represents a number from 0 to 20, preferably from 0 to 10, particularly preferably from 0 to 5.

In the general formula (1), examples of the linear or branched alkylene group having 1 to 20 carbon atoms which may be substituted on the hydroxyl group represented by R ² include methylene, ethylene, trimethylene, propylene and -Methyltrimethylene, tetramethylene, pentamethylene, 3-methyltetramethylene, 1,1-dimethyltrimethylene, hexamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, 2-hydroxyethylene, 2-
Hydroxybutylene, 2-hydroxyoctamethylene group and the like, preferably those having 1 to 10 carbon atoms, for example, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene group, nonamethylene group and the like.

In the general formula (1),-(CH ₂ ) _l- (O) _m- (CF
_{2) n} -CF ₃ and _{- (CH 2) x - (} O) y - (CF 2) The group represented by _z -CF _3, preferably has m and y are 0, for example, trifluoropropyl Group, pentafluorobutyl group, heptafluoropentyl group, nonafluorohexyl group, dodecafluoroheptyl group, tridecafluorooctyl group,
Examples include a pentadecafluorononyl group, a heptadecafluorodecyl group, a nonadecafluoroundecyl group, a heneicosafluorododecyl group, a pentacosafluorotetradecyl group, and a nonacosafluorohexadecyl group.
Among these, a group in which 1 or x is 2 and n or z is 4 to 12 is preferable, and a tridecafluorooctyl group and a heptadecafluorodecyl group are particularly preferable.

As the fluoroalkyl phosphate modified organo (poly) siloxane of the present invention, structural units represented by the following general formula (4) or general formulas (4) and (5)
What has a structural unit represented by these is preferable.

[0017]

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[Wherein R ¹ , R ² , p, l, m, n,
x, y, z, a, b and c have the same meanings as described above;
⁸ and R ⁹ are the same or different and represent an alkyl group, an alkoxyl group or a phenyl group. ]

In the general formulas (4) and (5), the alkyl group represented by R ⁸ and R ⁹ has 1 to 22 carbon atoms.
Are preferred, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl,
Examples include hexyl, octyl, tetradecyl, octadecyl and docosyl groups, and a methyl group is particularly preferred. As the alkoxyl group, an alkoxyl group having 1 to 22 carbon atoms is preferable, and examples thereof include methoxyl, ethoxyl, propoxyl, butoxyl, pentyloxyl, 2-ethylbutoxyl, 2-ethylhexyloxyl, and the like. Ethoxyl groups are preferred.

More preferred fluoroalkyl phosphate modified organo (poly) siloxanes of the present invention include those represented by the following general formula (2).

[0021]

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Wherein R ^{3 to} R ⁷ are the same or different,
Each represents an alkyl group, an alkoxyl group or a phenyl group, and at least one of X and q Y and Z is a fluoroalkyl phosphate group represented by the general formula (1), and the remainder is an alkyl group, an alkoxyl group or A phenyl group is shown, and q shows the number of 0-1000. ]

R ^{3 to} R ⁷ , X, Y and Z in the general formula (2)
An alkyl group in a group other than the phosphoric acid triester group,
Examples of the alkoxyl group and the phenyl group include the same ones as R ⁸ and R ⁹ in the general formulas (4) and (5), and among them, R ^{3 to} R ⁷ , X, Y and Z phosphate triesters It is particularly preferred that all of the groups except the groups are methyl groups.

In the general formula (2), q is 0 to 1
Although the number of 000 is shown, the number of 0 to 300 is preferable.

The fluoroalkyl phosphate-modified organo (poly) siloxane of the present invention is, for example, an organo (poly) siloxane having at least one hydrogen atom bonded to a silicon atom, which is represented by the following general formula (3): It can be produced by reacting a saturated group-containing fluoroalkyl phosphate.

[0026]

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[Wherein R ¹ , R ² , p, l, m, n,
x, y, z, a, b and c have the same meaning as described above. ]

As the organo (poly) siloxane used as a raw material in the production method of the present invention, the following general formulas (6) to (8)

[0029]

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In the formula (6), R ^{3 to} R ⁷ and q have the same meanings as described above, and at least one of X ′ and q Y ′ and Z ′ is a hydrogen atom, and the remainder is an alkyl group. It represents an alkoxyl group or a phenyl group. (7) In the formula, R ¹⁰ represents an alkyl group, an alkoxyl group or a phenyl group;
Represents at least one hydrogen atom, and the remainder represents an alkyl group, an alkoxyl group or a phenyl group, and r represents 3 to 100.
(Preferably 3 to 10). (8) wherein R ¹¹
To R ²¹ are the same or different and represent an alkyl group, an alkoxyl group or a phenyl group, and s, t and u are 1 to 1000
And v represents a number from 0 to 1000. In each formula, R ³
Among R ⁷ , R ¹⁰ , and R ^{11 to} R ²¹ , the alkyl group and the alkoxyl group preferably have 1 to 22 carbon atoms, and more preferably a methyl group, a methoxyl group, and an ethoxyl group, and particularly preferably a methyl group. And particularly preferably those represented by the general formula (6).

Specific examples of these organo (poly) siloxanes include, for example, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,5
7,7,7-octamethyltetrasiloxane, tris (trimethylsiloxy) silane, 1,1,3,3,5
5-hexamethyltrisiloxane, 1,1,1,3
5,5,5-heptamethyltrisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,1,3 , 3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane and the like.

In the present invention, such an organo (poly)
As the siloxane, those manufactured by a known method can be used, but commercially available products can also be used as they are, and specific examples thereof include TSF484, TSF483,
XF40-A2606, XF40-A1629, XF4
0-A5149 and XF40-A2484 (all manufactured by Toshiba Silicone Co., Ltd.) and the like.

The unsaturated group-containing fluoroalkyl phosphate represented by the general formula (3) used in the production method of the present invention is produced by a known method. CH ₂ = CH-R ^2- (OR ¹ ) _p
-,-(CH ₂ ) _l- (O) _m- (CF ₂ ) _n -CF ₃ and-(CH ₂ ) _x- (O) _y- (CF ₂ ) _z-
It can be synthesized by sequentially reacting the alcohol corresponding to CF ₃ directly or in the presence of a base.

That is, in the general formula (3), a = b =
When a fluoroalkylphosphate ester in which two fluoroalkyl groups are different from each other with c = 1 is intended, CH ₂ CHCH—R ² —
(OR ¹ ) _p -OH, CF _3- (CF ₂ ) _n- (O) _m- (CH ₂ ) _l -OH and CF _3- (CF ₂ )
_{z - (O) y - (} CH 2) is added the reaction by about 1-fold mol relative to sequentially phosphorus oxyhalide Three alcohol _x -OH.
A = b = c = 1 and the two fluoroalkyl groups are the same, or a = 2 and b = 1, c = 0 or b =
When a fluoroalkyl phosphate ester having 0 and c = 1 is intended, CH ₂ 2CH—R ² — (OR ¹ ) _p —OH and CF ₃ — (CF ₂ ) _n —
(O) _m- (CH ₂ ) ₁ -OH [or CF _3- (CF ₂ ) _z- (O) _y- (CH ₂ ) _x -OH] After adding and reacting about 1-fold mol (or about 2-fold mol) with respect to, the remaining one is added and reacted with about 2-fold mol (or about 1-fold mol).

The solvent used in this reaction is not particularly limited as long as it is inert to the reaction and can dissolve phosphorus oxyhalide. Examples thereof include ether solvents such as tetrahydrofuran and dioxane, hexane and heptane. And aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, but generally the phosphorus oxyhalide concentration is 60% by weight or less, preferably 3% by weight.
The amount is 0% by weight or less. Examples of the base that can be used in this reaction include organic tertiary amines such as triethylamine, tributylamine, and pyridine; and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. These bases can be used alone or in combination of two or more.

In order to carry out the production method of the present invention, an organo (poly) siloxane having at least one hydrogen atom bonded to a silicon atom and an unsaturated group-containing fluoroalkyl phosphate represented by the general formula (3) In a solvent capable of dissolving both raw materials such as toluene, hexane, chloroform, diisopropyl ether, and tetrahydrofuran in a weight of 1 to 100 times the total amount of the raw materials, or in a solvent-free state, in a proportion of 20 to 10;
The reaction may be performed at 0 ° C. for 1 to 10 hours.

In this reaction, a catalyst such as a transition metal such as platinum, rhodium, nickel or palladium, a compound of these transition metals, or a complex of these transition metals is used in order to promote the reaction. ^It is preferable to add ^-2 to 10 ^-6 times mol. The reaction ratio of the raw material organo (poly) siloxane and the unsaturated group-containing fluoroalkyl phosphate (3) may be appropriately determined according to the degree of modification of the modified organo (poly) siloxane which is the target compound. Although not limited, for example, when the number of SiH bonds in the raw material organo (poly) siloxane is J and all the J SiH bonds are modified, the unsaturated group-containing fluoroalkyl phosphate (3) is , J / a to 5 J / a moles of the organo (poly) siloxane may be used.

After completion of the reaction, activated carbon or the like is added to remove the catalyst, the mixture is filtered, and the solvent and volatile components are distilled off to obtain the fluoroalkyl phosphate modified organo (poly) siloxane of the present invention. .

The viscosity, solubility, emulsion stability and other properties of the fluoroalkyl phosphate modified organo (poly) siloxane of the present invention depend on the silicone derivatives (6) to (8) used as raw materials in the above reaction. It can be controlled by appropriately changing the combination of the kind and the amount of the fluoroalkyl phosphate (3).

The fluoroalkyl phosphate-modified organo (poly) siloxane of the present invention obtained as described above is excellent in water and oil repellency and its properties such as viscosity can be controlled depending on the purpose. When used as an oil agent in cosmetics, it is possible to make the cosmetics more durable and more comfortable to use. In this case, the amount of the fluoroalkyl phosphoric acid ester-modified organo (poly) siloxane of the present invention to be added to the cosmetic is not particularly limited.
90% by weight, especially 0.1-70% by weight, is preferred.

Further, other oils used in ordinary cosmetics can be used in the cosmetic of the present invention. Examples of such oils include cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; non-volatile silicones such as methylpolysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane; squalane and palm oil Animal and plant fats and oils; and other hydrocarbons, higher fatty acid esters, liquid paraffin, iso-liquid paraffin and the like.

Further, the cosmetics of the present invention may contain, if necessary, components to be added to ordinary cosmetics, for example, petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols, etc. Solid and semi-solid oil components; water-soluble and oil-soluble polymers; coloring agents such as inorganic and organic pigments, inorganic and organic pigments and organic dyes treated with silicone or fluorine compounds; anionic surfactants and cationic surfactants , Nonionic surfactants, surfactants such as dimethylpolysiloxane / polyoxyalkylene copolymer, polyether-modified silicone; other water, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances , UV absorbers, humectants, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, etc., do not impair the effects of the present invention. A range can be appropriately compounded. In particular, when a pigment surface-treated with a fluorine compound is used, it is preferable because makeup is not lost due to sebum.

The cosmetic of the present invention is not particularly limited in its dosage form, kind, etc., and can be produced according to a usual method. Examples of the type include oily cosmetics, emulsified cosmetics, lipsticks, blushers, foundations, hair tonics, hair styling agents, and the like.

[0044]

The present invention will be further described with reference to examples and test examples, but the present invention is not limited to these examples.

Embodiment 1

[0046]

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15 g of the reactive siloxane (a), 33.5 g of the fluoroalkyl phosphate (b) and 50 ml of toluene were mixed and heated to 70 ° C. Then, chloroplatinic acid (1% isopropyl alcohol (IPA) solution) 20
0 μl was added, and the mixture was aged at 70 ° C. for 4 hours. After completion of the reaction, 1 g of activated carbon was added, and the mixture was stirred at 60 ° C. for 1 hour. The activated carbon was filtered off, the solvent was distilled off under reduced pressure, and the fluoroalkyl phosphate modified organo (poly) siloxane 47.6 was used.
g (yield 98.1%).

¹ H-NMR (CDCl ₃ ) 0.04 ppm: Si (CH ₃ ) ₃ , -0.02 ppm: Si (CH ₃ ) ₂ , 0.50 ppm: Si-C H
₂ -CH ₂ , 1.65ppm: Si-CH ₂ -C H ₂ -CH ₂ -O, 2.73ppm: CF ₂ -C H ₂ -CH
₂ -O, 4.07ppm: POC H ₂ CH ₂

Embodiment 2

[0050]

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10 g of the reactive siloxane (c), 40.6 g of the fluoroalkyl phosphate (d) and 70 ml of toluene were mixed and heated to 70 ° C. Thereafter, 200 μl of chloroplatinic acid (1% IPA solution) was added, and the mixture was added at 80 ° C. for 8 hours.
Aged for hours. After completion of the reaction, 1 g of activated carbon was added, and
Stirred at C for 1 hour. The activated carbon was filtered off, and the solvent was distilled off under reduced pressure to obtain 49.7 g (yield 98.2%) of a fluoroalkyl phosphate modified organo (poly) siloxane.

¹ H-NMR (CDCl ₃ ) -0.02 ppm: Si-CH ₃ , 0.50 ppm: Si-C H ₂ -CH ₂ , 1.58 ppm: Si-CH
₂ -C H ₂ -CH ₂ -O, 2.75ppm: CF ₂ -C H ₂ -CH ₂ -O, 3.42ppm: Si-CH _{2-
CH 2 -C H 2 -O-CH} 2, 3.63ppm: Si-CH 2 -CH 2 -CH 2 -OC H 2, 4.07pp
m: POC H ₂ CH ₂

Embodiment 3

[0054]

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10 g of the reactive siloxane (e), 32.5 g of the fluoroalkyl phosphate (f) and 60 ml of toluene were mixed and heated to 70 ° C. Thereafter, 200 μl of chloroplatinic acid (1% IPA solution) was added, and the mixture was added at 75 ° C. for 8 hours.
Aged for hours. After completion of the reaction, 1 g of activated carbon was added, and
Stirred at C for 1 hour. The activated carbon was filtered off, and the solvent was distilled off under reduced pressure to obtain 40.9 g of a fluoroalkyl phosphate modified organo (poly) siloxane (yield 96.2).
%).

[0056] _{^{1 H-NMR (CDCl 3)}} -0.01ppm: Si-CH 3, 0.49ppm: Si-C H 2 -CH 2, 1.21ppm: Si-CH 2
-(C H ₂ ) ₈ -CH ₂ -CH ₂ -O, 1.58 ppm: Si-CH _2- (CH ₂ ) ₈ -C H ₂ -CH ₂ -O,
2.75ppm: CF ₂ -CH ₂ -CH ₂ -O, 4.10ppm: POCH ₂ CH ₂

Embodiment 4

[0058]

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19.7 g of the reactive siloxane (g), 30.0 g of the fluoroalkyl phosphate (h) and 70 ml of toluene were mixed and heated to 70 ° C. Thereafter, 200 μl of chloroplatinic acid (1% IPA solution) was added, and 70 ° C.
For 8 hours. After the reaction is completed, 1 g of activated carbon is added,
Stirred at 60 ° C. for 1 hour. The activated carbon was removed by filtration, and the solvent was distilled off under reduced pressure to obtain 48.3 g of a fluoroalkyl phosphate modified organo (poly) siloxane (yield: 9).
9.2%).

¹ H-NMR (CDCl ₃ ) -0.01 ppm: -CH ₂ -Si-C H ₃ , 0.02 ppm: Si (C H ₃ ) ₃ , 0.48 ppm: Si
-C H ₂ -CH ₂ , 1.58ppm: Si-CH ₂ -C H ₂ -CH ₂ -O, 2.75ppm: CF ₂ -C H ₂
-CH ₂ -O, 3.42ppm: Si-CH ₂ -CH ₂ -C H ₂ -O-CH ₂ , 3.63ppm: Si-CH
₂ -CH ₂ -CH ₂ -OC H ₂ , 4.07ppm: POC H ₂ CH ₂

Embodiment 5

[0062]

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20.0 g of the reactive siloxane (i), 33.2 g of the fluoroalkyl phosphate (j) and 90 ml of toluene were mixed and heated to 70 ° C. Thereafter, 200 μl of chloroplatinic acid (1% IPA solution) was added, and the mixture was added at 75 ° C.
For 8 hours. After the reaction is completed, 1 g of activated carbon is added,
Stirred at 60 ° C. for 1 hour. The activated carbon was separated by filtration and the solvent was distilled off under reduced pressure to obtain 52.6 g of a fluoroalkylphosphate modified organo (poly) siloxane (yield 9).
8.9%).

[0064] _{^{1 H-NMR (CDCl 3)}} -0.01ppm: Si-C H 3, 0.45ppm: Si-C H 2 -CH 2, 1.58ppm: Si-CH 2
-C H ₂ -CH ₂ -O, 2.75ppm: CF ₂ -C H ₂ -CH ₂ -O, 3.42ppm: Si-CH ₂ -C
H ₂ -C H ₂ -O-CH ₂ , 3.63 ppm: Si-CH ₂ -CH ₂ -CH ₂ -O- (C H ₂ C H ₂ O) ₉ -C
H ₂ (9 is the average), 4.11 ppm: POC H ₂ CH ₂

Embodiment 6

[0066]

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25.0 g of the reactive siloxane (k), 14.3 g of the fluoroalkyl phosphate (l) and 60 ml of toluene were mixed and heated to 70 ° C. Thereafter, 200 μl of chloroplatinic acid (1% IPA solution) was added, and the mixture was added at 75 ° C.
For 9 hours. After the reaction is completed, 1 g of activated carbon is added,
Stirred at 60 ° C. for 1 hour. The activated carbon was filtered off, and the solvent was distilled off under reduced pressure to obtain 38.8 g of a fluoroalkyl phosphate modified organo (poly) siloxane (yield 9).
8.7%).

¹ H-NMR (CDCl ₃ ) -0.01 ppm: Si-C H ₃ , 0.45 ppm: Si-C H ₂ -CH ₂ , 1.15 ppm: O-CH
₂ (C H ₂ ) ₆ CH ₂ CH ₂ -O, 1.48 ppm: Si-CH ₂ -C H ₂ -CH ₂ -O, O-CH ₂ (CH
₂ ) ₆ C H ₂ CH ₂ -O, 2.75 ppm: CF ₂ -C H ₂ -CH ₂ -O, 3.26 ppm: Si-CH _{2-
CH 2 -C H 2 -O-CH} 2, 3.75ppm: Si-CH 2 -CH 2 -CH 2 -OC H 2, 4.05pp
m: POC H ₂ CH ₂

Test Example Fluoroalkylphosphate modified organo (poly) siloxane synthesized in Examples 1 to 4 and the water resistance of the conventional product
Oil resistance, viscosity and solubility were compared according to the following criteria. Table 1 shows the results.

<Evaluation Criteria> Water resistance: contact angle with water (angle between oil film of each oil agent and water droplet)
１００: 100 ° or more, ○: 70 ° or more and less than 100 °, 7
Less than 0 ° was evaluated as x. Oil resistance: The contact angle with squalane (the angle between the oil film of each oil agent and the squalane droplet) is 30 ° or more ◎, 20 ° or more 30 °
Is less than ○, and less than 20 ° is x. Viscosity: 未 満 for less than 35 cst, ○ for 35 to 80 cst, 80 cs
Those exceeding t were marked as x. Solubility: The solubility in octamethylcyclotetrasiloxane was examined.

[0071]

[Table 1]

Example 7 Powder foundation: (Production method) (1) Treatment of pigment with fluorine compound 100 g of each untreated pigment was placed in a 1-liter round bottom flask (or kneader), and 500 ml of ion-exchanged water was added. To perfluoroalkyl phosphate dioxyethylamine salt [(C _m F _{2m + 1} C ₂ H ₄ O) _y PO (ONH ₂ (CH ₂ C
_{H 2 OH) 2) 3-} y] [m = having 6 to 18 (average chain length: 9), 1 <y
33 g of an approximately 17.5% aqueous solution of <2> was added, and the mixture was stirred at 40 ° C. Next, 40 ml of 1N hydrochloric acid was added to adjust the pH of the aqueous solution.
Was reduced to 3 or less, and perfluoroalkylphosphoric acid was precipitated on the surface of the powder, which was then filtered, washed with water and dried to obtain 105 g of the desired fluorine compound-treated pigment. (2) The treated pigment is mixed and pulverized through a pulverizer. This is transferred to a high-speed blender, and a binder and the like are mixed by heating, and the resulting mixture is added to the pigment and further mixed to make the mixture uniform. This is treated with a pulverizer, passed through a sieve, and the particle size is adjusted. The mixture is allowed to stand for several days and then compression-molded in a container such as a gold plate to obtain a powder foundation.

(Composition) (% by weight) (1) Fluorine compound-treated pigment (each of the following pigments treated by the above method) Titanium oxide 10.0 Sericite 30.0 Mica Balance Kaolin 5.0 Bengala 0.8 Iron oxide yellow 2.5 Black iron oxide 0.1 (2) Compound of Example 2 8.0 (3) Beeswax 2.0 (4) Preservative 0.2 (5) Fragrance trace amount

Example 8 Blush: (Preparation method) Blush having the following composition was obtained in the same manner as in Example 7.

(Composition) (% by weight) (1) Silicone-treated pigment (commercially available pigment treated with methyl hydrogen polysiloxane) Kaolin Balance Mica 13.0 Titanium oxide 12.0 Red No. 202 2.5 Iron oxide (Red, Yellow) (Black) 5.0 (2) Compound of Example 3 7.0 (3) Dimethylpolysiloxane (“KF96A”, 6cst, manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0 (4) Preservative 0.1 (5) ) Fragrance trace

Example 9 Powder Eye Shadow: (Preparation Method) A pigment other than titanium mica was first mixed and pulverized, and then titanium mica was mixed. Otherwise, the procedure of Example 7 is repeated to obtain the desired powder eye shadow.

(Composition) (% by weight) (1) Water-repellent / oil-repellent powder (treated in the same manner as in Example 7 (1) and subsequently mixed) Titanium mica 4.9 Sericite balance mica 25. 0 Iron oxide (red, yellow, black) 2.0 Ultramarine blue 9.0 Navy blue 12.0 (2) Compound of Example 2 8.0 (3) Squalane 2.0 (4) Vaseline 1.5 (5) Sorbitan Trioleate 1.0 (6) Preservative 0.1 (7) Fragrance trace

Example 10 Dual-Use Powder Foundation: (Preparation Method) A dual-use powder foundation having the following composition was obtained in the same manner as in Example 9.

(Composition) (% by weight) (1) Silicone-treated pigment (commercially available pigment treated with methyl hydrogen polysiloxane) Mica balance talc 4.8 titanium oxide 14.0 mica titanium 3.5 3.5 iron oxide (red, yellow, 8.2) Zinc oxide 4.5 Aluminum oxide 10.0 Barium sulfate 5.0 (2) Compound of Example 4 6.0 (3) Lanolin 3.0 (4) Vaseline 1.0 (5) Isopropylmilli State 1.0 (6) Preservative 1.5 (7) Fragrance trace

Example 11 Two-Layer Type Sunscreen Emulsion: (Preparation Method) After dissolving the oil phase at room temperature, the pigment is dispersed with a disper. The aqueous phase was added thereto with stirring and emulsified to obtain a two-layer sunscreen emulsion having the following composition.

(Composition) (% by weight) (1) Octamethylcyclotetrasiloxane 25.0 (2) Compound of Example 5 15.0 (3) Dimethylpolysiloxane / polyoxyalkylene copolymer 1.0 (4) ) Glycerin 2.0 (5) Ethanol 12.0 (6) Purified water balance (7) Octyl methoxycinnamate 2.0 (8) Silicone treated pigment (commercially available pigment treated with methyl hydrogen polysiloxane) Zinc oxide 5.5 Titanium oxide 2.0 Talc 5.0 (9) Fragrance trace

Example 12 Nutritional cream: (Preparation method) (1) to (5) were mixed and heated to 75 ° C.
(6), (7) and (10) are mixed into this mixture,
The mixture heated to 70 ° C. is added with stirring to emulsify. After the emulsification, the mixture is cooled to 60 ° C., (8) and (9) are added thereto, and further cooled to room temperature to obtain a nutritional cream.

(Composition) (% by weight) (1) Polyoxyethylene (50) hydrogenated castor oil 2.0 (2) Potassium sulfate 0.5 (3) Compound of Example 6 6.0 (4) Liquid paraffin 5 2.0 (5) Hexadecyl-2-ethylhexanoate 2.0 (6) Sodium benzoate 0.3 (7) Propylene glycol 2.0 (8) Acetic acid-dl-α-tocopherol 0.1 (9) Fragrance 0.1 (10) Purified water balance

Example 13 Hand cream: (Preparation method) (1) to (5) are mixed and heated to 75 ° C.
The mixture of (6) to (8) heated to 75 ° C. is gradually added thereto under stirring to emulsify. Cool to room temperature to obtain a hand cream.

(Composition) (% by weight) (1) polyoxyethylene (20) sorbitan palmitate 1.5 (2) aluminum chloride 0.8 (3) isopropyl myristate 4.5 (4) dimethylpolysiloxane (Shin-Etsu "KF-96A", manufactured by Chemical Industry Co., Ltd., 6 cst) 4.0 (5) Compound of Example 5 6.0 (6) Methyl paraoxybenzoate 0.2 (7) Sorbitol 10.0 (8) Purified water balance

Example 14 Cream Foundation: (Preparation Method) (1) to (6) are mixed and heated to 75 ° C.
(7) is dispersed by a disper. The mixture of (9) to (14) is heated to 75 ° C. and gradually added under stirring to emulsify. Then cooled to 30 ° C (8)
And (15), and further cooled to room temperature to obtain the desired creamy foundation (W / O type).

(Composition) (% by weight) (1) Dimethylpolysiloxane / polyoxyalkylene copolymer 2.0 (2) Compound of Example 1 10.0 (3) Dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd.) "KF-96A", 6cst) 5.0 (4) Aluminum stearate 0.2 (5) 1-isostearoyl-3-myristoyl-glycerol 2.0 (6) Octyl methoxycinnamate 2.0 (7) Fluorine compound-treated pigment (The following pigment is treated in the same manner as in Example 7 (1)) Talc 5.0 Titanium oxide 9.0 Iron oxide (red, yellow, black) 1.2 (8) Decamethylcyclopentasiloxane 15 0.0 (9) Butyl paraoxybenzoate 0.1 (10) Sodium benzoate 0.2 (11) Magnesium sulfate 0.5 (12) Glycerin 5.5 (13) 1,3-butylene Recall 2.5 (14) Purified water Balance (15) Perfume 0.1

Example 15 Antiseptic cream: (Preparation method) (6) to (11) are mixed so as to be uniform. This is added to the aqueous components (1) to (5) under stirring and emulsified to obtain a desired antiseptic cream.

(Composition) (% by weight) (1) Polyoxyethylene (50) hydrogenated castor oil 0.5 (2) Polyoxyethylene (20) sorbitan palmitate 1.0 (3) Glycerin 6.0 (4) 1,3-butylene glycol 6.0 (5) Purified water balance (6) Squalane 5.0 (7) Jojoba oil 5.0 (8) Octamethylcyclotetrasiloxane 18.0 (9) Octyl methoxycinnamate 2. 0 (10) Compound of Example 2 30.0 (11) Fungicide (Irgasan DP-300) 0.2

Each of the cosmetics obtained in Examples 7 to 15 had good cosmetic durability against sweat and sebum and was excellent in use feeling.

[0091]

Industrial Applicability The fluoroalkyl phosphate modified organo (poly) siloxane of the present invention has excellent water and oil repellency, and when used in cosmetics, does not cause makeup loss due to sweat or sebum. It gives a feeling and is also excellent in emulsion stability.

Claims (6)

[Claims] 1. The method of claim 1, wherein at least one silicon atom of the organo (poly) siloxane has the following general formula (1): [In the formula, R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and R ² represents a linear or branched alkylene group having 1 to 20 carbon atoms which may be substituted by a hydroxyl group. , P represents a number of 0 to 20, l and x are the same or different, and represent a number of 2 to 12, m and y are the same or different, 0 or 1, and n and z are the same or different And 0
A, b, and c each represent the number of groups in parentheses bonded to the phosphorus atom, and a + b + c = 3, a
Is 1 or 2, and b and c are 0 or 1. ] A fluoroalkyl phosphate modified organo (poly) siloxane, which is modified with a phosphate triester group represented by the formula: 2. The following general formula (2): Wherein R ^{3 to} R ⁷ are the same or different and each represents an alkyl group, an alkoxyl group or a phenyl group;
At least one of Y and Z is a phosphoric acid triester group represented by the general formula (1), and the remainder represents an alkyl group, an alkoxyl group or a phenyl group, and q represents a number of 0 to 1,000. The fluoroalkyl phosphate modified organo (poly) siloxane according to claim 1, which is represented by the following formula: 3. In the general formula (2), a group other than the phosphoric acid triester group represented by the general formula (1) among R ^{3 to} R ^{7 and} X, Y and Z is a methyl group. Fluoroalkyl phosphate modified organo (poly)
Siloxane. 4. The fluoroalkyl phosphate-modified organo (poly) siloxane according to claim 1, wherein m and y in the general formula (1) are 0. 5. An organo (poly) siloxane having at least one hydrogen atom bonded to a silicon atom has the following general formula (3): [In the formula, R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and R ² represents a linear or branched alkylene group having 1 to 20 carbon atoms which may be substituted by a hydroxyl group. , P represents a number of 0 to 20, l and x are the same or different, and represent a number of 2 to 12, m and y are the same or different, 0 or 1, n and z are the same or different And 0
A, b, and c each represent the number of groups in parentheses bonded to the phosphorus atom, and a + b + c = 3, a
Is 1 or 2, and b and c are 0 or 1. 3. The method for producing a fluoroalkyl phosphate modified organo (poly) siloxane according to claim 1, wherein the fluoroalkyl phosphate represented by the formula (1) is reacted. 6. A cosmetic containing the fluoroalkyl phosphate modified organo (poly) siloxane according to claim 1. Description: