JPH08165348A - Organopolysiloxane modified with polyaluminum salt of phosphoric ester, production thereof, and cosmetic containing same - Google Patents

Abstract

PURPOSE: To obtain an emulsifier which stably emulsifies a silicone oil for cosmetics and give cosmetics excellent in the feeling in use. CONSTITUTION: An organo(poly)siloxane having at least one hydrogen atom bonded to a silicon atom is reacted with a polyaluminum salt of a terminally unsatd. phosphoric diester represented by formula I (wherein R<1> is 2-20C linear or branched alkylene; R<2> is an optionally alkylated 1-50C linear or branched group; p is 0-200; M is a polyhydroxoaquaaluminum ion; and n is the valence of M) to give an organo(poly)siloxane modified with a polyaluminum salt of a phosphoric diester represented by formula II (wherein R<1> , R<2> , p, M, and n are each the same as in formula I) having a divalent residue formed from the polyaluminum salt. The modified organo(poly)siloxane is added in an amt. of 0.01-30-wt.% to a silicone oil to emulsify it to produce cosmetics.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane useful as a cosmetic material, a cosmetic material, etc., a process for producing the same, and a good feeling and stability in use. To cosmetics having properties.

[0002]

2. Description of the Related Art Silicone is known to have a high bond energy in the main chain and excellent heat resistance, acid resistance, weather resistance, etc., low surface tension, release properties, lubricity and water repellency. There is. Further, since the intermolecular force is small, the main chain is flexible and has high gas permeability, and since it is physiologically inactive, it has characteristics such as low toxicity and low irritation. For this reason, conventional silicone has been used in electrical, electronic, automobile, mechanical,
It is used in a wide range of fields such as medicine, cosmetics, textiles, paper, pulp, and building materials.

Particularly in the fields of cosmetics and cosmetics,
Dimethylpolysiloxane and cyclic silicone, which have no stickiness and are highly safe, are actively used as oils for hair finishing agents and cosmetics. Techniques and cosmetics that effectively utilize the characteristics of such silicone oils Research on application development for cosmetics and cosmetics has been conducted.

However, although silicone oil is important as an oil agent for perfume and cosmetics, an oil agent for cosmetics, etc., there are some problems in obtaining a product having higher functionality. For example, silicone oil has poor compatibility with other cosmetic oils, and it is difficult to dissolve it uniformly and to prepare a stable silicone oil-based product. It has the drawback of seeping out and separation. Also,
Since there is still no agent that can control the viscosity of silicone oil, cosmetics containing a large amount of silicone oil generally have low viscosity and are inferior in stability, and have many problems such as dripping during use. ing. Further, when silicone oil is used as an oil agent for cosmetics, an oil agent for cosmetics, etc., it is difficult to stably disperse substances having different specific gravities in the composition over time.

Therefore, for the purpose of solving the above drawbacks, studies have been made to emulsify silicone oil and use it as a base for cosmetics or cosmetics which makes the most of its properties. Typical silicone oil emulsifiers include polyether-modified organo (poly) siloxanes, which have a cloud point phenomenon which is a characteristic of nonionic surfactants having a polyether bond. Not only is it poor in stability, but it is not completely satisfactory in terms of usability.

[0006]

Therefore, it has been desired to develop an emulsifier that stably emulsifies a silicone oil for cosmetics or cosmetics and gives a cosmetic with an excellent feeling of use.

[0007]

Under such circumstances, the inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, a specific phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane was found to be used in various cosmetics. Stable emulsifying silicone oil for cosmetics or cosmetics and blending this with cosmetics gives a clean and good feeling without stickiness, is stable over time, and contains a large amount of silicone oil. It was found that dripping does not occur even in such a case, and the present invention has been completed.

That is, the present invention is one or more organo (poly) siloxane chains and one or more of the following general formula (1) bonded to the silicon atom.

[0009]

[Chemical 6]

[R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms. R ² : 1 to 1 carbon atoms which may be substituted by a hydroxyl group
50 linear or branched alkylene groups are shown. p: Indicates the number from 0 to 200. M: indicates a polyhydroxoaqua aluminum ion. n: shows the valence of M. ] A phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane having a molecular structure composed of a divalent phosphoric acid diester polyaluminum salt residue represented by: The present invention provides an intermediate for producing a compound and a method for producing the same.

In the general formula (1), R ¹ has 2 to 2 carbon atoms.
Examples of the alkylene group of 20 include ethylene, propylene,
Examples include trimethylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group, and the like.
Particularly, a linear alkylene group having 2 to 12 carbon atoms is preferable.

Further, the linear or branched alkylene group having 1 to 50 carbon atoms which may be substituted by the hydroxyl group of R ² includes methylene, ethylene, trimethylene, propylene, 1-methylpropylene, butylene and pentane. Methylene, 3-methylbutylene, 1,1-dimethylpropylene, hexamethylene, octamethylene, nonamethylene,
Examples thereof include decamethylene, undecamethylene, 2-hydroxyethylene, 2-hydroxybutylene, and 2-hydroxyoctamethylene groups, and linear alkylene groups having 1 to 10 carbon atoms are particularly preferable.

Although p represents a number of 0 to 200, a number of 0 to 10 is preferable, and a number of 0 to 1 is particularly preferable.

In the general formula (1), the polyhydroxoaquaaluminum ion represented by M ^{n +} is a polycondensation of hydroxoaquaaluminum ion, and has the following basic structural units (A), (B) and It is considered that (C) is contained in a ratio according to its basicity.

[0015]

[Chemical 7]

In the modified organo (poly) siloxane of the present invention, one or two or more organo (poly) siloxane chains and the above divalent phosphodiester polyaluminum salt residue are bonded at the silicon atom of the siloxane. The structure is not particularly limited as long as it has the above structure, but the most preferable one has a structure represented by the following general formula (2).

[0017]

Embedded image

[R ¹ , R ² , p, M, n: have the same meaning as described above. R ³ to R ^20: independently an alkyl group or an alkoxyl group or a phenyl group having 1 to 22 carbon atoms. Of these, R
⁷ and R ¹⁶ may together form an —O— group. q, r, s, t, u, v: each represents a number from 0 to 1000. However, all of them do not become 0 at the same time. ]

The modified organo (poly) siloxane of the present invention is obtained by adding the organo (poly) siloxane having at least one hydrogen atom bonded to a silicon atom to the following general formula (3):

[0020]

[Chemical 9]

[R ¹ , R ² , p, M, n: have the same meaning as described above. ] It can manufacture by making terminal unsaturated phosphoric acid diester polyaluminum salt represented by these react.

The organo (poly) siloxane used as a raw material in the production method of the present invention is not particularly limited as long as it has at least one hydrogen atom bonded to a silicon atom, but preferred specific examples are as follows. Can be mentioned.

[0023]

[Chemical 10]

[R ^{21 to} R ³¹ : each represents an alkyl group (preferably having 1 to 22 carbon atoms), an alkoxyl group (preferably having 1 to 22 carbon atoms) or a phenyl group. Y ¹ , f Y ² , Y ³ : at least one hydrogen atom,
The balance represents an alkyl group (preferably having 1 to 22 carbon atoms), an alkoxyl group (preferably having 1 to 22 carbon atoms) or a phenyl group. g Y ^{4 s} : At least one is a hydrogen atom, and the rest is an alkyl group (preferably having 1 to 22 carbon atoms), an alkoxyl group (preferably having 1 to 22 carbon atoms) or a phenyl group. f, j: Indicates a number from 0 to 1000. g: shows the number of 3-20. h, i, k: Indicates a number of 1 to 1000. ]

Specific examples of these organo (poly) siloxanes include, for example, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1, 1, 1, 3, 5,
7,7,7-octamethyltetrasiloxane, tris (trimethylsiloxy) silane, 1,1,3,3,5,5
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, methyltris (dimethylsiloxy) silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, and the like.

In the present invention, such an organo (poly) is used.
As the siloxane, those produced by a known method can be used, or commercially available products can be used as they are. Specific examples thereof include TSF484, TSF483,
XF40-A2606, XF40-A1629, XF4
0-A5149, XF40-A2484 (above, Toshiba Silicone make) etc. are mentioned.

Further, the terminal unsaturated phosphoric acid diester polyaluminum salt represented by the general formula (3) used in the production method of the present invention may be produced by a known method and may be produced by any production method, For example, those manufactured by the following method can be used. That is,
First, phosphorus oxyhalide and an alcohol having an unsaturated bond at the terminal in an amount of 2 to 4 times, preferably 2 to 2.5 times the molar amount thereof [CH ₂ ═CH—R ² — (OR ¹ ) _p —OH; R
¹ , R ² and p have the same meanings as described above. ] In the presence of a catalyst such as triethylamine, tributylamine and pyridine in a solvent such as tetrahydrofuran, diethyl ether, methylene chloride and toluene at -30 to -10 ° C.
The corresponding phosphodiester (4) is obtained by reacting for ~ 4 hours and then at 0-10 ° C for 2-12 hours.

[0028]

[Chemical 11]

[R ¹ , R ² , p: has the same meaning as described above. ]

This phosphoric acid diester (4) may be used as it is, but in order to improve dispersibility or solubility in an aqueous medium, alkali metals such as sodium and potassium, alkanolamines such as monoethanolamine and diethanolamine, It is preferably used after being converted into a salt of a basic amino acid such as lysine or arginine.

The phosphoric acid diester (4) or salt thereof thus obtained was subjected to the following rational formula (5) Al _a (OH) _b X _c .dH ₂ O (5) [X] in an aqueous medium. : Indicates an anion other than hydroxide ion having a valence of x. a, b, c: A positive integer satisfying 3a = b + cx is shown. d: Shows an integer of 0 or more. ] By reacting the basic polyaluminum salt represented by the following, a terminal unsaturated phosphodiester polyaluminum salt (3) is obtained.

Basic polyaluminum used here
The counter ion X of the salt (5) is not particularly limited, and chlorine,
In addition to halogen ions such as bromine and iodine, nitric acid and perchloric acid
And monovalent anions such as nitric acid.
It Specific examples of the basic polyaluminum salt include:
Al₂(OH)_FiveCl, Al₃(OH)₃Cl₆, Al
₁₆(OH)₄₂Cl₆, Al₃(OH)₃Br₆, Al₁₆(O
H)₄₂Br₆, Al₃(OH) ₃I₆, Al₁₆(OH)
₄₂(SO_Four)₃Etc. Is shown by these rational formulas
There are many unclear points about the structure of the compound in an aqueous medium,
For example Al₂(OH)_FiveCl · 2H₂Shown by the rational formula O
Aluminum chlorohydrate is 1
Two aluminum atoms replace one aluminum atom
Entrapped polynuclear ions, ie [Al₁₃O_Four(OH)
_{twenty four}(H₂O)₁₂]⁷⁺Is believed to exist
[Journal of the Society of Cosmetics
Tick Chemistry (Journal of the
Society of Cosmetic Chemi
sts), 33, 281-295 (198).
2)].

In the above reaction, phosphoric acid diester (4) or a salt thereof and 1 / (2n) to 10 times equivalent amount of basic polyaluminum salt (5) are respectively added to tetrahydrofuran, ethanol, methanol, Butanol, 1
-It is carried out by dissolving or suspending in a mixed solvent of water with a solvent such as propanol or isopropyl alcohol or water, and mixing at 20 to 70 ° C. Then, if necessary, the product is purified by recrystallization, washing and the like to obtain the terminal unsaturated phosphodiester polyaluminum salt (3).

The terminal unsaturated phosphoric acid diester polyaluminum salt (3) thus obtained is a novel compound which has not been described in the literature.

The modified organo (poly) siloxane of the present invention comprises the aforementioned Si (H) -containing organo (poly) siloxane and the above phosphoric acid diester polyaluminum salt (3) in an amount of 1 to 100 times the total weight of these. 20 to 20 in a solvent capable of dissolving both raw materials such as toluene, hexane, chloroform, diisopropyl ether, and tetrahydrofuran.
The reaction may be performed at 100 ° C for 1 to 10 hours.

In this reaction, for the purpose of accelerating the reaction, a transition metal such as platinum, rhodium, nickel or palladium, a compound of these transition metals, a catalyst such as a complex of these transition metals or the like is used in a total amount of 10 raw materials. ^It is preferable to add ^-4 to 10 ^-6 moles. The reaction ratio of the starting organo (poly) siloxane to the terminal unsaturated phosphoric acid diester polyaluminum salt may be appropriately determined according to the modification degree of the modified organo (poly) siloxane that is the target compound.
Although not particularly limited, for example, the number of Si—H bonds in the starting organo (poly) siloxane is J, and the J S
When all of the i-H bonds are modified, the terminal unsaturated phosphoric acid diester polyaluminum salt is J / 2 times or more moles of the organo (poly) siloxane, preferably J / 2.
It may be used in a molar amount of up to 5 J.

After the completion of the reaction, activated carbon or the like is added to remove the catalyst, the mixture is filtered, the solvent is distilled off, and then the acetone-soluble matter is removed, whereby the phosphoric acid diester polyaluminum salt-modified organo ( A poly) siloxane is obtained.

The thus obtained phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane functions as an emulsifier in the present invention, and its application is also in the field where silicone oil is used.
Electricity, electronics, automobiles, machinery, medicine, cosmetics, textiles, paper,
Pulp, building materials, paints, etc. are not particularly limited, but when used for cosmetics, it is preferably added in an amount of 0.01 to 30% by weight, particularly 0.3 to 6% by weight in the total amount. If it is less than 0.01% by weight, the silicone oil cannot be stably emulsified, and if it exceeds 30% by weight, the viscosity of the entire system is remarkably increased, the spreadability during use is poor, and a sticky feeling is imparted. Not preferable.

In addition to the above-mentioned essential components, the cosmetic composition of the present invention may contain dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclosiloxane, depending on the purpose, as long as the effects of the present invention are not impaired. In addition to silicone oil such as pentasiloxane,
Water, oil for general cosmetics, moisturizer, intercellular lipid (ceramide, etc.), ultraviolet absorber, chelate, pH adjuster, antiseptic,
Thickeners, pigments, fragrances, medicinal components, other emulsifiers, detergent components and the like can be appropriately added.

The cosmetic composition of the present invention can be made into a stable W / O or O / W emulsified cosmetic composition by mixing and agitating the above-mentioned components according to a conventional method, and adding a component forming an aqueous phase thereto. Further, powder is added to this emulsion, preferably 10 to 40.
A milky liquid or creamy foundation can be obtained by blending the composition in an amount of 15% by weight, more preferably 15 to 30% by weight. As the powder, powders generally used in cosmetics, for example, extender pigments such as talc, mica, kaolin, sericite; inorganic pigments such as titanium oxide, zinc oxide, iron oxide, ultramarine blue; titanium mica-based pearl pigment; and Blue 404
No. 202, red No. 401, yellow No. 401, etc., and one or more of these can be arbitrarily selected and used. It can also be used as a hair styling product, a hair cosmetic product such as shampoo and conditioner.

[0041]

INDUSTRIAL APPLICABILITY The phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane of the present invention is used for electricity, electronics, automobiles, machinery, pharmaceuticals, cosmetics, fibers, paper, pulp,
It is very useful in stably emulsifying silicone oils used in various fields such as building materials and paints, and constructing an emulsified system with a good feeling of use, especially as a material for cosmetics and cosmetics. is there.

Therefore, the cosmetic of the present invention containing this is free from the stickiness of silicone oil, does not impair the refreshing and good feeling of use and the characteristics such as water repellency, is stable with time, and is silicone. Even when a large amount of oil is blended, no dripping occurs, which is extremely useful.

[0043]

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

Example 1 Phosphoric acid diallyloxyethyl ester polyaluminum salt

[0045]

[Chemical 12]

[Wherein MAI is {[Al ₁₃ O ₄ (OH)
₂₄ (H ₂ O) ₁₂ ] ⁷⁺ } _1/7 . The same applies below. ]

Phosphoric acid diallyloxyethyl ester 50
g, sodium hydroxide 7.51 g, ion-exchanged water 50 g
And 10 ml of ethanol were mixed and the temperature was raised to 60 ° C. After that, basic aluminum chloride (Locron P,
37.1 g of ion exchange water 10
A solution dissolved in 0 ml was added dropwise, and the mixture was stirred for 3 hours while maintaining the above temperature. After completion of the reaction, the reaction product was filtered and washed with ion-exchanged water and ethanol to obtain 80.2 g of the title compound (a).

¹ H-NMR (CDCl ₃ ) δ (ppm) 3.66: -PO-CH ₂ -CH ₂ -O- 4.05: -PO- CH ₂ -CH ₂ -O- 4.17: -CH ₂ -O- CH ₃ -CH = CH ₂ 5.24: -CH ₂ -O-CH ₂ - CH = CH ₂ 5.89: -CH ₂ -O-CH ₂ -CH = CH ₂

Example 2 Diundecenyl phosphate polyaluminum salt

[0050]

[Chemical 13]

Diundecenyl phosphate 40.2
g, 4.2 g of sodium hydroxide, 50 g of ion-exchanged water and 90 ml of ethanol were mixed, and the temperature was raised to 60 ° C. Then basic aluminum chloride (Locron P, Ltd.)
A solution prepared by dissolving 20 g of Matsumoto Kosho Co., Ltd. in 60 ml of ion-exchanged water was added dropwise, and the mixture was stirred for 3 hours while maintaining the above temperature. After completion of the reaction, the reaction product was filtered and washed with deionized water and ethanol to obtain 55 g of the title compound (b).

¹ H-NMR (CDCl ₃ ) δ (ppm) 1.19: -PO-CH ₂ -CH _2- ( CH ₂ ) ₆ -CH ₂ -CH = CH ₂ 1.53: -PO-CH ₂ -CH _2- (CH ₂ ) ₆ -CH ₂ -CH = CH ₂ 1.87: -PO-CH ₂ -CH _2- (CH ₂ ) ₆ - CH ₂ -CH = CH ₂ 3.66: -PO- CH ₂ -CH _2- (CH ₂ ) ₆ -CH ₂ -CH = CH ₂ 4.94: -PO-CH ₂ -CH _2- (CH ₂ ) ₆ -CH ₂ -CH = CH ₂ 5.80: -PO-CH ₂ -CH _2- (CH ₂ ) ₆ -CH ₂ - CH = CH ₂

Example 3 Diallyloxynonyl ester of phosphoric acid polyaluminum salt

[0054]

Embedded image

Phosphoric acid diallyloxynonyl ester 4
6.2 g, sodium hydroxide 4.0 g, ion-exchanged water 5
0 g and 100 ml of ethanol were mixed and the temperature was raised to 60 ° C. After that, basic aluminum chloride (Locron)
P, manufactured by Matsumoto Kosho Co., Ltd.) 20 g of ion-exchanged water 10
A solution dissolved in 0 ml was added dropwise, and the mixture was stirred for 3 hours while maintaining the above temperature. After completion of the reaction, the reaction product was filtered and washed with deionized water and ethanol to obtain the title compound (c).

¹ H-NMR (CDCl ₃ ) δ (ppm) 1.30: —PO—CH ₂ —CH ₂ — ( CH ₂ ) ₅ —CH ₂ —CH ₂ —O—CH ₂ —CH = CH ₂ 1.58:- _{PO-CH 2 - CH 2 -} (CH 2) 5 - CH 2 -CH 2 -O-CH 2 -CH = CH 2 3.38: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 - CH ₂ -O-CH ₂ -CH = CH ₂ 3.94: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O- CH ₂ -CH = CH ₂ 4.03: -PO- CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH = CH ₂ 5.18: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O- CH ₂ -CH = CH ₂ 5.88: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ - CH = CH ₂

Example 4

[0058]

[Chemical 15]

20 g of the compound (a), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (a).
17 g of pentamethyldisiloxane was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. 1 g of activated carbon and 20 ml of methanol were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 36.8 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (d).

¹ H-NMR (CDCl ₃ ) δ (ppm) -0.05: Si (CH ₃ ) _3- O-Si ( CH ₃ ) _2- CH ₂ -0.01: Si ( CH ₃ ) _3- O-Si ( _{CH 3) 2 -CH 2 - 0.40} : -CH 2 -O-CH 2 -CH 2 - CH 2 -Si 1.49: -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.66: -PO-CH ₂ - CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 4.05: -PO- CH ₂ -CH ₂ -O-

Example 5

[0062]

Embedded image

20 g of the compound (c), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (c).
9.2 g of pentamethyldisiloxane was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. 1 g of activated carbon and 10 ml of methanol were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 28.5 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (e).

[0064] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.04: Si (CH 3) 3 -O-Si (CH 3) 2 -CH 2 - 0.01: Si (CH 3) 3 -O-Si ( _{CH 3) 2 -CH 2 - 0.35} : -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 - CH 2 -Si 1.21: -PO-CH 2 _{-CH 2 - (CH 2) 5} -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -Si 1.49: -PO-CH 2 - CH 2 - (CH 2) 5 - CH 2 -CH 2 -O-CH ₂ -CH ₂ -CH ₂ -Si 3.28: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 3.94: -PO- CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si

Example 6

[0066]

[Chemical 17]

20 g of the compound (b), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (b).
10.2 g of pentamethyldisiloxane was added. Chloroplatinic acid (1% isopropyl alcohol solution) 0.03 ml
Was added and aged at 70 ° C. for 7 hours. After adding 1 g of activated carbon and 10 ml of methanol and stirring at 50 ° C. for 1 hour,
Activated carbon was filtered and the filtrate was concentrated to obtain 29.5 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (f).

[0068] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.04: Si (CH 3) 3 -O-Si (CH 3) 2 -CH 2 - 0.01: Si (CH 3) 3 -O-Si ( _{CH 3) 2 -CH 2 - 0.37} : -PO-CH 2 -CH 2 - (CH 2) 8 - CH 2 -Si 1.19: -PO-CH 2 -CH 2 - (CH 2) 8 -CH 2 -Si _{1.54: -PO-CH 2 - CH} 2 - (CH 2) 8 -CH 2 -Si 3.67: -PO- CH 2 -CH 2 - (CH 2) 8 -CH 2 -Si

Example 7

[0070]

Embedded image

20 g of the compound (a), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (a).
7.7 g of 1,1,3,3-tetramethyldisiloxane was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours.
1 g of activated carbon and 20 ml of methanol were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 26.8 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (g).

[0072] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.05: -Si (CH 3) 2 -CH 2 - 0.41: -CH 2 -O-CH 2 -CH 2 - CH 2 -Si 1.49: - _{CH 2 -O-CH 2 - CH} 2 -CH 2 -Si 3.67: -PO-CH 2 - CH 2 -O- CH 2 -CH 2 -CH 2 -Si 4.07: -PO- CH 2 -CH 2 -O -

Example 8

[0074]

[Chemical 19]

20 g of compound (c), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (c) was dissolved,
4.2 g of 1,1,3,3-tetramethyldisiloxane was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours.
1 g of activated carbon and 10 ml of methanol were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 23.5 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (h).

[0076] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.04: -Si (CH 3) 2 -CH 2 - 0.40: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH _{2 -O-CH 2 -CH 2 -} CH 2 -Si 1.31: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -Si 1.55 _{: -PO-CH 2 - CH 2} - (CH 2) 5 - CH 2 -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.30: -PO-CH 2 -CH 2 - (CH 2) 5 _{-CH 2 - CH 2 -O- CH 2} -CH 2 -CH 2 -Si 3.99: -PO- CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 - CH ₂ -Si

Example 9

[0078]

Embedded image

20 g of the compound (b), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (b).
4.6 g of 1,1,3,3-tetramethyldisiloxane was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours.
1 g of activated carbon and 10 ml of methanol were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 24.1 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (i).

[0080] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.04: -Si (CH 3) 2 -CH 2 - 0.38: -PO-CH 2 -CH 2 - (CH 2) 8 - CH 2 -Si _{1.20: -PO-CH 2 -CH 2} - (CH 2) 8 -CH 2 -Si 1.56: -PO-CH 2 - CH 2 - (CH 2) 8 -CH 2 -Si 3.80: -PO- CH 2 - CH _2- (CH ₂ ) ₈ -CH ₂ -Si

Example 10

[0082]

[Chemical 21]

[In the formula, TMS represents a trimethylsilyl group. The same applies below. ]

20 g of the compound (a), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (a).
25.5 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added. Add 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) and incubate at 70 ℃.
Aged for hours. Activated carbon (1 g) and methanol (20 ml) were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to give 44.8 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (j).
I got

[0085] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.06: -Si (CH 3) -CH 2 - 0.01: Si (CH 3) 3 -O-Si (CH 3) -CH 2 - 0.43: _{-CH 2 -O-CH 2 -CH 2} - CH 2 -Si 1.50: -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.68: -PO-CH 2 - CH 2 -O- CH 2 - CH ₂ -CH ₂ -Si 4.09: -PO- CH ₂ -CH ₂ -O-

Example 11

[0087]

[Chemical formula 22]

20 g of the compound (c), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (c).
13.8 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added. Add 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) and incubate at 70 ℃.
Aged for hours. Activated carbon (1 g) and methanol (10 ml) were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to give a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (k) (32.9 g).
I got

[0089] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.04: -Si (CH 3) -CH 2 - 0.01: Si (CH 3) 3 -O-Si (CH 3) -CH 2 - 0.39: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.30: -PO-CH ₂ -CH _2- ( CH ₂ ) _{5- CH 2 -CH 2 -O-CH 2} -CH 2 -CH 2 -Si 1.56: -PO-CH 2 - CH 2 - (CH 2) 5 - CH 2 -CH 2 -O-CH 2 - CH 2 -CH _2- Si 3.29: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 3.97: -PO- CH ₂ -CH _2- ( CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si

Example 12

[0091]

[Chemical formula 23]

20 g of compound (b), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (b) was dissolved,
15.2 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added. Add 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) and incubate at 70 ℃.
Aged for hours. After adding 1 g of activated carbon and 10 ml of methanol and stirring at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to give 34.9 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (l).
I got

[0093] _{^{1 H-NMR (CDCl 3)}} δ (ppm) -0.05: -Si (CH 3) -CH 2 - 0.01: Si (CH 3) 3 -O-Si (CH 3) -CH 2 - 0.39: _{-PO-CH 2 -CH 2 - (} CH 2) 8 - CH 2 -Si 1.25: -PO-CH 2 -CH 2 - (CH 2) 8 -CH 2 -Si 1.58: -PO-CH 2 - CH 2 -(CH ₂ ) ₈ -CH ₂ -Si 3.83: -PO- CH ₂ -CH _2- (CH ₂ ) ₈ -CH ₂ -Si

Example 13

[0095]

[Chemical formula 24]

20 g of compound (a), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (a) was dissolved,
34.0 g of tris (trimethylsiloxy) silane was added. Chloroplatinic acid (1% isopropyl alcohol solution)
0.03 ml was added and the mixture was aged at 70 ° C. for 7 hours. 1 g of activated carbon and 20 ml of methanol were added, the mixture was stirred at 50 ° C. for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 53.8 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (m).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si ( CH ₃ ) ₃ -O-Si 0.40: -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.49: -CH ₂ -O-CH ₂ - CH ₂ -CH ₂ -Si 3.65: -PO-CH ₂ - CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 4.05: -PO- CH ₂ -CH ₂ -O-

Example 14

[0099]

[Chemical 25]

20 g of the compound (c), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (c).
18.4 g of tris (trimethylsiloxy) silane was added. Chloroplatinic acid (1% isopropyl alcohol solution)
0.03 ml was added and the mixture was aged at 70 ° C. for 7 hours. After adding 1 g of activated carbon and 10 ml of methanol and stirring at 50 ° C. for 1 hour, the activated carbon was filtered and the filtrate was concentrated to obtain 37.9 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (n).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si ( CH ₃ ) ₃ -O-Si 0.39: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH _{2- O-CH 2 -CH 2 - CH} 2 -Si 1.21: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -Si 1.54: - _{PO-CH 2 - CH 2 -} (CH 2) 5 - CH 2 -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.34: -PO-CH 2 -CH 2 - (CH 2) 5 -CH ₂ - CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 3.99: -PO- CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si

Example 15

[0103]

[Chemical formula 26]

20 g of the compound (b), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (b).
20.3 g of tris (trimethylsiloxy) silane was added. Chloroplatinic acid (1% isopropyl alcohol solution)
0.03 ml was added and the mixture was aged at 70 ° C for 7 hours. After adding 1 g of activated carbon and 10 ml of methanol and stirring at 50 ° C. for 1 hour, the activated carbon was filtered and the filtrate was concentrated to obtain 39.9 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (o).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si ( CH ₃ ) ₃ -O-Si 0.39: -PO-CH ₂ -CH _2- (CH ₂ ) ₈ -CH ₂ -Si 1.24: _{-PO-CH 2 -CH 2 - (} CH 2) 8 -CH 2 -Si 1.55: -PO-CH 2 - CH 2 - (CH 2) 8 -CH 2 -Si 3.88: -PO- CH 2 -CH 2 -(CH ₂ ) ₈ -CH ₂ -Si

Example 16

[0107]

[Chemical 27]

5 g of compound (a), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (a) was dissolved, X was added.
F40-A2606 (manufactured by Toshiba Silicone Co., Ltd.) 22.
1 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 50 ℃
After stirring for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 26.8 g of a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (p).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si ( CH ₃ ) ₂ 0.39: -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.49: -CH ₂ -O-CH ₂ - CH ₂ -CH ₂ -Si 3.64: -PO-CH ₂ - CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 4.03: -PO- CH ₂ -CH ₂ -O-

Example 17

[0111]

[Chemical 28]

10 g of compound (c), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (c) was dissolved,
XF40-A2606 (manufactured by Toshiba Silicone Co., Ltd.) 2
4.0 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 5
After stirring at 0 ° C. for 1 hour, activated carbon was filtered and the filtrate was concentrated to obtain 33.9 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (q).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si ( CH ₃ ) ₂ 0.40: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH _{2 -CH 2 - CH 2 -Si 1.22:} -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -Si 1.55: -PO-CH 2 _{- CH 2 - (CH 2)} 5 - CH 2 -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.35: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 - CH 2 -O- CH ₂ -CH ₂ -CH ₂ -Si 3.99: -PO- CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si

Example 18

[0115]

[Chemical 29]

10 g of the compound (b), 50 ml of hexane and 50 ml of toluene were mixed to dissolve the compound (b).
XF40-A2606 (manufactured by Toshiba Silicone Co., Ltd.) 2
6.4g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 5
After stirring at 0 ° C. for 1 hour, activated carbon was filtered and the filtrate was concentrated to obtain 36.0 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (r).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si ( CH ₃ ) ₂ 0.40: -PO-CH ₂ -CH _2- (CH ₂ ) ₈ -CH ₂ -Si 1.25: -PO-CH _{2 -CH 2 - (CH 2)} 8 -CH 2 -Si 1.57: -PO-CH 2 - CH 2 - (CH 2) 8 -CH 2 -Si 3.90: -PO- CH 2 -CH 2 - (CH 2 ) _8- CH ₂ -Si

Example 19

[0119]

Embedded image

5 g of compound (a), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (a) was dissolved, X was added.
F40-A1629 (manufactured by Toshiba Silicone Co., Ltd.) 34.
7 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 50 ℃
After stirring for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 38.8 g of a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (s).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si- CH ₃ 0.40: -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.51: -CH ₂ -O-CH _2- CH ₂ -CH ₂ -Si 3.66: -PO-CH ₂ -CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 4.04: -PO- CH ₂ -CH ₂ -O-

Example 20

[0123]

[Chemical 31]

10 g of compound (c), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (c) was dissolved,
XF40-A1629 (manufactured by Toshiba Silicone Co., Ltd.) 3
7.6g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 5
After stirring at 0 ° C. for 1 hour, activated carbon was filtered and the filtrate was concentrated to obtain 46.9 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (t).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si- CH ₃ 0.40: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - CH ₂ -Si 1.21: -PO-CH ₂ -CH _2- ( CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.54: -PO-CH ₂ - CH _{2 - (CH 2) 5 -} CH 2 -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.36: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 - CH 2 -O _{- CH 2 -CH 2 -CH 2 -Si} 3.98: -PO- CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -Si

Example 21

[0127]

Embedded image

10 g of compound (b), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (b) was dissolved,
XF40-A1629 (manufactured by Toshiba Silicone Co., Ltd.) 4
1.4 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 5
After stirring at 0 ° C. for 1 hour, activated carbon was filtered and the filtrate was concentrated to obtain 51.0 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (u).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si- CH ₃ 0.40: -PO-CH ₂ -CH _2- (CH ₂ ) ₈ -CH ₂ -Si 1.26: -PO-CH _{2- CH 2 - (CH 2) 8} -CH 2 -Si 1.58: -PO-CH 2 - CH 2 - (CH 2) 8 -CH 2 -Si 3.95: -PO- CH 2 -CH 2 - (CH 2) 8 -CH ₂ -Si

Example 22

[0131]

[Chemical 33]

5 g of compound (a), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (a) was dissolved, X was added.
F40-A5149 (manufactured by Toshiba Silicone Co., Ltd.) 68.
7 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 50 ℃
After stirring for 1 hour, the activated carbon was filtered and the filtrate was concentrated to obtain 72.8 g of phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (v).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si- CH ₃ 0.40: -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.52: -CH ₂ -O-CH _2- CH ₂ -CH ₂ -Si 3.67: -PO-CH ₂ -CH ₂ -O- CH ₂ -CH ₂ -CH ₂ -Si 4.02: -PO- CH ₂ -CH ₂ -O-

Example 23

[0135]

Embedded image

6 g of compound (c), 50 ml of hexane and 50 ml of toluene were mixed, and after compound (c) was dissolved, X was added.
F40-A5149 (manufactured by Toshiba Silicone Co., Ltd.) 44.
6 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 50 ℃
After stirring for 1 hour, the activated carbon was filtered and the filtrate was concentrated to obtain 49.9 g of a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (w).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si- CH ₃ 0.40: -PO-CH ₂ -CH _2- (CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - CH ₂ -Si 1.22: -PO-CH ₂ -CH _2- ( CH ₂ ) ₅ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si 1.55: -PO-CH ₂ - CH _{2 - (CH 2) 5 -} CH 2 -CH 2 -O-CH 2 - CH 2 -CH 2 -Si 3.37: -PO-CH 2 -CH 2 - (CH 2) 5 -CH 2 - CH 2 -O _{- CH 2 -CH 2 -CH 2 -Si} 4.00: -PO- CH 2 -CH 2 - (CH 2) 5 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -Si

Example 24

[0139]

Embedded image

6 g of compound (b), 50 ml of hexane and 50 ml of toluene were mixed to dissolve compound (b), and then X
F40-A5149 (manufactured by Toshiba Silicone Co., Ltd.) 49.
2 g was added. 0.03 ml of chloroplatinic acid (1% isopropyl alcohol solution) was added, and the mixture was aged at 70 ° C for 7 hours. Add 1g of activated carbon and 10ml of methanol, 50 ℃
After stirring for 1 hour, the activated carbon was filtered, and the filtrate was concentrated to obtain 54.8 g of a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane (x).

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.01: Si- CH ₃ 0.39: -PO-CH ₂ -CH _2- (CH ₂ ) ₈ -CH ₂ -Si 1.24: -PO-CH _{2- CH 2 - (CH 2) 8} -CH 2 -Si 1.56: -PO-CH 2 - CH 2 - (CH 2) 8 -CH 2 -Si 3.91: -PO- CH 2 -CH 2 - (CH 2) 8 -CH ₂ -Si

Test Example 1 Regarding the phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane of the present invention obtained in each Example,
The emulsifying ability of the cosmetic oil was evaluated.

(Evaluation method) 3% by weight of the compound shown in Table 1,
Dimethyl polysiloxane (KF96A, manufactured by Shin-Etsu Chemical,
6 cs) 60 wt% and ion-exchanged water 27 wt% were uniformly mixed at room temperature with a disper at 1000 rpm for 5 minutes, and the appearance when left at room temperature was visually observed and evaluated according to the following criteria. The results are shown in Table 1.

(Evaluation Criteria) ⊚: A stable and highly transparent emulsified system is constructed without separation. ◯: Stable emulsification without separation. Δ: Slightly separated. X: Separated.

[0145]

[Table 1]

[0146]

Table 2 Example 25 Sunscreen Jelly (Composition) (wt%) (1) Inventive Compound (f) 4 (2) Decamethylcyclopentasiloxane 66 (3) Methylphenylpolysiloxane 5 (4) p-Dimethyl Isooctyl aminobenzoate 2 (5) Purified water 20 (6) Fragrance Suitable amount

(Production method) Components (1) to (4) are heated and uniformly dissolved with a disper. Ingredients (5) and (6) were added to this with stirring to emulsify to obtain a sunscreen jelly. This was stable and excellent in usability. In addition, no dripping from the fingers occurred during use.

[0148]

Table 3 Example 26 Sunscreen cream (composition) (% by weight) (1) Inventive compound (k) 4 (2) Decamethylcyclopentasiloxane 60 (3) Dimethylpolysiloxane (6cs) 5 (4) Methoxy Octyl cinnamate 3 (5) Titanium oxide 5 (6) Purified water 20 (7) Perfume proper amount

(Production method) Components (1) to (4) are heated and uniformly dissolved by a disper. In this, component (5),
(6) and (7) were added with stirring to emulsify to obtain a sunscreen cream. This was stable and excellent in usability. In addition, no dripping from the fingers occurred during use.

[0150]

Table 27 Example 27 Emulsion-type detergent (composition) (% by weight) (1) Compound of the present invention (l) 3 (2) Polyoxyethylene triisostearate (20) Glyceryl 10 (3) Squalane 35 (4) Decamethylcyclopentasiloxane 42 (5) Purified water 10

(Production method) Components (1) to (4) are heated and uniformly dissolved with a disper. The component (5) was added to this with stirring and emulsified to obtain an emulsified detergent. This was stable and excellent in usability. In addition, no dripping from the fingers occurred during use.

[0152]

Table 5 Example 28 Creamy foundation (composition) (% by weight) (1) Inventive compound (n) 10 (2) Dimethylpolysiloxane (6cs) 5 (3) Octamethylcyclotetrasiloxane 40 (4) Glycerin 2 (5) Purified water remaining amount (6) Pigment: sericite 6 titanium oxide 8 iron oxide 12 (7) nylon powder 5 (8) dimethylpolysiloxane / polyoxyalkylene copolymer 1

(Production method) Components (1) to (3) and (8) were heated and uniformly dissolved in a disper, then components (6) and (7) were added and further dispersed by a disper. . Components (4) and (5) were added to this with stirring to emulsify to obtain a cream foundation. This was stable and excellent in usability. In addition, no dripping from the fingers occurred during use.

[0154]

Table 6 Example 29 O / W cream (composition) (wt%) (1) Compound (k) 3 of the present invention (2) Monocetyl phosphate 0.5 (3) Squalane 2 (4) Isopropyl palmitate 2 (5) ) Olive oil 2 (6) Dimethylpolysiloxane (6cs) 5 (7) Octamethylcyclotetrasiloxane 10 (8) Glycerin 5 (9) L-arginine 0.5 (10) Ethanol 5 (11) Purified water Remaining amount

(Production method) Components (1) to (7) are heated and uniformly dissolved with a disper. (8) to (11) were added to this with stirring and emulsified to obtain an O / W cream. This was stable and excellent in usability.
In addition, no dripping from the fingers occurred during use.

[0156]

Table 30 Example 30 Emulsified solid cosmetic (composition) (% by weight) (1) Compound of the present invention (o) 6 (2) Dimethylpolysiloxane (6cs) 35 (3) Pigment: sericite 16 Titanium oxide 16 Iron oxide 3 (4) Nylon powder 15 (5) Purified water 5 (6) Perfume proper amount

(Production method) Components (1) to (4) are heated and uniformly dissolved with a disper. Ingredients (5) and (6) were added to this with stirring to emulsify to obtain an emulsified cosmetic. This product was stable and had excellent usability. No dripping occurred during use.

Claims (7)

[Claims] 1. One or more organo (poly) siloxane chains and one or more of the following general formulas (1): [R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms. R ² : 1 to 1 carbon atoms which may be substituted by a hydroxyl group
50 linear or branched alkylene groups are shown. p: Indicates the number from 0 to 200. M: indicates a polyhydroxoaqua aluminum ion. n: shows the valence of M. ] A phosphoric acid diester polyaluminum salt-modified organopolysiloxane having a molecular structure composed of a divalent phosphoric acid diester polyaluminum salt residue represented by: 2. The phosphoric diester polyaluminum salt-modified organo (poly) siloxane according to claim 1, which is represented by the following general formula (2). Embedded image [R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms. R ² : 1 to 1 carbon atoms which may be substituted by a hydroxyl group
50 linear or branched alkylene groups are shown. R ³ to R ^20: independently an alkyl group or an alkoxyl group or a phenyl group having 1 to 22 carbon atoms. Of these, R
⁷ and R ¹⁶ may together form an —O— group. p: Indicates the number from 0 to 200. M: indicates a polyhydroxoaqua aluminum ion. n: shows the valence of M. q, r, s, t, u, v: each represents a number from 0 to 1000. However, all of them do not become 0 at the same time. ] 3. The phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane according to claim 2, wherein R ^{3 to} R ²⁰ in the general formula (2) are all methyl groups. 4. An organo (poly) siloxane having at least one hydrogen atom bonded to a silicon atom is added to the following general formula (3): [R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms. R ² : 1 to 1 carbon atoms which may be substituted by a hydroxyl group
50 linear or branched alkylene groups are shown. p: Indicates the number from 0 to 200. M: indicates a polyhydroxoaqua aluminum ion. n: shows the valence of M. ] The method for producing a phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane according to claim 1, wherein a terminal unsaturated phosphoric acid diester polyaluminum salt represented by the following formula is reacted. 5. A terminal unsaturated phosphoric acid diester polyaluminum salt represented by the following general formula (3). [Chemical 4] [R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms. R ² : 1 to 1 carbon atoms which may be substituted by a hydroxyl group
50 linear or branched alkylene groups are shown. p: Indicates the number from 0 to 200. M: indicates a polyhydroxoaqua aluminum ion. n: shows the valence of M. ] 6. The following general formula (4): [R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms. R ² : 1 to 1 carbon atoms which may be substituted by a hydroxyl group
50 linear or branched alkylene groups are shown. p: Indicates the number from 0 to 200. ] The terminal unsaturated phosphoric acid diester represented by or its salt, and the following rational formula (5) Al _a (OH) _b X _c · dH ₂ O (5) [X: other than hydroxide ion of valence x Indicates an anion. a, b, c: A positive integer satisfying 3a = b + cx is shown. d: Shows an integer of 0 or more. ] The basic polyaluminum salt represented by these is made to react in an aqueous medium, The manufacturing method of the terminal unsaturated phosphodiester polyaluminum salt of Claim 5 characterized by the above-mentioned. 7. A cosmetic containing the phosphoric acid diester polyaluminum salt-modified organo (poly) siloxane according to claim 1.