JP2002220472A - Phosphodiester-salt-denatured organo(poly)siloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphodiester-salt-denatured organo(poly)siloxane, capable of stably emusifying a silicone oil regardless of temperature, and also excellent in compatability with other ionic component, wherethrough the above organo(poly)siloxane is very useful and important as a cosmetic material such as a skin cosmetic, a skin cleaner and a hair cleaner. SOLUTION: A phosphodiester-salt-denatured organo(poly)siloxane is composed of a structural unit expressed by the general formulae (1) and (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific phosphodiester-modified organo (poly) siloxane which is useful as a component of cosmetics (fragrances and cosmetics).

[0002]

2. Description of the Related Art Organopolysiloxane (silicone oil) is widely used as a component of various cosmetics, in addition to a hair finish, because it has no stickiness and high safety. In addition, recently, in addition to the conventional use of cosmetics, application as a component of a cosmetic including a fragrance has been studied. In order to meet such uses, organo (poly) siloxane is required to have further improved compatibility, chemical resistance, solubility in water, lubricity, and the like.

In order to satisfy such demands, modified organopolysiloxanes having various functional groups introduced therein, for example, amino-modified, epoxy-modified, carboxylic acid-modified, mercapto-modified, alcohol-modified, polyether-modified, fluoroalkyl-modified, Alkyl-, ester- and alkoxy-modified organopolysiloxanes have been studied and developed.

[0004] In addition to modified organopolysiloxanes, phosphates of organic hydroxy compounds (including alkali metal salts thereof) are known to have excellent surface activity for emulsification of hydrophobic oils. In particular, it is known that the surface activity of diesters is remarkably superior to that of monoesters. Accordingly, phosphoric acid diester-modified organopolysiloxane is considered as an emulsifier for silicone oil having the properties of the above-mentioned modified organopolysiloxane and having excellent surface activity. For example, US Pat. No. 5,070,171 and 5,09
No. 3,452 discloses a method in which a phosphoric acid ester salt is introduced into a silicon atom of a siloxane bond portion (excluding both ends) of a main chain using 115% phosphoric acid, phosphorus pentoxide, or polyphosphoric acid. .

[0005]

The above-mentioned conventional modified organopolysiloxanes as described above have not yet been sufficiently satisfactory as components for cosmetics. For example, a polyether-modified organopolysiloxane has a cloud point phenomenon which is a characteristic of a nonionic surfactant having a polyether bond, and therefore has a problem that it has poor temperature stability in an emulsified system and is not suitable for practical use. Further, those disclosed in U.S. Pat. Nos. 5,070,171 and 5,093,452 use phosphorus pentoxide as a phosphorylating agent, so that a mixture of monoester and diester is obtained. Is insufficient as a compounding component.

Accordingly, it is an object of the present invention to provide a modified organo (poly) siloxane having excellent compatibility, emulsifying properties, etc., and suitable as a cosmetic ingredient.

[0007]

Under these circumstances, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have the structural units represented by the following general formulas (1) and (2). The specific phosphodiester salt-modified organo (poly) siloxane forms a stable emulsification system for various cosmetic silicone oils, and the compound is composed of a specific alcohol-modified organo (poly) siloxane and a phosphorus oxyhalide. Were found to be easily obtained by reacting with the above, and the present invention was completed.

That is, the present invention provides a phosphodiester salt-modified organo (poly) siloxane having structural units represented by the following general formulas (1) and (2).

[0009]

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Wherein R ¹ represents an alkylene group having 4 to 20 carbon atoms. R ² : 1 to 5 carbon atoms which may be substituted by a hydroxy group
And 0 represents a linear or branched alkylene group. p: Indicates the number of 0 to 200. M: represents a hydrogen atom or a monovalent cation. R ³ , R ⁴ , R ⁵ , R ⁶ : each represents an alkyl group, an alkoxy group, a phenyl group or a structural unit represented by the general formula (2). w indicates 0 or 1. ]

[0011]

Phosphodiester salt-modified organo (poly) siloxanes of the embodiment of the present invention (hereinafter, "modified organo (poly) siloxanes" abbreviated as) in the general formula representing the structural unit (1), the R ¹ Examples of the alkylene group having 4 to 20 carbon atoms include butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, and hexadecamylene. Methylene group and the like,
Particularly, a butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and undecamethylene groups are preferable.

The linear or branched alkylene group having 1 to 50 carbon atoms which may be substituted by the hydroxyl group of R ² includes ethylene, methylene, trimethylene, propylene, 1-methylpropylene, butylene, pentane and the like. Methylene, 3-methylbutylene, 1,1-dimethylpropylene, hexamethylene, octamethylene, decamethylene,
Undecamethylene, 2-hydroxyethylene, 2-hydroxybutylene, 2-hydroxyoctamethylene group and the like, among which methylene, ethylene, propylene,
Butylene, pentamethylene, hexamethylene and octamethylene groups are preferred.

P represents a number from 0 to 200, and particularly from 1 to 2
A number of 0 is preferred.

Further, M is a hydrogen atom or an alkali metal ion such as lithium, sodium, potassium, rubidium and cesium. Of these, sodium ion and potassium ion are particularly preferable.

Further, R ³ and R ⁴ in the general formula (1) and R ⁵ and R ⁶ in the general formula (2) representing another structural unit of the modified organo (poly) siloxane of the present invention.
The alkyl group is preferably an alkyl group having 1 to 22 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, pentyl, t-butyl, octyl, tetradecyl, docosyl, octadecyl and the like, and an alkoxy group Is preferably an alkoxy group having 1 to 22 carbon atoms, for example, methoxy, ethoxy, propoxy, pentyloxy, butoxy, 2-ethylbutoxy,
And a 2-ethylhexyloxy group. R ³ , R ⁴ ,
As R ⁵ and R ⁶ , among these, an alkyl group or an alkoxy group having 1 to 6 carbon atoms or a phenyl group is preferable, and a methyl group is particularly preferable.

The modified organo (poly) siloxane of the present invention is not limited as long as it has the structural units represented by the above-mentioned general formulas (1) and (2). A structure in which (1) and (2) are linearly connected, a structure in which the structural units (1) and (2) are connected in a network,
There is no particular limitation on the structure in which the structural units (1) and (2) are connected in a ring shape, a mixed type structure thereof, and the like. Further, the structural units (1) and (2) may be bonded in a random manner or may be bonded in a block manner.

The most preferred modified organo (poly) siloxane of the present invention has a structure represented by the following general formula (3).

[0018]

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Wherein R ¹ , R ² , p and M have the same meaning as described above. R ⁷ to R ^24: independently an alkyl or alkoxy group or a phenyl group having 1 to 22 carbon atoms. Of these, R
¹¹ and R ²⁰ may together form a divalent oxygen atom. q, r, s, t, u, v: each represents a number from 0 to 1000. ]

The modified organo (poly) siloxane of the present invention has the following general formulas (6) and (2)

[0021]

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Wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , p and w have the same meaning as described above. And an alcohol-modified organo (poly) siloxane having a structural unit represented by the following general formula (7): POX ₃ (7) wherein X represents a halogen atom. And then hydrolyzing the PX bond in the presence of an alkali.

The alcohol-modified organo (poly) siloxane having a structural unit represented by the general formula (6) or (2), which is a raw material of the production method of the present invention, is not particularly limited as long as it has these structural units. Not an alkyl group,
The number of alkoxy groups, phenyl groups, -R ^2- (OR ¹ ) _p -OH is not limited, and each structural unit is a linear structure, a network structure, a cyclic structure, or a mixture thereof. The structure of the mold is not particularly limited. In addition, the structural units (6) and (2) may be bonded in a random manner or may be bonded in a block-like manner. Preferred specific examples of the alcohol-modified organo (poly) siloxane are shown below.

[0024]

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[0025]

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Wherein R ^{47 to} R ⁵³ are each an alkyl group (preferably having 1 carbon atom;
An alkyl group having 1 to 22 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 22 carbon atoms) or a phenyl group. a, b, c: The numbers of 0 to 1000 are shown. ]

Such an alcohol-modified organo (poly) siloxane can be prepared by a known method (for example, JP-A-62-19).
No. 5389), commercially available products can be used as they are, and specific examples thereof include, for example, X-22-170A,
X-22-170, X-22-170B, X-22-1
70D, X-22-160AS, KF6001, KF6
002, KF6003, X-22-176B, X-22
-176D, X-22-4015, KF6005, KF
6007, KF6015, KF353A, KF354
A, KF355A (all manufactured by Shin-Etsu Chemical Co., Ltd.), T
SL9105, TSF4750, TSF4751, XF
42-220, XF42-811, XF42-831
(Toshiba Silicone Co., Ltd.), PS197, PX
101 (manufactured by Chisso Corporation) and the like.

Examples of the other raw material, phosphorus oxyhalide (7), include phosphorus oxychloride, phosphorus oxybromide, and phosphorus oxyiodide, with phosphorus oxychloride being particularly preferred.

Further, examples of the alkali used in the reaction include NaOH, KOH, CsOH and the like, and preferably NaOH and KOH.

In order to carry out the production method of the present invention, first, an alcohol-modified organo (poly) siloxane having the structural units represented by the general formulas (6) and (2) and an oxyhalogen represented by the general formula (7) Phosphorus chloride, if necessary, in the presence of a tertiary amine such as triethylamine, tributylamine, pyridine or N-methylmorpholine in an amount of 1 to 3 times the total amount of the raw materials, tetrahydrofuran, methylene chloride, 0 to 20 times the total amount of the raw materials, In a solvent capable of dissolving both raw materials such as toluene, the reaction is carried out at 0 to 30 ° C for 1 to 30 hours, preferably at first -50 to 10 ° C, particularly preferably -2.
After monoesterification by reacting at 0 to -30 ° C for 1 to 5 hours, the reaction is carried out at 0 to 30 ° C, particularly preferably at 0 to 15 ° C.
The reaction is carried out for up to 30 hours to diesterify. Next, an alkaline aqueous solution of 3 to 5 equivalents to the phosphorus oxyhalide (7) used is added, and the PX bond generated at -30 to 0 ° C. for 2 to 12 hours may be hydrolyzed.

The reaction ratio between the alcohol-modified organopolysiloxane as the raw material and the phosphorus oxyhalide may be appropriately determined according to the degree of modification of the target compound, the modified organo (poly) siloxane, and is not particularly limited. When the number of hydroxyl groups in the starting alcohol-modified organo (poly) siloxane is J, and all of the J hydroxyl groups are to be modified, the phosphorus oxyhalide should be 0.2 to 0% of the alcohol-modified organo (poly) siloxane. It may be used in a molar amount of 0.8 J times, preferably 0.3 to 0.6 J times.

After completion of the reaction, water and a solvent that is hardly miscible with water are added, and the mixture is stirred or shaken, allowed to stand, separated, and the aqueous layer is removed to remove excess phosphate and inorganic and organic by-products. Salt can be removed. Solvents that are hardly miscible with water used at this time include butanol, toluene, chloroform, dichloromethane, hexane, ethyl ether and the like, and when separation is difficult or when emulsification occurs, an emulsifier such as ethanol or 2-propanol is used. May be added. Further, the solvent is distilled off from the reaction-terminated liquid, and the resulting residue is washed with water to remove excess phosphate and inorganic and organic salts by-produced, or ethanol, butanol,
Toluene, chloroform, dichloromethane, hexane,
The residual phosphate may be dissolved in a solvent such as ethyl ether or the like, and the surplus phosphate precipitated as an insoluble substance and the inorganic and organic salts by-produced may be separated by filtration.

When the modified organo (poly) siloxane of the present invention is not soluble in an organic solvent, a water-miscible solvent such as methanol, ethanol, acetone or the like is added to the aqueous layer, and the precipitated modified organo (poly) siloxane of the present invention is precipitated. To separate.

[0034]

The phosphoric diester salt-modified organo (poly) siloxane of the present invention can be easily produced by reacting the corresponding alcohol-modified organo (poly) siloxane with a phosphorus halide. Not only can oil be emulsified stably irrespective of temperature, it is also very useful in that it has good compatibility with other ionic components. As important.

[0035]

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

Embodiment 1

[0037]

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3.1 g of phosphorus oxychloride (7-a) was dissolved in 20 g of tetrahydrofuran and cooled to -30.degree.
To this solution was added alcohol-modified dimethylpolysiloxane (6
-A) (X-22-170, manufactured by Shin-Etsu Chemical Co., Ltd.) 1
A solution prepared by dissolving 0 g and 4.1 g of triethylamine in 100 g of tetrahydrofuran was added dropwise over 30 minutes. -30 ° C
After aging for 2 hours, gradually raise the temperature and
Aged for hours. Thereafter, the mixture was cooled again to -30 ° C, and a solution in which 3.37 g of sodium hydroxide was dissolved in 10 g of water was added dropwise over 30 minutes. After stirring at 0 ° C for 12 hours, water 1 was added to the reaction solution.
00 g and 100 g of hexane were added and the layers were separated. The organic layer was separated, washed with water, and then the solvent was distilled off. The compound of the present invention (1) 1
1 g was obtained. The compound (1) of the present invention is used in an amount of 5 to 50 with respect to silicone oil which is usually used as a cosmetic component.
In the temperature range of ° C., a stable emulsifying power was exhibited regardless of the temperature. IR (neat): Si-O -Si 1050cm -1, P = O 1220cm -1 1 H-NMR (CDCl 3): - 0.1ppm Si-CH 3, 0.47ppm Si-CH 2,
1.49ppm Si-CH ₂ -C H ₂ , 3.42, 3.51ppm -CH ₂ -O-CH _2- , 3.
90ppm -CH ₂ -OP

[0039]

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Embodiment 2

[0041]

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1.7 g of phosphorus oxychloride (7-a) was dissolved in 10 g of tetrahydrofuran and cooled to -30 ° C.
To this solution was added alcohol-modified dimethylpolysiloxane (6
-B) (X-22-170A, manufactured by Shin-Etsu Chemical Co., Ltd.)
A solution of 40 g and 2.2 g of triethylamine dissolved in 150 g of tetrahydrofuran was added dropwise over 30 minutes. -30
After aging at 2 ° C. for 2 hours, the temperature was gradually raised and further aged at 5 ° C. for 6 hours. Thereafter, the mixture was cooled again to -30 ° C, and a solution prepared by dissolving 1.78 g of sodium hydroxide in 10 g of water was added.
Dropped in minutes. After stirring at 0 ° C. for 12 hours, 100 g of water and 150 g of hexane were added to the reaction solution, and the layers were separated. The organic layer is separated, washed with water, and then the solvent is distilled off. The compound of the present invention (2)
35 g were obtained. This compound (2) of the present invention is added to silicone oil which is usually used as a cosmetic ingredient in an amount of 5%.
In the temperature range of ５０50 ° C., a stable emulsifying power was exhibited regardless of the temperature. IR (neat): Si-O -Si 1060cm -1, P = O 1215cm -1 1 H-NMR (CDCl 3): - 0.1ppm Si-CH 3, 0.48ppm Si-CH 2,
1.47ppm Si-CH ₂ -C H ₂ , 3.46, 3.53ppm -CH ₂ -O-CH _2- , 4.
01ppm -CH ₂ -OP

[0043]

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Embodiment 3

[0045]

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2.4 g of phosphorus oxychloride (7-a) was dissolved in 15 g of tetrahydrofuran and cooled to -30 ° C.
To this solution, a solution prepared by dissolving 10 g of alcohol-modified dimethylpolysiloxane (6-c) and 3.2 g of triethylamine in 100 g of tetrahydrofuran, which was synthesized by the method described in JP-A-62-195389, was added dropwise over 30 minutes. After aging at -30 ° C for 2 hours, the temperature was gradually raised and further aged at 5 ° C for 6 hours. Thereafter, the mixture was cooled again to -30 ° C, and a solution of 2.50 g of sodium hydroxide dissolved in 15 g of water was added dropwise over 30 minutes. After stirring at 0 ° C. for 12 hours, 100 g of water and 200 g of hexane were added to the reaction solution, and the layers were separated. The organic layer was separated and washed with water, and then the solvent was distilled off to obtain 35 g of the present compound (3). This compound (3) of the present invention
Showed a stable emulsifying power in a temperature range of 5 to 50 ° C. irrespective of the temperature with respect to a silicone oil usually used as a cosmetic component. IR (neat): Si-O -Si 1070cm -1, P = O 1220cm -1 1 H-NMR (CDCl 3): - 0.1ppm Si-CH 3, 0.49ppm Si-CH 2,
1.30ppm Si-CH _2- (C H ₂ )-, 1.62ppm -C H ₂ -CH ₂ -OP, 3.81p
pm -CH ₂ -OP

[0047]

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Embodiment 4

[0049]

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5.7 g of phosphorus oxychloride (7-a) was dissolved in 20 g of tetrahydrofuran and cooled to -30 ° C.
To this solution, a solution prepared by dissolving 30 g of alcohol-modified dimethylpolysiloxane (6-d) and 7.5 g of triethylamine in 150 g of tetrahydrofuran, which was synthesized by the method described in JP-A-62-195389, was added dropwise over 30 minutes. After aging at -30 ° C for 2 hours, the temperature was gradually raised and further aged at 5 ° C for 6 hours. Thereafter, the mixture was cooled again to -30 ° C, and a solution of 6.0 g of sodium hydroxide dissolved in 25 g of water was added dropwise over 50 minutes. After stirring at 0 ° C. for 12 hours, 100 g of water and 250 g of hexane were added to the reaction solution, and the layers were separated. The organic layer was separated and washed with water, and then the solvent was distilled off to obtain 30 g of the present compound (4). This compound (4) of the present invention
It exhibited stable emulsifying power with respect to silicone oil which is usually used as a cosmetic component in the temperature range of 5 to 50 ° C irrespective of the temperature. IR (neat): Si-O -Si 1058cm -1, P = O 1220cm -1 1 H-NMR (CDCl 3): 0, -0.1ppm Si-CH 3, 0.40ppm Si-C
H ₂ , 1.24 ppm Si-CH _2- (C H ₂ )-, 1.57 ppm -C H ₂ -CH ₂ -OP,
3.83ppm -CH ₂ -OP

[0051]

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Embodiment 5

[0053]

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4.0 g of phosphorus oxychloride (7-a) was dissolved in tetrahydrofuran and cooled to -30.degree. An alcohol-modified dimethylpolysiloxane (6) synthesized by the method described in JP-A-62-195389 was added to this solution.
-E) A solution in which 25 g and 5.3 g of triethylamine were dissolved in 134 g of tetrahydrofuran was added dropwise over 30 minutes.
After aging at -30 ° C for 2 hours, the temperature was gradually raised and further aged at 5 ° C for 6 hours. Thereafter, the mixture was cooled again to -30 ° C, and a solution prepared by dissolving 4.2 g of sodium hydroxide in 15 g of water was added dropwise over 30 minutes. After stirring at 0 ° C. for 12 hours, 100 g of water and 200 g of hexane were added to the reaction solution, and the layers were separated. The organic layer was separated and washed with water, and then the solvent was distilled off to obtain 26 g of the present compound (5). This compound (5) of the present invention showed a stable emulsifying power in a temperature range of 5 to 50 ° C. irrespective of the temperature with respect to silicone oil which is usually used as a cosmetic component. IR (neat): Si-O -Si 1053cm -1, P = O 1220cm -1 1 H-NMR (CDCl 3): -0.1ppm Si-CH 3, 0.44ppm Si-CH 2,
1.27ppm Si-CH _2- (C H ₂ )-, 1.60ppm -C H ₂ -CH ₂ -OP, 3.80pp
m -CH ₂ -OP

[0055]

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Embodiment 6

[0057]

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1.5 g of phosphorus oxychloride (7-a) was dissolved in 10 g of tetrahydrofuran and cooled to -30 ° C.
To this solution was added alcohol-modified dimethylpolysiloxane (6
-G) (X-22-4502, manufactured by Shin-Etsu Chemical Co., Ltd.)
A solution of 40 g of triethylamine and 2.0 g of triethylamine dissolved in 50 g of tetrahydrofuran was added dropwise over 1 hour. -30 ° C
After aging for 4 hours, the temperature was gradually increased, and the mixture was further aged by stirring at 20 ° C. for 12 hours. Thereafter, a solution in which 2.1 g of sodium hydroxide was dissolved in 10 mL of water was added dropwise over 20 minutes. After stirring at 0 ° C. for 4 hours, 100 mL of water and 200 mL of ether were added to the reaction solution, and the layers were separated. The organic layer was separated, washed with water, and then the solvent was distilled off to obtain 35 g of the present compound (6).
This compound (6) of the present invention exhibited stable emulsifying power with respect to silicone oil, which is usually used as a cosmetic ingredient, in a temperature range of 5 to 50 ° C. regardless of the temperature. IR (neat): Si-O -Si 1075cm -1, P = O 1220cm -1 1 H-NMR (CDCl 3): 0ppm Si-CH 3, 0.5ppm Si-CH 2, 1.5pp
_{m Si-CH 2 -C H 2} , 3.5ppm -O-CH 2, 4.0ppm-CH 2 -OP

[0059]

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Embodiment 7

[0061]

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2.4 g of phosphorus oxychloride (7-a)
It was dissolved in 15 g of lahydrofuran and cooled to -30 ° C.
The solution described in JP-A-62-195389 was added to this solution.
-Modified dimethyl polysiloxa synthesized by the synthetic method
(6-c) 10 g and triethylamine 3.2 g
A solution dissolved in 100 g of lahydrofuran is dropped in 30 minutes
did. After aging at -30 ° C for 2 hours, gradually raise the temperature.
The mixture was further aged at 5 ° C. for 6 hours. Then again at -30 ° C
Cool and dissolve 3.5 g of potassium hydroxide in 15 g of water
The solution was dropped in 30 minutes. Reaction after stirring at 0 ° C for 12 hours
100 g of water and 200 g of hexane were added to the solution to separate layers.
Was. The organic layer was separated, washed with water, and then the solvent was distilled off.
36 g of compound (7) was obtained. This compound (7) of the present invention
For silicone oil which is usually used as a cosmetic ingredient
Stable in the temperature range of 5 to 50 ° C regardless of temperature
Showed emulsifying power. IR (neat): Si-O-Si 1070cm^-1, P = O 1220cm^{-1 1} H-NMR (CDCl_Three):-0.1ppm Si-CH_Three, 0.49ppm Si-CH_Two ,
1.30ppm Si-CH_Two-(CH ₂ )-, 1.62ppm -CH ₂ -CH _Two-O-P, 3.92
ppm -CH_Two-O-P

[0063]

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 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshiaki Fujikura 271-6 F-term (reference) 4J035 CA07U CA27M CA29M LB14

Claims (2)

[Claims] 1. An organo (poly) siloxane modified by a phosphoric acid diester salt having structural units represented by the following general formulas (1) and (2). Embedded image [Wherein, R ¹ represents an alkylene group having 4 to 20 carbon atoms. R ² : 1 to 5 carbon atoms which may be substituted by a hydroxy group
And 0 represents a linear or branched alkylene group. p: Indicates the number of 0 to 200. M: represents a hydrogen atom or a monovalent cation. R ³ , R ⁴ , R ⁵ , R ⁶ each represents an alkyl group, an alkoxy group, a phenyl group or a structural unit represented by the general formula (2). w indicates 0 or 1. ] 2. A phosphoric acid diester salt-modified organo (poly) siloxane represented by the following general formula (3). Embedded image [Wherein, R ¹ represents an alkylene group having 4 to 20 carbon atoms. R ² : 1 to 5 carbon atoms which may be substituted by a hydroxy group
And 0 represents a linear or branched alkylene group. M: represents a hydrogen atom or a monovalent cation. R ⁷ to R ^24: independently an alkyl or alkoxy group or a phenyl group having 1 to 22 carbon atoms. Of these, R
¹¹ and R ²⁰ may together form a divalent oxygen atom. q, r, s, t, u, v: each represents a number from 0 to 1000. However, both q and t do not become 0. ]