Organo(poly)siloxane modified with phosphoric ester and process for producing the same

The present invention relates to organo(poly)siloxanes modified by phosphates (including alkali metal salts thereof or the like) suitable as a component of cosmetics, and to a process for the manufacture of organo(poly)siloxanes modified by phosphates (including alkali metal salts thereof or the like) comprising reacting an organo(poly)siloxane having a group HO--(R.sup.4 O).sub.q --R.sup.5' --OR.sup.6).sub.r -- in its molecular chain, wherein R.sup.4 -R.sup.6 are alkylene groups, with an oxyhalogenated phosphorus; and further reacting it with an alkaline solution. These phosphate-modified organo(poly)siloxanes can stably emulsify silicone oils commonly used as cosmetic raw materials, irrespective of temperatures, and exhibit excellent compatibility with polar components and good foaming capability, so that they are suitable as a component of cosmetics such as skin cosmetics, skin detergents, hair cosmetics, hair detergents, and the like.

DESCRIPTION 
1. Field of the Invention 
The present invention relates to phosphate-modified organo(poly)siloxanes 
which are useful as a component of toiletries (perfumes and cosmetics), 
and further to a process for producing phosphate-modified 
organo(poly)siloxanes, which is suitable for the manufacture of said 
organo(poly)siloxanes whose terminals are modified by phosphates. 
2. Description of the Background Art 
Organopolysiloxanes (silicone oils) are commonly used as a component of 
hair-finishing agents, as well as a component of various cosmetics, 
because they impart no greasy feeling and are highly safe. Recently, in 
addition to the conventional use as a component of cosmetics, application 
of these compounds as a component of various toiletry items including 
perfumes has been studied. In order to conform to these new applications, 
further improvements in the characteristics of organopolysiloxanes, such 
as compatibility, resistance to chemicals, solubility in water, lubricity, 
and the like, are required. 
To satisfy these requirements, various organopolysiloxanes modified by 
introducing different functional groups, for example, amino-modified, 
epoxy-modified, carboxylic acid-modified, mercapto-modified, 
alcohol-modified, polyether-modified, fluoroalkyl-modified, 
alkyl-modified, ester-modified, and alkoxy-modified organopolysiloxanes 
have been studied and developed. 
On the other hand, phosphoric esters of organic hydroxy compounds 
(including alkali metal salts thereof and the like) are known to have an 
excellent surface activity. In particular, phosphoric monoesters are known 
to exhibit much higher surface activity than phosphoric diesters. For 
example, alkali metal salts or alkanol amine salts of phosphoric monoester 
of a long chain alkyl alcohol are water-soluble, and their aqueous 
solutions exhibit strong foaming capability and detergency, while the 
salts of phosphoric diester are scarcely soluble in water, exhibit almost 
no foaming capability, and moreover cause defoaming activity. 
As compounds which have both the characteristics of the above-described 
phosphoric esters of organic hydroxy compounds and the aforementioned 
modified organopolysiloxanes, U.S. Pat. No. 5,070,171 and U.S. Pat. No. 
5,093,452 disclosed certain compounds in which salts of phosphoric ester 
are introduced to the silicon atoms of the siloxane bonds in its main 
chain (excluding the both ends) via a lower alkylene group (limited only 
to the group having 3 carbon atoms) or polyalkyleneoxy groups, as 
connective groups, using 115% phosphoric acid, phosphorus pentoxide, or 
polyphosphoric acid. 
However, the above-described conventional modified organopolysiloxanes are 
not necessarily satisfactory as a component of toiletries. 
Polyether-modified organopolysiloxanes, for example, have a problem in 
that they have poor heat stability in emulsion systems due to the cloud 
point phenomenon which is characteristic to the nonionic surface active 
agents comprising polyether bonds, rendering them unsuitable for practical 
use. The compounds disclosed in U.S. Pat. No. 5,070,171 and U.S. Pat. No. 
5,093,452 are not satisfactory as an ingredient of toiletries, since they 
have only a small phosphorylation rate because of defects in the 
preparation method and are composed of a mixture with a small content of 
monoesters which are useful as surfactants. In addition, since the 
alkylene groups are of short chain, the overall hydrophilic-hydrophobic 
characteristic is imbalanced, giving rise to weak surface activity. They 
are thus not satisfactory as ingredients to be incorporated into 
toiletries. 
Accordingly, an object of the present invention is to provide a modified 
organo(poly)siloxane exhibiting excellent compatibility, emulsifying 
capability, foaming capability, and the like, which is suitable for use as 
an ingredient of toiletries. Another object is to provide a novel process 
for the manufacture of a modified organo(poly)siloxane, which can be 
applied to the preparation of said modified organo(poly)siloxanes of the 
present invention. 
DISCLOSURE OF THE INVENTION 
The present invention relates to a phosphate-modified organo(poly)siloxane 
represented by the following formula (1): 
##STR1## 
wherein R, which may be the same or different, indicates an alkyl group or 
an alkoxy group having 1 to 22 carbon atoms, or a group represented by the 
following formula (2) or (3): 
##STR2## 
(wherein R.sup.4 and R.sup.6 represent an alkylene group having 2 to 4 
carbon atoms, R.sup.5 indicates a linear or branched alkylene group having 
4 to 50 carbon atoms, which may or may not contain hydroxy groups, M.sup.1 
and M.sup.2 indicate a hydrogen atom, an alkali metal, an ammonium group, 
an alkyl amine or an alkanol amine, q is a number of 0 to 200, r is 0 or 
1); R.sup.1 and R.sup.2 designate a group represented by the following 
formula (2') or (3'), 
##STR3## 
(wherein R.sup.4 and R.sup.6 designate the same groups as defined above, 
R.sup.5' indicates a linear or branched alkylene group having 1 to 50 
carbon atoms, which may or may not contain hydroxy groups, q, r, M.sup.1 
and M.sup.2 are the same as defined previously), or an alkyl group or an 
alkoxy group having 1 to 22 carbon atoms, provided that at least one of 
R.sup.1, R.sup.2 and R represents the group indicated by the formula (2) 
or (2'); and n indicates a number of 0 to 1,000. 
Further, the present invention relates to a process for the manufacture of 
an organo(poly)siloxane having at least one group represented by the 
following formula: 
##STR4## 
wherein R.sup.4, R.sup.5', R.sup.6, M.sup.1, M.sup.2, q and r are the same 
as defined previously, as a group bonded to the silicon atoms in the 
molecular chain, which comprises reacting an alcohol-modified 
organo(poly)siloxane having at least one group represented by formula 
HO--(R.sup.4 O).sub.q --R.sup.5' --OR.sup.6).sub.r, wherein R.sup.4, 
R.sup.5', R.sup.6, q and r are the same as defined previously, as a group 
bonded to the silicon atoms in the molecular chain, with an oxyhalogenated 
phosphorus, and hydrolyzing the bonds between the phosphorus and the 
halogen. 
The above-described organo(poly)siloxanes modified by phosphates excel in 
foaming capability and emulsifying capability, as well as heat stability 
in emulsion systems and compatibility with other ionic components. 
Furthermore, the above-described process is useful in that it can be 
applied to the manufacture of other phosphate-modified 
organo(poly)siloxanes.

BEST MODES FOR CARRYING OUT THE INVENTION 
In the present invention, the term "organo(poly)siloxanes" means various 
organopolysiloxanes from high molecular weight organopolysiloxanes to low 
molecular weight organosiloxanes. "Phosphate" as used in "modified by 
phosphate" or "phosphate-modified" in the present invention includes 
phosphates themselves and the above-mentioned alkali metal salts, ammonium 
salts, alkyl amine salts or alkanol amine salts of a phosphate. 
R in formula (1) represents an alkyl group or an alkoxy group having 1 to 
22 carbon atoms, or a group represented by formula (2) or (3). Among these 
preferred groups are alkyl or alkoxy groups having 1 to 6 carbon atoms or 
groups represented by formula (2) wherein R.sup.5 is an alkylene group 
having 4 to 15 carbon atoms, with methylene group and groups represented 
by formula (2) wherein R.sup.5 is an alkylene group having 6 to 12 carbon 
atoms being particularly preferred. Also, even though n in formula (1) 
designates a number of 0 to 1,000, a range of 0 to 100, particularly 0 to 
50, or more particularly 0 to 10, is preferred when the compounds are used 
as ingredients of toiletries. In formula (2), (2'), (3) or (3'), 
preferable R.sup.5 or R.sup.5' are those having 4 to 15 carbon atoms, 
particularly those having 6 to 12 carbon atoms; a preferable value for q 
is 0 to 15; and a preferable value for r is 0. For M.sup.1 and M.sup.2 in 
formula (2), a hydrogen atom or an alkali metal is particularly preferred. 
Given as examples of oxyhalogenated phosphorus compounds used in the 
present invention are phosphorus oxychloride, phosphorus oxybromide, and 
the like. Of these, phosphorus oxychloride is particularly preferred. 
The phosphate-modified organo(poly)siloxanes, including the compounds 
represented by the above formula (1), are prepared in the following 
manner. An organo(poly)siloxane having groups represented by formula (2) 
or (2'), as a group bonded to the silicon atoms in its molecular chain, 
can be prepared by reacting an alcohol-modified organo(poly)siloxane 
having at least one group represented by formula (3) or (3'), as a group 
bonded to the silicon atoms in the molecular chain, with an oxyhalogenated 
phosphorus compound, followed by hydrolyzing the bond between the 
phosphorus and the halogen. 
Now, the process of the present invention will be discussed on each 
manufacturing step. First, an alcohol-modified organo(poly)siloxane having 
at least one group represented by formula (3) or (3'), as a group bonded 
to the silicon atoms in the molecular chain (hereinafter referred to as 
"alcohol-modified organo(poly)siloxane"), is reacted with an 
oxyhalogenated phosphorus compound in the presence or absence of a 
solvent. 
Any alcohol-modified organo(poly)siloxanes can be used in the present 
invention, so long as the same have at least one group represented by (3) 
or (3') bonded to the silicon atom in the molecular chain, with no 
restriction being imposed on the position of the bond. Any type of 
structures, named generically as branched type, both-end type, one-end 
type, T-structure type, and the like, depending on the linked position of 
the specified groups, can therefore be used. The compounds represented by 
the following formulas can be given as examples of these alcohol-modified 
organo(poly)siloxanes. 
##STR5## 
wherein j, k, l and m designate a number of 0 to 1,000. 
Although alcohol-modified organo(poly)siloxanes prepared by known methods 
can be used, commercial products may also be used as they are. Given as 
examples of such commercial products are X-22-170, X-22-170A, X-22-170B, 
X-22-170D, X-22-160AS, KF6001, KF6002, KF6003, X-22-176B, X-22-176D, 
X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSL-9105, 
TSF4705, TSF4751, XF42-220, XF42-811, XF42-831 (manufactured by Toshiba 
Silicone Co., Ltd.); and PS197, PX101 (manufactured by Chisso Corp.). 
There are no particular restrictions to the reaction method of 
alcohol-modified organo(poly)siloxane and oxyhalogenated phosphorus. For 
example, it is possible to apply a method in which each compound is 
dissolved in an appropriate solvent and the solutions are mixed together 
to proceed the reaction. 
Examples of the solvents used for dissolving alcohol-modified 
organo(poly)siloxanes include tetrahydrofuran, methylene chloride, 
toluene, diethyl ether, and the like. The amount of the solvent to be used 
here is preferably less than 10-fold, more preferably less than 3-fold, of 
the weight of the alcohol-modified organo(poly)siloxane. Examples of the 
solvents used for dissolving an oxyhalogenated phosphorus compound include 
tetrahydrofuran, methylene chloride, toluene, ether, and the like. The 
amount of the solvent to be used here is preferably less than 20-fold, 
more preferably less than 10-fold, of the weight of the oxyhalogenated 
phosphorus compound. 
Although the mixing ratio of an alcohol-modified organo(poly)siloxane and 
an oxyhalogenated phosphorus compound is not particularly restricted, it 
is preferable to mix 0.5 to 2, or more preferably 0.9 to 1.5, equivalent 
of oxyhalogenated phosphorus to 1 equivalent of hydroxyl group contained 
in the alcohol-modified organo(poly)siloxane. 
Although the mixing method of an alcohol-modified organo(poly)siloxane and 
an oxyhalogenated phosphorus compound is not particularly restricted, it 
is possible to apply a method, for example, in which an alcohol-modified 
organo(poly)siloxane solution is added dropwise to an oxyhalogenated 
phosphorus solution, while stirring if required. 
In this instance, the method of the dropwise addition is not particularly 
limited. Any methods, for example, dripping the total volume at a time, 
dripping portions at appropriate intervals, or dripping little by little 
in portions, can be applied. The temperature in the reaction system at the 
time of dripping is preferably -50.degree. to 10.degree. C., with a more 
preferable temperature range being -30.degree. to 0.degree. C. Upon 
completion of the reaction, it is preferable, as needed, to perform an 
aging operation for 1 to 5 hours within the aforementioned temperature 
range. For the purpose of neutralization of the by-produced hydrochloric 
acid, it is possible to have a tertiary amine such as triethylamine, 
tributylamine, pyridine, N-methylmorpholine, and the like coexist in the 
reaction system. 
Next, in order to hydrolyze the bonds between phosphorus and halogen in the 
reaction product prepared in the preceding step, an alkaline solution may 
be added, for example, by applying a similar dripping method as described 
above, and reacted. 
The alkaline solution used here includes a solution of sodium hydroxide, 
potassium hydroxide, ammonium, alkyl amine, alkanol amine, or the like. 
Among these, particularly preferred are a solution of sodium hydroxide and 
a solution of potassium hydroxide. The concentration of the alkaline 
solution is not particularly limited. It can be appropriately adjusted 
taking the concentrations of the alcohol-modified organo(poly)siloxane and 
the oxyhalogenated phosphorus into consideration. In addition, the 
temperature of the reaction system is preferably maintained at the same 
temperature range as described previously, and the reaction time is 
preferably 1 to 15 hours. 
After completing the reactions in this manner, the phosphate-modified 
organo(poly)siloxane produced is separated from the reaction system. A 
further purification operation may be additionally performed on the 
phosphate-modified organo(poly)siloxanes thus produced, as needed. This 
purification operation is not particularly limited and can be carried out, 
for example, by the following methods. 1) A method comprising adding water 
and a non-hydrophilic solvent such as butanol, toluene, etc., and if 
required, further adding a demulsifier such as ethanol, 2-propanol, or the 
like, to the reaction solution; stirring the mixture; allowing the mixture 
to stand still for phase separation; and removing the water layer 
containing extra phosphates and by-produced inorganic and organic salts. 
2) A method of removing the solvent from the reaction mixture by 
evaporation; then washing the residue with water to remove the extra 
phosphates and the like, or dissolving the residue into a solvent such as 
ethanol, propanol, butanol, toluene, etc. to filtrate the precipitated 
extra phosphates and the like. 3) A method of adding a hydrophilic solvent 
such as ethanol, acetone, etc. to the separated water layer to precipitate 
the target compound. This last-mentioned method is applicable to the case 
where the phosphate-modified organo(poly)siloxanes produced are 
undissolvable in an organic solvent. 
EXAMPLES 
The present invention will be described in more detail by way of examples 
which are not intended to be limiting the present invention. 
Example 1 
A solution of 820 mg of phosphorus oxychloride dissolved in 3 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 10 g of one-end type alcohol-modified dimethylpolysiloxane represented 
by the following formula, 
##STR6## 
(trademark: X-22-170A, alcohol equivalent 31, manufactured by Shin-Etsu 
Chemical Co., Ltd.) and 540 mg of triethylamine dissolved in 10 g of 
tetrahydrofuran was added dropwise over 20 minutes, and reacted. The 
reaction mixture was left for aging for 4 hours, while maintaining the 
temperature below -20.degree. C. Then, a solution of 1.0 g of sodium 
hydroxide dissolved in 3 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The stirring was continued for 12 
hours at 0.degree. C. and the reaction was terminated. 50 g of 
ion-exchanged water was added to the reaction mixture, followed by further 
addition of a mixed solvent of diethyl ether and ethanol to extract the 
reaction product. The organic layer was washed with ion-exchanged water 
and the water layer was removed. 10 g of phosphate-modified 
dimethylpolysiloxane of the present invention was obtained by removing the 
solvent by evaporation under a reduced pressure. This phosphate-modified 
dimethylpolysiloxane exhibited a stable emulsifying capability, 
irrespective of temperatures within the range of 0.degree. to 50.degree. 
C., to silicone oils commonly used in cosmetic compositions. It also 
exhibited excellent compatibility with polar solvents such as water, lower 
alcohols, and the like. 
This compound was analyzed by NMR and IR (neat method). The results of NMR 
analysis are given below and the IR spectrum is presented in FIG. 1. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 8.2 
##STR7## 
.sup.1 H-NMR (CDCl.sub.3); .delta.(ppm) 0.1 (broad s, 147H, Si--CH.sub.3), 
0.5 (m, 2H, --O--Si--CH.sub.2 --CH.sub.2 --CH.sub.2 --O--), 1.6 (m, 2H, 
--O--Si--CH.sub.2 CH.sub.2 CH.sub.2 --O--), 3.4 (m, 2H, --CH.sub.2 
--O--(CH.sub.2).sub.2 --O--P), 3.55 (m, 2H, --CH.sub.2 --O--CH.sub.2 
--CH.sub.2 --O--P), 3.72, 3.91 (m, 2H, --CH.sub.2 --O--P). 
These analytical results confirmed that this phosphate-modified 
dimethylpolysiloxane has the structure defined by the following formula. 
##STR8## 
Example 2 
A solution of 15.2 g of phosphorus oxychloride dissolved in 15 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50 g of both-end type alcohol-modified dimethylpolysiloxane represented 
by the following formula, 
##STR9## 
(trademark: X-22-160AS, alcohol equivalent 112, manufactured by Shin-Etsu 
Chemical Co., Ltd.) and 10 g of triethylamine dissolved in 40 g of 
tetrahydrofuran was added dropwise over 40 minutes, and reacted. The 
reaction mixture was left for aging for 4 hours, while maintaining the 
temperature of the reaction system below -20.degree. C. Then, a solution 
of 20.7 g of sodium hydroxide dissolved in 40 g of ion-exchanged water was 
added dropwise to the reaction mixture over 40 minutes. The stirring was 
continued for 12 hours at 0.degree. C. and the reaction was completed. 
Then, after removing the solvent from the mixture by evaporation, 300 g of 
ion-exchanged water was added to the mixture and insoluble substances were 
removed by filtration. 100 ml of ethanol was added to the filtrate and 
solid substance formed was removed by filtration to obtain 52 g of 
phosphate-modified dimethylpolysiloxane of the present invention. This 
dimethylpolysiloxane exhibited a stable emulsifying capability, 
irrespective of temperatures within the range of 0.degree. to 50.degree. 
C., to silicone oils commonly used in cosmetic compositions. It also 
exhibited excellent compatibility with polar solvents such as water, lower 
alcohols, and the like. 
This compound was analyzed by NMR and IR (KBr method). The results of NMR 
analysis are given below and the IR spectrum is presented in FIG. 2. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 8.2 
##STR10## 
.sup.1 H-NMR (D.sub.2 O); .delta.(ppm) 0.1 (broad s, 66H, Si--CH.sub.3), 
0.52 (m, 4H, --O--Si--CH.sub.2 --CH.sub.2 --), 1.55 (m, 4H, 
--O--Si--CH.sub.2 CH.sub.2 CH.sub.2 --O--), 3.6 (m, 8H, --CH.sub.2 
--O--CH.sub.2 --), 3.8 (m, 4H, --CH.sub.2 --O--P--). 
These analytical results confirmed that this phosphate-modified 
dimethylpolysiloxane has the structure defined by the following formula. 
##STR11## 
Example 3 
A solution of 7.8 g of phosphorus oxychloride dissolved in 10 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 80 g of both-end type alcohol-modified dimethylpolysiloxane represented 
by the following formula, 
##STR12## 
(trademark: KF6002, alcohol equivalent 35, manufactured by Shin-Etsu 
Chemical Co., Ltd.) and 5.0 g of triethylamine dissolved in 30 g of 
tetrahydrofuran was added dropwise over 50 minutes, and reacted. The 
reaction mixture was left for aging for 4 hours, while maintaining the 
temperature of the reaction system below -20.degree. C. Then, a solution 
of 10.6 g of sodium hydroxide dissolved in 20 g of ion-exchanged water was 
added dropwise to the reaction mixture over 40 minutes. The mixture was 
continuously stirred for 12 hours at 0.degree. C. and the reaction was 
completed. Then, after removing the solvent by evaporation, the mixture 
was washed with ion-exchanged water (300 g.times.3). The water was 
evaporated to obtain 82 g of phosphate-modified dimethylpolysiloxane of 
the present invention. This dimethylpolysiloxane exhibited a stable 
emulsifying capability, irrespective of temperatures within the range of 
0.degree. to 50.degree. C., to silicone oils commonly used in cosmetic 
compositions. It also exhibited excellent compatibility with polar 
solvents such as water, lower alcohols, and the like. 
This compound was analyzed by NMR and IR (KBr method). The results of NMR 
analysis are given below and the IR spectrum is presented in FIG. 3. 
.sup.31 P-NMR(CD.sub.3 OD+CDCl.sub.3); .delta.(ppm) 8.0 
##STR13## 
.sup.1 H-NMR(CD.sub.3 OD+CDCl.sub.3); .delta.(ppm) -0.2 (broad s, 246H, 
Si--CH.sub.3), 0.35 (m, 4H, --O--Si--CH.sub.2 --CH.sub.2 --CH.sub.2 
--O--), 1.43 (m, 4H, --O--Si--CH.sub.2 CH.sub.2 CH.sub.2 --O--), 3.28 (m, 
4H, --CH.sub.2 --O--CH.sub.2 CH.sub.2 O--P--), 3.44 (m, 4H, --CH.sub.2 
O--CH.sub.2 CH.sub.2 O--P--), 3.73 (m, 4H, --CH.sub.2 O--P--). 
These analytical results confirmed that this phosphate-modified 
dimethylpolysiloxane has the structure defined by the following formula. 
Comparative Example 1 
To 100 g of a solution of alcohol-modified dimethylpolysiloxane (trademark: 
X-22-4015, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by 
the following formula, 
##STR14## 
(wherein s:t=26:1), was added 1.7 g of solid phosphorus pentoxide in 
portions. The mixture was gradually heated up to 70.degree. C. and stirred 
for 1 hour while maintaining the temperature at 70.degree. C. Then, the 
mixture was heated up to 100.degree. C. and again stirred for 4 hours. 
After leaving the mixture to go down to room temperature, a 20% sodium 
hydroxide solution was added to neutralize the reaction mixture. .sup.31 
P-NMR (CDCl.sub.3 +ethanol) was measured on the resulting product to 
confirm a signal reflecting an unreacted phosphorus at 2.4 ppm, a signal 
reflecting a phosphoric monoester at 1.4 ppm, a signal reflecting 
phosphoric diester at 1.0 ppm, and a signal reflecting a pyrophosphoric 
acid at -8.3 ppm. Further, from the measurement of .sup.1 H-NMR 
(CDCl.sub.3) on this product after washing with water, the phosphorylation 
rate (phosphorylated --OH equivalent.times.100/original --OH equivalent) 
was found to be less than 30%. This dimethylpolysiloxane exhibited a poor 
emulsification stability to silicone oils commonly used in cosmetic 
compositions in the temperature range of 0.degree. to 50.degree. C. It 
also exhibited inferior compatibility with polar solvents such as water, 
lower alcohols, and the like. 
Comparative Example 2 
50 g of the same alcohol-modified dimethylpolysiloxane of both-end type 
(trademark: X-22-160AS) used in Example 2 and 3.5 g of phosphorus 
pentoxide were used and processed in the same manner as in Comparative 
Example 1. As a result of .sup.31 P-NMR (CDCl.sub.3) measurement on the 
formed product, the molar ratio of unreacted phosphoric 
acid:monoester:diester was confirmed to be 3:2:1. Neither emulsification 
stability nor compatibility of this dimethylpolysiloxane was satisfactory, 
as in the product of Comparative Example 1. 
Example 4 
A solution of 5.3 g of phosphorus oxychloride dissolved in 10 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 70 g of alcohol-modified dimethylpolysiloxane used in Comparative 
Example 1 (trademark: X-22-4015) and 3.5 g of triethylamine dissolved in 
30 g of tetrahydrofuran was added dropwise over 30 minutes, and reacted. 
The reaction mixture was left for aging for 4 hours, while maintaining the 
temperature of the reaction system below -20.degree. C. Then, a solution 
of 7.0 g of sodium hydroxide dissolved in 15 g of ion-exchanged water was 
added dropwise to the reaction mixture over 30 minutes. The mixture was 
continuously stirred for 12 hours at 0.degree. C. and the reaction was 
completed. Then, after removing the solvent by evaporation, the mixture 
was washed with ion-exchanged water (300 g.times.3). Water was evaporated 
to obtain 69 g of phosphate-modified dimethylpolysiloxane (phosphate 
conversion rate: greater than 95%). This phosphate-modified 
organopolysiloxane exhibited a stable emulsifying capability, irrespective 
of temperatures within the range of 0.degree. to 50.degree. C., to 
silicone oils commonly used in cosmetic compositions. It also exhibited 
excellent compatibility with polar solvents such as water, lower alcohols, 
and the like. 
This compound was analyzed by NMR and IR (KBr method). The results of NMR 
analysis are given below and the IR spectrum is presented in FIG. 4. 
.sup.- P-NMR(CD.sub.3 OD+CDCl.sub.3); .delta.(ppm) 7.87 
##STR15## 
.sup.1 H-NMR(CD.sub.3 OD+CDCl.sub.3); .delta.(ppm) -0.10 (broad s, 155H, 
Si--CH.sub.3), 0.33 (m, 2H, O--Si----CH.sub.2 --CH.sub.2), 1.46 (m, 2H, 
O--Si--CH.sub.2 CH.sub.2 CH.sub.2), 3.27 (m, 2H, --CH.sub.2 --O--CH.sub.2 
CH.sub.2 --O--P), 3.35, 3.44 (m, 2H, --CH.sub.2 OCH.sub.2 CH.sub.2 O--P), 
3.53, 3.73 (m, 2H, --CH.sub.2 O--P--). 
Example 5 
##STR16## 
A solution of 13.2 g of phosphorus oxychloride dissolved in 20 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 28.2 g of one-end type alcohol-modified dimethylsiloxane synthesized by 
a known method (Japanese Patent Laid-open No. 195389/1987), represented by 
the above formula, and 8.7 g of triethylamine dissolved in 30 g of 
tetrahydrofuran was added dropwise over 20 minutes. The mixture was left 
for aging for 4 hours, while maintaining the temperature of the reaction 
system below -20.degree. C. Then, a solution of 17.5 g of sodium hydroxide 
dissolved in 30 g of ion-exchanged water was added dropwise to the 
reaction mixture over 20 minutes. The mixture was continuously stirred for 
12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 70 g of 
ion-exchanged water, and further adding a mixed solvent of ether and 
ethanol. The organic layer was washed with ion-exchanged water, followed 
by removal of the water layer. The solvent was evaporated under a reduced 
pressure to obtain 32 g of phosphate-modified dimethylsiloxane of the 
present invention. 
This phosphate-modified dimethylsiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 8.0 .sup.1 H-NMR (CDCl.sub.3); 
.delta.(ppm) -0.03 (--O--Si (CH.sub.3).sub.2 --CH.sub.2 --), -0.06 
((CH.sub.3).sub.3 Si--O), 0.5 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.8 --CH.sub.2 --CH.sub.2 --O--P), 1.6 (--CH.sub.2 
--CH.sub.2 --O--P), 3.8 (--CH.sub.2 --O--P), IR; Si--O--Si 1050 cm.sup.-1, 
Si--C 1245 cm.sup.-1, 840 cm.sup.-1. 
Example 6 
##STR17## 
A solution of 5.5 g of phosphorus oxychloride dissolved in 20 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50.0 g of branched type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 3.7 g of triethylamine dissolved in 
50 g of tetrahydrofuran was added dropwise over 30 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 7.3 g of sodium 
hydroxide dissolved in 10 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 100 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
52 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.- P-NMR(CDCl.sub.3); .delta.(ppm) 7.9 .sup.1 H-NMR(CDCl.sub.3); 
.delta.(ppm) 0.1 (Si--CH.sub.3), 0.5 (Si--CH.sub.2), 1.3 (--CH.sub.2 
--(CH.sub.2).sub.8 --CH.sub.2 --CH.sub.2 --O--P), 1.7 (--CH.sub.2 
--CH.sub.2 --O--P), 3.9 (--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, 
Si--C 1260 cm.sup.-1, 800 cm.sup.-1. 
Example 7 
##STR18## 
A solution of 6.5 g of phosphorus oxychloride dissolved in 20 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 40.0 g of both-end type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 4.3 g of triethylamine dissolved in 
40 g of tetrahydrofuran was added dropwise over 30 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 8.5 g of sodium 
hydroxide dissolved in 10 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 100 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
41 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as, water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 7.9 .sup.1 H-NMR(CDCl.sub.3); 
.delta.(ppm) 0.1 (Si--CH.sub.3), 0.5 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.8 --CH.sub.2 --CH.sub.2 --O--P), 1.6 (--CH.sub.2 
--CH.sub.2 --O--P), 3.8 (--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, 
Si--C 1260 cm.sup.-1, 800 cm.sup.-1. 
Example 8 
##STR19## 
A solution of 11.0 g of phosphorus oxychloride dissolved in 20 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50.0 g of alcohol-modified dimethylpolysiloxane (KF-355A; manufactured 
by Shin-Etsu Chemical Co., Ltd.) represented by the above formula, and 7.3 
g of triethylamine dissolved in 25 g of tetrahydrofuran was added dropwise 
over 30 minutes. The mixture was left for aging for 4 hours, while 
maintaining the temperature of the reaction system below -20.degree. C. 
Then, a solution of 14.7 g of sodium hydroxide dissolved in 20 g of 
ion-exchanged water was added dropwise to the reaction mixture over 20 
minutes. The mixture was continuously stirred for 5 hours at 0.degree. C. 
and the reaction was completed. The tetrahydrofuran layer was separated 
and the solvent was evaporated under a reduced pressure. The insoluble 
substances were removed by filtration by adding ethanol. The ethanol was 
evaporated under reduced pressure to obtain 57 g of phosphate-modified 
dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as, water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 7.8 .sup.1 H-NMR(CDCl.sub.3); 
.delta.(ppm) 0.1 (Si--CH.sub.3), 0.5 (Si--CH.sub.2), 1.5 (Si--CH.sub.2 
--CH.sub.2 --CH.sub.2 --O), 3.4 (--O----CH.sub.2 --), 3.9 (--CH.sub.2 
--O--P), IR; Si--O--Si 1025 cm.sup.-1, Si--C 1270 cm.sup.-1, 800 
cm.sup.-1. 
Example 9 
##STR20## 
A solution of 11.6 g of phosphorus oxychloride dissolved in 30 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50.0 g of both-end type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 7.6 g of triethylamine dissolved in 
40 g of tetrahydrofuran was added dropwise over 30 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 15.1 g of sodium 
hydroxide dissolved in 20 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 100 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
52 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 7.9 .sup.1 H-NMR (CDCl.sub.3); 
.delta.(ppm) 0.1 (Si--CH.sub.3) 0.5 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.8 --CH.sub.2 --CH.sub.2 --O--P), 1.6 (--CH.sub.2 
--CH.sub.2 --O--P), 3.8 (--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, 
Si--C 1260 cm.sup.-1, 800 cm.sup.-1. 
Example 10 
##STR21## 
A solution of 23.7 g of phosphorus oxychloride dissolved in 30 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 30.0 g of both-end type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 15.6 g of triethylamine dissolved in 
40 g of tetrahydrofuran was added dropwise over 30 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 30.9 g of sodium 
hydroxide dissolved in 40 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 100 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
42 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 8.0 .sup.1 H-NMR (CDCl.sub.3); 
.delta.(ppm) 0.1 (Si--CH.sub.3), 0.5 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.8 --CH.sub.2 --CH.sub.2 --O--P), 1.6 (--CH.sub.2 
--CH.sub.2 --O--P), 3.8 (--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, 
Si--C 1260 cm.sup.-1, 800 cm.sup.-1. 
Example 11 
##STR22## 
A solution of 20.1 g of phosphorus oxychloride dissolved in 30 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50.0 g of both-end type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 13.2 g of triethylamine dissolved in 
40 g of tetrahydrofuran was added dropwise over 30 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 26.2 g of sodium 
hydroxide dissolved in 40 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 100 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
52 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 7.9 .sup.1 H-NMR(CDCl.sub.3); 
.delta.(ppm) 0.1 (Si--CH.sub.3), 0.5 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.8 --CH.sub.2 --CH.sub.2 --O--P), 1.6 (--CH.sub.2 
--CH.sub.2 --O--P), 3.8 (--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, 
Si--C 1260 cm.sup.-1, 800 cm.sup.-1. 
Example 12 
##STR23## 
A solution of 13.2 g of phosphorus oxychloride dissolved in 20 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 30.0 g of one-end type alcohol-modified dimethylsiloxane synthesized by 
a known method (Japanese Patent Laid-open No. 195389/1987), represented by 
the above formula, and 8.7 g of triethylamine dissolved in 30 g of 
tetrahydrofuran was added dropwise over 20 minutes. The mixture was left 
for aging for 4 hours, while maintaining the temperature of the reaction 
system below -20.degree. C. Then, a solution of 17.5 g of sodium hydroxide 
dissolved in 30 g of ion-exchanged water was added dropwise to the 
reaction mixture over 20 minutes. The mixture was continuously stirred for 
12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 70 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
32 g of phosphate-modified dimethylsiloxane of the present invention. 
This phosphate-modified dimethylsiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 7.9 .sup.1 H-NMR(CDCl.sub.3 ); 
.delta.(ppm) 0.03 (--O--Si (CH.sub.3).sub.2 --CH.sub.2 --), 0.06 
((CH.sub.3).sub.3 Si--O), 0.5 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.5 --CH.sub.2 --CH.sub.2 --O--P), 1.5 (O--CH.sub.2 
--CH.sub.2), (--CH.sub.2 --CH.sub.2 --O--P), 3.3 (--O--CH.sub.2), 3.9 
(--CH.sub.2 --O--P), IR; Si--O--Si 1050 cm.sup.-1, Si--C 1245 cm.sup.-1, 
840 cm.sup.-1. 
Test Example 1 
Foaming capability of the above-described phosphate-modified 
dimethyl(poly)siloxanes were measured by the following method. 
Measurement Method 
100 ml of 1% aqueous solution of each compound was charged in a cylinder of 
6.5 cm diameter, and subjected to reversal agitation at 1,000 rpm and 
allowed to stand still for 30 seconds. The height of the foam remained was 
then measured. The results are presented below. 
##STR24## 
From the above results, it was made clear that the foaming capability can 
be promoted by introducing a longer chain alkyl group and by using a 
compound with a shorter silicon chain, i.e., (n) smaller than 10. In 
addition, the two compounds used in Comparative Examples, both of which 
did not fall in the group defined in the aforementioned formula (2), were 
found poor in the foaming capability. 
Example 13 
##STR25## 
A solution of 5.4 g of phosphorus oxychloride dissolved in 10 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50.0 g of side chain type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 3.6 g of triethylamine dissolved in 
40 g of tetrahydrofuran was added dropwise over 20 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 7.1 g of sodium 
hydroxide dissolved in 15 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 70 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
51 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to silicone oils commonly used in cosmetic compositions. It 
also exhibited excellent compatibility with polar solvents such as water, 
lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 8.0 .sup.1 H-NMR(CDCl.sub.3); 
.delta.(ppm) 0.0 (CH.sub.3 --Si--O), 0.4 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.5 --CH.sub.2 --CH.sub.2 --O--P), 1.5 (O--CH.sub.2 
--CH.sub.2), (--CH.sub.2 --CH.sub.2 --O--P), 3.4 (--O--CH.sub.2), 4.0 
(--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, Si--C 1265 cm.sup.-1, 
800 cm.sup.-1. 
Example 14 
##STR26## 
A solution of 7.9 g of phosphorus oxychloride dissolved in 15 g of 
tetrahydrofuran was cooled to -30.degree. C. To this solution, a solution 
of 50.0 g of both-end type alcohol-modified dimethylpolysiloxane 
synthesized by a known method (Japanese Patent Laid-open No. 195389/1987), 
represented by the above formula, and 5.2 g of triethylamine dissolved in 
40 g of tetrahydrofuran was added dropwise over 20 minutes. The mixture 
was left for aging for 4 hours, while maintaining the temperature of the 
reaction system below -20.degree. C. Then, a solution of 10.3 g of sodium 
hydroxide dissolved in 20 g of ion-exchanged water was added dropwise to 
the reaction mixture over 20 minutes. The mixture was continuously stirred 
for 12 hours at 0.degree. C. and the reaction was completed. The reaction 
product was extracted from the reaction mixture by adding 70 g of 
ion-exchanged water and a mixed solvent of ether and ethanol. The organic 
layer was washed with ion-exchanged water, followed by removal of the 
water layer. The solvent was evaporated under reduced pressure to obtain 
52 g of phosphate-modified dimethylpolysiloxane of the present invention. 
This phosphate-modified dimethylpolysiloxane exhibited a stable emulsifying 
capability, irrespective of temperatures within the range of 0.degree. to 
50.degree. C., to the silicone oils commonly used in cosmetic 
compositions. It also exhibited excellent compatibility with polar 
solvents such as water, lower alcohols, and the like. 
.sup.31 P-NMR(CDCl.sub.3); .delta.(ppm) 8.0 .sup.1 H-NMR(CDCl.sub.3); 
.delta.(ppm) -0.1 (CH.sub.3 --Si--O), 0.4 (Si--CH.sub.2), 1.2 (--CH.sub.2 
--(CH.sub.2).sub.5 --CH.sub.2 --CH.sub.2 --O--P), 1.5 (O--CH.sub.2 
--CH.sub.2), (--CH.sub.2 --CH.sub.2 --O--P), 3.3 (--O--CH.sub.2), 4.0 
(--CH.sub.2 --O--P), IR; Si--O--Si 1020 cm.sup.-1, Si--C 1260 cm.sup.-1, 
800 cm.sup.-1. 
FIELD OF INDUSTRIAL APPLICATION 
The phosphate-modified organo(poly)siloxanes of the present invention can 
stably emulsify silicone oils commonly used in cosmetic compositions, 
irrespective of temperatures, and exhibit excellent compatibility with 
polar components and good foaming capability. These characteristics make 
the phosphate-modified organo(poly)siloxanes of the present invention 
suitable for use as a component for toiletries, such as skin cosmetics, 
skin detergents, hair cosmetics, hair detergents, and the like. In 
addition, according to the process of the present invention, phosphates or 
the salts thereof can be easily introduced to the silicon atoms at any 
desired position of organo(poly)siloxanes to obtain phosphate-modified 
organo(poly)siloxanes.