JPH0625421A - Phosphoric ester having organosiloxane group and its production - Google Patents

Abstract

PURPOSE:To obtain a phosphoric ester which is capable of stably emulsifying a silicone oil and is excellent in compatibility with other ionic ingredients by reacting specific compounds. CONSTITUTION:This phosphoric ester is represented by the formula (Q)pB {wherein B is a residue of an organosiloxane having an Si-bonded alkyl group and an Si-bonded group (a) represented by formula I which residue has been formed by removing the group (a), formula I representing formulae II and III [where R<3> is H, a 1-36C (fluoro)alkyl, or an alkenyl and D is a 1-22C alkyl]; Q is a group which is represented by formula IV or I and bonded to the Si atom to which the group (a) was bonded, provided that at least one of the p X groups of Q is represented by formula IV (where A is H or a specific group; formula V representing formulae VI and VII); and (P) is a number of 1 or larger and up to the total number of the groups (a)}.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphoric acid ester having an organosiloxane group and a method for producing the same, and more particularly to a phosphoric acid ester having an organosiloxane group useful as a material for perfume cosmetics and a method for producing the same.

[0002]

2. Description of the Related Art Silicone has a high bond energy in the main chain and has high heat resistance, acid resistance, and
It is known that it is excellent in weather resistance and has low surface tension and has releasability, lubricity, water repellency and the like. Furthermore, since the intermolecular force is small, the main chain is flexible and gas permeability is high,
In addition, it is characterized by low toxicity and low irritation because it is composed of physiologically inactive atoms. For these reasons, silicones are used in a wide range of fields such as electricity, electronics, automobiles, machines, medical care, cosmetics, foods, fibers, paper, pulp and building materials.

Particularly in the fields of cosmetics and cosmetics,
Dimethylpolysiloxane and cyclic silicone, which are not sticky and have a high level of safety, are actively used as a finishing agent for hair and as an oil component in cosmetics. Further, recently, researches on the application of silicone to the field of perfume and cosmetics have been very active, and the applications of silicone are also diverse. Therefore, in addition to the characteristics of conventional silicones, new requirements such as improved compatibility with other organic substances, improved chemical resistance, improved water solubility, improved lubricity, and the addition of chemically reactive groups to silicone Characteristics are born.

Therefore, in order to satisfy the above-mentioned required characteristics, modified silicones in which various functional groups are introduced into silicone have been developed. As modified silicones, modified silicones such as amino modified, epoxy modified, carboxylic acid modified, mercapto modified, alcohol modified, polyether modified, fluoroalkyl modified, alkyl modified, ester modified, and alkoxy modified have been developed. Such modified silicones have been used as a material for perfumed cosmetics in order to make the best use of their respective characteristics, but satisfactory ones have not yet been obtained.

For example, a polyether-modified silicone in which a silicone has a hydrophilic group to improve the water solubility can control the hydrophilic group of the silicone by the amount of the polyether bond, and is used as a raw material for cosmetics. And cyclic silicone can be emulsified, and because they are nonionic, they have good compatibility with ionic components. However, since the nonionic surfactant having a polyether bond has a cloud point phenomenon, which is a characteristic of the nonionic surfactant, the temperature stability of the emulsification system is poor and it is not suitable for an actual compounding system.

[0006]

Under these circumstances, the inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, introduced a phosphoric acid group into an organosiloxane to form a betaine structure, and further through a phosphoric acid group. By introducing a group such as alkyl and alkenyl, it was found that a phosphate ester having high emulsification performance, temperature stability of the emulsion system and good compatibility with other ionic components can be obtained, and the present invention is completed. Came to.

That is, the present invention provides a phosphoric acid ester represented by the following general formula (1).

[0008]

[Chemical 10]

[0009]

[Chemical 11]

Further, the present invention has the following general formula (2):

[0011]

[Chemical 12]

A phosphoric acid ester represented by the following general formula (3)

[0013]

[Chemical 13]

The present invention provides a method for producing a phosphoric acid ester represented by the above general formula (1) by reacting with an amino-modified organosiloxane represented by

In the above general formula (1), the group R ^{1 represented} by A ¹
_{- [(OCH 2) l -CH} (OH) CH 2] m - (OR 2) n
Examples of-(wherein, 1, m, n, R ¹ and R ² have the same meanings as described above) include the groups shown below.

That is, when R ¹ is a linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms which may be substituted by one or more F atoms, and when m = 0 and n = 0, examples are: Linear or branched octyl group, decyl group, dodecyl group, octadecyl group, tetracosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-tetradecyl octadecyl group, monomethyl branched isostearyl group , Octenyl group, decenyl group, dodecenyl group, hexadecenyl group, octadecenyl group, tetracocenyl group, triacontenyl group, tridecafluorooctyl group, heptadecafluorodecyl group, heneicosafluorododecyl group, pentacosafluorotetradecyl group, Nonacosafluorohexadecyl group, triacontafluoroocta Syl group, 2-pentafluoroethyl pentafluorohexyl group, 2-tridecafluorohexyl tridecafluorodecyl group, 2-heptadecafluorooctyl heptadecafluorododecyl group, 2-heneicosafluorodecyl heneicosafluorotetradecyl group Groups and the like;

R ¹ is a phenyl group substituted by a linear or branched alkyl group having 1 to 15 carbon atoms, m = 0 and n = 0
In the case of, examples include octylphenyl group, nonylphenyl group and the like;

When R ¹ is a linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms which may be substituted by one or more F atoms, and m = 0 and 0 <n ≦ 30 Is polyoxyethylene (3 mol) dodecyl ether group, polyoxypropylene (3 mol) decyl ether group, polyoxyethylene (8 mol) polyoxypropylene (3 mol) dodecyl ether group, polyoxyethylene (4 mol) octade Cenyl ether group, polyoxyethylene (3 mol) tridecafluorooctyl ether group,
Polyoxyethylene (5 mol) heptadecafluorodecyl ether group, polyoxyethylene (3 mol) heneicosafluorododecyl ether group, polyoxyethylene (5 mol) 2-tridecafluorohexyl tridecafluorodecyl ether group, etc. And polyoxyalkylene alkyl ether groups or polyoxyalkylene alkenyl ether groups;

R ¹ is a straight-chain alkyl group having 1 to 36 carbon atoms which may be substituted by one or more F atoms, and 2-hydroxydodecyl is an example when l = 0, m = 1 and n = 0. Group, 2-hydroxyhexadecyl group, 2-hydroxytridecafluorononyl group, 2-hydroxypentadecafluorodecyl group, 2-hydroxyalkyl group such as 2-hydroxyheptadecafluoroundecyl group, and the like;

R ¹ is an alkyl group or an alkenyl group which may be substituted by one or more F atoms, l = 1, m = 1 and n
In the case of = 0, examples are 2-hydroxy-3-dodecyloxypropyl group, 2-hydroxy-3-monomethyl-branched isostearyloxypropyl group, 2-hydroxy-
3-octadecenyloxypropyl group, 2-hydroxy-3-heptadecafluorodecyloxypropyl group, 2
2-hydroxy-3-alkyloxyl group such as -hydroxy-3- (2-heptafluoroethylpentafluorohexyloxy) propyl group or 2-hydroxy-3-
Examples thereof include an alkenyloxypropyl group.

The phosphoric acid ester (1) of the present invention is represented by the following general formula (1-1), (1-2), (1-3) or (1-).
Those represented by 4) are preferable.

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16]

[0025]

[Chemical 17]

The phosphoric acid ester residue in the phosphoric acid ester (1) of the present invention may be bonded to any position of the organosiloxane structure.
As shown in (1-4), those linked to the side chain, both ends or side ends are preferable.

The phosphoric acid ester (1) of the present invention is produced, for example, according to the following reaction.

[0028]

[Chemical 18]

In this reaction, the phosphoric acid ester (2) used as a starting material is, for example, JP-A-62-12319.
It is produced by the method described in Japanese Patent Publication No. 1 and Japanese Patent Publication No. 59-4478. According to the method described in JP-B-59-4478, a compound in which A is a hydrogen atom in the general formula (2) can be obtained, but the compound is derived from a ring-opened product of epihalohydrin or derived from epihalohydrin depending on the method. The by-product and unreacted phosphate are included. In the method for producing a phosphoric acid ester of the present invention, when a phosphoric acid ester (2) containing a ring-opened product of epihalohydrin or a by-product derived from epihalohydrin is reacted with an amino-modified organosiloxane (3), ring-opening of epihalohydrin is performed. Substance or a by-product derived from epihalohydrin reacts with the amino-modified organosiloxane (3) to form a by-product, which makes it extremely difficult to remove it from the reaction-terminated product. Therefore, the ring-opened product of epihalohydrin and the impurity which is a by-product derived from epihalohydrin must be removed before reacting the phosphate ester (2) with the amino-modified organosiloxane (3).

On the other hand, unreacted phosphate is not always reacted with the amino-modified organosiloxane (3), and since it is water-soluble, it can be easily removed from the reaction-finished product by an operation such as washing with water. It need not be removed before reacting with the organosiloxane (3).

The ring-opened product of epihalohydrin and the by-product derived from epihalohydrin are removed by reacting a suitable phosphate such as monoalkali metal phosphate with epihalohydrin in the presence of alkali, and then terminating the reaction product with ethanol. , Propanol, 2-propanol, acetone, etc., the objective phosphate ester represented by the formula (2) (when A is a hydrogen atom in the formula) and unreacted phosphate precipitates. This is possible by filtering these and further washing with the above-mentioned solvent.

The amino-modified organosiloxane (3) which is the other raw material is, for example, a reaction of the following epoxy-modified organosiloxane (4) or (5) with an amine compound (6) (US Pat. No. 3,389,160). It is manufactured by Gazette).

[0033]

[Chemical 19]

(In the formula, B, D, R ³ and p have the same meanings as described above.) As the above epoxy-modified organosiloxane (4) or (5),

[0035]

[Chemical 20]

Side chain type, both-end type, one-end type, etc.
Examples thereof include polysiloxanes called T structure type, but not limited to these, and polyether modified groups other than epoxy modified groups, alcohol modified groups, alkyl modified groups and the like can be included in the same molecule. Also included are those that include.

As such an epoxy-modified organosiloxane, a commercially available product can be used as it is.

Commercial products include, for example, B2405 and PX.
103, PS404, PS920, PS922 (all manufactured by Chisso Corporation); KF100T, KF101, KF10
2, KF103, X-22-173B, KF105, X
-22-163A, X-22-163B, X-22-1
63C, X-22-169AS, X-22-169B,
X-22-173B (manufactured by Shin-Etsu Chemical Co., Ltd.); TSL
9906, TSL9905, TSL9946, TSL9
986, TSF4730, XF42-802, XF42
-803, XF-3965, XF42-A2454, X
F42-A2479, XF42-A2262, XF42
-A2263 (all manufactured by Toshiba Silicone Co., Ltd.) and the like.

Specific examples of the amino-modified organosiloxane (3) thus obtained are represented by the following formulas (7) to (1)
Examples include those represented by 2).

[0040]

[Chemical 21]

[0041]

[Chemical formula 22]

(In the formula, R ¹⁷ represents a methyl group, a methoxy group or an ethoxy group, and a to l each represent a degree of polymerization.)

The ratio of the amount of the phosphoric acid ester (2) to the amino-modified organosiloxane (3) used in the above reaction is not particularly limited, but may be the same as the amino group equivalent of the amino-modified organosiloxane (3). On the other hand, the halogen content of the phosphoric acid ester (2) is preferably equimolar or more, and preferably 2 to 10 times equivalent.

In order to carry out the above reaction, first, an amino-modified organosiloxane (3) is added to the compound in an amount of from 1 to 10% by weight.
10 times weight, more preferably 2 times to 5 times weight of ethanol, propanol, 2-propanol, toluene,
It is dissolved in a solvent capable of dissolving the compound such as acetone.
The type of solvent is not limited as long as it is a solvent that can dissolve the amino-modified organosiloxane (3), but a solvent that is miscible with a solvent that can dissolve the phosphate ester (2) described below is preferable.

On the other hand, as the solvent for the phosphoric acid ester (2), a solvent capable of dissolving the phosphoric acid ester (2), for example, water,
Methanol, ethanol, propanol, 2-propanol, acetone, etc. are mentioned. Phosphate ester (2)
Is dissolved in an equivalent weight to 10 times, preferably 2 times to 5 times the weight of the compound.

The reaction is started by dropping a solution of the phosphoric acid ester (2) into the solution of the amino-modified organosiloxane (3), and the solution of the phosphoric acid ester (2) is added with the solution of the amino-modified organosiloxane (3). The solution may be added dropwise. Alternatively, (2) may be added to an equimolar aqueous alkali solution such as sodium hydroxide to form an epoxy body (13), and then added dropwise to (3) or its hydrochloride solution and mixed.

[0047]

[Chemical formula 23]

The dropping temperature is 30 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C. The dropping method may be batch dropping, divided dropping, or slow dropping over a certain period of time. After the dropping is completed, the above temperature is maintained and aging is performed.
The end point of the reaction can be determined by measuring the amino group content in the reaction mixture by a method such as titration and determining the reaction rate. When the desired reaction rate can be achieved, the reaction may be terminated, but when the reaction rate is low, the unreacted amino-modified organosiloxane (3) that remains and the desired phosphoric acid ester of the present invention (1 Since it is extremely difficult to separate the above), the reaction rate of the amino group is preferably as high as possible.

After completion of the reaction, water and a solvent which is difficult to mix with are added to the product, and the mixture is stirred or shaken, and then allowed to stand, and layers are separated,
Then, by removing the aqueous layer, it is possible to remove the excess phosphoric acid ester (2) and the inorganic salt produced as a by-product.

Solvents that are not easily miscible with water include butanol, toluene, chloroform, dichloromethane, hexane, ethyl ether and the like. When it is difficult to separate layers or when emulsifying, ethanol, 2-
A demulsifier such as propanol may be added.

Further, the solvent is distilled off from the reaction product, and the residue is washed with water to remove excess phosphoric acid ester (2) and inorganic salt produced as a by-product, or butanol, toluene, chloroform, dichloromethane, hexane. Excess phosphoric acid ester (2) precipitated as an insoluble matter by dissolving the residue with a solvent such as ethyl ether and the inorganic salt produced as a by-product may be filtered off. In addition, excess phosphoric acid ester (2) is passed through the mixed bed resin of anion exchange resin and cation exchange resin through the reaction product.
It is also possible to remove by-produced inorganic salts. In addition, these purification methods may be combined if necessary.

[0052]

The phosphoric acid ester having an organosiloxane group of the present invention can stably emulsify silicone oil irrespective of temperature and has good compatibility with other ionic components. Skin cleanser, hair cosmetics,
It is extremely useful as a perfume cosmetic material such as a hair cleanser.

Further, according to the production method of the present invention, various hydrocarbon residues, fluoro residues and the like can be easily introduced, so that it is possible to produce a phosphoric acid ester having an organosiloxane group according to the purpose. .

[0054]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Reference Example 1 506.4 g (3.2 sodium monohydrogen phosphate dihydrate)
5 mol) in 1345 g of deionized water,
16.7 g of 6% sodium hydroxide was added and the temperature was raised to 80 ° C. 240.2 g of epichlorohydrin in this aqueous solution
(2.60 mol) was added dropwise over 5 hours and aged for 8 hours. The reaction completion product was put into 5,000 g of acetone and -5.
After cooling to ℃, the deposited precipitate was separated by filtration, washed with acetone and dried to give a mixture of 3-chloro-2-hydroxypropylphosphoric acid sodium salt and monosodium hydrogenphosphate 5
12 g was obtained. The content of sodium 3-chloro-2-hydroxypropylphosphate of this product was 33.5% by the determination of chlorine.

Example 1 50% dimethylamine aqueous solution (Katayama Chemical Co., Ltd.) 20
0 g was dissolved in 250 g of ethanol and further side chain type epoxy modified organosiloxane (Yoshiba Silicone Co., Ltd. Y
207 g of F3965 epoxy equivalent 931) at room temperature
Drop over time. Then, the temperature was raised to 80 ° C. and aging was carried out for 9 hours to obtain a reaction product having a two-layer structure. Subsequently, ethanol, water, and excess dimethylamine were removed by an evaporator to obtain a tertiary amine-containing organosiloxane as a brown liquid. The amine value was 57.7 KOHmg / g (theoretical value 57.
It was 5).

31.7 g of the tertiary amine-containing organosiloxane was dissolved in 90 g of isopropyl alcohol to prepare 8
The temperature was raised to 0 ° C. Dodecyl-3-chloro-2 was added to this solution.
A solution of 49.6 g of sodium hydroxypropylphosphate in 120 g of ion-exchanged water was added dropwise over 3 hours. Then, it was aged at 80 ° C. for 30 hours. At this time, the reaction rate of the amino group was 100%. After the aging, the solvent was distilled off under reduced pressure, and the resulting residue was mixed with butanol 50
0 g was added to remove insolubles by filtration, and 250 g of ion-exchanged water was further added to the filtrate, and the solution was passed through Bio-Rad's ion-exchange resin AG501-X8 (20-50 mesh), and the solvent was distilled off under reduced pressure. 26 g of phosphoric acid ester
Got

Elemental analysis values (calculations of the compounds obtained below
Values and measured values) ¹H-NMR spectrum
Torr (internal standard TMS, solvent CDCl₃) Is shown.

Elemental analysis value C H N P Si calculated value 41.4 8.8 1.1 2.4 24.1 measured value 40.7 8.5 1.2 2.2 23.5 The chemical formula is shown below. .

[0060]

[Chemical formula 24]

Example 2 50% dimethylamine aqueous solution (Katayama Chemical Co., Ltd.) 10
0 g was dissolved in 150 g of ethanol, and both ends type epoxy modified organosiloxane (manufactured by Toshiba Silicone Co., Ltd.)
XF42-A2262 epoxy equivalent 3300) 333g
Is added dropwise at room temperature over 1 hour. Then, the temperature was raised to 80 ° C. and aging was carried out for 12 hours to obtain a reaction product having a two-layer structure.
Subsequently, ethanol, water, and excess dimethylamine were removed by an evaporator to obtain a tertiary amine-containing organosiloxane as a brown liquid. Amine value is 16.7 KOHmg / g
(Theoretical value 16.8).

40 g of the above-mentioned tertiary amine-containing organosiloxane was dissolved in 120 g of isopropyl alcohol to obtain 80
The temperature was raised to ° C. Dodecyl-3-chloro-2-to this solution
A solution prepared by dissolving 18.1 g of hydroxypropylphosphoric acid sodium salt in 50 g of ion-exchanged water was added dropwise over 2 hours. Then, it was aged at 80 ° C. for 30 hours. At this time, the reaction rate of the amino group was 100%. After completion of the aging, the solvent was distilled off under reduced pressure, butanol (500 g) was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was further added to the filtrate to prepare a solution of ion exchange resin AG501-X8 manufactured by Bio-Rad. (20-50 mesh)
The solvent was distilled off under reduced pressure to obtain 30 g of a desired phosphoric acid ester.

Elemental analysis values (calculations of the compounds obtained below
Value and measured value) are shown in FIG. ¹H-NMR spectrum
Torr (internal standard TMS, solvent CDCl₃) Is shown.

Elemental analysis value C H N P Si calculated value 35.8 8.3 0.4 0.8 33.0 measured value 34.7 8.0 0.5 0.7 33.2 Chemical formula is shown below. .

[0065]

[Chemical 25]

Example 3 50% dimethylamine aqueous solution (Katayama Chemical Co., Ltd.) 20
0 g was dissolved in 250 g of ethanol, and further both ends type epoxy modified organosiloxane (X- manufactured by Shin-Etsu Chemical Co., Ltd.).
211-g of 22-163A epoxy equivalent 950) is dripped at room temperature over 1 hour. Then, raise the temperature to 80 ° C and
Aging was carried out for 0 hour to obtain a reaction product having a two-layer structure. Subsequently, ethanol, water, and excess dimethylamine were removed by an evaporator to obtain a tertiary amine-containing organosiloxane as a brown liquid. The amine value is 56.0 KOHmg / g (theoretical value 5
It was 6.4).

40 g of the tertiary amine-containing organosiloxane was dissolved in 120 g of isopropyl alcohol to obtain 80
The temperature was raised to ° C. Dodecyl-3-chloro-2-to this solution
A solution prepared by dissolving 60.7 g of sodium hydroxypropylphosphate in 140 g of ion-exchanged water was added dropwise over 5 hours. Then, it was aged at 80 ° C. for 20 hours. At this time, the reaction rate of the amino group was 100%. After aging,
The solvent was distilled off under reduced pressure, and 500 g of butanol was added to the obtained residue.
Was added to remove insoluble matter by filtration, and a solution obtained by adding 250 g of ion-exchanged water to the filtrate was passed through Bio-Rad ion exchange resin AG501-X8 (20-50 mesh), and the solvent was distilled off under reduced pressure. 28 g of phosphoric acid ester was obtained.

The elemental analysis values (calculated values and measured values) of the obtained compound are shown. Elemental analysis value C H N P Si calculated value 41.7 8.8 1.1 2.3 24.3 measured value 41.0 8.6 0.9 2.1 23.8 The chemical formula is shown.

[0069]

[Chemical formula 26]

Example 4 50% dimethylamine aqueous solution (Katayama Chemical Co., Ltd.) 10
0 g was dissolved in 150 g of ethanol, and both ends type epoxy-modified organosiloxane (X- manufactured by Shin-Etsu Chemical Co., Ltd.).
184 g of 22-169B epoxy equivalent 1670) is added dropwise at room temperature over 1 hour. Then, the temperature was raised to 80 ° C. and aging was carried out for 12 hours to obtain a reaction product having a two-layer structure. Subsequently, ethanol, water, and excess dimethylamine were removed by an evaporator to obtain a tertiary amine-containing organosiloxane as a brown liquid. The amine value was 32.3 KOHmg / g (theoretical value 32.7).

30 g of the above-mentioned tertiary amine-containing organosiloxane was dissolved in 90 g of isopropyl alcohol and dissolved at 80 ° C.
The temperature was raised to. A solution prepared by dissolving 26.3 g of sodium dodecyl-3-chloro-2-hydroxypropylphosphate in 60 g of ion-exchanged water was added dropwise to the solution over 3 hours. Then, it was aged at 80 ° C. for 32 hours. At this time, the reaction rate of the amino group was 100%. After completion of the aging, the solvent was distilled off under reduced pressure, butanol (500 g) was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was further added to the filtrate to prepare a solution of ion exchange resin AG501-X8 manufactured by Bio-Rad. (20-50 mesh), and the solvent was distilled off under reduced pressure to obtain 14 g of a desired phosphoric ester.

The elemental analysis values (calculated values and measured values) of the obtained compound are shown. Elemental analysis value C H N P Si calculated value 39.3 8.6 0.7 1.5 29.0 actual measured value 38.8 8.4 0.8 1.3 29.1 The chemical formula is shown.

[0073]

[Chemical 27]

Example 5 50% dimethylamine aqueous solution (Katayama Chemical Co., Ltd.) 10
0 g was dissolved in 150 g of ethanol, and one-terminal epoxy-modified organosiloxane (X- manufactured by Shin-Etsu Chemical Co., Ltd.) was further dissolved.
274 g of 22-173B epoxy equivalent 2490) is added dropwise at room temperature over 1 hour. Then, the temperature was raised to 80 ° C. and aging was carried out for 10 hours to obtain a reaction product having a two-layer structure. Subsequently, ethanol, water, and excess dimethylamine were removed by an evaporator to obtain a tertiary amine-containing organosiloxane as a brown liquid. The amine value was 22.0 KOHmg / g (theoretical value 22.1).

12 g of sodium dodecyl-3-chloro-2-hydroxypropylphosphate was dissolved in 250 ml of ethanol and 50 ml of ion-exchanged water, 16 ml of 2N sodium hydroxide aqueous solution was added, and the mixture was mixed for 30 minutes under water cooling. To this solution was added the above-mentioned tertiary amine-containing organosiloxane 40.
g was dissolved in 200 ml of ethanol, 2.5 ml of 6N hydrochloric acid was added to the solution to give a tertiary amine hydrochloride, and the mixture was aged at 50 ° C. for 5 hours. At this time, the reaction rate of the amino group is 100.
%Met. After completion of the aging, the reaction mixture was passed through an ion exchange resin (20-50 mesh) ("AG501-X8" manufactured by Bio-Rad), and the solvent was distilled off under reduced pressure to obtain 21 g of a desired phosphate ester.

The elemental analysis values (calculated values and measured values) of the obtained compound are shown. Elemental analysis value C H N P Si calculated value 36.7 8.5 0.5 1.1 31.8 measured value 36.0 8.3 0.6 0.9 30.8 The chemical formula is shown.

[0077]

[Chemical 28]

Example 6 40 g of the tertiary amine-containing organosiloxane obtained in Example 3 was dissolved in 120 g of isopropyl alcohol.
The temperature was raised to 0 ° C. 69.7 g of hexadecyl-3-chloro-2-hydroxypropylphosphoric acid sodium salt was added to this solution.
What was melt | dissolved in 160 g of ion-exchanged water was dripped over 3 hours. Then, it was aged at 80 ° C. for 27 hours. At this time, the reaction rate of the amino group was 100%. After the aging, the solvent was distilled off under reduced pressure, and the resulting residue was mixed with butanol 50
0 g was added to remove insolubles by filtration, and 250 g of ion-exchanged water was further added to the filtrate, and the solution was passed through Bio-Rad's ion-exchange resin AG501-X8 (20-50 mesh), and the solvent was distilled off under reduced pressure. 27 g of phosphoric acid ester
Got

The elemental analysis values (calculated values and measured values) of the obtained compound are shown. Elemental analysis value C H N P Si calculated value 43.5 9.0 1.0 1.0 2.2 23.4 measured value 42.5 8.3 0.8 1.9 24.0 A chemical formula is shown.

[0080]

[Chemical 29]

Example 7 40 g of the tertiary amine-containing organosiloxane obtained in Example 3 was dissolved in 120 g of isopropyl alcohol.
The temperature was raised to 0 ° C. 3-Chloro-2-hydroxypropylphosphoric acid sodium salt 10 obtained in Reference Example 1 was added to this solution.
Dissolve 1.1 g in 240 g of ion-exchanged water
It dripped over time. Then, it was aged at 80 ° C. for 18 hours. At this time, the reaction rate of the amino group was 100%.
After completion of the aging, the solvent was distilled off under reduced pressure, butanol (500 g) was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was further added to the filtrate to prepare a solution of ion exchange resin AG501-X8 manufactured by Bio-Rad. After passing through (20-50 mesh), the solvent was distilled off under reduced pressure to obtain 21 g of a desired phosphate ester.

The elemental analysis values (calculated values and measured values) of the obtained compound are shown. Elemental analysis value C H N P Si calculated value 35.3 8.0 1.2 2.7 27.9 measured value 35.3 8.1 1.3 2.5 28.0 The chemical formula is shown.

[0083]

[Chemical 30]

[Brief description of drawings]

FIG. 1 ¹ H—N of the phosphoric acid ester obtained in Example 1.
An MR spectrum is shown.

FIG. 2 ¹ H—N of phosphoric acid ester obtained in Example 2
An MR spectrum is shown.

Claims (6)

[Claims] 1. A phosphoric acid ester represented by the following general formula (1). [Chemical 1] [Chemical 2] 2. The phosphoric acid ester according to claim 1, which is represented by the following general formula (1-1). [Chemical 3] 3. The phosphoric acid ester according to claim 1, which is represented by the following general formula (1-2). [Chemical 4] 4. The phosphoric acid ester according to claim 1, which is represented by the following general formula (1-3). [Chemical 5] 5. The phosphoric acid ester according to claim 1, which is represented by the following general formula (1-4). [Chemical 6] 6. The following general formula (2): And a phosphoric acid ester represented by the following general formula (3): The following general formula (1) is characterized by reacting with an amino-modified organosiloxane represented by A method for producing a phosphoric acid ester having an organosiloxane group represented by: