JP3202762B2 - Novel phosphobetaine and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphobetaine useful as a base for hair and skin cosmetics, a detergent, an emulsifier, a conditioning agent and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Alkyl sulfates, polyoxyethylene alkyl sulfates, alkylbenzene sulfonates and the like have hitherto been widely used as emulsifiers and detergents for hair and skin cosmetics. However, since many of them are relatively irritating to the skin, in recent years, cleaners and emulsifiers having a less irritating effect on the skin, such as alkyl phosphates and acylated amino acid salts, have been used. .

[0003]

By the way, recently, with the diversification of consumer needs and the trend toward higher quality, in addition to the above-mentioned low irritation to the skin, there are also conditioning effects such as giving a good feeling to the skin and hair. There is a need for skin and hair cosmetics. Therefore, there has been a demand for the development of a compound which has no irritation, has an excellent conditioning effect, and can be used by being incorporated into skin and hair cosmetics.

[0004]

Under such circumstances, the present inventors have synthesized many phosphate ester compounds and studied their properties. As a result, a novel phosphobetaine represented by the following general formula (1) was obtained. The present inventors have found that they have low irritation to the skin, have excellent conditioning effects, emulsifying ability, detergency, etc., and can be blended into skin and hair cosmetics such as detergents, and have completed the present invention. That is, the present invention provides the following general formula (1)

[0005]

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And a process for producing the same.

[0007]

In the general formula (1), in Z, the alkylene glycol includes ethylene glycol, propanediol, butanediol and the like; the polyalkylene glycol includes polyethylene glycol having a condensation degree of 2 or more.

In the general formula (1), examples of the linear alkyl group represented by R ¹ , R ² or R ³ include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, and the like; examples of the branched-chain alkyl group include methylhexyl, ethylhexyl, methylheptyl, and ethyl. Examples include heptyl, methylnonyl, methylundecenyl, methylheptadecyl, hexyldecyl, octyldecyl and the like. Further, as a linear or branched alkenyl group, for example, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,
Octenyl, nonenyl, decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,
Groups such as docosenyl, tricosenyl, tetracosenyl and the like can be mentioned.

Examples of the linear or branched alkyl group substituted by a hydroxyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, Hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl, hydroxyeicosyl, hydroxyhenecosyl, hydroxycosyl, hydroxytricosyl , Hydroxytetracosyl, hydroxymethylhexyl, hydroxyethylhexyl, hydroxymethylheptyl, hydro Phenoxyethyl heptyl, hydroxymethyl nonyl, hydroxymethyl undecenyl, hydroxymethyl hepta decanyl, hydroxyhexyl decyl, it includes groups such as hydroxyethyl octyl decyl butyl. Examples of the linear or branched alkenyl group substituted with a hydroxyl group include, for example, hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl, hydroxyhexenyl, hydroxyheptenyl, hydroxyoctenyl, hydroxynonenyl, and hydroxyde. Cenyl, hydroxydodecenyl, hydroxyundecenyl, hydroxytridecenyl, hydroxytetradecenyl, hydroxypentadecenyl, hydroxyhexadecenyl, hydroxyheptadecenyl, hydroxyoctadecenyl, hydroxy Examples include nonadecenyl, hydroxyeicosenyl, hydroxyheneicosenyl, hydroxydocosenyl, hydroxytricosenyl, hydroxytetracosenyl, and the like.

The cationic group represented by M ¹ or M ² includes, for example, an alkali metal, an ammonium group, an alkylammonium group, and a trialkanolamine. Further, m is a number of 0 or more, and n is a number of 1 or more, and m is preferably 0.

The phosphobetaine (1) of the present invention is produced, for example, according to the following reaction formula.

[0013]

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Wherein Z, R ¹ , R ² , R ³ , M ¹ , M
² , m and n have the same meaning as described above, and X ⁻ represents an anion.]

That is, the phosphobetaine (1) of the present invention is produced by reacting the phosphoric ester represented by the general formula (2) with the epoxy compound represented by the general formula (3).

The phosphoric ester (2) used in this reaction
For example, phosphoric acid esters of polyglycerin having a degree of condensation of 2 or more; phosphoric acid esters of crosslinked epichlorohydrin of sugar alcohols such as sorbitol, mannitol, maltitol, and lactitol; Phosphoric acid ester of sugar crosslinked with epichlorohydrin; pentaerythritol, pentaerythritol condensate or phosphoric acid ester of crosslinked epichlorohydrin; ethylene glycol phosphate; diethylene glycol phosphate; triethylene glycol phosphate; degree of condensation: 4
Inorganic or organic salts such as the above-mentioned phosphates of polyethylene glycol; phosphates of propanediol; phosphates of butanediol can be mentioned. These phosphate esters (2) can be prepared by a known method,
For example, it can be easily produced by the method described in Japanese Patent Publication No. 50-8052.

The other starting material, epoxy compound (3), can be easily produced according to a known method, for example, by reacting a corresponding trialkylamine or trialkenylamine with epihalohydrin.

X ⁻ in the general formula (3) is not particularly limited, and examples thereof include a halogen atom and an anion such as an alkyl sulfate.

In order to carry out the present reaction, for example, the above-mentioned phosphate (2) and epoxy compound (3) are selected from polar solvents such as water, methanol, ethanol, isopropanol, dimethylformamide, dimethylsulfoxide or the like. The reaction may be carried out at a temperature of 20 to 150 ° C, preferably 40 to 90 ° C, in the presence of two or more mixed solvents, preferably in the presence of water or a mixed solvent of water and a lower alcohol. The amount of the epoxy compound (3) used in this reaction may be appropriately set according to the number of m and n of the phosphobetaine (1) of the present invention to be produced. Number of acid residues (m
+ N) is preferably 0.1 to 20 moles compared to + n).

The reaction product contains, in addition to the phosphobetaine (1) of the present invention, an inorganic salt, an unreacted epoxy compound (3) or an epoxy ring-opened product thereof as a by-product. The proportion of each component in the reaction product depends on conditions such as the types of the starting phosphoric acid ester (2) and the epoxy compound (3) used, their reaction molar ratio, the amount of the reaction solvent used, and the reaction temperature. . Therefore, depending on the purpose of use, the reaction product can be used as it is, but when a higher purity product is required, for example, a solvent separation method, a dialysis method, a recrystallization method, a partition chromatography, an ion exchange method, or the like. It may be appropriately purified and used by a known method such as chromatography and gel filtration.

[0021]

The novel phosphobetaine (1) of the present invention obtained as described above has low irritation to skin and hair,
And it has an excellent conditioning effect and can be used for shampoos, rinses, cosmetics and the like.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1 115.5 g of polyglycerin (average degree of condensation 6) was added to water 46
And dissolve 38.4 g of phosphorus oxychloride thereinto.
The mixture was added dropwise in about 2 hours while stirring at ５5 ° C.
At this time, the pH after the reaction was constantly maintained at 13.5 by adding a 10N aqueous solution of sodium hydroxide, and sodium hydroxide was added dropwise until no change in the pH was observed even after the addition of phosphorus oxychloride was completed. The reaction mixture was neutralized with a cation exchange resin (Dowex 50X4H ⁺ type), concentrated under reduced pressure, and adjusted to pH 10 by adding an aqueous solution of sodium hydroxide. Next, 120 ml of ethanol was added and the mixture was cooled. The precipitated inorganic salt was separated by filtration, and the lower layer of the filtrate separated into two layers was separated. Water was added to make 250 ml, and 1 l of methanol was further added, and the precipitated sodium salt of polyglycerin / phosphate ester was separated by filtration and dried. This crude product is again
The resulting solution was dissolved in 00 ml and reprecipitated by adding ethanol to obtain 95 g of purified polyglycerin / phosphate sodium salt.

Reference Example 2 In a reactor, polyethylene glycol (average molecular weight: 400)
80 g (0.2 mol), 94 g of 104% phosphoric acid (1.0 g
Mol) and stirred at 70 ° C. for 20 hours. After cooling to room temperature, 25 g of water was added, and then the temperature was raised to 60 ° C.
Stirring was performed for 0 hours. Return to room temperature, add 350 g of water,
177 g (0.87 mol) of magnesium chloride under ice-water cooling
Was dissolved in 200 g of water, and the pH of the system was further adjusted.
22% ammonia water was added until the pH became 8. The generated white salt was separated by filtration, and the obtained filtrate was cooled with ice water under cooling with a cation exchange resin (DOWEX manufactured by Dow Chemical Company, DOWEX (50W-X)).
8)) until the pH reached 0.5. The amount of the phosphoric acid monoester was measured with a potentiometric titrator (AT-118, manufactured by Kyoto Electronics Co., Ltd.) (0.2 mol), 27 g of 30% sodium hydroxide (0.2 mol) was added, and the solvent was distilled off under reduced pressure.
83.1 g of polyethylene glycol phosphate sodium salt as a white solid was obtained.

[0025]

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Mass spectrometry (FAB ionization method) M / Z 517 (M + H) ⁺ (M = C ₁₈ H ₃₈ O ₁₃ PNa)

Example 1 Polyglycerin (average degree of condensation: 6) / phosphate sodium salt synthesized according to Reference Example 1 in a reactor
2 g (0.050 mol) and 300 g of water were added and heated to 60 ° C. Next, a solution of 18 g (0.12 mol) of glycidyltrimethylammonium chloride dissolved in 50 g of ion-exchanged water was added dropwise over 1 hour while maintaining the reaction system at 60 ° C. Thereafter, the reaction was maintained at 60 ° C. for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by ion exchange chromatography (ion exchange resin; AG501-X8 manufactured by BIO-RAD) to obtain polyglycerin -｛(2-hydroxy -3-N,
14.73 g of ( N, N-trimethylammonio) propyl} phosphate was obtained (isolation yield: 45%). ¹ H-NMR (D ₂ O); (FIG. 3) δ (ppm) 3.14 (S, 9H, a ), 4.39 (broad, 1H, c ), 3.34 to 4.04 (m, 34H, b )

[0028]

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Example 2 Polyglycerin (average degree of condensation: 6) / phosphate sodium salt synthesized according to Reference Example 1 in a reactor
3 g (0.075 mol) and 400 g of water were added and heated to 60 ° C. Next, 27 g of glycidyl dimethyl lauryl ammonium chloride (0.
18 mol) in 75 g of ion-exchanged water was added dropwise over 1 hour. Thereafter, the reaction was maintained at 60 ° C. for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure,
The obtained crude product is subjected to ion exchange chromatography (ion exchange resin; AG501-X manufactured by BIO-RAD).
8) and purified with polyglycerol- {(2-hydroxy
(S-3-N, N-dimethyl-N-lauryl ammonium)
33.5 g of propyl diphosphate was obtained (isolation yield 5
5%). _{^{1 H-NMR (D 2 O}} ); δ (ppm) 0.86 (t, 3H, a), 1.29 (b, 18H, b), 1.75 (b, 2H, c), 3.27~4.09 (broad, m, 36H , d ), 3.12 (s, 6H, e ), 4.38
(b, 1H, f )

[0030]

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Example 3 A reactor was charged with 52.3 g (0.12 mol of phosphoric acid groups) of polyethylene glycol phosphate sodium salt and 400 g of water according to Reference Example 2 and heated to 60 ° C.
Then, while maintaining the reaction system at 60 ° C., 36 g (0.24 mol) of glycidyltrimethylammonium chloride was added to 2 parts.
A solution dissolved in 00 g of water was added dropwise over 2 hours. Thereafter, the reaction was carried out at 60 ° C. for 15 hours, and it was confirmed by a potentiometric titration value (AT-118, manufactured by Kyoto Electronics Co., Ltd.) that no phosphoric acid monoester remained. After completion of the reaction, the solvent was distilled off under reduced pressure, and the solution was concentrated to 400 ml. This solution was purified by ion-exchange chromatography (ion-exchange resin; AG501-X8 manufactured by BIO-RAD), the solvent was removed by lyophilization, and pure polyethylene glycol- {(2-hydroxy-3-) as a white powder was obtained.
26.5 g of N, N, N-trimethylammonio) propyl diphosphate was obtained (isolation yield: 41.7%).

[0032]

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Mass spectrometry (FAB ionization method) M / Z 609 (M + H) ⁺ (M = C ₂₄ H ₅₁ O ₁₄ NP)

Example 4 A reactor was charged with 52.3 g (0.12 mol of phosphoric acid groups) of polyethylene glycol phosphate sodium salt synthesized according to Reference Example 2 and 400 g of water, and heated to 60 ° C. Then, a solution of 87.8 g (0.24 mol) of glycidyldimethyldodecylammonium chloride dissolved in 200 g of a 30% aqueous ethanol solution was added dropwise over 3 hours while maintaining the temperature at 60 ° C. Thereafter, the reaction was carried out at 60 ° C. for 20 hours, and a potential difference measuring device (AT-ATK, manufactured by Kyoto Electronics Co., Ltd.) was used.
118), it was confirmed that no phosphoric acid monoester remained. After completion of the reaction, the solvent was distilled off under reduced pressure.
It was concentrated to 0 ml. This solution was subjected to ion exchange chromatography (ion exchange resin; AG5 manufactured by BIO-RAD).
01-X8), the solvent was removed by lyophilization and pure polyethylene glycol -− (2
-Hydroxy-3-N, N-dimethyl-N-dodecylua
39 g of ( monmonio) propyl diphosphate was obtained (47.4% isolated yield).

[0035]

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Mass spectrometry (FAB ionization method) M / Z 763 (M + H) ⁺ (M = C ₃₅ H ₇₃ O ₁₄ NP)

[Brief description of the drawings]

FIG. 1. ³¹ P of polyethylene glycol phosphate
It is a figure which shows -NMR (decoupling) spectrum.

FIG. 2: ³¹ P of polyethylene glycol phosphate
It is a figure which shows -NMR (no decoupling) spectrum.

FIG. 3. Polyglycerin- {(2-hydroxy-3-
It is a figure which shows the < ¹ > H-NMR spectrum of ( N, N, N-trimethylammonio) propyl} phosphate.

FIG. 4. Polyethylene glycol- ｛(2-hydroxy
-3-N, N, N-trimethylammonio) propyl}
It is a figure which shows the < ¹ > H-NMR spectrum of a phosphate.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-184092 (JP, A) JP-A-4-182492 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 9/09 C07F 9/10 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The following general formula (1): A phosphobetaine represented by 2. The phosphobetaine according to claim 1, wherein m is 0 in the general formula (1). 3. A compound of the general formula (2) The phosphoric ester represented by the general formula (3) Wherein R ¹ , R ² and R ³ are the same or different and each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms which may have a hydrogen group; X ^- is characterized by reacting an epoxy compound represented by represents an anion] has the general formula (1) embedded image [Wherein, Z, R ¹ , R ² , R ³ , M ¹ , M ² , m and n have the same meanings as described above].