JP3076136B2 - New carbobetaine and its production method - 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 carbobetaine compound useful as a base or a humectant for hair and skin cosmetics.

[0002]

2. Description of the Related Art Conventionally, humectants have been incorporated into shampoos, rinses, facial cleansers and various cosmetics for the purpose of imparting a moist feel to hair and skin.
Heretofore, propylene glycol, glycerin, urea, sorbitol, alkylene oxide adducts of alcohols and the like have been used as humectants. However,
These materials were not always satisfactory in terms of moisture retention, moisture absorption, moisture absorption rate, and the like, and were not satisfactory in terms of feeling such as stickiness.

On the other hand, natural polysaccharide components such as hyaluronic acid
In terms of moisturizing performance and feel, they are relatively superior to those described above. However, since the natural polysaccharide component is expensive, there is a disadvantage that its use range is limited to relatively expensive cosmetics.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a compound which is excellent in moisturizing property, has a good feel and can be produced at low cost.

[0005]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, it has been found that a compound represented by the following general formula (1) is excellent in moisturizing properties and can be produced at low cost. The present invention was found to be useful as a base for skin cosmetics and the like, as a humectant, and the like, and completed the present invention.

That is, the present invention provides the following general formula (1)

[0007]

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Wherein Z, R ¹ , R ² , A ¹ , A ² , m
And n indicate the following. Z: represents a residue obtained by removing m + n hydroxyl groups from glycerin or a glycerin condensate. A ¹ and A ² may be the same or different and represent a linear or branched alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group. R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms which may have a hydroxyl group. R ² represents a linear or branched alkyl or alkenyl group having 2 to 24 carbon atoms which may have a hydroxyl group. m, n: m is 0 or more, n is 1 or more, and m + n
Is the same as the valence of Z. ) And a method for producing the same.

The carbobetaine of the present invention is represented by the above general formula (1), wherein Z represents glycerin or a residue obtained by removing m + n hydroxyl groups from a glycerin condensate. The glycerin is condensed in a chain, linear or branched chain in the presence of an alkali catalyst, such as diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nona Polyglycerol having an average degree of condensation of 20 or less, such as glycerin, decaglycerin, dodecaglycerin, tetradecaglycerin, hexadecaglycerin, and octadecaglycerin, is preferred, and those having a degree of condensation of 10 or less are particularly preferred. Further, as the group represented by Z, a group obtained by removing one hydroxyl group from glycerin or diglycerin is particularly preferable.

In the general formula (1), A ¹ , A ²
The groups represented by may be the same or different and represent a linear or branched alkylene group having 1 to 6 carbon atoms.
¹ is particularly preferably an ethylene group, a propylene group or a 2-hydroxy-1,3-propylene group, and A ² is particularly preferably a methylene group, an ethylene group, a propylene group or a butylene group.

R ¹ in carbobetaine (1) represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, which may have a hydroxyl group, specifically, a methyl group, an ethyl group , Propyl group, butyl group, pentyl group,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl , Tricosyl group, tetracosyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, undecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl Group, heptadecenyl group, octadecenyl group, nonadecenyl group, eicosenyl group, heneicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, methylhexyl group, ethylhexyl group, methylhepti group Group, an ethyl heptyl group, methylnonyl group, methyl undecenyl group, methyl heptadecanol group, hexyldecyl group, octyldecyl group, a 2-hydroxypropyl group.

R ² represents a linear or branched alkyl or alkenyl group having 2 to 24 carbon atoms which may have a hydroxyl group. Specifically, R ² is the same as R ¹ except for a methyl group. Can be used.

The carbobetaine (1) of the present invention can be produced, for example, according to the following formula.

[0014]

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(Where Z, A ¹ , A ² , R ¹ , R ² , m
And n represent the same as described above, X represents a halogen atom,
M represents a cation. ) That is, the amino compound (2)
Is reacted with the compound (3) to obtain the betaine compound (1) of the present invention.

In this reaction, the amount of the compound (3) used is 1 to 5 equivalents, preferably 1 to 2 equivalents, based on the number of amino groups of the amino compound (2). . This reaction is carried out in the presence of an inert solvent at a temperature in the range of 20 to 120C, preferably 40 to 90C. As the inert solvent used here,
One or more mixed solvents selected from polar solvents such as water, methanol, ethanol, isopropyl alcohol, dimethylformamide, and dimethylsulfoxide are used. Among them, water alone or a mixed solvent of water and a lower alcohol is used. Is preferred. The cation of M in the formula (3) is not particularly limited, but is preferably an alkali metal ion, an ammonium ion, or an alkanol ammonium ion having 2 to 9 carbon atoms.

The reaction product obtained by the above reaction contains unreacted amino compound (2), compound (3) and other by-products in addition to the carbobetaine (1) of the present invention. It can be purified by known methods such as solvent fractionation, ion exchange chromatography, and electrodialysis.

The compound (2) which is a raw material of the present invention
Can be produced, for example, by a known method represented by the following formula.

[0019]

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(Wherein, Z, X, R ¹ , R ² , m and n are the same as described above). That is, glycerin or a glycerin condensate is reacted with epihalohydrin to give glycidyl etherified glycerin. Alternatively, a glycerin condensate (4) is obtained and reacted with a dialkylamine (5) to obtain a compound (2). The reaction between the compound (4) and the compound (5) is performed by the compound (5) / compound (4)
And the reaction temperature is preferably from room temperature to 80 ° C. At this time, the reaction may be performed without a solvent, but a lower alcohol such as methanol, ethanol, or isopropanol, or an organic solvent such as chloroform may be used. Further, the reaction proceeds even without a catalyst. On the other hand, examples of the compound (3) include sodium chloroacetate and lithium bromovalerate. In addition, the manufacturing process of the carbobetaine (1) of the present invention using glycerin as a starting material is as follows.

[0021]

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(Wherein R ¹ and R ² are as defined above)

The carbobetaine (1) of the present invention thus obtained is excellent in moisturizing properties and can be produced at low cost, so that it can be widely used in shampoos, rinses, various cosmetics and the like.

[0024]

According to the present invention, carbobetaine (1) is used for hair,
An extremely good moisturizing effect can be given to the skin, and according to the production method of the present invention, carbobetaine (1) can be produced at low cost.

[0025]

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.

Example 1 Preparation of carbobetaine (1):
36.5 g (0.31 mol) of methylhexylamine was charged into the reactor, and the mixture was stirred at room temperature for 2,3-dihydroxypropyl.
300 g (2.0 mol) of 2,3-epoxypropyl ether was added dropwise over 5 hours. After dropping, gradually raise the temperature to 50
The reaction was performed at 4 ° C. for 4 hours. While keeping the reaction system at 50 ° C,
A solution in which 54.1 g (0.47 mol) of sodium chloroacetate was dissolved in 50 g of water was added dropwise over 2 hours, followed by a reaction at 50 ° C. for 6 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, 1.3 l of ethanol was added thereto, and the ethanol-insoluble portion was removed by filtration. The obtained ethanol-soluble part was concentrated under reduced pressure, and purified by silica gel column chromatography (elution solvent: chloroform / methanol) by thin layer chromatography until a single spot was obtained.
1-carboxy-N-methyl-N-hexyl-N-
(2,6,7-trihydroxy-4-oxaheptyl)
24.9 g (yield 25%) of methaneaminium hydroxide inner salt was obtained.

[0027]

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Mass spectrometry (FAB ionization method); M / Z 322 (M + H) ⁺ (M = C ₁₅ H ₃₁ O ₆ N)

Example 2 Preparation of carbobetaine (1):
35.3 g (0.30 mol) of methylhexylamine was charged into the reactor, and polyglycerin was added at room temperature (average degree of condensation: 4).
Of epichlorohydrin (average number of moles added: 3 mol) was added dropwise at room temperature over 5 hours. After the dropwise addition, the temperature was gradually raised and the reaction was carried out at 50 ° C. for 6 hours.
While maintaining the reaction system at 50 ° C., a solution in which 63.3 g (0.55 mol) of sodium chloroacetate was dissolved in 100 g of water was added dropwise over 2 hours, followed by reaction at 50 ° C. for 6 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, 1.5 l of ethanol was added thereto, and the ethanol-insoluble portion was removed by filtration. The ethanol was removed from the obtained ethanol-soluble part under reduced pressure, and the residue was redissolved in 2.0 l of water. 85.1 g (yield 42%) of a carboxybetaine compound of polyglycerin (average degree of condensation: 4). It had an average of 3 carboxybetaine groups per mole of polyglycerin.

[0030]

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────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuyasu Imai 2-10-10 Shozuzawa, Itabashi-ku, Tokyo (72) Inventor Yoshiaki Fujikura 271-6 Yamamotocho, Utsunomiya-shi, Tochigi Prefecture (56) References CHEMICAL ABSTRACT S114 : 163513 (1991) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 229/04 C07C 227/18 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. A carbobetaine represented by the following general formula (1). Embedded image ^{(Wherein, Z, R 1, R 2} , A 1, A 2, m and n are those of the following Z:.. Represents a residue obtained by removing (m + n) hydroxyl group from glycerin or glycerin condensate A ¹ , A ² : may be the same or different and represent a linear or branched alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group R ¹ : 1 carbon atom which may have a hydroxyl group Represents a linear or branched alkyl or alkenyl group having from 24 to 24. R ² represents a linear or branched alkyl or alkenyl group having ^{2 to} 24 carbon atoms which may have a hydroxyl group, m, n: m is 0 or more and n is 1 or more, and m + n
Is the same as the valence of Z. ) 2. The betaine compound according to claim ¹ , wherein in the general formula (1), A ¹ is a 2-hydroxy-1,3-propylene group. 3. In the general formula (1), Z represents a condensation degree of 1 to 3.
3. Carbobetaine according to claim 1 or 2, which is a residue obtained by removing m + n hydroxyl groups from 10 polyglycerins. 4. In the general formula (1), n is 1;
R¹Is a methyl group and R ^TwoIs a straight or branched chain having 2 to 18 carbon atoms
The carbohydrate according to claim 1, 2 or 3, which is a chain alkyl group.
Betaine. 5. The carbobetaine according to claim 1, wherein A ² is a methylene group or an ethylene group in the general formula (1). 6. The carbobetaine according to claim 1, wherein m is 0 in the general formula (1). 7. The following general formula (2): (Wherein, Z, R ¹ , R ² , A ¹ , m and n represent the following: Z: a residue obtained by removing m + n hydroxyl groups from glycerin or a glycerin condensate. R ¹ : a hydroxyl group And represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms which may have R ² : a linear or branched alkyl or alkenyl group having 2 to 24 carbon atoms which may have a hydroxyl group. A ¹ : a linear or branched alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, m and n: m is 0 or more, n is 1 or more, and m + n
Is the same as the valence of Z. ) And the following general formula (3) XA ² —CO ₂ M (3) (wherein X, A ² and M represent the following. X: represents a halogen atom. A ² : A linear or branched alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group. M: represents a cation.) A compound represented by the following general formula ( 1) (Wherein, Z, R ¹ , R ² , A ¹ , A ² , m and n are the same as those described above).