JP5037472B2 - Process for producing betaine ester-containing mixtures - Google Patents

Description

  The present invention relates to a betaine ester-containing mixture, a method for producing the mixture, and a hair cosmetic containing the mixture.

  When imparting good flexibility and smoothness to the hair and further oily feeling, a dosage form in which a long-chain alcohol such as cetanol is emulsified in a gel form with a surfactant is used. As the surfactant, a cationic surfactant is suitable. Among them, betaine esters are surfactants that can impart flexibility, smoothness, and even oily feeling especially when wet.

  As a method for producing this betaine ester, Patent Document 1 discloses a production method in which glycine betaine and alcohol are reacted using a dehydrating solvent such as toluene and a sulfonic acid-based acid catalyst. Patent Document 2 discloses a monochloroacetic acid ester and trimethylamine. A production method in which a reaction is carried out with a dialkyl ketone solvent has been reported. However, these methods have a problem that the manufacturing process becomes long because the solvent needs to be removed from the viewpoint of safety.

In addition, when a quaternization reaction is performed by reacting a halogen compound and an amine compound, and the solvent is not removed from the reaction end product and used as it is, water or ethanol is used as the solvent. However, when these are used, hydrolysis or transesterification with ethanol occurs and betaine ester decreases, so when the reaction end product is used as it is, long-chain alcohol cannot be emulsified in gel form, and it has flexibility to hair. There is a problem that smoothness and oiliness cannot be obtained.
JP-A 49-76818 JP 58-157750 A

  An object of the present invention is to provide a betaine ester-containing mixture that can emulsify a long-chain alcohol in a gel state even when the reaction-finished product is used as it is, and can impart sufficient flexibility, smoothness, and oily feeling to the hair. It is to provide a manufacturing method.

  In the present invention, a monohalogencarboxylic acid alkyl ester and a tertiary amine are represented by the general formula (1)

[Wherein R ⁶ is R ⁸ —O— (AO) _n —CH ₂ — (R ⁸ is a linear or branched alkyl group or alkenyl group having 1 to 40 carbon atoms, and A is a C 2 to 4 carbon atom. An alkylene group, n represents a group represented by the number of 0 to 50 representing the average number of added moles of an oxyalkylene group, and R ⁷ represents a linear or branched alkyl group or alkenyl group having 1 to 40 carbon atoms. . ]
Is reacted with a secondary alcohol represented by the following formula (hereinafter referred to as secondary alcohol (1)) as a reaction solvent.

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 40 carbon atoms, R ² is a linear or branched alkylene group having 1 to 5 carbon atoms, R ³ , R ⁴ and R ⁵ is the same or different and is a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 1 to 24 carbon atoms, and X represents a halogen atom. ]
A method for producing a betaine ester-containing mixture comprising a betaine ester represented by the following (hereinafter referred to as betaine ester (2)) and a secondary alcohol (1), and a betaine ester-containing mixture obtained by this method and the mixture: A hair cosmetic composition is provided.

  The betaine ester-containing mixture obtained by the production method of the present invention can be used without removing the secondary alcohol (1) used as a solvent, and there is no decrease in yield. Manufacture is possible with a simple manufacturing flow that is not necessary. Furthermore, the hair cosmetic containing the mixture produced by this production method has good emulsifying properties such as oils, and can impart good flexibility, smoothness and oily feeling to the hair.

In the betaine ester (2), R ¹ is preferably a linear or branched alkyl group or alkenyl group having 10 to 36 carbon atoms, particularly 12 to 22 carbon atoms, and R ² is a methylene group, ethylene group, or n-propylene group. R ³ , R ⁴ and R ⁵ are preferably a methyl group, an ethyl group, a hydroxyethyl group or a hydroxypropyl group. X is preferably a chlorine atom.

The monohalogen carboxylic acid alkyl ester used in the present invention has the formula (3)
R ¹ -O-CO-R ² -X (3)
(Wherein R ¹ , R ² and X have the above-mentioned meanings)
The alcohol is esterified with a monohalogen carboxylic acid or a lower alkyl ester thereof, an acid chloride, an acid anhydride or the like (hereinafter referred to as carboxylic acid ester (3)). Examples of the carboxylic acid ester (3) include monochloroacetic acid cetyl ester, monochloroacetic acid stearyl ester, monobromoacetic acid tetradecyl ester, monochloropropionic acid cetyl ester, and monochloroacetic acid cetyl ester is preferable.

  The tertiary amine used in the present invention has the formula (4)

(Wherein R ³ , R ⁴ and R ⁵ have the above-mentioned meanings)
(Hereinafter referred to as amine (4)). Examples of the amine (4) include trimethylamine, triethylamine, dimethylethylamine, dimethylethanolamine, dimethylpropanolamine, and triethanolamine, with trimethylamine and dimethylethylamine being preferred.

In the secondary alcohol (1), R ⁶ represents a group represented by R ⁸ —O— (AO) _n —CH ₂ —, and R ⁸ is a linear or branched chain having 1 to 20 carbon atoms, particularly 1 to 18 carbon atoms. Are preferably an ethylene group or a propylene group, n is preferably 0 to 30, particularly preferably 3 to 30, and R ⁷ is a linear or branched alkyl group having 1 to 5 carbon atoms or Alkenyl groups are preferred, and methyl groups are more preferred. When R ⁷ is a methyl group, it can be produced by adding an alkylene oxide to an alcohol, then adding 1 mol or more of propylene oxide, and adjoining the terminal hydroxyl group with a propylene group. In this case, the secondary alcohol (1) is more preferably a propylene oxide adduct of a higher alcohol having 8 to 18 carbon atoms.

  From the viewpoint of improving the yield, the molar ratio of the carboxylic acid ester (3) and the amine (4) during quaternization is preferably (3) :( 4) = 1: 1 to 1: 1.5, and 1: 1.01 to 1: 1.2 is more preferable. The weight ratio (2) :( 1) of betaine ester (2) to secondary alcohol (1) in the betaine ester-containing mixture is preferably 5 so that the melting point of the reaction product is 100 ° C. or lower. : 95 to 95: 5, more preferably 20:80 to 90:10, particularly preferably 50:50 to 90:10.

  In order to produce a betaine ester-containing mixture by the method of the present invention, for example, after adding all of amine (4) to a mixture of carboxylic acid ester (3) and secondary alcohol (1) under a pressure of 0.1 to 1.0 MPa. The reaction is carried out at a reaction temperature of 40 to 100 ° C. for 1 to 5 hours. The reaction can also be carried out while gradually adding amine (4).

  The betaine ester-containing mixture thus obtained can be used as it is, blended with other raw materials, and emulsified in a gel form to obtain a hair cosmetic. Further, if necessary, it can be blended after removing any of the carboxylic acid ester (3), the amine (4) and the secondary alcohol (1). Further, when a compound having a lower melting point is required for blending, for example, propylene glycol can be added to lower the melting point before blending.

  In addition, the betaine ester (2) can be separated from the betaine ester-containing mixture of the present invention and used for various applications, but in this case, if the secondary alcohol (1) can be allowed to remain in terms of safety, Advantageously, the purification can be simple or unnecessary, and the betaine ester (2) can be obtained efficiently.

  The content of betaine ester (2) in the hair cosmetic composition of the present invention is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight. Good feel is obtained at 0.1% by weight or more, and there is no problem in stability of the product such as precipitation, solidification and layering during storage at 20% by weight or less.

  If necessary, the hair cosmetic using the betaine ester-containing mixture of the present invention can further use an oil agent such as long-chain alcohol or ester oil, or silicone. Examples of the long-chain alcohol include long-chain alcohols having a linear or branched alkyl group or alkenyl group having 8 to 40 carbon atoms, preferably 12 to 26, and mixtures thereof, myristyl alcohol, cetanol, cetyl alcohol, Stearyl alcohol, aralkyl alcohol, behenyl alcohol, caranavir alcohol, and seryl alcohol are preferred, and cetanol is particularly preferred. In addition, cetanol as used in the field of this invention has cetyl alcohol as a main component and contains long-chain alcohols, such as stearyl alcohol and oleyl alcohol. Examples of ester oils include lower alkyl esters of fatty acids, and isopropyl palmitate is preferred.

  Examples of silicone include (A) dimethylpolysiloxane, (B) methylphenylpolysiloxane, (C) amino-modified silicone [when amino-modified silicone is used as an aqueous emulsion, the amino-modified contained in the aqueous emulsion. The amount of silicone is preferably 20 to 60% by weight, more preferably 30 to 50% by weight. Preferred amino-modified silicone aqueous emulsions include SM8704C (manufactured by Torre Silicone Co., Ltd.) and DC939 (manufactured by Dow Corning Co., Ltd.). ), (D) fatty acid modified polysiloxane, (E) alcohol modified silicone, (F) aliphatic alcohol modified polysiloxane, (G) polyether modified silicone, (H) epoxy modified silicone, (I) fluorine modified silicone, ( Examples include J) cyclic silicones and (K) alkyl-modified silicones.

  The content of the oil in the hair cosmetic composition of the present invention is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. Flexibility and moist feeling are exhibited at 0.1% by weight or more, and there is no problem in product stability at 30% by weight or less. The content of silicone is preferably 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight. If it is 0.01% by weight or more, a silicone-specific feel is exhibited, and if it is 20% by weight or less, there is no problem in stability of the product. When the silicone is an aqueous emulsion, the content is a solid content.

  The hair cosmetic composition of the present invention includes cationic surfactants other than betaine esters (2), anionic surfactants, nonionic surfactants, surfactants such as amphoteric surfactants, hydrocarbons, lanolin derivatives, Higher fatty acids, fats and oils, glycerin, humectants, cationic polymers, polysaccharides, polypeptides, pearling agents, solvents, liquid crystal forming bases, aromatic sulfonic acids, dyes, fragrances, propellants, chelating agents, pH adjustment Additives, preservatives, antidandruff agents and the like can be appropriately blended within a range not impairing the object of the present invention.

  The hair cosmetic composition of the present invention can be used for hair lining, hair conditioner, hair treatment, hair pack, hair cream and the like.

  % In the examples is% by weight.

Example 1
150.0 g of cetyl ester of monochloroacetic acid and 79.0 g of adduct of 5 mol of propylene oxide of myristyl alcohol were charged into an autoclave, 41.3 g of dimethylethylamine was injected and reacted at 60 ° C. for 5 hours. After completion of the reaction, excess dimethylethylamine was distilled off under reduced pressure to obtain 260.8 g of a glycine betaine cetyl ester mixture (hereinafter referred to as mixture 1). When the mixture 1 was analyzed by liquid chromatography, it was found that the glycine betaine cetyl ester was 70% and the propylene oxide 5-mol adduct of myristyl alcohol was 30%. The composition of the following comparative example was also determined in the same manner.

Comparative Example 1
A glycine betaine cetyl ester mixture (hereinafter referred to as comparative mixture 1) was obtained in the same manner as in Example 1 except that 79.0 g of water was used instead of the propylene oxide 5 mol adduct of myristyl alcohol and the reaction temperature was 50 ° C. It was. The composition of Comparative Mixture 1 was charged with 70% glycine betaine cetyl ester and 30% water, but glycine betaine cetyl ester did not reach 50% due to hydrolysis by water.

Example 2 and Comparative Example 2
The hair rinse agent which has the composition of Table 1 was manufactured by the conventional method using the mixture 1 and the comparison mixture 1. About these hair rinse agents, the emulsified state was observed visually, and also the softness etc. were sensory-evaluated by the following method. The results are shown in Table 1.

<Evaluation method>
20 g of hair (length 20 cm, average diameter 60 μm) of a Japanese woman who had not been chemically treated such as cold perm was bundled and washed with 5 g of shampoo. The composition of this shampoo is 15% polyoxyethylene alkyl (carbon number 12) ether ether sulfate (ethylene oxide average addition mole number 2.5) 15%, diethanolamide 3%, balance water. Thereafter, 2.0 g of the hair rinse agent prepared above was uniformly applied and rinsed with running water at 40 ° C. for 30 seconds. One expert panelist evaluated the softness, smoothness and oiliness of the hair during rinsing according to the following criteria.
A: Very good, B: Good, X: Bad

注）
*：花王株式会社製、カルコール6870、以下同様

note)
*: Kao Corporation, Calcoal 6780, and so on

Example 3
A hair rinse agent having the following composition was produced.
Mixture 1 2.0%
Cetanol 4.0%
Isopropyl palmitate 0.5%
Dimethylpolysiloxane (average molecular weight 9000) 1.5%
Polyether-modified silicone 0.5%
Propylene glycol 2.0%
50% aqueous citric acid solution 0.06%
Fragrance, methyl paraben Appropriate amount Purified water balance This rinse agent was emulsified in a gel form, and the flexibility, smoothness and oiliness of the hair during rinsing were very good.

Claims (6)

Monohalocarboxylic acid alkyl ester and tertiary amine are represented by the general formula (1)

[Wherein R ⁶ is R ⁸ —O— (AO) _n —CH ₂ — (R ⁸ is a linear or branched alkyl group or alkenyl group having 1 to 40 carbon atoms, and A is a C 2 to 4 carbon atom. An alkylene group, n represents a group represented by the number of 0 to 50 representing the average number of added moles of an oxyalkylene group, and R ⁷ represents a linear or branched alkyl group or alkenyl group having 1 to 40 carbon atoms. . ]
Is reacted with a secondary alcohol represented by the general formula (2) as a reaction solvent.

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 40 carbon atoms, R ² is a linear or branched alkylene group having 1 to 5 carbon atoms, R ³ , R ⁴ and R ⁵ is the same or different and is a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 1 to 24 carbon atoms, and X represents a halogen atom. ]
A method for producing a betaine ester-containing mixture comprising a betaine ester represented by the formula (1) and a secondary alcohol represented by the general formula (1): In the mixture of monohalogenated carboxylic acid alkyl ester and secondary alcohol, the total amount of the tertiary amine is added under pressure, or the monohalogenated carboxylic acid alkyl ester and the tertiary amine are reacted while gradually adding. The method according to claim 1. The method according to claim 1 or 2, wherein the monohalogen carboxylic acid alkyl ester and the tertiary amine are reacted in a molar ratio of monohalogen carboxylic acid alkyl ester: tertiary amine = 1: 1 to 1: 1.5. A betaine ester represented by general formula (2) and a secondary alcohol represented by general formula (1) are represented by betaine ester represented by general formula (2) and 2 represented by general formula (1). The method according to any one of claims 1 to 3, wherein a betaine ester-containing mixture containing a weight ratio with a secondary alcohol (2) :( 1) = 5: 95 to 95: 5 is produced. The betaine ester containing mixture obtained by the method of any one of Claims 1-4. A hair cosmetic comprising the betaine ester-containing mixture according to claim 5 .