JPH06228079A - New sulfobetaine, its production and use - Google Patents

Abstract

PURPOSE:To obtain a new compound excellent in humectancy and moist feeling and useful for cosmetics and cleansing agents. CONSTITUTION:A compound of formula I [A is (OH-substituted) 2-12C alkylene; R<1> and R<2> are (OH-substituted) 1-12C alkyl or 2-12C alkenyl], e.g. 1-hydroxy-2- sulfoethyl-N,N-dimethyl-N-hydroxyethyl-N-methanealminium hydroxide inner salt. Furthermore, the compound of formula I is obtained by reacting a compound of formula II with a compound of formula III (X is halogen; M is H or cation).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sulfobetaine, a method for producing the same, and uses thereof, and more specifically, a novel sulfobetaine useful as a base for various cosmetics, a moisturizing agent, etc., and a method for producing the same. The present invention relates to a cosmetic composition and a cleaning composition containing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
For the purpose of imparting a moisturizing feel to hair and skin, cosmetics such as shampoo and conditioner, body wash such as body shampoo, etc., include propylene glycol, glycerin, urea, sorbitol, and alkylene oxide adducts of alcohol as moisturizers. Has been added.

However, none of these moisturizing effects are sufficient, and in addition, their hygroscopicity, hygroscopic speed, touch and the like are also unsatisfactory. Further, although natural polysaccharide components such as hyaluronic acid are relatively excellent in moisturizing performance and feel, they have the drawback that their use range is limited to relatively expensive cosmetics because they are expensive. Was there.

Therefore, it has been desired to develop a compound which is excellent in moisturizing properties and feel and is inexpensive and which can be incorporated into hair cosmetics such as shampoo and rinse and various skin cosmetics.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such circumstances, and as a result, the specific sulfobetaine described below is an excellent moisturizing agent for various cosmetics, detergents, etc., and is simple and inexpensive. The present invention has been completed and the present invention has been completed.

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

[0007]

[Chemical 4]

(In the formula, A represents a linear or branched alkylene group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group, and R ¹ and R ² are the same or different and are substituted with a hydroxyl group. And optionally represents a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkenyl group having 2 to 12 carbon atoms).

Secondly, the present invention provides the following general formula (2):

[0010]

[Chemical 5]

(Wherein A, R ¹ and R ² have the same meanings as defined above) and a compound represented by the following general formula (3)

[0012]

[Chemical 6]

A method for producing sulfobetaine (1), which comprises reacting with a compound represented by the formula (wherein X represents a halogen atom and M represents a hydrogen atom or a cation). Is.

Thirdly, the present invention provides a cosmetic containing the sulfobetaine (1).

Fourthly, the present invention provides a detergent composition containing the sulfobetaine (1).

Specific examples of A in the general formula (1) include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group. Etc. These may be substituted with a hydroxyl group. Among these alkylene groups, those having 2 to 6 carbon atoms are particularly preferable.

Specific examples of the alkyl group represented by R ¹ and R ^{2 in the} general formula (1) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples thereof include nonyl group, decyl group, undecyl group, dodecyl group, and the like, and specific examples of the alkenyl group include vinyl group, allyl group and the like. These may be substituted with a hydroxyl group. Of these,
A methyl group is particularly preferred.

In the method for producing sulfobetaine (1) of the present invention, 1 to 5 of compound (3) is added to compound (2).
It is preferable that the reaction is carried out in a double mole, particularly 1 to 2 mole.

In the compound (3), the halogen atom represented by X includes fluorine, chlorine, bromine and iodine, and the cation represented by M is sodium,
Examples thereof include alkali metal ions such as potassium and lithium and ammonium ions.

The above reaction is carried out in an inert solvent in the range of 20 to 120.
C., preferably 40 to 90.degree. C. Examples of the inert solvent used here include water, methanol, ethanol, isopropyl alcohol, dimethylformamide, and a mixture of two or more polar solvents such as dimethylsulfoxide, but among them, only water or water. A mixed solvent with a lower alcohol is preferable,
Especially water / lower alcohol 80 / 20-50 / 80
A mixed solvent of (weight ratio) is preferable because the yield is improved.

The obtained reaction product is an unreacted product,
Since it contains by-products and the like, it is preferably purified by a known method such as a solvent fractionation method, an ion exchange chromatography method, or an electrodialysis method, if necessary.

Sulfobetaine (1) thus obtained
Has an excellent moisturizing property, and thus can be applied to various cosmetics.

To obtain the cosmetic of the present invention using sulfobetaine (1), 0.1 to 20% by weight, particularly 0.5 to 10% by weight, of sulfobetaine (1) is added to the cosmetic. Preferably.

In the cosmetic of the present invention, in addition to the above-mentioned sulfobetaine (1), components used in ordinary cosmetics, such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycols higher than that,
Propylene glycol, dipropylene glycol, higher polypropylene glycols, butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol, glycerin, diglycerin, further polyglycerins, sorbitol, mannitol, xylitol , Sugar alcohols such as maltitol, ethylene oxide (hereinafter abbreviated as EO) adduct of glycerins, propylene oxide (hereinafter abbreviated as PO) adduct, EO and PO adducts of sugar alcohols, galactose, glucose,
Monosaccharides such as fructose and EO and PO adducts thereof, polysaccharides such as maltose and lactose and EO and PO adducts thereof, liquid paraffin, squalane,
Hydrocarbons such as petrolatum and solid paraffin, olive oil,
Natural oils such as jojoba oil, evening primrose oil, coconut oil and beef tallow, isopropyl myristate, cetyl isooctanoate, ester oils such as neopentyl glycol dicaprate, silicone oils such as methyl silicone and methyl phenyl silicone, isostearic acid, olein Oily components such as higher fatty acids such as acids; POE alkyl ether, POE branched alkyl ether, POE sorbitan ester, POE
Nonionic surfactant such as glycerin fatty acid ester, POE hydrogenated castor oil, sorbitan ester, glycerin fatty acid ester, polyglycerin fatty acid ester, anionic surfactant such as phosphoric acid type, sulfonic acid type, sulfuric acid type, carboxylic acid type Agents, other amphoteric surfactants, cationic surfactants, etc .; vitamins, bactericides such as triclosan, trichlorocarban, dipotassium glycyrrhizinate,
Anti-inflammatory agents such as tocopherol acetate, zinc pyrithione,
Antidandruff agents such as octopirox, activators, agents such as ultraviolet absorbers; preservatives such as methylparaben and butylparaben, foaming agents such as alkylamine oxides and fatty acid alkanolamides, inorganic salts, polyethylene glycol stearate ethanol, etc. Viscosity modifiers, pearlizing agents, fragrances, pigments, antioxidants; montmorillonite, saponite,
Water-swelling clay minerals such as heclite, veegum, kunivia, smecton; Carrageenan, xanthan gum, sodium alginate, pullulan, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and other polysaccharides, carboxyvinyl polymers, polyvinylpyrrolidone, etc. Other macromolecules such as molecules; extender pigments such as titanium oxide, kaolin, mica, sericite, zinc white, and talc; pigments such as polymer powders such as polymethylmethacrylic acid and nylon powder; Can be appropriately blended within a range that does not impair the above.

The cosmetic composition of the present invention can be produced by a conventional method, and its dosage form can be any dosage form such as liquid form, cream form, solid form, powder form, and particularly liquid form or cream form. It is preferable to make the shape.

On the other hand, in order to obtain the detergent composition of the present invention using sulfobetaine (1), sulfobetaine (1) is blended in the composition in an amount of 0.5 to 50% by weight, particularly 1 to 30% by weight. It is preferable.

In the detergent composition of the present invention, various surfactants usually used in detergents can be optionally used within the range not impairing the effects of the present invention.

Specifically, as the anionic surfactant, for example, as the sulfate or sulfonate type,
Alkyl sulfate, polyoxyethylene alkyl sulfate,
Sulfosuccinic acid type, taurate type, isethionate type,
Examples of the surfactant include α-olefin sulfonic acid-based surfactants, examples of the carboxylate-based surfactant include fatty acid soap, ether carboxylic acid-based surfactant, and acylated amino acid-based surfactant, and examples of the phosphate-based surfactant include alkyl. Examples thereof include phosphoric acid ester-based surfactants.

Examples of the amphoteric surfactant include carbobetaine-based, phosphobetaine-based, sulfobetaine-based and imidazolinium betaine-based amphoteric surfactants.

The nonionic surfactants include polyoxyalkylene addition type, polyoxypropylene / polyoxyethylene addition type, amine oxide type, mono- or diethanolamide type, sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid. Examples thereof include esters, alkyl saccharide-based sugars, N-polyhydroxyalkyl fatty acid amide-based sugars, and polyhydric alcohols.

Examples of the cationic surfactants include mono- or dialkyl addition type quaternary ammonium salts having a linear or branched alkyl group and those obtained by adding an alkylene oxide to the alkyl group. A linear monoalkyl quaternary ammonium salt having a number of 12 to 16 and a quaternary ammonium salt having a branched alkyl group having a carbon number of 20 to 28 are preferably used.

These surfactants may be used alone or in combination of two or more, and the compounding amount thereof may vary depending on the dosage form, but is 2 to 60% by weight, particularly 10 to 50% by weight in the detergent composition of the present invention. Weight percent is preferred. The weight ratio of sulfobetaine (1) is preferably 1: 2 to 1:50, and more preferably 1: 3 to 1:30.

In the detergent composition of the present invention, in addition to the above-mentioned components, components used in ordinary detergents, for example, ethylene glycol, diethylene glycol, triethylene glycol, and more polyethylene glycols, propylene glycol, dipropylene. Glycols, polypropylene glycols higher than them, butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol, glycerin, diglycerin, further polyglycerins, sorbitol, mannitol, xylitol, maltitol, etc. Sugar alcohols, ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO) adducts of sugar alcohols, EO or PO adducts of sugar alcohols, galactose, glucose, fructose, etc. And its EO or PO adducts, polyhydric alcohols such as maltose, polysaccharides of lactose sugar and its EO or PO adducts; hydrocarbons such as liquid paraffin, squalane, vaseline, solid paraffin, olive oil, jojoba oil, evening primrose oil , Natural oils such as coconut oil and tallow, isopropyl myristate, cetyl isooctanoate,
Ester oils such as neopentyl glycol dicaprate, silicone oils such as dimethyl silicone and methylphenyl silicone, oily ingredients such as higher fatty acids such as isostearic acid and oleic acid; vitamins, fungicides such as triclosantrichlorocarban, dipotassium glycyrrhizinate, Anti-inflammatory agents such as tocopherol acetate, anti-dandruff agents such as zinc pyrithione and octopirox, activators, agents such as UV absorbers; water-swelling clay minerals such as montmorillonite, saponite, hecklite, veegum, cunibia, smectons; carrageenan, Xanthan gum, sodium alginate, pullulan, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose,
Polysaccharides such as hydroxypropylcellulose, other polymers such as carboxyvinyl polymers, synthetic polymers such as polyvinylpyrrolidone; extenders such as titanium oxide, kaolin, mica, sericite, zinc white, talc, polymethylmethacrylic acid, Pigments such as nylon powder and other polymer powders; preservatives such as methylparaben and butylparaben; viscosity modifiers such as inorganic salts, polyethylene glycol stearate and ethanol; pearling agents; perfumes; pigments; antioxidants, etc. It can be appropriately blended within a range that does not impair the effects of the invention.

The detergent composition of the present invention can be produced by an ordinary method, and its dosage form can be any dosage form such as liquid, paste, solid or powder. It is particularly preferable that the liquid or paste is used.

[0035]

According to the present invention, a sulfobetaine compound having excellent moisturizing properties can be obtained easily and at low cost. In addition, the cosmetics using this do not stick to the skin or hair and give a good moist feeling.

[0036]

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

Example 1 Preparation of 1-hydroxy-2-sulfoethyl-N, N-dimethyl-N-hydroxyethyl-N-methanaminium hydroxide innersalt N, N-dimethylethanolamine in a 500 ml four-necked flask. 18.9 g (0.21 mol), water 20.4 g
(1.13 mol) was added and the temperature was raised to 70 ° C. 5-Chloro-2-hydroxy-1-propanesulfonic acid sodium salt 50.1 g (0.25 mol), water 90 g (5.00
Mol) was added dropwise in about 1 hour. Then, the same temperature was maintained and stirring was performed for 7 hours. After cooling to room temperature, the product was directly purified by ion exchange chromatography (ion exchange resin; Bio-Rad, AG501-X8), and the solvent was distilled off under reduced pressure to give 33.2 g (0.15 mol) of the title compound (monomer). The yield was 70%). HPLC of this thing
(Column: Shimadzu's Shimadzu gel SCR101
N ", eluent; water, detector; RI) Purity was 99.5%. The structural formula is shown below.

[0038]

[Chemical 7]

Mass spectrum data: M / Z (FA
B); 228 (M + H) ¹ H-NMR (D ₂ O) chart is shown in FIG. 1.

Example 2 Preparation of 1-Hydroxy-2-sulfoethyl-N, N-dimethyl-N- (2,3-dihydroxypropyl) -N-methanaminium hydroxide innersalt N 1 N 4-neck flask was charged with N. , N-dimethylamine 50%
Aqueous solution 81 g (pure content 0.9 mol) was added, and glycidol 32 g (0.4 mol) was added dropwise at room temperature over 30 minutes.
Then, after stirring at room temperature for 1 hour, the temperature was raised to 50 ° C. and N ₂ was added.
The residual dimethylamine was removed by air flow. Water 1
00 g was added, the temperature was raised to 60 ° C., and 164 g of 3-chloro-2-hydroxy-1-propanesulfonic acid sodium salt was added.
A mixed solution of (0.8 mol) and 400 g of water was added dropwise in about 1 hour. Then, the same temperature was maintained and stirring was performed for 5 hours. After cooling to room temperature, ion exchange chromatography (ion exchange resin; manufactured by Bio-Rad, AG501-X)
8) and the solvent was distilled off under reduced pressure to obtain 67 g (0.26 mol) of the title compound (yield 65%). The structural formula is shown below.

[0041]

[Chemical 8]

Mass spectrum data: M / Z (FA
B); 257 (M + H ) shows a _{^{1 H-NMR (D 2 O}} ) chart in FIG.

Example 3 An anti-dandruff shampoo having the following composition was prepared.

[0044]

[Table 1] (Composition) (% by weight) Lauryl dimethylamine acetate betaine 10 N-lauroyl glutamate sodium 10 Piroctone auramine (Octopirox, Hoechst) 0.5 Ethylene glycol distearate 2 Compound of Example 1 5 fragrance 0.5 water balance

This anti-dandruff shampoo had no squeaky feeling when washing and rinsing hair, and after washing it was not sticky and moist.

Example 4 A hair treatment having the following composition was prepared.

[0047]

(Composition) (wt%) 2-dodecylhexadecyltrimethylammonium chloride 2 stearyltrimethylammonium chloride 2 Compound of Example 1 5 Stearyl alcohol 5 Lanolin 3 Liquid paraffin 3 Polypeptide (collagen hydrolyzate) 5 Hydroxyethylcellulose (1% aqueous solution viscosity 8,000cp) 0.5 Polyethylene (5) oleyl ether 0.5 Methylparaben 0.2 Perfume 0.4 Water balance

This hair treatment had an excellent effect of imparting flexibility to the hair, was not sticky, and gave a moist feel.

Example 5 A lotion having the following composition was prepared.

[0050]

Table 3 (Composition) (wt%) Lactic acid 0.03 Sodium lactate 0.84 Compound of Example 1 5 Glycerin 2 Polyoxyethylene oleyl ether (20EO adduct) 1 Ethanol 10 Perfume 0.3 Water balance

This lotion did not lose its moisturizing effect due to sweat, was not sticky, and had a moist feeling.

Example 6 A powder bathing agent having the following composition was prepared.

[0053]

Table 4 (Composition) (% by weight) Sodium hydrogen carbonate 67 Dextrin 30 Compound of Example 1 2 Perfume 0.5 Dye 0.5

The powder bathing agent had an excellent moisturizing effect on the skin and gave a moist feeling.

Example 7 A paste-like face wash having the following composition was prepared.

[0056]

Table 5 (Composition) (wt%) Sodium sesquilauryl phosphate 25 Dipotassium myristyl sulfosuccinate 5 Cocoyl diethanolamide 2 Polyethylene glycol monostearate 4 Compound of Example 1 5 Carboxy vinyl polymer 0.5 Paraben 0.3 Perfume 0 .3 Purified water balance

This facial cleanser had a refreshed feeling after washing, had a moist feel, and did not have a refreshing feel.

Example 8 A liquid body shampoo having the following composition was prepared.

[0059]

[Table 6] (Composition) (% by weight) Lauryl phosphate triethanolamine 20 Alkyl saccharide [C ₁₂ -O- (G) _2.5 ] ^{* 1} 5 Lauroyl sarcosine sodium 5 Compound of Example 1 8 Xanthan gum 0.5 Propylene glycol 3 Perfume 0.7 Purified water balance * 1: C ₁₂ is a lauryl group and G is glucose.

This body shampoo was moist without causing a lump after washing.

Example 9 A dishwashing detergent having the following composition was prepared.

[0062]

Table 7 (Composition) (wt%) Polyoxyethylene (4) lauryl ether sodium sulfate 8 Polyoxyethylene (20) myristyl ether 5 Lauryl dimethylamine oxide 3 Ethanol 3 Compound of Example 2 3 Perfume 0.1 Water balance

The dishwashing detergent was moist with less bulkiness after use.

[Brief description of drawings]

FIG. 1 is a drawing showing a ¹ H-NMR chart of the compound obtained in Example 1.

FIG. 2 is a drawing showing a ¹ H-NMR chart of the compound obtained in Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C07C 303/22 C08L 71/02 LQE 9167-4J C11D 1/92 (72) Inventor Yoshiaki Fujikura Tochigi Prefecture 271-6 Yamamotocho, Utsunomiya City (72) Inventor Kazuyasu Imai 2-10-10 Shozuzawa, Itabashi-ku, Tokyo

Claims (4)

[Claims] 1. The following general formula (1): (In the formula, A has 2 to 2 carbon atoms which may be substituted with a hydroxyl group.
12 represents a straight-chain or branched-chain alkylene group, and R ¹ and R ² are the same or different, and may be a hydroxyl group-substituted straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms or the number of carbon atoms. 2 to 12 showing a linear or branched alkenyl group). 2. The following general formula (2): (In the formula, A, R ¹ and R ² are the same as defined above.)
And a compound represented by the following general formula (3): The method for producing sulfobetaine according to claim 1, which comprises reacting with a compound represented by the formula (wherein X represents a halogen atom and M represents a hydrogen atom or a cation). 3. A cosmetic comprising the sulfobetaine according to claim 1. 4. A detergent composition comprising the sulfobetaine according to claim 1.