JPH06128202A - Novel carboxybetaine, its production method and its use - Google Patents

Abstract

(57) [Summary] [Structure] The following general formula (1) (In the formula, R ¹ and R ² each represent a linear or branched alkyl group having 1 to 5 carbon atoms and having a hydroxyl group, and the rest are linear or branched alkyl groups having 1 to 5 carbon atoms. A chain alkyl group and X represents a hydrogen atom or a cation), a method for producing the same, and a humectant, a cosmetic composition and a detergent composition containing the same. [Effect] It has excellent moisturizing properties and can be applied to shampoo, rinse and various cosmetics. Moreover, it can be easily and inexpensively produced from easily available raw materials.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carboxybetaine having excellent moisturizing property, a method for producing the same, and a moisturizing agent, cosmetic composition and detergent composition containing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
In order to give a moist feel to hair and skin, a moisturizing agent is incorporated into many shampoos, conditioners, cosmetics and the like. Usually, as a moisturizer, propylene glycol, glycerin, urea, sorbitol, an alkylene oxide adduct of alcohol, and the like have been used.

However, none of these compounds is always satisfactory in terms of moisture retention, hygroscopicity, moisture absorption rate, feel and the like. Further, although natural polysaccharide components such as hyaluronic acid are excellent in moisturizing properties and feel, they are not easily available and are expensive, so that their use range is limited to relatively high-grade cosmetics.

Therefore, it has been desired to develop a compound which has excellent moisturizing properties, is easily available and is inexpensive, and which can be incorporated into shampoos, rinses, cosmetics and the like.

[0005]

In such a situation, the inventors of the present invention have conducted diligent research, and as a result, the following general formula (1) is obtained.
The present invention has been completed by finding that carboxybetaine represented by is excellent in moisturizing property, is useful as various cosmetic bases, and can be produced easily and inexpensively.

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

[0007]

[Chemical 3]

(In the formula, one or both of R ¹ and R ² represent a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms and having a hydroxyl group, and the rest are straight-chain alkyl groups having 1 to 5 carbon atoms. A chain or branched chain alkyl group, and X represents a hydrogen atom or a cation) and a method for producing the same, and a moisturizing agent, a cosmetic composition and a detergent composition containing the carboxybetaine. It is provided.

The carboxybetaine of the present invention is represented by the above general formula (1). In the formula, the alkyl group having 1 to 5 carbon atoms represented by R ¹ and R ² is a methyl group, an ethyl group or a straight chain. Or branched-chain propyl, butyl and pentyl groups, and examples of the linear or branched alkyl group having a hydroxyl group and having 1 to 5 carbon atoms include those in which the above-mentioned alkyl group is substituted with a hydroxyl group. Include 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1,2-dihydroxypropyl group, 1-
Examples thereof include a hydroxybutyl group and a 1-hydroxypentyl group. Above all, preferred as R ¹ and R ² are methyl group, 1-hydroxyethyl group, 1-hydroxypropyl group and 1,2-dihydroxypropyl group. At least one of R ¹ and R ² is an alkyl group having a hydroxyl group.

In the general formula (1), X represents a hydrogen atom or a cation, and the cation is an alkali metal,
Examples thereof include alkaline earth metals, amines, basic amino acids, quaternary ammonium and the like. Specific examples include cations such as sodium, potassium, magnesium, calcium, ethanolamine, methylethanolamine, dimethylethanolamine, diethanolamine, methyldiethanolamine, triethanolamine, lysine, arginine and choline.

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

[0012]

[Chemical 4]

(Wherein R ¹ , R ² and X are the same as those described above, and Y is a halogen atom), that is, an amine compound represented by the general formula (2) and a general formula (3). By reacting the carboxylic acid salt with an carboxylic acid salt in the presence of an inert solvent and salt exchange, if desired, the desired carboxyventine (1) can be obtained.

Examples of the compound (2) as a raw material include monoalkylalkanolamines and dialkanolamines. Specifically, 2- (methylamino)
Examples thereof include ethanol, diethanolamine, 2- (ethylamino) ethanol, 2- (propylamino) ethanol and the like.

The compound (3) as the other raw material is represented by the above general formula (3), and the halogen atom represented by Y in the formula is a fluorine atom, a chlorine atom,
A bromine atom and an iodine atom are exemplified. Specific examples of the compound (3) include sodium chloroacetate, sodium bromoacetate, chloroacetic acid and the like.

In order to carry out the above reaction, the compound (3) is used in an amount of 2 to 10 times, preferably 2 to 10 times the molar amount of the compound (2).
Allow 4 times molar reaction. The reaction is preferably carried out in the presence of an inert solvent at 20 to 120 ° C, particularly 40 to 90 ° C. Examples of the inert solvent used here include water, methanol, ethanol, isopropanol, dimethylformamide, polar solvents such as dimethylsulfoxide, and mixed solvents of two or more selected from these,
Of these, lower alcohols and mixed solvents of water and lower alcohols are preferred.

During the reaction, 1 to 3 relative to the compound (2).
The presence of a double mole of base is preferable because the reaction can proceed efficiently. Examples of the base used here include sodium hydroxide and potassium hydroxide.

The reaction product obtained as described above includes, in addition to the desired product, carboxybetaine (1), an inorganic salt as a by-product, an unreacted amine compound, a compound represented by the general formula (3), and And / or a hydrolyzate thereof. The ratio of each component in the reaction product depends on the types of raw materials used, the reaction ratio thereof, the type and amount of the solvent used, the reaction temperature and the like. Therefore, although the reaction product can be used as it is depending on the purpose of use, when a higher-purity product is required, for example, a known method such as a solvent fractionation method, an ion exchange chromatography method, or an electrodialysis method is known. It can be purified by the purification method of.

In the carboxybetaine (1) thus obtained, when X in the formula is a cation other than a hydrogen atom, the cation can be exchanged for a hydrogen atom by ion exchange chromatography. After this, X can be easily salt-exchanged by neutralizing with a desired base.

Since carboxybetaine (1) has excellent moisturizing properties, it can be applied not only as a moisturizing agent, but also as a cosmetic agent for skin and hair, and a detergent such as shampoo and kitchen detergent.

To obtain the cosmetic of the present invention using carboxybetaine (1), 0.1 to 20% by weight, particularly 0.5 to 10% by weight of carboxybetaine (1) is blended in the cosmetic. Is preferred.

In the cosmetic of the present invention, in addition to the above-mentioned carboxybetaine (1), components used in ordinary cosmetics, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols higher than that, propylene glycol, dipropylene. Glycol,
Further polypropylene glycols, 1,3-butylene glycol, butylene glycols such as 1,4-butylene glycol, glycerin, diglycerin, further polyglycerins, sorbitol, mannitol,
Sugar alcohols such as xylitol and 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, fructose, etc. Monosaccharides and their EO and PO adducts,
Polysaccharides such as maltose and lactose and polyhydric alcohols such as EO and PO adducts; hydrocarbons such as liquid paraffin, squalane, vaseline and solid paraffin, natural oils such as olive oil, 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, oily components such as higher fatty acids such as isostearic acid and oleic acid; POE alkyl ethers, PO
E-branched alkyl ether, POE sorbitan ester,
POE glycerin fatty acid ester, POE hydrogenated castor oil, sorbitan ester, glycerin fatty acid ester,
Nonionic surfactants such as polyglycerin fatty acid ester, anionic surfactants such as phosphoric acid type, sulfonic acid type, sulfuric acid type, carboxylic acid type, and other amphoteric surfactants,
Cationic surfactants; vitamins, triclosan,
Antibacterial agents such as trichlorocarban, dipotassium glycyrrhizinate, tocopherol acetate, antidandruff agents such as zinc pyrithione and octopirox, activators, UV absorbers; preservatives such as methylparaben and butylparaben, alkyl Foaming agents such as amine oxides and fatty acid alkanolamides, inorganic salts, viscosity modifiers such as polyethylene glycol stearate ethanol, pearling agents, fragrances, pigments, antioxidants; montmorillonite, saponite, hecklite, bee gum, kunibia, smecton, etc. Water-swelling clay minerals; polysaccharides such as carrageenan, xanthan gum, sodium alginate, pullulan, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Other polymers such as carboxyvinyl polymer, polyvinylpyrrolidone and other synthetic polymers; titanium oxide, kaolin,
Extenders such as mica, sericite, zinc white, and talc, pigments such as polymethylmethacrylic acid and polymer powder such as nylon powder, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

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, cream, solid, powder, etc. It is preferably creamy.

On the other hand, in order to obtain the detergent composition of the present invention using carboxybetaine (1), carboxybetaine (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 a 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.

As the nonionic surfactant, polyoxyalkylene addition type, polyoxypropylene / polyoxyethylene addition type, amine oxide type, mono- or diethanolamide type, other sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid are used. 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, and particularly carbon. Number 12-16 linear monoalkyl quaternary ammonium salt, number 4 having a branched alkyl group having 20-28 carbon atoms
A graded ammonium salt or the like is preferably used.

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

[0033]

EFFECTS OF THE INVENTION Since the carboxybetaine of the present invention has excellent moisturizing properties, it can be applied to detergent compositions such as shampoos, rinses, and various cosmetics. Moreover, the present compound can be easily and inexpensively produced using readily available raw materials.

[0034]

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

Example 1 101.9 g of 2- (methylamino) ethanol in a reactor
After adding (1.356 mol) and 100 g of water, an aqueous solution of 385.5 g (3.31 mol) of sodium chloroacetate was added dropwise at room temperature over 1 hour. After dropping, gradually raise the temperature,
The temperature was 70 ° C. Then add 113% 48% sodium hydroxide.
g (1.356 mol) was added dropwise and reacted for 15 hours. After the reaction was completed, the solution was concentrated to dryness, 1.5 l of methanol was added, and the insoluble matter was filtered off. The product was further purified by washing with ethanol, the solvent was distilled off under reduced pressure, and N-methyl-N- (1
66 g of -hydroxyethyl) -N-carboxymethylglycine sodium salt was obtained.

[0036]

[Chemical 5]

Example 2 50.0 g (0.48 mol) of diethanolamine and 100 g of water were placed in a reactor, and sodium chloroacetate 12 was added.
A 0.4 g (1.03 mol) aqueous solution was added dropwise over 1 hour. After the dropping, the temperature was gradually raised to 80 ° C. Then 4
40 g of 8% sodium hydroxide was added dropwise and reacted for 20 hours. After the reaction was completed, the solution was concentrated to dryness, and 1 l of methanol was added.
Was added and the insoluble matter was filtered off. Purification by further washing with ethanol and evaporation of the solvent under reduced pressure give N, N- (di-
41 g of 1-hydroxyethyl) -N-carboxymethylglycine sodium salt was obtained.

[0038]

[Chemical 6]

Example 3 N-methyl-N- (1-hydroxyethyl) -N-carboxymethylglycine sodium salt 2 obtained in Example 1
0 g was dissolved in 100 g of water and subjected to ion exchange chromatography (Organo Co., Amberlite IR-12).
0B), N-methyl-N- (1-hydroxyethyl) -N-carboxymethylglycine was obtained, and the pH was adjusted to 7.0 with triethanolamine. The solvent was concentrated to dryness and N-methyl-N- (1-hydroxyethyl) -N-
Carboxymethylglycine / triethanolamine salt 1
9 g were obtained.

[0040]

[Chemical 7]

Example 4 After obtaining N-methyl-N- (1-hydroxyethyl) -N-carboxymethylglycine in the same manner as in Example 3, the pH was adjusted to 7.0 using an aqueous choline solution, and the solution was added. Was concentrated to dryness to obtain N-methyl-N- (1-hydroxyethyl) -N-carboxymethylglycine / choline salt.

Example 5 In the same manner as in Example 1, dimethylamine was reacted with sodium chloroacetate in the presence of NaOH to obtain N, N-dimethyl-N-carboxymethylglycine sodium salt, and then as Example 3. Similarly, after removing Na by ion exchange chromatography, pH was adjusted with triethanolamine.
After adjusting to 7.0, the solution was concentrated and dried to obtain N, N-dimethyl-N-carboxymethylglycine / triethanolamine salt.

Example 6 Evaluation of Moisturizing Property The moisturizing property of carboxybetaine of the present invention was evaluated in the following manner. The results are shown in Table 1.

Evaluation method: A 2 wt% aqueous solution of each sample was prepared, and 10 μl of the sample solution per cm ² was applied to the flexion side of the human forearm conditioned at 20 ° C./40% RH,
Leave for 10 minutes. Before and after this process, SKICON-2
00 (manufactured by IBS Co., Ltd.) was used to measure the skin conductance, and the moisturizing ability was determined from the ratio of the conductance before and after the treatment. (N = 10) (Moisturizing capacity = conductance after treatment / conductance before treatment)

[0045]

[Table 1]

From the above results, the compound of the present invention was coated 1
It can be seen that the conductance after 0 minutes is higher than that of the blank, and that it has an excellent moisturizing ability.

[0047]

Table 2 Example 7 A paste-like face wash having the following composition was prepared. Sodium sesquilauryl phosphate 25 (wt%) Myristyl sulfosuccinate dipotassium 5 Cocoyl diethanolamide 2 Polyethylene glycol monostearate 4 Compound of Example 1 5 Carboxyvinyl polymer 0.5 Paraben 0.3 Perfume 0.3 Purified water balance This face wash The material was refreshed after washing, had a moist feel, and had no feeling of freshness.

[0048]

Table 3 Example 8 A liquid body shampoo having the following composition was prepared. Lauryl phosphate triethanolamine 20 (wt%) alkylsaccharide [C ₁₂ -O- (G) _2.5] ^* 1 5 lauroyl sarcosine compound thin sodium 5 Example 3 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.

[0049]

Table 4 Example 9 An anti-dandruff shampoo having the following composition was prepared. Lauryl dimethylamine betaine acetate 10 (% by weight) Sodium N-lauroylglutamate 10 Piroctone auramine (Octopirox, Hoechst) 0.5 Ethylene glycol distearate 2 Compound of Example 3 5 Perfume 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.

[0050]

Table 5 Example 10 A dishwashing detergent having the following composition was prepared. Polyoxyethylene (4) sodium lauryl ether sulfate 8 (wt%) polyoxyethylene (20) myristyl ether 5 lauryl dimethylamine oxide 3 ethanol 3 compound of Example 2 3 fragrance 0.1 water balance There was little bulkiness of the hand after use, and it was moist.

[0051]

Table 6 Example 11 A hair treatment having the following composition was prepared. 2-Dodecylhexadecyltrimethylammonium chloride 2 (wt%) Stearyltrimethylammonium chloride 2 Compound of Example 4 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 Fragrance 0.4 Water balance This hair treatment is excellent in imparting flexibility to hair and is non-greasy and gives a moist feel. Met.

[0052]

Table 12 Example 12 A lotion having the following composition was prepared. Lactic acid 0.03 (wt%) Sodium lactate 0.84 Compound of Example 5 5 Glycerin 2 Polyoxyethylene oleyl ether (20EO adduct) 1 Ethanol 10 Perfume 0.3 Water balance This lotion loses its moisturizing ability with sweat. It was not moisturized, was not sticky, and had a moist feeling.

[0053]

Table 8 Example 13 A powder bathing agent having the following composition was prepared. Sodium hydrogencarbonate 67 (wt%) Dextrin 30 Compound 2 of Example 5 Fragrance 0.5 Dye 0.5 This powder bathing agent had an excellent moisturizing effect on the skin and gave a moist feeling.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location C11D 1/90 (72) Inventor Kazuyasu Imai 2-10-10 Shozusawa, Itabashi-ku, Tokyo (72) Inventor Yoshiaki Fujikura 271-6 Yamamotocho, Utsunomiya City, Tochigi Prefecture

Claims (5)

[Claims] 1. The following general formula (1): (In the formula, R ¹ and R ² each represent a linear or branched alkyl group having 1 to 5 carbon atoms and having a hydroxyl group, and the rest are linear or branched alkyl groups having 1 to 5 carbon atoms. Represents an alkyl group of a chain, and X represents a hydrogen atom or a cation). 2. The following general formula (2): (In the formula, R ¹ and R ² each represent a linear or branched alkyl group having 1 to 5 carbon atoms and having a hydroxyl group, and the rest are linear or branched chain having 1 to 5 carbon atoms. Represented by the following general formula (3) Y—CH ₂ —COOX (3) (wherein Y represents a halogen atom and X represents a hydrogen atom or a cation). The method for producing carboxybetaine according to claim 1, which comprises reacting with a compound and optionally performing salt exchange. 3. A moisturizer comprising carboxybetaine according to claim 1. 4. A cosmetic containing the carboxybetaine according to claim 1. 5. A detergent composition containing the carboxybetaine according to claim 1.