JP2006022085A - Betaine-type compound, method for producing the same, and detergent composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a betaine-type surfactant exhibiting a high surface activity even in a wider pH region or in hard water, and having excellent low-temperature stability and compatibility with other surfactants. <P>SOLUTION: The betaine-type compound is represented by general formula (1) (wherein, R<SP>1</SP>is a 6-20C alkyl group; R<SP>2</SP>is a methyl group, an ethyl group or a hydroxyethyl group; R<SP>3</SP>is a methyl group, an ethyl group or a -CH<SB>2</SB>COOH group; and n is an integer of 1-3). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel betaine-type compound, a method for producing the same, and a detergent composition containing the novel betaine-type compound.

Soap, which is one of the most versatile surfactants, has a refreshing feeling of use, but has the disadvantage that the pH showing the surface activity is alkali side and the surface activity is extremely deteriorated in hard water. Have. As a surfactant to eliminate the disadvantages of soap,
For example, imidazoline-type amphoteric surfactants and carbobetaine-type amphoteric surfactants (Patent Document 1) have been proposed, but these amphoteric surfactants exhibit surface activity in a wide pH range and have high surface activity even in hard water. However, the foaming power was not sufficient, and there were drawbacks such as a feeling of use being felt.

  The alkylaminocarboxylic acid type amphoteric surfactant (Patent Document 2) has a good feeling of use, but has disadvantages such as low temperature stability and poor compatibility with other surfactants.

  In order to solve these problems, a method of adding an alkylene oxide or the like to an alkylaminocarboxylic acid type amphoteric surfactant has been disclosed (Patent Document 3), but the effect is not sufficient.

  In addition, when the alkylaminocarboxylic acid type amphoteric surfactant nitrogen is quaternized and derived into a betaine type, when monochloroacetic acid is added to a tertiary amine to obtain a betaine product, steric hindrance of the substituent of the tertiary amine In the case where is large, there has been a problem that the yield of betaine formation is low, and thus it has not been studied.

  In recent years, the hair color boom has increased the number of people who enjoy coloring with oxidative hair dyes and bleaching agents, and as a result, hair damage has been reduced and a higher color retention effect has been demanded.

  Various improvements in dyeing techniques have been made to meet these demands, but there are few examples of studying color fading in washing dyed hair.

(Patent Document 4)
(A) 1 type or 2 or more types chosen from anionic surfactant and amphoteric surfactant, and (B) Arginine and / or its salt are contained,
(C) A technology relating to a shampoo composition for use on dyed hair characterized by a pH of 4 to 7 has been disclosed, but the pH is limited from a weakly acidic region to a neutral region, and is neutral. In the vicinity, the effect of the invention weakened and was not satisfactory. Furthermore, there are cases where the performance of anionic surfactants and amphoteric surfactants added due to pH restrictions cannot be fully exhibited, and improvements have been demanded.
JP-A-56-10156 JP 47-33109 A Japanese Patent Publication No. 53-20489 JP 2002-47147 A

The problem to be solved by the present invention is to provide a novel betaine surfactant that exhibits high surface activity even in a wider pH range and in hard water, and is excellent in low-temperature stability and compatibility with other surfactants. . Another problem to be solved by the present invention is to provide a production method for obtaining the novel betaine surfactant in a high yield.

  Further, another problem to be solved by the present invention is that it has high color retention for dyed hair, dyed keratin fibers or dyed keratin fibers, and is sufficient for removing foreign substances adhering to the hair. Detergent hair with high foaming power, detergent composition for dyed keratin fibers, and advantageous detergent composition with viscosity buildability containing novel betaine, or novel betaine and sulfate type anion and specific ratio It is to provide a liquid detergent composition in which viscosity reduction due to dilution due to mixing is small.

  In order to solve the above problems, the present inventors have intensively studied various types of betaine-type compounds. As a result, the novel N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid betaines are obtained in a wide pH range or in hard water. It was found to exhibit high surface activity, excellent low-temperature stability, compatibility with other surfactants, and thickening.

  Moreover, the method of obtaining this betaine compound with a high yield was also discovered. Furthermore, when this betaine is blended in a detergent composition for dyed hair and dyed keratin fibers, it has high color retention, sufficient detergency and high foaming power, and has a refreshing and good feeling of use. I found out.

It has been found that this betaine product is not only excellent in compatibility with other surfactants, but also can build a wide range of viscosities by mixing with other surfactants. In particular, when mixed with a sulfate-based surfactant at a specific blending ratio, the liquid exhibits a unique viscoelastic behavior that does not change its viscosity even if the blended liquid detergent composition is diluted twice with water (weight ratio). Found the construction of a cleaning agent, and completed the present invention. That is, the first invention,
General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. And n represents an integer of 1 to 3).

The second invention relates to a betaine compound wherein the betaine compound is represented by the general formula (1), wherein R ¹ , R ² and n are the same as defined above, and R ³ is represented by a —CH ₂ COOH group. It is.

  The third invention is the general formula (2)

(Wherein, R ¹ is the same as defined above) and the general formula (3)

(Wherein R ² and n are as defined above, M represents a counter ion comprising a hydrogen atom or an alkali metal) and obtained by reacting with an N-alkylaminocarboxylic acid (salt). General formula (4)

(Wherein, R ¹ , R ² , n and M are as defined above) N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid (salt);
When the target product is R ^{3 in the} general formula (1) is a —CH ₂ COOH group, sodium monochloroacetate,
When R ^{3 in the} general formula (1) is an alkyl group, the target is the general formula (5)

(In the formula, R ⁴ represents an alkyl group having 1 or 2 carbon atoms.)
Dialkyl sulfuric acid represented by the general formula (6)

(In the formula, R ⁴ represents an alkyl group having 1 or 2 carbon atoms, and X represents a halogen atom.)
Characterized by reacting at least one selected from alkyl halides represented by:
General formula (1)

(Wherein, R ¹ , R ² , R ³ and n are the same as defined above).

The fourth invention provides an epoxy alkane represented by the general formula (2) and an N-alkylaminocarboxylic acid represented by the general formula (3) when producing the betaine compound represented by the general formula (1). N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid represented by the general formula (4) obtained by reacting an acid in a solvent containing 2-propanol is used. The present invention relates to a method for producing the betaine compound represented by (1).

  The fifth invention is represented by the general formula (1) by reacting N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid represented by the compound of the general formula (4) with sodium monochloroacetate. Betaine, wherein 0.2 to 1.0 equivalent of sodium glycolate is added to the N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid when producing a betaine-type compound The present invention relates to a method for producing a mold compound.

  The sixth invention relates to a cleaning composition comprising 0.1 to 50% by weight of a betaine type compound represented by the general formula (1).

  The seventh invention is (component A) an amphoteric surfactant other than the betaine type compound represented by the general formula (1) and (component B) the betaine type compound represented by the general formula (1); Contains at least one surfactant selected from surfactant, semipolar surfactant, anionic surfactant, nonionic surfactant, and cationic surfactant, and component A / (component A + component) A cleaning composition, wherein B) is 0.1 to 99% by weight.

  The eighth invention relates to a detergent composition for dyeing hair, comprising 0.1 to 50% by weight of a betaine type compound represented by the general formula (1).

  The ninth invention relates to a detergent composition for dyed keratin fibers, comprising 0.1 to 50% by weight of a betaine compound represented by the general formula (1).

Furthermore, the tenth invention contains (Component A) a betaine compound represented by the general formula (1) and (Component B) a sulfate-based anionic surfactant, and the content ratio of the two is a weight ratio. The present invention relates to a liquid detergent composition in which the viscosity does not decrease even when diluted, characterized in that component B = 10: 10 to 14: 6.

  The novel betaine-type compound of the present invention exhibits high surface activity even in a wide pH range and hard water, and is excellent in low-temperature stability and compatibility with other surfactants.

  In addition, when this betaine type compound is blended in a detergent composition for dyed hair and dyed keratin fibers, it has high color retention, sufficient detergency and high foaming power, and also has a good feeling of use. .

  This betaine type compound can build a wide viscosity by mixing with other surfactant. In particular, when mixed with a sulfate-based surfactant at a specific mixing ratio, even if the mixed liquid detergent composition is diluted twice with water (weight ratio), it exhibits a unique viscoelastic behavior that does not change its viscosity. A cleaning agent can be constructed.

  The detergent composition containing the novel betaine-type compound of the present invention has excellent foaming properties and feeling of use, particularly when used for washing hair dyed with an oxidative hair dye or the like. Shampoo compositions that show moderate detergency, condition the hair and improve color retention, and are also useful for detergents such as keratin fibers dyed in the same way as dyed hair and their clothing It is.

  By combining the novel betaine-type compound of the present invention with other surfactants, it is possible to obtain a liquid detergent composition capable of adjusting the viscosity with a wide range of viscosity realization regions depending on the blending ratio thereof, Furthermore, when mixed with a sulfur-containing anionic surfactant at a specific ratio, the composition does not change its viscosity even when diluted with water to about 2 times. The present invention relates to a liquid detergent composition having high viscoelasticity.

  Examples of the betaine type compound represented by the general formula (1) of the present invention include N- (2-hydroxydodecyl) -N, N-dimethylglycine, N- (2-hydroxydodecyl) -N-methyl-N. -Carboxymethylglycine, N- (2-hydroxydodecyl) -N, N-dimethyl-β-alanine, N- (2-hydroxydodecyl) -N-methyl-N-carboxymethyl-β-alanine, N- (2 -Hydroxydodecyl) -N-hydroxyethyl-N-methylglycine, N- (2-hydroxydodecyl) -N-hydroxyethyl-N-methyl-β-alanine and the like and salts thereof.

  The betaine type compound represented by the general formula (1) of the present invention is obtained by addition reaction of the epoxyalkane represented by the general formula (2) and the aminocarboxylic acid represented by the general formula (3). N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid represented by general formula (4), monochloroacetic acid (salt), dialkyl sulfuric acid represented by general formula (5), or general formula (6) It can be produced by adding an alkyl halide represented by Preferred examples of the epoxy alkane represented by the general formula (2) used for obtaining the betaine type compound represented by the general formula (1) of the present invention include 1,2-epoxydodecane, 1,2- Examples thereof include epoxytetradecane and a mixture thereof.

  Further, preferred examples of the aminocarboxylic acid represented by the general formula (3) include sarcosine, N-methyl-β alanine, N-ethyl glycine, N-hydroxyethyl-β alanine, and the like.

  The addition reaction of epoxy alkane and aminocarboxylic acid is preferably carried out in an aqueous solvent containing 10 to 90% by weight of 2-propanol. If the amount of 2-propanol in the aqueous solvent is less than 10% by weight, not only the time until the reaction is terminated, but also self-opening of the epoxyalkane occurs, and diol type impurities increase, which is not preferable.

  Moreover, when 2-propanol exceeds 90 weight%, precipitation of the aminocarboxylic acid of a raw material generate | occur | produces and it is unpreferable.

  At this time, it is important to use 2-propanol in the aqueous solvent. When other lower alcohols such as methanol and ethanol are used, the addition reaction easily proceeds with the lower alcohol and the raw material epoxyalkane, and when acetone and THF are used as a solvent, the addition reaction does not proceed, which is not preferable. .

  The reaction of adding monochloroacetic acid to the N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid represented by the general formula (4) is carried out by a usual method. At this time, glycolic acid is converted to monochloroacetic acid. On the other hand, it is important to add 0.2 to 1.0 equivalent. A glycolic acid addition amount of 0.2 equivalent or less is not preferable because the addition rate of monochloroacetic acid is lowered. If the added amount of glycolic acid is 1.0 equivalent or more, the touch when used in hair shampoos and the like is deteriorated, which is not preferable.

  The details of the reaction will be described by taking the production of N- (2-hydroxylauryl) -N-methyl-β-alanine betaine as an example.

  A reactor equipped with an apparatus capable of refluxing the reaction solvent is charged with 1,2-epoxide decane at a ratio of 0.8 to 0.98 mole per mole of N-methyl-β-alanine. At this time, it is important that the number of moles of epoxyalkane charged does not exceed the number of moles of aminocarboxylic acid charged. If the amount of the epoxy alkane added exceeds the aminocarboxylic acid, the epoxy alkane may remain in the reaction product, which is undesirable because it causes skin irritation. Further, an aqueous solvent containing 10 to 90% by weight of 2-propanol is added, and the temperature is raised to the reflux temperature of the aqueous solvent to proceed the addition reaction. The end point of the reaction becomes clear by analyzing the epoxyalkane in the contents by gas chromatography. After 2-propanol was distilled off, the temperature was raised to 90 ° C., 0.5 equivalent of glycolic acid was added to N- (2-hydroxylauryl) -N-methyl-β-alanine, and 1.0 equivalent of monochloro was added. Aqueous sodium acetate (30%) and 1.5 equivalents of aqueous sodium hydroxide (48%) are added dropwise over 5 hours. The end point of the reaction is revealed by analyzing the content of monochloroacetic acid by liquid chromatography. After confirming the completion of the reaction by liquid chromatography, the pH is adjusted and diluted with water to the desired concentration to obtain the N- (2-hydroxydodecyl) -N-methyl β-alanine betaine compound of the present invention. If necessary, inorganic salts generated as a by-product by RO membrane or electrodialysis may be removed.

  The detergent composition containing the novel betaine compound of the present invention is used for washing dyed hair, dyed pubic hair, dyed keratin fibers and fabrics composed of dyed keratin fibers (hereinafter referred to as “dyed keratin-like materials”). If so, it can be washed with less color fading. The content of the betaine compound represented by the general formula (1) of the present invention in the detergent composition for dyed keratin-like materials is preferably 0.1 to 50% by weight. If the content is less than 0.1%, the anti-fading effect on the dyed keratin-like product is not sufficient, and if the content exceeds 50% by weight, there are problems such as deterioration of the feeling of use and insufficient stability of the preparation. It is not preferable. In particular, when it is used as a hair shampoo for dyed hair, it is not preferred because the touch is deteriorated.

  The anti-fading effect on this dyed keratin-like material is manifested when used in combination with commonly used anionic surfactants, nonionic surfactants, amphoteric surfactants, amphoteric surfactants, and semipolar surfactants. It is preferable to blend the betaine type compound represented by the general formula (1) in an amount of 50% by weight or more of the surfactant amount.

Further, the novel betaine-type compound of the present invention has the property of thickening when used in combination with anionic surfactants as well as other amphoteric and zwitterionic surfactants. When the novel betaine compound of the present invention and an anionic surfactant are used in combination, the following two points have the characteristic of exhibiting a viscosity behavior different from other amphoteric and zwitterionic surfactants.
(A) The rate of increase in viscosity at a position where the addition amount relative to the anion is small is higher than that of other amphoteric and zwitterionic surfactants.
(B) A liquid detergent that is formulated with a specific ratio with a sulfate-based or sulfonic acid-based anionic surfactant does not reduce viscosity due to dilution.

  The property of the above (A) is that the novel betaine-type compound of the present invention can increase the viscosity of the blending system by adding a smaller amount to the liquid detergent composition mainly composed of anions than other amphoteric and zwitterionic surfactants. Therefore, it is excellent in the effect as a thickener.

  The property (B) is manifested by mixing the betaine compound of the present invention with a sulfate or sulfonate anion in a weight ratio of 10:10 to 14: 6. The viscosity constructed by blending in this range does not change even when the composition is diluted twice with water (weight ratio).

  Outside this range, viscosity maintaining ability at the time of dilution does not occur.

  Examples of the sulfate-based and sulfonic acid-based anions used at this time include polyoxyethylene alkyl ether sulfate ester salt, lauryl sulfate ester triethanolamine salt, alkylbenzene sulfonate salt, and alkane sulfonate salt.

  Anionic surfactants, nonionic surfactants, amphoteric surfactants, semipolar surfactants, zwitterionic surfactants, cationic interfaces used in combination with detergent compositions containing the novel betaine type compounds of the present invention The active agent will be described in detail.

Anionic activators include fatty acid soaps such as soap base, sodium laurate, sodium palmitate, coconut soap,
Higher alkyl sulfate salts: for example, sodium lauryl sulfate, potassium lauryl sulfate, lauryl sulfate triethanolamine,
Alkyl ether sulfate ester salt: for example, POE lauryl sulfate triethanolamine, POE sodium lauryl sulfate,
N-acyl amino acid salts: for example, lauroyl sarcosine sodium, lauroyl-β-alanine sodium, lauroyl-N-methyl-β-alanine sodium, N-lauroyl glutamate monosodium, N-stearoyl glutamate disodium, N-myristoyl-L-glutamic acid Monosodium, N-palmitoyl aspartate diethanolamine, coconut fatty acid silk peptide,
Higher fatty acid amide sulfonates: for example, N-myristoyl-N-methyl taurine sodium, coconut fatty acid methyl taurine sodium, lauroyl methyl taurine sodium.
Phosphate ester salts, such as sodium POE oleyl ether phosphate, POE stearyl ether phosphate, sodium POE lauryl amide ether phosphate,
Sulfosuccinate: for example, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate,
Alkylbenzene sulfonate: for example, sodium linear dodecyl benzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, linear dodecyl benzene sulfonic acid,
Higher fatty acid ester sulfate ester salt: for example, hydrogenated coconut oil fatty acid sodium glycerin sulfate, sulfated oil such as funnel oil, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate ester salt,
Higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamide sodium succinate, sodium caseinate and the like.

As a cationic surfactant,
Alkyltrimethylammonium salts: for example, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide,
Dialkyldimethylammonium salts, such as distearyldimethylammonium chloride,
Alkyl pyridium salts, such as cetyl pyridium chloride,
Alkyldimethylbenzylammonium salt: benzethonium chloride, benzalkonium chloride and the like.

As an amphoteric surfactant or a zwitterionic surfactant,
Amidoamine amphoteric surfactants: for example 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, N-lauroyl-N′-carboxymethyl-N′-hydroxyethylethylenediamine sodium, N-coconut fatty acid acyl-N '-Carboxyethyl-N'-hydroxyethylethylenediamine sodium,
Amidoacetic acid betaine type amphoteric surfactant: for example, coconut fatty acid amidopropyl betaine, myristic acid amidopropyl betaine,
Amidosulfobetaine-type amphoteric surfactants such as amidopropyl hydroxysulfobetaine laurate, alkylacetic acid betaine-type amphoteric surfactants, alkylsulfobetaine-type amphoteric surfactants, etc. The amidosulfobetaine-type zwitterionic surfactant represented by the formula (7) is a surfactant having a weak hair color decoloring ability in the low pH region, and is therefore a preferable surfactant to be used in the hair color detergent composition of the present invention. .

[Wherein R ⁵ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ⁶ and R ⁷ represent a substituent selected from a hydrogen atom, a methyl group and an ethyl group, and s represents an integer of 2 or 3. ]
Examples of the semipolar surfactant include lauryltrimethylamine oxide and lauric acid amidopropylamine oxide.

Nonionic surfactants include glycerin fatty acid esters such as glyceryl monostearate, glyceryl monostearate, glyceryl monoisostearate,
Polyoxyethylene glycerin fatty acid esters: for example, POE glyceryl monostearate, POE glyceryl monooleate,
Polyglycerol fatty acid esters: for example, diglyceryl monostearate, tetraglyceryl tristearate, decaglyceryl pentastearate,
Sorbitan fatty acid esters: for example, sorbitan monolaurate, sorbitan sesquistearate, sorbitan monooleate,
Polyoxyethylene sorbitan fatty acid esters: for example, monococonut fatty acid POE sorbitan, tristearic acid POE sorbitan, trioleic acid POE sorbitan,
Polyoxyethylene sorbite fatty acid esters: for example, monolauric acid POE sorbite, tetraoleic acid POE sorbit,
Polyethylene glycol fatty acid esters: for example, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate,
Polyoxyethylene alkyl ethers: for example, POE lauryl ether, POE cetyl ether, POE stearyl ether,
Polyoxyethylene polyoxypropylene alkyl ethers: For example, POE / POP cetyl ether, POE / POP decyl tetradecyl ether,
Polyoxyethylene alkyl phenyl ethers: POE nonyl phenyl ether, POE octyl phenyl ether, POE branched octyl phenyl ether,
Polyoxyethylene alkylamines: for example, POE stearylamine, POE oleylamine,
Fatty acid alkanolamides: for example, coconut fatty acid diethanolamide, coconut fatty acid monoethanolamide, lauric acid diethanolamide, palm kernel oil fatty acid diethanolamide. , Polyoxyethylene alkanolamides: for example, POE lauric acid monoethanolamide, POE coconut fatty acid monoethanolamide, POE beef tallow fatty acid monoethanolamide,
Further examples include acetylene glycol, POE acetylene glycol, POE lanolin, POE lanolin alcohol, POE castor oil, POE hydrogenated castor oil, POE phytosterol, POE cholestanol, and POE nonylphenyl formaldehyde condensate.

  It is more preferable to use in combination with the hair-absorbing and film-forming polymer or silicone as an additive component, since the effect of preventing discoloration of the detergent composition for dyed keratin-like materials of the present invention may increase. .

Examples of silicones include dimethyl silicone oils: for example, methylpolysiloxane, octamethyltrisiloxane, high polymerization degree methylpolysiloxane, and the like.
Cyclic polysiloxanes: For example, decamethyl polysiloxane, dodecamethyl polysiloxane, tetramethyltetrahydrogen polysiloxane and the like are preferable examples.
Preferred examples of polyether-modified silicones include dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxyethylene) siloxane / methyl (polyoxypropylene) siloxane copolymer, and the like.
Amino-modified silicones such as amodimethicone are preferred examples,
Further, methylphenyl polysiloxane, methyl hydrogen polysiloxane, trimethylsiloxysilicic acid, silicon resin forming a three-dimensional network structure, silicon rubber and the like can be mentioned.

  Examples of the polymer capable of adsorbing hair and forming a film include anionic polymers, cationic polymers, and amphoteric polymers.

  Preferable examples of the anionic polymer include chitin / chitosan derivatives such as carboxymethyl chitin, carboxymethyl chitosan, and succinylated carboxymethyl chitosan.

  As the cationic polymer, Polyquaternium-1, Polyquaternium-2, Polyquaternium-3, Polyquaternium-3 described in the International Nomenclature Cosmetic Ingredient Name (INCI name) and the component name display of the permission standard for each cosmetic variety 4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10, polyquaternium-11, polyquaternium-12, Polyquaternium-13, polyquaternium-14, polyquaternium-15, polyquaternium-16, polyquaternium-17, polyquaternium-18, polyquaternium-19, polyqua Titanium-20, polyquaternium-22, polyquaternium-24, polyquaternium-27, polyquaternium-28, polyquaternium-29, polyquaternium-30, polyquaternium-31, polyquaternium- 32, polyquaternium-33, polyquaternium-34, polyquaternium-35, polyquaternium-36, polyquaternium-37, polyquaternium-39, polyquaternium-42, polyquaternium-43, Examples thereof include polyquaternium-44 and a mixture thereof, and preferable examples include a halide of guar hydroxypropyltrimethylammonium.

  In addition, other ingredients usually used in cosmetics as long as they do not interfere with the effects of the invention, such as animal, plant, fish and shellfish, microorganism-derived extracts, powder ingredients, liquid fats, solid fats, waxes, hydrocarbons, higher fatty acids, Higher alcohols, esters, moisturizers, water-soluble polymers, thickeners, coating agents, UV absorbers, flame retardants, sequestering agents, lower alcohols, sugars, amino acids, organic amines, synthetic resin emulsions, pH adjustment One or more kinds of agents, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water and the like may be used as necessary.

(Example)
Next, examples will be shown and described in more detail, but the present invention is not limited to these examples. In addition,% in an Example and a comparative example means weight%.

In accordance with the following Examples 1 to 6, various N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid betaine type surfactant compositions were synthesized.
The analysis method and conditions of the product are as follows.

(Gas chromatography matography)
Column: THERMON-3000 5% SHINCARBON A 60-80mash
Injection temperature: 280 ℃
Detector: FID
Detector temperature: 280 ° C
Temperature rise conditions: 150 ° C (5 minutes hold) -10 ° C / min -230 ° C (10 minutes hold)

(Liquid chromatography)
Column: Inertsil ODS-2 (GL Science)
Oven temperature: 40 ° C
Detector: RI
Eluent: 0.1M NaH ₂ PO ₄ (pH = 2.5) / MeOH = 35/65
Eluent flow rate: 1ml / min.
Further, for each sample, the low-temperature stability and the discoloration of the dyed hair were measured.

Synthesis of N- (2-hydroxydodecyl) -N, N-dimethylglycine
A 3000 mL 4-necked flask was charged with 630.1 g of a sarcosine sodium aqueous solution (pure content 37.6%, 236.9 g, 2.13 mol) and 1200 g of 2-propanol and heated to 70 ° C. Here, 374.4 g (2.03 mol) of 1,2-epoxydodecane (trademark: α-olefin oxide C12, manufactured by Asahi Denka Co., Ltd.) was added dropwise over 1.5 hours. After completion of dropping, the mixture was heated to 82 ° C. and stirred for 4 hours. Thereafter, desalting was performed under reduced pressure, cooling to room temperature, adding water to adjust the concentration, and then adjusting to pH 7 with hydrochloric acid (active ingredient concentration 20%). From the gas chromatography analysis, this surfactant solution contained 19.2% surfactant, 0.7% diol, and 0.2% ether.

  The reaction product was desolvated under reduced pressure and then ice-cooled, and 260 g (2.06 mol) of dimethyl sulfate was added dropwise over 4 hours. After raising the temperature to 100 ° C. and refluxing for 2 hours to decompose unreacted dimethyl sulfate, the mixture was cooled to room temperature, water was added to adjust the concentration, and the pH was adjusted to 7 with hydrochloric acid (active ingredient concentration 25%). From the liquid chromatography analysis, the yield of this betaine-type compound was 95%.

Product ^H 1 -NMR heavy water measured in Example 1
0.9ppm 3H
1.3-1.5 ppm 18H
3.4ppm 6H
3.5-4.3 ppm 5H

Synthesis of N- (2-hydroxydodecyl) -N-methyl-N-carboxymethyl-β-alanine
An N-methyl-β-alanine aqueous solution (159.8 g, pure content: 27.9%, 44.6 g, 0.36 mol) and 2-propanol (200 g) were charged into a 1 L 4-necked flask and heated to 60 ° C. Here, 62.4 g (0.34 mol) of 1,2-epoxydodecane (trademark: α-olefin oxide C12, manufactured by Asahi Denka Co., Ltd.) was added dropwise over 1.75 hours. After completion of dropping, the mixture was heated to 82 ° C. and stirred for 3 hours. Thereafter, desalting was performed under reduced pressure, cooling to room temperature, adding water to adjust the concentration, and then adjusting to pH 7 with hydrochloric acid (active ingredient concentration 20%). From the gas chromatography analysis, this surfactant solution contained 19.4% surfactant, 0.3% diol, and 0.3% ether.

  The reaction product was desolvated, cooled to room temperature, 12.6 g (0.17 mol) of glycolic acid and 14.0 g (0.17 mol) of 48% NaOH were added, the temperature was raised to 90 ° C., and 30% aqueous solution of sodium monochloroacetate 104.0 g (0.33 mol) and 41.2 g (0.49 mol) of 48% NaOH aqueous solution were added dropwise over 5 hours. After cooling to room temperature and adding water to adjust the concentration, the pH was adjusted to 7 with hydrochloric acid (active ingredient concentration 25%). From the liquid chromatography analysis, the yield of this betaine-type compound was 90%.

Product ^H 1 -NMR heavy water measured in Example 2
0.9ppm 3H
1.3-1.5 ppm 18H
2.8 ppm 2H
3.3ppm 3H
3.5-4.3 ppm 7H

N- (2-hydroxyalkyl) -N-hydroxyethyl-N-methylglycine
Put 504.0g of N-Me-monoethanolamine (1.05 equivalent of epoxy) in a 2 liter 4-neck flask and raise the temperature to 80 ° C. 1256.8g of C _12,14 epoxy (Daicel, AOEX24 DG-009) 6.39 mol) was added dropwise over 3 hours and stirred at 80 ° C. overnight. After confirming that the epoxy residue was ND by gas chromatography, the excess amine was distilled off with a vacuum pump at 80 ° C to obtain 1735 g of N-2-hydroxylauryl-N-2-hydroxyethyl-N-methylamine. It was.

  To a 5-liter four-necked flask, 810.1 g (2.98 mol) of N-2-hydroxylauryl-N-2-hydroxyethyl-N-methylamine and 1961 g of water were added, and the temperature was raised to 70 ° C. An 80% aqueous solution of sodium monochloroacetate (493.0 g, 1.4 equivalents of amine) and 400 g of 48% NaOH (1.2 equivalents of monochloroacetic acid) were added dropwise over 2 hours in the range of pH = 7-8. The temperature was raised to 97 ° C., and aging was carried out for 17 hours while appropriately adding 40 g of 48% NaOH (0.1 equivalent of monochloroacetic acid) in the range of pH = 7-8. After cooling to room temperature, water was added to take up an N-2-hydroxylauryl-N-2-hydroxyethyl-N-methylglycine aqueous solution with a total weight of 3775 g. Dry residue = 35.4%, NaCl = 6.3%, active ingredient (dry residue-NaCl) = 29.1%, glycolic acid = 2.8%, betaine yield from HPLC (UV) = 92%.

Product H ¹ -NMR of Example 3 Measurement in heavy water
0.9ppm 3H
1.3-1.5 ppm 20H
3.4ppm 3H
3.5-4.3 ppm 9H

Synthesis of N- (2-hydroxydodecyl) -N-methyl-N-dicarboxymethyl-β-alanine
A 500 mL 4-necked flask was charged with 48.28 g (0.36 mol) of iminodiacetic acid, 51.4 g of IPA, 124.2 g of water, and 59.2 g of 48% NaOH (0.72 mol) and heated to 70 ° C. Here, 62.4 g (0.34 mol) of 1,2-epoxydodecane (trade name: α-olefin oxide C12, manufactured by Asahi Denka Co., Ltd.) was added dropwise over 1.0 hour. After completion of dropping, the mixture was heated to 82 ° C. and stirred for 3 hours. Thereafter, the solvent was removed under reduced pressure. After removing the solvent, the solution was cooled to room temperature and the concentration was adjusted by adding water, and then adjusted to pH 7 with hydrochloric acid (solid content concentration 20%). The analytical values in this activator solution were an activator content of 19.0%, a diol form of 0.7%, and an ether form of 0.3%.

The reaction product was desolvated under reduced pressure and then ice-cooled, and 88.4 g (0.70 mol) of dimethyl sulfate was added dropwise over 4 hours. After raising the temperature to 100 ° C. and refluxing for 2 hours to decompose unreacted dimethyl sulfate, the mixture was cooled to room temperature, water was added to adjust the concentration, and the pH was adjusted to 7 with hydrochloric acid (active ingredient concentration 25%). From the liquid chromatography analysis, the yield of this betaine type compound was 94%.
Product H1-NMR in Example 4 Measurement in heavy water
0.9ppm 3H
1.3-1.5 ppm 18H
3.4ppm 3H
3.5-4.3 ppm 7H

Synthesis of N- (2-hydroxydodecyl) -N-methyl-N-carboxymethyl-β-alanine The same reaction as in Example 2 was performed except that glycolic acid was not added in the step of adding monochloroacetic acid. After cooling to room temperature and adding water to adjust the concentration, the pH was adjusted to 7 with hydrochloric acid (active ingredient concentration 25%). From the liquid chromatography analysis, the yield of this betaine type compound was 50%.

  Comparing Example 2 and Example 5, in quaternization with monochloroacetic acid for a tertiary amine having a large steric hindrance such as N- (2-hydroxydodecyl) -N-methyl-β-alanine, at the start of quaternization It can be seen that the reaction yield of N- (2-hydroxydodecyl) -N-methyl-N-carboxymethyl-β-alanine is significantly different between Example 2 in which glycolic acid was added in advance and Example 5 in which glycolic acid was not added. .

  Various performance evaluations were performed using the betaine compounds experimentally produced in Examples 1 to 5 and N-dimethylalkyl acetate betaine (lauryl acetate betaine) and amidoacetate betaine (laurate amidopropyl acetate betaine) having a similar structure, and the present betaine was used. The characteristics of viscosity behavior when combined with other surfactants were clarified.

1. Experiment on thickening effect
(A) Thickening test Two-component liquid detergent compositions were blended at the blending ratios shown in Tables 1 and 2 below, and the viscosity was measured at 25 ° C with a B-type viscometer. In addition, the ratio of a mixing | blending component is a pure part weight ratio.

  SLES itself has a pure 20% viscosity of 11 mPa · s. Comparing the examples and the comparative examples, it can be seen that the novel betaine of the present invention can obtain a large viscosity by adding a small amount.

  Although it is difficult to thicken a surfactant having a carboxylic acid in a hydrophilic group, as is clear from Table 2, the betaine type compound of the present invention sufficiently thickens a fatty acid salt which is a carboxylic acid type anion. I can do it.

(B) Dilution viscosity maintenance test

  The ratio of the betaine of Example 3 to SLES (POE (3) sodium lauryl ether sulfate (Eoal 20C, manufactured by Kao Corporation)) was 12: 8 so that the total surfactant concentration was 20% by weight. Blended into The initial viscosity (mPa · s) was measured, and distilled water was added to dilute until the pure surfactant concentration became the concentration shown in Table 3, and the viscosity at the time of dilution (mPa · s) was measured.

The ratios in the table are betaine: SLES weight ratio

  As shown in Table 3, the viscosity of the present betaine and a sulfate-based or sulfonic acid-based anion such as POE lauryl ether sulfate in the range of 10:10 to 14: 6 is up to 2-fold dilution. It can be seen that it has a slightly increasing nature. If this property is outside the above specific range, the viscosity is reduced by dilution, and this viscoelastic property is lost.

2. Experiment on foaming power The foaming characteristics of the present betaine were evaluated by the following method.

(A) Mixer Foaming Power Test Foaming power when adding hard water to the betaine compound and soap of Production Example 1 was measured by a mixer method (surfactant concentration = 0.25%, 40 ° C., pH = 10).

  From Table 4, it can be seen that the betaine compound of Example 1 has excellent foaming power and has surface activity even in hard water.

(B) Ross Miles Foaming Power Test Foaming power at each pH of the betaine compound of Production Example 1 and amidopropyl betaine laurate (Softazoline LPB manufactured by Kawaken Fine Chemical Co., Ltd.) was measured by the Ross Miles method (surface activity) Agent concentration = 0.25%, 40 ° C).

As is clear from Table 5, it can be seen that the foaming power of the betaine compound of Example 1 is very excellent in the entire range of pH = 4 to 10. It can also be seen that the foaming power is higher than that of amidopropyl betaine-type softazolin LPB.
3. Anti-fading effect Samples were prototyped according to the following table, and low temperature stability, hair color decoloring performance evaluation and hair manicure decoloring performance evaluation, which are the characteristics of the present betaine, were performed. The total amount of surfactant in each sample was kept at 15% by weight.

Storage stability Temperature-5C 1 day Storage stability at each temperature was evaluated by the following evaluation.

○: Transparent uniform liquid △: Dullness occurs ×: Solidification

Hair color decoloration performance evaluation 2% aqueous solution of POE (3) sodium lauryl ether sulfate (Kao Co., Ltd., Emar 20C) using a white hair bundle (BM-W, manufactured by Beaulux Co., Ltd., length 10cm, weight 1g) After thoroughly washing with a hair dryer, it was dried with a hair dryer.

  After drying, the hair bundle is dyed with a commercially available hair dye (manufactured by Shiseido Co., Ltd., trade name: masheri lasting hair color, color: sheer ash) according to the method specified for the product, and then washed thoroughly with water. Dry with a hair dryer.

  The dried hair bundle after drying is packed in a bottle with a capacity of 100 ml, and 100 ml of an aqueous solution obtained by diluting the specimen composition with distilled water so that the pure content of the active agent is 0.5% is poured and sealed with a lid. Shaking on the sun.

After the shaking, the lid was opened and the dyed hair bundle in the sample bottle was taken out, washed thoroughly with water and dried with a hair dryer. The color difference (ΔE) of the dyed hair bundle after drying was measured with a color difference meter (Nippon Denshoku Industries Co., Ltd., Spectrophotometer SE 2000).
The smaller the value of ΔE, the higher the color fading prevention effect.

Hair Manicure Depilation Performance Evaluation Chinese hair including white hair was bundled with the cuticle direction aligned to create a hair bundle of about 30 cm in length and about 20 g in weight. The hair bundle was thoroughly washed with a 2% aqueous solution of POE (3) sodium lauryl ether sulfate (Eoal 20C, manufactured by Kao Corporation), and then dried with a hair dryer.

  After drying, the hair bundle is dyed with a commercially available hair dye (made by Dariya Co., Ltd., trade name: Salon de Pro Hair Manicure Speedy, color: Honey Brown), and then washed thoroughly with water. And dried with a hair dryer.

  Weigh 100 mg of hair from the dyed hair bundle after drying (within an error of ± 1 mg, approx. 60), pack it into a 20 ml bottle, and dilute the sample composition with distilled water so that the active agent content is 0.5%. 20 ml of the diluted aqueous solution was poured, sealed with a lid, and allowed to stand at room temperature for 14 hours.

After 14 hours, the lid was opened, 15 ml of the solution in the sample bottle alone was collected with a dropper, and the color difference (ΔE) was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., MODEL 1001DP).
The smaller the value of ΔE, the higher the color fading prevention effect.

Evaluation of dyeing yarn decolorization performance Commercially available yarn (red) was cut to a length of 10 cm to create a hair bundle of 1 g in weight, packed in a 100 ml bottle, and the sample composition was 0.5% pure in the active agent 100 ml of an aqueous solution diluted with distilled water was poured, sealed with a lid, and shaken at room temperature for 2 days.

After the shaking, the lid was opened and the hair bundle in the sample bottle was taken out, washed thoroughly with water and dried with a hair dryer. The color difference (ΔE) of the hair bundle after drying was measured with a color difference meter (Nippon Denshoku Industries Co., Ltd., Spectrophotometer SE 2000).
The smaller the value of ΔE, the higher the color fading prevention effect.

  From the results in Table 6, the shampoo compositions of the present invention all have a high hair manicure removing effect, that is, an excellent effect of removing stains adhering to the hair surface, and a low hair color decoloring effect and a dyed yarn decoloring effect. is doing. For this reason, there is little color fading of the dyed keratin-like material, and the effect is maintained from acidic to weakly alkaline. This is a performance not exhibited by conventional surfactants, and has the advantage that the pH of the cleaning composition can be set in a wide range.

  Moreover, if it is N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid which is the substance before betainization of Example 2, although the low hair color decoloring effect and the low dyeing yarn decoloring effect can be implement | achieved, detergent composition It turns out that the low-temperature stability of a thing deteriorates.

  Examples of blend formulations using the present betaine and adding other ingredients to the base formulation that expresses viscoelastic properties, foaming properties, and anti-fading ability of dyed keratin-like materials are included. .

  All prescriptions are obtained by measuring all ingredients except the fragrance, raising the temperature to 80 ° C., holding for 10 minutes, cooling, adding the fragrance at 60 ° C., and cooling to room temperature.

(Pearl shampoo for dyed hair)
Polyoxyethylene (2) Lauryl ether sulfate Na salt (25%) 10.0
Lauric acid amidopropyl hydroxysulfobetaine (30%) 5.0
Polyoxypropylene palm fatty acid isopropanolamide 1.0
Betaine of Example 1 (25%) 50.0
EDTA 0.1
Methylparaben 0.2
Piroctone Olamine 0.7
Ethylene glycol distearate 1.5
Carboxymethyl succinylated chitosan solution (Note 3) 2.0
Glycerin 2.0
Perfume Appropriate amount Dipotassium glycyrrhizinate 0.5
Citric acid pH = 6.5
Purified water to 100
The abundance ratio of the betaine-type surfactant of Example 1 is 71%. The surfactant pure component concentration is 17.5%. The hair color decolorization performance test result of this formulation having good foaming and foamy creamyness was 8.4.

(Shampoo for dyeing hair)
Polyoxyethylene (2) lauryl ether sulfate Na salt 3.0
Polyoxyethylene (3) Lauric acid monoethanolamide sulfonic acid Na salt (30%) 5.0
Palm fatty acid diethanolamide 1.5
Composition of Example 3 (29.1%) 60.0
Polyquaternium-7 (Note 4) 0.5
Carboxymethyl succinylated chitosan solution (Note 3) 1.0
Citric acid pH = 6.5
Glycerin 1.5
Perfume Appropriate amount Dipotassium glycyrrhizinate 0.1
Purified water to 100
The abundance ratio of the betaine surfactant of Example 3 is 82%. The surfactant concentration is 21.2%. The hair color decolorization performance test result of this formulation was 4.1.
(Note 1) Kao Corporation Emar 20C
(Note 2) Kawaken Fine Chemical Co., Ltd. Alanon ALE
(Note 3) Kawaken Fine Chemical Co., Ltd. Kitaqua (Note 4) Lion Corp. Lipoflow MN

  The novel betaine-type compound of the present invention exhibits high surface activity even in a wide pH range and in hard water, and is useful as a surfactant because it is excellent in low-temperature stability and compatibility with other surfactants.

  In addition, when this betaine type compound is blended in a detergent composition for dyed hair and dyed keratin fibers, it has high color retention, sufficient detergency and high foaming power, and also has a good feeling of use. Therefore, it is also useful as a detergent composition for dyed keratin fibers.

  This betaine type compound can build a wide viscosity by mixing with other surfactant. In particular, when mixed with a sulfate-based surfactant at a specific blending ratio, the liquid exhibits a unique viscoelastic behavior that does not change its viscosity even if the blended liquid detergent composition is diluted twice with water (weight ratio). Useful as a cleaning agent.

Claims (10)

General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. And n represents an integer of 1 to 3). The betaine-type compound is a compound in which, in the general formula (1), R ¹ , R ² and n are the same as defined above, and R ³ is represented by a —CH ₂ COOH group. 1. The betaine type compound described in 1. General formula (2)

(Wherein, R ¹ represents an alkyl group having 6 to 20 carbon atoms) and the general formula (3)

(Wherein, R ² represents a methyl group, an ethyl group or a hydroxyethyl group, n represents an integer of 1 to 3, and M represents a counter ion comprising a hydrogen atom or an alkali metal). -General formula (4) obtained by reacting alkylaminocarboxylic acid (salt)

(Wherein, R ¹ , R ² , n and M are as defined above) N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid (salt);
When the target product is R ^{3 in the} general formula (1) is a —CH ₂ COOH group, sodium monochloroacetate,
When R ^{3 in the} general formula (1) is an alkyl group, the target is the general formula (5)

(Wherein R ⁴ represents an alkyl group having 1 or 2 carbon atoms) or a general formula (6)

(Wherein, R ⁴ is the same as defined above, X represents a halogen atom), and is reacted with at least one selected from alkyl halides represented by:
General formula (1)

(Wherein, R ¹ , R ² and n are the same as defined above, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group). In producing the betaine compound represented by the general formula (1), the epoxyalkane represented by the general formula (2) and the N-alkylaminocarboxylic acid represented by the general formula (3) are mixed with 2-propanol. The N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid represented by the general formula (4) obtained by reacting in a solvent containing the general formula (4) is used. A method for producing a betaine compound represented by 1). The betaine type compound represented by the general formula (1) is produced by reacting N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid represented by the compound of the general formula (4) with sodium monochloroacetate. In this case, 0.2 to 1.0 equivalent of sodium glycolate is added to the N- (2-hydroxyalkyl) -N-alkylaminocarboxylic acid. A method for producing a betaine compound represented by (1). General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. A detergent composition comprising 0.1 to 50% by weight of a betaine type compound represented by: wherein n represents an integer of 1 to 3. (Component A) General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. And n represents an integer of 1 to 3), and (Component B) an amphoteric surfactant other than the betaine compound represented by the general formula (1), a zwitterionic surfactant , Containing at least one surfactant selected from a semipolar surfactant, an anionic surfactant, a nonionic surfactant, and a cationic surfactant, and component A / (component A + component B) A cleaning composition, which is 0.1 to 99% by weight. General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. A detergent composition for dyeing hair, comprising 0.1 to 50% by weight of a betaine-type compound represented by the formula: General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. A detergent composition for dyeing keratin fibers, comprising 0.1 to 50% by weight of a betaine type compound represented by the formula: (Component A) General formula (1)

(In the formula, R ¹ represents an alkyl group having 6 to 20 carbon atoms, R ² represents a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a methyl group, an ethyl group, or a —CH ₂ COOH group. And n represents an integer of 1 to 3) and (Component B) a sulfate-based and sulfonic acid-based anionic surfactant. A liquid detergent composition in which the viscosity does not decrease even when diluted, wherein Component B = 10: 10 to 14: 6.