JP5542769B2 - Method for improving low-temperature stability of aqueous solutions containing long-chain acyliminodiacetic acid type surfactant compounds - Google Patents

Description

  The present invention relates to a method for improving the low temperature stability of an aqueous solution containing a long-chain acyliminodiacetic acid type surfactant compound. The low-temperature stable mixed aqueous solution obtained by the method of the present invention is used as a liquid detergent.

  Detergent compositions such as kitchen cleaners, hair cleaners and body cleaners are generally based on anionic surfactants, mainly higher fatty acid salts (soaps), alkyl sulfates, sulfonates, etc. Is used. However, for example, when soap is used for washing the skin, soap scum (higher fatty acid Ca salt) is generated and adheres to the skin at the time of rinsing, so that the lubricity of the skin surface is remarkably lowered, and a squeaky feeling or a feeling of tension is generated. There were drawbacks. Further, when alkyl sulfates, sulfonates, and the like are used for washing hair, there is no squeaky feeling or tightness, but there are drawbacks such as poor foaming and poor hair lubricity.

  In addition, the detergent composition containing acyliminodiacetate is a kind of surfactant that has excellent lubricity after use, less squeaky feeling and tightness, and has an excellent feeling of use. (JP-A-2-84496 (Patent Document 1), JP-A-5-117139 (Patent Document 2), JP-A-6-80987 (Patent Document 3)).

  Although these conventional detergents are improved in detergency, foaming power, feeling in use, etc., acyliminodiacetate has a tendency to be easily crystallized due to its high craft point and molecular structure. Therefore, the liquid detergent composition containing it has a problem of low storage stability at low temperatures, particularly low temperature stability from a weakly acidic region to a neutral region, and is a practical component as a surfactant component. It was difficult.

  In addition, acyliminodiacetate has a property that it is difficult to increase the viscosity even when a thickener such as a fatty acid alkanolamide is added to the acyliminodiacetate in the solution state, and by adding an alkyl ether sulfate and a fatty acid amidopropyl betaine. When acyliminodiacetate is added to the high viscosity region of the resulting composition, it exhibits a hydrotropic effect of destroying the high viscosity structure and lowering the viscosity. For this reason, in the detergent composition mix | blended in the quantity which the washing | cleaning feeling of acyliminodiacetate expresses, there existed a problem that the viscosity became difficult to control. Because of these properties, acyliminodiacetate is a surfactant that has been known for a long time, but until now, it has been difficult to formulate it effectively using its properties, and therefore the above problems are desired to be improved. It was.

  As for the improvement of the low temperature stability of acylimino dibasic acid salt, as disclosed in JP-A-8-60182 (Patent Document 4), an attempt has been made to solve the problem by making the dibasic acid group moiety asymmetric. ing. Thereby, the effect of improving the low temperature stability is recognized, but there is a problem that the lubricity after washing is inferior to that of acyliminodiacetate. For this reason, development of the low temperature stability improvement method of acyliminodiacetate containing aqueous solution was desired.

Japanese Patent Laid-Open No. 2-84496 Japanese Patent Laid-Open No. 5-117139 Japanese Patent Laid-Open No. 6-80987 JP-A-8-60182

  An object of the present invention is to contain an acyliminodiacetic acid compound, which has been known to be inferior in low-temperature stability and difficult to increase in viscosity, as a main ingredient, and also has low-temperature or high-temperature stability, viscosity reachability, and a refreshing after use. It is to provide a method for improving the feeling.

  The present inventor has proceeded with studies on a compound that lowers the Kraft point of acyliminodiacetate, and mixed with N-long chain acyl-N-alkyl-neutral amino acid salt having a specific structure at a specific ratio. And found that the effect is remarkable. Furthermore, when acyliminodiacetic acid and N-long chain acyl-N-alkyl-neutral amino acid salt, which are normally considered not to be thickened by a thickener, are within the range of the blending ratio of the present invention, It has been found that thickening is possible by adding a zwitterionic and / or semipolar surfactant, or that viscosity reachability by a polymer thickener is remarkably improved. In addition, when the sample prepared by the method of the present invention was used as a cleaning agent, the present invention was completed by experimentally confirming that it does not impair the refreshing feeling after cleaning, which seems to be characteristic of acyliminodiacetate. .

［上記式（１）中、Ｒ¹ は炭素原子数５から１９のアルキル基又はアルケニル基を表し、Ｍ¹ 及びＭ² は、それぞれ互いに独立に、水素原子、アルカリ金属原子、アルカリ土類金属原子、アルカノールアミンのカチオン残基、塩基性アミノ酸のカチオン残基から選ばれる少なくとも１種を表す］
を含む水溶液に、下記一般式（２）で示されるＮ−長鎖アシル−Ｎ−アルキル−中性アミノ酸化合物及び一般式（３）で示されるＮ−長鎖アシル−Ｎ−アルキル−タウリン化合物：

［式中、Ｒ² 及び、Ｒ⁴ は、炭素原子数５から１９のアルキル基又はアルケニル基を示し、Ｒ³ 及びＲ^3aはそれぞれ他から独立に炭素原子数１〜３のアルキル基を示し、Ｍ³ 及びＭ⁴ は、それぞれ互いに独立に、水素原子、アルカリ金属原子、アルカリ土類金属原子、アルカノールアミンのカチオン残基及び、塩基性アミノ酸のカチオン残基から選ばれた少なくとも１種を表し、ｎは１〜３の整数を表す。］
を、
前記成分１と成分２との配合重量比を８：２〜２：８の範囲内に調整して混合する、ことを特徴とする長鎖アシルイミノジ酢酸型界面活性剤化合物含有水溶液の低温安定性改善方法である。
本発明方法において、前記方法により得られる前記成分１及び成分２を含む混合水溶液中の、前記成分１の含有率を４〜１６重量％に調整することが好ましい。
本発明方法において、前記方法により得られる、前記成分１及び成分２を含む混合水溶液中の、前記成分１及び成分２の合計含有率を１０〜２０重量％に調整することが好ましい。
本発明の方法において、成分３として、両性界面活性剤及び／又は双性界面活性剤及び／又は半極性界面活性剤をさらに含有させてもよい。 That is, the method of the present invention
Long-chain acyliminodiacetic acid type surfactant compound represented by the following general formula (1) (component 1):

[In the above formula (1), R ¹ represents an alkyl or alkenyl group having 5 to 19 carbon atoms, and M ¹ and M ² are each independently a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. Represents at least one selected from a cation residue of an alkanolamine and a cation residue of a basic amino acid]
N-long chain acyl-N-alkyl-neutral amino acid compound represented by the following general formula (2) and N-long chain acyl-N-alkyl-taurine compound represented by the general formula (3):

[Wherein R ² and R ⁴ represent an alkyl group or an alkenyl group having 5 to 19 carbon atoms, R ³ and R ^3a each independently represent an alkyl group having 1 to 3 carbon atoms, M ³ and M ⁴ each independently represent at least one selected from a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a cation residue of an alkanolamine, and a cation residue of a basic amino acid, n represents an integer of 1 to 3. ]
The
The low-temperature stability improvement of an aqueous solution containing a long-chain acyliminodiacetic acid-type surfactant compound, wherein the blending weight ratio of the component 1 and the component 2 is adjusted within a range of 8: 2 to 2: 8 and mixed. Is the method.
In the method of the present invention, it is preferable to adjust the content ratio of the component 1 in the mixed aqueous solution containing the component 1 and the component 2 obtained by the method to 4 to 16% by weight.
In the method of the present invention, the total content of the component 1 and the component 2 in the mixed aqueous solution containing the component 1 and the component 2 obtained by the method is preferably adjusted to 10 to 20% by weight.
In the method of the present invention, as the component 3, an amphoteric surfactant and / or a zwitterionic surfactant and / or a semipolar surfactant may be further contained.

The first component used in the method of the present invention is an acyliminodiacetic acid compound (component 1) represented by the general formula (1).
In the general formula (1), R ¹ represents a linear or branched alkyl group or alkenyl group having 5 to 19 carbon atoms, preferably 9 to 17 carbon atoms. Cationic M ¹ and M ² that form a salt with the carboxyl group of the compound of formula (1) are independently of each other hydrogen atom, alkali metal atom, alkaline earth metal atom, alkanolamine cation residue, and basicity. It represents at least one selected from cation residues of amino acids. The acyliminodiacetic acid compound of formula (1) has two hydrophilic groups in one molecule, but when the pH of the resulting mixed aqueous solution is between 4.5 and 5.0, one of the hydrophilic groups is medium. When the pH is 9.0 to 10.0, the second hydrophilic group is neutralized. In the method of the present invention, the surface activity is remarkably exhibited from the state in which the first hydrophilic group is neutralized to the state in which the second hydrophilic group is neutralized. The mixed aqueous solution (hereinafter referred to as the above mixed aqueous solution) preferably has a pH of 4.5 to 10.0, and more preferably has a pH of the mixed aqueous solution of 5.5 to 7.5. .
Component 1 may be a compound of the formula (1) constituting it, in which two or more different R ¹ groups, M ¹ groups and M ² groups are mixed.

  Preferable examples of the acyliminodiacetic acid compound include lauroiliminodiacetic acid monosodium salt, lauroiliminodiacetic acid monopotassium salt, lauroiliminodiacetic acid monotriethanolamine salt, lauroylumiminodiacetic acid disodium salt, palm fatty acid iminodiacetic acid monosodium salt And coconut fatty acid iminodiacetic acid monopotassium salt and coconut fatty acid iminodiacetic acid monotriethanolamine salt.

  The second component used in the method of the present invention is an N-long chain acyl-N-alkyl-neutral amino acid compound represented by the general formula (2) and an N-long chain acyl-N-alkyl represented by the general formula (3). -Component 2 consisting of at least one selected from taurine compounds.

  Preferable examples of the N-long chain acyl-N-alkyl-neutral amino acid compound represented by the general formula (2) include lauroyl-N-methyl-β-alanine sodium salt, lauroyl-N-methyl-β-alanine potassium Salt, lauroyl-N-methyl-β-alanine triethanolamine salt, lauroyl-N-methyl-β-alanine arginine salt, lauroyl sarcosine sodium salt, lauroyl sarcosine potassium salt, lauroyl sarcosine triethanolamine salt, lauroyl sarcosine arginine salt, Examples include coconut fatty acid-N-methyl-β-alanine sodium salt, coconut fatty acid sarcosine sodium salt, palm kernel fatty acid-N-methyl-β-alanine sodium salt, palm kernel fatty acid sarcosine sodium salt, and the like.

  Preferable examples of the N-long-chain acyl-N-alkyl-taurine compound represented by the general formula (3) include lauroyl-N-methyl-taurine sodium salt, coconut fatty acid-N-methyl-taurine sodium salt, palm kernel fatty acid -N-methyl-taurine sodium salt and the like.

In the general formulas (2) and (3), R ³ and R ^3a do not represent a hydrogen atom, and in the compounds represented by the general formulas (2) and (3), when R ³ = H The corresponding lauroylglycine compound and lauroyl-β-alanine compound do not have the effect of improving the low temperature stability of acyliminodiacetate.

The blending ratio of the acyliminodiacetic acid compound constituting the component (1) and the N-acyl-N-alkyl-amino acid compound and / or the N-long chain acyl-N-alkyl-taurine compound constituting the component (2) will be described.
In the liquid detergent composition of the present invention, the blending mass ratio of Component 1 and Component 2 is in the range of 8: 2 to 2: 8.
When component 1 is mixed in a large amount exceeding the above range, the effect of improving the low temperature stability becomes insufficient. On the other hand, when component 2 is added in a large amount exceeding the above range, the expression of lubricity due to the acyliminodiacetic acid compound becomes insufficient.

  Further, the mixed aqueous solution containing component 1 and component 2 obtained by the method of the present invention is obtained by adding amphoteric, zwitterionic or semipolar surfactant (component 3) in addition to components 1 and 2 above. The mixed aqueous solution can be thickened, or the sensitivity of developing the thickening effect by adding another thickening agent is improved. That is, the viscosity reachability is improved satisfactorily.

［上記式（４）中、Ｒ⁵ は炭素原子数９〜１７のアルキル基又はアルケニル基を表し、Ｒ⁶ 及びＲ⁷ は、それぞれ、互に独立に水素原子、メチル基及びエチル基から選ばれる置換基を表し、ｓは２乃至は３の整数を表し、ｒは０又は１の整数を表す。］
式（４）の化合物としては、好適には、ラウリン酸アミドプロピルヒドロキシスルホベタイン、ラウリルヒドロキシスルホベタイン等が挙げられる。 Component 3 will be further described.
Examples of the amphoteric surfactant include a sulfobetaine type amphoteric surfactant compound represented by the following general formula (4).

[In the above formula (4), R ⁵ represents an alkyl or alkenyl group having 9 to 17 carbon atoms, and R ⁶ and R ⁷ are each independently selected from a hydrogen atom, a methyl group and an ethyl group. Represents a substituent, s represents an integer of 2 to 3, and r represents an integer of 0 or 1; ]
Preferable examples of the compound of the formula (4) include lauric acid amidopropyl hydroxysulfobetaine and lauryl hydroxysulfobetaine.

［上記式（５）中、Ｒ⁸ は炭素原子数９〜１７のアルキル基又はアルケニル基を表し、Ｒ⁹ 及びＲ¹⁰はそれぞれ他から独立に水素原子、メチル基、エチル基から選ばれる置換基を表し、ｓ’は２乃至３の整数を表し、ｒ’は０又は１の整数を表す。］
式（５）の化合物は、好適には、ラウリルジメチル酢酸ベタイン、ヤシ脂肪酸アミドプロピルベタイン、ミリスチン酸アミドプロピルベタイン等を包含する。 Examples of amphoteric surfactants include amidoamine type amphoteric surfactant compounds and betaine acetate type amphoteric surfactant compounds.
The betaine acetate type amphoteric surfactant compounds are represented by the following general formula (5).

[In the above formula (5), R ⁸ represents an alkyl or alkenyl group having ⁹ to 17 carbon atoms, and R ⁹ and R ¹⁰ are each independently a substituent selected from a hydrogen atom, a methyl group, and an ethyl group. S ′ represents an integer of 2 to 3, and r ′ represents an integer of 0 or 1. ]
Compounds of formula (5) preferably include lauryl dimethyl acetate betaine, coconut fatty acid amidopropyl betaine, myristic amidopropyl betaine and the like.

［上記式（６−１）及び（６−２）中、Ｒ¹¹及びＲ¹²はそれぞれ他から独立には炭素原子数９〜１７のアルキル基又はアルケニル基を表し、ｓ”及びｓ''' は、それぞれ他から独立に２乃至は３の整数を表し、ｖ，ｗ，ｖ’及びｗ’はそれぞれ他から独立に１〜３の整数を表し、Ｍ⁵ 及びＭ⁶ は、それぞれ他から独立にはアルカリ金属原子、アルカリ土類金属原子、又はアルカノールアミンのカチオン残基を示し、ｙは１又は２の整数を表す。］ Amidoamine type amphoteric surfactant compounds include compounds represented by the following general formulas (6-1) and (6-2).

[In the above formulas (6-1) and (6-2), R ¹¹ and R ¹² each independently represents an alkyl or alkenyl group having 9 to 17 carbon atoms, and s ″ and s ′ ″. Represents an integer of 2 to 3 independently of each other, v, w, v ′ and w ′ represent an integer of 1 to 3 independently of each other, and M ⁵ and M ⁶ are independent of each other. Represents an alkali metal atom, an alkaline earth metal atom, or a cation residue of an alkanolamine, and y represents an integer of 1 or 2.]

  These compounds of the formulas (6-1) and (6-2) include a group of surfactant compounds generally referred to as imidazolinium betaines. It has been clarified that imidazolinium betaine surfactants form the structures of the above general formulas (6-1) to (6-2) by hydrolyzing the imidazoline ring at an intermediate stage of the synthesis route. (For example, JP-B-59-51532, JP-B-35-4762, Cosmet Toiletries, Vol195, No11, p45-48, 1980).

  Preferable examples of these amidoamine type amphoteric surfactant compounds include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauroyl-N′-carboxymethyl-N′-hydroxyethylethylenediamine sodium N-coconut fatty acid acyl-N′-carboxyethyl-N′-hydroxyethylethylenediamine sodium and the like.

［式（７）中Ｒ¹³は炭素原子数９〜１７のアルキル基又はアルケニル基を表し、Ｒ¹⁴及びＲ¹⁵はそれぞれ他から独立に、水素原子、メチル基及びエチル基から選ばれる置換基を表し、ｔは２乃至は３の整数を表し、ｐは０又は１の整数を表す。］
式（７）の化合物は、好適には、ラウリルジメチルアミンオキシド、ラウリン酸アミドプロピルアミンオキシド等が挙げられる。 Examples of the semipolar surfactants include amine oxides, which are compounds represented by the following general formula (7).

[In formula (7), R ¹³ represents an alkyl group or alkenyl group having 9 to 17 carbon atoms, and R ¹⁴ and R ¹⁵ each independently represents a substituent selected from a hydrogen atom, a methyl group, and an ethyl group. T represents an integer of 2 to 3, and p represents an integer of 0 or 1. ]
Preferred examples of the compound of formula (7) include lauryl dimethylamine oxide, lauric acid amidopropylamine oxide, and the like.

Even in the amphoteric, zwitterionic and semipolar surfactant compounds of Component 3 above, the combination of them and the acyliminodiacetic acid compound has an effect of improving the low temperature stability, but the effect is small. In order to improve the low temperature stability only by the combination, a large excess of the component 3 is necessary, and the usability when the mixed aqueous solution is used as a liquid detergent composition is deteriorated.
That is, the weight ratio of the total amount of component 1 and component 2 to component 3 is preferably in the range of 9: 1 to 7: 3. In this case, a good low temperature is obtained without impairing the washing feeling of acyliminodiacetic acid. It is possible to provide a liquid detergent composition having stability and having an appropriate composition viscosity or viscosity reachability. When the total amount of component 1 and component 2 is blended in a large amount exceeding the above weight ratio, the feeling of use due to the acyliminodiacetic acid compound is not impaired, but the viscosity of the obtained mixed aqueous solution is low, Further, even when a known thickener such as fatty acid alkanolamide, polyoxyethylene (120EO) methyl glucosidediolate, polyoxyethylene (160) sorbitan triisostearate or the like is added as the fourth component, the increase in viscosity is slight. In addition, it is difficult to control the viscosity of the mixed aqueous solution. On the contrary, when the component 3 is blended in a large amount exceeding the above range, the viscosity control of the obtained mixed aqueous solution becomes easy, but the feeling of use of the acyliminodiacetic acid compound is not felt.

  In the method of the present invention, as long as the effects of the present invention are not impaired, other water-soluble components usually used in cosmetics are added to the mixed aqueous solution obtained by the method of the present invention, and water-insoluble components are appropriately added to the extent that can be solubilized. It can be selectively added.

  As an anionic activator used as an additive component, higher alkyl sulfate ester salts such as sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate. Alkyl ether sulfate salts such as POE lauryl sulfate triethanolamine, POE sodium lauryl sulfate; N-acyl amino acid salts such as sodium lauroyl-β-alanine, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N -Myristoyl-L-glutamate monosodium, N-palmitoyl aspartate diethanolamine, coconut fatty acid silk peptide; phosphate ester salts such as POE oleyl ether sodium phosphate, POE stearyl ether phosphate, POE lauryl amide ether phosphate; sulfosuccinic acid Salts such as sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sulfo Sodium succinate, sodium lauryl polypropylene glycol sulfosuccinate; alkyl benzene sulfonates such as sodium linear dodecyl benzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, linear dodecyl benzene sulfonic acid; higher fatty acid ester sulfates such as hydrogenated coconut oil Fatty acid sodium glycerine sulfate; and α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamide succinate, sodium caseinate and the like It is done.

  Examples of the cationic surfactant used as an additive component include alkyl trimethyl ammonium salts such as stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, and lauryl trimethyl ammonium bromide. Dialkyldimethylammonium salts, such as distearyldimethylammonium chloride. Alkyl pyridium salts such as cetyl pyridium chloride. Examples thereof include alkyldimethylbenzylammonium salt, benzethonium chloride, benzalkonium chloride and the like.

  Nonionic surfactants used as additive components include glycerin fatty acid esters such as glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monoisostearate; polyoxyethylene glycerin fatty acid esters such as monostearic acid, POE glyceryl monooleate POE glyceryl; polyglyceryl fatty acid esters such as diglyceryl monostearate, tetraglyceryl tristearate, decaglyceryl pentastearate; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan sesquistearate, monoolein Acid sorbitan; polyoxyethylene sorbitan fatty acid esters, such as monococonut fatty acid POE sorbitan, tristearic acid P E sorbitan, POE sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as monolauric acid POE sorbite, tetraoleic acid POE sorbitol; polyethylene glycol fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, monoolein Polyethylene glycol acid, polyethylene glycol distearate; polyoxyethylene alkyl ethers such as POE lauryl ether, POE cetyl ether, POE stearyl ether; polyoxyethylene polyoxypropylene alkyl ethers such as POE · POP cetyl ether, POE · POP decyl Tetradecyl ether; polyoxyethylene alkylphenyl ether POE nonylphenyl ether, POE octylphenyl ether, POE branched octylphenyl ether; polyoxyethylene alkylamines such as POE stearylamine, POE oleylamine; fatty acid alkanolamides such as palm fatty acid diethanolamide, palm fatty acid mono Ethanolamide, lauric acid diethanolamide, palm kernel oil fatty acid diethanolamide; polyoxyethylene alkanolamides such as POE lauric acid monoethanolamide, POE coconut fatty acid monoethanolamide, POE beef tallow fatty acid monoethanolamide; and acetylene glycol, POE acetylene Glycol, POE lanolin, POE lanolin alcohol, POE castor oil, POE hydrogenated castor oil, POE Phytosterol, POE cholestanol, POE nonylphenyl formaldehyde condensate and the like.

  Examples of the humectant used as an additive component include glycerin, propylene glycol, 1,3-butylene glycol, sorbitol, sodium lactate, pyrrolidone carboxylic acid and salts thereof.

  Water-soluble polymers used as additive components include guar gum, queen seed, pectin, gelatin, xanthan gum, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and salts, algin salts, polyvinyl alcohol, carboxyvinyl polymer, poly Examples include sodium acrylate, bentonite, chitin / chitosan derivatives, hyaluronic acid and salts, collagen and derivatives thereof.

  Examples of the coating agent used as an additive component include polyvinyl alcohol, polyvinyl pyrrolidone, cationized cellulose, cationized cellulose, and silicone.

  Examples of ultraviolet absorbers used as additive components include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts, benzophenone derivatives such as dihydroxydimethoxybenzophenone, paraaminobenzoic acid, paraaminobenzoic acid Paraaminobenzoic acid derivatives such as ethyl acrylate, ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, methoxycinnamic acid derivatives, salicylic acid derivatives such as octyl salicylate, phenyl salicylate, urocanic acid and derivatives, 4-tert-butyl- 4'-methoxydibenzoylmethane, 2- (hydroxy-5'-methylphenyl) benzotriazole, methyl anthranilate and the like can be mentioned.

Examples of the anti-inflammatory agent used as an additive component include glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives, allantoin, hydrocortisone acetate, and azulene.
Examples of the sequestering agent used as an additive component include ethylenediaminetetraacetic acid and sodium salts, phosphoric acid, citric acid, ascorbic acid, succinic acid, gluconic acid, sodium polyphosphate, sodium metaphosphate, and the like.

Examples of the lower alcohol used as the additive component include ethanol, propyl alcohol, ethylene glycol, and diethylene glycol.
Examples of the saccharide used as the additive component include glucose, lactose, sucrose, starch, carboxymethyl starch, and cyclodextrin.
Examples of the pH adjuster used as the additive component include citric acid, hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, ammonia, and the like.

Examples of skin nutrients used as additive components include vitamins A, B1, B2, B6, E and derivatives thereof, pantothenic acid and derivatives thereof, and bithion.
Examples of the antioxidant used as the additive component include vitamin E, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.
Antioxidant aids used as additive components include ascorbic acid, phytic acid, kephalin, maleic acid and the like, but the blending components are not limited thereto.

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the technical scope of the present invention is not limited to these examples.
In the following examples, the following tests were conducted.

Low-temperature stability and sensory evaluation by mixing component 1 and component 2 With respect to the following components, a liquid detergent with a surfactant component of 20% by weight was prototyped according to Table 1, and low-temperature stability and sensory evaluation by hand-washing tests were performed. .
(Component 1) Sodium N-lauroiriminodiacetate: Component 1
(Component 2) Lauroyl sarcosine sodium: Abbreviation; SLE
Lauroyl-N-methyl-β-alanine sodium: abbreviation; ALE
Methyl taurate sodium laurate: Abbreviation; LMT
(Comparative component) N-coconut fatty acid acylglycine sodium: Abbreviation; GCS

Regarding the preparation of the samples, the respective components shown in Table 1 were blended, heated to 80 ° C., and after confirming that they were uniformly dissolved, various samples were prepared by cooling with stirring. The prepared samples were evaluated under the following conditions.
Temperature stability test The aqueous solution prepared in the composition described later is left in a 5 ° C and 20 ° C incubator by the same test method as the compatibility test described later, and the state of the sample is measured after 3 days. Was evaluated according to the following criteria.
○: Transparent dissolution △: Kusumi, cloudiness (uniform)
X: Crystal precipitation

Hand-washing test For 10 subjects, the following standard sample was applied to 1.5 g of the hand, and the hand-washing test was carried out by applying each sample of Table 1 to 1.5 g of the hand, based on the texture after hand washing. went. The lubricity (smooth feeling) after washing was evaluated as follows with reference to a standard sample having the following composition.
3 points: Lubricant felt stronger than the standard sample 2 points: Lubricant felt equivalent to or slightly stronger than the standard sample 1 point: The standard sample did not change 10 It was evaluated with.
○: Average score is 2.5 or more △: Average is 2.0 to 2.5 points ×: Average is 1.5 to 2.0 points

Pure composition weight% of the standard sample
Sodium polyoxyethylene lauryl sulfate 10.0
Palm Fatty Acid-N-Methyl-β-Alanine Sodium 10.0
Lauric acid diethanolamide 2.0
Amount to make citric acid pH = 6.0 Amount to make purified water 100 in total However, the numerical value in the notation indicates the weight% of pure surfactant.

Examples 1-10 and Comparative Examples 1-5
In each of Examples 1 to 10 and Comparative Examples 1 to 5, a mixed aqueous solution having the composition shown in Table 1 was prepared by the following method and subjected to the above test and the following test.

Preparation method of composition In each of Examples 1 to 10 and Comparative Examples 1 to 5, the required amount of each component was mixed in a precise balance, and distilled so that the component concentration of the entire mixed aqueous solution obtained was 20%. Add water, adjust the pH by adding 50% aqueous citric acid or 10% aqueous sodium hydroxide so that the pH shown in Table 1 is obtained, and then add a balanced amount of distilled water to prepare the desired mixed aqueous solution. did.
Measurement concentration: Total surfactant 20 pure weight%
Measurement pH: 6.0 (prepared with citric acid and sodium hydroxide)
Measurement temperature: 20 ° C., 5 ° C. (compatibility), 25 ° C. (viscosity)
Viscometer: B-type viscometer (manufactured by Toki Sangyo Co., Ltd.)
Measurement: The appearance of the mixed aqueous solution left to stand for 3 days was observed with the naked eye. The criteria for determining compatibility are as follows: ○: Transparent dissolution △: Kusumi / cloudiness (uniform)
X: Crystal precipitation The test results are shown in Table 1.

As shown in Table 1, the aqueous solution containing only acyliminodiacetic acid (Comparative Example) shows crystal precipitation even when stored at 20 ° C., but the low temperature stability is improved by blending Component 2 of the present invention in a specific amount or more. It turned out to go. However, it has been found that excessive blending of Component 2 (Comparative Example 5) improves low-temperature stability, but tends to hinder the smooth feeling (lubricity) after washing, which is a characteristic feel of acyliminodiacetate.
Moreover, it turned out that the N-coconut fatty-acid acylglycine sodium which has the similar structure of the component 2 has no effect which improves low-temperature stability (Comparative Examples 3 and 4).

Examples 11-17
Viscosity and Viscosity Reachability of Mixed Aqueous Solution Conventionally, it is known that the N-acylamino acid compound used as component (1) has a property that it is difficult to thicken, and the acyliminodiacetic acid compound used as component 2 is also thickened. However, by adding amphoteric, zwitterionic, and semipolar surfactants to this, it is possible to increase the viscosity while maintaining the lubricity considered to be derived from the acyliminodiacetic acid compound within a specific range. It is possible to make a mixed aqueous solution that can be easily thickened by adding the fourth component.
Examples are shown in Examples 11-17.

Samples described in Table 2 were prepared and subjected to a low temperature stability test, a hand washing test, and a viscosity measurement at 25 ° C. Regarding the low temperature stability and the hand washing test method, the same test method as in Examples 1 to 10 was used, and the viscosity was measured under the following conditions.
Equipment used for viscosity measurement conditions Toki Sangyo B-type viscometer Measuring temperature 25 ° C
When the rotor viscosity is 100 mpa · S or less HM-1
When the viscosity is 100 mpa · S or higher HM-2
Sample used for blending (component 1) Sodium N-lauroiriminodiacetate Abbreviation: Component 1
(Component 2) Lauroyl-N-methyl-β-alanine sodium
Abbreviation: ALE
(Component 3) Lauric acid amidopropylamine oxide Abbreviation: LAO
Laminated amidopropyl acetate betaine Abbreviation: LPB
Lauric acid amidopropyl hydroxysulfobetaine
Abbreviation: LSB
(Attached component) Polyoxyethylene (120EO) methylglucosidediolate
Abbreviation: DOE120
The results are shown in Table 2.

As is clear from Table 2, by adding an amphoteric (LPB), a zwitter (LSB), and a semipolar (LAO) surfactant within the specific weight blending ratio range to the mixed aqueous solution obtained by the method of the present invention, Viscosity that does not hinder practical use: Viscosity can be increased to about 500 to 3000 mPa · s. In Example 14, the prepared sample itself has a relatively low viscosity, but when a thickener is added as the fourth component, the viscosity tends to increase.
When the mixed aqueous solution obtained by the method of the present invention needs to be further thickened by enhancing the low temperature stability while leaving the lubricity which is a characteristic feeling of use, the components 1 and 2 are mixed with 8: It is effective to mix at a weight blending ratio of 2 to 2: 8, and further blend component 3 at a weight blending ratio of 9: 1 to 7: 3 with respect to the total weight of component 1 and component 2. It shows that there is. Example 16 and Example 17 are examples of the present invention. However, since the blending amount of component 3 with respect to component 1 and component 2 is small, viscosity increase is increased even when the same amount of thickener as in Example 15 is used. I was not able to admit.

Example 18
A shampoo having the following composition was produced using the method of the present invention. The evaluation of the low-temperature stability test was good, and the texture after shampooing was excellent with good unity.
Ingredient pure weight%
Sodium polyoxyethylene lauryl sulfate 5.0
Sodium Lauroiliminodiacetate (Component 1) 5.0
Lauroyl sarcosine sodium (component 2) 5.0
Lauric acid amidoamine oxide 3.0
Amount of citric acid pH = 6 Rheodor TW-IS399C (Q1) ^{* 1} 1.0
Methylparaben 0.2
Piroctone Olamine 0.5
Fragrance 0.1
Dipotassium glycyrrhizinate 0.2
Purified water Amount to make 100 total [註] * ₁ : Trademark, polyoxyethylene (160) sorbitan triisostearate,
Made by Kao Corporation.

  According to the method of the present invention, it is possible to obtain a mixed aqueous solution containing an acyliminodiacetic acid compound as a main component, but having high stability at low temperatures and high temperatures, easy to increase viscosity, excellent in reachability of viscosity, and excellent in refreshing feeling after use. It became possible.

Claims (4)

Long-chain acyliminodiacetic acid type surfactant compound represented by the following general formula (1) (component 1):

[In the above formula (1), R ¹ represents an alkyl or alkenyl group having 5 to 19 carbon atoms, and M ¹ and M ² are each independently a hydrogen atom, an alkali metal atom, or an alkaline earth metal. Represents at least one selected from an atom, a cation residue of an alkanolamine, and a cation residue of a basic amino acid]
An N-long chain acyl-N-alkyl-neutral amino acid compound represented by the following general formula (2) and an N-long chain acyl-N-alkyl-taurine compound represented by the general formula (3): At least one selected from (component 2):

[In the above formulas (2) and (3), R ² and R ⁴ each independently represents an alkyl or alkenyl group having 5 to 19 carbon atoms, and R ³ and R ^3a are each independently Independently represents an alkyl group having 1 to 3 carbon atoms, and M ³ and M ⁴ are each independently a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an alkanolamine cation residue, or a basic amino acid. It represents at least one selected from cationic residues, and n represents an integer of 1 to 3. The low-temperature of the aqueous solution containing a long-chain acyliminodiacetic acid type surfactant compound, wherein the mixing weight ratio of the component 1 and the component 2 is adjusted within the range of 8: 2 to 2: 8 A way to improve stability.   The method of Claim 1 which adjusts the content rate of the said component 1 in the mixed aqueous solution containing the said component 1 and the component 2 obtained by the said method to 4 to 16 weight%.   The method of Claim 1 or 2 which adjusts the total content rate of the said component 1 and the component 2 in the mixed aqueous solution containing the said component 1 and the component 2 obtained by the said method to 10 to 20 weight%. Component 3 is an amphoteric surfactant and / or the following general formula (4):

[In the above formula (4), R ⁵ represents an alkyl or alkenyl group having 9 to 17 carbon atoms, and R ⁶ and R ⁷ are each independently selected from a hydrogen atom, a methyl group and an ethyl group. Represents a substituent, s represents an integer of 2 to 3, and r represents an integer of 0 or 1; ]
The method according to any one of claims 1 to 3, further comprising a surfactant and / or a semipolar surfactant represented by the formula: