JPH0791556B2 - Cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a detergent composition that is hypoallergenic and exhibits good detergency and foamability, and particularly contains a water-soluble polymer, The present invention relates to a liquid detergent composition which has good viscosity characteristics and good finish of the article to be washed, and has good liquid stability.

[Conventional technology and its problems]

The following general formula (I ′), which is conventionally called an imidazoline-type amphoteric surfactant, (In the formula, R represents an alkyl group having 7 to 23 carbon atoms, a hydroxyalkyl group, an aralkyl group or an alkenyl group.) Since the sodium salt of the secondary amide amino acid represented by the formula is low in irritation to skin, eyes, etc., It is used as a main washing activator for baby shampoo and bath salts.

However, the sodium salt of the secondary amide amino acid is not always sufficient in detergency and foamability as compared with general anionic surfactants such as alkyl sulfates and alkyl ether sulfates, and thus is not suitable for general detergents. Is not widely used. In addition, since the sodium salt of this secondary amide amino acid is mixed with a large amount of water-soluble inorganic salt such as salt produced as a by-product during its production, it is thickened or conditioned when used as a base for liquid shampoo and the like. It was difficult to give sex. That is, various water-soluble polymers are generally used for thickening and imparting conditioning properties, but since many of these polymers are insoluble in concentrated salt solutions, conventional polymers containing a large amount of inorganic salts are used. It was difficult to mix it with the sodium salt of the secondary amide amino acid of 1.

[Means for solving problems]

In such an actual situation, the present inventor has conducted diligent research and, as a result, subjecting the sodium salt to electrodialysis in the presence of a mineral acid or a mineral acid and triethanolamine or ammonia, the following general formula (I) (Wherein R represents an alkyl group having 7 to 22 carbon atoms, a hydroxyalkyl group, an aralkyl group or an alkenyl group, and X represents a hydrogen atom, an ammonium ion or a triethanolammonium ion) or a secondary amide amino acid thereof When converted to salts (ammonium salt, triethanolamine salt), hypoallergenicity is not impaired, foamability and detergency are improved, and water-soluble inorganic salts that are mixed in are removed (hereinafter desalted The present invention has been completed based on the finding that the above water-soluble polymer can be easily blended.

That is, the present invention has the general formula (Wherein R represents an alkyl group having 7 to 23 carbon atoms, a hydroxyalkyl group, an aralkyl group or an alkenyl group, and M represents an alkali metal), a secondary amide amino acid alkali metal salt represented by And a general formula (I) obtained by electrodialysis in the presence of triethanolamine or ammonia (In the formula, R represents an alkyl group having 7 to 23 carbon atoms, a hydroxyalkyl group, an aralkyl group or an alkenyl group, and X represents a hydrogen atom, an ammonium ion or a triethanolammonium ion), or a secondary amide amino acid thereof A liquid containing 1 to 45% by weight of a salt and 0.05 to 10% by weight of a water-soluble polymer other than polyacrylic acid or a salt thereof which is insoluble in a concentrated salt solution, and the content of a water-soluble inorganic salt is 1% by weight or less. A cleaning composition is provided.

The secondary amide amino acid of formula (I) or a salt thereof used in the present invention is produced, for example, by the following method.

When an alkyl imidazoline represented by the formula (II) or an amidoamine represented by the formula (III) which is a ring-opening compound thereof is reacted with a monohaloacetic acid such as sodium monochloroacetate or a salt thereof in the presence of an alkali, the above-mentioned formula (I ') A salt such as the secondary amide amino acid sodium salt of However, at this time, a large amount of an inorganic salt such as an alkali metal halide is produced as a by-product.

(In the formula, R represents the same as above.) To the mixed solution containing the salt of the secondary amide amino acid and the inorganic salt thus obtained, an equimolar or more mineral acid of the secondary amide amino acid was added to obtain an electric charge. By conducting an analysis, an acid-type secondary amide amino acid [in the formula (I), R = H] can be obtained in a state where the inorganic salt content is low. Further, if this acid type secondary amide amino acid is neutralized with ammonia or triethanolamine, an ammonium salt or triethanolamine salt of the secondary amide amino acid can be obtained.

Moreover, after adding a mineral acid in an equimolar amount or more of the secondary amide amino acid to a mixed solution containing the salt of the secondary amide amino acid and the inorganic salt, electrodialysis is performed while adding ammonia or triethanolamine in an equimolar amount or more. By carrying out, the ammonium salt or triethanolamine salt of the secondary amide amino acid represented by the formula (I) can be obtained in a state where the inorganic salt content is low.

The secondary amide amino acid of the formula (I) or a salt thereof used in the present invention has a lower content of the water-soluble inorganic salt, and when the liquid detergent is used, components such as a water-soluble polymer are easily compounded, and It is easy to control the shape retention when used as a solid detergent. Therefore, the content of the water-soluble inorganic salt is preferably 0.2 mol or less per 100 g (in the case of salt, as the acid-type secondary amide amino acid) in terms of the acid-type secondary amide amino acid.
The content of such an inorganic salt can be lowered by prolonging the time of electrodialysis.

In the formula (I), the acyl group RCO can be synthesized from a linear or branched saturated fatty acid having 8 to 20 carbon atoms or an unsaturated fatty acid. Most preferred of these are lauric acid or coconut oil fatty acid.

In the present invention, a water-soluble polymer that is insoluble in a concentrated salt solution refers to one that is insoluble in a 10 wt% saline solution, and is incorporated into an aqueous liquid detergent for the purpose of thickening or improving a feeling of finish. It is something. Examples of such polymers include the following cationic polymers, anionic polymers, nonionic polymers and amphoteric polymers.

Cationic polymer: Adsorbs and remains on the skin, hair and fibers to improve the feeling of finish after washing.

Cationic cellulose derivative In the formula (1), A represents a residue of an anhydroglucose unit, l ₁ is an integer of 50 to 20,000, and each T represents a substituent represented by the following general formula (2).

In the formula (2), R ₂₁ , R ₂₂ : an alkylene group having 2 or 3 carbon atoms m ₁ : 0 to an integer of 10; n ₁ : 0 to an integer of 3; p ₁ : 0 to an integer of 10; R ₂₃ : An alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group R ₁ , R ₂ , R ₃ which are the same or different, and which have an alkyl group having up to 10 carbon atoms, an aryl group, an aralkyl group or a nitrogen atom in the formula A heterocycle may be formed.

X: represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid, etc.)

The degree of cation substitution of cationic cellulose is 0.01 to 1,
That is, the average value of n ₁ per anhydroglucose unit is
0.01 to 1, preferably 0.02 to 0.5 is preferable. Also, m ₁ + p ₁
Is 1 to 3 on average. If the degree of substitution is 0.01 or less,
It is not sufficient, and may be 1 or more, but 1 or less is preferable from the viewpoint of reaction yield. The molecular weight of the cationic cellulose used herein is between about 100,000 and 3,000,000.

Cationic starch In the formula (3), B: starch residue l ₂ : a positive integer R _1-3 , R ₂₃ , X: the same as above. The cationic substitution degree of the cationic starch is 0.01 to 1, that is, 0.01 to 1 per anhydrous glucose unit. It is preferable that 0.02 to 0.5 cationic groups are introduced. Substitution degree is 0.01
The following is not sufficient and may be 1 or more, but 1 or less is preferable from the viewpoint of reaction yield.

Diallyl quaternary ammonium salt / acrylamide copolymer In the formulas (4) and (5), R ₄ and R _{5 are the} same or different and are hydrogen, an alkyl group (having 1 to 18 carbon atoms), a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, cyano. alkyl group, an alkoxyalkyl group, carboalkoxy group _{R 6, R 7, R 8} , R 9: the same or when a hydrogen, a lower alkyl group (1-3 carbon atoms), phenyl group l _3:. 1 to 50 integer m _2: 1 to 50 integer n _2: from 150 to 8,000 integer X: the molecular weight of the same diallyl quaternary ammonium salt / acrylamide copolymers and the approximately 30,000 to 2,000,000 preferably 100,000 to 100 The range of ten thousand is good.

Quaternized polyvinylpyrrolidone derivative In the formula (6), R _{10 is a} hydrogen atom or an alkyl group having 1 to 3 carbon atoms R ₁₁ , R ₁₂ , and R _{13 are the} same or different and are a hydrogen atom and 1 to 1 carbon atoms.
4 alkyl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group, carboalkoxy group, Y: NH group oxygen atom or an amide bond in X: the same as p _2: 1 to 10 integer m ₃ + n ₃ = integer of 20 to 8000 The quaternized polyvinylpyrrolidone derivative has a molecular weight of 10,000 to 2,000,000, preferably 50,000 to 1,500,000.

The content of the cationic nitrogen derived from the cationic polymer contained in the vinyl polymer is based on the vinyl polymer.
It is 0.004 to 0.2% by weight, preferably 0.01 to 0.15% by weight. Less than 0.004% by weight is not sufficiently effective, 0.2% by weight
Although the above performance is good, it causes coloring of the vinyl polymer and is economically disadvantageous.

Polyglycol polyamine condensate In the formula (7), R ₁₄ , R ₁₆ , R ₁₇ , R ₁₉ : a hydroxyalkylene group having 2 to 4 carbon atoms R ₁₅ , R ₁₈ : an alkylene group having 2 to 3 carbon atoms x, y: an integer of 10 to 20 m ₄ : integer of 2 to 4 n ₄ : integer of 2 to 6 p ₃ : integer of 1 to 50 R ₂₀ : linear or branched alkyl group having 6 to 20 carbon atoms adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymerization Product (Cartaletin produced by Sandos, USA) Anionic polymer: Used mainly for thickening liquid detergents.

Alginic acid derivative In the formula, the left side is D-Mannronic acid and the right side is L-
Gulironic acid is a heteropolysaccharide that is a copolymer of both, and n ₅ is an integer of about 50 to 1000, and the average value of n ₅ is preferably 100 to 300.

Carboxymethyl cellulose derivative The degree of ether substitution of carboxymethyl cellulose is 0.4-
It is 3.0, preferably 0.5 to 1. n ₆ is an integer of about 50 to 6000, and the average value of n ₆ is preferably 100 to 300.

 Carrageenan gum arabic gum tragacanth Nonionic polymer: Used mainly for thickening liquid detergents.

Cellulose derivative In formula (10), R ₂₄ , R ₂₅ , R ₂₆ : hydrogen atom, group CH ₂ CH ₂ O _m5 (m ₅ is 1 to 5)
Number of), - CH ₃ or -C ₃ H ₆ OH n _8: Number of 50 to 500 such as hydroxyethyl al loin, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, and the like.

Among the above cellulose derivatives, hydroxyethyl cellulose is commercially available under the trade names of Cellosize (UCC) and Natrosol (Hercules), and for the purpose of the present invention, ethylene oxide per glucose residue is used. The addition amount is preferably 1.0 to 4.0, particularly preferably 1.8 to 3.0.

Also, as the methyl cellulose, Climinal MC (Henkel) is used, and as the hydroxypropyl cellulose,
Krucsel (Hercules), and hydroxypropylmethyl cellulose such as Metroose (Shin-Etsu Chemical Co., Ltd.) and Climinal MHPC (Henkel) are commercially available. It is preferable that the methoxy groups of these methylcelluloses are present in an amount of 10 to 40%, particularly 20 to 30%, and the hydroxypropoxy groups are present in an amount of 1 to 20%, especially 5 to 15%, based on the total molecular weight.

Polyvinyl alcohol derivative Polyvinyl alkyl ether derivative Polyethylene oxide derivative Amphoteric polymer: It is mainly added for the purpose of improving the feeling of finishing after washing. A monomer having an anionic group such as carboxylic acid and sulfonic acid, and a basic nitrogen group. Copolymerized with a monomer containing a, a polymerized amphoteric monomer such as a carboxybetaine-type monomer, a cationic polymer modified to introduce a carboxyl group, an anion group such as a sulfonic acid group, or an anion And the like, in which a basic polymer is modified and a basic nitrogen-containing group is introduced. This amphoteric polymer has a high charge density of anion groups and cation groups, and becomes rather salt-soluble when the ratio is close to 1: 1.
It is preferable to introduce a neutral hydrophilic group as appropriate.

As a preferred specific example, for example, a molecular weight of 1,000 to 1,000,00
The following polymers of 0 are mentioned.

(1) A monomer obtained from a vinyl compound having a carboxyl group selected from acrylic acid, methacrylic acid, maleic acid, and alfachloroacrylic acid, and methacrylic acid, or a dialkylaminoalkyl acrylate, a dialkylaminoalkylmethacrylamide, And a polymer formed by copolymerization with a basic monomer obtained from a substituted vinyl compound containing at least one basic nitrogen atom selected from acrylamide and acrylamide.

(2) a) At least 1 selected from acrylamide or methacrylamide substituted with an alkyl group at the nitrogen position.
B) at least one acidic comonomer containing one or more reactive carboxyl groups, and c) acrylic acid and methacrylic acid primary, secondary
Polymers containing moieties obtained from primary, tertiary and quaternary amine-substituted esters and at least one basic comonomer such as quaternary compounds of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl.

(3) general formula: OC-R ₂₇ -CO-Z was partially obtained from polyamide or fully crosslinked alkylated polyaminoamide.

(In the formula, R ₂₇ is a saturated dicarboxylic acid, a monofatty acid, or an ethylenic double bond dicarboxylic acid, a divalent group obtained from an ester of a lower alcohol having 1 to 6 carbon atoms and the above acid, or the above-mentioned A group obtained by addition of an arbitrary acid and a bis-primary amine or a bis-secondary amine is shown, and Z is a bis-primary, mono-, or bis-secondary polyalkylene polyamine group.) This polyamide Is epihalohydrin, diepoxide,
A cross-linking agent selected from dianhydrides and bis-unsaturated derivatives is added at 0.025 to 0.35 mol per amine group of polyaminoamide to effect cross-linking, and acrylic acid, chloroacetic acid, or alkane sultone, or a salt thereof acts. And is alkylated.

(4) The following formula: A polymer having a zwitterionic part of

(In the formula, R ₂₈ represents a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide, or methacrylamide group, m ₆ and m ₇ represent an integer of 1 to 3, and R ₂₉ and R ₃₀ represent hydrogen and methyl. , Ethyl, or propyl, R ₃₁ and R
₃₂ is a hydrogen atom or the sum of carbon atoms in R ₃₁ and R ₃₂ is 10
The detergent composition of the present invention comprises a secondary amide amino acid of formula (I) or a salt thereof as a main washing active ingredient, and is a solid, liquid, cream, paste or aerosol. It can be made into various dosage forms such as a shape.

In the present invention, the "main cleaning active ingredient" means, when there are a plurality of cleaning active ingredients, the most abundant component, and is 1/3 or more, preferably 1/2 or more, of the total cleaning active ingredients in a weight ratio. It is preferably 2/3 or more. Other cleaning active ingredients include anionic, cationic, amphoteric and nonionic surfactants.

In the present invention, in the case of the liquid detergent composition of the second invention, the secondary amide amino acid of formula (I) or its salt is 1 to
45% by weight (hereinafter simply referred to as%), preferably 2
20%, more preferably 5 to 15%. Further, a water-soluble polymer which is insoluble in a concentrated salt solution is blended in an amount of 0.05 to 10%, preferably 0.1 to 5%, more preferably 0.2 to 2%.

In this case, the total amount of the water-soluble inorganic salt mixed from the secondary amide amino acid or its salt and other surfactants is 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The content of this water-soluble inorganic salt is a target value by adjusting the amount of the inorganic salt contained in the secondary amide amino acid or its salt according to the amount of the inorganic salt mixed from other surfactants. It can be:

Water is used as the medium, preferably 30 to 98% of the total composition.

The detergent composition of the present invention contains, in addition to the above-mentioned essential components, alkyl sulfates, alkyl ether sulfates, alkanolamides of higher fatty acids, N-acyl amino acid salts, N-alkyl amino acid salts, sulfosuccinic acid ester surfactants. Agent,
Ingredients generally used in detergents, such as imidazoline-based amphoteric surfactants, can be added within a range that does not impair the performance. If necessary, add oils, fragrances, UV absorbers for dyes, humidity control agents, hydrotropes, preservatives, antioxidants, and anti-dandruff agents, bactericides, anti-inflammatory agents, vitamins and other medicinal agents. You can

〔The invention's effect〕

According to the present invention, a detergent which is hypoallergenic and has excellent detergency can be obtained. Therefore, hair for infants, skin cleaner, wool for housewives with rough hands, detergent for kitchen, person washing hair daily It is preferably used as a daily shampoo for. Are also suitable as further occupationally Shiyanpu and hypoallergenic beauty for Shiyanpu for a long period of time contact forced people.

〔Example〕

Next, synthetic examples and examples will be described, but the present invention is not limited to these examples.

Synthesis example 1. 1-hydroxyethyl-2-lauryl imidazoline 268 g (1 mol), water 90 g and sodium hydroxide 2 g were put into a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, and stirred. Meanwhile, the temperature was raised to 80 ° C., and stirring was continued at the same temperature for about 2 hours to open the imidazoline ring. Next, a separately prepared solution of 233 g (2 mol) of sodium monochloroacetate and 2347.2 g of water was dropped into this container over about 1 hour. The solution temperature during the dropping was kept at 70 to 80 ° C. Following this, 200 g of a 40% aqueous sodium hydroxide solution was further added dropwise at the same temperature over 4 hours. After completion of dropping, aging was carried out at a temperature of 75 to 80 ° C. to obtain an about 12% aqueous solution of N-lauroyl-N′-2-hydroxyethyl-N′-sodium carboxymethylethylenediamine. After cooling this solution, 213.8 g of 35% hydrochloric acid was added dropwise over about 3 hours. Thus, 3354 g of a 12% aqueous solution of N-lauroyl-N'-2-hydroxylethyl-N'-sodium carboxymethylethylenediamine hydrochloride represented by The solution was a pale brown viscous liquid, and the pH of its 1% aqueous solution was 2.5.

3354 g of the aqueous solution thus obtained was subjected to electrodialysis.

The electrodialysis method is shown in Fig. 1 and is an anion exchange membrane (C).
Compartment (organic matter chamber) sandwiched between the cation exchange membrane (A) and
To N-lauroyl-N'-2-hydroxyethyl-
N'-2-hydroxyethyl-N'-sodium carboxymethylethylenediamine hydrochloride solution, 1% saline solution in the adjacent compartment (electrolyte chamber), and 3% sodium sulfate solution as the polar solution. The solution was circulated and a direct current was applied. The electrodialyzer used in this synthesis example has 10 0.02 m ² anion and cation exchange membranes each. The applied current had an initial current density of 1.5 amps / dm ^{2 and} was energized for 15 hours. The final current density after 15 hours was 0.1 amp / dm ² .

After conducting electrical analysis in this manner, water dried under reduced pressure was completely removed to obtain white powder crystals. From the amine value, AV, IR and NMR analysis of this product, N-lauroyl-N'-2
It was confirmed that -hydroxyethyl-N'-carboxymethylethylenediamine was produced. The purity of the acid form is 97% according to the analysis of Na and Cl, and the amount of salt is N-
Lauroyl-N'-2-hydroxyethyl-N'-carboxymethylethylenediamine 100 g 1.4 g (0.024
Mol). Further, the crystal was recrystallized from ethanol-acetone and the result of elemental analysis was as follows: It was confirmed to be the target acid represented by.

The results of elemental analysis are shown below.

The salt content of the obtained product is 0 for 100 g of the target acid.
It was less than 12g.

This acid was dissolved in water so that the concentration was as high as possible, and triethanolamine or concentrated ammonia water was added dropwise so as to have a pH of 7.0 to obtain a hydroxide solution of a neutralized product, which was used in the following examples. .

Synthesis Example 2. 1-Hydroxyethyl-2-lauryl imidazoline (268 g, 1 mol), water (90 g) and sodium hydroxide (2 g) were placed in a four-necked flask equipped with a stirrer, a condenser and a fruit-filling funnel thermometer and stirred. While raising the temperature to 80 ° C., stirring was continued at the same temperature for about 2 hours to open the imidazoline ring. Next, 233 g (2 mol) of separately prepared sodium monochloroacetate
And a solution of 427.0 g of water was charged into this container. Next, while maintaining the temperature of the solution at 70 to 80 ° C., 200 g of 40% NaOH aqueous sodium hydroxide solution was added dropwise over 4 hours. After completion of dropping, aging is further carried out at a temperature of 75 to 80 ° C. to obtain N-lauroyl-N ′.
An approximately 30% aqueous solution of 2-hydroxyethyl-N'-sodium carboxymethylethylenediamine was obtained. To this solution was added 149.2 g (1 mol) of triethanolamine and the solution was cooled. The solution is a light brown liquid,
The pH was about 9.

The solution thus obtained was subjected to electrodialysis.

The electrodialysis method is shown in Fig. 1 and is an anion exchange membrane (A).
And the cation exchange membrane (C) between the compartments (organic matter room)
To N-lauroyl-N'-2-hydroxyethyl-N '
-A mixed solution of sodium carboxymethylethylenediamine and triethanolamine, 1% NaCl water in the adjacent compartment (electrolyte compartment), and 3% as the polar liquid.
Glauber's salt water was circulated overnight, and a direct current was applied. At this time, 213.8 g of 35% HCl (2.05
(Electrolyte) was applied uniformly over about 4 hours to perform electrodialysis.

The electrodialyzer used in this synthesis example had 10 0.02 m ² anion and cation exchange membranes each.
The applied current has an initial current density of 2 amps / dm ² ,
I energized for 12 hours. The final current density after 12 hours was 0.1 amp / dm ² .

A 35% solution of N-lauroyl-N'-2-hydroxyethyl-N'-triethanolaminocarboxymethylethylenediamine was thus obtained. Na of this product
And analysis of triethanolamine in liquid chromatography confirmed that the counterions were exchanged 98%. Also, from the analysis of Cl, 1.43% (0. 0) was obtained with respect to 143 g of N-lauroyl-N'-2-hydroxyethyl-N'-triethanolaminocarboxymethylethylenediamine (100 g as an acid form).
It was confirmed to be 024 mol). A part of the obtained product was dried under reduced pressure and confirmed to be the above substance by IR analysis.

Synthesis Example 3. A 4-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel thermometer was charged with 268 g (1 mol) of 1-hydroxyethyl-2-laurylimidazoline, 90 g of water and 2 g of sodium hydroxide while stirring. Raise the temperature to 80 ℃ and keep it at about 2 for about 2
Stirring was continued for imidazoline ring opening. next,
Separately prepared sodium monochloroacetate 233g (2mol) and water
427 g of solution was charged into this container. Next, while maintaining the temperature of the solution at 70 to 80 ° C., 200 g of 40% NaOH aqueous sodium hydroxide solution was added dropwise over 4 hours. 75 more after dropping
Aged at a temperature of ~ 80 ° C to give N-lauroyl-N'-2.
An approximately 30% aqueous solution of -hydroxyethyl-N'-sodium carboxymethylethylenediamine was obtained.

The solution thus obtained was subjected to electrodialysis.

The electrodialysis method is shown in Fig. 1 and is an anion exchange membrane (A).
And the cation exchange membrane (C) between the compartments (organic matter room)
To N-lauroyl-N'-2-hydroxyethyl-N '
-Sodium carboxymethylethylenediamine solution, 1% NaCl water in the adjacent compartment (electrolyte compartment),
Further, as a polar liquid, 3% Glauber's salt water was circulated overnight to apply a direct current. At this time, electrodialysis was performed while uniformly adding 535 g (2.0 mol) of 20% NH ₄ Cl to this mixed solution over about 4 hours.

The electrodialyzer used in this synthesis example had 10 0.02 m ² anion and cation exchange membranes each.
The applied current has an initial current density of 2 amps / dm ² ,
I energized for 12 hours. The final density after 12 hours was 0.1 amp / dm ² .

In this way, a 20% solution of N-lauroyl-N'-2-hydroxyethyl-N'-ammoniocarbomethylethylenediamine was obtained. Analysis of Na and N% of this product showed 95% exchange of counterions and analysis of Cl revealed N-lauroyl-N'-2-hydroxyethyl-N '.
-Ammonio carboxymethyl ethylenediamine 105g
It was confirmed that NaCl was 2.1% (0.036 mol) with respect to (100 g of acid type).

Moreover, a part of the obtained product was dried under reduced pressure and confirmed to be the above substance by IR analysis.

Example 1 Various detergents having the compositions shown in Table 1 were evaluated for super-foaming power, detergency and skin irritation. The results are shown in Table 1.

The performance evaluation was carried out by the following method.

Detergency test 5 cm x 5 cm wool muslin cloth with 2% carbon black
Stain with almost the same composition as scalp oil containing (paraffin 12%, wax ester 21%, triglyceride 26%, higher fatty acid
32%, cholesterol 5%, monoglyceride 2%) Apply evenly and dry. Use a 3% solution of this detergent on the soiled cloth.
Put it in a stainless steel cylinder of about 1000 ml containing 500 ml, shake for 6 minutes in a constant temperature bath of 40 ° C., rinse the contaminated cloth thoroughly in running water, dry and measure the reflectance. The cleaning rate is calculated by the following formula.

The residual sebum was extracted and quantified, and the degreasing rate was determined in the same manner.

Skin irritation test method As a skin irritation test method, a 24-hour closed patch test for humans was performed. That is, 20 test subjects were patch-applied with a patch test adhesive bandage impregnated with 0.1 ml of a 0.2% aqueous solution as a surfactant-effective component for 24 hours, and the irritation was evaluated 24 hours after the removal of the patch. As for the judgment result, those showing erythema with sticking were regarded as positive, and the positive rate was shown.

Foaming power 4 ° D so that the final concentration of the active ingredient in the surfactant is 0.2%
It was diluted with H 2 hard water and measured by the inversion stirring method. The measurement was carried out at 40 ° C. with the addition of 0.5% lanolin, and the results are shown in terms of foam volume (ml).

Example 2 Table 2 shows a comparison of amide amino acid type active agents according to their structures.

Example 3 Table 3 shows the results of evaluation of the solubility and low temperature stability of a versatile water-soluble polymer of various detergents having the compositions shown in Table 3.

The solubility and low temperature stability were evaluated according to the following criteria. The low temperature stability indicates the result of storage at -5 ° C for 1 week.

[Low temperature stability]

○: Transparent liquid △: Semi-transparent liquid ×: Precipitation Example 4 Table 4 shows the results of evaluation of moisturizing feeling and the like of various detergents having the compositions shown in Table 4.

The performance was evaluated by the following method.

Moisture sensation A 20 cm long hair bundle of 20 g was immersed in 40 ° C warm water, 1 g of the cleaning composition was applied, and after lathering for 1 minute, rinsing was performed. The following criteria were evaluated by the panelists.

○: Stable, △: Slightly stable, ×: Stainless, dissolution and precipitation behavior of quaternary nitrogen-containing cellulose ether 10% Surfactant solution 0.5% of cationized cellulose was added and dissolved at that time. The behavior and the precipitation behavior when diluted 10 times were evaluated according to the following criteria.

[Dissolution behavior]

○: Complete dissolution △: Partially dissolved ×: Not dissolved [Precipitation behavior] ○: Large amount of precipitation △: Partial precipitation ×: No precipitation Example 5 Table 5 shows the results of evaluation of the solubility and low temperature stability of a versatile water-soluble polymer of various detergents having the compositions shown in Table 5.

The solubility and low temperature stability were evaluated according to the following criteria.

[Low temperature stability]

○: Transparent liquid △: Semi-transparent liquid ×: Precipitation Examples 6 to 8 All of the shampoos, wool / light detergents, and dishwasher detergents shown below had very low irritation to the skin and good detergency.

Example 6 Shampoo: Example 7 Wool / Light detergent: Example 8 Dishwasher cleaner: Example 9 The anti-dandruff composition shown below had extremely weak irritation to the skin and good anti-dandruff effect.

Example 10 The bathroom cleaning agent shown below exhibits a good cleaning property and efficiently removes the soap residue attached to the bathtub or the like.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of the electrodialysis tank used in the present invention.

Claims (1)

[Claims] 1. A general formula (Wherein R represents an alkyl group having 7 to 23 carbon atoms, a hydroxyalkyl group, an aralkyl group or an alkenyl group, and M represents an alkali metal), a secondary amide amino acid alkali metal salt represented by And a general formula (I) obtained by electrodialysis in the presence of triethanolamine or ammonia (In the formula, R represents an alkyl group having 7 to 23 carbon atoms, a hydroxyalkyl group, an aralkyl group or an alkenyl group, and X represents a hydrogen atom, an ammonium ion or a triethanolammonium ion), or a secondary amide amino acid thereof A liquid containing 1 to 45% by weight of a salt and 0.05 to 10% by weight of a water-soluble polymer other than polyacrylic acid or a salt thereof which is insoluble in a concentrated salt solution, and the content of a water-soluble inorganic salt is 1% by weight or less. Cleaning composition.