JPH08100198A - Cleaning agent composition - Google Patents

Abstract

PURPOSE: To obtain a cleaning agent composition containing a specific amidoether derivative mixture and a cationic polymer, having low stimulation, good in feeling after cleaning and in foamability, and excellent in conditioning effect and useful for cleaning of skin and hair, etc. CONSTITUTION: This cleaning agent composition contains (A) preferably >=5wt.% of an amidoether derivative mixture composed of an amidoether carboxylic acid (salt) expressed by formula I [R<1> is a 5-23C alkyl or alkenyl, etc.; R<2> is H, (CH2 CH2 O)n CH2 COOM (M is H or an alkali metal, etc.; (n) is 1-20) or a 1-3C alkyl, etc.] and an amidoether expressed by formula II [R<3> is H, (CH2 CH2 O)m H or a 1-3C alkyl; (m) is 1-20] at a total of >=50wt.% in the solid component in a weight ratio of the formula I/the formula II of 99/1 to 10/90, and containing a glycerol derivative expressed by formula III [R<4> is H or (CH2 CH2 O)n CH2 COOM, etc.] at <=5wt.% in the solid component, and (B) preferably 0.05-1.5wt.% of a cationic polymer such as a cationic cellulose derivative, etc. The composition preferably has pH at 4-7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition, and more specifically, it is less irritating to the skin and the like, has an excellent foaming property, has a creamy foam quality, and has a good feeling at the time of cleaning, The present invention relates to a detergent composition having excellent conditioning effects such as smoothness afterwards.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a surfactant for detergents, alkyl sulfate ester salt, polyoxyethylene alkyl sulfate ester salt, alkylbenzene sulfonate, α, which has the characteristics of high foamability
-Anionic surfactants such as olefin sulfonates are widely used. However, all of these anionic surfactants have skin irritation to varying degrees, but when they are continuously used, they have a problem of roughening the skin.

On the other hand, alkyl saccharide-based surfactants, sulfosuccinic acid-based surfactants, ethercarboxylic acid-based surfactants, amide ethercarboxylic acid-based surfactants, etc. are known as mild surfactants. Has been. However, although alkyl saccharide-based surfactants have high foaming properties, they have strong creases during cleaning and rinsing, and therefore are used in combination with conditioning agents such as cationic polymers (JP-A-2-42013). Although it has been proposed, it is not technically easy to add a large amount to shampoo or the like. In addition, sulfosuccinic acid-based surfactants have poor foaming properties by themselves, and a method in which they are used in combination with other surfactants (Japanese Patent Laid-Open No. 2-218797) has been proposed. Often used in combination.
Furthermore, commercially available ether carboxylic acid type surfactants and amido ether carboxylic acid type surfactants also have poor foaming properties, and are used only as auxiliary surfactants in detergents that require high foaming properties. ing.

This amide ether carboxylic acid type surfactant is commercially available from Chem Y of Germany under the trade name of "Akipo".
In addition to the raw material amide ether, impurities derived from the raw material polyoxyethylene glyceryl ether,
It contains polyoxyethylene glyceryl ether carboxylic acid, inorganic salts and the like.

[0005] As a technique known so far regarding application of an amide ether carboxylic acid type surfactant to a detergent, amide ether carboxylic acid, polyoxyethylene alkyl sulfuric acid ester, fatty acid diethanol amide, higher alcohol alkylene oxide are known. Detergent combined with adduct, acyl sarcosinate, etc. (European Patent No. 102118), a method of using amide ether carboxylic acid type surfactant and polyoxyethylene alkyl sulfate ester in combination (European Patent No. 215504) ), A foam bath in which amide ether carboxylic acid starting from fats and oils is combined with lauryl sulfate ester, lauryl ether sulfate ester, alkyl ether carboxylic acid, quaternary compound obtained by reacting lauric acid with glycidyl trimethyl ammonium chloride, etc. Agents, shampoo agents, shower agents and the like (JP-B 63-291996, JP-EP 2
19893), detergents containing amide ether carboxylic acid or alkyl ether carboxylic acid salt containing soap as a main component (US Pat. No. 4,865,757), and the like.

However, none of these detergents is still satisfactory in terms of foamability. Therefore, there has been a demand for the development of a cleansing agent which has low irritation on the skin and the like, has a high foaming property, and has an excellent conditioning effect.

[0007]

Under the above circumstances, the inventors of the present invention have investigated a detergent containing amide ether carboxylic acid, and as a result, have found that polyoxyethylene glyceryl ether and polyoxyethylene glyceryl which are impurities derived from raw materials. It was found that the foaming property was inferior with a substance containing a large amount of ether carboxylic acid or a pure amide ether carboxylic acid itself. And as a result of further study, if the amide ether derivative mixture containing amide ether in a specific ratio and the content of the glycerin derivative is not more than a fixed ratio, is used in combination with the cationic polymer,
It has been found that a cleaning agent having low irritation to the skin, a high foaming property, a creamy foam quality, an excellent feel during cleaning, and an excellent conditioning effect such as smoothness after cleaning can be obtained, and the present invention completed.

That is, the present invention relates to a detergent composition containing the following components (A) and (B). (A) an amide ether carboxylic acid represented by the general formula (1) or a salt thereof and an amide ether represented by the general formula (2),
(1) :( 2) = 99: 1 to 1: 9 in total 50 by weight ratio in solid content
An amide ether derivative mixture containing at least 5% by weight and containing less than 5% by weight of solid content of the glycerin derivative represented by the general formula (3).

[0009]

Embedded image

(Wherein R ¹ represents a linear or branched alkyl or alkenyl group having 5 to 23 carbon atoms or a phenyl group substituted with such an alkyl group, R ² represents a hydrogen atom,-( CH ₂ CH ₂ O) _n CH ₂ COOM,-(CH ₂ CH ₂ O) _m H or an alkyl group having 1 to 3 carbon atoms, M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanolamine Or a basic amino acid, n and m may be the same or different and each represents a number of 1 to 20, R ³ is a hydrogen atom, — (CH ₂ CH ₂ O) _m H or an alkyl group having 1 to 3 carbon atoms. represents a group, R ⁴ is a hydrogen _{atom, - (CH 2 CH 2 O} ) n CH 2 COOM or - (CH ₂ CH
₂ O) _m H is shown. R ¹ , M, n and m in the general formulas (1), (2) and (3) may be the same or different. ) (B) Cationic polymer

In the amide ether derivative mixture which is the component (A) used in the present invention, in the general formula (1) or (2),
R ¹ is an alkyl group or an alkenyl group having 7 to 17 carbon atoms, or a phenyl group substituted with such an alkyl group, for example, a heptyl group, a nonyl group, an undecyl group,
Tridecyl group, pentadecyl group, heptadecyl group, heptadecenyl group and the like, especially undecyl group and tridecyl group are preferable, R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n and m are 1 to 15 Further, a number of 1 to 10, particularly 2 to 7, is preferable, and examples of M include sodium, potassium, magnesium, calcium, monoethanolamine, diethanolamine, triethanolamine, arginine, lysine, and the like.
Among these, sodium, potassium, magnesium and calcium are preferable, and magnesium is particularly preferable from the viewpoint of the feel of hair during rinsing and after drying.

Specific preferred examples of the amide ether carboxylic acid or its salt (1) in the component (A) include capric acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 15) and lauric acid monoethanolamide poly. Oxyethylene ether acetic acid (n = 1 to 15),
Myristic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), palmitic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 1)
15), stearic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), oleic acid monoethanolamide polyoxyethylene ether acetic acid (n =
1-20), behenic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1-20), lauric acid-N-
Methyl ethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), myristic acid-N-methyl ethanolamide polyoxyethylene ether acetic acid (n = 1 to 1)
5), palmitic acid-N-methylethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), stearic acid-N-methylethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), lauric acid isopropanolamide poly Oxyethylene ether acetic acid (n = 1 to 1
5), myristic acid isopropanolamide polyoxyethylene ether acetic acid (n = 1 to 15), palmitic acid isopropanolamide polyoxyethylene ether acetic acid (n = 1 to 15), stearic acid isopropanolamide polyoxyethylene ether acetic acid (n = 1) 15), lauric acid diethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), myristic acid diethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), palmitic acid diethanolamide polyoxyethylene ether acetic acid (n = 1-15), stearic acid diethanolamide polyoxyethylene ether acetic acid (n = 1-15), etc.
Or more preferable specific examples thereof are lauric acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 10), myristic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 10),
Palmitic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 10), stearic acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 10)
10) and the like or salts thereof, and particularly preferred specific examples thereof are lauric acid monoethanolamide polyoxyethylene ether acetic acid (n = 2 to 7) and myristic acid monoethanolamide polyoxyethylene ether acetic acid (n = 2 to 2). 7).

Preferred specific examples of the amide ether (2) in the component (A) include, for example, capric acid monoethanolamide polyoxyethylene ether (n = 1 to 15) and lauric acid monoethanolamide polyoxyethylene ether (n = 1-15), myristic acid monoethanolamide polyoxyethylene ether (n = 1-15), palmitic acid monoethanolamide polyoxyethylene ether (n = 1-15), stearic acid monoethanolamide polyoxyethylene ether (n = 1 to 15), oleic acid monoethanolamide polyoxyethylene ether (n = 1 to 20), behenic acid monoethanolamide polyoxyethylene ether (n = 1 to 20), lauric acid-
N-methylethanolamide polyoxyethylene ether (n = 1 to 15), myristic acid-N-methylethanolamide polyoxyethylene ether (n = 1 to 15), palmitic acid-N-methylethanolamide polyoxyethylene ether ( n = 1 to 15), stearic acid-N-methylethanolamide polyoxyethylene ether (n = 1)
~ 15), lauric acid isopropanolamide polyoxyethylene ether (n = 1 to 15), myristic acid isopropanolamide polyoxyethylene ether (n = 1)
~ 15), palmitic acid isopropanolamide polyoxyethylene ether (n = 1 to 15), stearic acid isopropanolamide polyoxyethylene ether (n =
1 to 15), lauric acid diethanolamide polyoxyethylene ether (n = 1 to 15), myristic acid diethanolamide polyoxyethylene ether (n = 1 to 1)
5), palmitic acid diethanolamide polyoxyethylene ether (n = 1 to 15), stearic acid diethanolamide polyoxyethylene ether (n = 1 to 15) and the like are more preferable specific examples. Oxyethylene ether (n = 1 to 1
0), myristic acid monoethanolamide polyoxyethylene ether (n = 1 to 10), palmitic acid monoethanolamide polyoxyethylene ether (n = 1 to 1)
0), stearic acid monoethanolamide polyoxyethylene ether (n = 1 to 10) and the like. Particularly preferred specific examples include lauric acid monoethanolamide polyoxyethylene ether (n = 2 to 7) and myristic acid monoester. Examples include ethanolamide polyoxyethylene ether (n = 2 to 7).

The total content of the amide ether carboxylic acid or its salt (1) and the amide ether (2) in the amide ether derivative mixture of the component (A) is 50% by weight or more in the solid content of the component (A). Must be above 60% by weight,
It is preferably 70% by weight or more, and particularly preferably 80% by weight or more. If the total content of these is less than 50% by weight in the solid content, the foaming property is poor, which is not preferable.

The weight ratio of the amide ether carboxylic acid or its salt (1) and the amide ether (2) contained in the component (A) is (1) :( 2) = 99: 1 to 10:90. It is necessary to be present, and it is preferably 95: 5 to 60:40, and particularly preferably 92: 8 to 70:30. If the ratio of the amide ether (2) is less than the above range (less than 1% by weight), the foaming property is poor, and if it exceeds the above range (more than 90% by weight), creaking at the time of foaming and rinsing is strong, Not preferable.

Further, the content of the glycerin derivative (3) in the component (A) is required to be 5% by weight or less, and particularly 3% by weight or less, in the solid content of the component (A). It is preferably not included. When the content of the glycerin derivative (3) exceeds 5% by weight in the solid content, the foamability is remarkably reduced, which is not preferable. Further, the content of the inorganic salt such as sodium chloride, which is an impurity other than the glycerin derivative (3) in the component (A), is preferably low.

The method for producing the amide ether derivative mixture which is the component (A) is not particularly limited, and it can be produced directly by reacting a part of the amide ether, and the amide ether can be directly converted into the amide ether carboxylic acid. It can also be added afterwards. As a method for synthesizing an amide ether derivative mixture, a method of producing an alkanolamide from a fatty acid lower alcohol ester such as a fatty acid methyl ester as a starting material, a method of producing an alkanolamide from a fat or oil as a starting material, and an alkanolamide from a fatty acid Methods and the like. Among them, the method of producing a fatty acid lower alcohol ester such as fatty acid methyl ester as a starting material is preferable because it is less colored and does not substantially contain the glycerin derivative as an impurity. Other methods, for example, starting from an oil / fat having a coconut oil fatty acid composition as a starting material, and in the case of a method of directly alkoxylating and carboxymethylating an alkanolamide, a large amount of a glycerin derivative derived from an oil / fat is produced and the compound (1)
Also, the yield of (2) will be low, which is not preferable in practice.
Further, in the case of a method in which a fatty acid is used as a starting material and reacted with an alkanolamine to form an alkanolamide, coloring is remarkable because the amidation reaction is at a high temperature, which is not preferable.
The ratio of the amide ether carboxylic acid (1) and the amide ether (2) in the amide ether derivative mixture of the component (A) is a molar ratio or a mixing method when the amide ether (2) is reacted with an alkali monohaloacetic acid salt or the like. It can be adjusted by selecting the reaction conditions of.

These components (A) can be used alone or in combination of two or more. The amount of the component (A) in the detergent composition of the present invention is not particularly limited, but is preferably 3% by weight or more, and particularly preferably 5% by weight or more from the viewpoint of foaming property.

The cationic polymer which is the component (B) used in the present invention includes a cationized cellulose derivative, a cationic starch, a cationized guar gum derivative, a diallyl quaternary ammonium homopolymer, a diallyl quaternary ammonium salt and acrylamide. Polymer, copolymer of diallyl quaternary ammonium salt and acrylic acid, polymer consisting of three components of diallyl quaternary ammonium / acrylic acid / acrylamide, quaternized polyvinylpyrrolidone derivative,
Examples thereof include polyglycol polyamine condensates. Of these, cationized cellulose derivatives, diallyl quaternary ammonium homopolymers, and copolymers of diallyl quaternary ammonium salts with acrylamide and / or acrylic acid are preferable.

As the cationized cellulose derivative, for example, those represented by the following general formula (4) are preferable.

[0021]

Embedded image

[In the formula, A represents a residue of an anhydroglucose unit, a represents an integer of 50 to 20,000, and each R ⁵ represents a substituent represented by the following general formula (5).

[0023]

[Chemical 4]

(R ⁶ and R ⁷ represent an alkylene group having 2 or 3 carbon atoms, b and d each represent an integer of 0-10,
c represents an integer of 0 to 3, R ⁸ represents an alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group, and R ⁹ and R ¹⁰
And R ¹¹ each represents an alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group, or may form a heterocycle together with the nitrogen atom in the formula. X ₁ ^- is chlorine ion,
It shows anions such as bromine ion, iodine ion, sulfate ion, sulfonate ion, methylsulfate ion, phosphate ion, and nitrate ion. )]

The cation substitution degree of the cationized cellulose derivative is preferably 0.01 to 1, that is, the average value of c per anhydroglucose unit is 0.01 to 1, particularly preferably 0.02 to 0.5. The sum of b and d is preferably 1 to 3 on average. If the degree of cation substitution is less than 0.01, a sufficient effect cannot be obtained, and if it exceeds 1, the reaction yield will decrease. The molecular weight of the cationized cellulose derivative is 100,000 to 3,000,0.
00 is preferable.

As the cationic starch, for example, those represented by the following general formula (6) are preferable.

[0027]

Embedded image

[Wherein B represents a starch residue, R ¹² represents an alkylene group or a hydroxyalkylene group, and R ¹³ and R
¹⁴ and R ¹⁵ each represent an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, or may form a heterocycle together with the nitrogen atom in the formula. X ₂ ⁻ represents an anion such as chlorine ion, bromine ion, iodine ion, sulfate ion, sulfonate ion, methyl sulfate ion, phosphate ion, and nitrate ion, and e represents a positive integer. ]

The degree of cation substitution of the cationic starch is 0.01 to
One in which 0.01 to 1, particularly 0.02 to 0.5, cationic groups are introduced per anhydroglucose unit is preferable. If the degree of substitution is less than 0.01, a sufficient effect cannot be obtained, and if it exceeds 1, the reaction yield will decrease.

As the cationized guar gum derivative, for example, those represented by the following general formula (7) are preferable.

[0031]

[Chemical 6]

[Wherein D represents a guar gum residue,
^{R 12, R 13, R 14} , R 15, X 2 - and e are as defined above. ]

The degree of cation substitution of the cationized guar gum derivative is 0.01 to 1, that is, 0.01 to 1, especially 0.02 to 0.5.
Those in which individual cationic groups are introduced into the sugar unit are preferred.

This type of cationic polymer is disclosed in Japanese Patent Publication Sho 58
-35640, Japanese Patent Publication No. 60-46158, and Japanese Patent Laid-Open No. 58-539
No. 96 publication and is commercially available from Celanese-Stein Hall under the trademark "Jaguar".

The copolymer of diallyl quaternary ammonium salt and acrylamide is, for example, the following general formula (8) or
What is represented by (9) is preferable.

[0036]

[Chemical 7]

[In each formula, R ¹⁶ and R ¹⁷ are each a hydrogen atom, an alkyl group (having 1 to 18 carbon atoms), a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group or Represents a carboalkoxyalkyl group, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each represent a hydrogen atom, a lower alkyl group (having 1 to 3 carbon atoms) or a phenyl group, and X ₃ ⁻ represents chlorine ion, bromide ion, iodine And anions such as ions, sulfates, sulfonates, methylsulfates, and nitrates, f and g each represent an integer of 1 to 50, and h represents an integer of 150 to 8,000. ]

The copolymer of diallyl quaternary ammonium salt and acrylamide has a molecular weight of about 30,000 to 2,000,000,
Particularly, the range of 100,000 to 1,000,000 is preferable.

The copolymer of diallyl quaternary ammonium salt and acrylic acid is, for example, the following general formula (10) or (11)
What is represented by is preferable.

[0040]

Embedded image

[In each formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ ,
R ²¹ , R ²² , X ₃ ⁻ , f, g and h have the same meanings as described above. ]

As the quaternized polyvinylpyrrolidone derivative, for example, those represented by the following general formula (12) are preferable.

[0043]

[Chemical 9]

[In the formula, R ²² represents a hydrogen atom or a carbon number of 1 to 3;
R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group or a carboalkoxyalkyl group. ,
Y represents an oxygen atom or a group —NH—, and X ₄ ^— represents chlorine ion, bromine ion, iodine ion, sulfate ion, sulfonate ion, alkyl sulfate ion having 1 to 4 carbon atoms, phosphate ion, nitrate ion, and the like. Indicates anion, i + j = 20〜
8000 represents an integer, and k represents an integer of 1 to 10. ]

The molecular weight of the quaternized polyvinylpyrrolidone derivative is preferably 10,000 to 2,000,000, and particularly preferably 50,000 to 1,500,000.
The content of the cationic nitrogen derived from the cationic polymer contained in the quaternized polyvinylpyrrolidone derivative is preferably 0.004 to 0.2%, and particularly preferably 0.01 to 0.15% with respect to the vinyl polymer. If it is less than 0.004%, a sufficient effect cannot be obtained, and 0.2%
If it exceeds, the performance is good, but it causes coloration and is economically disadvantageous.

As the polyglycol polyamine condensate, for example, those represented by the following general formula (13) are preferable.

[0047]

[Chemical 10]

[Wherein R ²⁶ , R ²⁸ , R ^29, and R ³¹ each represent a hydroxyalkylene group having 2 to 4 carbon atoms, and R ^26
27 and R ³⁰ each represent an alkylene group having 2 or 3 carbon atoms, R ³² represents a linear or branched alkyl group having 6 to 20 carbon atoms, l and r represent an integer of 10 to 20, and p Is 2-6
Is an integer, q is an integer of 2 to 4, and s is an integer of 1 to 50. ]

In addition, a copolymer of adipic acid / dimethylaminohydroxypropylethylenetriamine (calcaretin manufactured by Sandos, USA), and JP-A-53-139734.
Any of the cationic polymers described in JP-A-60-36407 can be used.

These components (B) can be used alone or in combination of two or more. The amount of component (B) in the detergent composition of the present invention is not particularly limited, but is preferably 0.01 to 5% by weight, particularly preferably 0.05 to 1.5% by weight. If the blending amount of the component (B) is less than 0.01% by weight, the conditioning effect such as foamy creamyness, feeling at the time of washing, smoothness of the skin and hair after washing is poor, and the blending amount exceeds 5% by weight. Then, a residual feeling on the skin or hair after washing occurs, which is not preferable in terms of feeling.

The detergent composition of the present invention has a pH of 2 to 10, more preferably pH 4 to 8, and especially pH 4 to 7 due to the known acidic or alkaline chemicals used in conventional detergent compositions.
Is preferably adjusted to pH (pH measurement condition: effective 5% by weight aqueous solution).

In addition to the above-mentioned essential components, the detergent composition of the present invention contains anionic surfactants other than amide ether carboxylic acid, nonionic surfactants and amphoteric surfactants as long as the effects of the present invention are not impaired. , Various components such as a cationic surfactant and a conditioning component can be blended.

Examples of such anionic surfactants include fatty acid salts, polyoxyalkylene alkyl ether acetate salts,
Alkyl sulfate, polyoxyalkylene alkyl ether sulfate, sulfosuccinic acid surfactant, sulfosuccinamate surfactant, polyoxyalkylene alkyl amide ether sulfate, monoglyceride sulfate, olefin sulfonate, alkane sulfonate , Acylated isethionates, acylated amino acids, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, and the like, and nonionic surfactants include alkyl polyglucosides, sucrose fatty acid esters, and polyglycerin fatty acid esters. , Polyoxyalkylene alkyl ethers, alkylamine oxides, fatty acid polyhydric alcohol esters, and the like, and as the cationic surfactant,
Linear or branched mono- or di-long alkyl fourth
Tertiary ammonium salt or mono- or di-long chain alkyl tertiary
Examples of the amphoteric surfactant include amide amino acid-based surfactants, carbobetaine-based surfactants, sulfobetaine-based surfactants, amide sulfobetaine-based surfactants, and imidazolinium betaine-based surfactants. Agents, amino acid-based betaine surfactants, phosphobetaine-based surfactants, and the like.Conditioning ingredients include higher alcohols, silicones, silicone derivatives, lanolin, squalene, hydrocarbons, protein derivatives, fatty acid esters of polyethylene glycol, etc. Examples include oil solutions.

Other components commonly used in detergent compositions, for example, water-soluble polymers such as methylcellulose, hydroxyethylcellulose, carboxyvinyl polymer, and polysaccharides such as xanthan gum; polyoxyalkylene sorbitan ester, polyoxyethylene glycol. Viscosity modifiers such as distearate and ethanol; Chelating agents such as ethylenediaminetetraacetic acid (EDTA) and phosphonates; Preservatives such as methylparaben and butylparaben; Nutritional components such as vitamins and their precursors, lecithin, gelatin, etc. Animal and plant extracts or derivatives thereof; polymer fine powders such as nylon and polyethylene; anti-inflammatory agents such as potassium glycyrrhizinate; fungicides and anti-dandruff agents such as triclosan, trichlorocarban, octopirox, zinc pyrithione;
An antioxidant such as dibutylhydroxytoluene; a pearling agent, an ultraviolet absorber, a pH adjusting agent, a dye, a fragrance, etc. may be added, if necessary, within a range that does not impair the effects of the present invention.

The detergent composition of the present invention can be applied to detergents for various purposes such as detergents for skin and hair, as well as detergents for dishes and detergents for clothes. In this case, (A)
Ingredients and other surfactants, the total compounding amount as a surfactant in the entire composition is 30% by weight or more for solid dosage forms, 20% by weight or more for paste dosage forms, liquid If the dosage form is, it is preferably 10% by weight or more.

[0056]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Synthesis Example 1 Synthesis of Amido Ether Carboxylic Acid Sodium Salt Containing Amido Ether: Methyl laurate 214.4 g (1 mol), monoethanolamine 61.7 g (1.02 mol) and sodium methoxide
88.2 g of ethylene oxide was added to the product obtained by heating 15.3 g of a 30 wt% methanol solution at 90 ° C. and 50 mmHg for 5 hours.
(2 mol) was introduced at 100 to 110 ° C. and a gauge pressure of 0 to 3.5 atm. 331 g of the reaction mixture was heated to 70-75 ° C and 174.8 g (1.5 mol) of sodium monochloroacetate (SMCA) and 65.2 g of solid sodium hydroxide were added over 4 hours. SM
CA and sodium hydroxide were divided into 5 parts and added at the start of the reaction and at 1, 2, 3, and 4 hours after the start of the reaction. After the addition at the 4th hour, the mixture was aged for 1 hour. Next, the reaction temperature was adjusted to 85 ° C., 5.3 g of water was added, and the mixture was aged for 1 hour to obtain 592 g of a carboxymethylation reaction mixture. 500 water to the reaction mixture
g was added, a 36% aqueous hydrochloric acid solution was added at 90 ° C. to adjust the pH to 2.8, and the mixture was stirred for 1 hour and then allowed to stand for 1 hour to perform layer separation to obtain 545 g of an acid type product. The acid type compound was adjusted to pH 7 with a 30% sodium hydroxide aqueous solution, and water was added to form a transparent solution to obtain an amide ether derivative mixture 2 shown in Table 1.

Synthesis Examples 2 to 6 Synthesis of Amido Ether Carboxylic Acid Sodium Salt Containing Amido Ether: In the same manner as in Synthesis Example 1, amide ether derivative mixtures 1, 3, 5 and 6 shown in Table 1 were obtained. The molar ratios of SMCA to amide ether were 1.7, 1.5 and 1.4, respectively, and the molar ratios of solid sodium hydroxide were 1.85, 1.63 and 1.52.
And In addition, 30% after reaction without conversion and purification to acid form
Amide ether derivative mixture 4 in the same manner as in Synthesis Example 1 except that the pH was kept at 7 with an aqueous solution of 15% sodium hydroxide.
I got

Synthesis Example 7 Synthesis of Amido Ether Carboxylic Acid Magnesium Salt Containing Amido Ether: The acid type product obtained in Synthesis Example 1 was neutralized to pH 6 to 7 with a 30% aqueous magnesium hydroxide suspension, Water was added to form a transparent solution, and the amide ether derivative mixture 7 shown in Table 1 was obtained.

Comparative Synthesis Example 1 Synthesis of Amido Ether Carboxylic Acid Sodium Salt from which Amido Ether was Removed: After obtaining a carboxymethylation reaction mixture in the same manner as in Synthesis Example 1, ethanol was added to this reaction mixture to precipitate a solid. It was Then, this was filtered, and ethanol was added to the filtered material to wash it, thereby removing amide ether. Further, the acid type was prepared in the same manner as in Synthesis Example 1 and then neutralized with a 30% aqueous sodium hydroxide solution to obtain an amide ether derivative mixture 8.

Comparative Synthesis Example 2 Synthesis of Amido Ether Carboxylic Acid Sodium Salt Containing Amido Ether: An amide ether was obtained in the same manner as in Synthesis Example 1, and the molar ratio of SMCA and solid sodium hydroxide to this amide ether was 0.05 each. The reaction was carried out under the conditions, and then the same treatment as in Synthesis Example 1 was carried out to obtain an amide ether derivative mixture 9.

Comparative Synthesis Example 3 Synthesis of Amidoethercarboxylic Acid Sodium Salt Containing Glycerin Derivative: Purified coconut oil 510.6 g (2.2 mol) was dissolved at 35 ° C. Next, 138.8 g (2.3 mol) of monoethanolamine and 5.1 g of a 30 wt% methanol solution of sodium methoxide were added to 70 parts.
298 g (6.75 mol) of ethylene oxide was added to the product obtained by heating at 105 ° C. for 2 hours and at 105 ° C. for 6 hours to 100 to 11
It was introduced at 0 ° C. and a gauge pressure of 0 to 3.5 atm over 30 minutes. 675 g of the reaction mixture was heated to 70 to 75 ° C. and 281.7 g of SMCA (2.41
Mol) and 105.1 g of solid sodium hydroxide were added over 4 hours. SMCA and sodium hydroxide were divided into 5 portions and added at the start of the reaction and at 1, 2, 3, and 4 hours after the start of the reaction. After the addition at the 4th hour, the mixture was aged for 1 hour. Next, the reaction temperature is set to 85 ° C., 5 g of water is added, and the mixture is aged for 1 hour,
1039 g of reaction mixture was obtained. 500 g of water was added to this reaction mixture, and a 36% hydrochloric acid aqueous solution was added at 50 ° C. to adjust the pH to 7, and the mixture was diluted with water until a transparent solution was obtained to obtain an amide ether derivative mixture 10 shown in Table 1.

[0063]

[Table 1]

Example 1 A detergent composition (pH 6.5) having the composition shown in Table 2 was prepared, and the foaming amount, foam quality, hair feel, and skin irritation were evaluated for each. The results are shown in Table 2. In addition, the blending weight% shown in Table 2 is a value of the effective component of the activator (the amide ether carboxylates are solid components). The pH was adjusted with an aqueous sodium hydroxide solution and citric acid.

<Evaluation Method> The amount of foam, the quality of the foam and the feel of the hair were evaluated by 20 professional panelists according to the following evaluation criteria. The amount and quality of foam is 20 g of healthy Japanese women's hair.
(15 cm) was evaluated by applying 1 g of the cleaning agent and lathering for 1 minute, and the feel of the hair was evaluated when lathering for 1 minute, rinsed, and dried with a dryer. Result is
Table 2 shows the average scores of 20 people according to the following criteria. For skin irritation, each cleaning composition was applied to the healthy skin of 5 guinea pigs 4 times, and the reaction of the 4th time was evaluated according to the following evaluation criteria. The results are shown in Table 2 from the average score of 5 animals according to the following criteria.

<Standard> (1) Foaming amount A. Rating: Very good lathering ... score 4. Good lather ... Score 3. Foaming but slightly lacking ... Score 2. Poor bubbling-Score 1. B. Judgment: Average score 3.5 to 4.0 ... ◎. Average score 2.5-3.4 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(2) Foam quality A. Evaluation: The foam quality is creamy and slips very well ... A score of 4. The foam quality is creamy and slips .... Score 3. The quality of the foam is rather coarse and it does not slip a little ... Score 2. The foam quality is rough and does not slip .... Score 1. B. Judgment: Average score 3.5 to 4.0 ... ◎. Average score 2.5-3.4 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(3) Feeling when foaming shampoo A. Evaluation: There is no squeak and it is easy to pass a finger ... Squeeze is a little strong, and the fingers are a little bad ... Score 2. Strong squeaky, poor finger passage ... Score 1. B. Judgment: Average score 2.5 to 3.0 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(4) Feeling after rinsing A. Evaluation: Smooth and soft ... Score 4. No squeak and smooth ... Score 3. Squeeze is slightly strong, smoothness is slightly poor ... Score 2. Strongly squeaky and bad ... Score 1. B. Judgment: Average score 3.1 to 4.0 ... ◎. Average score 2.5-3.0 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(5) Feeling after Drying Hair A. Evaluation: Smooth and soft ... Score 4. The fingers are smooth and smooth, and the score is 3. Slightly poor finger passage and slightly poor smoothness ... Score 2. Poor fingering: Score 1 B. Judgment: Average score 3.1 to 4.0 ... ◎. Average score 2.5-3.0 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(6) Skin Irritation A. Evaluation: non-irritating (no reaction was observed) ... 5. Slightly irritating (slight erythema is recognized) ... Score 4. Mild irritation (clear erythema is observed) ・ ・ ・ Score 3. Moderate irritation (clear erythema with edema) .... Score 2. Highly irritating (clear erythema with necrosis or asphyxia) score 1. B. Judgment: Average score 3.5 to 5.0 ... ○. Average score 2.5-3.4 ... △. Average score 1.0-2.4 ... ×.

[0072]

[Table 2]

Example 2 A pH 6 conditioning shampoo having the following composition was prepared. It was hypoallergenic to the skin and had excellent foamability, foam quality, and feel during shampooing and washing hair.

[Table 3] (% by weight) Mixture of amide ether derivative 3 14 Polyoxyethylene (3) lauryl ether sulfate Na 5 Lauric acid diethanolamide 3 Cationized guar gum (Jaguar C-13-S, manufactured by Celanese Stein Hall) 0.5 Ethylene glycol distearate 3 Citric acid Proper amount Sodium hydroxide Proper amount Perfume 0.2 Ion-exchanged water balance

Example 3 A body shampoo of pH 5.5 having the following composition was prepared. This one is hypoallergenic to the skin, foaming,
It was excellent in foam quality and smoothness of skin after washing.

(Table 4) (wt%) Mixture of amide ether derivative 6 10 Sodium polyoxyethylene (4.5) lauryl ether acetate (Akipo RLM45, manufactured by Chemwai Co.) 10 Cationic polymer (Gafcoat 755N, manufactured by Gaff, vinylpyrrolidone dimethylaminoethylac) Ethyl sulfate quaternary product of relate copolymer) 0.3 Citric acid Appropriate amount Sodium hydroxide Appropriate amount Perfume 0.2 Ion-exchanged water balance

Example 4 An anti-dandruff shampoo of pH 6.5 having the following composition was prepared.
This one is hypoallergenic to the skin, has an anti-dandruff effect,
The foamability and the feel after washing hair were excellent.

[Table 5] (wt%) Amide ether derivative mixture 4 15 Ammonium lauryl sulfate 5 Cationized cellulose (Polymer JR-400, UCC) 0.3 Zinc pyrithione 1 Carboxyvinyl polymer (Carbopol 941, Goodrich) 0.5 Citric acid Suitable amount Sodium hydroxide Suitable amount Fragrance 0.2 Ion-exchanged water balance

Example 5 A dishwashing detergent having the following composition and having a pH of 6 was prepared. It was hypoallergenic to the skin, and was excellent in detergency, foaming property, foam quality, and hand feel after washing.

(Table 6) (% by weight) Amide ether derivative mixture 1 15 Lauryl amine oxide 4 Lauric acid diethanolamide 2 Cationized polymer (Mercoat 280, manufactured by Merck & Co., Copolymer of dimethyldiallyl ammonium chloride and acrylic acid) 0.1 Citric acid Suitable amount Sodium hydroxide qs Ethanol 3 Fragrance 0.2 Ion-exchanged water balance

Example 6 A conditioning shampoo of pH 6.7 having the following composition was prepared. This one is hypoallergenic to the skin,
The foamability, foam quality, and feel of hair during rinsing and after drying were excellent.

(Table 7) (% by weight) Amide ether derivative mixture 3 15 Cationized polymer (mercoat 100, manufactured by Merck, polymer of dimethyldiallyl ammonium chloride) 0.2 Lauric acid diethanolamide 4 Citric acid Adequate amount Sodium hydroxide Adequate amount Perfume 0.1 Ion exchange Water balance

Example 7 A conditioning shampoo of pH 7.0 having the following composition was prepared. This one is hypoallergenic to the skin,
The foamability and foam quality were excellent, and the feel of the hair during rinsing and after drying was particularly excellent.

[Table 8] (% by weight) Amide ether derivative mixture 7 15 Cationized cellulose (Polymer JR, UCC) 1 Laurylamine oxide 4 Lactic acid Appropriate amount Sodium hydroxide Appropriate amount Perfume 0.1 Ion exchange water balance

Example 8 A conditioning shampoo of pH 7.0 having the following composition was prepared. This one is hypoallergenic to the skin,
The foamability and foam quality were excellent, and the feel of the hair during rinsing and after drying was particularly excellent.

[Table 9] (wt%) Amide ether derivative mixture 7 16 Cationized polymer (mercoat 100, manufactured by Merck, a polymer of dimethyldiallyl ammonium chloride) 0.5 Coconut fatty acid diethanolamide 4 Citric acid Adequate amount Sodium hydroxide Adequate amount Perfume 0.1 Ion exchange Water balance

Example 9 A conditioning shampoo of pH 6.5 having the following composition was prepared. This one is hypoallergenic to the skin,
The foamability and foam quality were excellent, and the feel of the hair during rinsing and after drying was particularly excellent.

[Table 10] (% by weight) Amide ether derivative mixture 7 20 Coconut fatty acid amide propyldimethylamino acetic acid betaine 4 Cationized cellulose (Polymer JR, UCC) 1 Dimethyl polysiloxane (5 million cs) 0.5 Lactic acid Suitable amount Sodium hydroxide Suitable amount Fragrance 0.1 Ion-exchanged water balance

[0081]

The cleaning composition of the present invention is less irritating to the skin and the like, has excellent foaming properties, and has a creamy foam quality.
It has a good feel during washing and an excellent conditioning effect such as smoothness after washing.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C11D 1:06 1:72)

Claims (5)

[Claims] 1. A detergent composition containing the following components (A) and (B). (A) an amide ether carboxylic acid represented by the general formula (1) or a salt thereof and an amide ether represented by the general formula (2),
(1) :( 2) = 99: 1 to 10:90 in the solid content in a total weight ratio of 50
An amide ether derivative mixture containing at least 5% by weight and the content of the glycerin derivative represented by the general formula (3) is at most 5% by weight in the solid content. (In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 5 to 23 carbon atoms or a phenyl group substituted with such an alkyl group, R ² represents a hydrogen atom,-(C
H ₂ CH ₂ O) _n CH ₂ COOM,-(CH ₂ CH ₂ O) _m H or an alkyl group having 1 to 3 carbon atoms, M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanolamine Or a basic amino acid, n and m may be the same or different and each represents a number of 1 to 20, R ³ is a hydrogen atom, — (CH ₂ CH _2
2 O) _m H or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents a hydrogen atom,-(CH ₂ CH ₂ O) _n CH ₂ COOM or-(CH ₂ CH ₂ O) _m H. R ¹ , M, n and m in the general formulas (1), (2) and (3) may be the same or different. ) (B) Cationic polymer 2. In the general formulas (1) and (2), R ¹ is a linear or branched alkyl group or alkenyl group having 7 to 17 carbon atoms or a phenyl group substituted with such an alkyl group. , R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n and m are each a number of 1 to 10. 3. The component (A) comprises the amide ether carboxylic acid represented by the general formula (1) or a salt thereof and the amide ether represented by the general formula (2) as (1) :( 2) = 95. : 60 to 40: 40 by weight in total in the solid content, and the general formula
The cleaning composition according to claim 1 or 2, which is an amide ether derivative mixture in which the content of the glycerin derivative represented by (3) is 3% by weight or less based on the solid content. 4. The cleaning composition according to claim 1, wherein the component (A) is made of a fatty acid alkanolamide synthesized from a fatty acid lower alcohol ester. 5. The cleaning composition according to any one of claims 1 to 4, which has a pH of 4 to 7.