JP2747661B2 - Detergent composition - Google Patents

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 particularly, to a detergent composition which is less irritating to the skin and the like, has excellent foaming properties, has a creamy foam, has a good feel at the time of washing, and has good washing properties. The present invention relates to a cleaning composition having excellent conditioning effects such as smoothness afterwards.

[0002]

2. Description of the Related Art
Alkyl sulfate, polyoxyethylene alkyl sulfate, alkyl benzene sulfonate, α,
-Anionic surfactants such as olefin sulfonates are widely used. However, these anionic surfactants have varying degrees of skin irritation, and there is a problem that the skin becomes rough when used continuously.

On the other hand, as surfactants having low irritation, alkyl saccharide surfactants, sulfosuccinic surfactants, ether carboxylic acid surfactants, amide ether carboxylic acid surfactants and the like are known. Have been. However, although alkyl saccharide-based surfactants have high foaming properties, they have strong blemishes during washing and rinsing, and are therefore used in combination with a conditioning agent such as a cationic polymer (Japanese Patent Laid-Open No. 2-42013). Although it has been proposed, it is not technically easy to mix a large amount into a shampoo or the like. In addition, sulfosuccinic surfactants alone have poor foaming properties, and a method of using them 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-based surfactants and amide ether carboxylic acid-based surfactants also have poor foaming properties, and are used only as auxiliary surfactants in detergents that require high foaming properties. ing.

[0004] This amide ether carboxylic acid type surfactant is commercially available from Chem Y in Germany under the trade name of "Akipo".
In addition to the raw material amide ether, polyoxyethylene glyceryl ether, which is an impurity derived from the raw material,
Polyoxyethylene glyceryl ether carboxylic acid, inorganic salts and the like are included.

[0005] Techniques which have heretofore been known for application of amide ether carboxylic acid surfactants to detergents include amide ether carboxylic acids, polyoxyethylene alkyl sulfates, fatty acid diethanolamides, higher alcohol alkylene oxides. Detergent in which an adduct, acyl sarcosinate and the like are combined (European Patent No. 102118), and a method in which an amide ether carboxylic acid surfactant is used in combination with a polyoxyethylene alkyl sulfate (European Patent No. 215504) ), A foam bath in which an amide ether carboxylic acid starting from an oil or fat is combined with lauryl sulfate, lauryl ether sulfate, alkyl ether carboxylic acid, or a quaternary product obtained by reacting lauric acid with glycidyltrimethylammonium chloride. Agents, shampoo agents, shower agents and the like (JP-B 63-291996, JP-EP 2
No. 19893), and a detergent containing soap as a main component and an amide ether carboxylic acid or an alkyl ether carboxylate (US Pat. No. 4,865,575).

[0006] However, none of these detergents has been satisfactory in terms of foaming properties. Accordingly, there has been a demand for the development of a cleaning agent which has low irritation to the skin and the like, high foaming properties, and excellent conditioning effects.

[0007]

Under these circumstances, the present inventors have studied a cleaning agent containing amide ether carboxylic acid and found that impurities such as polyoxyethylene glyceryl ether and polyoxyethylene glyceryl derived from raw materials were used. It was found that a foam containing a large amount of ether carboxylic acid or pure amide ether carboxylic acid itself had poor foaming properties. And as a result of further investigation, if the amide ether derivative mixture containing a specific ratio of amide ether and the content of the glycerin derivative is equal to or less than a certain ratio and a cationic polymer are used in combination,
The present invention has been found to provide a cleaning agent which has a low irritation to the skin, a high foaming property, a foamy quality is creamy, an excellent feel at the time of washing, and an excellent conditioning effect such as smoothness after washing. 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 a weight ratio of 50
An amide ether derivative mixture containing at least 5% by weight of a glycerin derivative represented by the general formula (3) and not more than 5% by weight of the solid content.

[0009]

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(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, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or 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, and R ³ represents a hydrogen atom,-(CH ₂ CH ₂ O) _m H or an alkyl 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
Shows the 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

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 or 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,
A tridecyl group, a pentadecyl group, a heptadecyl group, a heptadecenyl group and the like, particularly an undecyl group and a tridecyl group are preferred.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 And further preferably a number of 1 to 10, particularly preferably 2 to 7, and examples of M include sodium, potassium, magnesium, calcium, monoethanolamine, diethanolamine, triethanolamine, arginine, lysine and the like,
Of these, sodium, potassium, magnesium, and calcium are preferred, and magnesium is particularly preferred in terms of hair feel during rinsing and after drying.

Preferred examples of the amide ether carboxylic acid or its salt (1) in the component (A) include, for example, monoethanolamide capric acid polyoxyethylene ether acetic acid (n = 1 to 15) and monoethanolamide polylaurate. 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-
Methylethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), myristic acid-N-methylethanolamide 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), isopropanolamide polyoxyethylene ether acetic acid myristic acid (n = 1 to 15), isopropanolamide polyoxyethylene ether acetic acid palmitate (n = 1 to 15), isopropanolamide polyoxyethylene ether acetic acid stearic 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),
Or a salt thereof, as more preferred specific examples, 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 1)
10) and the like and salts thereof. Particularly preferred specific examples 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 examples of the amide ether (2) in the component (A) include, for example, monoethanolamide polyoxyethylene ether of capric acid (n = 1 to 15) and monoethanolamide polyoxyethylene ether of lauric acid (n = 1 to 15), myristic acid monoethanolamide polyoxyethylene ether (n = 1 to 15), palmitic acid monoethanolamide polyoxyethylene ether (n = 1 to 15), stearic acid monoethanolamide polyoxyethylene ether (n = 1-15), oleic acid monoethanolamide polyoxyethylene ether (n = 1-20), behenic acid monoethanolamide polyoxyethylene ether (n = 1-20), 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), isopropanolamide polyoxyethylene ether palmitate (n = 1 to 15), isopropanolamide polyoxyethylene ether stearic acid (n =
1-15), 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, and particularly preferred specific examples are lauric acid monoethanolamide polyoxyethylene ether (n = 2 to 7) and myristic acid Ethanolamide polyoxyethylene ether (n = 2 to 7) may be mentioned.

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). Need to be more than 60% by weight
It is preferably at least 70% by weight, particularly preferably at least 80% by weight. If the total content of these components is less than 50% by weight of the solid content, the foaming properties are 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 that the ratio be in the range of 95: 5 to 60:40, particularly 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), the whisking and rinsing are strong, Not preferred.

Further, the content of the glycerin derivative (3) in the component (A) must be 5% by weight or less in the solid content of the component (A), and 3% by weight or less, particularly substantially Preferably, it is not included. When the content of the glycerin derivative (3) exceeds 5% by weight in the solid content, the foaming property is remarkably reduced, which is not preferable. It is preferable that 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 small.

The method for producing the amide ether derivative mixture as the component (A) is not particularly limited, and it can be directly produced by reacting a part of the amide ether. It can be added later. As a method of synthesizing the amide ether derivative mixture, a method of producing an alkanolamide using fatty acid lower alcohol esters such as fatty acid methyl ester as a starting material, a method of producing alkanolamide using oils and fats as a starting material, and a method of producing alkanolamide using fatty acids as a starting material Method and the like. Among them, a method of producing a fatty acid lower alcohol ester such as a fatty acid methyl ester as a starting material is preferable because the coloring is less and the glycerin derivative which is an impurity is not substantially contained. In the case of other methods, for example, a method in which a fat or oil having a coconut oil fatty acid composition is used as a starting material and directly converted into an alkanolamide and then subjected to alkoxylation and carboxymethylation, a large amount of a glycerin derivative derived from the fat or oil is produced and the compound (1)
And (2) are not practically preferable because the yield is low.
In the case of a method in which a fatty acid is reacted with an alkanolamine as a starting material to form an alkanolamide, the coloration is remarkable due to the high temperature of the amidation reaction, which is not preferable.
The ratio of the amide ether carboxylic acid (1) to the amide ether (2) in the amide ether derivative mixture of the component (A) is determined by the molar ratio and the mixing method when the amide ether (2) is reacted with an alkali monohaloacetate or the like. Can be adjusted by selecting the reaction conditions.

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

The cationic polymer as 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, and a copolymer of diallyl quaternary ammonium salt and acrylamide. A polymer, a copolymer of diallyl quaternary ammonium salt and acrylic acid, a polymer composed of three components of diallyl quaternary ammonium / acrylic acid / acrylamide, a quaternized polyvinylpyrrolidone derivative,
And 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 preferred.

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

[0021]

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[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]

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(R ⁶ and R ⁷ each represent an alkylene group having 2 or 3 carbon atoms, b and d each represent an integer of 0 to 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, an aryl group or an aralkyl group having 1 to 18 carbon atoms, or may form a heterocyclic ring together with a nitrogen atom in the formula. X ₁ ^- is a chlorine ion,
It represents an anion such as bromine ion, iodine ion, sulfate ion, sulfonate ion, methyl sulfate ion, phosphate ion and nitrate ion. )]

The degree of cation substitution of the cationized cellulose derivative is preferably 0.01 to 1, that is, the average value of c per anhydroglucose unit is preferably 0.01 to 1, particularly preferably 0.02 to 0.5. The average 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 even if it exceeds 1, the reaction yield decreases. The molecular weight of the cationized cellulose derivative is 100,000-3,000,0
00 is preferred.

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

[0027]

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[In the formula, 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, an aryl group or an aralkyl group having 1 to 10 carbon atoms, or may form a heterocyclic ring together with a nitrogen atom in the formula. X ₂ ^- represents an anion such as chloride ion, bromine ion, iodine ion, sulfate ion, sulfonate ion, methyl sulfate ion, phosphate ion, nitrate ion, and e represents a positive integer. ]

The degree of cationic substitution of the cationic starch is 0.01 to
1, that is, those having 0.01 to 1, especially 0.02 to 0.5 cationic groups introduced per anhydroglucose unit are preferred. If the degree of substitution is less than 0.01, a sufficient effect cannot be obtained, and even if it exceeds 1, the reaction yield decreases.

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

[0031]

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[Wherein D represents a guar gum residue;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X ₂ ^- and e have the same meaning as described 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 two cationic groups are introduced into the sugar unit are preferred.

This type of cationic polymer is disclosed in
-35640, JP-B-60-46158 and JP-A-58-539
No. 96, and is commercially available from Celanese-Stein Hall under the trademark "Jaguar".

As the copolymer of diallyl quaternary ammonium salt and acrylamide, for example, the following general formula (8) or
Those represented by (9) are preferred.

[0036]

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[In each formula, R ¹⁶ and R ¹⁷ each represent a hydrogen atom, an alkyl group (C 1-18), a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group or R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each represent a hydrogen atom, a lower alkyl group (1 to 3 carbon atoms) or a phenyl group; X ₃ ^- represents chlorine ion, bromine ion, iodine And an anion such as an ion, a sulfate ion, a sulfonate ion, a methyl sulfate ion, a nitrate ion, etc., f and g each represent an integer of 1 to 50, and h represents an integer of 150 to 8,000. ]

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

As the copolymer of diallyl quaternary ammonium salt and acrylic acid, for example, the following general formula (10) or (11)
Is preferably represented by

[0040]

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

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

[0043]

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Wherein R ²² is a hydrogen atom or a group having 1 to 3 carbon atoms.
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-; X ₄ ^- represents a chlorine ion, a bromine ion, an iodine ion, a sulfate ion, a sulfonate ion, an alkyl sulfate ion having 1 to 4 carbon atoms, a phosphate ion, a nitrate ion, or the like. Indicates an anion, i + j = 20 to
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, particularly preferably 50,000 to 1.5,000,000.
The content of the cationic nitrogen derived from the cationic polymer contained in the quaternized polyvinylpyrrolidone derivative is preferably 0.004 to 0.2%, particularly preferably 0.01 to 0.15%, based on the vinyl polymer. If it is less than 0.004%, sufficient effect cannot be obtained, and 0.2%
If it exceeds, it is good in performance but causes coloring, and it is economically disadvantageous.

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

[0047]

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Wherein R ²⁶ , R ²⁸ , R ²⁹ and R ³¹ each represent a hydroxyalkylene group having 2 to 4 carbon atoms;
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 each represent an integer of 10 to 20; Is 2-6
Represents an integer of 2 to 4, and s represents an integer of 1 to 50. ]

In addition, a copolymer of adipic acid / dimethylaminohydroxypropylethylenetriamine (Cartaretin manufactured by Sandos, USA) and JP-A-53-139734
And 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 cleaning 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. When the amount of the component (B) is less than 0.01% by weight, the conditioning effects such as foamy creaminess, feel during washing, and smoothness of the skin and hair after washing are inferior, and the amount exceeds 5% by weight. This causes a feeling of residue on the skin and hair after washing, which is not preferable in terms of feel.

Further, the cleaning composition of the present invention can be prepared using known acidic or alkaline chemicals used in conventional cleaning compositions at pH 2 to 10, more preferably pH 4 to 8, especially pH 4 to 7.
(PH measurement conditions: 5% by weight aqueous solution of active ingredient).

In the cleaning composition of the present invention, in addition to the above-mentioned essential components, anionic surfactants other than amide ether carboxylic acids, nonionic surfactants, amphoteric surfactants, as long as the effects of the present invention are not impaired. And various components such as a cationic surfactant and a conditioning component.

Examples of such anionic surfactants include fatty acid salts, polyoxyalkylene alkyl ether acetates,
Alkyl sulfate, polyoxyalkylene alkyl ether sulfate, sulfosuccinic acid surfactant, sulfosuccinamate surfactant, polyoxyalkylene alkylamide ether sulfate, monoglyceride sulfate, olefin sulfonate, alkane sulfonate , Acylated isethionate, acylated amino acid, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, and the like. Nonionic surfactants include alkyl polyglucoside, sucrose fatty acid ester, and polyglycerin fatty acid ester. , Polyoxyalkylene alkyl ethers, alkylamine oxides, fatty acid polyhydric alcohol esters and the like, and as the cationic surfactant,
Linear or branched mono- or dilong-chain alkyl quaternary
Quaternary ammonium salts or mono- or di-long-chain alkyl tertiary
And amphoteric surfactants such as amidoamino acid surfactants, carbobetaine surfactants, sulfobetaine surfactants, amidosulfobetaine surfactants, and imidazolinium betaine surfactants. Agents, amino acid-based betaine surfactants, phosphobetaine-based surfactants, and the like, and the conditioning components include higher alcohols, silicones, silicone derivatives, lanolin, squalene, hydrocarbons, protein derivatives, fatty acid esters of polyethylene glycol, and the like. Oils and the like.

Other components commonly used in detergent compositions, for example, water-soluble polymers such as polysaccharides such as methylcellulose, hydroxyethylcellulose, carboxyvinyl polymer and xanthan gum; polyoxyalkylene sorbitan esters, polyoxyethylene glycol Viscosity modifiers such as distearate and ethanol; chelating agents such as ethylenediaminetetraacetic acid (EDTA) and phosphonates; preservatives such as methylparaben and butylparaben; nutrients such as vitamins or their precursors; Animal or 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 and zinc pyrithione;
An antioxidant such as dibutylhydroxytoluene; a pearlizing agent, an ultraviolet absorber, a pH adjuster, a coloring matter, a fragrance, and the like can be blended as needed within a range not to 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 dishes, detergents for clothes, etc., in addition to detergents for skin and hair. In this case, (A)
The total amount of surfactants in the total composition, including the total amount of components and other surfactants, is 30% by weight or more for solid dosage forms, 20% by weight or more for paste dosage forms, liquid In the case of the above dosage form, the content 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 sodium salt of amide ether carboxylic acid containing amide ether: 214.4 g (1 mol) of methyl laurate, 61.7 g (1.02 mol) of monoethanolamine and sodium methoxide
88.2 g of ethylene oxide was added to a product obtained by heating 15.3 g of a 30% by weight methanol solution at 90 ° C. and 50 mmHg for 5 hours.
(2 moles) was introduced at 100-110 ° C and a gauge pressure of 0-3.5 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 five 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 was raised 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 in this reaction mixture
g was added thereto, the pH was adjusted to 2.8 by adding a 36% hydrochloric acid aqueous solution at 90 ° C., and the mixture was stirred for 1 hour and allowed to stand still for 1 hour to obtain 545 g of an acid type product. The acid-type compound was adjusted to pH 7 with a 30% aqueous sodium hydroxide solution, and water was added to form a transparent solution. Thus, an amide ether derivative mixture 2 shown in Table 1 was obtained.

Synthesis Examples 2 to 6 Synthesis of Amide Ether Carboxylic Acid Sodium Salt Containing Amide 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 ratio of SMCA to amide ether was 1.7, 1.5, 1.4, respectively, and the molar ratio of solid sodium hydroxide was 1.85, 1.63, 1.52.
And In addition, without conversion / purification to the 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 sodium hydroxide solution.
I got

Synthesis Example 7 Synthesis of magnesium amide ether carboxylate containing amide ether: The acid-form product obtained in Synthesis Example 1 was neutralized to pH 6 to 7 with a 30% aqueous magnesium hydroxide suspension. Water was added to make a clear solution to obtain an amide ether derivative mixture 7 shown in Table 1.

Comparative Synthesis Example 1 Synthesis of amide ether carboxylic acid sodium salt from which amide ether was removed: A carboxymethylation reaction mixture was obtained in the same manner as in Synthesis Example 1, and ethanol was added to this reaction mixture to precipitate a solid. Was. Then, this was filtered, and ethanol was added to the filtrate to wash it, thereby removing amide ether. Further, after converting into an acid form in the same manner as in Synthesis Example 1, the mixture was neutralized with a 30% aqueous sodium hydroxide solution to obtain an amide ether derivative mixture 8.

Comparative Synthesis Example 2 Synthesis of Amide Ether Carboxylic Acid Sodium Salt Containing Amide 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 mixture was reacted under the same conditions, and then treated in the same manner as in Synthesis Example 1 to obtain an amide ether derivative mixture 9.

Comparative Synthesis Example 3 Synthesis of sodium salt of amide ether carboxylic acid containing glycerin derivative: 510.6 g (2.2 mol) of purified coconut oil was dissolved at 35 ° C. Next, 138.8 g (2.3 mol) of monoethanolamine and 5.1 g of a 30% by weight methanol solution of sodium methoxide were added to 70 g of the mixture.
298 g (6.75 mol) of ethylene oxide were added to a product obtained by heating at 105 ° C for 6 hours and at 105 ° C for 6 hours.
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 70-75 ° 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 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 raised to 85 ° C., 5 g of water was added, and the mixture was aged for 1 hour.
1039 g of a reaction mixture was obtained. To the reaction mixture was added 500 g of water, adjusted to pH 7 by adding a 36% hydrochloric acid aqueous solution at 50 ° C., and diluted with water until a clear solution was obtained. Thus, an amide ether derivative mixture 10 shown in Table 1 was obtained.

[0063]

[Table 1]

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

<Evaluation Method> The foaming amount, foam quality and feel of the hair were evaluated by 20 specialized panelists according to the following evaluation criteria. Foaming amount and foam quality are healthy Japanese women's hair 20g
(15 cm) was evaluated when 1 g of a detergent was applied and lathered for 1 minute, and the feel of the hair was evaluated when lathered, rinsed and dried with a dryer. Result is
The results are shown in Table 2 based on the average score of 20 subjects according to the following criteria. For the skin irritation, each cleaning composition was applied four times to healthy skin of five guinea pigs, and the fourth reaction was evaluated according to the following evaluation criteria. The results are shown in Table 2 from the average score of the five animals according to the following criteria.

<Criterion> (1) Foaming A. Rating: very good lather ... score 4. Good lather ... score 3. Bubbling but slightly lacking ... Score 2. Poor foaming ... Score 1. B. Judgment: Average score 3.5-4.0 ... Average score 2.5-3.4 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

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

(3) Feel of Shampoo Whisk A. Evaluation: There is no creaking and finger passing is good. Scratch is slightly strong, finger passing is somewhat poor ... score 2. Strong squeakiness and poor finger passage ... Score 1. B. Judgment: Average score 2.5-3.0 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(4) Feeling of Rinse A. Evaluation: Smooth and soft ... Score 4. No squeak and smooth ... Score 3. Scratch is slightly strong, smoothness is slightly poor ... score 2. Strong squeakiness ... 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. Good finger movement and smooth ... Score 3. Finger passing is slightly poor, smoothness is slightly poor ... score 2. Poor finger passage ... 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: No irritation (no response was observed) ... Score 5. Slightly irritating (faint erythema is recognized) ... score 4. Mild irritation (clear erythema is recognized) ... score 3. Moderate irritation (clear erythema with edema) ... score 2. Strong irritation (clear erythema with necrosis or asphyxia) score 1. B. Judgment: Average score 3.5-5.0 ... ○. Average score 2.5-3.4 ... △. Average score 1.0-2.4 ... ×.

[0072]

[Table 2]

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

[Table 3] (% by weight) Amide ether derivative mixture 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 qs Sodium hydroxide qs Fragrance 0.2 ion exchange water balance

Example 3 A body shampoo having the following composition and a pH of 5.5 was prepared. It is hypoallergenic, foamy,
The foam quality and the skin smoothness after washing were excellent.

Table 4 (% by weight) Amide ether derivative mixture 6 10 Sodium polyoxyethylene (4.5) lauryl ether acetate (Akipo RLM45, manufactured by Chemwai) 10 Cationic polymer (Guffcoat 755N, manufactured by Gaff, vinylpyrrolidone dimethylaminoethyl alcohol) Ethyl sulphate quaternary compound of a relate copolymer) 0.3 Citric acid proper amount Sodium hydroxide proper amount Fragrance 0.2 ion exchange water balance

Example 4 An anti-dandruff shampoo having the following composition and a pH of 6.5 was prepared.
It is hypoallergenic to the skin, has an anti-dandruff effect,
The foaming property and the feeling after washing the hair were excellent.

Table 5 (% by weight) Amide ether derivative mixture 4 15 Ammonium lauryl sulfate 5 Cationic cellulose (Polymer JR-400, manufactured by UCC) 0.3 Zinc pyrithione 1 Carboxyvinyl polymer (Carbopol 941, manufactured by Goodrich) 0.5 Citric acid Sodium hydroxide appropriate amount Fragrance 0.2 ion exchange 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 properties, foam quality and hand feel after washing.

(Table 6) Amide ether derivative mixture 1 15 Laurylamine oxide 4 Lauric acid diethanolamide 2 Cationized polymer (Mercoat 280, Merck Co., copolymer of dimethyldiallylammonium chloride and acrylic acid) 0.1 Citric acid Sodium hydroxide Appropriate amount Ethanol 3 Flavor 0.2 Ion exchange water Balance

Example 6 A conditioning shampoo having the following composition and having a pH of 6.7 was prepared. It is hypoallergenic to the skin,
The foam was excellent in foaming properties, foam quality, and feel of the hair at the time of rinsing and after drying.

(Table 7) Amide ether derivative mixture 3 15 Cationized polymer (Mercoat 100, Merck Co., Ltd., polymer of dimethyldiallylammonium chloride) 0.2 Lauric acid diethanolamide 4 Citric acid Appropriate amount Sodium hydroxide Appropriate amount Perfume 0.1 Ion exchange Water balance

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

(Table 8) Amide ether derivative mixture 7 15 Cationic cellulose (Polymer JR, manufactured by UCC) 1 Laurylamine oxide 4 Lactic acid Appropriate amount Sodium hydroxide Appropriate amount Fragrance 0.1 Ion exchange water Balance

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

(Weight%) Amide ether derivative mixture 7 16 cationized polymer (Mercoat 100, Merck Co., Ltd., polymer of dimethyldiallyl ammonium chloride) 0.5 Coconut fatty acid diethanolamide 4 Citric acid Appropriate amount Sodium hydroxide Appropriate amount Perfume 0.1 Ion exchange Water balance

Example 9 A conditioning shampoo having the following composition and a pH of 6.5 was prepared. It is hypoallergenic to the skin,
The foaming properties 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 amidopropyldimethylaminoacetic acid betaine 4 Cationized cellulose (manufactured by Polymer JR, UCC) 1 Dimethylpolysiloxane (5 million cs) 0.5 Lactic acid Appropriate amount Sodium hydroxide Appropriate amount Fragrance 0.1 Deionized water Balance

[0081]

EFFECTS OF THE INVENTION The cleaning composition of the present invention has little irritation to the skin and the like, has excellent foaming properties, has a creamy quality,
It has a good feel during washing and is excellent in conditioning effects such as smoothness after washing.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C11D 3/20 C11D 3/20 3/37 3/37 (56) References JP-A-8-100198 (JP, A) JP-A-8-100198 JP-A-8-100199 (JP, A) JP-A-6-16534 (JP, A) JP-A-6-73394 (JP, A) JP-A-63-291996 (JP, A) JP-A-5-310540 (JP, A) JP-A-56-99994 (JP, A) JP-A-62-1799 (JP, A) JP-A-59-101449 (JP, A) JP-A-7-138592 (JP, A) European patent application Published 102118 (EP, A)

Claims (5)

(57) [Claims] 1. A cleaning composition comprising 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 by weight in solid content in total of 50
An amide ether derivative mixture containing at least 5% by weight of a glycerin derivative represented by the general formula (3) and not more than 5% by weight of the solid content. (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,-(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, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or an alkanolamine. Or n represents a basic amino acid, n and m may be the same or different and each represents a number of 1 to 20, R ³ represents a hydrogen atom,-(CH ₂ CH
₂ O) _m H or an alkyl group having 1 to 3 carbon atoms, and 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 or alkenyl group having 7 to 17 carbon atoms or a phenyl group substituted with such an alkyl group. And 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) Component (A) is 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) = 95 : A total of 60% by weight or more in solid content in a weight ratio of 5 to 60:40, and a general formula
3. The cleaning composition according to claim 1, wherein the composition 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 obtained from a fatty acid alkanolamide synthesized from a fatty acid lower alcohol ester as a raw material. 5. The cleaning composition according to claim 1, which has a pH of 4 to 7.