JPH08325597A - Detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent composition having low skin stimulation and excellent foaming properties, foam quality and conditioning effect after washing, and containing a specific amido ether compound and nitrogen containing compound. CONSTITUTION: The composition contains a mixture of amido ether derivatives (A) consisting of a compound (A1) of formula I R<1> is a 5-23C (branched) alkyl R<1> 0 , an alkenyl, (R<1> 0 )-substituted phenyl; R<2> is H, a group (R<2> 1 ) of the formula: (CH2 CH2 O)n CH2 COOM [M is H, an alkali (alkaline earth) metal, ammonium, an alkanolamine, a basic amino, acid; n is an integer of 1-20], a group (R<2> 2 ) of the formula: (CH2 CH2 O)m H (m is equal to n), a 1-3C alkyl} and a compound (A2 ) of formula II (R<3> is equal to R<2> excluding R<2> 1 ) at a weight ratio A1 :A2 -99:1-10:90 in an amount of more than 50wt.% in the solid base, and containing a compound of formula III (R<4> is H, R<2> 1 , R<2> 2 ) less than 5wt.% in the solid base and (B) a quaternary ammonium salt or a tertiary amine.

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 having excellent foaming properties, creamy foam quality, and a very high conditioning effect after washing.

[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.

Further, a quaternary ammonium salt or a tertiary amine has been blended with a detergent for hair in order to impart a conditioning effect to the hair after washing.

However, when a quaternary ammonium salt or a tertiary amine is used in combination with an anionic surfactant, there is a problem that its foaming property is deteriorated, and a sufficient conditioning effect cannot be obtained. Therefore, other conditioning components are used. Was used together.

On the other hand, ether carboxylic acid type surfactants and amido ether carboxylic acid type surfactants are known as mild surfactants. This amido ether carboxylic acid type surfactant is available in Germany Chem Y
It is marketed by the company under the trade name of "Akipo". This product includes amide ether carboxylic acid, amide ether which is the raw material, and polyoxyethylene glyceryl ether and polyoxyethylene glyceryl ether which are impurities derived from the raw material. Carboxylic acid, inorganic salts, etc. are included.

[0006] Conventionally known techniques for applying amide ether carboxylic acid surfactants to detergents are amide ether carboxylic acids, polyoxyethylene alkyl sulfates, fatty acid diethanol amides and higher alcohol alkylene oxides. 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.

As described above, the ether carboxylic acid type surfactant and the amido ether carboxylic acid type surfactant have a problem that they have a low foaming power although they are mildly irritating. When a salt or a tertiary amine is added, the foamability is further lowered, and there is a problem that the performance required as a detergent cannot be exhibited.

Therefore, there has been a demand for the development of a detergent composition which has a low irritation to the skin and the like, a high foaming property and a high conditioning effect.

[0009]

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. As a result of further studies, if an amide ether derivative mixture containing amide ether in a specific ratio and the content of the glycerin derivative is less than a certain ratio is used in combination with a quaternary ammonium salt, it will be reduced to the skin and the like. It was found that a cleaning agent that is irritating, has a high foaming property, and has a high conditioning effect,
The present invention has been 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).

[0011]

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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, 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) Quaternary ammonium salt or tertiary amine

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.
Of these, sodium, potassium and magnesium are preferable.

Specific preferred examples of the amide ether carboxylic acid or its salt (1) in the component (A) include, for example, capric acid monoethanolamide polyoxyethylene ether acetic acid (n = 1 to 15), 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).

Specific preferred examples of the amide ether (2) in the component (A) include 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 in the solid content of the component (A), and 3% by weight or less, particularly substantially. 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 directly produced by reacting a part of the amide ether, or 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 from the viewpoint of foamability, it is 5 to 50% by weight, and further 6
-30% by weight, especially 7-25% by weight is preferred.

Of the component (B) used in the present invention, the fourth
The primary ammonium salt is not particularly limited, and examples thereof include those represented by the following general formulas (B-1) and (B-2).

[0022]

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[Wherein at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an alkoxyl group, alkenyloxy group, alkanoylamino group, alkylalkanoylamino group, hydroxyalkyl having a total carbon number of 8 to 28] An alkanoylamino group, an alkenoylamino group, an alkylalkenoylamino group or an alkyl group or an alkenyl group which may be substituted with a hydroxyalkylalkenoylamino group, the rest being a benzyl group, an alkyl group having 1 to 5 carbon atoms, or Represents a hydroxyalkyl group, and R ⁹ has 2 to 2 carbon atoms
3 represents an alkylene group, Z ⁻ represents a halogen ion or an organic anion, and a represents an integer of 1 to 20. ]

Of the above quaternary ammonium salts, the general formula
(B-1) is preferable, and further preferable examples of the quaternary ammonium salt represented by general formula (B-1) include, for example, the following general formulas (B-1a) to (B-1c). ).

[0025]

[Chemical 4]

The branched quaternary ammonium salt represented by the general formula (B-1a) is synthesized using, for example, an oxo alcohol having 8 to 16 carbon atoms as a raw material. Examples thereof include a dialkyldimethylammonium salt having an alkyl group, a dialkylmethylhydroxyethylammonium salt and a dialkylmethylbenzylammonium salt.

In the present invention, the branching ratio of R ^{10 in} the formula (B-1a) is 10
Usually, the content of -100% is usually used, but the content of 10-50% is particularly preferable. Further, those having a total carbon number of R ¹⁰ of 8 to 16 are used, but those having a constant distribution are preferable, and those having the distribution shown below are particularly preferable. C ₈ ~C _11: 5% or less _{C 12: 10~35% C 13:} 15~40% C 14: 20~45% C 15: 5~30% C 16: 5% or less according branched quaternary ammonium salt A specific example of is a dialkyldimethylammonium chloride having an alkyl group having 8 to 16 carbon atoms and a branching rate of 10 to 50%.

The branched quaternary ammonium salt represented by the general formula (B-1b) is usually a Guerbet alcohol having 8 to 28 carbon atoms.

[0029]

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[In the formula, R ¹³ and R ¹⁴ have the same meanings as described above. ] Is a raw material and is synthesize | combined. Preferable examples of the branched quaternary ammonium salt include alkyltrimethylammonium salt having an alkyl group derived from Guerbet alcohol, alkyldimethylbenzylammonium salt, dialkyldimethylammonium salt, dialkylmethylhydroxyethylammonium salt, dialkylmethylbenzylammonium salt. Salt etc. are mentioned. Further, specific examples of particularly preferable ones among these are:
Examples thereof include 2-decyltetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylammonium chloride, di-2-hexyldecyldimethylammonium chloride and di-2-octyldodecyldimethylammonium chloride.

Preferred examples of the methyl-branched quaternary ammonium salt represented by the general formula (B-1c) include those in which the sum of d and e is 15.

General formulas (B-1), (B-2), (B-1a), (B-1b) and
Specific examples of Z ⁻ which is the anion component of the quaternary ammonium salt represented by (B-1c) include halogen ions such as chlorine, iodine and bromine; methosulfate, ethosulfate, metphosphate and etphos Examples thereof include organic anions such as fate.

The tertiary amine in the component (B) is not particularly limited, and examples thereof include those represented by the following general formulas (B-3) and (B-4).

[0034]

[Chemical 6]

[In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁹ and a have the same meanings as described above. ]

Of the above tertiary amines, the following general formula (B-3a)
Amidoamines represented by are preferred.

[0037]

[Chemical 7]

[In the formula, R ¹⁸ is a linear or branched carbon number 6
To 26 alkyl groups or alkenyl groups, R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, R ²⁰ represents an alkylene group having 1 to 4 carbon atoms, and R ²¹ represents a carbon atom. An alkyl group or a hydroxyalkyl group of the numbers 1 to 4 is shown. ]

Preferred examples of the tertiary amine (B-3a) include palmitic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dipropylaminoethylamide, palmitic acid dimethylaminopropylamide and palmitic acid diethylaminopropyl. Amide, palmitic acid dipropylaminopropylamide, stearic acid dimethylaminoethylamide, stearic acid diethylaminoethylamide, stearic acid dipropylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminopropylamide, stearic acid dipropylaminopropyl Amide, palmitic acid dimethylaminoethylmethylamide,
Examples thereof include palmitic acid dimethylaminopropylmethylamide, palmitic acid dimethylaminoethylhydroxyethylamide, and palmitic acid dimethylaminopropylhydroxyethylamide.

These components (B) can be used alone or in combination of two or more. The content of component (B) in the detergent composition of the present invention is not particularly limited, but is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 0.2 to 4% by weight. If the blending amount of the component (B) is less than 0.05% by weight, the conditioning effect on hair cannot be obtained, and if the blending amount exceeds 10% by weight, the foaming property is deteriorated, which is not preferable.

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 essential components, the detergent composition of the present invention contains anionic surfactants, nonionic surfactants and amphoteric surfactants other than amide ether carboxylic acid, as long as the effects of the present invention are not impaired. Various components such as 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 amphoteric surfactants, amide amino acid-based surfactants, carbobetaine-based surfactants, sulfobetaine-based surfactants. Surfactants, amide sulfobetaine-based surfactants, imidazolinium betaine-based surfactants, amino acid-based betaine surfactants, phosphobetaine-based surfactants and the like, conditioning agents include higher alcohols, silicones, silicones. Derivatives, lanolin, squalene, hydrocarbons, protein derivatives, oil agents such as fatty acid esters of polyethylene glycol, cationized cellulose, cationized guar gum, mercoat 55
Examples thereof include cationized polymers such as 0 (manufactured by Merck).

In addition, water-soluble polymers such as polysaccharides such as methyl cellulose, hydroxyethyl cellulose, carboxyvinyl polymer, xanthan gum and the like which are commonly used in other detergent compositions; 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 their derivatives; Polymer fine powders such as nylon and polyethylene; Anti-inflammatory agents such as potassium glycyrrhizinate; Disinfectants 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 skin and hair, as well as detergents for various purposes such as detergents for dishes, detergents for clothes and foam baths.
In this case, the total amount of the component (A) and other surfactants added, as the surfactant in the entire composition,
The solid dosage form is preferably 30% by weight or more, the paste dosage form is 20% by weight or more, and the liquid dosage form is preferably 10% by weight or more.

[0046]

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 amide ether carboxylic acid sodium salt containing amide ether: 214.4 g (1 mol) of methyl laurate, 61.7 g of monoethanolamine
(1.02 mol) and 30% by weight sodium methoxide in a methanol solution (15.3 g) were heated at 90 ° C. and 50 mmHg for 5 hours to obtain a product, and 88.2 g (2 mol) of ethylene oxide was added.
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. 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, bring the reaction temperature to 85 ° C. and water 5.
3 g was added and the mixture was further aged for 1 hour to obtain 592 g of a carboxymethylation reaction mixture. To the reaction mixture was added 500 g of water, and the pH was adjusted to 2.8 by adding 36% hydrochloric acid aqueous solution at 90 ° C,
After stirring for an hour, the mixture is allowed to stand for 1 hour to form an acid product.
545 g were obtained. 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 ratio of sodium monochloroacetate to amide ether was 1.
7, 1.5, 1.4 and the molar ratio of solid sodium hydroxide to amide ether is 1.85, 1.63, 1.
52. Further, an amide ether derivative mixture 4 was obtained in the same manner as in Synthesis Example 1 except that conversion to the acid form and purification were not carried out and the pH was kept at 7 with a 30% aqueous sodium hydroxide solution after the reaction.

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, and water was added. In addition, an amido ether derivative mixture 7 shown in Table 1 was obtained as a transparent solution.

Comparative Synthesis Example 1 Synthesis of Amido Ether Carboxylic Acid Sodium Salt from which Amido Ether was Removed: In the same manner as in Synthesis Example 1, a carboxymethylation reaction mixture was obtained, and then ethanol was added thereto to precipitate a solid. After filtration, ethanol was added to the filtered product for washing to remove amide ether. Further, the mixture was made into an acid form in the same manner as in Synthesis Example 1 and then neutralized with sodium hydroxide to obtain amide ether derivative mixture 8
I got

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

Comparative Synthesis Example 3 Synthesis of Amidoethercarboxylic Acid Sodium Salt 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 wt% methanol solution of sodium methoxide were heated at 70 ° C. for 2 hours and at 105 ° C. for 6 hours, and the product obtained was 298 g of ethylene oxide (6.75). Mol) was introduced at 100 to 110 ° C. and a gauge pressure of 0 to 3.5 atm over 30 minutes. Reaction mixture 675
g was heated to 70-75 ° C and 281.7 g (2.41 mol) of SMCA 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. Then set the reaction temperature
The temperature was raised to 85 ° C., 5 g of water was added and the mixture was aged for 1 hour to obtain 1039 g of a reaction mixture. To this reaction mixture was added 500 g of water, 50
A 36% hydrochloric acid aqueous solution was added at 0 ° 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.

[0053]

[Table 1]

Example 1 A detergent composition (pH 6.5) having the composition shown in Tables 2 and 3 was prepared, and the foaming amount, foam quality, hair feel, and skin irritation were evaluated for each. . The results are shown in Tables 2 and 3. The blending weight% shown in Tables 2 and 3
Is the value of the effective content of the activator (the solid content of the amide ether carboxylates). 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. Evaluation
The average scores of 20 persons are shown in Tables 2 and 3 according to the following criteria. The skin irritation was evaluated by applying each detergent composition to the healthy skin of five guinea pigs four times, and the reaction at the fourth time was evaluated according to the following evaluation criteria. The results are shown in Tables 2 and 3 from the average score of 5 animals according to the following criteria.

<Standard> (1) Foaming amount A. Evaluation: Good foaming: score 3. Foaming but slightly lacking ... Score 2. Poor bubbling-Score 1. B. Judgment: Average score 2.5 to 3.0 ... ○. 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, without squeaky ...... score 3. Squeeze is slightly strong, smoothness is slightly poor ... Score 2. Strongly squeaky and bad ... Score 1. B. Judgment: Average score 2.5 to 3.0 ... ○. Average score 1.5-2.4 ... △. Average score 1.0-1.4 ... ×.

(5) Feeling after drying hair A. Evaluation: Good finger-feeling and smoothness ... Score 3. Slightly poor finger passage and slightly poor smoothness ... Score 2. Poor fingering: Score 1 B. Judgment: Average score 2.5 to 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 ... ×.

[0062]

[Table 2]

[0063]

[Table 3]

Example 2 A conditioning shampoo of pH 5.9 having the following composition was prepared. This one is hypoallergenic to the skin,
It was excellent in foamability, foam quality, and feel during shampooing and after washing hair.

(Table 4) (% by weight) Amide ether derivative mixture 2 14 Polyoxyethylene (2) lauryl ether sulfate Na 5 Palm fatty acid diethanolamide 2 2-decyl tetradecyl trimethyl ammonium chloride 0.2 Fragrance 0.2 Citric acid Adequate amount Sodium hydroxide Adequate amount Ion exchange Water balance

Example 3 A conditioning type body shampoo having the following composition and a pH of 6.5 was prepared. It was hypoallergenic to the skin and was excellent in foamability, foam quality and smoothness of the skin after washing.

[Table 5] (% by weight) Amide ether derivative mixture 4 10 Lauroyl methyl taurine sodium 5 2-Octyldodecyltrimethylammonium chloride 0.2 Perfume 0.1 Citric acid proper amount Sodium hydroxide proper amount Ion-exchanged water balance

Example 4 A conditioning type body shampoo having the following composition and having a pH of 5.7 was prepared. It was hypoallergenic to the skin and was excellent in foamability, foam quality and smoothness of the skin after washing.

(Table 6) (% by weight) Amide ether derivative mixture 6 10 Polyoxyethylene lauryl ether acetic acid Na (Akipo RLM, manufactured by Chemwai Co.) 5 Monostearyl trimethyl ammonium chloride 0.2 Ethylene glycol monostearate 2 Hydroxyethyl cellulose 0.3 Perfume 0.2 Citric acid Suitable amount Sodium hydroxide suitable amount Ion exchange water balance

Example 5 A conditioning shampoo of pH 6.6 having the following composition was prepared. This product was excellent in foaming property, foam quality, gloss of dried hair after washing, combing and cohesion of hair.

[Table 7] (wt%) Amide ether derivative mixture 3 10 Polyoxyethylene (2) lauryl ether ammonium sulfate 6 Lauryl diethanolamide 2 Monocetyltrimethylammonium chloride 0.3 Fragrance 0.1 Citric acid qs Sodium hydroxide qs Ion-exchanged water balance

Example 6 A dishwashing agent having the following composition and a pH of 6.5 was prepared. It was hypoallergenic to the skin, and was excellent in detergency, foaming property, foam quality, and hand feel after washing.

[Table 8] (% by weight) Mixture of amide ether derivative 1 15 Laurylamine oxide 4 Lauric acid diethanolamide 2 Dialkyldimethylammonium chloride [C _{12 to} C ₁₅ commercially available oxo method synthetic alcohol (equivalent mixture of 45 and 23 of dovanol) , Mitsubishi Petrochemical Co., Ltd.) branched quaternary ammonium salt, branching ratio 20% by weight] 0.1 Carboxyvinyl polymer 0.3 Perfume 0.2 Citric acid proper amount Sodium hydroxide proper amount Ion-exchanged water balance

Example 7 A conditioning shampoo of pH 6.9 having the following composition was prepared. This product was hypoallergenic to the skin, and was excellent in foamability, foam quality, and feel of hair during shampoo and after washing hair.

[Table 9] (% by weight) Amide ether derivative mixture 7 12 Polyoxyethylene (3) sodium lauryl ether sulfate 5 Stearic acid Dimethylaminopropylamide 0.3 Perfume 0.1 Citric acid Proper amount Sodium hydroxide Proper amount Ion-exchanged water balance

Example 8 A conditioning shampoo of pH 6.7 having the following composition was prepared. This product was hypoallergenic to the skin, and was excellent in foamability, foam quality, and feel of hair during shampoo and after washing hair.

(Table 10) (% by weight) Amide ether derivative mixture 7 17 Lauryl amine oxide 4 Monostearyl trimethyl ammonium chloride 0.5 Ethylene glycol monostearate 2 Citric acid Proper amount Sodium hydroxide Proper amount Perfume 0.3 Ion-exchanged water balance

Example 9 A conditioning shampoo of pH 6.1 having the following composition was prepared. This product was hypoallergenic to the skin, and was excellent in foamability, foam quality, and feel of hair during shampoo and after washing hair.

[Table 11] (% by weight) Amide ether derivative mixture 7 17 Coconut fatty acid diethanolamide 4 Stearic acid Dimethylaminopropylamide 1 Citric acid Appropriate amount Sodium hydroxide Appropriate amount Fragrance 0.3 Ion-exchanged water balance

Example 10 A conditioning shampoo of pH 6.5 having the following composition was prepared. This product was hypoallergenic to the skin, and was excellent in foamability, foam quality, and feel of hair during shampoo and after washing hair.

(Table 12) (% by weight) Amide ether derivative mixture 7 17 Dodecyl polyglucoside 3 Palm fatty acid amide propyl dimethylamino acetic acid betaine 2 Cationized cellulose (Polymer JR, UCC) 1 Monostearyl trimethyl ammonium chloride 0.5 Citric acid Proper amount Hydroxylation Sodium suitable amount Fragrance 0.3 Ion-exchanged water balance

[0073]

The detergent composition of the present invention has excellent foaming properties, creamy foam quality, and excellent conditioning effect on hair after washing.

[Procedure amendment]

[Submission date] March 5, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

Embedded image (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,
_{- (CH 2 CH 2 O)} n CH 2 COOM, - (CH 2 C
H 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, an alkanolamine or a basic amino acid, and n and m may be the same or different and each is 1 to 2
Indicates the number of 0, ^{R 3} is a hydrogen _{atom, - (CH 2 CH 2 O} )
_m H or an alkyl group having 1 to 3 carbon atoms, 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. General formula (1), (2)
And (3) R ¹ , M, n, and m in each other may be the same or different. ) (B) Quaternary ammonium salt or tertiary amine

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

Embedded image

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C11D 1:52)

Claims (7)

[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) Quaternary ammonium salt or tertiary amine 2. The cleaning composition according to claim 1, wherein the quaternary ammonium salt is a branched quaternary ammonium salt. 3. The cleaning composition according to claim 1, wherein the tertiary amine is amidoamine. 4. 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, The cleaning composition according to any one of claims 1 to 3. 5. 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 any one of claims 1 to 4, 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. 6. 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. 7. The detergent composition according to claim 1, which has a pH of 4 to 7.