JPH107633A - Fatty acid amidoethercarboxylic acid or its salt, its production and detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fatty acid amidoethercarboxylic acid or its salt excellent in foaming, stability in hard water and detergency, mild hair and skin and useful as a detergent. SOLUTION: This fatty acid amidoethercarboxylic acid or its salt is represented by formula I R<1> is an 8-22C alkyl or alkenyl; R<2> is H, a 1-5C alkyl, (C2 H4 O)m H, etc.; R<3> is H or methyl; M is H, an alkali metal, etc.; (n) and (m) are each a number of 1-20} and obtained, for example, by reacting a fatty acid or a fatty acid ester with an alkanolamine to form a fatty acid alkanolamide, performing an addition reaction of ethylene oxide to the resultant fatty acid alkanolamide in the presence of a basic catalyst to form a fatty acid amidoetheralcohol of formula II (R<2> ' is H, a 1-5C alkyl, etc.), further reacting the resultant fatty acid amidoetheralcohol with an unsaturated compound of formula III (X is CN, etc.) to form a fatty acid amidoether derivative of formula IV (R<2> '' is H, a 1-5C alkyl, etc.) and thereafter hydrating the fatty acid amidoether derivative in the presence of a basic or acidic material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel fatty acid amide ether carboxylic acid or a salt thereof, which is foamed, has excellent hard water resistance, has excellent detergency, is mild on hair and skin, is useful as a detergent, and a method for producing the same. And a detergent composition containing the same.

[0002]

2. Description of the Related Art Among the surfactants, anionic surfactants are widely used as components of detergents generally used in the industrial field and at home. This anionic surfactant has various structures, but recently, an anionic surfactant having good water solubility, good detergency and good foaming, and mild on the skin and hair has been desired. Among the studies corresponding to these, amide ether carboxylic acids that are mild to the skin and a method for producing the same are disclosed in Japanese Patent Publication No. 8-311.
No. 4, JP-A-8-20566.

However, the amide ether carboxylic acid and the salt thereof described in Japanese Patent Publication No. 8-3114 are derivatives of acetic acid having 2 carbon atoms, and
The amide ether carboxylic acid and the salt thereof described in No. 6 have an alkylene chain having 3 or more carbon atoms at the nitrogen atom, and all of them satisfy foaming properties, creamy properties, and easiness of rinsing. Hard to say. Further, in the production methods disclosed therein, the fatty acid ester of fatty acid monoethanolamide having poor water solubility is generated during the reaction between the fatty acid and monoethanolamine and the addition reaction of ethylene oxide, which is not preferable.

[0004]

DISCLOSURE OF THE INVENTION The present invention has no problems during production, has excellent water solubility, has good detergency and foams, and is useful as a mild surfactant for skin and hair.
It is an object of the present invention to provide a novel fatty acid amide ether carboxylic acid or a salt thereof, a method for producing the same, and a detergent composition containing the same.

[0005]

According to the present invention, there is provided a fatty acid amide ether carboxylic acid having an amide group and an ether group in a molecule represented by the following general formula (1) or a salt thereof.

Embedded image In the formula, R ¹ ; a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms R ² ; a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or-(C ₂ H _{4 O) mH, - (C} 2 H 4 O) mCH 2
CHR ³ COOM R ³ ; hydrogen atom or methyl group M; hydrogen atom, alkali metal, alkaline earth metal equivalent to monovalent, ammonium, or substituted ammonium n, m; For example, a fatty acid or a fatty acid ester is reacted with an alkanolamine, ammonia or an amine to form a fatty acid alkanolamide or a fatty acid amide, and then the resulting fatty acid alkanolamide or the fatty acid amide is treated with ethylene in the presence of a basic catalyst. Oxide is added, and at this time, the addition reaction is allowed to proceed while a basic catalyst is added on the way, thereby obtaining the following general formula (2)

Embedded image 中 wherein, R ¹ ; a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms R ² ′; a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or — (C ₂ H ₄ O) mH M; to produce a fatty acid amide ether alcohol represented by the respective number from 1 to 20}; hydrogen atom, an alkali metal, a monovalent to the corresponding alkaline earth metal, ammonium or substituted ammonium n, m, Then, to the obtained fatty acid amide ether alcohol, in the presence of a basic catalyst,
The following general formula (3)

Embedded image Wherein an unsaturated compound represented by {wherein, R ³ ; a hydrogen atom or a methyl group X; —CN or —COOR ⁴ R ⁴ ; a hydrogen atom or a lower alkyl group} is reacted to obtain a compound represented by the following general formula (4)

Embedded image In the formula, R ² ″; a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or — (C ₂ H ₄ O) _m H, — (C ₂ H ₄
O) _m CH ₂ CHR ³ X R ¹ , R ³ , X, n; forming a fatty acid amide ether derivative represented by the same｝ as defined above, followed by hydrolysis in the presence of a basic substance or an acidic substance Characterized by the following general formula (1)

Embedded image {Wherein R ¹ , R ² , R ³ , M, n; the same as defined above}, a method for producing a fatty acid amide ether carboxylic acid having an amide group and an ether group in a molecule or a salt thereof is provided. Is done. Still further, according to the present invention, there is provided a detergent composition comprising a fatty acid amide ether carboxylic acid or a salt thereof.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the fatty acid amide ether carboxylic acid and a salt thereof of the present invention,
R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms.
18 alkyl groups or alkenyl groups. Specific examples of R ¹ CO include a lauroyl group, a coco alkyloyl group,
Examples include, but are not limited to, myristoyl groups, palmitoyl groups, stearoyl groups, oleoyl groups, tallow alkyloyl groups, and hardened tallow alkyloyl groups.

In the general formula (1), R ² represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms,
Or _{- (C 2 H 4 O)} mH, or _{- (C 2 H 4 O)} mC 2 H 4 C
OOM, preferably a hydrogen atom, a methyl group or an ethyl group.

In the general formula (1), R ³ is a hydrogen atom or a methyl group.

Further, in the general formula (1), M is a hydrogen atom, an alkali metal, an alkaline earth metal corresponding to monovalent,
Represents ammonium or organic ammonium, preferably a hydrogen atom, sodium, potassium, ammonium,
Triethanolamine, calcium and magnesium.

Further, in the general formula (1), n and m represent a number of 2 to 6, and preferably 1 to 10.

The following Table 1 shows a production example of one kind of the fatty acid amide ether carboxylic acid or its salt (1) of the present invention, for example, when ethanolamine is used as alkanolamine and ammonia is used as ammonia or amine. Shown in

[Table 1] {Wherein R ¹ , R ³ , M, X, n; R ⁵ as defined above; hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms}

Next, the raw materials, intermediates and reaction conditions of each step in the method for producing a fatty acid amide ether carboxylic acid or a salt thereof of the present invention will be described.

The raw material fatty acid or fatty acid ester represented by the general formula (5) includes R in the general formula (5).
¹ is as described in detail in the description of the general formula (1), and R ⁵ is a hydrogen atom, a linear or molecular alkyl group having 1 to 4 carbon atoms, and specific examples thereof include methyl. Group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group and the like. In addition, fatty acid esters are more preferable than fatty acids, and methyl esters and ethyl esters are particularly preferable from the viewpoint that the reaction temperature may be low, the reaction time is short, or the color tone of the product is good.

Examples of the alkanolamine as a raw material include monoethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine and the like, with monoethanolamine being particularly preferred.
Further, as the raw material amine, the primary amine having the R ² group is used.

The unsaturated compound as a raw material represented by the general formula (3) is acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, or their lower alkyl esters. Examples of the lower alkyl esters include methyl ester and ethyl ester. Esters are preferred.

Next, each reaction step will be described. [Production method of fatty acid amide ether alcohol (2)] In the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, a fatty acid or fatty acid ester (5) and monoethanolamine, etc. Alkanolamine (6) with 90-
After reaction at 180 ° C, preferably 110 to 170 ° C for 1 to 10 hours, preferably 1 to 5 hours, a catalyst is added, and room temperature to 100 ° C, preferably 60 to 90 ° C, for 1 to 48 hours, preferably Aged for 2 to 24 hours to produce fatty acid alkanolamides (7) such as fatty acid monoethanolamide containing almost no fatty acid monoethanolamide fatty acid ester. Ethylene oxide is added to the obtained fatty acid alkanolamide (7) in the presence of a base catalyst.
At this time, a catalyst is added in portions to suppress by-products of amide esters due to the decomposition of amide groups.
Aging is preferably performed at 60 to 90 ° C for 1 to 48 hours, preferably 2 to 24 hours.

<Amidation reaction conditions of fatty acid ester (5) with alkanolamine (6)> Ratio of raw material used: 1.0 to fatty acid ester (5)
-1.2 times mole (preferably 1.01 to 1.08 times mole) of alkanolamine catalyst; basic catalyst (alcoholate, alkali hydroxide,
(Addition of alkali carbonate, etc.) during the reaction and at the time of ripening. Addition of reaction temperature: 90 to 180 ° C (preferably 110 to 170 ° C)
℃) Aging temperature; room temperature to 100 ° C (preferably 60 to 90 ° C) Pressure; 1 to 760 mmHg (preferably 30 to 500 m
mHg) Reaction time; 1 to 24 hours (preferably 2 to 10 hours) Aging time: 1 to 48 hours (preferably 2 to 24 hours)

<Addition reaction conditions of ethylene oxide to fatty acid alkanolamide (7)>Catalyst; acidic or basic catalyst Basic catalyst: alkali metal hydroxide, alkali metal carbonate, alkali metal alcoholate, amine, etc. Acid catalyst ... Boron trifluoride, magnesium oxide, etc. Preferably, potassium hydroxide, sodium hydroxide,
Sodium methylate Addition of the reaction and the ripening separately at the reaction temperature: 10 to 180 ° C (preferably 30 to 150 ° C)
℃) Aging temperature; room temperature to 100 ° C (preferably 60 to 90 ° C) Reaction molar ratio: amide alcohol / ethylene oxide =
0-20 (preferably 1.0-10) Reaction time; 1-10 hours (preferably 2-8 hours) Aging time; 1-48 hours (preferably 2-24 hours) It may be summed or desalted.

[Fatty acid amide ether alcohol (2)
Method for the production of the above] A fatty acid or a fatty acid ester (5) is reacted with ammonia or an amine (8) in the presence of a basic catalyst while further adding a catalyst on the way, and then to the obtained fatty acid amide (9). Ethylene oxide is subjected to an addition reaction and aging in the presence of a basic catalyst while further adding a catalyst on the way.

<Amidation reaction condition of fatty acid ester etc. (5) with ammonia or amine (8)> The amidation reaction of fatty acid ester etc. (5) with ammonia or amine (8) is carried out by the above-mentioned fatty acid ester and alkanolamine. Can be carried out under the same conditions as in the case of the amidation reaction.

<Reaction Conditions for Addition of Ethylene Oxide to Fatty Acid Amide (9)>Catalyst; Basic catalyst (alkali hydroxide, alkali carbonate, etc.) Addition during reaction and ripening Reaction temperature: 130 ° C. to 200 ° C. ℃ (preferably 150 ℃ ~
180 ° C) Aging temperature; room temperature to 100 ° C (preferably 60 to 90 ° C) Reaction molar ratio: fatty acid amide / ethylene oxide = 1 to 1
20 (preferably 2 to 10) Reaction time; 1 to 10 hours (preferably 2 to 8 hours) Ripening time; 1 to 48 hours (preferably 2 to 24 hours) After ripening, neutralize and desalinate the product You may.

[Fatty acid amide ether carboxylic acid (1)
Production method thereof] In the presence of a basic catalyst, a fatty amide ether alcohol represented by the general formula (2) and an acrylonitrile or methacrylonitrile represented by the general formula (3) {hereinafter, (meth) acrylonitrile Abbreviation｝
With the corresponding amide ether nitrile (4
), Followed by hydrolysis with a basic substance or an acidic substance to produce a fatty acid amide ether carboxylic acid having an amide group and an ether group in the molecule or a salt thereof (1). .

<With fatty acid amide ether alcohol (2)
Reaction conditions with (meth) acrylonitrile (3)> Raw material use ratio: 0.2 to 5 times (preferably 0.5 to 3 times) mol of (meth) acrylonitrile relative to fatty acid amide ether alcohol (meth) If the molar ratio of acrylonitrile is low, unreacted amide ether alcohol remains, but foaming, detergency and the like are not adversely affected, or it is rather preferable. Catalysts; Basic catalysts Alcoholates of alkali metals and alkaline earth metals (C ₁ to
C ₃ ), hydroxide, carbonate Solvent: A solvent may be used, but a solvent may be used. Benzene, toluene, xylene, dibutyl ether, etc. Reaction temperature; 0 to 180 ° C (preferably 30 to 140 ° C)
C) Reaction time; 0.5 to 20 hours (preferably 1 to 10 hours) During the reaction, it is preferable to add a small amount of a polymerization inhibitor such as hydroquinone.

<Hydrolysis reaction conditions of amide ether nitrile (4)>
The hydrolysis is carried out in the presence of a basic substance or an acidic substance in a molar amount of 0 to 3 times (preferably 1.01 to 1.2). Basic substance; hydroxide or carbonate of alkali metal or alkaline earth metal (preferably 20% sodium hydroxide or potassium hydroxide) Acidic substance; hydrochloric acid, sulfuric acid, etc. Reaction temperature; 50-100 ° C (preferably 60 ~ 90
C) Reaction time; 0.5 to 100 hours (preferably 1 to 20 hours)
Time) Carboxylate aqueous solution having amide group and ether group obtained by hydrolysis with basic substance may be used as it is as a detergent composition, but acidic substances (hydrochloric acid, sulfuric acid, etc.)
Is separated as acidic (pH 1 to 4) with the acid of (1),
The desired basic substance can be used as a salt. When hydrolyzing with an acidic substance, it can be separated with an acid and used as it is or as a desired salt.

[Production Method of Fatty Acid Amide Ether Carboxylic Acid] In the presence of a basic catalyst, a fatty amide ether alcohol represented by the general formula (2) and acrylic acid represented by the general formula (3) or Methacrylic acid (hereinafter abbreviated with (meth) acrylic acid) or their esters to form the corresponding amide ether carboxylic acids or esters (4), in the case of esters, followed by acidic substances A carboxylic acid having a amide group and an ether group in the molecule or a salt thereof (1) by forming a carboxylic acid, a carboxylate as desired, and hydrolyzing with a desired basic substance to form a corresponding carboxylate; Can be manufactured.

<Fatty acid amide ether alcohol (2)
Of (meth) acrylic acid or its ester (3) and subsequent hydrolysis reaction conditions> Reaction of fatty acid amide ether alcohol (2) with (meth) acrylic acid or its ester and subsequent hydrolysis The reaction can be carried out under the same conditions as in the case where (meth) acrylonitrile is used.

The thus-obtained fatty acid amide ether carboxylic acid of the present invention or a salt thereof is excellent in hard water resistance, foams well, and is mild to skin and hair. The detergent composition containing it is effective for detergents for clothes, detergents for tableware and vegetables, shampoos, body shampoos and the like.

Hereinafter, the case where the fatty acid amide ether carboxylic acid or a salt thereof of the present invention is used as a detergent will be described. [Cleaning composition] The cleaning composition of the present invention comprises the fatty acid amide ether carboxylic acid represented by the general formula (1) or a salt thereof in an amount of 0.5 to 70% by weight (preferably 3 to 50% by weight). )) Can be prepared. At this time, another surfactant can be used in combination with the N-alkylamide ether carboxylic acid or a salt thereof.

The surfactants that can be used together are shown below. [Surfactants that can be used in combination] Can be used with all anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. It is preferably used in combination with a surfactant. Preferred surfactants for use in combination are shown below. Anionic surfactants: alkyl sulfates, polyoxyethylene alkyl sulfates or fatty acid salts, alkyl benzene sulfonates, alkyl sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, monoalkyl phosphate salts, alkyls Or a hydroxyalkyl ether carboxylate, an alkyl amide ether sulfate, an acyl sarcosinate, an acyl tauride, a fatty acid monoglyceride sulfate, an acyl amino acid salt, etc. Nonionic surfactants; higher alcohol ethoxylates,
Sucrose fatty acid ester, alkyl polyglucoside, polyglycerin fatty acid ester, fatty acid diethanolamide,
Cationic surfactants such as alkylamine oxides, alkylamidoamine oxides, polyoxyethylene fatty acid esters, methyl or ethyl glucoside fatty acid esters; mono- or di-long alkyl quaternary ammonium salts, mono- or di-long chains containing ether or ester groups Alkyl quaternary ammonium salts or their corresponding hydrochlorides, sulfates, organic acid salts of amines, etc. Amphoteric surfactants; carboxybetaines, sulfobetaines, phosphobetaines, amidoamino acids, imidazolinium betaine surfactants, etc.

The cleaning composition of the present invention may further contain, if necessary, known auxiliary components to be added to the cleaning composition. Such auxiliary components include builders,
Humectants, viscosity modifiers, preservatives, anti-inflammatory agents, antioxidants,
Examples include ultraviolet absorbers, sequestering agents, bactericides, water-soluble polymer compounds, water-soluble inorganic substances, organic and inorganic compounds used for pH control, pearlescent agents, pigments, fragrances, enzymes and the like.

[0031]

EXAMPLES The present invention will be described below more specifically based on examples.

EXAMPLE 1 108 g (0.5 mol) of methyl laurate, 31.5 g (0.52 mol) of monoethanolamine and 2 g of 20% sodium hydroxide were added to a 1 liter autoclave, and the mixture was reduced under reduced pressure (200 mmHg). ), After heating at 150 ° C. for 1 hour, adding 2 g of 20% sodium hydroxide,
The degree of reduced pressure was increased, the mixture was aged at 150 mmHg and 80 ° C. for 5 hours, and left overnight. Based on the ester group in the infrared absorption spectrum of the obtained lauric acid monoethanolamide, 1
735cm absorption around is not observed ^-1, absorption of an amide group was observed at about 1630 cm ^-1. 2 g of 2
0% sodium hydroxide is added, and 66 g (1.5 mol) of ethylene oxide is gradually injected over 30 minutes while maintaining the temperature at 100 to 120 ° C. After the completion of the injection, the reaction was carried out for about 1 hour, and 2 g of 20% sodium hydroxide was added thereto.
Aged for hours. From the increase in the weight of the reaction product, the number of moles of ethylene oxide added was about 2.8 mol. The reaction mixture was neutralized with phosphoric acid and filtered under pressure to obtain lauric acid amide ether alcohol (n = 3.8). 500m with stirrer, reflux condenser, dropping funnel and thermometer
146.5 g (0.4 mol) of lauric acid amide ether alcohol and 16 g of 20% sodium hydroxide were added to a 1 l four-necked flask, and heated to 100 ° C. , A small amount of hydroquinone was added, and 26.5 g (0.5 mol) of acrylonitrile was added dropwise while maintaining the temperature at 80 ° C. After dropping,
After aging at the same temperature for 1 hour, unreacted acrylonitrile was distilled off under reduced pressure to obtain a cyanoethylated product. 100 ml of ion-exchanged water was added to the cyanoethylated product, concentrated hydrochloric acid (0.5 mol equivalent) was added, and the mixture was heated at 100 ° C. for 5 hours. After washing with water, 140 g (0.32 mol) of lauric acid amide ether propionic acid (n = 3.8) was obtained.
(Lauric acid amide ether alcohol (n = 3.5)
79.9%). 17 in the infrared absorption spectrum
25 cm ^-1, amide group 1640 cm ^-1, 1,120 cm
The absorption of an ether group was observed near ^-1 . This product was neutralized with caustic soda to prepare a 30% aqueous solution. The product was well soluble in water, foamed well, and remained unchanged even in hard water.

Example 2 To a 1 liter autoclave were added 108 g (0.5 mol) of methyl laurate, 31.5 g (0.52 mol) of monoethanolamine and 0.6 g of sodium methylate, and the mixture was reduced under reduced pressure (160 mmHg). ), Heated at 110 ° C for 2 hours, further added with 0.6 g of sodium methylate, aged at 160 mmHg and 80 ° C for 5 hours, and the generated methanol was completely distilled off. After slowly cooling to room temperature, lauric acid monoethanolamide is obtained. 0.6 g of sodium methylate is added to the reaction product,
While maintaining the temperature at 0 ° C., 88 g (2.0 mol) of ethylene oxide is gradually injected over 30 minutes. After the completion of the injection, the reaction was carried out for about 1 hour. Further, 0.6 g of sodium methylate was added, followed by aging at 70 ° C. for 6 hours. From the increase in the weight of the reaction product, the number of moles of ethylene oxide added was about 3.9 mol. The reaction mixture was neutralized with acetic acid to obtain lauric acid amide ether alcohol (n = 4.9). The product is based on ester groups in the infrared absorption spectrum.
No absorption around 35 cm ^-1 was observed. 500ml with stirrer, reflux condenser, dropping funnel, thermometer
165.8 g (0.4 mol) of lauric acid amide ether alcohol and 16 g of 20% sodium hydroxide (0.08 mol) were added to a four-necked flask, and the mixture was heated to 100 ° C., and the reaction solution became transparent. After cooling to 80 ° C., a small amount of hydroquinone was added, followed by dropwise addition of 21.0 g (0.4 mol) of acrylonitrile while maintaining the temperature at 80 ° C. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours, and unreacted acrylonitrile was distilled off under reduced pressure to obtain a cyanoethylated product. 100 ml of ion-exchanged water is added to the cyanoethylated product, and concentrated hydrochloric acid (equivalent to 0.5 mol) is further added to the resulting solution.
After heating at 5 ° C. for 5 hours, stirring was stopped and the mixture was allowed to stand for separation. This was further washed twice with warm ion-exchanged water, and 164 g (0.34 mol) of lauric amide ether propionic acid (n =
4.9) was obtained. (84.3% yield from lauric acid amide ether alcohol (n = 4.9)). In the infrared absorption spectrum, a carboxylic acid group was found at 1725 cm ⁻¹ ,
Absorption of an ether group was observed around cm ^-1 . This product was neutralized with triethanolamine to prepare a 30% aqueous solution. It dissolved well in water and had good foaming, and the foaming did not change even in hard water.

Example 3 To a 1 liter autoclave were added 214 g (1.0 mol) of methyl laurate, 62.8 g (1.03 mol) of monoethanolamine and 1 g of sodium methylate, and the mixture was added under reduced pressure (160 to 200 mmHg). ), After heating at 150 ° C for 2 hours, further adding 1 g of sodium methylate, increasing the degree of vacuum, aging at 50 mmHg and 80 ° C for 4 hours, and distilling off methanol to obtain lauric acid monoethanolamide. 1 g of sodium methylate is added to the reaction product, and 92.4 g (2.1 mol) of ethylene oxide is gradually injected over 1 hour while maintaining the temperature at 100 to 120 ° C. After the completion of the injection, the reaction was carried out for about 2 hours, and 1 g of sodium methylate was added.
Aged for hours. From the increase in the weight of the reaction product, the number of moles of ethylene oxide added was about 2.0 mol. The reaction mixture was neutralized with phosphoric acid to obtain lauric acid amide ether alcohol (n = 3). This product did not show absorption near 1735 cm ^-1 based on the ester group in the infrared absorption spectrum. In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 132.4 g (0.4 mol) of lauric acid amide ether alcohol and 16 g of 20% sodium hydroxide (0.1%) were added.
08 mol) and heated to 90 ° C., and after the reaction solution became transparent, cooled to 80 ° C., a small amount of hydroquinone was added, and then 34.4 g (0.4 mol) of methyl acrylate was added. The solution was added dropwise while maintaining the temperature at 80 ° C. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours, and unreacted methyl acrylate was distilled off under reduced pressure. 100 ml of ion-exchanged water was added to the product, concentrated hydrochloric acid (equivalent to 0.5 mol) was added, and the mixture was heated at 100 ° C. for 5 hours.
It was washed once with ion-exchanged water, and 114 g (0.28 mol) of lauric amide ether propionic acid (n = 4.0) was used.
I got (Lauric acid amide ether alcohol (n =
70.7% from 4.0)). Carboxylic acid in 1725 cm ^-1 in the infrared absorption spectrum, 1640 cm ^-1 in the amide group, the absorption of ether group in the vicinity of 1,120 cm ^-1 was observed. This was further washed twice with ion-exchanged water, and the pH was adjusted to 6 by adding triethanolamine. The product was well soluble in water, foamed well, and remained unchanged even in hard water.

COMPARATIVE EXAMPLE 1 108 g (0.5 mol) of methyl laurate, 31.5 g (0.52 mol) of monoethanolamine and 4 g of 20% caustic soda were added to a 1 liter autoclave, and under reduced pressure (200 mmHg), After a heating reaction at 150 ° C. for 1 hour, the degree of reduced pressure was increased, the mixture was aged at 150 mmHg and 80 ° C. for 5 hours, and left overnight. The infrared absorption spectrum of the obtained lauric acid monoethanolamide was 1630 cm ^-1.
Amide absorption was observed near 1735 cm ^-1
In the vicinity, absorption based on the ester group was observed. To this product is added 4 g of 20% caustic soda,
, 66 g (1.5 mol) of ethylene oxide are gradually injected over 30 minutes. After press-fitting, about 6
Aged for hours. Due to an increase in the weight of the reaction product, the number of moles of ethylene oxide added was about 2.8 mol. At this stage, in addition to the absorption of the amide group and the ether group in the infrared absorption spectrum, absorption due to the ester group was observed at around 1735 cm ^-1 . The reaction mixture was neutralized with phosphoric acid and filtered under pressure to obtain lauric acid amide ether alcohol (n = 3.8). 146.5 g (0.4 mol) of lauric acid amide ether alcohol and 16 g of 20% sodium hydroxide were added to a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and heated to 100 ° C. After the reaction solution becomes transparent, 8
After cooling to 0 ° C., a small amount of hydroquinone was added, followed by 26.5 g (0.5 mol) of acrylonitrile at 80 ° C.
The solution was dropped. After completion of the dropwise addition, the mixture was aged at the same temperature for 1 hour, and unreacted acrylonitrile was distilled off under reduced pressure to obtain a cyanoethylated product. This cyanoethylated compound has 100
After adding 5 ml of ion-exchanged water and further adding concentrated hydrochloric acid (equivalent to 0.5 mol) and heating at 100 ° C. for 5 hours, the stirring was stopped and the mixture was separated by standing, and this was further washed twice with warm ion-exchanged water. , 1
38 g (0.31 mol) of lauric amide ether propionic acid (n = 3.8) were obtained. (Yield from lauric acid amide ether alcohol (n = 3.8) 78.7)
%). In the infrared absorption spectrum, absorption of a carboxylic acid group was observed at 1,725 cm ^-1 and absorption of an ester group was observed near 1,735 cm ^-1 . The product was neutralized with caustic soda to prepare a 30% aqueous solution. A 5% aqueous solution of this product turned cloudy when left in the refrigerator overnight.

Comparative Example 2 An aqueous solution of a compound corresponding to the salt of amide ether carboxylic acid described in JP-B-8-3114 was prepared as Comparative Example 2.

Comparative Example 3 An aqueous solution of a compound corresponding to the salt of amide ether carboxylic acid described in JP-A-8-20566 was prepared as Comparative Example 3.

The following tests were carried out on the aqueous solutions of Examples 1 to 6 and Comparative Examples 1 to 3 to evaluate the performance, and the results are shown in Table 1. [Test Example] 1) Low-temperature stability test A 10% surfactant solution was prepared and placed in a freezer at -5 ° C.
After storage for a week, the state of the solution was visually observed. 2) Foaming test A foaming test was carried out according to JIS K3362 by diluting with water adjusted to 5 ° C. (German hardness) so that the amount of surfactant becomes 0.2%. 3) Rinsing properties Hands were washed with a 0.5% surfactant solution, and the feel of rinsing with tap water was evaluated. ：: good Δ: slightly poor ×: poor The results are shown in Table 1.

[0039]

[Table 1] * TEA: triethanolamine

Formulation Example 1 Shampoo composition (% by weight) Product obtained in Example 17 (in terms of solid) Polyoxyethylene (EO 3) lauryl ether disodium sulfosuccinate 3 Lauroyl diethanolamide 4 Lauroylamidopropyl dimethylamine Oxide 0.5 Cationized cellulose 0.1 Sodium benzoate 0.3 Dye qs Flavor qs Citric acid qs Purified water balance This shampoo had a rich lather and a good feel during use.

Formulation Example 2 Detergent composition for tableware and vegetables (% by weight) Product obtained in Example 1 16 (in terms of solids) Polyoxyethylene (EO 3) Sodium lauryl sulfate 5 Lauryl dimethylamine oxide 3 Denatured ethanol 5 Benzo Sodium acid 0.5 Dye, flavor appropriate amount Citric acid appropriate amount Tap water balance This dishwashing vegetable detergent has good foaming and good rinsing properties.

Formulation Example 3 Body shampoo composition (% by weight) Product obtained in Example 3 15 (in terms of solids) Triethanolamine myristate 10 Amidopropyl betaine laurate 3 Propylene glycol 5 Dye, perfume Appropriate amount Citric acid Appropriate amount Triethanolamine Appropriate amount Purified water Balance This body shampoo had good foaming and good skin and hair feel after use.

[0043]

The fatty acid amide ether carboxylic acid and the salt thereof of the present invention are novel compounds, compounds which are excellent in foaming, hard water resistance and detergency, mild on hair and skin, and extremely excellent as a surfactant. It is. The detergent composition containing the compound is effective for washing clothes, tableware, washing vegetables, shampoo, body shampoo, etc., has good foaming, and is excellent in creaminess and ease of rinsing. In addition, the production method of the present invention can suppress the formation of by-products, and can produce the compound industrially advantageously.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 65/22 NQJ C08G 65/22 NQJ C11D 1/06 C11D 1/06 // C07B 61/00 300 C07B 61/00 300

Claims (3)

[Claims] 1. A fatty acid amide ether carboxylic acid having an amide group and an ether group in a molecule represented by the following general formula (1) or a salt thereof. Embedded image In the formula, R ¹ ; a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms R ² ; a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or-(C ₂ H _{4 O) mH, - (C} 2 H 4 O) mCH 2
CHR ³ COOM R ³ ; hydrogen atom or methyl group M; hydrogen atom, alkali metal, alkaline earth metal equivalent to monovalent, ammonium, or organic ammonium n, m; 2. A method of reacting a fatty acid or a fatty acid ester with an alkanolamine, ammonia or an amine to form a fatty acid alkanolamide or a fatty acid amide, and then adding a basic catalyst to the obtained fatty acid alkanolamide or the fatty acid amide. Below, ethylene oxide is added, and at this time, the addition reaction is allowed to proceed while a basic catalyst is added on the way to obtain a compound represented by the following general formula (2). 中 wherein, R ¹ ; a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms R ² ′; a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or — (C ₂ H ₄ O) mH M; to produce a fatty acid amide ether alcohol represented by the respective number from 1 to 20}; hydrogen atom, an alkali metal, a monovalent to the corresponding alkaline earth metal, ammonium or organic ammonium n, m, Then, the obtained fatty acid amide ether alcohol is added to the following general formula (3) in the presence of a basic catalyst. In the formula, an unsaturated compound represented by R ³ ; a hydrogen atom or a methyl group X; —CN or —COOR ⁴ R ⁴ ; a hydrogen atom or a lower alkyl group} is reacted to obtain a compound represented by the following general formula (4): 4] In the formula, R ² ″; a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or — (C ₂ H ₄ O) _m H, — (C ₂ H ₄
O) _m CH ₂ CHR ³ X R ¹ , R ³ , X, n; forming a fatty acid amide ether derivative represented by the same｝ as defined above, followed by hydrolysis in the presence of a basic substance or an acidic substance Characterized by the following general formula (1): A method for producing a fatty acid amide ether carboxylic acid having an amide group and an ether group in a molecule or a salt thereof, represented by {wherein R ¹ , R ² , R ³ , M, n; 3. A detergent composition comprising the fatty acid amide ether carboxylic acid according to claim 1 or a salt thereof.