JPH11140035A - Amide ether carboxylic acid compound, anionic surfactant and detergent composition containing the surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound having excellent foaming power, foam stability and detergency even in hard water of high hardness, having low irritation and easiness to biodegradability to the hair and skin, and useful as a cleaning component having excellent use feeling. SOLUTION: This compound is expressed by formula I R<1> is a 6-30C alkyl or alkenyl; R<2> is H or a group of formula II; A and B are each a 2-3C alkylene; R<3> is CH3 or CH2 COOM; (m) and (n) are each an average added mol number; M is H or a salt-forming cation}, e.g. amide ether sodium carboxylate. The compound of the formula I is obtained by condensing an α-halogenated carboxylic acid (e.g. α-chloropropionic acid, monochlorosuccinic acid, etc.), or its salt with a fatty acid alkanolamide or a polyoxyalkylene fatty acid alkanolamide in the presence of a basic catalyst (e.g. sodium hydroxide, potassium hydroxide, etc.), preferably in an amount of 0.1-5 wt.% of the compound or its salt at 60-100 deg.C for 2-6 hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is excellent in foaming power, foam stability and detergency even in hard water having high hardness, has low irritation to hair and skin, and is easily biodegradable. An amide ether carboxylic acid compound, an anionic surfactant, and a detergent composition using the same, which are useful as a detergent component excellent in use feeling, such as having a less feeling of being wet during rinsing and having a refreshing feeling after rinsing, etc. Things.

[0002]

2. Description of the Related Art Conventionally, in household use such as hair, body, clothing, tableware, etc., components of a cleaning agent generally used include petroleum anionic surfactants, nonionic surfactants and cationic surfactants. Is widely used. Among them, anionic surfactants are used as main activators, and sodium alkyl sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium alkylbenzene sulfonate and the like are used in large quantities. However, since these anionic surfactants are irritating to the skin and hair, research on the development of low-irritating surfactants has been actively conducted, and various surfactants have been proposed and developed. ing. For example, ether carboxylate,
Amide ether carboxylate and the like. But,
All of these surfactants, on the skin, hair,
Although it is hypoallergenic, it has excellent biodegradability in addition to slimy feeling when rinsing, refreshing feeling after rinsing, etc.
At present, the detergency and foaming power are inferior to those of the petroleum-based surfactants described above. Therefore, various proposals have been made in order to make use of those characteristics and to supplement the detergency and foaming power which are serious drawbacks in practical use. For example, in the case of ether carboxylic acids, a method using an alkyl ether fatty acid salt having a specific alkyl chain (JP-A-55-144099) and a method using an ionic surfactant in combination (JP-A-1-2015)
No. 21), a method in combination with an alkanolamide (JP-A-5-214365), a method in combination with an amphoteric surfactant (JP-A-3-109498) and the like.
In the case of amide ether carboxylic acid, a method in combination with a nonionic surfactant (JP-A-8-239688) and a method in combination with a betaine-type amphoteric surfactant (JP-A-8-2396)
No. 89) has been proposed.

[0004] However, in the method of using the alkyl ether fatty acid salt having the specific chemical structure and the method of using together with other surfactants such as a foaming agent, the levels thereof are all alkyl ethoxy sulfate and alkyl amine. The foaming power of existing surfactant compositions containing an oxide or a fatty acid alkanolamide does not reach the level of foam stability, is not yet satisfactory, and in terms of detergency, foaming power, Performance improvement was required.

[0005]

The present invention is excellent in foaming power, foam stability and detergency even in hard water having high hardness.
Anionic interface useful as a detergent component that has low irritating properties to hair and skin and is easily biodegradable, and has little wet feeling during rinsing, and is excellent in feeling of use such as freshness of skin after rinsing. It is an object of the present invention to provide an active compound and a detergent composition using the same.

[0006]

According to the present invention, there is provided an amide ether carboxylic acid compound represented by the following general formula (1), which is useful as an anionic surfactant.

Embedded image(Where R¹Is a straight or branched chain having 6 to 30 carbon atoms on average
A higher alkyl or alkenyl group of  A and B represent alkyl groups having 1 to 3 carbon atoms, and A and B each have 2 to 3 carbon atoms.
Represents an alkylene group of^ThreeIs -CH_ThreeOr -CH_TwoCO
OM is shown, and m and n are average addition mole numbers.
Represents a number of 1 to 20, and the rest represents a number of 0 to 20, and M represents hydrogen or
(Shows a salt-forming cation)
An anionic surfactant comprising an acid compound is provided. Sa
Furthermore, according to the present invention, the anionic surfactant is reduced in amount.
A cleaning composition containing at least one kind is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R¹
Is 6 to 30, preferably 10 to 24 linear or
Is a branched higher alkyl or alkenyl group.
The optimum carbon chain length depends on the type of terminal carboxyl group and
It is greatly affected by the pH of the purified liquid, etc.
In terms of stability and detergency, a C10 to C24
Tomb, dodecyl, tetradecyl, hexadecyl,
Octadecyl, octadecenyl, undecyl, 2
-Hexyldecyl group, 2-octylundecyl group, and
2-decyltetradecyl group and the like.
It can be in German or mixed form. It is an alkyl group having 1 to 3 carbon atoms. R^ThreeIs CH_Three,is there
Or CH_TwoCOOM.  The oxyacid residue excluding the hydroxyl group is shown. These oxyacid residues
The type of the group is selected depending on the conditions of use and the purpose of use.
Anionic surfactants with any oxyacid residue can be used in hair
Hypoallergenic to hair and skin
Foaming even in hard pH water and high hardness hard water
Power, detergency, slimy feeling when rinsing, after rinsing
It has an excellent feeling of use such as flatness, but especially apple
When the acid is used as the residue, foaming in the acidic condition of pH 4 to 6
By having power and foam stability, and chelating ability
Excellent builder effect. A and B each have 2 or more carbon atoms
Shows an alkylene group. Therefore, AO and BO are alkylene
An oxide group, specifically, an ethylene oxide group,
Alternatively, it is a propylene oxide group. Each
It can be in German or mixed form. m, n
Is the average number of added moles of the alkylene oxide group,
One of them is 1 to 20, and the other (the other) is 0 to 20
Is a number. The type of alkylene oxide and the average addition
The number of carboxyl groups, the type of terminal carboxyl group, and washing when used
It is greatly affected by the pH of the solution,
It is selected from the required performance from them. Terminal carboxy
In the case of a lactic acid residue in which the hydroxyl group is a monobasic acid,
The type of oxide group depends on foaming power, foam stability and detergency.
From, ethylene oxide group is preferable, and the average
The number of moles added is from 0 to 20, preferably from 1 to 10.
is there. Dibasic acid with large hydrophilic terminal carboxyl group
In the case of malic acid residue, there is an ethylene oxide group
Or the propylene oxide group is
Is used in mixed form. The number of moles added is also foaming power,
0 to 10, preferably from the viewpoint of foam stability and detergency
Is 1 to 5. The counter ion M of the carboxyl group is
It is hydrogen or a salt-forming cation. For salt-forming cations
Is an alkali metal such as sodium, potassium, lithium, etc.
Ions; alkaline earth gold such as calcium and magnesium
Genus ion; ammonium ion; alkanolamine
(Mono, di or tri-ethanolamine, n- or iso-
Organic propane amines).
Monium ion and the like. Use two or more of them
You can also.

The anionic surfactant of the present invention, even when used alone, is excellent in foaming power, foam stability and detergency, but is used in combination with fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide. As a result, it has been found that a synergistic effect is exhibited especially in the foam stability. The combined ratio of the anionic surfactant of the present invention and a fatty acid alkanolamide or a polyoxyethylene fatty acid alkanolamide is 100/0 to 100% by weight.
10/90, preferably 95/5 to 5/5 in terms of foam stability.
20/80. As the fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide used in combination, those derived from the raw material of the anionic surfactant of the present invention can be used. Although it can be added separately to the anionic surfactant of the present invention, it is preferable to leave it as an unreacted product at the time of production from the viewpoint of workability and economical efficiency at the time of production.

The anionic surfactant represented by the general formula (1) of the present invention can be produced by various methods.
For example, it can be obtained by condensing an α-halogenated carboxylic acid or a salt thereof with a fatty acid alkanolamide or a polyoxyalkylene fatty acid alkanolamide by the following formula in the presence of a basic catalyst.

Embedded image (Wherein, G represents halogen) Examples of the α-halogenated carboxylic acid include α-chloropropionic acid, α-bromopropionic acid, monochlorosuccinic acid, monobromosuccinic acid, and salts thereof. Among them, α-chloropropionic acid, monochlorosuccinic acid, and salts thereof are preferable from the viewpoint of reactivity and economy.

The fatty acid alkanolamide is produced by a conventional method, for example, by condensing a fatty acid glyceride, a fatty acid alkyl ester, or a fatty acid with monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine or the like in the presence of an alkali catalyst. Can be used. Among them, those using fatty acid alkyl esters as raw materials are preferable in terms of color tone and impurities. Polyoxyalkylene fatty acid alkanolamide, fatty acid alkanolamide as a raw material,
It can be produced by adding an alkylene oxide in the presence of a basic catalyst by a conventional method.

As the basic catalyst, sodium hydroxide,
Potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like are used. These basic catalysts are in the range of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the monohalogenoxy acid or a salt thereof. The method of reacting a monohalogenoxy acid or a salt thereof with a fatty acid alkanolamide or a polyoxyalkylene fatty acid alkanolamide is performed by heating a mixture of a monohalogenoxy acid salt and a fatty acid alkanolamide or a polyoxyalkylene fatty acid alkanolamide under reduced pressure. A method of gradually dropping an aqueous solution of a basic catalyst into the solution, a method of heating the mixture of both raw materials and the solid basic catalyst, and reacting the mixture under reduced pressure, heating a fatty acid alkanolamide or a polyoxyethylene fatty acid alkanolamide under reduced pressure. Any method such as a method in which a monohalogenoxy acid or an aqueous solution thereof and an aqueous solution of a basic catalyst are gradually dropped and reacted. Examples of the basic catalyst include an alkali metal alkoxide, an alkali hydroxide, and an alkali carbonate. Preferably, sodium hydroxide or from the viewpoint of economy and handling,
Potassium hydroxide. The amount of these basic catalysts used is
The amount is from equimolar to 1.5 times the molar amount of the monohalogenoxy acid. Further, the pH during the reaction is preferably kept at 7 to 13 from the viewpoint of the reaction rate and the hydrolysis of the amide group.

This reaction can be carried out without a solvent. However, in order to reduce the viscosity of the product in the latter half of the reaction and to evaporate the water to make the reaction proceed smoothly, Solvents such as hexane, toluene, xylene, chloroform, carbon tetrachloride, dioxane, tetrahydrofuran, dimethylformamide, and dimethylacetamide can also be used. The amount used is suitably from 1.0 to 5.0 in terms of weight ratio with respect to the polyoxyalkylene ether oxyacid ester. The reaction molar ratio of the monohalogenoxy acid to the fatty acid alkanolamide or polyoxyalkylene fatty acid alkanolamide is selected from the characteristics of the anionic surfactants to be produced and their reactivity, and is 0.1 to 0.1 in molar ratio. 2.0, preferably 0.2 to 1.5 in terms of foam stability, reaction rate and the like.
It is. The reaction temperature is 50 to 120 ° C, especially 60 to 1
It is preferable to carry out in the range of 00 ° C. When the reaction temperature is lower than 50 ° C., the reaction rate is low, and when the reaction temperature is higher than 120 ° C., the product is undesirably colored. The reaction time varies depending on the reaction method and the reaction reagent, but is 1 to 10 hours, preferably 2 hours.
~ 6 hours. The anionic surfactant of the present invention obtained as described above includes an unreacted fatty acid alkanolamide or a polyoxyalkylene fatty acid alkanoylamide, an oxyacid salt as a reaction by-product, and an inorganic salt. Contains. As it is, it can be used as an anionic surfactant with good foam stability, but it is possible to remove impurities using silica gel column chromatography or acidifying the reaction product and utilizing the difference in solubility in water. It can also be used after purification using a known purification method.

The anionic surfactant of the present invention is excellent in foaming power, foam stability and detergency even in hard water of high hardness, has low irritation to hair and skin, and is readily biodegradable. In addition, it has less slimy feeling during rinsing, and has excellent characteristics in use such as a refreshing feeling of the skin after rinsing. In particular, when the terminal group has a malic acid residue, pH 4
In the acidic region from to 6, in addition to obtaining rich and stable foaming, by using in combination with the following surfactant,
It was unexpectedly found that a synergistically superior detergency was obtained. Such surfactants include higher alcohol ethoxylates, higher alcohol ethoxypropoxylates, nonylphenol ethoxylates, alkyl sulfates, polyoxyethylene alkyl sulfates, higher fatty acid salts, α-olefin sulfonates, α-sulfo fatty acids Examples include ester salts, alkyl or hydroxyalkyl ether carboxylate salts, acyl amino acid salts, and the like. The mixing ratio [B] / [A] of the existing surfactant B to the anionic surfactant A represented by the general formula (1) is 2/98 to 90/10 by weight, preferably, 20/80 ~
70/30. If the mixing ratio is higher than the above range, the characteristics of the anionic surfactant of the present invention cannot be sufficiently exhibited.
The amount of the anionic surfactant of the present invention in the detergent composition varies depending on the dosage form of the detergent, but when it is liquid, it is 0.5 to 50% by weight in the composition, If
70% by weight, and in the case of a solid type, 1 to 80% by weight is suitable. The pH when the detergent is dissolved in water varies depending on the type and use of the active agent to be blended, but the preferred range is pH 5 to 8 for shampoo, body shampoo and kitchen detergent.
In a laundry detergent, 7 to 11 are preferable. If the pH deviates from the above range, it is not preferable in terms of irritation to the skin and damage to the washing target. Other anionic surfactants that can be used in combination include alkyl benzene sulfonates, alkyl sulfonates, monoalkyl phosphates, alkyl amide ether sulfates, N-acyl taurides,
N-acyl-N-methyl tauride, alkyl sarcosinate, fatty acid monoglyceride sulfate, alkyl iminodicarboxylate, secondary amide type N-acyl amino acid salt, tartaric acid alkyl amide, malic acid alkyl amide, citric acid alkyl amide And the like. Examples of nonionic surfactants that can be used in combination include fatty acid alkanolamides, sucrose fatty acid esters, alkyl (poly) glycosides, polyglycerin fatty acid esters, and fatty acids 2,3.
-Dihydroxypropylamide, fatty acid polyoxyethylene amide, alkylamine oxide, alkylamidoamine oxide, polyoxyethylene fatty acid ester,
Methyl or ethyl glycoside, fatty acid ester, acyl glucamide and the like can be mentioned. Examples of the amphoteric surfactant that can be used in combination include carboxybetaine, sulfobetaine, phosphobetaine, amide amino acid, imidazolinium betaine surfactant, and the like.

[0014] The cleaning composition of the present invention may contain, if necessary, known auxiliary components to be added to the cleaning agent. Such auxiliary components include builders, humectants, viscosity modifiers, preservatives, anti-inflammatory agents, antioxidants, ultraviolet absorbers, sequestering agents, anti-migration agents, bactericides, water-soluble polymers Examples include compounds, water-soluble inorganic salts, organic and inorganic substances used for pH adjustment, pearlescent agents, pigments, fragrances, enzymes, and floaters.

[0015]

According to the present invention, even in high-hardness hard water, it has excellent foaming power, foam stability and detergency, is less irritating to hair and skin, and is easily biodegradable. The present invention provides a novel anionic surfactant useful as a detergent component having a reduced feeling of sliminess upon rinsing and an excellent feeling of use such as a refreshing feeling of the skin after rinsing. Therefore, the detergent composition containing the surfactant of the present invention can be widely used as a shampoo, a body shampoo, a hand soap, a dish and vegetable detergent, a clothing detergent, a residential detergent and the like.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. In addition,% shown below shows weight%.

Synthesis Example 1 243 g of lauric acid monoethanolamide and 0.3 g of sodium methoxide were charged into a 1000 ml glass autoclave equipped with an ethylene oxide introducing tube, a nitrogen blowing tube, and a thermometer. Close and close the system for 0.5
After reducing the pressure to mmHg, the pressure was returned to normal pressure with nitrogen. After repeating this operation three times, the mixture was gradually heated to 100 ° C. under reduced pressure to distill off methanol produced as a by-product. Subsequently, 44 g of ethylene oxide was added while maintaining the reaction temperature at 110 to 120 ° C. and the gauge pressure at 3 kg / cm ³ or less. The mixture was further stirred and aged at the same temperature for 1 hour to obtain a lauric acid monoethanolamide oxide 1 mol adduct. This lauric acid monoethanolamide ethylene oxide 1 mol adduct 100 g
And 68.2 g of sodium α-chloropropionate were charged into a 500 ml glass separable flask equipped with a dropping funnel, a Liebig condenser, a nitrogen blowing tube and a thermometer, and the air in the system was replaced with nitrogen. Subsequently, the mixture is heated with stirring, and heated at 75 ° C. under a reduced pressure of 25 mmHg.
53.3 g of a 5% aqueous solution of NaOH was added dropwise over 2 hours to remove generated water. After dropping, dioxane 100m
Then, water remaining at 70 to 80 ° C. under a reduced pressure of 25 mmHg was removed as an azeotrope of dioxane water, and the mixture was stirred and aged for 2 hours under the same conditions. After dissolving the product in pure water, the pH was adjusted to 7.0 with 6N hydrochloric acid to obtain 484 g of an aqueous 17% sodium amide ether carboxylate (yield: 62%, by liquid phase chromatography analysis).

Synthesis Example 2 A 500 ml glass separable flask equipped with a dropping funnel, a Liebig condenser, a nitrogen blower and a thermometer was charged with 100 g of lauric acid monoethanolamide and 121 g of sodium monochlorosuccinate. The air was replaced. Then, heat with stirring,
0-80 ° C., 40% Na under reduced pressure of 20-30 mmHg
63 g of an OH aqueous solution was added dropwise over 1.5 hours to remove generated water. After completion of the dropwise addition, 150 ml of dioxane was added, water remaining at 70 to 80 ° C. under a reduced pressure of 25 mmHg was removed as an azeotropic mixture of dioxane water, and the mixture was stirred and aged for 2 hours under the same conditions. The product was dissolved in pure water, adjusted to pH 7.0 with 6N hydrochloric acid, and 608 g of a 15% aqueous solution of sodium amide ether carboxylate (yield 5%).
5%, quantitative method was based on Synthesis Example 1).

SYNTHESIS EXAMPLE 3 The procedure of Synthesis Example 2 was repeated, except that lauric acid diethanolamide was used instead of lauric acid monoethanolamide, and sodium α-chloropropionate was used instead of sodium monochlorosuccinate. 21% aqueous solution of sodium amide ether carboxylate (yield 6
0%, quantification method was based on Synthesis Example 1).

SYNTHESIS EXAMPLE 4 In Synthesis Example 2, a stearic acid monoethanolamide 5 mol adduct was obtained in the same manner as in Synthesis Example 2 except that stearic acid monoethanolamide was used instead of lauric acid monoethanolamide. Subsequently, the reaction and post-treatment were carried out in the same manner to obtain a 15% aqueous solution of sodium amide ether carboxylate having a pH of 7.1 (yield 53%, quantitative method according to Synthesis Example 1).

Examples 1 to 3 and Comparative Examples 1 to 3 The performance of various anionic surfactants was evaluated as follows. Table 1 shows the results. 1) Foaming power Using artificial hard water adjusted to a hardness of 3 ° DH using CaCl ₂ , mixed soil (lanolin / paraffin) as a soil component in a 0.9% surfactant concentration aqueous solution adjusted to a predetermined pH. / Triolein / tristearin weight ratio = 90/4
/ 4/2) 20 ml of a solution containing 0.2% was prepared,
Place in a 100 ml stoppered Epton tube and at room temperature,
Shaking was performed 20 times for 10 seconds, and the foam volume one minute after that was measured. The evaluation was performed using the following criteria in comparison with the amount of bubbles of polyoxyethylene lauryl ether sulfate (P = 3). ◎: Many bubbles ○: Same bubbles ×: Little bubbles 3) Feeling of use Using a hair bundle (30 g), wash with a 10% solution of each sample, rinse with tap water, and dry. The sensory evaluation was performed on the moist feeling and the refreshing feeling of the hair bundle. The average value of the panelists of five males and females was calculated, and when the average value was 2.5 or more (○), when the average value was 2.4 to 1.5 (△), 1.
The case of 4 or less was judged as (x). In addition, the following criteria were used for evaluation. 3: Excellent 2: Normal 1: Inferior

[0022]

[Table 1]

Next, an example of a specific formulation using the anionic surfactant of the present invention as a detergent component will be shown.

Example 4 Shampoo Composition Compound 8 of Synthesis Example 1 (% by weight) N Lauroylmethyltaurine Na 4 Coconut fatty acid diethanolamide 2 Alkylimidozolinium betaine 2 Propylene glycol 5 Dye, perfume Appropriate amount Purified water balance ＰＨ pH (undiluted solution) 7.2 This shampoo is hypoallergenic to skin The foaming during washing was good, the feeling of sliminess during rinsing was small, the skin after rinsing was refreshing, and the use feeling was good.

Example 5 Body Soap Compound of Synthesis Example 2 20 (% by weight) Lauroylglutamate Na 5 Coconut fatty acid diethanolamide 2 Ethylene glycol fatty acid ester 3 Ethanol 3 Propylene glycol 5 Dye, perfume Appropriate amount Purified water Balance ────── ＰＨ pH (undiluted solution) 6.0 This body soap is less irritating to the skin. There was abundant foaming, less slimy feeling during rinsing, and the skin feeling after washing was good as well.

Example 6 Detergent Composition for Vegetables and Vegetables Compound of Synthesis Example 3 20 (% by weight) Polyoxyethylene lauryl alcohol (P = 10) 13 Amidopropyltrimethylamine oxide laurate 3 Ethanol 5 Pigment, flavoring appropriate amount Purified water balance ─ ────────────────────────────────── pH (undiluted solution) 7.5 This dishwashing vegetable detergent foams, And good detergency,
In addition, there was little sliminess during rinsing, and the skin was hypoallergenic.

Example 7 Detergent composition for clothing Alcohol ethoxylate 20 (% by weight) (Synthetic secondary alcohol, P = 8) Alcohol ethoxylate 5 (C12 alcohol, P: 12) Compound of Synthesis Example 4 7.5 Tri Ethanolamine 3 Sodium chloride 1.5 Ethanol 2 Propylene glycol 3 Purified water Balance ────────────────────────────────── ＰＨ pH (undiluted solution) 10.2 This detergent for clothes has strong detergency, good foaming during washing, and has low irritation to the skin.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 65/32 C08G 65/32 C11D 1/06 C11D 1/06

Claims (1)

[Claims] (A) an amino group represented by the following general formula (1):
Doether carboxylic acid compounds. Embedded image(Where R¹Is a linear or branched higher alkyl group having an average of 6 to 30 carbon atoms.
Alkyl or alkenyl groups, A and B each represent an alkyl group having 2 to 3 carbon atoms;^ThreeIs -CH_ThreeOr -CH_TwoRepresents COOM, m and n are average number of moles added, one of which is 1 to 20,
The remainder is a number from 0 to 20, and M represents hydrogen or a salt-forming cation.
Anionic surfactant consisting of a compound. [Claim 3] The amount of the anionic surfactant according to claim 2 is reduced.
And at least one cleaning composition.