JPH11193396A - Anionic surfactant and detergent composition containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an anionic surfactant which exhibits good foaming even under weakly acidic to weakly alkaline conditions, hardly irritates hair or skin, provides a good feeling in use, and is useful as a detergent component by using a hydroxyalkyl glyceryl ether carboxylic acid compd. SOLUTION: A compd. of formula I is used. In the formula, R<1> is 6-30C alkyl or alkenyl; R<2> is H, CH3 or CH2 COOM; X is a group of formula II or III; G is a group of formula IV or V; n is 1-10; and M is H or a salt-forming cation. The compd. can be produced by condensing an epoxyalkane and epichlorohydrin in the presence of a basic catalyst and reacting the resultant hydroxyalkyl glyceryl ether or hydroxyalkyl polyglyceryl ether with an α- halogenocarboxylic acid or its salt in the presence of a basic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is directed to an acidic-weakly alkaline (pH 4-8) condition and hard water having high hardness.
The present invention relates to an anionic surfactant which has good detergency and foaming power, and is excellent in use feeling and skin irritation, and is useful as a detergent component, and a detergent composition using the same.

[0002]

2. Description of the Related Art Conventionally, petroleum-based anionic surfactants and nonionic surfactants have been widely used as components of household cleaning agents for cleaning hair, body, clothing, tableware and the like. I have. Recently, surfactants used in the above applications, in addition to excellent detergency, foaming power,
It is required to have a multifunctional and high-performance level, such as good foaming feeling during rinsing, a refreshing feeling after rinsing, etc., and low irritation to the skin, as well as environmental safety. Therefore, in order to satisfy such demands, development has been advanced from both sides of a detergent composition and a surfactant. In the case of a detergent composition, the pH is changed from weakly acidic to neutral to suppress irritation to the skin,
On the other hand, in the case of a surfactant, it can be used under the same conditions, and is selected from the viewpoint of cleaning performance, safety, use feeling, and environmental safety, and the constituent elements are composed of carbon, hydrogen, and oxygen, and environmentally friendly. Alkyl ether carboxylic acids having no carboxyl group at the terminal hydrophilic group and having soap-like properties have attracted attention as next-generation surfactants.

[0003] However, in the case of these alkyl ether carboxylic acids, the skin is less irritating and less slimy at the time of rinsing, and a refreshing feel is obtained, but compared to existing petroleum surfactants. , Detergency and foaming power are poor, and in particular, their performance is greatly reduced in high hardness hard water.
Therefore, much research has been done to solve these serious problems in practical use. For example, a method using an alkyl ether fatty acid salt having a specific alkyl chain (JP-A-55-144099), a method using it in combination with an ionic surfactant (JP-A-1-201521), a method using it in combination with an alkanolamide (Japanese (Japanese Unexamined Patent Publication No. Hei 5-214365) and a method using a combination with an amphoteric surfactant (JP-A-3-109498).
No.) have been proposed.

However, in the method using the alkyl ether fatty acid salt having the specific chemical structure, or in the method using in combination with another surfactant such as a foaming agent, the performance levels of the alkyl ethoxy sulfate and the alkyl ethoxy sulfate are all low. It does not reach the level of foaming power and foam stability of existing surfactant compositions containing amine oxides or fatty acid alkanolamides. In particular, shampoos,
When used as a surfactant for body shampoos, etc., it is not yet satisfactory in terms of foaming power and foam stability, and for practical use, surfactants are required to further improve performance. Was.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides good foaming even in acidic to weakly alkaline conditions (pH 4 to 8),
Offers an anionic surfactant that is less irritating to hair and skin, has a good feeling of use such as slimy feeling when rinsing, and a feeling of residue on the skin, and provides an excellent anionic surfactant as a cleaning component. An object of the present invention is to provide a detergent composition containing an agent.

[0006]

According to the present invention, there is provided an anionic surfactant comprising a hydroxyalkyl glyceryl ether carboxylic acid compound represented by the following general formula (1).

Embedded image Further, according to the present invention, there is provided a cleaning composition containing at least one kind of the above-mentioned anionic surfactant.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ is
6 to 30 linear or branched higher alkyl or alkenyl groups. The optimal carbon chain length is greatly affected by the type of the terminal carboxyl group, the pH of the washing solution, etc., and is preferably a decyl group, a dodecyl group, or a tetradecyl group having 10 to 24 carbon atoms from the viewpoint of foaming power and foam stability. , A hexadecyl group, an octadecyl group, an octadecenyl group, an undecyl group, a 2-hexyldecyl group, a 2-octylundecyl group, a 2-decyltetradecyl group, etc., each of which may be used alone or in combination. it can.

Embedded image R ² represents H, CH ₃ or CH ₂ COOM.

In the above anionic surfactant, the following general formula (3)

Embedded image (Wherein R ² and M have the same meanings as described above), and the terminal hydrophilic group is an oxyacid residue obtained by removing the hydroxyl group from an oxyacid selected from glycolic acid, lactic acid and malic acid. Show. These oxyacid residues are selected according to the purpose of use. Anionic surfactants having any oxyacid residue are also excellent in foaming power, slimy feeling upon rinsing, and feeling in use such as residual feeling on the skin in a wide pH range from acidic to alkaline. It has excellent irritancy to hair and skin, but especially its foaming power in hard water with high hardness
Those having lactic acid and malic acid as residues are excellent, and p
The foaming power in the acidity of H4 to 6 and the builder effect due to the chelating power with the alkaline earth metal are excellent when malic acid is used as a residue. G represents a divalent glycerin residue, which is represented by the following formula (4) or (5).

Embedded image

Embedded image n represents the average number of condensation of G, and the average number of condensation is 1
10 to 10, preferably 1 to 5 from the viewpoint of detergency and foaming power.

The carboxyl counter ion M includes hydrogen and salt-forming cations. Salt-forming cations include alkali metals, alkaline earth metals, ammonium,
Substituted ammonium and the like. The substituted ammonium may be of various types derived from organic amines such as alkanolamines such as mono, di, and triethanolamine.

The anionic surfactant represented by the general formula (1) of the present invention can be produced by various known methods. For example, a hydroxyalkyl glyceryl ether produced by condensing an epoxy alkane and epichlorohydrin in the presence of a basic catalyst, or a hydroxyalkyl polyglyceryl ether as a raw material, which is added to an α-halogen carboxylic acid in the presence of a basic catalyst. Alternatively, it can be produced by reacting a salt thereof. Examples of the α-halogenocarboxylic acid or a salt thereof include monochloroacetic acid, monobromoacetic acid, α-chloropropionic acid, α-bromopropionic acid, monochlorosuccinic acid, monobromosuccinic acid, and salts thereof.
Preferred are monochloroacetic acid, α-chloropropionic acid, monochlorosuccinic acid, and salts thereof from the viewpoint of economy and reactivity. The method of reacting a monohalogenoxy acid or a salt thereof with a hydroxyalkyl glyceryl ether or a hydroxyalkyl polyglyceryl ether comprises heating a mixture of a monohalogenoxy acid salt and the hydroxyalkyl glyceryl ether with an aqueous solution of a basic catalyst under reduced pressure. , A method of reacting the mixture of the raw materials and the solid basic catalyst under reduced pressure, heating the hydroxyalkyl glyceryl ether under reduced pressure, a monohalogenoxy acid or an aqueous solution thereof, Any method such as a method of reacting by gradually dropping an aqueous solution of a neutral catalyst can be used.

Examples of the basic catalyst include alkali metal alkoxide, alkali hydroxide, alkali carbonate and the like.
It is selected according to the reaction method and the like. Preferably, economical,
From the viewpoint of handling, it is sodium hydroxide or potassium hydroxide. The amount of these basic catalysts used is from equimolar to 1.5 times the molar amount to the monohalogenoxy acid. 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 product viscosity in the latter half of the reaction and to evaporate water and make the reaction proceed smoothly, hexane is used at the beginning of the reaction or in the latter half of the reaction. Solvents such as toluene, xylene, chloroform, carbon tetrachloride, dioxane, tetrahydrofuran, dimethylformamide and dimethylacetamide can also be used. The amount used is 1.0 to 5.0 in weight ratio to the hydroxyalkyl glyceryl ether.
Is appropriate. The reaction molar ratio of the monohalogenoxyoxy acid to the hydroxyalkyl glyceryl ether is selected from the viewpoint of the amount of the hydroxyalkyl (poly) glyceryl ether remaining as unreacted and their reactivity. 2.0, preferably 0.2 to 1.5 from the viewpoint of foaming power, reaction rate and the like.
The reaction is preferably performed at a temperature in the range of 50 to 120C, particularly preferably 60 to 100C. When the reaction temperature is lower than 50 ° C., the reaction rate is low, and when the reaction temperature is 120 ° C. or higher, the product is preferably colored. The reaction time varies depending on the reaction method and the reaction reagent, but is 1 to 10 hours, preferably 2 to 6 hours.

In the reaction of a hydroxyalkyl glyceryl ether with a monohaloacetic acid or a salt thereof, the monohaloacetic acid or a salt thereof is added to the hydroxyl group at the α-position or the β-position of the hydroxyalkyl glyceryl ether. It can be suitably used as a surfactant. In the reaction of epoxy alkane with glycerin or polyglycerin, glycerin,
Alternatively, polyglycerin is added to the oxirane ring of the epoxy alkane by ring opening and added to its α-position or β-position, and any of them can be suitably used as an anionic surfactant. Thus obtained anionic surfactant of the present invention, in addition to the above, unreacted hydroxyalkyl glyceryl ether or hydroxyalkyl polyglyceryl ether, reaction by-product dihydroxyalkane, oxyacid salt, And a small amount of an inorganic salt. Both components are water-soluble, and the reaction product can be used as an anionic surfactant with excellent foaming power as it is by simply adjusting the pH. When the product is used, it can be purified by a known purification method such as solvent extraction and silica gel column chromatography.

The anionic surfactant of the present invention can be used in combination with an existing surfactant. In this case, the surfactant used in combination includes an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Anionic surfactants are used in combination for the purpose of further improving detergency and foaming power, and alkyl sulfates, polyoxyethylene alkyl sulfates, α-sulfofatty acid ester salts,
α-olefin sulfonate, alkyl or hydroxyalkyl ether carboxylate, N-acylated taurine, N-acylated methyltaurine, N-acylated glycine, N-acylated aspartic acid, N-acylated sarcosine, N -Acylated glutamic acid, higher fatty acid salt, alkyl benzene sulfonate, alkyl sulfonate,
Monoalkyl phosphate, alkyl amide ether sulfate, fatty acid monoglyceride sulfate, alkyl iminodicarboxylate, secondary amide N-
Acyl amino acid salts, alkyltartaric acid alkylamides, malic acid alkylamides, citric acid alkylamides and the like can be mentioned. Nonionic surfactants, like anionic surfactants, are used for the purpose of further reducing irritation to the skin and hair, in addition to detergency and foaming power, and the anionic surfactant of the present invention is also used. In addition to hydroxyalkyl glyceryl ethers and hydroxyalkyl polyglyceryl ethers, which are precursors, higher alcohol ethoxylates, higher alcohol ethoxypropoxylates, nonylphenol ethoxylates, fatty acid alkanolamides, sucrose fatty acid esters, alkyl (poly) glycosides, polyglycerin fatty acids Esters, fatty acid 2,3-dihydroxypropylamide, fatty acid polyoxyethylene amide, alkylamine oxide, alkylamidoamine oxide,
Examples include polyoxyethylene fatty acid esters, methyl or ethyl glycosides, fatty acid esters, acylglucamides, and the like.

The amphoteric surfactant is used for the purpose of further improving foaming power and mildness on the skin,
Amido-amino acid-type amphoteric surfactant, long-chain alkyldimethylcarboxymethylbetaine, sulfobetaine, imidazolium betaine, glycine-type, alamin-type amino acid-type amphoteric surfactant, carboxybetaine, sulfobetaine, phosphobetaine, amide amino acid, imidazoly And an ammonium betaine-based surfactant. The anionic surfactant (A) represented by the general formula (1) can be used by mixing with the existing surfactant (B). Their mixing ratio (A) / (B) is 98/2 by weight.
-10/90, preferably 80 / 20-30 / 70. If the mixing ratio is 9/91 or less, 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.
It is preferably from 50 to 50% by weight, 1 to 70% by weight in the case of a paste, and 1 to 80% by weight in the case of a solid. The pH when the detergent is dissolved in water depends 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, and 7 to 11 for clothing detergent. Is preferred. pH less than 4.9, and pH
If it is 11.1 or more, it is not preferable in terms of irritation to the skin and damage to the washing target.

The cleaning composition of the present invention may contain, if necessary, known auxiliary components to be added to the cleaning composition. Such auxiliary ingredients include builders, humectants,
Viscosity modifiers, preservatives, anti-inflammatory agents, antioxidants, ultraviolet absorbers, sequestering agents, anti-migration agents, bactericides, water-soluble polymer compounds, water-soluble inorganic salts, organics used for pH control and Inorganic compounds, pearlescent agents, pigments, fragrances, enzymes,
Bleaching agents and the like.

[0016]

According to the present invention, foaming is good even under acidic to weakly alkaline conditions (pH 4 to 8), hypoallergenic to the skin and hair, and furthermore, the skin feels slimy when rinsing, A novel anionic surfactant which is excellent in use feeling and useful as a cleaning component, for example, has a low residual property, is provided. 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 dishwashing vegetable detergent, a clothing detergent, a residential detergent, and the like.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments.

Synthesis Example 1 In a 500 ml four-necked flask equipped with a vacuum stirrer, a Liebig condenser, and a thermometer, 100 g of hydroxydodecylglyceryl ether and 63.3 g of sodium monochloroacetate were charged, and the conditions were 80 ° C. and 25 mmHg. While stirring, 55.4 g of 40% aqueous NaOH solution
The distilled water was removed by dropwise addition over time. Subsequently, 150 ml of dioxane was added, and the mixture was reacted and aged for 1.5 hours under the same conditions while distilling off water and dioxane.
The product was dissolved in pure water, adjusted to pH 7.0 with 6N hydrochloric acid, and 465.4 g of a 23.0% aqueous solution of sodium hydroxydodecylglyceryl ether glycolate (yield 83).
%, By liquid phase chromatography).

Synthesis Example 2 Synthesis Example 1 was repeated except that sodium monochloroacetate was replaced by sodium α-chloropropionate and hydroxydodecyl glyceryl ether, and hydroxytetradecyl diglyceryl ether was used. Thus, a 25% aqueous solution of sodium hydroxytetradecyl diglyceryl ether lactate of 1.0 (yield: 68%, quantitative method is based on Synthesis Example 1) was obtained.

Synthesis Example 3 Synthesis Example 1 was repeated except that sodium monochlorosuccinate was used in place of sodium monochloroacetate.
25% aqueous solution of sodium hydroxydodecylglyceryl ether malate having a pH of 7.0 (yield 65%,
The quantification method was based on Synthesis Example 1).

SYNTHESIS EXAMPLE 4 The procedure of Synthesis Example 1 was repeated, except that hydroxydodecylglyceryl ether was replaced with hydroxyoctadecylglyceryl ether and sodium monochloroacetate.
A 15% aqueous solution of H7.0 hydroxy sodium octadecylglyceryl ether malate (yield 68%, quantitative method based on Synthesis Example 1) was obtained.

The evaluation methods used in the examples are as follows. 1. Evaluation as garment surfactant 1) using a foaming power CaCl ₂ using an artificial hard water prepared in hardness 3 ° DH, the surfactant concentration 0.9 wt% aqueous solution adjusted to a predetermined pH, soil components As mixed soil (lanolin / paraffin / triolein / tristearin = 90/4 /
4/2) 20 ml of a solution to which 0.2% by weight was added was prepared, placed in a 100 ml stoppered Epton tube, shaken 20 times at room temperature for 10 seconds, and the foam volume one minute later was measured. .

In the evaluation, the following criteria were used in comparison with the bubble amount of polyoxyethylene lauryl ether sulfate (P = 3). ◎: Many bubbles ○: Same bubbles ×: Little bubbles 2) Feeling of use Using a hair bundle (30 g), wash with a 10% solution of each sample, rinse with tap water, and then 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 men and women was calculated, and when the average value was 2.5 or more (○), when the average value was 2.4 to 1.5 (△),
The case of 1.4 or less was judged as (x). In addition, the following criteria were used for evaluation. 3: Excellent 2: Normal 1: Inferior

Examples 1-3 and Comparative Examples 1-2 Various compounds were evaluated for their performance. Table 1 shows the results.

[0025]

[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 of Synthesis Example 2 8 (% 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) 7.5 This shampoo is hypoallergenic to the skin, has good lathering, In addition, there was little sliminess during rinsing, the skin after rinsing was light, and the feel in use was good.

Example 5 Body soap Compound of Synthesis Example 3 20 (% by weight) Na lauroylglutamate 5 Coconut fatty acid diethanolamide 2 Ethylene glycol fatty acid ester 3 Ethanol 3 Propylene glycol 5 Dye, flavor Suitable amount Purified water Balance ━━━━━━ ＰＨ pH (undiluted solution) 6.0 This body soap is less irritating to the skin and rich when used. There was foaming, and there was little slimy feeling during rinsing and little feeling of remaining on the skin, and the feel during use was good.

Example 6 Detergent Composition for Vegetables and Vegetables Compound in Synthesis Example 1 12 (% by weight) Polyoxyethylene lauryl alcohol (p = 10) 13 Amidopropyltrimethylamine oxide laurate 3 Ethanol 5 Dye, Fragrance Appropriate amount Purified water Balance ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ pH (undiluted solution) 7.0 This dishwashing vegetable detergent is Irritating,
Foaming and detergency were good, and the feel upon use was also good.

Example 7 Cloth detergent composition Alcohol ethoxylate 20 (% by weight) (synthetic secondary alcohol, p = 8) Alcohol ethoxylate 5 (C ₁₂ alcohol, p = 12) Compound of Synthesis Example 4 7.5 Triethanolamine 3 Sodium chloride 1.5 Ethanol 2 Propylene glycol 3 Purified water Balance ｐＨ pH ( Undiluted solution) 7.0 This clothing detergent was hypoallergenic to the skin, had a strong detergency, and had good foaming during washing.

Claims (2)

[Claims] 1. An anionic surfactant comprising a hydroxyalkyl glyceryl ether carboxylic acid compound represented by the following general formula (1). Embedded image 2. A detergent composition comprising at least one anionic surfactant according to claim 1.