JPH0489461A - Novel ether betaine compound and surfactant composed thereof - Google Patents

Abstract

NEW MATERIAL:The ether betaine compound of formula I (R<1> is 6-22C alkyl, alkenyl or hydroxyalkyl; R<2> and R<3> are 1-3C alkyl; (9 is 1-3; (m) is 3-5). EXAMPLE:N-(3-dodecyloxypropyl)-N,N-dimethylammoniobutanate. USE:A surfactant giving extremely low irritation to the skin and having high frothing power and detergency. PREPARATION:The compound of formula I can be produced by reacting an alcohol of formula II (especially preferably a 10-14C n-alcohol) with acrylonitrile of formula III in the presence of an alkaline substance (e.g. KOH), reacting the resultant compound of formula IV with H2 in the presence of a Raney-nickel catalyst to obtain a compound of formula V, reacting the compound with a 1-3C aldehyde and H2, saponifying the obtained compound of formula VI with a compound of formula VII in the presence of KOH and adjusting the pH of the product with hydrochloric acid.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an ether betaine compound, and more specifically, a novel interface that is hypoallergenic, has excellent foaming power and detergency, and is useful as a detergent. This invention relates to an ether betaine compound which is an activator.

[Problems to be solved by conventional techniques and inventions] Recently,
For shampoos, due to the increasing number of hair washes and awareness of the problem of rough hands when washing dishes, there is an extremely high demand for bases that are hypoallergenic, non-allergenic, and have high foaming and cleaning power. Since conventional bases cannot meet all of these requirements, products are formulated with various boosters to prevent rough hands or protect hair. As a result, there were many problems, such as an increase in the cost of the product and an inability to obtain product stability at high and low temperatures.

Conventionally, amphoteric surfactants have been known as surfactants that are mildly irritating to the skin and ocular mucous membranes.

Ampholytic surfactants are blended into shampoos and dishwashing detergents by utilizing their properties, and for example, betaine as shown below is well known.

<Alkyl betaine> C.I.

■ RN　C82CO00 CR3 <Amidoalkylbetaine> 0 CHx 111° RCNHC3H6N CHzCOOoCH.

Hydroxysulfobetaine> CH30H However, when these amphoteric surfactants are used as surfactants in shampoos and dishwashing detergents, conventionally,
Although it is less irritating than anionic active agents such as alkyl ether sulfates (ES) and alkyl sulfates (AS) used for such purposes,
Because its detergency and foaming power are not sufficient, it is not used alone or as the main activator in detergents.
These hetain type activators were generally used in combination with ES or AS. As a result, the reality is that the hypoallergenic feature of these hetain type amphoteric surfactants cannot be fully utilized in conventional detergents.

An object of the present invention is to obtain a surfactant that is hypoallergenic and has good detergency and foaming power.

[Means to solve the problem]

In view of this current situation, the present inventors conducted intensive studies and found that
We have discovered a new surfactant that is extremely low irritation to skin, hair, etc. and has excellent detergency and foaming power, and have completed the present invention.

That is, the present invention provides an etherhetaine compound represented by the following general formula (1) and a surfactant comprising this compound.

R'-0-(CHz), l-N-(CH2), -
C-0(1) (wherein R1 represents a straight-chain or branched alkyl group, alkenyl group, or hydroxyalkyl group having 6 to 22 carbon atoms, and R2 and R3 each represent an alkyl group having 1 to 3 carbon atoms. (n is an integer of 1 to 3, and m is an integer of 3 to 5.) As the ether betaine type surfactant, Japanese Patent Application Laid-Open No. 1986-
Publication No. 89458 (Toho Chemical ■) contains the following general formula (2
) is disclosed.

(In the formula, R4 is an alkyl group or alkenyl group having 8 to 24 carbon atoms, R5, R& is an alkyl group or alkylol group having 5 or less carbon atoms, and 2 is CI)1. and/or C5Hb,p
represents an integer from 1 to 50. ) All of the compounds disclosed in this publication are of the acetate type, that is, the distance between N and 000 is one methylene chain, and according to the evaluation of the present inventors, their function as a detergent is insufficient. Furthermore, skin irritation was not necessarily low. The present inventors have found that betaine type, which has an ether Φ θ group in the alkyl chain and the distance between N and C00 in the methylene chain is 3 or more, has high performance as a surfactant and is not irritating to the skin. They found that this decreases. The above-mentioned patent publication does not contain any description suggesting such a thing, and in this respect, the present invention is sharply distinguished from the invention disclosed in the above-mentioned patent publication. Also,
There are no documents that describe this fact.

Although there are no particular limitations on the method for producing the ether betaine compound of the present invention represented by the general formula (1), it can be produced by the route shown by the following formula for boat fishing.

Ni thread catalyst R3 (wherein RI, R2, R3 have the above meanings, and X is)
＼It is a rogen atom. ) The alcohol represented by the formula R'O)l used as a raw material is a straight or branched alkyl group having 6 to 22 carbon atoms,
Alcohols having an alkenyl group or a hydroxyalkyl group are particularly preferred, and linear alcohols having 10 to 14 carbon atoms are particularly preferred.

Further, for example, those using a branched alcohol obtained by reducing Emazol 875 (manufactured by Emery Co., Ltd.) have good properties as a surfactant and are therefore preferable. The reaction and product systems can be aqueous or water-solvent systems containing lower alcohols or polyols.

Furthermore, inorganic salts are produced in the final amphotericization stage, but if these have a negative effect on the storage stability of the compounding system, they may be removed by means such as dialysis.

The ether betaine compound of the present invention represented by the general formula (1) has low skin irritation, high foaming properties, excellent detergency, and is useful as an amphoteric surfactant. In addition, in combination with the ether betaine compound of the present invention, if necessary, within the range of the blending system and blending amount that does not offset its characteristic hypoallergenicity.
For example, other surfactants such as anionic surfactants (AS, ES, etc.), nonionic surfactants, amphoteric surfactants, etc. may be used.

〔Example〕

Next, the present invention will be explained in more detail based on examples.
The scope of the present invention is not limited thereby.

Example 1 A 4 1 liter cell with stirrer, cooling tube, addition funnel and temperature needle
186g of dodecyl alcohol (MW
= 186.1 mol) and potassium hydroxide 3.4 g (Men =
56.1) was added, and the temperature was raised to 100°C without stirring. While maintaining this temperature, reduce the pressure of the reaction system (30mm
Hg) to dissolve potassium hydroxide.

After confirming complete dissolution, the temperature was lowered to 60°C and returned to normal pressure with nitrogen.

Next, 53 g (MW 53) of acrylonitrile was added dropwise over approximately 1 hour while maintaining the temperature at 60°C, and
Time aging was performed.

1! of this reaction mixture! Place in autoclave and add 1 more
5 g of 0% NaOH aqueous solution and 1.5 g of Raney Ni catalyst were also charged. After purging the system with nitrogen, hydrogen was introduced and the pressure reducing valve was adjusted to maintain the pressure at 25 atmospheres. The temperature was raised to 130° C. while stirring, and while maintaining this temperature, the reaction was carried out until the concentration of the acrylonitrile adduct of alcohol in the system became 1% or less by gas chromatography.

Next, at this temperature, 165 g of a 40% formalin aqueous solution was injected using a pressure-resistant pump over about 2 hours, followed by aging for 3 hours. After cooling, the residual pressure was blown out, the reaction mixture was taken out, and the catalyst was removed by filtration.

This reaction mixture was distilled under reduced pressure (120-150°C 10
．． 2-1, QmmHg) to obtain 260 g of N-(3-dobusyloxypropyl)-N,N-dimethylamine.

Next, 20N-(3-dobyloxyprovir)-N,N
- 250 g (0.92 mol) of dimethylamine, 250 g of ethanol and 179.4 g of ethyl 4-bromobutyrate (
MW-195,0.92 mol) was charged into a similar 4-tube flask and reacted at 80°C for 12 hours.After the reaction was completed, ethanol was removed, and 447 g of a 15% potassium hydroxide aqueous solution was charged to carry out the saponification reaction. went.

Thereafter, the pH was adjusted to 6.0 with hydrochloric acid. In this way, N-(3-dobusyloxypropyl)-N of the following structure
, an approximately 37% aqueous solution of N-dimethylammoniobutanate was obtained.

C.I.

A portion of this aqueous solution was evaporated to dryness, and it was confirmed by IR analysis and mass spectrometry that the above compound had been obtained.

lR3-, <IR analysis> Carboxylic acid ion and 111 at 1600 cm-'
Strong absorption characteristic of ether bonds was observed at 0 cm-'.

<Mass spectrometry> Equipment: 5X-102 mass spectrometer manufactured by JEOL ■Measurement conditions: Introduction method: Direct; Ionization method: F A B (Fast AtomBo
Analysis results: Fragment 358 was a molecular ion peak of (M+1), and it was confirmed that the compound was the betaine compound of the present invention.

Example 2 Synthesis was performed in the same manner as in Example 1 using myristyl alcohol instead of dodecyl alcohol as the alcohol, and N-(3tetradecyloxypropyl) with the following structure was synthesized.
-N,N-dimethylammoniobutanate was obtained. The structure was confirmed in the same manner as in Example 1.

Example 3 After methyl esterifying Emazol 875 in a conventional manner,
Isostearyl alcohol having a branched alkyl group was obtained by reduction. Using this alcohol instead of dodecyl alcohol, following the same procedure as in Example 1, N-(3
-isostearoyloxypropyl)-N,N-dimethylammoniobutanate was obtained. The structure was confirmed in the same manner as in Example 1.

Example 4 In Example 1, instead of ethyl 4-bromobutyrate, 5-
Using ethyl bromovalerate, N-(3-dobusyloxypropyl)-N,N dimethylammoniopentanate having the following structure was obtained. The structure was confirmed in the same manner as in Example 1.

Example 5 In Example 1, instead of ethyl 4-bromobutyrate, 6-
Using ethyl bromocaproate, N-(3-
Dobsiloxyprovir) N,N-dimethylammoniohexanate was obtained.

The structure was confirmed in the same manner as in Example 1.

Example 6 267.4 g of N,N-dimethylethanolamine (MW = 89.1.3 mol) and 40 g of sodium hydroxide were placed in a 4-tube flask similar to Example 1, and the temperature was raised to 130°C without stirring. did. After aging at that temperature for about 1 hour, it was cooled to room temperature. Furthermore, lauryl chloride 20
4.8 g (MW=204.8.1 mol) was added dropwise.

Aging was performed at the same temperature for about 1 hour. After ripening,
Perform vacuum distillation (130°C to 140'C10, 6 to 1
．． 0mmHg), N-(2-dobutyloxyethyl)-N
, 155 g of N-dimethylamine was obtained.

Subsequently, it was reacted with ethyl 4-bromobutyrate in the same manner as in Example 1 to obtain N-(2-dobutyloxyethyl)-N with the following structure.
, N-dimethylammoniobutanate was obtained. Example 1
The structure was confirmed in the same way.

H3 H2 Test Example The surfactants obtained in Examples 1 to 6 and the control compounds 1 to 3 shown below were evaluated for skin irritation, foaming power, and detergency by the methods shown below.

The results are shown in Table 1.

<Control Compound 1> In Example 1, instead of ethyl 4-bromobutyrate,
N-(3-dobusyloxypropyl)-N,N dimethylammonioacetate was synthesized using sodium monochloroacetate and used as control compound 1.

Control Compound 2> In Example 1, N-(3-dobusyloxyprovir)
-N-dodecyl- instead of -N,N-dimethylamine
Using N,N-dimethylamine, N-dodecyl-N,N
-dimethylammoniobutanate was synthesized and used as control compound 2.

<Control Compound 3> N-, which is conventionally known to be a hypoallergenic surfactant.
Dodenru N,N-dimethylammonioacetate was used as control compound 3.

- Test method for skin irritation As a test method for skin irritation, a 24-hour closed patch test was conducted on humans. That is, a patch test bandage impregnated with 0.1 m of a 0.2% aqueous solution containing a surfactant as the active ingredient was applied to 20 subjects for 24 hours, and the irritation was determined 24 hours after removal. . The test result was determined to be positive if it showed clear erythema, and was expressed as a positive rate. The lower the value, the lower the skin irritation.

・Foaming power As the surfactant active ingredient, the final concentration is 0.2% 4
It was diluted with °DH hard water and measured using an inversion stirring method. Measurements were carried out at 40°C with the addition of 0.3% lanolin, and the results were
J). The higher the value, the higher the foaming power.

・Cleaning power test A stain with approximately the same composition as scalp sebum (paraffin 12
%, wax ester 21%, triglyceride 26%,
32% higher fatty acids, 5% cholesterol, 2% monoglycerides) is applied evenly and dried. This contaminated cloth was placed in a stainless steel cylinder of about 10001 d containing 500 d of detergent solution with active agent active content of 0.6% and pH 7.0.4° DH, and shaken for 6 minutes in a constant temperature bath at 40°C. ,
The contaminated cloth was rinsed under running water and dried, the reflectance was measured, and the cleaning rate was determined using the following formula. The higher the value, the greater the cleaning power.

Cleaning rate (%) Table 1 [Effects of the invention] According to the present invention, it has extremely low irritation to the skin,
Moreover, a novel etherhetaine compound which is a surfactant having high foaming power and good detergency can be provided.

Claims (1)

[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 is a straight or branched alkyl group having 6 to 22 carbon atoms, alkenyl group or hydroxyalkyl group, R
^2 and R^3 each represent an alkyl group having 1 to 3 carbon atoms. n represents an integer of 1 to 3, and m represents an integer of 3 to 5. ) An ether betaine compound represented by 2. A surfactant comprising the ether betaine compound according to claim 1.