JPH0489468A - Novel betaine compound, its production and surfactant containing the same - Google Patents

Abstract

NEW MATERIAL:The betaine compound of formula I [R<1> is straight or branched-chain 8-22C alkyl, alkenyl or hydroxyalkyl; X is H or hydroxyl; R<2> to R<4> are 1-4C alkyl; Y is CH2CH(OH)CH2SO3 or (CH2)2-5SO3; (n) is 0 or 1-5; X is H or hydroxyl when (n) is 1 and X is H when (n) is 0, 2, 3, 4 or 5]. EXAMPLE:N-(3-dodecyloxypropyl)-N-(3-trimethylammonio-2-hydroxypropyl) amino-2-hydroxypropylene sulfonate. USE:It has mild action to the skin and excellent frothing power and detergency, and is useful as a surfactant for the cleaning of hair and body. PREPARATION:The compound of formula I can be produced e.g. by reacting a compound of formula II with acrylonitrile, hydrogenating the product and reacting the obtained compound with a compound of formula III (Z is halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel betaine compound and a method for producing the same. More specifically, the present invention relates to a novel betaine compound useful as a surfactant for hair or body cleansing, which has a mild effect on the skin and has excellent foaming and detergent powers, and a method for producing the same.

[Problems to be solved by conventional techniques and inventions] In recent years,
Surfactants used in detergents and the like are required to have excellent surfactant properties as well as other properties such as biodegradability, safety, and low irritation to the eyes and skin. Acylated amino acid type surfactants and imidacilline type surfactants have come to be widely used as surfactants that meet these requirements.

However, although these surfactants generally have excellent safety, they have poor foaming power and cleaning power, which are particularly important as surfactant properties, so they cannot be used alone as ingredients in shampoos, etc. Generally, it is used in combination with anionic surfactants such as alkyl ether sulfates and alkyl sulfates.

Such anionic surfactants are highly irritating to the skin and may cause skin irritation.

For this reason, there is a strong desire for an active agent that has excellent foaming power and detergency, and is highly safe.

[Means to solve the problem]

In view of the above-mentioned current situation, the present inventors conducted intensive studies to obtain a surfactant that has excellent detergency and foaming power for hair and body washing, and is highly safe. We have discovered a new betaine compound and completed the present invention.

That is, the present invention provides - formation (1) [wherein R1 is a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group, X is H or a hydroxyl group, and R2-R4 are each Carbon number 1
~4 alkyl group, Y is -clhcH(OH)C12S
Indicates O3 or -(CH2)Z~5S03. n represents O or an integer from 1 to 5; when n = 1, X = ) l or a hydroxyl group; when n = o, 2, 3, 4.5, X
= indicates H. The present invention provides a novel hetain compound represented by the following formula, a method for producing the same, and a surfactant containing the same.

The present invention will be explained in detail below.

There is no report regarding the hetain compound represented by the above-mentioned -formation (1) in conventional literature, patents, etc., and the hetain compound of the present invention is novel.

The hetain compound of the present invention represented by -formation (1) above can be produced by the following two production methods <1> or <2>.

Production method 1>"Amination" General formula (2) % formula % (2) [In the formula, R1 has the above-mentioned meaning. ] is reacted with acrylonitrile in the presence of a basic catalyst to form ethernitrile, and then hydrogenated in the presence of a hydrogenation catalyst to form - (3) % formula % (3) [In the formula, "has the above-mentioned meaning.] To obtain an ether amine represented by the following, the general formula (4) % formula % [In the formula, Z is a halogen atom and A is OH, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms;
R' and n have the same meanings as above. ] A compound represented by is reacted using 1 to 3 times the mole, and -
Formation (5) A compound represented by the formula % [wherein R'+X, R'' to R'+A, and n have the same meanings as above] is produced.

"Betaination" Next, the compound represented by -formation (5) and -formation (
6) % formula % (6) [In the formula, Z has the same meaning as above and represents an alkali metal as in the former. ] The metal salt of 3-halo 2-hydroxypropylene sulfonic acid represented by is reacted in an amount of 1 to 3 times the mole of the compound represented by -formation (5), or the -
A compound represented by formation (5) and -formation (7) Z(CHz)z~SSO,M (7)
[In the formula, Z and old have the same meanings as above. ] By reacting a metal salt of haloalkylene sulfonic acid represented by 1 to 3 times the molar amount of the compound represented by -formation (5), hetaine represented by -formation (1) above can be obtained. compounds can be manufactured.

A reaction example of the present invention is specifically shown below using a formula.

CH.

e θ R'0CH2CH2CH2NH2+ CICH2CH
CH2-N-CH3C1 (3)
0) I CHz (4゛) OHCH3 (5') (In the formula, R1 has the same meaning as above.) Ether amine and the compound represented by the above-formation (4) (Compound (4)
) is usually carried out by dropping the ether amine into an aqueous solution of compound (4), and then keeping the pH at 8 to 12. For this purpose, an alkaline solution such as sodium hydroxide or potassium hydroxide is added to the reaction solution as necessary. The reason for maintaining the pH of the reaction system within the above range during the reaction is to allow the ether amine to react with the compound (4). For this purpose, an alkaline pH of 8 or more is preferable from the viewpoint of reaction rate, and a pH of over 12 is not preferable because it causes hydrolysis of compound (4).

The reaction proceeds even at room temperature, but the higher the temperature, the faster the reaction. However, if the temperature and pH are high, the hydrolysis of compound (4) will be accelerated, so the temperature should be lower than 100°C, preferably 9°C.
It is below 0°C.

In the method of the present invention, the molar ratio of compound (4) and ether amine is usually 1/1 to 3/1, preferably 1/1 to 3/1.
．． It is 1/1 to 1.5/1. From this range, the compound (4
) If the amount of compound (4) is less than this range, the reaction rate will decrease, and if the amount of compound (4) is more than this range, a large amount of compound (4) or a hydrolyzate of compound (4) will remain in the reaction mixture, which is not preferable.

The end point of the reaction between ether amine and compound (4) can be confirmed by analyzing the remaining amount of ether amine in the reaction solution using high performance liquid chromatography. The prepared compound represented by general formula (6) or (7) (hereinafter referred to as compound (
6), (abbreviated as (7)) is added dropwise to convert into betaine. Then, add the above alkaline aqueous solution to pH 8.
~ 12, preferably pH 9 ~ 11,
Meanwhile, the temperature is 50~100''C1 preferably 70~9
Keep at 0°C. When the temperature is below 50°C, the rate of hetainization is slow, and when the temperature is above 100°C, compound (6) or (7)
) hydrolysis is promoted.

In the method of the present invention, the molar ratio between compound (6) or (7) and the compound represented by general formula (5) (hereinafter abbreviated as compound (5)), which is the betaine compound precursor, is usually 1.
/1 to 3/1, preferably 1.1/1 to 1.5/
It is 1. When the amount of compound (6) or (7) is less than this range, the reaction rate decreases, and when the amount of compound (6) or (7) is more than this range, compound (6) or (7) or compound (6) Otherwise, a large amount of the hydrolyzate of (7) remains in the reaction mixture, which is not preferable.

The reaction time for amination in the process of the invention varies depending on the applied temperature, p)l, but is generally between l and 12
It takes time. Further, the reaction time for betaination in the latter stage also varies depending on the applied temperature and pH, but generally takes 1 to 12 hours.

The reaction solution in the method of the present invention may be either an aqueous solution or a mixed solution of an aqueous solution and a lower alcohol such as ethanol or isopropyl alcohol, or a diol such as 1,3-propanediol or propylene glycol.

Production method <2>"Amination" After reacting the primary alcohol represented by -formation (2) above with acrylonitrile in the presence of a basic catalyst to form ethernitrile, in the presence of a hydrogenation catalyst is hydrogenated to obtain an ether amine represented by the above -formation (3), and this ether amine and -formation (8) [wherein R
2-R', A have the above meanings. ] by reacting with a glycidyl trialkylammonium salt represented by -
i Formula (9) % Formula % (9) [In the formula, R1, RZ to R', and A have the above-mentioned meanings.

] is obtained.

Next, hetainization was carried out under the same conditions as described in the above production method <1> to form -formation (10) [wherein R', R
2-R', Y have the above meanings. ] is obtained.

This manufacturing method can be concretely expressed by the following formula.

R”OH+ CHz = CHCN-→R0CHzCt
hCNH0 -n R'OCH, CH2CH2NH'2z (8゛) OHCH3 (5") 0■ CH (1゛) (wherein R1 has the same meaning as above) - Formation (8)
In the reaction of the glycidyl trialkylammonium salt represented by (hereinafter abbreviated as compound (8)) and ether amine, the molar ratio of compound (8) to ether amine is 1/1 to 3/1. When the molar ratio is below this range, the reaction rate decreases, and when the molar ratio exceeds this range, a large amount of compound (8) or a hydrolyzate of compound (8) remains in the reaction mixture, which is preferable. do not have. The reaction temperature is 30 to 120°C, preferably 50 to 90°C.

When the reaction temperature is below this range, the reaction rate is slow, and when it exceeds this range, coloring etc. occur, which is not preferable. In the reaction between the ether amine and the compound (8), in order to ensure reactivity and allow the reaction to proceed to a certain level, it is preferable to prepare an appropriate amount of aqueous alkaline solution and maintain the pH at 8 to 12. If pl+ is less than this range, the reaction rate will be slow, and if it exceeds this range, many by-products will be produced and the yield will be reduced.

In addition, in the present production method 2>, the conditions for betaineization are as described in the production method 1>.

All reactions of the present invention may be carried out in air or in an inert gas atmosphere, but an inert gas atmosphere is preferable from the viewpoint of coloring and the like.

Examples of the aliphatic primary alcohol represented by the above-mentioned formula (2) used in the present invention include octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, oleyl alcohol, behenyl alcohol, and isostearyl alcohol. , coconut aliphatic alcohol, and the like.

The betaine compound represented by -formation (1) obtained by the method of the present invention has surface activity, and a surfactant containing such a compound as a main component has excellent foaming power and detergency, and is low irritation. Because of this, it can be used not only as a base for hair washing, but also as a hair washing base.
It can also be used as a base for body cleansing.

[Example] Next, the present invention will be described in detail based on Examples, but the scope of the present invention is not limited by these.

Example 1 An 11-volume container equipped with an amino stirrer, a cooling tube, a thermometer, and a dropping funnel (5).
4 Dodecyl alcohol (1186) in a flask
186 g and 3.4 g of potassium hydroxide (156,1) were charged. Thereafter, the above mixture was heated to 100°C while stirring.
While maintaining this temperature, reduce the pressure of the reaction system (30
mmHg), and after confirming that potassium hydroxide had dissolved, the temperature was lowered to 60°C, and the pressure was returned to normal pressure with nitrogen. Next, 53g of acrylonitrile (MW 53.1)
was added dropwise over about 1 hour while maintaining the temperature at around 60°C, and then aged for 1 hour. Afterwards, the reaction product was taken out and the entire amount was charged into a No. 11 autoclave together with 5 g of a 10% caustic soda aqueous solution and 1.5 g of Raney Ni catalyst. After that, hydrogen was introduced, the pressure valve was adjusted to maintain the pressure at 25 atm, and the temperature was increased to 130° while stirring.
The reaction mixture was heated to C.C., and the reaction was carried out for 3 hours while maintaining this temperature, and then cooled. The reaction mixture is then filtered and then distilled.
200 g of N-(3-dobusyloxypropyl)amine was obtained.

Obtained N-(3-dobusyloxypropyl)amine 20
0 g (0.82 mol) was added to an 11-volume -4 tube flask equipped with a stirrer, cooling tube, and dropping funnel, and 200 g (0.82 mol) of ion-exchanged water was added.
g and 100 g of ethanol. after that,
The mixture was heated to 75°C without stirring. next,
While maintaining the above temperature, insert the pH electrode into the liquid and
A 0% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 10. Next, 309 g of a 50% aqueous solution of 3chloro-2-hydroxypropyltrimethylammonium chloride (MW 188) was added dropwise over 2 hours. During this time, 40% sodium hydroxide was appropriately added dropwise to maintain the pH at 10.

After the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, heating and stirring were continued while maintaining pH 1o, and N-(3dodecyloxypropyl ) The remaining amount of amine was confirmed.

Six hours after the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, N-(3
When the concentration of amine (-dobusyloxypropyl) in the system reached 1%, the process proceeded to the next step, betaination.

Betaine Addition (1) Next, after heating the above mixture to 80°C, 537 ml of a 30% aqueous solution of sodium 3-chloro-2-hydroxypropylenesulfonate (MW 196.5) prepared in advance was added.
g was added dropwise over 2 hours. During this time, a 40% alkaline aqueous solution was appropriately added dropwise to maintain the pH at 10. While maintaining pH 10 and continuing heating and stirring, the reaction was carried out by high performance liquid chromatography until the concentration of betaine precursor compound (5) in the system reached 1%, and then the reaction was terminated.

After this reaction solution was purified using an electrodialyzer, a portion was evaporated to dryness, and the -formation (1
) compound, N-(3-F decyloxypropyl)-N-
(3-)Samethylammonio-2-hydroxypropyl)amino 2-hydroxypropylene sulfonate (having the following structural formula) was obtained.

OHC1(3 C+ 2H250(CH2) 3-N-CH2CHCH
2-N-CH3 <IR analysis> Strong absorption peculiar to sulfonic acid ions was observed at 1200 cm-' (8,33μ).

<Mass spectrometry> Equipment: 5X-102 mass spectrometry type manufactured by JEOL Ltd. Measurement conditions: Introduction method Direct: Ionization method F A B (Fast AtomBo
mberdment) Analysis results: Three main molecular weight peaks of fragment ions were observed, and 497 was the parent ion peak of group +1), confirming that it was a betaine compound with the above structure.

Example 2 The same procedure as in Example 1 was carried out except that tetradecyl alcohol was used instead of dodecyl alcohol as the raw material alcohol, and it was confirmed in the same manner as in Example 1 that the obtained compound had the following structure. did.

OHCH:I Cl4H290(CH2)3-N-CH2CHCH2-
N-CH3HzCH3 IO-CH-CH2SO3゜Example 3 Same as Example 1 except that 2-bromoethanesulfonic acid sorta was used instead of 3-chloro-2-hydroxypropylenesulfonic acid sodium t) as the raw material for betaination. It was conducted under the following conditions. It was confirmed that the obtained compound had the following structure.

OHCH3 CI 2HzsO(CHz)z-N-CHzCHCHz
-N-CI(3CH, CH3 CH2-5O,.

IR3,'<IRanalysis> Strong absorption peculiar to sulfonic acid ions was observed at 1200 cm-' (8,33u).

Mass spectrometry It was carried out under the same conditions as in Example 1.

A parent ion peak of 467 (M+1) was observed, confirming that it was a betaine compound with the above structure.

Test Examples The hetain compounds of the present invention obtained in Examples 1 to 3, and as control compounds, compounds conventionally known to be extremely mild to the skin (control compounds 1 and 2 below)
The skin irritation, foaming power,
The detergency was tested by the following method.

The results are shown in Table 1.

<Control compounds> Control compound 1: Softazoline CH (N-cocoyl-N'hydroxyethyl N'-sodium carboxymethylethylenediamine) manufactured by Yoken ■ Control compound 2: Alanone ALE (N-lauroyl-N methyl-β manufactured by Yoken ■) - Sodium alanine) Control compound 3: Emar TD manufactured by Kao ■ (triethanolamine lauryl sulfate) <Test method> - Test method for skin irritation As a test method for skin irritation, a 24-hour closed patch test was conducted on humans. . That is, 0.11III1 of a 0.2% aqueous solution containing a surfactant as an active ingredient was administered to 20 subjects.
A patch test bandage impregnated with was applied for 24 hours, and 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.

・Foaming power Surfactant active ingredient so that the final concentration is 0.2%4
°D) l Diluted with hard water and measured by inversion stirring method. The measurement was carried out at 40°C with the addition of 0.3% lanolin, and the results were expressed as foam volume (-).

・Cleaning power test 5cm x 5cn+ wool muslin cloth containing 2% carbon black and Dirty Halafin 1, which has almost the same composition as scalp oil.
2%, wax esters 21%, triglycerides 26%
, higher fatty acids 32%, cholesterol 5%, and monoglycerides 2%) were applied uniformly and dried. This contaminated cloth was placed in a stainless steel cylinder of approximately 1000 d containing 500 mm of detergent solution with active agent active content of 0.6% and PU of 7.0.4° DH, and placed in a constant temperature bath at 40° C. for 6 minutes. Shake;
Rinse the contaminated cloth thoroughly under running water and measure the reflectance after drying. Determine the cleaning rate using the following formula.

Cleaning rate (%) Chapter 1 Table

Claims (1)

[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group,
is H or a hydroxyl group, R^2 to R^4 are each an alkyl group having 1 to 4 carbon atoms, and Y is -CH_2CH(OH)
CH_2SO_3 or -(CH_2)_2_~_5SO
_3 is shown. n represents 0 or an integer of 1 to 5; when n = 1, X = H or a hydroxyl group; n = 0, 2,
3, 4, and 5 indicate X=H. ] A betaine compound represented by 2. General Formula (2) R^1OH (2) [In the formula, R^1 represents a linear or branched C8-C22 alkyl group, alkenyl group, or hydroxyalkyl group. ] After reacting the aliphatic primary alcohol represented by the following with acrylonitrile, hydrogenation is performed to obtain the general formula (3) R^1OCH_2CH_2CH_2NH_2 (3) [wherein R^1 has the same meaning as above. [In the formula, Z is a halogen atom, and X is a H or hydroxyl group]. , R^2 to R^4 each represent an alkyl group having 1 to 4 carbon atoms, and A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms. n represents 0 or an integer from 1 to 5, n=1
In the case of X=H or a hydroxyl group, n=0, 2
, 3, 4, and 5 indicate X=H. ] By reacting with a compound represented by the general formula (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) n has the same meaning as above. ] This compound is then combined with the general formula (6) ZCH_2CH(OH)CH_2SO_3M(6) [wherein Z has the same meaning as above and M represents an alkali metal. [In the formula,
Z and M have the same meanings as above. 2. The method for producing a betaine compound according to claim 1, wherein a metal salt of a haloalkylene sulfonic acid represented by the following formula is reacted. 3. General Formula (2) R^1OH (2) [In the formula, R^1 represents a linear or branched C8-C22 alkyl group, alkenyl group, or hydroxyalkyl group. ] After reacting the aliphatic primary alcohol represented by the following with acrylonitrile, hydrogenation is performed to obtain the general formula (3) R^1OCH_2CH_2CH_2NH_2(3) (wherein R^1 has the same meaning as above. [In the formula, R^2 to R^4 each represent the number of carbon atoms]. 1 to 4 alkyl group, A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms.] By reacting with a glycidyl trialkylammonium salt represented by the general formula (9) ▲ Formula, There are chemical formulas, tables, etc. ▼ (9) [In the formula, R^1, R^2 to R^4, and A have the same meanings as above.] A compound represented by is produced, and then this compound and
General formula (6) ZCH_2CH(OH)CH_2SO_3M(6) [In the formula, Z represents a halogen atom and M represents an alkali metal. [In the formula,
Z and M have the same meanings as above. General formula (10) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (10) [In the formula, R^1, R^2, R^3 and R^4 have the same meanings as above, and Y is -CH_2CH(OH)CH_2SO
Indicates _3 or -(CH_2)_2_~_5SO_3. ] A method for producing a betaine compound represented by: 4. A surfactant containing the betaine compound according to claim 1.