JP2818466B2 - Novel betaine compound, method for producing the same, and surfactant containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel betaine compound and a method for producing the same. More specifically, the present invention relates to a betaine compound which has a mild action on the skin and has excellent foaming and detergency, and is useful as a surfactant for washing hair or body and a method for producing the same.

[Conventional technology and its problems]

In recent years, surfactants used in detergents and the like have been demanded to have excellent properties such as biodegradability, safety, and low irritation to eyes and skin, in addition to surface activity. As surfactants satisfying these requirements, acylated amino acid surfactants and indazoline surfactants have been widely used.

However, these surfactants are generally excellent in safety and the like, but are inferior in foaming power and detergency, which are particularly important as surfactant properties, so that they themselves can be used alone as a component of shampoos and the like. In general, a combination with an anionic surfactant such as an alkyl ether sulfate or an alkyl sulfate is generally used.

Such an anionic surfactant has a strong irritating property to the skin, and may cause skin irritation. For this reason, foaming power,
There is a strong demand for an active agent having excellent detergency and high safety.

[Means for solving the problem]

In view of the above circumstances, the present inventors have conducted intensive studies on compounds having excellent detergency, foaming power, and high safety for washing hair and body, and as a result, a novel betaine compound represented by the following general formula was obtained. The inventors have found that the object of the present invention is met, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula (1): [Wherein, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group, X is H or hydroxyl group, and R ^{2 to} R ⁴ are alkyl groups having 1 to ⁴ carbon atoms. , Y is _{-CH 2 CH (OH) CH 2} SO 3 or - (CH ₂₎ 2~5 SO ₃
Is shown. n represents 0 or an integer of 1 to 5; when n = 1, X = H or a hydroxyl group; and when n = 0, 2, 3, X = H. ], A process for producing the same, and a surfactant containing the same.

 Hereinafter, the present invention will be described in detail.

There are no reports on the betaine-type compound represented by the general formula (1) in conventional literatures, patents and the like, and the betaine compound of the present invention is novel.

The betaine-type compound of the present invention represented by the general formula (1) can be produced by the following two production methods <1> or <2>.

Production method <1>"Amination" For the primary amine, the general formula (2) [In the formula, Z represents a halogen atom, X represents H or a hydroxyl group, R ^{2 to} R ⁴ 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
Has the same meaning as described above. Is reacted using 1 to 3 moles of the compound represented by
General formula (3) [Wherein, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group, X is H or hydroxyl group, and R ^{2 to} R ⁴ are alkyl groups having 1 to ⁴ carbon atoms. And A represent OH, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. n has the same meaning as described above. ] The compound represented by these is produced.

"Betainization" Then, the compound (3) and the general formula (4) ZCH ₂ CH (OH) CH ₂ SO ₃ M (4) [wherein, Z represents a halogen atom and M represents an alkali metal. The metal salt of 3-halo-2-hydroxypropylenesulfonic acid represented by the formula (1) is reacted with the compound (4) in an amount of 1 to 3 moles relative to the compound (3), or formula _{(5) Z (CH 2)} 2~5 SO 3 M (5) wherein, Z and M are as defined above. The compound (5) can be produced by reacting the compound (5) with the compound (3) in an amount of 1 to 3 moles relative to the compound (3).

The reaction example of the present invention is specifically shown by the following formula.

(Wherein R ¹ , X, and n have the same meaning as described above.) The reaction between the primary amine and the compound (2) is usually carried out by dropping the primary amine into an aqueous solution of the compound (2). pH 8
It is preferable to keep it at 12. For this purpose, an alkali solution such as sodium hydroxide or potassium hydroxide is charged into the reaction solution as needed. During the reaction, the pH of the reaction system
Is maintained in the above range in order to react the primary amine with the compound (2). For this purpose, it is preferable to be on the alkaline side of pH 8 or more in terms of reaction rate,
When it exceeds, hydrolysis of the compound (2) occurs, which is not preferable. The reaction proceeds at room temperature, but the higher the temperature, the faster the reaction. However, when the temperature and the pH are high, the hydrolysis of the compound (2) is promoted, so that the temperature is 100 ° C or lower, preferably 90 ° C or lower.

In the method of the present invention, the molar ratio of the compound (2) to the primary amine is usually from 1/1 to 3/1, preferably from 1.1 / 1 to 3/1.
1.5 / 1. When the amount of the compound (2) is smaller than this range, the reaction rate decreases, and when the amount of the compound (2) is larger than this range, a large amount of the compound (2) or a hydrolyzate of the compound (2) remains in the reaction mixture. It is not preferable. The end point of the reaction between the primary amine and the compound (2) can be confirmed by analyzing the remaining amount of the primary amine in the reaction solution by using high performance liquid chromatography. Subsequently, an aqueous solution of the compound represented by the general formula (4) or (5), which has been prepared in advance, is added dropwise to perform betaine formation. Then, the above-mentioned alkaline aqueous solution was pH 8-12,
The pH is preferably adjusted to 9 to 11, while maintaining the temperature at 50 to 100 ° C, preferably 70 to 90 ° C. Temperature is 50 ℃
Below, the rate of betaine formation is slow, and at 100 ° C. or higher, hydrolysis of the compound represented by the general formula (4) or (5) is promoted.

In the method of the present invention, the molar ratio of the compound represented by the general formula (4) or (5) to the compound (3), which is the precursor of the betaine compound, is usually 1/1 to 3/1, preferably
1.1 / 1 to 1.5 / 1. When the amount of the compound (4) or (5) is smaller than this range, the reaction rate is decreased. When the amount of the compound (4) or (5) is larger than this range, the compound (4) or (5) or the compound (4) is used. Alternatively, a large amount of the hydrolyzate (5) remains in the reaction mixture, which is not preferable.

The reaction time for amination in the method of the present invention varies depending on the applied temperature and pH, but generally requires 1 to 12 hours. The reaction time of the subsequent betaine formation also varies depending on the applied temperature and pH, but is generally 1 to
It takes 12 hours.

The reaction solution in the method of the present invention may be any of an aqueous solution or a mixed solution of the 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" Primary amine and general formula (6) [Wherein, R ^{2 to} R ⁴ are an alkyl group having 1 to ⁴ carbon atoms, A is OH,
It represents a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. With a glycidylalkylammonium salt represented by the general formula (7): [In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group, R ^{2 to} R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, A is OH, halogen atom Or an alkyl sulfate group having 1 to 4 carbon atoms. ] The compound shown by these is obtained.

Next, betaine conversion is carried out under the same conditions as described in the above production method <1> to obtain a desired betaine compound (1).

 The present manufacturing method is specifically shown by the following formula.

(Wherein R ¹ and M have the same meanings as described above) In the reaction of the glycidyltrialkylammonium salt represented by the general formula (6) with a primary amine, the compound represented by the general formula (6) The molar ratio with the primary 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, the compound represented by the general formula (6) or the hydrolyzate of the general formula (6) is contained in the reaction mixture. Undesirably remains in a large amount.
The reaction temperature is 30 to 120 ° C, preferably 50 to 90 ° C.
If the reaction temperature is lower than this range, the reaction rate is low, and if it is higher than this range, coloring or the like occurs, which is not preferable. The reaction between the primary amine and the glycidyltrialkylammonium salt (6) is carried out by adding an appropriate amount of an aqueous alkali solution to maintain the reactivity and to advance a certain reaction.
Is preferably maintained at 8 to 12. If the pH is below this range, the reaction rate will be low, and if it is outside this range, a large amount of by-products will be produced and the yield will decrease.

In the production method <2>, the conditions for betaine formation are as described in the production method <1>.

The reaction of the present invention may be all performed in air or in an inert gas atmosphere, but is preferably performed in an inert gas atmosphere in terms of coloring and the like.

The primary amine R ¹ NH ₂ (R ¹ has the same meaning as described above) used in the present invention includes, for example, octylamine,
Decylamine, dodecylamine, tetradecylamine,
Examples include hexadecylamine, octadecylamine, oleylamine, behenylamine, isostearylamine, and coconut aliphatic amine.

The betaine compound of the formula (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, detergency, and low irritation. It can be used not only as a hair washing base but also as a body washing base.

〔Example〕

Next, the present invention will be described in detail based on examples,
The scope of the present invention is not limited by these.

Example 1 Amination [Synthesis of Compound (3)] 185 g of dodecylamine (MW 185), 200 g of ion-exchanged water and ethanol were placed in a one- and four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel. 100g was charged. Thereafter, the mixture was heated to 75 ° C. with stirring. next,
While maintaining the above temperature, insert the pH electrode into the
An aqueous solution of sodium hydroxide was added dropwise to adjust the pH to 10. next,
489 g of a 50% aqueous solution of 3-chloro-2-hydroxypropylenetrimethylammonium salt (MW 188) was added dropwise over 2 hours. During this period, 40% sodium hydroxide was appropriately added dropwise to maintain the pH at 10. After dropping of 3-chloro-2-hydroxypropylenetrimethylammonium salt is completed, pH
Heating and stirring were continued while maintaining the value of 10, and the remaining amount of dodecylamine was confirmed every hour by high performance liquid chromatography.

Six hours after the completion of dropping of 3-chloro-2-hydroxypropylenetrimethylammonium salt, the concentration of dodecylamine in the system became 1%, and the process proceeded to the next step, betaine formation.

Betaine [Synthesis of Compound (1)] Next, after heating the above mixture to 80 ° C, 655 g of a previously prepared 30% aqueous solution of 3-chloro-2-hydroxypropylenesulfonic acid sodium (MW 196.5) was added. It was dropped in 2 hours. During this period, a 40% alkaline aqueous solution was appropriately added dropwise to maintain the pH at 10. While maintaining the pH 10 and continuing the heating and stirring, the reaction was performed by high performance liquid chromatography until the concentration of the betaine precursor compound (3) in the system became 1%, and the reaction was terminated.

After the reaction solution was purified using an electrodialysis apparatus, a part thereof was evaporated to dryness, and the compound of the formula (1), N-dodecyl-N- (3-trimethylammonio-) was analyzed by IR analysis and mass spectrometry. 2-hydroxypropylene) amino-2-
Hydroxypropylene sulfonate (having the following structural formula) was obtained.

Results of IR analysis and mass spectrometry <IR analysis> Strong absorption specific to sulfonate ion was observed at 1200 cm ^-1 (8.33 µ).

<Mass spectrometry>Instrument; JEOL Ltd. SX-102 type mass spectrometry Measurement conditions; Introduction method Direct; Ionization method FAB (Fast Atom Bomberdment) Analysis result; Molecular weight of fragment ion 439 102 58 Three main peaks 439 was the parent ion peak of (M + 1), confirming that it was a betaine compound having the above structure.

Example 2 The same procedure as in Example 1 was carried out except that tetradecylamine was used as the raw material amine, and the obtained compound was confirmed to have the following structure in the same manner as in Example 1.
The test results of the foaming power, detergency, skin irritation and the like are shown in Table 1 together with the results of Example 1.

Example 3 It carried out like Example 1 except using 3-chloropropylene trimethyl ammonium salt as a raw material. Confirm that the obtained compound has the following structure,
The test results of the foaming power, detergency, skin irritation and the like are shown in Table 1 together with the results of Example 1.

Results of IR analysis and mass spectrometry <IR analysis> Strong absorption specific to sulfonate ion was observed at 1200 cm ^-1 (8.33 µ).

<Mass Spectrometry> The analysis was performed under the same conditions as in Example 1.

423 (M + 1), which is the parent ion peak, was observed, confirming that the betaine compound had the above structure.

Example 4 The same conditions as in Example 1 were used except that sodium 2-bromoethanesulfonate was used as a raw material for betaine formation. It was confirmed that the obtained compound had the following structure, and the test results such as foaming power, detergency, and skin irritation were shown in Table 1 together with the results of Example 1.

Results of IR analysis and mass spectrometry <IR analysis> Strong absorption specific to sulfonate ion was observed at 1200 cm ^-1 (8.33 µ).

<Mass Spectrometry> The analysis was performed under the same conditions as in Example 1.

A parent ion peak of 409 (M + 1) was observed, confirming that the betaine compound had the above structure.

Example 5 The same operation as in Example 1 was performed except that oleylamine was used as a primary amine and propane sultone was used as a raw material for betaine formation. Table 1 shows the test results of the obtained compounds having the following structures, such as foaming power, detergency, and skin irritation, together with the results of Example 1.

Results of IR analysis and mass spectrometry <IR analysis> Strong absorption specific to sulfonate ion was observed at 1200 cm ^-1 (8.33 µ).

<Mass Spectrometry> The analysis was performed under the same conditions as in Example 1.

A parent ion peak of 505 (M + 1) was observed, confirming that the betaine compound had the above structure.

Test Examples • Test method for skin irritation As a test method for skin irritation, a 24-hour closed patch test was performed on humans. That is, a band test adhesive bandage impregnated with 0.1% of a 0.2% aqueous solution containing a surfactant as an active ingredient was applied to 20 subjects for 24 hours, and the irritation was determined 24 hours after removal of the adhesive. As a result of determination, those showing clear erythema were defined as positive, and the positive rate was shown.

・ Foaming power 4 so that the final concentration is 0.2% as a surfactant effective component.
希 釈 The sample was diluted with DH hard water and measured by a reverse stirring method. The measurement was carried out at 40 ° C. with the addition of 0.3% lanolin, and the results were indicated by the amount of foam (ml).

-Detergency test 5% x 5cm wool muslin cloth with 2% carbon black
Soil of almost the same composition as scalp fat containing (paraffin 12%, wax ester 21%, triglyceride 26%, higher fatty acids
32%, cholesterol 5%, monoglyceride 2%) is applied uniformly and dried. Use this stained cloth with activator effective component 0.
About 1000ml containing 500ml of 6%, pH7.0, 4 ゜ DH detergent solution
And shaken for 6 minutes in a constant temperature bath at 40 ° C., rinse the contaminated cloth well in running water, and after drying, measure the reflectance. The cleaning rate is determined by the following equation.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1/92 C11D 1/92 // A61K 7/075 A61K 7/075 7/50 7/50 C07C 211/63 C07C 211/63

Claims (4)

(57) [Claims] 1. The general formula (1) [Wherein, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group, X is H or hydroxyl group, and R ^{2 to} R ⁴ are alkyl groups having 1 to ⁴ carbon atoms. , Y is _{-CH 2 CH (OH) CH 2} SO 3 or - (CH ₂₎ 2~5 SO ₃
Is shown. n represents 0 or an integer of 1 to 5; when n = 1, X = H or a hydroxyl group; and when n = 0, 2, 3, X = H. ] The betaine compound represented by these. Wherein the aliphatic primary amine R ¹ NH ₂ (R ¹ represents a straight or branched chain alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group.) And the general formula (2) [In the formula, Z represents a halogen atom, X represents H or a hydroxyl group, R ^{2 to} R ⁴ 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 of 1 to 5; when n = 1, X = H or a hydroxyl group; and when n = 0, 2, 3, X = H. And a compound represented by the general formula (3) [Wherein, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group, X is H or hydroxyl group, and R ^{2 to} R ⁴ are alkyl groups having 1 to ⁴ carbon atoms. And A represent OH, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. n has the same meaning as described above. To produce a compound represented by the formula
And general formula (4) ZCH ₂ CH (OH) CH ₂ SO ₃ M (4) wherein Z represents a halogen atom and M represents an alkali metal. A metal salt of 3-halo-2-hydroxypropylenesulfonic acid represented by the general formula (5) or Z (CH ₂ ) _2-5 SO ₃ M (5) wherein Z and M has the same meaning as described above. 2. The method for producing a betaine compound according to claim 1, wherein the metal salt of the compound represented by the formula is reacted. Wherein the aliphatic primary amine R ¹ NH ₂ (R ¹ represents a straight or branched chain alkyl group having from 8 to 22 carbon atoms, alkenyl or hydroxyalkyl group) and the general formula (6) [Wherein, R ^{2 to} R ⁴ are an alkyl group having 1 to ⁴ carbon atoms, A is OH,
It represents a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. With a glycidylalkylammonium salt represented by the general formula (7): [However, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group, R ^{2 to} R ⁴ are an alkyl group having 1 to ⁴ carbon atoms, A is OH, a halogen atom or It represents an alkyl sulfate group having 1 to 4 carbon atoms. To produce a compound represented by the following formula:
And general formula (4) ZCH ₂ CH (OH) CH ₂ SO ₃ M (4) wherein Z represents a halogen atom and M represents an alkali metal. A metal salt of 3-halo-2-hydroxypropylenesulfonic acid represented by the general formula (5) or Z (CH ₂ ) _2-5 SO ₃ M (5) wherein Z and M has the same meaning as described above. Wherein the metal salt of the compound represented by the general formula (8) is reacted: Wherein R ¹ , R ² , R ³ and R ⁴ have the same meaning as described above, and Y is -C
_{H 2 CH (OH) CH 2} SO 3 or - indicates a (CH ₂₎ 2~5 SO _3. ] The manufacturing method of the betaine compound represented by these. 4. A surfactant containing the betaine compound according to claim 1.