JP2003171358A - Amidoamine derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a compound imparting excellent softness to fibers, and capable of imparting excellent softness and smoothness to the hair and having good biodegradability and environmental safeguard to toxicities of fishes and toxicities of algae, or the like. <P>SOLUTION: This invention provides an amine represented by formula (1) [wherein R<SP>1</SP>is an 8-40C alkyl group or alkenyl group; A is a 2-3C alkylene group; (n) is 0-30 as an average value; (m) is an integer of 2-3; R<SP>2</SP>is a 1-5C alkylene group; R<SP>3</SP>and R<SP>4</SP>are each hydrogen atom, a 1-5C alkylene, alkenyl group or hydroxyalkyl group or a 6-28C aryl group, arylalkyl group, or the like; (p) is an integer of 1-3; (q) and (r) are each an integer of 0-2; (p+q+r) is 3], its acid salt or its quaternary ammonium salt and a surfactant composed thereof. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention shows excellent softness to fibers, can impart excellent softness and smoothness to hair, and further has an environment such as biodegradability, fish toxicity and algae toxicity. The present invention relates to a novel amine, an acid salt thereof or a quaternary ammonium salt thereof, which has good safety.

[0002]

BACKGROUND OF THE INVENTION Various cationic surfactants and acid salts of amines have hitherto been used as conditioning agents for fibers and hair. The performance required at that time is, for example, the texture and softness at the time of finishing with a fabric softener, and with hair cosmetics,
Oily feel, flexibility to hair from wet to dry
It is smooth.

Due to such performance requirements, conventionally, a quaternary ammonium salt having a long-chain alkyl group such as stearyl trimethyl ammonium chloride or distearyl dimethyl ammonium chloride has been used as a surfactant.

However, the above-mentioned quaternary ammonium salt accumulates without being biodegraded or has an adverse effect on aquatic organisms such as fish and algae when the residue after treatment is released to the natural world such as rivers. There is a problem of environmental safety.
Examples of the improved product include quaternary ammonium salts such as methylbis (cured tallow alkanoyloxyethyl) -2-hydroxyethylammonium methylsulfate and dimethylbis (alkanoyloxyethyl) ammonium chloride, and tertiary tertiary salts such as dimethylaminopropyl-octadecaneamide. Amine acid salts are on the market. However, although these compounds have improved biodegradability, they cannot be said to be sufficiently satisfactory in flexibility and environmental safety.

The object of the present invention is to show excellent flexibility to fibers, to impart excellent flexibility and smoothness to hair, and further to be environmentally safe such as biodegradability, fish toxicity and algae toxicity. The object is to provide a compound having good properties.

[0006]

The present invention is based on the general formula (1)
Amine (hereinafter referred to as amine (1)), its acid salt or quaternary ammonium salt thereof, particularly quaternary ammonium salt represented by general formula (2) (hereinafter quaternary ammonium salt (2)) And a surfactant composed of these.

[0007]

[Chemical 3]

[Wherein R¹Is a straight chain with 8 to 40 carbon atoms
Or branched chain alkyl or alkenyl group, A is the number of carbon atoms
2-3 alkylene groups, n is a number from 0 to 30 on average, m
Is an integer of 2 to 3, R²Is a straight or branched chain having 1 to 5 carbon atoms
Branched alkylene group, R³And R ^FourAre the same or different,
Hydrogen atom or a straight or branched chain alkyl group having 1 to 5 carbon atoms
Alkyl group, alkenyl group or hydroxyalkyl group,
Ruyl or aryl group having 6 to 28 carbon atoms
Is a R group, and further R³And R^FourIs a ring, either alone or in combination
You may form. p is an integer of 1 to 3, q and r are 0 to 2
And p + q + r is 3. Note that n × p A's,
p R¹, N, m and R², Q R³, R R^FourIs the same
It may be one or different. ]

[0009]

[Chemical 4]

[Wherein R ¹ , A, n, m, R ² , R ³ ,
R ⁴ , p, q and r have the above-mentioned meanings. R ⁵ has 1 carbon
5 to a linear or branched alkyl group or hydroxyalkyl group, and X ⁻ represents an anion group. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formulas (1) and (2), R ¹ is preferably a linear or branched alkyl group or alkenyl group having 10 to 28 carbon atoms, and further having 12 to 24 carbon atoms. A straight chain or branched chain alkyl group or an alkenyl group is preferable, and a straight chain alkyl group having 12 to 24 carbon atoms is particularly preferable. n represents the average number of moles of alkylene oxide added, and the average number is preferably 0 to 20 and 5
The following is more preferable. R ² is preferably a linear or branched alkylene group having 1 to 3 carbon atoms, more preferably a linear alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

R ³ and R ⁴ are preferably a linear or branched alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or an aryl group or arylalkyl group having 6 to 10 carbon atoms, and particularly 1 to 2 carbon atoms. The straight chain alkyl group or hydroxyalkyl group is preferred. When R ³ and R ⁴ are combined to form a ring, the total number of carbon atoms is preferably 4-10.
A member ring and a 6-membered ring are particularly preferable. p is preferably an integer of 1 or 2, and 1 is particularly preferable. R ⁵ is preferably a linear or branched alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and more preferably a methyl group or an ethyl group.

X ⁻ represents an anion group, and is preferably a halogen ion, a sulfate ion, a carboxylate ion having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, or an alkyl sulfate ion having 1 to 4 carbon atoms, Further, Cl ⁻ , CH ₃ SO ₄ ⁻ and CH ₃ CH ₂ SO ₄ ⁻ are more preferable.

Examples of the amine (1) include the followings.

[0015]

[Chemical 5]

The acid salt of amine (1) is obtained by neutralizing amine (1) with at least one selected from inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Organic acids include short-chain monocarboxylic acids such as acetic acid and propionic acid; long-chain monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and erucic acid; malonic acid, succinic acid. , Dicarboxylic acids such as glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid and citric acid; polyglutamic acid and other polycarboxylic acids Carboxylic acids; acidic amino acids such as glutamic acid and aspartic acid; alkyl sulfates, alkyl sulfonates, alkyl phosphates and the like. Among these,
Inorganic acids, short-chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, acidic amino acids are preferable, and further hydrochloric acid, sulfuric acid, acetic acid, succinic acid, glycolic acid, lactic acid, malic acid,
Citric acid and glutamic acid are more preferable.

Examples of the quaternary ammonium salt (2) include the followings.

[0018]

[Chemical 6]

The amine (1), its acid salt or its quaternary ammonium salt can be produced by the following production methods 1, 2 and 3.

<Production Method 1> Production Method 1-1 General Formula (3) R ¹ -O- (AO) _n -C _m H _2m -NH ₂ (3) (wherein R ¹ , A, n and m has the same meaning as described above.), a primary amine (hereinafter referred to as primary amine (3)), and a general formula (4)

[0021]

[Chemical 7]

(In the formula, R ⁶ is a hydrogen atom or a carbon number of 1 to
4 represents a straight chain or branched chain alkyl group represented by R ² ,
p, R ³ , R ⁴ , q and r have the same meanings as described above. ) An amino compound represented by the formula (hereinafter referred to as the amino compound (4)) is reacted with a catalyst if necessary to perform amidation to obtain the amine (1). -Production method 1-2 A method of obtaining a corresponding acid salt of an amine by neutralizing the amine (1) obtained in the production method 1-1 with an acid. - a production method 1-3 amine obtained in Production method 1-1 (1), the general formula ⁽⁵⁾ R 5 -X (5) (wherein, R ⁵ and X are as defined above.) By reacting a quaternizing agent represented by (hereinafter referred to as quaternizing agent (5)),
Further, a method of obtaining a quaternary ammonium salt by performing salt exchange if necessary.

<Production Method 2> ・ Production method 2-1 Primary amine (3) and general formula (6)

[0024]

[Chemical 8]

(In the formula, R ⁷ is a linear or branched alkyl group having 1 to 4 carbon atoms, Y is a halogen atom, and R ² has the same meaning as described above.) The ester (6) is reacted with an alcoholate catalyst as needed to perform amidation, and then the compound represented by the general formula (7)

[0026]

[Chemical 9]

(Wherein R ¹ , A, n, m, R ² and Y have the same meanings as described above), and a haloamide compound (hereinafter referred to as haloamide compound (7)) is obtained. Haloamide compound and general formula (8)

[0028]

[Chemical 10]

(Where s = 3-q-r and R ³ ,
R ⁴ , q and r have the same meanings as described above. ) And an amine (hereinafter referred to as amine (8)) represented by the formula (1) to perform an amination reaction by adding an alkaline agent as necessary, and further desalting as necessary to obtain the amine (1). . -Manufacturing method 2-2 The amine (1) obtained in manufacturing method 2-1 was used as manufacturing method 1-2.
A method of obtaining a corresponding amine acid salt by neutralizing with an acid in the same manner as in. -Manufacturing method 2-3 The amine (1) obtained in manufacturing method 2-1 was used as the manufacturing method 1-3.
The method of obtaining a corresponding quaternary ammonium salt by quaternization in the same manner as in.

<Production Method 3> Haloamide compound (7) and general formula (9)

[0031]

[Chemical 11]

Where z = 2-q-r and R ³ ,
R ⁴ , R ⁵ , q and r have the same meanings as described above. ) And an amine represented by () (hereinafter referred to as amine (9)) are reacted by adding an alkaline agent as necessary, and further salt exchange is performed as necessary to obtain a quaternary ammonium salt.

In the following, amine (1), the corresponding acid salt and the fourth
The details of the method for producing the primary ammonium salt will be described.

In the production method 1-1, first, the primary amine (3) and 0.5 to 3 equivalents, preferably 0.9 to 1.5 equivalents of the amino compound (4) relative to the primary amine (3) are used. ), 50 to 250 ° C., preferably 70 to 2
0.5 to 2 at a temperature of 30 ° C. with a catalyst if necessary
Amidation is carried out for 0 hours to obtain amine (1).

As the primary amine (3) used here, long-chain alcohols such as dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosanol and tetracosanol, ethylene oxide adducts thereof and propylene. Cyanoethylation of the oxide adduct with acrylonitrile followed by hydrogenation with a catalyst, or halogenated terminal OH of the ethylene oxide adduct and propylene oxide adduct to the long chain alcohols described above, N-alkyl polyoxyethylene amine obtained by making it react with ammonia, N-alkyl polyoxypropylene amine, etc. are mentioned.

As the amino compound (4), N,
N-dimethylglycine, 3- (dimethylamino) propionic acid, 4- (dimethylamino) butanoic acid, N, N-diethylglycine, 3- (diethylamino) propionic acid, 4- (diethylamino) butanoic acid, N- (2 -Hydroxyethyl) -N-methylglycine, 3- (N- (2
-Hydroxyethyl) -N-methylamino) propionic acid, N, N-bis (2-hydroxyethyl) glycine,
Methyliminodiacetic acid, ethyliminodiacetic acid, nitrilotriacetic acid, pyrrolidinylacetic acid, N-methyl-N-phenylaminoacetic acid, N-methyl-N-tolylaminoacetic acid, etc.,
Examples thereof include methyl ester, ethyl ester and isopropyl ester.

As the amidation catalyst, in the case of the above-mentioned methyl ester, ethyl ester, isopropyl ester and the like, a general alcoholate catalyst can be used, and sodium methylate, sodium ethylate and the like can be mentioned.

In the production method 1-2, the amine (1) obtained as described above and 0.5 to 3 equivalents, preferably 0.9 to 1.5 equivalents, of the amine (1) are used. Using an acid as indicated above, at temperatures of 0-100 ° C., preferably 20-95 ° C., if necessary water or methanol,
Neutralization with a solvent such as ethanol or a lower alcohol such as isopropyl alcohol or acetone can be performed to obtain the corresponding acid salt of amine (1).

In the production method 1-3, the amine (1) obtained as described above and the amine (1) are 0.5 to 3 times mol, preferably 0.9 to 1.5 times mol of the amine (1). Quaternization is carried out at a temperature of 20 to 140 ° C., preferably 40 to 120 ° C. for 0.5 to 20 hours in the absence of solvent or in the solvent, using a molar quaternizing agent (5), and thereafter, After treatment according to the method, and if necessary, salt exchange is performed using an ion exchange resin or the like, a quaternary ammonium salt having a necessary counter ion can be obtained.

Examples of the quaternizing agent (5) used here include lower alkyl halides such as methyl chloride and di-lower alkyl sulfuric acids such as dimethylsulfate and diethylsulfate.

Examples of the solvent for the quaternization reaction include water, methanol, ethanol, isopropyl alcohol, acetone and the like.

In the production method 2-1, first, the primary amine (3) and 0.5 to 3 times mol, preferably 0.95 to 1.5 times mol, of the haloester relative to the primary amine (3). Using (6), -10 to 100 ° C, preferably 0 to
Amidation is carried out at a temperature of 70 ° C. for 1 to 40 hours using an alcoholate catalyst if necessary and a solvent if necessary to obtain a haloamide compound (7).

Then, 0.5 to 20 equivalents, preferably 0.9 to 5 equivalents of the amine (8) are used with respect to the haloamide compound (7), and the mixture is 0 to 120 ° C., preferably 10 to 8.
If necessary, an alkaline agent is added at a temperature of 0 ° C., and if necessary, a solvent is used to carry out an amination reaction for 1 to 40 hours, and further desalting is carried out if necessary to obtain an amine ( 1) can be obtained.

As the haloester (6) used here, monochloroacetic acid, 3-chloropropionic acid, 4-
Examples include methyl ester such as chlorobutyric acid, ethyl ester, isopropyl ester and the like.

Examples of the amine (8) include dimethylamine, monomethylamine, ammonia, diethylamine, monoethylamine, diethanolamine, monoethanolamine, methylethylamine, methylethanolamine, pyrrolidine, N-methylaniline and methyltolylamine. Can be mentioned.

Examples of the alcoholate catalyst include sodium methylate and sodium ethylate. Examples of the solvent include methanol, ethanol, isopropyl alcohol and the like. As an alkaline agent, NaO
H, KOH, Na carbonate, Na bicarbonate, etc. may be mentioned.

In Production Method 2-2, the amine (1) obtained as described above is neutralized with an acid in the same manner as in Production Method 1-2, and the acid of the corresponding amine (1) is obtained. A salt can be obtained.

In Production Method 2-3, the amine (1) obtained as described above can be quaternized in the same manner as in Production Method 1-3 to obtain a quaternary ammonium salt.

In the production method 3, the haloamide compound (7) and 0.5 to 20 equivalents, preferably 0.9 to 5 equivalents of the amine (9) with respect to the haloamide compound are used at 20 to 140 ° C. Preferably, at a temperature of 30 to 120 ° C., an alkali agent is added if necessary, and if necessary, a solvent is used for reaction for 0.5 to 20 hours, and desalting treatment is performed if necessary. Then, after-treatment is carried out according to a conventional method, and if necessary, salt exchange is carried out using an ion exchange resin or the like, whereby a quaternary ammonium salt having a necessary counter ion can be obtained.

As the amine (9) used here,
Examples include trimethylamine, triethylamine, triethanolamine, dimethylamine, monomethylamine, diethylamine, monoethylamine, diethanolamine, monoethanolamine, methylethylamine, methylethanolamine, pyrrolidine, N-methylaniline, and methyltolylamine.

Examples of the solvent include water, methanol, ethanol, isopropyl alcohol, acetone and the like. As an alkaline agent, NaOH, KOH, N carbonate
a, sodium hydrogencarbonate and the like.

The structures of the amine (1), its acid salt and its quaternary ammonium salt of the present invention can be confirmed by nuclear magnetic resonance spectrum and infrared absorption spectrum.

The amine (1), its acid salt and its quaternary ammonium salt of the present invention are novel surfactants, and have excellent flexibility for fibers and excellent flexibility for hair. It is also useful as a base material that can impart smoothness and has excellent environmental safety such as biodegradability, fish toxicity, and algae toxicity. That is, it can be used for a fabric softener and a hair cosmetic such as hair rinse and hair treatment.

[0054]

Example 1 Octadecanol (270.5 g) and potassium hydroxide (0.1 g) were placed in an autoclave equipped with a stirrer and a thermometer, and dehydration was carried out at a temperature of 120 ° C. and a vacuum degree of 2.6 kPa for 1 hour. Then, the mixture was cooled to a temperature of 60 ° C., 58.4 g of acrylonitrile was introduced over 1 hour, and the mixture was kept for 1 hour to complete the reaction. Next, 1.9 g of Raney nickel, 0.3 g of sodium hydroxide, and 16.1 g of ion-exchanged water were added, the hydrogenation reduction reaction was carried out at a temperature of 130 ° C. for 3 hours, and then the catalyst was removed by filtration. Further, it is purified by distillation to obtain the corresponding 3-octadecyloxypropylamine 294.
3 g was obtained.

Next, 262.1 g of 3-octadecyloxypropylamine and 82.5 g of N, N-dimethylglycine were charged into a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and a nitrogen introduction tube, and the mixture was heated at 180 ° C. The temperature was raised to. After the water produced was distilled off, the reaction was carried out at the same temperature for 8 hours, crystallization with acetone was performed, and after drying, 297.1 g of the target product (hereinafter referred to as amine i) was obtained as a pale yellow powder. ^{From the 1} H-NMR spectrum and IR spectrum, it was confirmed that amine i had the following structure.

[0056]

[Chemical 12]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.40 ppm (t, 2 H) b 3.48 ppm (t, 2 H) c 1.78 ppm (m, 2 H) d 3.38 ppm (m 2H) e 2.94 ppm (s, 2H) f 2.28 ppm (s, 6H) IR spectrum (KBr tablet) 1655 cm ⁻¹ , 1529 cm ⁻¹ , 1122 cm ⁻¹ Example 2 In a 2 liter beaker, Example 82.5 g of amine i obtained by the same method as 1 and 36.0 g of 50% lactic acid aqueous solution,
Ion-exchanged water (900 g) was added, and the mixture was stirred at a temperature of 60 ° C. for 2 hours for neutralization and then lyophilized to obtain 100.4 g of a target substance (lactate of amine i) as a white powder. ^{From the 1} H-NMR spectrum and IR spectrum, it was confirmed that the lactate salt of amine i had the following structure.

[0058]

[Chemical 13]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.40 ppm (t, 2 H) b 3.49 ppm (t, 2 H) c 1.79 ppm (m, 2 H) d 3.36 ppm (m 2H) e 3.31 ppm (s, 2H) f 2.57 ppm (s, 6H) g 4.20 ppm (q, 1H) h 1.41 ppm (w, 3H) IR spectrum (KBr tablet) 1684 cm ^-1 , 1589 cm ⁻¹ , 1122 cm ⁻¹ Example 3 Example ^{1 was} placed in an autoclave equipped with a stirrer and a thermometer.
Amine i obtained in the same manner as in 82.5 g, methyl chloride 12.1 g, isopropyl alcohol 41.3 g
Was added, and the mixture was reacted at 90 ° C. for 7 hours, crystallized with acetone, and dried to obtain 80.5 g of the target product (hereinafter referred to as quaternary ammonium salt i) as a pale yellow powder. ^{From the 1} H-NMR spectrum and IR spectrum, it was confirmed that the quaternary ammonium salt i had the following structure.

[0060]

[Chemical 14]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.38 ppm (t, 2 H) b 3.45 ppm (t, 2 H) c 1.78 ppm (m, 2 H) d 3.30 ppm (m 2H) e 4.17 ppm (s, 2H) f 3.36 ppm (s, 9H) IR spectrum (KBr tablet) 1682 cm ^-1 , 1560 cm ^-1 , 1120 cm ^-1 Example 4 Docosanol 326 instead of octadecanol 326 .6g
By using the same raw materials and conditions as in Example 1 except that was used, 345.3 g of the corresponding 3-docosyloxypropylamine was obtained.

Then, 307.0 g of 3-docosyloxypropylamine and 110.2 g of N, N-dimethylglycine ethyl ester were charged into a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and a nitrogen introduction tube. 28 as a catalyst
% Methanol solution of sodium methylate (%) was added and reacted at 100 ° C. for 3 hours while distilling off the produced ethanol, followed by crystallization with acetone and drying, followed by pale yellow powder to obtain the desired product. (Hereinafter referred to as amine ii) 34
8.8 g was obtained. ^{From 1} H-NMR spectrum and IR spectrum, it was confirmed that amine ii had the following structure.

[0063]

[Chemical 15]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.39 ppm (t, 2 H) b 3.47 ppm (t, 2 H) c 1.78 ppm (m, 2 H) d 3.37 ppm (m 2H) e 2.94 ppm (s, 2H) f 2.28 ppm (s, 6H) IR spectrum (KBr tablet) 1658 cm ^-1 , 1531 cm ^-1 , 1124 cm ^-1 Example 5 In a 2 liter beaker, the example 93.8 g of amine ii obtained in the same manner as in 4 and 36.0 g of 50% lactic acid aqueous solution,
Ion-exchanged water (900 g) was added, the mixture was stirred at a temperature of 70 ° C. for 2 hours for neutralization, and then freeze-dried to obtain 111.8 g of the desired product (lactate of amine ii) as a white powder. ^{From 1} H-NMR spectrum and IR spectrum, amine i
It was confirmed that the lactate salt of i has the following structure.

[0065]

[Chemical 16]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.41 ppm (t, 2 H) b 3.48 ppm (t, 2 H) c 1.78 ppm (m, 2 H) d 3.36 ppm (m 2H) e 3.30 ppm (s, 2H) f 2.58 ppm (s, 6H) g 4.19 ppm (q, 1H) h 1.41 ppm (w, 3H) IR spectrum (KBr tablet) 1684 cm ^-1 , 1591 cm ^-1 , 1121 cm ^-1 Example 6 3-docosyloxypropylamine 383.69 g obtained in the same manner as in Example 4 was placed in a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and a dropping funnel. Methanol 10
00 g and 9.6 g of a 28% sodium methylate methanol solution as a catalyst were added, 113.9 g of chloroacetic acid methyl ester was added dropwise over 1 hour while maintaining the temperature at 20 to 30 ° C., and then the mixture was reacted for 24 hours. After the reaction, the precipitated crystals were filtered, washed with 1000 g of methanol and dried to obtain 432.6 g of 2-chloro-N- (3-docosyloxypropyl) -acetamide as a white powder.

Next, in an autoclave equipped with a stirrer and a thermometer, 138.1 g of the above-mentioned 2-chloro-N- (3-docosyloxypropyl) -acetamide, 21.3 g of trimethylamine and 69.1 g of isopropyl alcohol.
Was charged and reacted at 65 ° C. for 5 hours. After the reaction, crystallization with acetone was performed, and after drying, 148.0 g of the desired product (hereinafter referred to as quaternary ammonium salt ii) was obtained as a white powder. ¹
From the 1 H-NMR spectrum and IR spectrum, it was confirmed that the quaternary ammonium salt ii has the following structure.

[0068]

[Chemical 17]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.39 ppm (t, 2 H) b 3.45 ppm (t, 2 H) c 1.78 ppm (m, 2 H) d 3.30 ppm (m 2H) e 4.17 ppm (s, 2H) f 3.36 ppm (s, 9H) IR spectrum (KBr tablet) 1682 cm ⁻¹ , 1561 cm ⁻¹ , 1121 cm ⁻¹ Example 7 Stirrer, thermometer, dehydration tube, In a four-necked flask equipped with a dropping funnel, 327.6 g of 3-octadecyloxypropylamine obtained by the same method as in Example 1 and 9 methanol
00 g and 3.9 g of a 28% sodium methylate methanol solution as a catalyst were added, 113.9 g of chloroacetic acid methyl ester was added dropwise over 1 hour while maintaining the temperature at 15 to 25 ° C., and the reaction was carried out for 30 hours. After the reaction, the precipitated crystals are filtered and washed with 300 g of methanol,
After drying, 371.8 g of white powder of 2-chloro-N- (3-octadecyloxypropyl) -acetamide was obtained.

Next, 161.6 g of the above-mentioned 2-chloro-N- (3-octadecyloxypropyl) -acetamide was placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
And 170.69 g of pyrrolidine and 400 g of isopropyl alcohol were added, and the mixture was reacted at 40 ° C. for 6 hours. After the reaction
After adding 33.1 g of a 48.3% sodium hydroxide aqueous solution and 50 g of ion-exchanged water, excess pyrrolidine and the solvent were distilled off under reduced pressure. Furthermore, desalting and crystallization with acetone were performed, and after drying, 124.8 g of the desired product (hereinafter referred to as amine iii) was obtained as a white powder. ^{From 1} H-NMR spectrum and IR spectrum, amine i
It was confirmed that ii has the following structure.

[0071]

[Chemical 18]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.40 ppm (t, 2 H) b 3.47 ppm (t, 2 H) c 1.79 ppm (m, 2 H) d 3.33 ppm (m 2H) e 3.14 ppm (s, 2H) f 2.60 ppm (m, 4H) g 1.80 ppm (m, 4H) IR spectrum (KBr tablet) 1655 cm ^-1 , 1522 cm ^-1 , 1122 cm ^-1 Example 8 In a four-necked flask equipped with a stirrer, thermometer, cooling tube,
2-Chloro-N- (3-octadecyloxypropyl) -acetamide 161.6 obtained by a method similar to that in Example 7.
g, N-methylaniline 257.2 g and isopropyl alcohol 395 g were added and reacted at 60 to 70 ° C. for 30 hours. After the reaction, 48.3% sodium hydroxide aqueous solution 3
After adding 3.1 g and 80 g of ion-exchanged water, excess N-methylaniline and the solvent were distilled off under reduced pressure. Furthermore, desalting and crystallization with acetone were performed, and after drying, 151.4 g of the desired product (hereinafter referred to as amine iv) was obtained as a white powder. ^{From 1} H-NMR spectrum and IR spectrum, amine i
It was confirmed that v has the following structure.

[0073]

[Chemical 19]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.40 ppm (t, 2 H) b 3.49 ppm (t, 2 H) c 1.81 ppm (m, 2 H) d 3.35 ppm (m 2H) e 3.86 ppm (s, 2H) f 3.00 ppm (s, 3H) g 6.73 ppm (w, 2H) h 7.27 ppm (m, 2H) i 6.85 ppm (t, 1H) -IR Spectrum (KBr tablet) 1653 cm ^-1 , 1523 cm ^-1 , 1122 cm ^-1 Example 9 Instead of octadecanol, 407.1 g of an ethylene oxide average 3.1 mol adduct of octadecanol was used, and distillation purification was not performed. The corresponding ether primary amine 445.6 was obtained under the same starting materials and conditions as in Example 1 except for the above.

Next, in a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and a nitrogen introduction tube, 232.1 g of the above ether primary amine and 72.2 of N, N-dimethylglycine were added.
g was charged and the temperature was raised to 190 ° C. After reacting at the same temperature for 8 hours while distilling off the produced water, excess N, N-dimethylglycine was removed by washing with water to obtain 297.1 g of the target product (hereinafter referred to as amine v) as a pale yellow solid. It was ^{From 1} H-NMR spectrum and IR spectrum, it was confirmed that amine v had the following structure.

[0076]

[Chemical 20]

¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) a 3.40 ppm (t, 2 H) b 3.48 ppm (t, 2 H) c 1.79 ppm (m, 2 H) d 3.38 ppm (m 2H) e 2.94 ppm (s, 2H) f 2.27 ppm (s, 6H) g, h 3.50 to 3.65 ppm (12.4H) IR spectrum (KBr tablet) 1655 cm ^-1 , 1527 cm ^-1 1120 cm ⁻¹ Examples 10 to 11, Comparative Example 1 Amines i and v obtained in Examples 1 and 9 and formula (1
0) Comparative amine (manufactured by Nikko Chemicals Co., Ltd.)
NIKKOL amidoamine MPS) was used to produce a hair rinse composition having the composition shown in Table 1 by a conventional method. These hair rinse agents were evaluated by the following methods. The results are shown in Table 1.

[0078]

[Chemical 21]

<Evaluation Method> After the emulsifying hair rinse agent was produced, the emulsified state after standing at room temperature (25 ° C.) for 3 hours was evaluated according to the following criteria.

◯: Emulsified gel is kept stable Δ: Slightly separated ×: Separation / Emulsion storage stability As an accelerated test of storage of hair rinse agent, stored at 50 ° C. for 3 weeks, and gel emulsified state is based on the following criteria. It was evaluated by.

○: Emulsified gel is kept stable △: Slightly separated ×: Separation / Performance during application to hair, during rinsing and after drying Japanese women who have not undergone chemical treatment such as cold perm 20 g of hair (length 20 cm, average diameter 60 μm) was bundled and washed with 5 g of shampoo. This shampoo composition has polyoxyethylene alkyl (C12)
Sodium ether sulfate (average ethylene oxide addition mole number 2.5) 15%, diethanolamide 3%, and the balance water.

Thereafter, the prepared hair rinse agent was heated to 50 ° C.,
Apply 2.0 g of the product stored for 3 weeks evenly, and about 40 seconds for 40 seconds
Rinse with running water at 0 ° C. The rich feeling during application and rinsing and its durability, flexibility, smoothness, soft feeling after drying, and combing feeling were sensory-evaluated by five specialized panelists based on the following criteria.

A: 4 or more people answered that they are effective B: 3 people answered that it was effective C; 2 people answered that it was effective D; 1 or less respondents answered

[0084]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toru Kato             Kao Co., Ltd. 1334 Minato, Wakayama City, Wakayama Prefecture             Inside the laboratory F-term (reference) 4C083 AC072 AC121 AC302 AC352                       AC582 AC851 AC852 AD151                       BB01 BB53 CC39 EE01 EE06                       EE07 EE21                 4H006 AA01 AA03 AB12 AB68 AB72                       BJ50 BP10 BU32 BV22                 4L033 AB01 AC02 AC15 BA46 BA86

Claims (4)

[Claims] 1. An amine represented by the general formula (1) and an acid thereof.
A salt or a quaternary ammonium salt thereof. [Chemical 1] [In the formula, R¹Is a straight or branched chain having 8 to 40 carbon atoms
Alkyl group or alkenyl group, A is an alkyl group having 2 to 3 carbon atoms
Xylene group, n is 0 to 30 on average, m is 2 to 3
Number, R²Is a linear or branched alkyl group having 1 to 5 carbon atoms.
Ren group, R³And R ^FourAre the same or different and are hydrogen atom or
Is a linear or branched alkyl group having 1 to 5 carbon atoms,
Lucenyl group or hydroxyalkyl group, or carbon number
6 to 28 aryl group or arylalkyl group is shown,
Furthermore R³And R^FourMay form a ring alone or in combination.
Yes. p is an integer of 1 to 3, q and r are integers of 0 to 2, and p
+ Q + r is 3. Note that n × p A and p R¹,
n, m and R², Q R³, R R^FourAre the same but different
You can ] 2. The quaternary ammonium salt according to claim 1, which is a compound represented by the general formula (2). [Chemical 2] [In the formula, R ¹ , A, n, m, R ² , R ³ , R ⁴ , p, q and r have the above-mentioned meanings. R ⁵ is a linear or branched alkyl group having 1 to ⁵ carbon atoms or a hydroxyalkyl group, X
^- represents an anion group. ] 3. R ¹ is a linear or branched alkyl or alkenyl group having 10 to 28 carbon atoms, and R ² is 1 carbon atom.
~ 3 linear or branched alkylene group, p is 1-2
The amine, its acid salt or its quaternary ammonium salt according to claim 1 or 2, which is an integer of 4. A surfactant comprising the amine according to any one of claims 1 to 3, an acid salt thereof or a quaternary ammonium salt thereof.