JPH11106370A - Production of quaternary ammonium salt good in color tone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound good in color tone and useful as a base agent for fabric softeners, hair conditioners and the like by reacting a tertiary amine with a quaternizing agent in the presence of a solvent at a specific temperature and subsequently distilling off the solvent. SOLUTION: This method for producing a quaternary ammonium salt of formula III (D is a 1-4C alkyl or a hydroxyalkyl; X is an anion) (e.g. a compound of formula IV) comprises reacting 1 mole of a tertiary amine of formula I [R<1> is a 1-35C alkyl or an alkenyl; (x) is 2-6; A and B are each a 1-6C alkyl, a hydroxyalkyl or the like) (e.g. a compound of formula II) preferably in an amount of 1 mole with a quaternizing agent preferably in an amount of 0.95-2 fold-moles in a solvent at 60-80 deg.C preferably for 3-7 hr and subsequently distilling out a part of the solvent preferably by the use of a thin film type evaporator. The amount of the solvent distilled out therein is preferably 1-20 wt.% based on the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a quaternary ammonium salt. More specifically, the present invention relates to a method for producing a quaternary ammonium salt useful as a base for a softener such as a cloth or a conditioning agent for hair in a good hue.

[0002]

2. Description of the Related Art
A commercially available product as a fabric softener or a hair conditioning agent is a quaternary ammonium salt having two long-chain alkyl groups in one molecule such as di (hardened tallowalkyl) dimethylammonium chloride. Is a composition containing as a base. However, the quaternary ammonium salt has a problem in that when the residue after treatment is released into the natural world such as a river, it accumulates almost without biodegradation. Methyl bis (hardened tallow alkanoyloxyethyl) 2-hydroxyethylammonium methyl sulfate and dimethylbis (alkanoyloxyethyl) ammonium chloride are commercially available as improved products, and these are produced in comparison with the above quaternary ammonium salts. Although the degradability is improved, it cannot be said that the base material has sufficient flexibility and environmental safety.

The present inventors have provided a quaternary ammonium salt which imparts excellent flexibility to fibers and hair and has good biodegradability, as represented by the following general formula (II):

[0004]

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[Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having ^{1 to} 35 carbon atoms. x: represents an integer of 2 to 6. A, B: the same or different, each represent an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms or wherein _{-C y H 2y O- (YO)} Z -R,
A group represented by ² or a group represented by the formula -C _x H _2x NHCOR ¹ ; Here, R ¹ and x have the same meanings as above, R ² represents a group represented by the formula —COR ¹ or H 2, y is an integer of 2 to 6, Y is a straight or branched chain having 2 to 3 carbon atoms. A chain alkylene group is represented, and z is a number of 0 to 20 representing an average addition mole number of the alkylene oxide. D: represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. X: represents an anionic group. ] Quaternary ammonium salt represented by
A sufficiently satisfactory hue could not be obtained by the conventional production methods, and it was difficult to use it as it was, thus requiring a purification step.

Accordingly, an object of the present invention is to provide a fiber or hair having excellent flexibility and a biodegradability of 4th degree.
It is an object of the present invention to provide a method for producing a quaternary ammonium salt in a good hue state which can be sufficiently used in actual use without a special purification step.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the fourth most suitable for the above-mentioned object has been obtained.
A method for producing a quaternary ammonium salt has been found, and the present invention has been completed. That is, the present invention provides a compound represented by the general formula (I):

[0008]

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[Wherein, R ¹ , A, B, x: have the above meanings. ]
The tertiary amine represented by is quaternized with a quaternizing agent in the presence of a solvent to produce a quaternary ammonium salt represented by the general formula (II). The present invention further provides a method for producing a quaternary ammonium salt having a good hue, wherein a part of the solvent used is distilled off after the reaction.

[0010]

Embodiments of the present invention will be described below in detail.

In the tertiary amine represented by the general formula (I) of the present invention, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 35 carbon atoms, preferably 7 carbon atoms. To 23, more preferably a straight-chain alkyl group or straight-chain alkenyl group having 11 to 21 carbon atoms.

Specific examples of the acyl group represented by R ¹ CO— include acetic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, isostearic acid, oleic acid, linoleic acid, arachinic acid, behenic acid, erucic acid, lignoceric acid, serotinic acid, montanic acid, melicic acid, tallow fatty acid, coconut oil fatty acid, these hardened fatty acids, and mixtures thereof And acyl groups derived from lower alkyl esters such as methyl esters and ethyl esters thereof, and tallow fatty acids, coconut oil fatty acids, and acyl groups derived from these hardened fatty acids or lower alkyl esters thereof. preferable.

[0013] A and B are the same or different, each represent an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms or a group or the formula represented by the formula _{-C y H 2y O- (YO)} Z -R 2, -C _x H _2x NH
A group represented by COR ¹ (R ¹ , R ² , x, y, Y, and z have the above-mentioned meanings) is shown. Specific examples of the alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms include: Examples include groups such as methyl, ethyl, propyl, butyl, hexyl, and hydroxyethyl, preferably methyl, ethyl, and hydroxyethyl groups, and more preferably a methyl group.

Y represents a linear or branched alkylene group having 2 to 3 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. Also,
The z Y's may be the same or different.

X and y are the same or different and each represents an integer of 2 to 6, preferably an integer of 2 to 3. z represents a number of 0 to 20 indicating the average number of added moles of the alkylene oxide, preferably 0 to 10, and more preferably 0 to 5.

Specific examples of the tertiary amine represented by the general formula (I) include the following.

[0017]

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In the present invention, the tertiary amine represented by the above general formula (I) is quaternized with a quaternizing agent in the presence of a solvent, and if necessary, an ion exchange resin or the like is used. To obtain a quaternary ammonium salt represented by the general formula (II).

In the general formula (II), specific examples of the alkyl or hydroxyalkyl group having 1 to 4 carbon atoms represented by D include groups such as methyl, ethyl, propyl, butyl and hydroxyethyl. Is a methyl, ethyl or hydroxyethyl group, more preferably a methyl group. Preferred as the anionic group represented by X are halogen atoms, sulfates, carbonates, alkyl carboxylates which may be substituted with a hydroxyl group having 1 to 4 carbon atoms, or alkyl sulfates having 1 to 4 carbon atoms (CH ₃ SO ₄ , C ₂ H ₅ SO ₄ etc.), and more preferably a Cl anion or a CH ₃ SO ₄ anion.

The following are specific examples of the quaternary ammonium salt represented by the general formula (II).

[0021]

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[0022]

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In the present invention, the quaternization reaction is carried out at 60 to 80 ° C.
Preferably, it is performed at a temperature of 65 to 75 ° C. If the quaternization reaction temperature is lower than 60 ° C., the reaction yield decreases, and if it exceeds 80 ° C., a quaternary ammonium salt having good hue cannot be obtained. The reaction time of the quaternization reaction in the present invention is not particularly limited, but is preferably 3 to 7 hours.

In the quaternization reaction of the present invention, the quaternizing agent is preferably 0.5 to 10 times, more preferably 0.95 times, 1 mole of the tertiary amine represented by the general formula (I).
Use up to twice the molar amount. Examples of the quaternizing agent used herein include lower alkyl halides such as methyl chloride, and di-lower alkyl sulfates such as dimethyl sulfate and diethyl sulfate.

The solvent used in the quaternization reaction of the present invention includes water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone and the like, and ethyl alcohol and isopropyl alcohol are preferred. The amount of the solvent is 10 to the tertiary amine represented by the general formula (I).
~ 50% by weight is preferred.

In the present invention, after performing such a quaternization reaction, a part of the solvent used, preferably
1 to 20% by weight, more preferably 2 to 10% by weight, of the quaternary ammonium salt is distilled off. As a method of distilling off the solvent, topping under normal atmospheric pressure or reduced pressure,
Although a method using a thin-film evaporator is exemplified, a method using a thin-film evaporator is preferable. By thus distilling off a part of the solvent after the reaction, the hue of the obtained quaternary ammonium salt after storage is improved.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The percentages in the examples are on a weight basis unless otherwise specified.

Example 1 N- (3-hardened tallow alkanoylaminopropyl) -N
-(Hardened tallow alkanoyloxyethyl) -N-methylamine 240.7 g (0.4 mol) and ethyl alcohol 83.3 g
Was charged into a 1 liter autoclave equipped with a nitrogen bubbling tube and sealed. The inside of the autoclave was replaced with nitrogen (pressure 0.3 MPa to normal pressure, repeated 5 times), the temperature was raised to 50 ° C, and stirring was started. Next, 22.2 g of methyl chloride (0.44 mol, 1.1 equivalent times of amine) was injected, and the temperature was raised to 65 ° C.
A time reaction was performed. After completion of the reaction, residual pressure blowing was performed.
This product had a total amine value of 1.5 and an amine conversion of 9
It was 7.6%. The color of the obtained quaternary ammonium salt was Gardner 1.

Next, the reaction product was heated to about 80 ° C. under nitrogen bubbling (flow rate of nitrogen: 50 to 100 ml / min), and then topped, whereby 13.9 g of ethyl alcohol (4th (5% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was 1 or less Gardner.

Further, 60 g of this quaternary ammonium salt is placed in a 100 ml container capable of replacing with nitrogen, and the oxygen concentration in the system is reduced to 1%
The following was stored in a 60 ° C constant temperature bath for 60 days. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 2 A quaternary compound was prepared in the same manner as in Example 1 except that 24.2 g of methyl chloride (0.48 mol, 1.2 equivalent times of the amine) was injected and the quaternization reaction was carried out at 65 ° C. for 6 hours. An ammonium salt was obtained. The resulting reaction product had a total amine value of 0.5 and an amine conversion of 99.
% Or more, and the hue was Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 3 26.26 g of methyl chloride (0.52 mol, 1.3 equivalent times with respect to amine)
And a quaternary ammonium salt was obtained in the same manner as in Example 1 except that the quaternization reaction was carried out at 65 ° C. for 5 hours.
The total amine value of the obtained reaction product is 0.4, and the reaction rate of amine is
It was 99% or more, and the hue was Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 4 A quaternary compound was prepared in the same manner as in Example 1 except that 30.3 g (0.60 mol, 1.5 equivalent times of amine) of methyl chloride was injected and the quaternization reaction was carried out at 65 ° C. for 5 hours. An ammonium salt was obtained. The resulting reaction product had a total amine value of 0.4 and an amine conversion of 99.
% Or more, and the hue was Gardner 1-2.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1-2. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. 4th after storage
The hues of the quaternary ammonium salts were Gardner 2-3, which were hues sufficiently usable as softeners and hair conditioning agents.

Example 5 A quaternary ammonium salt was obtained in the same manner as in Example 2 except that the quaternization reaction was performed at 75 ° C. for 4 hours. The resulting reaction product had a total amine value of 0.4, an amine conversion of 99% or more, and a hue of Gardner 1-2.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 2-3, which was a hue that could be sufficiently used as a softener and a hair conditioning agent.

Comparative Example 1 A quaternary ammonium salt was obtained in the same manner as in Example 2 except that the quaternization reaction was performed at 85 ° C. for 4 hours. The resulting reaction product had a total amine value of 0.3, an amine conversion of 99% or more, and a hue of Gardner 4.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 4. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 5 to 4, which was a color that could not be used as a softener and a hair conditioning agent.

Comparative Example 2 A quaternary ammonium salt was obtained in the same manner as in Example 2 except that the quaternization reaction was performed at 95 ° C. for 3 hours. The resulting reaction product had a total amine value of 0.3, an amine conversion of 99% or more, and a hue of Gardner 6.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 6. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 7 to 8, which was a color that could not be used as a softener or hair conditioning agent.

Comparative Example 3 Example 2 was repeated except that the quaternization reaction was carried out at 105 ° C. for 3 hours.
As above, a quaternary ammonium salt was obtained. The resulting reaction product had a total amine value of 0.3, an amine conversion of 99% or more, and a hue of Gardner 8.

Next, the reaction product was topped under the same conditions as in Example 1, and the same amount of ethyl alcohol as in Example 1 was distilled off. The color of the obtained quaternary ammonium salt was Gardner 8. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 9, which was a color that could not be used as a softener or hair conditioning agent. .

Example 6 A quaternary reaction was carried out in the same manner as in Example 2 to obtain a quaternary ammonium salt. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1. Next, the reaction product is cooled to an autoclave temperature of 60 to
Reduce the pressure gradually while maintaining the temperature at 65 ° C.
13.9 g of ethyl alcohol (5 to quaternary ammonium salt)
%) Was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1-2.

Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 2-3, which was a hue that could be sufficiently used as a softener and a hair conditioning agent.

Example 7 A quaternary reaction was carried out in the same manner as in Example 2 to obtain a quaternary ammonium salt. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1. Next, the reaction product was topped with a laboratory thin film evaporator. That is, after the completion of the reaction, cooled to 55 ℃,
The residual pressure was blown, and the reaction product was taken out to a dropping funnel capable of replacing with nitrogen. The thin-film evaporator is purged with nitrogen, the above-mentioned dropping funnel is connected to the sample feed line while keeping the evaporator wall temperature at 55 to 75 ° C and the degree of vacuum in the system at 200 to 500 hPa, and the feed amount is 30 to 80 ml. / Min, and about 13 g of ethyl alcohol (about 5% based on the quaternary ammonium salt) was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1.

Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 1-2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 8 A quaternary ammonium salt was obtained in the same manner as in Example 2 except that the amount of ethyl alcohol was changed to 72.2 g. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1, and 2.8 g of ethyl alcohol (1% based on the quaternary ammonium salt) was distilled off. The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 3, which was a hue that could be sufficiently used as a softener and a hair conditioning agent.

Example 9 A quaternary ammonium salt was obtained in the same manner as in Example 2 except that the amount of ethyl alcohol was changed to 77.7 g. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 8.3 g of ethyl alcohol (3% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 10 A quaternary ammonium salt was obtained in the same manner as in Example 2 except that the amount of ethyl alcohol was changed to 97.2 g. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 27.8 g of ethyl alcohol (10% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 11 Example 2 was repeated except that the amount of ethyl alcohol was changed to 124.9 g.
As above, a quaternary ammonium salt was obtained. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 55.5 g of ethyl alcohol (20% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 12 The procedure of Example 2 was repeated, except that 83.3 g of isopropyl alcohol was used instead of ethyl alcohol as the solvent.
A quaternary ammonium salt was obtained. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 13.9 g of isopropyl alcohol (5% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 2, which was a color that could be sufficiently used as a softener and a hair conditioning agent.

Example 13 N- (3-hardened tallow alkanoylaminopropyl) -N
-(Hardened tallow alkanoyloxyethyl) -N-hydroxyethylamine 269.4 g (0.4 mol) and ethyl alcohol 86.9 g were charged into a 1 liter autoclave equipped with a nitrogen bubbling tube and sealed. The inside of the autoclave was replaced with nitrogen (pressure 0.3 MPa to normal pressure, repeated 5 times), the temperature was raised to 50 ° C, and stirring was started. Then methyl chloride
24.2 g (0.48 mol, 1.2 equivalent times of amine) was injected and 65
C., and the reaction was carried out for 6 hours.

After completion of the reaction, residual pressure blowing was performed. The total amine value of this product was 0.8, and the conversion of the amine was 98.6%. The color of the obtained quaternary ammonium salt was Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 14.5 g of ethyl alcohol (5% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 2-3, which was a hue that could be sufficiently used as a softener and a hair conditioning agent.

Example 14 A quaternary compound was prepared in the same manner as in Example 13 except that 30.3 g of methyl chloride (0.6 mol, 1.5 equivalent times with respect to amine) was injected and the quaternization reaction was carried out at 65 ° C. for 5 hours. An ammonium salt was obtained. The resulting reaction product had a total amine value of 0.5 and an amine conversion of 99.
% Or more, and the hue was Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 14.5 g of ethyl alcohol (5% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 3 to 2, which was a hue that could be sufficiently used as a softener and a hair conditioning agent.

Comparative Example 4 A quaternary ammonium salt was obtained in the same manner as in Example 13 except that the quaternization reaction was performed at 95 ° C. for 4 hours. The reaction product obtained had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 6.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 14.5 g of ethyl alcohol (5% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 6-7. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 8 to 7, which was a color that could not be used as a softener and a hair conditioning agent.

Example 15 262.6 g (0.4 mol) of N, N-bis (3-hardened tallow alkanoylaminopropyl) -N-methylamine and 84.8 g of ethyl alcohol were charged into a 1 liter autoclave equipped with a nitrogen bubbling tube, and sealed. did. The inside of the autoclave was replaced with nitrogen (pressure 0.3 MPa to normal pressure, repeated 5 times), the temperature was raised to 50 ° C, and stirring was started. Then methyl chloride
24.2 g (0.48 mol, 1.2 equivalent times of amine) was injected and 65
C., and the reaction was carried out for 6 hours. After completion of the reaction, residual pressure blowing was performed. The total amine value of this product was 0.6, and the conversion of the amine was 99.0%. The color of the obtained quaternary ammonium salt was Gardner 1.

Next, the reaction product was topped under the same conditions as in Example 1 to distill off 14.1 g of ethyl alcohol (5% based on the quaternary ammonium salt). The color of the obtained quaternary ammonium salt was Gardner 1-2. Further, this quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 2-3, which was a hue that could be sufficiently used as a softener and a hair conditioning agent.

Comparative Example 5 N- (3-hardened tallow alkanoylaminopropyl) -N
-(Hardened tallow alkanoyloxyethyl) -N-methylamine 240.7 g (0.4 mol) and 69.4 g of ethyl alcohol were charged into a 1 liter autoclave and sealed. The inside of the autoclave was replaced with nitrogen (pressure 0.3 MPa to normal pressure, repeated 5 times), the temperature was raised to 50 ° C, and stirring was started. Next, 22.2 g (0.44 mol, 1.1 equivalent times of amine) of methyl chloride was injected thereinto, heated to 65 ° C., and reacted for 7 hours. After the reaction,
Residual pressure blowing was performed. The total amine value of this product was 1.7, and the conversion of the amine was 97.6%. The color of the obtained quaternary ammonium salt was Gardner 1.

The obtained quaternary ammonium salt was prepared in Example 1.
Was stored under the same conditions as described above. The color of the quaternary ammonium salt after storage was Gardner 13 to 14, which was a color that could not be used as a softener and a hair conditioning agent.

Comparative Example 6 A quaternary compound was prepared in the same manner as in Comparative Example 5 except that 24.2 g of methyl chloride (0.48 mol, 1.2 equivalents to the amine) was injected and the quaternization reaction was carried out at 65 ° C. for 6 hours. An ammonium salt was obtained. The resulting reaction product had a total amine number of 0.6 and an amine conversion of 99.
% Or more, and the hue was Gardner 1.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The color of the quaternary ammonium salt after storage was Gardner 13 to 14, which was a color that could not be used as a softener and a hair conditioning agent.

Comparative Example 7 26.26 g of methyl chloride (0.52 mol, 1.3 equivalent times of amine)
And a quaternary ammonium salt was obtained in the same manner as in Comparative Example 5 except that the quaternization reaction was carried out at 65 ° C. for 5 hours.
The resulting reaction product has a total amine value of 0.6 and an amine conversion of
It was 99% or more, and the hue was Gardner 1-2.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 15 to 16, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 8 A quaternary compound was prepared in the same manner as in Comparative Example 5 except that 30.3 g of methyl chloride (0.60 mol, 1.5 equivalent times with respect to amine) was injected and the quaternization reaction was carried out at 65 ° C. for 5 hours. An ammonium salt was obtained. The resulting reaction product had a total amine value of 0.5 and an amine conversion of 99.
% Or more, and the hue was Gardner 1-2.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 16 to 17, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 9 A quaternary ammonium salt was obtained in the same manner as in Comparative Example 6, except that the quaternization reaction was carried out at 75 ° C. for 4 hours. The resulting reaction product had a total amine value of 0.4, an amine conversion of 99% or more, and a hue of Gardner 1-2.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 18 or higher, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 10 A quaternary ammonium salt was obtained in the same manner as in Comparative Example 6, except that the quaternization reaction was performed at 85 ° C. for 4 hours. The resulting reaction product had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 4.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 18 or higher, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 11 A quaternary ammonium salt was obtained in the same manner as in Comparative Example 6, except that the quaternization reaction was performed at 95 ° C. for 3 hours. The resulting reaction product had a total amine value of 0.2, an amine conversion of 99% or more, and a hue of Gardner 6.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 18 or higher, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 12 N- (3-hardened tallow alkanoylaminopropyl) -N
-(Hardened tallow alkanoyloxyethyl) -N-hydroxyethylamine 269.4 g (0.4 mol) and ethyl alcohol 72.4 g were charged into a 1 liter autoclave equipped with a nitrogen bubbling tube and sealed. The inside of the autoclave is purged with nitrogen (pressure 0.3 MPa to normal pressure, repeated 5 times),
C. and the stirring was started. Then 24.2 g of methyl chloride
(0.48 mol, 1.2 equivalent times with respect to amine), and the mixture was heated to 65 ° C. and reacted for 6 hours. After completion of the reaction, residual pressure blowing was performed. The total amine value of the product was 0.7, and the conversion of the amine was 98.8%. The color of the obtained quaternary ammonium salt was Gardner 1.

The obtained quaternary ammonium salt was prepared in Example 1.
Was stored under the same conditions as described above. The hue of the quaternary ammonium salt after storage was Gardner 16 to 17, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 13 A quaternary compound was prepared in the same manner as in Comparative Example 12 except that 30.3 g (0.60 mol, 1.5 equivalent times of amine) of methyl chloride was injected and the quaternization reaction was carried out at 65 ° C. for 5 hours. An ammonium salt was obtained. The resulting reaction product had a total amine number of 0.6 and an amine conversion of 99.
% Or more, and the hue was Gardner 1.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 18 or higher, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 14 A quaternary ammonium salt was obtained in the same manner as in Comparative Example 12 except that the quaternization reaction was performed at 95 ° C. for 4 hours. The reaction product obtained had a total amine value of 0.5, an amine conversion of 99% or more, and a hue of Gardner 6.

Next, the obtained quaternary ammonium salt was stored under the same conditions as in Example 1. The hue of the quaternary ammonium salt after storage was Gardner 18 or higher, which was a hue that could not be used as a softener and a hair conditioning agent.

Comparative Example 15 26,6 g (0.4 mol) of N, N-bis (3-hardened tallow alkanoylaminopropyl) -N-methylamine and 88.4 g of ethyl alcohol were charged into a 1 liter autoclave and sealed. Replace the autoclave with nitrogen (pressure 0.3M
Pa to normal pressure, repeated 5 times), the temperature was raised to 50 ° C., and stirring was started. Next, 24.2 g (0.48 mol, 1.2 equivalent times of amine) of methyl chloride was injected thereinto, the temperature was raised to 65 ° C., and the reaction was carried out for 6 hours. After completion of the reaction, residual pressure blowing was performed. The total amine value of this product was 0.6, and the conversion of the amine was 99.0% or more. The color of the obtained quaternary ammonium salt was Gardner 1-2.

The obtained quaternary ammonium salt was prepared in Example 1.
Was stored under the same conditions as described above. The color of the quaternary ammonium salt after storage was Gardner 12 to 13, which was a color that could not be used as a softener or a hair conditioning agent.

[0090]

According to the present invention, a quaternary ammonium salt having a good hue can be produced.

Claims (3)

[Claims] 1. A compound of the general formula (I) [Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having ^{1 to} 35 carbon atoms. x: represents an integer of 2 to 6. A, B: the same or different, each represent an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms or wherein _{-C y H 2y O- (YO)} Z -R,
A group represented by ² or a group represented by the formula -C _x H _2x NHCOR ¹ ; Here, R ¹ and x have the same meanings as above, R ² represents a group represented by the formula —COR ¹ or H 2, y is an integer of 2 to 6, Y is a straight or branched chain having 2 to 3 carbon atoms. A chain alkylene group is represented, and z is a number of 0 to 20 representing an average addition mole number of the alkylene oxide. The tertiary amine represented by the general formula (II) is quaternized with a quaternizing agent in the presence of a solvent. [Wherein, R ¹ , A, B, x: have the above-mentioned meanings. D: represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. X: represents an anionic group. When producing the quaternary ammonium salt represented by
A method for producing a quaternary ammonium salt having a good hue, wherein the reaction is carried out at a temperature of about 80 ° C., and after the reaction, a part of the solvent used is distilled off. 2. The method for producing a quaternary ammonium salt according to claim 1, wherein the solvent is distilled off using a thin film evaporator. 3. The method for producing a quaternary ammonium salt according to claim 1, wherein the amount of the solvent distilled off is 1 to 20% by weight based on the quaternary ammonium salt.