JP2625068B2 - Novel ammonium salt, process for preparing the same, intermediate amidoamine, and hair treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ammonium salt, a method for producing the same, and a hair treating agent containing the same. More specifically, it gives fibers excellent flexibility and hair has excellent flexibility and tackiness.
The present invention relates to a novel ammonium salt capable of imparting a smooth feeling and having good biodegradability, a method for producing the same, and a hair treating agent containing the same. The present invention further relates to an intermediate amidoamine for producing the ammonium salt and a method for producing the same.

[0002]

2. Description of the Related Art
Most of the products commercially available as fabric softeners or hair treatment agents are quaternary ammoniums having two long-chain alkyl groups in one molecule, such as di (hardened tallowalkyl) dimethylammonium chloride. A composition comprising a salt.

[0003] 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, the quaternary ammonium salt is hardly biodegraded and accumulates.
As an improved product, ethyl bis [ethyl (hardened tallow alkyl)]-2-hydroxyethylammonium methylsulfate has been marketed, but this product is more biodegradable than the above quaternary ammonium salt but has flexibility. Is significantly inferior. To solve this, EP-23 is used as a formulation example.
Although 9910, EP-309052 and the like are disclosed, they cannot be said to be sufficient.

[0004] Accordingly, an object of the present invention is to provide an ammonium salt which is excellent in flexibility and suitable as a flexible base having good biodegradability. Another object of the present invention is to provide an intermediate amidoamine useful for producing the ammonium salt. It is a further object of the present invention to provide a hair treatment agent which has excellent flexibility and good biodegradability.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that a specific ammonium salt is most suitable for the above object, and have completed the present invention. That is, the present invention provides a novel ammonium salt represented by the general formula (1), a method for producing the same, and a hair treatment agent containing the ammonium salt.

[0006]

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Wherein R ¹ and R ² are an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and R ³ is a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group. An alkenyl group, R ⁴ is a straight-chain or branched alkyl group or alkenyl group having 7 to 35 carbon atoms which may be substituted with a hydroxyl group, R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is 2 to 6 Integer, X represents a halogen atom, a sulfate, a carboxylate which may be substituted with a hydroxyl group having 1 to 4 carbon atoms or an alkyl sulfate having 1 to 4 carbon atoms.) In the general formula (1), R ¹ and R ² are Each is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, specifically, methyl, ethyl, propyl, butyl,
Examples include groups such as hydroxyethyl, and a methyl group is preferred.

[0008] R ³ good carbon atoms 8 to be substituted with a hydroxyl
36 linear or branched alkyl or alkenyl groups, specifically, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl,
Groups such as docosyl, 2-tetradecyloctadecyl, and 2-dodecylhexadecyl are exemplified, and octadecyl and docosyl are preferred.

R ⁴ has 7 to 7 carbon atoms which may be substituted by a hydroxyl group.
35 linear or branched alkyl or alkenyl groups, specifically, heptyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, nonadecyl,
Examples thereof include a group such as heneicosyl or a mixed alkyl group thereof, and preferably an alkyl group derived from hardened tallow fatty acid and hardened palm oil fatty acid.

R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a hydrogen atom, and groups such as methyl, ethyl, propyl, and butyl. It is.

N is an integer of 2 to 6, preferably 3
It is. X is a halogen atom, sulfate, having 1 to 1 carbon atoms
A carboxylate which may be substituted with 4 hydroxyl groups or an alkyl sulfate having 1 to 4 carbon atoms, preferably chloro or methyl sulfate.

Examples of the compound represented by the general formula (1) include the following.

[0013]

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The ammonium salt represented by the general formula (1) is
General formula (2)

[0015]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and n have the same meanings as described above)
(3) R ⁵ X (3) (wherein R ⁵ and X have the same meanings as described above), and can be produced by reacting with an acidic substance or a quaternizing agent.

As the acidic substance represented by the general formula (3),
Examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and glycolic acid. Examples of the quaternizing agent include lower alkyl halides such as methyl chloride and di-lower alkyl sulfuric acids such as dimethyl sulfate.

When reacting an amidoamine represented by the general formula (2) with an acidic substance represented by the general formula (3),
0.8 to 1.5 equivalents of the acidic substance represented by the general formula (3) with respect to the amidoamine represented by (2), water or ethanol,
The reaction may be carried out in a solvent such as isopropanol, acetone or hexane, and then post-treated according to a conventional method.
The amidoamine represented by the formula (2) is replaced by a compound represented by the formula (3):
When reacting with a quaternizing agent, the quaternizing agent represented by the general formula (3) is used in an amount of 0.5 to 2.0 at a temperature of 70 to 120 ° C. using 0.8 to 2.0 times the mol of the amidoamine represented by the general formula (2). The reaction is completed by stirring for 10 hours without solvent or in a solvent such as water, methanol, ethanol, or isopropanol, and then post-treatment may be performed according to a conventional method. If necessary, an ammonium salt having a necessary counter ion can be obtained by performing salt exchange using an ion exchange resin or the like.

The amidoamine represented by the general formula (2) used in the above reaction is also a novel substance, and examples thereof include the following.

[0020]

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The amidoamine represented by the general formula (2) is produced by the following method. That is, the general formula (4)

[0022]

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(Wherein R ¹ , R ² and n have the same meanings as described above) to a diamine represented by the general formula (5) R ³ Y (5) (wherein R ³ is as defined above) Has the same meaning, and Y represents a halogen atom.) The alkylating agent represented by the general formula (7)

[0024]

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(Wherein R ¹ , R ² , R ³ and n have the same meanings as described above). The obtained diamine is further added to the general formula (6) R ⁴ COOR ⁶ (6) (wherein, R ⁴ has the same meaning as described above, and R ⁶ represents H or an alkyl group having 1 to 3 carbon atoms.) Amidation is carried out by reacting a fatty acid or a fatty acid ester represented by the formula to obtain an amidoamine represented by the general formula (2).

The alkylating agent represented by the general formula (5) used for the alkylation in the present invention includes 1-chlorooctane, 1-bromodecane, 1-chlorododecane,
-Chlorotetradecane, 1-chlorohexadecane, 1-
Examples include chlorooctadecane, 1-chloroeicosane, 1-chlorodocosan, 1-chloro-2-tetradecyloctadecane, 1-chloro-2-dodecylhexadecane, and the like, or a mixture thereof.

The fatty acid or fatty acid ester represented by the general formula (6) used for amidation in the present invention includes octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid,
Docosanoic acid, 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-hexyldecanoic acid, 2-octyldodecanoic acid, 2-decyltetradecanoic acid, 2-dodecylhexadecanoic acid, 2-tetradecyloctadecanoic acid, 2-hexadecyleico Examples thereof include sanic acid, hardened tallow fatty acid, hardened palm oil fatty acid, methyl ester, ethyl ester, propyl ester of these fatty acids, and the like, and mixtures thereof. More preferred are hardened tallow fatty acid and hardened palm oil fatty acid.

More specifically, the production of the amidoamine represented by the general formula (2) can be explained as follows. In the alkylation to the diamine represented by the general formula (4), the diamine represented by the general formula (4) is 0.5 to 5 moles,
Preferably, 1 to 2 moles of the alkylating agent represented by the general formula (5) is added, and the alkylation reaction is performed for 0.5 to 30 hours. Then, the fatty acid or fatty acid ester represented by the general formula (6) is used in an amount of 0.5 to 4 times, preferably 0.8 to 2.0 times the mol of the obtained diamine represented by the general formula (7) without a catalyst or a catalyst. 1-30 at 100-220 ° C in the presence of
Perform amidation reaction under normal pressure or reduced pressure over time,
An amidoamine represented by the general formula (2) is obtained.

The catalyst used for the amidation of the present invention includes sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, sodium hydroxide, potassium hydroxide and the like.

The ammonium salt of the present invention represented by the general formula (1) exhibits excellent properties as a surfactant and is suitable for use as a hair treatment agent for protecting hair. The hair treatment composition of the present invention contains an ammonium salt represented by the general formula (1), and contains the ammonium salt represented by the general formula (1) in the hair treatment composition.
The content of the ammonium salt represented by the formula is the same as that in the case of using a conventionally used quaternary ammonium compound, and is preferably about 0.1 to 20% by weight, more preferably
0.1 to 10% by weight. The excess ammonium salt of the general formula (1) is washed from the hair without any problem, achieving very good wet combability and good dry combability.

The dosage form of the hair treatment agent provided by the present invention includes a hair rinse, a hair conditioner, a hair treatment, a hair pack, a hair cream, a styling lotion, a styling mousse, a conditioning mousse, a hair spray and the like. Furthermore, as a combination component constituting these hair treatment agents, in addition to conventional cationic or nonionic activators such as mono- or dialkyl quaternary ammonium salts, higher alcohols, higher esters, hydrocarbons, fatty acids, Fats and oils such as silicone oil, humectants such as glycerin and urea, cationic polymers, high molecular weight polysaccharides, high molecular weight substances such as polypeptides, lower alcohols, propylene glycol, solvents such as diethylene glycol monoethyl ether of the present invention It can be used as long as the effect is not impaired. Further, a bactericide, an emulsifier, a fragrance, a coloring agent and the like can be used in combination.

The hair treatment composition of the present invention exhibits extremely excellent flexibility to hair both when wet and dry , and furthermore , when compared to a conventional hair treatment composition containing a cationic active agent as a main component.
Gives a dry feeling without stickiness when drying . Also the general formula
The ammonium salt represented by (1) exhibits excellent performance as a fiber softening agent.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 A four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel was used.
307 g of N, N-dimethylaminopropylamine and 433 g of 1-chlorooctadecane were added and the alkylation reaction was carried out at 100 ° C. for 15 hours. After the completion of the reaction, the mixture was allowed to stand and separated to separate the upper layer, followed by purification by distillation to obtain 185 g of a diamine. Boiling point 190-200 ° C / 0.25mmHg. The above diamine 121 was placed in a four-necked flask equipped with a stirrer, thermometer, and dropping funnel.
g and 95 g of hardened tallow fatty acid were added and the temperature was raised to 180 ° C. The amidation reaction was carried out at the same temperature for 12 hours while distilling off the generated water to obtain 210 g of amidoamine. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0035]

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NMR spectrum (CDCl ₃ , internal standard TMS):
2.2ppm (s, 6H) NC H ₃ , 2.3ppm (m, 2H) C H ₂ -CO-N

[0037]

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IR spectrum (KBr tablet): 1640 cm ^-1 Example 2 An autoclave equipped with a stirrer, thermometer and pressure gauge was charged with 120 g of the amidoamine obtained in Example 1, 11 g of methyl chloride and 65 g of isopropanol (IPA). 4 hours at 5 ° C
Grading reaction was carried out to obtain 125 g of the desired quaternary ammonium salt. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0039]

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NMR spectrum (CDCl ₃ , internal standard TMS):
2.3ppm (t, 2H) C H ₂ -CO-N, 3.45ppm (s, 9H) NC H ₃

[0041]

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IR spectrum (KBr tablet): 1635 cm ^-1 Example 3 Amidoamine obtained in Example 1 in a 1 liter beaker
50 g was dispersed in 500 ml of water, and subsequently 10 ml of a 35% hydrochloric acid solution was added thereto, followed by thoroughly stirring. Thereafter, water was removed by freeze-drying to obtain 52.5 g of the desired amidoamine hydrochloride. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0043]

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NMR spectrum (CDCl ₃ , internal standard TMS):
2.3ppm (t, 2H) C H ₂ -CO-N, 2.8ppm (s, 6H) NC H ₃

[0045]

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IR spectrum (KBr tablet): 1645 cm ^-1 , 15
50 cm ^-1 Example 4 a stirrer, a thermometer, a four-neck flask equipped with a dropping funnel
307 g of N, N-dimethylaminopropylamine and 517 g of 1-chlorodocosane were added, and an alkylation reaction was performed at 100 ° C. for 20 hours. After the completion of the reaction, the mixture was allowed to stand and separated to separate the upper layer, followed by purification by distillation to obtain 185 g of a diamine. Boiling point 200-210 ° C / 0.1mmHg. 121 g of the above diamine and 59 g of lauric acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and heated to 180 ° C. The amidation reaction was carried out at the same temperature for 12 hours while distilling off generated water, to obtain 174 g of amidoamine. NMR spectrum, IR
The following structure was confirmed from the spectrum.

[0047]

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NMR spectrum (CDCl ₃ , internal standard TMS):
2.2ppm (s, 6H) NC H ₃ , 2.35ppm (m, 2H) C H ₂ -CO-N

[0049]

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IR spectrum (KBr tablet): 1640 cm ^-1 Example 5 In an autoclave equipped with a stirrer, thermometer and pressure gauge, 120 g of the amidoamine obtained in Example 4, 10 g of methyl chloride, IPA
The quaternization reaction was carried out at 80 ° C. for 5 hours to obtain 123 g of the desired quaternary ammonium salt. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0051]

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NMR spectrum (CDCl ₃ , internal standard TMS):
2.25ppm (t, 2H) C H ₂ -CO-N, 3.4ppm (s, 9H) NC H ₃

[0053]

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IR spectrum (KBr tablet): 1640 cm ^-1 Examples of the formulation of the hair treatment agent proposed in the present invention include the following.

Formulation Example 1: Hair rinse Quaternary ammonium salt synthesized in Example 2 2.0% Cetyl alcohol 3.0% Hydroxyethyl cellulose 0.2% Polyoxyethylene (10 mol) Oleyl alcohol ether 1.0% Glycerin 5.0% Polypeptide 2.0% Fragrance 0.3% Methyl paraben 0.1% Dye trace amount Purified water Residual prescription example 2: Amidoamine hydrochloride synthesized in Hair treatment Example 3 1.5% Stearyl trimethyl ammonium chloride 1.0% Dimethyl polysiloxane (500cs) 1.0% Cetyl alcohol 6.0% Liquid paraffin 3.0% Polyoxyethylene (5 mol) oleyl 0.3% alcohol ether 0.5% perfume methylparaben 0.1% dye trace purified water balance formulation example 3: quaternary ammonium salts 2.0% cetyltrimethylammonium synthesized in hair cream example 5 chloride 1.0% Se Example Stearyl alcohol 6.0% 6.0% dipropylene glycol Glycerin 10.0% Liquid paraffin 3.0% 0.3% Perfume Methylparaben 0.1% dye trace Purified water balance Formulation 4: quaternary ammonium salts 0.5% synthesized in styling lotion Example 2 Polyvinylpyrrolidone 3.0% propylene Glycol 2.0% Polyoxyethylene (20 mol) Stearyl alcohol ether 1.5% Ethyl alcohol 15.0% Fragrance 0.3% Methyl paraben 0.1% Pigment trace amount Purified water Residue Test example 1 Was gradually added and emulsified to obtain a hair rinse composition (hair treatment agent).

Composition ammonium salt 1% (compound of the present invention or control compound) Cetyl alcohol 3% Propylene glycol 3% Water Residual The hair rinse composition thus obtained was applied to hair bundles by 10% each. , Leave for 3 minutes after application, 30
Rinse with warm water at ℃ for a certain time, dry with a towel and wet
The time was evaluated. Then, the hair bundle was dried with a dryer, and the evaluation at the time of DRY was performed. The evaluation was carried out by a panel of 10 persons by the tactile sensation by hand, and evaluated according to the following criteria. The results are shown in Table 1.

Flexibility (WET, DRY) ：: Soft feeling △: Insufficient soft feeling ×: Smoothness lacking soft feeling (WET, DRY) ：: Good sliding △: Smooth sliding Good ×: Bad slippery moist feeling (WET) ○: Moisturized △: Slightly moisturized ×: Non-moistened sticky (WET, DRY) ○: No sticky Δ: Slightly sticky ×: Sticky softness (DRY) Time) ○: Smooth △: Slightly soft ×: Not soft

[0058]

[Table 1]

[0059]

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[0060]

Ammonium salt represented by the general formula (1) of the present invention exhibits flexibility, is useful as a biodegradable excellent softening base, in particular, when used as a hair treatment agent, wetting of the hair < Shows flexibility both when dry and when dry, and when dry
It shows an extremely excellent effect in a dry feeling without stickiness . Further, the amidoamine represented by the general formula (2) is useful as an intermediate in producing the ammonium salt represented by the general formula (1), and via this compound, the amidoamine represented by the general formula (1) The ammonium salt represented can be easily produced.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-57562 (JP, A)

Claims (7)

(57) [Claims] 1. An ammonium salt represented by the general formula (1). Embedded image (Wherein, R ¹ and R ² each represent an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms; R ³ represents a linear or branched alkyl group or alkenyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group; R ⁴ has 7 to 7 carbon atoms which may be substituted with a hydroxyl group;
35 linear or branched alkyl or alkenyl groups, R ⁵
Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is 2 to
An integer of 6, X is a halogen atom, sulfate, carbon number 1
A carboxylate or an alkyl sulfate having 1 to 4 carbon atoms which may be substituted with a hydroxyl group having 4 to 4 carbon atoms; ) 2. The ammonium salt according to claim ¹ , wherein R ¹ and R ² are methyl groups, and n is 3. 3. A compound of the general formula (2) ^{(Wherein, R 1, R 2, R} 3, R 4 and n are. Of the same meaning as defined above) to the amidoamine represented by the general formula (3) R ⁵ X (3) (wherein, R ⁵ And X has the same meaning as described above.) The method for producing an ammonium salt represented by the general formula (1) according to claim 1, wherein an acidic substance or a quaternizing agent represented by the formula (1) is reacted. 4. An amidoamine represented by the general formula (2). Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ and n have the same meaning as described above.) 5. The amidoamine according to claim 4, wherein R ¹ and R ² are methyl groups and n is 3. 6. A compound of the general formula (4) (Wherein, R ¹ , R ² and n have the same meaning as described above) to the diamine represented by the general formula (5) R ³ Y (5) (wherein, R ³ has the same meaning as described above) Wherein Y represents a halogen atom, and the primary amine moiety is alkylated by reacting with an alkylating agent represented by the following general formula (6): R ⁴ COOR ⁶ (6) wherein R ⁴ is Wherein R ⁶ is H or an alkyl group having 1 to 3 carbon atoms.) Wherein a fatty acid or a fatty acid ester represented by the general formula (2) is reacted. A method for producing the amidoamine represented. 7. A hair treatment agent comprising the ammonium salt according to claim 1.