JP3014558B2 - Novel ammonium salt, process for producing the same, intermediate aminoalkyloxyester, 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 can impart excellent flexibility to fibers, can impart excellent softness and non-stickiness to hair, and can provide a biodegradable ammonium salt and its production. And a hair treatment agent containing the same. Furthermore, the present invention relates to an intermediate aminoalkyloxyester 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.
Methyl bis [hardened tallow alkanoyloxyethyl] -2-hydroxyethylammonium methyl sulfate has been marketed as an improved product, which has a good biodegradability but a remarkable flexibility as compared with the quaternary ammonium salt. Inferior. EP-239910, EP-309052 and the like are disclosed as formulation examples for solving this, but they cannot be said to be sufficient yet.

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 aminoalkyloxyester useful for producing the ammonium salt. Another object of the present invention is to provide a hair treatment agent which is excellent in flexibility and has good biodegradability.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an ammonium salt of a specific aminoalkyloxyester compound is most suitable for the above-mentioned object. completed. That is,
The present invention provides an 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 by a hydroxyl group. An alkenyl group, R ⁴ is a linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms which may be substituted with a hydroxyl group, R ⁵ is H or an alkyl group having 1 to 4 carbon atoms, 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. However, R ¹ , R ² and
R ⁵ is a methyl group, R ³ is an octyl group, and R ⁴ CO is octano.
And R ¹ and R ⁵ are methyl groups and R ² is
Doxyethyl group, R ³ is oleyl group and R ⁴ CO is oleo
Except when it is an yl group. ) In the general formula (1), R ¹ ,
R ² represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, specifically, methyl, ethyl, propyl,
Examples include groups such as butyl and hydroxyethyl, and a methyl group is preferable.

R ³ represents a straight-chain or branched alkyl or alkenyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group. Specific examples include decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, hydroxyoctadecyl and the like. And preferably a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and a mixture thereof.

R ⁴ represents a straight-chain or branched alkyl group or alkenyl group having 7 to 35 carbon atoms which may be substituted by a hydroxyl group. Specifically, heptyl, nonyl, undecyl,
Examples thereof include groups such as tridecyl, pentadecyl, heptadecyl, nonadecyl, heneicosyl, hydroxyheptadecyl, and a mixture thereof, and are preferably an alkyl group derived from hardened tallow fatty acid.

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

Examples of the ammonium salt represented by the general formula (1) (hereinafter abbreviated as ammonium salt (1)) include the following.

[0012]

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The ammonium salt (1) of the present invention is produced by the following method. That is, the general formula (2)

[0014]

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(Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, provided that R ¹ and R ² are methyl groups and R ³ is an octyl group
And R ⁴ CO is an octanoyl group. )) (Hereinafter abbreviated as aminoalkyloxyester (2)) to the general formula (3) R ⁵ X (3) (wherein, R ⁵ and X have the same meanings as described above) ) (Hereinafter abbreviated as acidic substance (3) or quaternizing agent (3)).

Examples of the acidic substance (3) 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 (3) include lower alkyl halides such as methyl chloride and dimethyl sulfate. And the like.

When the acidic substance (3) is reacted with the aminoalkyloxyester (2), 0.8 to 1.5 equivalents of the acidic substance (3) with respect to the aminoalkyloxyester (2) are used.
Water or ethanol, isopropanol, acetone,
The reaction may be carried out in a solvent such as hexane and then post-treated according to a conventional method.
When the quaternizing agent (3) is reacted with (2), the quaternizing agent (3) is used in an amount 0.8 to 2.0 times the mol of the aminoalkyloxyester (2) at 0.5 to 10 at 70 to 120 ° C. The reaction is completed by stirring over a period of time without solvent or in a solvent such as water, methanol, ethanol, isopropanol, or acetone,
Thereafter, post-processing 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 aminoalkyloxyester (2) used in the above reaction is also a novel substance, and examples thereof include the following.

[0019]

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The aminoalkyloxyester of the present invention
(2) is manufactured by the following method. That is, the general formula
(Four)

[0021]

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(Wherein R ¹ , R ² and R ³ have the same meanings as above) (hereinafter abbreviated as aminoalcohol (4)) to the general formula (5) R ⁴ COOR ⁶ (5) (wherein, R ⁴ has the same meaning as above, and R ⁶ is H or C 1
And represents an alkyl group of 1 to 3. ) Represented by a fatty acid or fatty acid ester (hereinafter referred to as “fatty acid or fatty acid ester”).
(Abbreviated as (5)) to obtain an aminoalkyloxyester (2).

More specifically, the production of the aminoalkyloxyester (2) of the present invention can be explained as follows. Esterification reaction using a fatty acid or fatty acid ester (5) at a molar ratio of 1.6 to 4 times the amount of amino alcohol (4) at 100 to 220 ° C for 1 to 30 hours under normal pressure or reduced pressure in the absence or presence of a catalyst. To obtain an aminoalkyloxyester (2).

The fatty acid or fatty acid ester (5) used for the esterification 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-hexadecyleicosanoic acid, Hardened tallow fatty acids, hardened palm oil fatty acids or methyl esters of these fatty acids, ethyl esters, propyl esters and the like, or mixtures thereof,
Preferred is hardened tallow fatty acid.

The catalyst used in the esterification of the present invention includes sodium methylate, sodium ethylate,
Examples thereof include potassium methylate, potassium ethylate, sodium hydroxide and potassium hydroxide, and the amount of addition is 0.05 to 5.0% by weight based on the amino alcohol (4).

The ammonium salt (1) and the aminoalkyloxyester (2) of the present invention have an infrared absorption spectrum,
Its structure was confirmed by nuclear magnetic resonance spectrum.

The ammonium salt (1) of the present invention 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 (1) .The content of the ammonium salt (1) in the hair treatment composition is different from that of a case where a conventionally used quaternary ammonium compound is used. The same amount is preferred, about 0.1-20% by weight, more preferably 0.1-10% by weight. Excess ammonium salt (1)
Can be washed off from the hair without problems, a very good wet combability is achieved and the dry combability is also good.

Examples of the dosage form of the hair treatment agent provided by the present invention include a hair rinse, a hair conditioner, a hair treatment, a hair pack, a hair cream, a styling lotion, a styling mousse, a conditioning mousse, and a hair spray. 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 has a sticky property when dried, as compared with conventional hair treatment compositions containing a cationic active agent as a main component. Gives a dry feeling without. The ammonium salt (1) of the present invention also shows excellent performance as a fiber softening agent.

[0030]

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.
The percentages in the examples are on a weight basis unless otherwise specified.

EXAMPLE 1 130 g of 1- (N, N-dimethylamino) -2-hydroxypropyloctadecyl ether and 108 g of hardened tallow fatty acid were placed in a four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and heated to 180 ° C. Warmed. The esterification reaction was carried out at the same temperature for 10 hours while distilling off generated water, to obtain 220 g of aminoalkyloxyester. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0032]

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NMR spectrum (CDCl ₃ , internal standard TMS): 2.25 ppm (s, 6H) NCH ₃ , 2.2 ppm (m, 2H) C
H ₂ -COO- 3.5ppm (m, 4H) -C H ₂ -OC H _2- , 5.15ppm (m, 1H)
C H OCO-IR spectrum (KBr tablet): 1740 cm ^-1 , 1170 cm ^-1 Example 2 In an autoclave equipped with a stirrer, thermometer and pressure gauge, 120 g of the aminoalkyloxyester obtained in Example 1 and 11 g of methyl chloride were obtained. Then, 60 g of isopropanol was added, and a quaternization reaction was carried out at 80 ° C. for 6 hours to obtain 129 g of the target ammonium salt. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0034]

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NMR spectrum (CDCl ₃ , internal standard TMS): 2.35 ppm (t, 2H) CH ₂ —COO—, 3.4 ppm (m, 4H)
_{-C H 2 -OC H 2 - 3.5ppm} (s, 9H) NC H 3, 5.45ppm (m, 1H)
C H OCO-IR spectrum (KBr tablet): 1740 cm ^-1 , 1160 cm ^-1 Example 3 In a 1 liter beaker, 50 g of the aminoalkyloxyester obtained in Example 1 was dispersed in 500 ml of water, followed by 35% Hydrochloric acid solution (10 ml) was added and mixed well. Thereafter, water was removed by freeze-drying to obtain 52.5 g of the desired hydrochloride of aminoalkyloxyester. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0036]

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NMR spectrum (CDCl ₃ , internal standard TMS): 2.5 ppm (t, 2H) CH ₂ —COO—, 2.8 ppm (m, 4H)
_{-C H 2 -OC H 2 - 3.4ppm} (s, 6H) NC H 3, 5.35ppm (m, 1H)
C H OCO-IR spectrum (KBr tablet): 1740 cm ^-1 , 1160 cm ^-1 Example 4 50 g of the aminoalkyloxyester obtained in Example 1 was dispersed in 500 ml of water in a 1 liter beaker, followed by 20% Sulfuric acid solution (22 ml) was added and mixed well. Thereafter, water was removed by freeze-drying to obtain 54.4 g of the objective aminoalkyloxyester sulfate. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0038]

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NMR spectrum (CDCl ₃ , internal standard TMS): 2.5 ppm (t, 2H) CH ₂ —COO—, 2.8 ppm (m, 4H)
_{-C H 2 -OC H 2 - 3.45ppm} (s, 6H) NC H 3, 5.4ppm (m, 1H)
C H OCO-IR spectrum (KBr tablet): 1745 cm ⁻¹ , 1410 cm ⁻¹ , 1195 cm ⁻¹ , 1155 cm ⁻¹ Example 5 A four-necked flask equipped with a stirrer, thermometer, and dropping funnel was 1- Add 145 g of (N, N-dimethylamino) -2-hydroxypropyl dodecyl ether and 170 g of docosanoic acid and add 200
The temperature was raised to ° C. The esterification reaction was carried out at the same temperature for 18 hours while distilling off generated water, to obtain 300 g of aminoalkyloxyester. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0040]

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NMR spectrum (CDCl ₃ , internal standard TMS): 2.2 ppm (s, 6H) NCH ₃ , 2.3 ppm (m, 2H)
C H ₂ -COO- 3.5ppm (m, 4H) -C H ₂ -OC H _2- , 5.2ppm (m, 1H)
C H OCO-IR spectrum (KBr tablet): 1740 cm ^-1 , 1165 cm ^-1 Example 6 In an autoclave equipped with a stirrer, thermometer and pressure gauge, 120 g of the aminoalkyloxyester obtained in Example 5 and 11 g of methyl chloride were obtained. Then, 60 g of isopropanol was added, and a quaternization reaction was carried out at 80 ° C. for 6 hours to obtain 130 g of the target ammonium salt. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0042]

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NMR spectrum (CDCl ₃ , internal standard TMS): 2.3 ppm (t, 2H) CH ₂ —COO—, 3.3 ppm (m, 4H)
_{-C H 2 -OC H 2 - 3.5ppm} (s, 9H) NC H 3, 5.4ppm (m, 1H)
C H OCO-IR spectrum (KBr tablet): 1740 cm ⁻¹ , 1165 cm ^{−1 Further} , examples of formulation of the hair treatment agent proposed in the present invention include the following examples.

Formulation Example 1: Hair rinse 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% Flavor 0.3% Methyl paraben 0.1 % Dye Trace amount Purified water Residual prescription example 2: Aminoalkyloxyester hydrochloride synthesized in Hair treatment Example 1.5% Stearyltrimethylammonium chloride 1.0% Dimethylpolysiloxane (500cs) 1.0% Cetyl alcohol 6.0% Liquid paraffin 3.0% Polyoxy ethylene (5 mol) oleyl 0.3% methylparaben 0.1% alcohol ether 0.5% perfume dye trace purified water balance formulation example 3: synthesized aminoalkyloxy ester sulfate 2.0% cetyltrimethyl in hair cream example 4 Nmo chloride 1.0% cetostearyl alcohol 6.0% Dipropylene glycol 6.0% Glycerin 10.0% Liquid paraffin 3.0% perfume 0.3% Methylparaben 0.1% dye trace Purified water balance Formulation Example 4: 0.5% synthesized ammonium salts styling lotion Example 6 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 The following components were heated and dissolved at 70 ° C, and then stirred. , 70 ° C. ion-exchanged water 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 10% of the hair rinse composition thus obtained was applied to the hair bundle. , 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)す: 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

[0047]

[Table 1]

[0048]

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[0049]

The ammonium salt of the present invention represented by the general formula (1) is useful as a flexible base having excellent flexibility and biodegradability. It shows extremely excellent flexibility in both drying and a dry feeling without stickiness in drying.
Further, the aminoalkyloxyester 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 aminoalkyloxyester represented by the general formula ( The ammonium salt represented by 1) can be easily produced.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuyuki Yahagi 6-1-6-749 Oshima, Koto-ku, Tokyo (56) References International Publication 91/17424 (WO, A1) Lipids, Vol. 27, No. 5 No. 331-338 (1992) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 219/04 C07C 213/02 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] [Claim 1] General formula (1) (Wherein, R ¹ and R ² are an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, R ³ is 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
Represents H or an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, sulfate, carboxylate which may be substituted by a hydroxyl group having 1 to 4 carbon atoms, or alkyl sulfate having 1 to 4 carbon atoms. Provided that R ¹ , R ² and R ⁵ are methyl
Group, R ³ is octyl group and R ⁴ CO is octanoyl group
And R ¹ and R ⁵ are methyl groups, and R ² is hydroxyethyl.
And R ³ is an oleyl group and R ⁴ CO is an oleoyl group
Except in cases. The ammonium salt represented by). 2. A method according to claim ¹ , wherein R ¹ , R ² and R ⁵ are methyl groups and R ⁴ CO ₂
The ammonium salt according to claim 1, wherein is a hardened tallow fatty acid residue. 3. A compound of the general formula (2) (In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.)
An aminoalkyloxyester represented by the general formula
The general formula according to claim 1, wherein an acid or a quaternizing agent represented by (3) R ⁵ X (3) (wherein R ⁵ and X have the same meanings as described above) is reacted. A method for producing an ammonium salt represented by (1). 4. A compound of the general formula (2) ^{(Wherein, R 1, R 2, R} 3 and R ⁴ are the same as defined above. However
R ¹ and R ² are methyl groups, R ³ is an octyl group, and R ⁴ CO is
Except when it is an octanoyl group. ) An aminoalkyloxyester represented by the formula: 5. The aminoalkyloxyester according to claim ⁴ , wherein R ¹ and R ² are methyl groups, and R ⁴ CO ₂ is a hardened tallow fatty acid residue. 6. A compound of the general formula (4) (Wherein, R ¹ , R ² and R ³ have the same meanings as described above) to the amino alcohol represented by the general formula (5) R ⁴ COOR ⁶ (5) (wherein R ⁴ is Meaning, R ⁶ is H or carbon number 1
And represents an alkyl group of 1 to 3. 5. The reaction of a fatty acid or a fatty acid ester represented by the formula:
A method for producing an aminoalkyloxyester represented by the general formula (2) described above. 7. A hair treatment agent comprising the ammonium salt according to claim 1 or 2.