JPH09278728A - New quaternary ammonium salt, its production and surfactant composition, and hair cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new composition expressed by a specific formula, capable of imparting excellent flexibility to fibers and excellent flexibility and smoothness to hair, having good biodegradability by microorganisms and used for flexibilizers, etc. SOLUTION: This new quaternary ammonium salt is expressed by formula I [R<1> is a 1-35C alkyl or alkenyl; R<2> and R<3> are each H, an acyl derived from an 8-36C (un) saturated fatty acid; R<4> is a 1-4C alkyl, hydroxyalkyl; A is a (substituted) 1-10C alkylene; Y and Z are each a 2-3C alkylene; (n) and (m) are each an average addition mole number of alkylene oxide. and are each 1-20: X is an anion]. The ammonium salt is obtained, e.g., by reacting a dihydroxyamine body of formula II [(a) and (b) are each 0-20] with a fatty acid or its ester of the formula R<1> COOR<5> (R<5> is H or a 1-4C alkyl) to bring the acid or ester into an amide, then reacting the obtained dihydroxyamine compound of formula III with an agent, which brings the compound to a quaternary derivative of the formula R<4> X and, if needed, carrying out a salt exchange.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel quaternary ammonium salt, a method for producing the same, a surfactant composition, and a hair cosmetic composition containing the same, and more particularly, to impart excellent flexibility to fibers. However, a novel quaternary ammonium salt which can impart excellent flexibility and smoothness to hair and is also excellent in biodegradability, a method for producing the same, a surfactant composition, and hair containing the same Regarding cosmetics.

[0002]

2. Description of the Related Art
Most of the commercially available products as a softening agent for fibers or a hair treatment agent are quaternary ammonium having two long-chain alkyl groups in one molecule as represented by di (cured tallow alkyl) dimethylammonium chloride. It is a composition containing salt. However, the above-mentioned quaternary ammonium salt has a problem that when the residue after the treatment is released to the natural world such as a river, it is hardly biodegraded and accumulates.
Methylbis (hardened tallow alkanoyloxyethyl) 2-hydroxyethylammonium methylsulfate, dimethylbis (alkanoyloxyethyl) ammonium chloride and the like are commercially available as improved products thereof, but these are compared with the above quaternary ammonium salt. Although its biodegradability has been improved, it cannot be said to be a base that is sufficiently satisfactory in flexibility and environmental safety.

Therefore, an object of the present invention is to impart excellent flexibility to fibers, excellent flexibility and smoothness to hair, and further quaternary ammonium having good biodegradability. It is intended to provide a salt, a surfactant composition containing the same, and a hair cosmetic composition.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found a novel quaternary ammonium salt most suitable for the above purpose and completed the present invention.
That is, the present invention provides a novel quaternary ammonium salt represented by the general formula (I) and a method for producing the same.

[0005]

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(Wherein R ¹ represents a linear or branched alkyl group or alkenyl group having ¹ to 35 carbon atoms, R ² and R ³ are the same or different, and H or saturated or C 8 to 36 carbon atoms; An acyl group derived from an unsaturated fatty acid is shown, and R ⁴ has 1 to 4 carbon atoms.
A represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group, and Y and Z are the same or different and have 2 to 3 carbon atoms. Represents a linear or branched alkylene group, n
Y's and m Z's may be the same or different. n and
m is the same or different and is a number of 1 to 20 which represents the average number of moles of alkylene oxide added, and X represents an anionic group. ) Further, the present invention is a mono-form represented by the following general formula (I-1) 0 to 60% by weight, a di-form represented by the general formula (I-2) 0 to
90% by weight, and tri-form 0 represented by the general formula (I-3)
A surfactant composition comprising 100% by weight is provided.

[0007]

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(In the formula, R ¹ , R ⁴ , A, X, Y, Z, n and m have the same meanings as described above, R ^{2 ″} and R ^{3 ″} are the same or different and have 8 to 36 carbon atoms. And an acyl group derived from a saturated or unsaturated fatty acid.) Further, the present invention provides a hair cosmetic composition containing a quaternary ammonium salt represented by the above general formula (I). It is a thing.

[0009]

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

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

R ² and R ³ are the same or different and each represents an acyl group derived from H or a saturated or unsaturated fatty acid having 8 to 36 carbon atoms, preferably both R ² and R ³ have both carbon atoms. An acyl group derived from a saturated or unsaturated fatty acid having 8 to 36 carbon atoms, more preferably an acyl group derived from a linear saturated fatty acid having 8 to 24 carbon atoms, and particularly preferably a carbon number
It is an acyl group derived from 12 to 22 straight-chain saturated fatty acids.

R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms or a hydroxyalkyl group, specifically, methyl, ethyl,
Propyl, butyl, hydroxyethyl groups and the like,
Of these, a methyl group, an ethyl group, and a hydroxyethyl group are preferable, and a methyl group is more preferable.

A represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group, preferably a linear alkylene group having 2 to 6 carbon atoms, more preferably 2 to 6 carbon atoms. 3 is a straight chain alkylene group.

Y and Z are the same or different and have 2 to 3 carbon atoms.
The straight-chain or branched alkylene groups are preferably the same or different and are ethylene groups or propylene groups, and more preferably ethylene groups. In addition, n Y and
The m Zs may be the same or different.

N and m are the same or different and each represents a number of 1 to 20 showing the average number of moles of alkylene oxide added,
Preferably they are the same or different and are 1-10, more preferably 1-5.

X represents an anion group, but is preferably a halogen atom, a sulfate, a carboxylate optionally substituted with a hydroxyl group having 1 to 4 carbon atoms or an alkyl sulfate having 1 to 4 carbon atoms (CH ₃ SO ₄ , C ₂ H ₅ SO ₄ etc.),
More preferably Cl or CH ₃ SO ₄ .

Preferred specific examples of the quaternary ammonium salt represented by the general formula (I) include the following.

[0018]

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[0019]

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The quaternary ammonium salt represented by the general formula (I) of the present invention (hereinafter abbreviated as quaternary ammonium salt (I)) comprises steps (1) and (4) and step (1). , (2) and
(4), steps (1), (3) and (4), or steps (1), (2),
It can be produced by performing (3) and (4) in this order.

Step (1) General formula (II)

[0022]

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(In the formula, A, Y and Z have the same meanings as described above, and a and b are the same or different and each represents a number from 0 to 20.)
And a general formula (III) R ¹ COOR ⁵ (III) (in the formula, R ¹ has the same meaning as described above, R ⁵ represents H or an alkyl group having 1 to 4 carbon atoms) The fatty acid represented by the formula (1) or its ester is reacted to perform amidation to obtain the dihydroxyamide compound represented by the general formula (IV), or the amidation and the esterification are simultaneously performed to form the dihydroxyamide compound represented by the general formula (V). To obtain the amide ester compound.

[0024]

[Chemical 12]

(In the formula, R ¹ , A, Y, Z, a and b have the same meanings as described above, R ^{1 ′} represents a linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms, R ^{1 "} is H or formula -COR
^{1 '} (R ^1'has the above meaning) and at least one of the two R ¹ 's is a group represented by the formula -COR ^1' .) Step (2) General The dihydroxyamide compound represented by the formula (IV) is further reacted with an alkylene oxide having 2 to 3 carbon atoms,
General formula (VI)

[0026]

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A step of obtaining a dihydroxyamide compound represented by the formula: wherein R ¹ , A, Y, Z, n and m have the same meanings as described above.

Step (3) The dihydroxyamide compound represented by the general formula (IV) or (VI) and the general formula (VII) R ⁶ COOR ⁵ (VII) (wherein R ⁵ has the same meaning as described above). , R ⁶ has 7 to 35 carbon atoms
Represents a linear or branched alkyl group or alkenyl group. ) One or two of fatty acids or esters thereof represented by
Ester reaction of one or more species to give a compound of general formula (VIII)

[0029]

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(In the formula, R ¹ , A, Y, Z, n and m have the same meanings as described above, R ^{2 ′} and R ^{3 ′} are the same or different, and are H or saturated C 8 -36 or A step of obtaining an amide ester compound represented by an acyl group derived from an unsaturated fatty acid, at least one of which is an acyl group derived from a saturated or unsaturated fatty acid having 8 to 36 carbon atoms.

Step (4) A dihydroxyamide compound represented by the general formula (IV) or (VI), or an amide ester compound represented by the general formula (V) or (VIII), and a general formula (IX) R ⁴ A quaternizing agent represented by X (IX) (wherein R ⁴ and X have the same meanings as described above) is reacted, and if necessary, salt exchange is performed. Obtaining the quaternary ammonium salt represented.

Each step will be described below. Step (1) This step includes a dihydroxyamine body represented by the general formula (II) (hereinafter abbreviated as dihydroxyamine body (II)),
A fatty acid represented by the general formula (III) or an ester thereof (hereinafter abbreviated as a fatty acid or an ester (III)), preferably a dihydroxyamide compound represented by the general formula (IV) by reacting a fatty acid for amidation (Hereinafter abbreviated as a dihydroxyamide compound (IV)) or an amidation compound and an esterification are carried out simultaneously to obtain an amide ester compound represented by the general formula (V) (hereinafter abbreviated as an amide ester compound (V)). It is a process of obtaining.

The dihydroxyamine compound (II) used here is N- (3-aminopropyl) diethanolamine, N- (2-aminoethyl) diethanolamine, ethylenediamine, propylenediamine, or an ethylene oxide or propylene oxide addition thereof. Things etc. are mentioned. Further, as the fatty acid or its ester (III), acetic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid,
Palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, tallow fatty acid, coconut oil fatty acid, etc. and mixtures thereof,
And lower alkyl esters such as methyl ester and ethyl ester thereof.

In this step, by changing the reaction conditions of the dihydroxyamine compound (II) and the fatty acid or its ester (III), only the amidation or the amidation and the esterification are simultaneously carried out to obtain the dihydroxyamide compound.
(IV) or the amide ester compound (V) or a mixture thereof is obtained. For example, dihydroxyamide compound (IV)
To obtain 1 mol of dihydroxyamine compound (II), a fatty acid or its ester (III) is used in an amount of 0.5 to 3 times, preferably 0.9 to 1.5 times, at 60 to 270 ° C.
Preferably, at a temperature of 80 to 250 ° C, if necessary, using an alkali catalyst such as NaOH or sodium methylate, 0.5 to
Amidation reaction is carried out for 30 hours, and unreacted dihydroxyamine compound (II) or fatty acid or its ester (I
II) etc. are distilled off, the catalyst is neutralized and removed, and the product is purified by distillation. When the amide ester compound (V) is obtained, a fatty acid or its ester (III) having a carbon number of 8 to 36 is used, and the fatty acid or its ester (III) is added to 1 mol of the dihydroxyamine compound (II). ) Is used in an amount of 1.1 to 10 times mol, preferably 1.2 to 4 times mol, and 60 to 270 ° C.
Preferably, at a temperature of 80 to 250 ° C., if necessary, using an alkali catalyst such as NaOH or sodium methylate or an acid catalyst such as p-toluenesulfonic acid or sulfuric acid, the amidation reaction and the esterification in 0.5 to 40 hours. The reaction is carried out at the same time, and if necessary, the unreacted dihydroxyamine compound (II), fatty acid or its ester (III), etc. are distilled off, the catalyst is neutralized or removed, and adsorption treatment is carried out for purification.

During the above amidation and esterification reactions, if necessary, an inert gas such as nitrogen may be blown into the reaction system or the reaction may be carried out under an inert gas stream, or a reduced pressure reaction or the like may be performed. You can go. Moreover, when the obtained product may be a mixture of the dihydroxyamide compound (IV) and the amide ester compound (V), the conditions may be appropriately adjusted based on the above findings.

Step (2) In this step, the dihydroxyamide compound (IV) obtained in the above step (1) is further reacted with an alkylene oxide having 2 to 3 carbon atoms to give a dihydroxy compound represented by the general formula (VI). This is a step of obtaining an amide compound (hereinafter abbreviated as dihydroxyamide compound (VI)).

Examples of the alkylene oxide having 2 to 3 carbon atoms include ethylene oxide and propylene oxide, and ethylene oxide is preferable. The addition reaction temperature of alkylene oxide is preferably 40 to 200 ° C, 60 to 200 ° C.
180 ° C is more preferred.

Step (3) In this step, the dihydroxyamide compound (IV) or (VI)
And a fatty acid represented by the general formula (VII) or an ester thereof (hereinafter abbreviated as fatty acid or ester (VII)), preferably one or more fatty acids are subjected to an ester reaction to give a compound represented by the general formula (VIII) Is a step of obtaining an amide ester compound represented by (hereinafter abbreviated as amide ester compound (VIII)).

Fatty acid or ester thereof used here
As (VII), caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid,
Examples thereof include arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, tallow fatty acid, coconut oil fatty acid and the like, and mixtures thereof, and lower alkyl esters such as methyl ester and ethyl ester thereof.

In the amide ester compound (VIII), R
^When a compound in which ^{2 ′} and R ^{3 ′} are both an acyl group derived from a saturated or unsaturated fatty acid having 8 to 36 carbon atoms is used, the amount of the fatty acid or its ester (VII) used is the dihydroxyamide compound ( IV) or (VI) per mole of 0.
It is preferably 5 to 10 mol, more preferably 0.8 to 4 mol.
Further, in the amide ester compound (VIII), R ^{2 ′} or
When a partial esterified product in which either R ^{3 ′} is a hydrogen atom is obtained, the amount of the fatty acid or its ester (VII) used in this esterification reaction is the dihydroxyamide compound (IV) or (VI) 1 5 moles or less relative to moles,
It is preferably 2 mol or less.

The esterification reaction is carried out at a temperature of 60 to 270 ° C., preferably 80 to 250 ° C., if necessary, an acid catalyst such as p-toluenesulfonic acid, sulfuric acid or an alkali catalyst such as NaOH or sodium methylate. For 0.5 to 40 hours,
If necessary, the unreacted fatty acid or its ester (VII) and the like are distilled off, the catalyst is neutralized and removed, and purification such as adsorption treatment is carried out.
During this esterification reaction, if necessary, an inert gas such as nitrogen may be blown into the reaction system, or the reaction may be carried out under an inert gas stream, or a reduced pressure reaction or the like may be carried out.

Step (4) This step is represented by the dihydroxyamide compound (IV) or (VI) or the amide ester compound (V) or (VIII) obtained in the above step and the general formula (IX). A quaternary ammonium salt (I) is obtained by reacting a quaternary agent (hereinafter abbreviated as quaternary agent (IX)), and further performing salt exchange.
This is the step of obtaining

In the quaternization reaction, the quaternizing agent (IX) is used in an amount of 0.9 to 10 with respect to 1 mol of the dihydroxyamide compound (IV) or (VI) or the amide ester compound (V) or (VIII).
30 to 140 times, preferably 0.95 to 2.0 times by mole
It is carried out at a temperature of 40 ° C., preferably 40 to 100 ° C. for 0.1 to 20 hours using a solvent if necessary. Then, post-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 to obtain a quaternary ammonium salt (I). Examples of the quaternizing agent (IX) used here include lower alkyl halides such as methyl chloride and di-lower alkyl sulfuric acids such as dimethyl sulfuric acid and diethyl sulfuric acid. Examples of the solvent for the quaternization reaction include water, methanol, ethanol, isopropyl alcohol, acetone and the like.

The quaternary ammonium salt (I) of the present invention is
It is a novel surfactant, can impart excellent flexibility to fibers, and is useful as a soft base having excellent biodegradability. Further, it can impart excellent flexibility and smoothness to hair, and can be applied to hair rinses and hair treatments which are hair cosmetics.

In the present invention, of the quaternary ammonium salt (I) obtained as described above, 0 to 60% by weight of the mono-form represented by the general formula (I-1), the general formula ( I
-2) represented by the formula (I-0-90% by weight)
A surfactant composition consisting of 0 to 100% by weight of the tri-form represented by 3) is particularly preferable in terms of flexibility, and further 0 to 50% by weight of the mono-form represented by the general formula (I-1), General formula (I
-2) represented by the formula (I-)
A surfactant composition comprising 10 to 100% by weight of the tri-form represented by 3) is preferable.

This surfactant composition can be obtained by mixing the above-mentioned mono-form, di-form and tri-form so as to have the above-mentioned blending composition.
During the esterification reaction in (3), a mixed composition can be obtained by changing the amount of the fatty acid or its ester (III) or (VII) used and the reaction rate of esterification to an arbitrary degree of esterification (more than 0 and 2 or less). It is also possible to directly obtain a mixed composition by obtaining a (generally equilibrium composition), further reacting with a quaternizing agent (IX), and performing salt exchange if necessary.

The hair cosmetic composition of the present invention contains the quaternary ammonium salt (I) as an essential component. These can be used alone or in combination of two or more, and in particular, the above-mentioned general compounds can be used. Mono-form 0 represented by the formula (I-1)
60% by weight, particularly 0 to 50% by weight, 0 to 90% by weight of the di-form represented by the general formula (I-2), particularly 0 to 80% by weight, and a tri-formula represented by the general formula (I-3). 0 to 100% by weight, especially 10 to
Those containing 100% by weight of the surfactant composition are preferred.

The hair cosmetic composition of the present invention comprises a hair rinse, a hair conditioner, a hair treatment, a hair pack,
It can be used in hair creams, styling lotions, styling mousses, conditioning mousses, hair mousses, hair sprays, shampoos, non-rinsing conditioning agents, permanent or basic hair colors, perms and the like. In this case, the quaternary ammonium salt (I) of the present invention is preferably incorporated in the hair cosmetic composition of the present invention in an amount of 0.1% by weight or more, particularly 0.1 to 20% by weight, more preferably 0.1 to 20% by weight.
It is preferable to add 10% by weight.

In the hair cosmetic composition of the present invention, in addition to the quaternary ammonium salt (I) of the present invention, oils and fats and silicones can be used alone or in combination. Examples of fats and oils include higher alcohols having a linear or branched alkyl group or alkenyl group, liquid paraffin, petrolatum,
Hydrocarbons such as solid paraffin, liquid lanolin, lanolin derivatives such as lanolin fatty acid, higher fatty acid esters,
Examples thereof include higher fatty acids, fats and oils such as long-chain amidoamine having an alkyl group or an alkenyl group, and animal and vegetable fats and oils such as mink oil and olive oil. Among these, monoglycerides derived from saturated or unsaturated linear or branched fatty acids having 12 to 24 carbon atoms, higher alcohols and higher fatty acids having a linear or branched alkyl group or alkenyl group having 12 to 26 carbon atoms are preferable, Especially oleic acid monoglyceride, palmitic acid monoglyceride, behenic acid monoglyceride, fatty acid monoglyceride such as isostearic acid monoglyceride, higher alcohol such as cetyl alcohol, stearyl alcohol, arachin alcohol, behenyl alcohol, caranavir alcohol, ceryl alcohol, stearic acid, myristic acid, Higher fatty acids such as behenic acid, isostearic acid, 18-methylicosanoic acid and coconut oil fatty acid are preferred.

Examples of silicones include dimethylpolysiloxane and methylphenylpolysiloxane, as well as various modified silicones such as amino-modified silicone and polyether-modified silicone. When blending these oils and fats and silicones, 0.01% by weight or more is preferably blended in the hair cosmetic composition of the present invention, particularly 0.01 to 30% by weight,
Further, it is preferable to add 0.05 to 20% by weight.

In the hair cosmetic composition of the present invention, in addition to the above-mentioned components, conventional mono- or di- (long-chain alkyl) may be added, if necessary.
Cationic activators such as quaternary ammonium salts, nonionic activators, humectants such as glycerin and urea, cationic polymers, polymeric substances such as polysaccharides and polypeptides, α
-Hydroxycarboxylic acids, aromatic sulfonic acids, dyes, fragrances, propellants, solvents, chelating agents, pH adjusters, preservatives, anti-dandruff agents, etc. can be appropriately blended within the range not impairing the object of the present invention. .

Further, the quaternary ammonium salt (I) of the present invention, especially the mono-form 0 represented by the above general formula (I-1).
To 60% by weight, di-form represented by the general formula (I-2) 0-90% by weight, and tri-form represented by the general formula (I-3) 0-100
The surfactant composition composed of wt% is also useful as a soft base of a soft finish, and can impart sufficient softness to fibers. Such a softening base is preferably contained in the softening finish in an amount of 0.5 to 50% by weight, more preferably 2 to 20% by weight.
% By weight, and other components such as a viscosity modifier, a storage stability improver, a pH adjuster, a hydrotrope, a pigment, a dye, a defoaming agent, and a fragrance, which are compounded in conventional softening agents. By doing so, a soft finish having excellent flexibility can be obtained.

[0053]

EXAMPLE The quaternary ammonium salt (I) of the present invention is described below.
The present invention will be described in more detail with reference to the production examples, the surfactant composition examples of the present invention, and the hair cosmetic formulation examples of the present invention.
It is not limited to the prescription example. The percentages in the examples are on a weight basis unless otherwise specified.

Production Example 1 568 g of stearic acid and 324 g of N- (3-aminopropyl) diethanolamine were placed in a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and an N ₂ introduction tube, and the temperature was raised to 150 ° C. Amidation reaction was performed for 6 hours to obtain N, N-bis (2-hydroxyethyl) -3-stearoylaminopropylamine.

Next, 200 g of lauric acid and the N, N-bis (2-hydroxyethyl) -3-stearoylaminopropyl obtained above were placed in a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and an N ₂ introduction tube. 214 g of amine was charged, the temperature was raised to 190 ° C., and dehydration reaction was carried out for 8 hours to obtain an amide / diester reaction product.

Further, 317 g of the above amide / diester reaction product, 80 g of isopropyl alcohol and 26 g of methyl chloride were charged into an autoclave equipped with a stirrer and a thermometer and reacted at 90 ° C. for 8 hours. After the reaction, excess methyl chloride and isopropyl alcohol were distilled off, crystallization with acetone was performed, and after drying, 332 g of a powdery compound represented by the following formula (A) (hereinafter abbreviated as compound A)
I got ^The following structure was confirmed from ¹ H-NMR and IR spectra.

[0057]

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[0058] ¹ H-NMR spectrum (CDCl _3, internal standard TMS) 2.0 ~2.22 ppm (t 6H ) -CH 2 C H 2 CO- 2.32 ppm (t 2H) NHCH 2 C H 2 CH 2 -N + 3.25 ppm (t 2H) NHC H ₂ CH ₂ CH ₂ -N ⁺ 3.65 ppm (s 3H) C H ₃ -N ⁺ -3.75 to 3.9 ppm (6H) NHCH ₂ CH ₂ C H ₂ -N ⁺ -C H ₂ CH ₂ OCO 4.53 ppm (t 4H) N ⁺ -CH ₂ C H ₂ OCO IR spectrum (KBr tablet) 1741 cm ^-1 , 1651 cm ^-1 Manufacturing Example 2 Manufactured in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube. N, N-bis (2-hydroxyethyl) -3-stearoylaminopropylamine (214 g) synthesized in the same manner as in Example 1 and isopropyl alcohol (110 g) were charged, the temperature was raised to 60 ° C, and dimethylsulfate (61.8 g) was maintained at that temperature. Was added dropwise over 1 hour and then aged at 60 ° C. for 2 hours. After the reaction,
After isopropyl alcohol was distilled off and the residue was dried, 270 g of a compound represented by the following formula (B) (monoalkyl compound, hereinafter abbreviated as compound B) was obtained. ^The following structure was confirmed from ¹ H-NMR and IR spectra.

[0059]

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¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) 0.88 ppm (t 3H) C H _3- (CH ₂ ) ₁₄ -CH ₂ -CH ₂ CO- 1.25 ppm (t 28H) CH _3- (C H ₂ ) ₁₄ -CH ₂ -CH ₂ CO- 1.6 ppm (t 2H) CH _3- (CH ₂ ) ₁₄ -C H ₂ -CH ₂ CO- 2.07 ppm (t 2H) CH _3- (CH ₂ ) _14- CH ₂ -C H ₂ CO- 2.35 ppm (t 2H) NHCH ₂ C H ₂ CH ₂ -N ⁺ 3.25 ppm (t 2H) NHC H ₂ CH ₂ CH ₂ -N ⁺ 3.70 ppm (s 3H) C H _3- N ⁺ -3.8 to 4.1 ppm (10H) NHCH ₂ CH ₂ C H ₂ -N ⁺ -C H ₂ -C H ₂ OH IR spectrum (KBr tablet) 1652 cm ^-1 Production Example 3 Stirrer, thermometer, dehydration tube, A four-necked flask equipped with an N ₂ introduction tube was charged with 568 g of stearic acid and 162 g of N- (3-aminopropyl) diethanolamine, heated to 170 ° C. and dehydrated for 6 hours, and further equipped with a thermometer and a capillary. Fractional distillation was performed in a pear-shaped flask to obtain an amide / monoester product. Next, in a four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, the amide monoester compound 277.6
g and 110 g of isopropyl alcohol were charged, the temperature was raised to 60 ° C., and while maintaining the temperature, 49.4 g of dimethylsulfate was added dropwise over 30 minutes, followed by aging at 60 ° C. for 3 hours. After the reaction, isopropyl alcohol was distilled off, and crystallization with acetone was performed. After drying, 320 g of a powdery compound represented by the following formula (C) (dialkyl body, hereinafter abbreviated as compound C) was obtained.
^The following structure was confirmed from ¹ H-NMR and IR spectra.

[0061]

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¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) 0.86 ppm (t 6H) C H _3- (CH ₂ ) ₁₄ -CH ₂ -CH ₂ CO- 1.23 ppm (t 56H) CH _3- (C H ₂ ) ₁₄ -CH ₂ -CH ₂ CO- 1.62ppm (t 4H) CH _3- (CH ₂ ) ₁₄ -C H ₂ -CH ₂ CO- 2.05 to 2.25ppm (t 4H) CH _3- (CH ₂ ) ₁₄ -CH ₂ -C H ₂ CO- 2.35 ppm (t 2H) NHCH ₂ C H ₂ CH ₂ -N ⁺ 3.22 ppm (t 2H) NHC H ₂ CH ₂ CH ₂ -N ⁺ 3.35 ppm (t 2H) NHCH ₂ CH ₂ C H ₂ -N ⁺ 3.70 ppm (s 3H) C H ₃ -N ⁺ -3.80 to 4.1 ppm (6H) N ⁺ -C H ₂ CH ₂ OCO, N ⁺ -C H ₂ CH ₂ O
H 4.50 ppm (t 2H) N + -CH 2 C H 2 OCO IR spectrum (KBr tablet) 1743cm ^-1, 1650cm ^-1 Preparation Example 4 a stirrer, a thermometer, 4 provided with the dehydration tube, N ₂ inlet A neck flask was charged with 341 g of stearic acid and 64.8 g of N- (3-aminopropyl) diethanolamine, heated to 180 ° C., and dehydrated for 12 hours to obtain an amide / diester reaction product. Next, in a four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 288 g of the amide / diester reaction product and 144 g of isopropyl alcohol were charged, and the temperature was raised to 65 ° C. After dropping, the mixture was aged at 65 ° C. for 5 hours. After the reaction, isopropyl alcohol was distilled off, and crystallization with acetone was performed. After drying, 315 g of a powdery compound represented by the following formula (D) (trialkyl compound, hereinafter abbreviated as compound D) was obtained. ¹ H-N
The following structure was confirmed from the MR and IR spectra.

[0063]

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¹ H-NMR spectrum (CDCl ₃ , internal standard TMS) 0.9 ppm (t 9H) C H _3- (CH ₂ ) ₁₄ -CH ₂ -CH ₂ CO- 1.3 ppm (t 84H) CH _3- (C H ₂ ) ₁₄ -CH ₂ -CH ₂ CO- 1.65ppm (t 6H) CH _3- (CH ₂ ) ₁₄ -C H ₂ -CH ₂ CO- 2.05 to 2.25ppm (t 6H) CH _3- (CH ₂ ) ₁₄ -CH ₂ -C H ₂ CO- 2.35 ppm (t 2H) NHCH ₂ C H ₂ CH ₂ -N ⁺ 3.25 ppm (t 2H) NHC H ₂ CH ₂ CH ₂ -N ⁺ 3.7 ppm (s 3H) C H ₃ -N ⁺ -3.78 to 3.9 ppm (6H) NHCH ₂ CH ₂ C H ₂ -N ⁺ -C H ₂ CH ₂ OCO 4.55 ppm (t 4H) N ⁺ -CH ₂ C H ₂ OCO IR spectrum (KBr tablet) 1743 cm ^-1 , 1650 cm ^-1 Manufacturing Example 5 144 g of caprylic acid and 120.2 g of ethylenediamine were charged into a four-necked flask equipped with a stirrer, thermometer, dehydration tube, and N ₂ introduction tube, and amidation reaction was carried out at 120 ° C. for 5 hours. After that, the unreacted ethylenediamine was distilled off in a pear-shaped flask equipped with a thermometer and a capillary, and the amidation reaction product was further fractionated to obtain a monoamide compound. . Next, the above monoamide compound 93.1 was placed in an autoclave equipped with a stirrer and a thermometer.
After charging g, 88 g of ethylene oxide was reacted at 80 ° C. for 5 hours to obtain a monoamidoethylene oxide adduct (average EO addition 4 mol).

Next, in a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and an N ₂ introduction tube, 153.6 g of palmitic acid and 144.8 g of the above monoamide ethylene oxide adduct were charged,
The temperature was raised to 170 ° C., and dehydration reaction was carried out for 8 hours to obtain an amide / ester reaction product (average degree of esterification: 1.5 mol). Further, 215.7 g of the above-mentioned amide / ester reaction product, 100 g of isopropyl alcohol and 37.1 g of dimethylsulfate were charged in a four-necked flask equipped with a stirrer, a thermometer, and a condenser, and reacted at 60 ° C. for 5 hours. After the reaction, isopropyl alcohol was distilled off, and after drying, a compound represented by the following formula (E) in powder form (trialkyl content 55%, hereinafter abbreviated as compound E):
g was obtained. ^The following structure was confirmed from ¹ H-NMR and IR spectra.

[0066]

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(In the formula, n + m = 4, R is H or -COC ₁₅ H
_The average degree of esterification = 1.5 mol. ) Hydroxyl value = 33, Saponification value = 99 ¹ H-NMR spectrum (CDCl ₃ , internal standard TM
S) 2.05 to 2.25 ppm (t 5H) -CH ₂ -C H ₂ CO- 3.3 ppm (t 2H) NHC H ₂ CH ₂ -N ⁺ 3.7 ppm (s 3H) C H ₃ -N ⁺ -3.5 to 4.1 ppm (15H) NHCH ₂ C H ₂ -N ⁺ -(C H ₂ -C H ₂ O) _n-
H, N ⁺ -(C H ₂ -C H ₂ O) _m-1 -C H ₂ CH ₂ OCO 4.2 to 4.6 ppm (3H) N ⁺ -(CH ₂ CH ₂ O) _m-1 -CH ₂ C H ₂ OC
O IR spectrum (KBr tablet) 1742 cm ^-1 , 1652 cm ^-1 Production Example 6 214 g of N, N-bis (2-hydroxyethyl) -3-stearoylaminopropylamine synthesized in the same manner as in Production Example 1 was placed in an autoclave. After being charged, 88 g of ethylene oxide was reacted at 90 ° C. for 6 hours to obtain a monoamido ethylene oxide adduct (average EO addition 6 mol).
Next, in a four-necked flask equipped with a stirrer, a thermometer, a dehydration tube, and a N ₂ introduction tube, 241.6 g of the above monoamide-ethylene oxide adduct (average EO addition 6 mol) and stearic acid 227.
2 g was charged, the temperature was raised to 180 ° C., and dehydration reaction was carried out for 15 hours to obtain an amide / diester reaction product.

Next, 4 equipped with a stirrer, a thermometer and a cooling pipe
340.8 g of the above amide diester reaction product in a one-necked flask,
150 g of isopropyl alcohol was charged, the temperature was raised to 65 ° C., 37.1 g of dimethylsulfate was added dropwise over 1 hour while maintaining the temperature, and the mixture was aged at 65 ° C. for 5 hours. After the reaction, isopropyl alcohol was distilled off, and crystallization with acetone was performed. After drying, 365 g of a powdery compound represented by the following formula (F) (hereinafter abbreviated as compound F) was obtained. ¹ H-NM
The following structures were confirmed from R and IR spectra.

[0069]

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(In the formula, n + m = 6.) Hydroxyl value = 4, Saponification value = 89 ¹ H-NMR spectrum (CDCl ₃ , internal standard TM
S) 2.35 ppm (t 2H) NHCH ₂ C H ₂ CH ₂ -N ⁺ 3.25 ppm (t 2H) NHC H ₂ CH ₂ CH ₂ -N ⁺ 3.7 ppm (s 3H) C H ₃ -N ⁺ -3.5 to 4.05 ppm (22H) NHCH ₂ CH ₂ C H ₂ -N ⁺ -(C H ₂ -C H
₂ O) _n-1 -C H ₂ CH ₂ OCO 4.2 to 4.6 ppm (4H) N ⁺ -(CH ₂ CH ₂ ) _n-1 -CH ₂ C H ₂ OCO IR spectrum (KBr tablet) 1742 cm ^-1 , 1650 cm ^-1 Examples 1 to 8 Regarding the surfactant compositions having the compositions shown in Table 1, the flexibility was evaluated according to the following criteria. The results are shown in Table 1.

<Method for evaluating flexibility> (1) Method for preparing dispersion liquid 0.5% by weight of isopropyl alcohol was added to a surfactant composition for evaluating flexibility and melted.
Gradually dropwise added to deionized water maintained at 60 ° C., an emulsion containing 5% by weight of the surfactant composition was prepared. Then 0.01 wt% NaCl was added into the emulsion and cooled.

(2) Treatment and evaluation Commercial cotton towel was used as a commercial detergent "Attack" (Kao Corporation)
(Registered trademark) was repeatedly washed 5 times to remove the detergent on the cloth, and then the dispersion liquid prepared in (1) above was added at 1.5% of the weight of the cloth, and the bath ratio was 1/30 at 25 ° C. After being treated with stirring for 3 minutes at room temperature, it was dried in a room and left in a constant temperature and humidity room at 20 ° C. and 65% RH for 24 hours. For these cloths,
The flexibility was evaluated. For the evaluation of flexibility, a pair of comparisons were performed using a cloth prepared and treated in the same manner with dimethyl distearyl ammonium chloride as a control, and evaluated according to the following criteria.

[0073]

[0074]

[Table 1]

Formulation Example 1 (hair rinse) A hair rinse having the following composition was produced. The obtained hair rinse was able to impart excellent flexibility and smoothness to the hair.

<Composition> Surfactant composition of Example 3 1.0 wt% Cetyl alcohol 3.0 wt% Behenic acid 1.0 wt% Diethylene glycol monoethyl ether 3.0 wt% Hydroxyethyl cellulose 0.5 wt% Water 91.1 wt% Perfume 0.4 wt% Formulation example 2 (Styling lotion) A styling lotion having the following composition was produced. The obtained styling lotion was able to impart excellent flexibility and smoothness to hair.

<Composition> Surfactant composition of Example 4 0.5% by weight Polyethylene glycol 0.5% by weight Acrylic resin alkanolamine solution 5.0% by weight 2-benzyloxyethanol 1.0% by weight Methacrylic ester polymer 1.0% by weight Ethanol 20.0% by weight Perfume 0.4% by weight Water balance ─────────────────────────────── 100.0% by weight Formulation 3 (conditioning foam) A conditioning foam was manufactured. The obtained conditioning foam was able to impart excellent flexibility and smoothness to hair.

<Composition> Surfactant composition of Example 5 0.5% by weight Octyldodecyl myristate 1.0% by weight Dipropylene glycol 1.0% by weight Glycerin 2.5% by weight Liquid paraffin 2.5% by weight Polyoxyethylene (20) sorbitan monostearate 0.2 wt% Glycolic acid 0.5 wt% 1 mol adduct of isostearyl pentaerythryl glycidyl ether 0.5 wt% Ethanol 5.0 wt% Methylparaben 0.1 wt% Perfume 0.1 wt% Propellant (LPG) 10.0 wt% Water balance ───── ─────────────────────────────── 100.0% by weight

[0079]

The quaternary ammonium salt (I) and the surfactant composition of the present invention have flexibility and are easily decomposed by microorganisms. The hair cosmetic composition containing the quaternary ammonium salt (I) as a main component exhibits excellent softness to hair and is mild to skin.

Claims (9)

[Claims] 1. A novel quaternary ammonium salt represented by the general formula (I). Embedded image (In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having ¹ to 35 carbon atoms, R ² and R ³ are the same or different, and are H or saturated or unsaturated fatty acid having 8 to 36 carbon atoms. Represents an acyl group derived from, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms or a hydroxyalkyl group, and A represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group. And Y and Z are the same or different and have 2 to 2 carbon atoms.
3 represents a straight-chain or branched alkylene group, and n Y and
The m Zs may be the same or different. n and m are the same or different and each is a number of 1 to 20 which represents the average number of moles of alkylene oxide added, and X represents an anionic group. ) 2. The quaternary according to claim 1, wherein in the general formula (I), R ² and R ³ are the same or different and each is an acyl group derived from a saturated or unsaturated fatty acid having 8 to 36 carbon atoms. Ammonium salt. 3. In the general formula (I), R ¹ has 7 to 7 carbon atoms.
23 straight chain alkyl group, R ² and R ³ are the same or different, and an acyl group derived from a straight chain saturated fatty acid having 8 to 24 carbon atoms, R ⁴
Is a methyl group, an ethyl group or a hydroxyethyl group, A is a linear alkylene group having 2 to 6 carbon atoms, Y and Z are ethylene groups or propylene groups, and n and m are the same or different and are 1 to 10
Number, X is a halogen atom, sulfate, carbon number 1-4
The quaternary ammonium salt according to claim 1 or 2, which is a carboxylate optionally substituted with a hydroxyl group or an alkyl sulfate having 1 to 4 carbon atoms. 4. In the general formula (I), R ¹ has 11 to 11 carbon atoms.
21 straight-chain alkyl group, R ² and R ³ are the same or different and are acyl groups derived from straight-chain saturated fatty acids having 12 to 22 carbon atoms, R ⁴
Is a methyl group, A is a linear alkylene group having 2 to 3 carbon atoms, Y
And Z are ethylene groups, and n and m are the same or different and are 1 to
The number of 5, the quaternary ammonium salt according to claim 1 or 2 wherein X is Cl or CH ₃ SO _4. 5. The following steps (1) and (4), steps (1) and (2)
And (4), steps (1), (3) and (4), or steps (1) and (2)
, (3) and (4) are performed in this order, and the method for producing a quaternary ammonium salt according to any one of claims 1 to 4. Step (1) General formula (II) (In the formula, A, Y and Z have the same meanings as described above, and a and b
Are the same or different and represent a number of 0 to 20. ) And a general formula (III) R ¹ COOR ⁵ (III) (wherein R ¹ has the same meaning as described above, R ⁵ represents H or an alkyl group having 1 to 4 carbon atoms). A) a fatty acid represented by the formula (4) or an ester thereof is reacted to perform amidation to obtain a dihydroxyamide compound represented by the general formula (IV), or amidation and esterification are simultaneously performed to obtain a dihydroxyamide compound Obtaining the represented amide ester compound. Embedded image (In the formula, R ¹ , A, Y, Z, a and b have the same meanings as described above, R ^{1 ′} represents a linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms, and R ^{1 ″} Represents a group represented by H or the formula —COR ^{1 ′} (R ^{1 ′} has the above-mentioned meaning), and at least one of the two R ^{1 ″ s} is a group represented by the formula —COR ^{1 ′} . ) Step (2) The dihydroxyamide compound represented by the general formula (IV) is further reacted with an alkylene oxide having 2 to 3 carbon atoms,
General formula (VI) (In the formula, R ¹ , A, Y, Z, n and m have the same meaning as described above.) A step of obtaining a dihydroxyamide compound. Step (3) a dihydroxyamide compound represented by the general formula (IV) or (VI) and a general formula (VII) R ⁶ COOR ⁵ (VII) (in the formula, R ⁵ has the same meaning as described above, R ⁶ Has 7 to 35 carbon atoms
Represents a linear or branched alkyl group or alkenyl group. ) One or two of fatty acids or esters thereof represented by
Ester reaction of one or more species to give a compound of general formula (VIII) (In the formula, R ¹ , A, Y, Z, n and m have the same meanings as described above, R ^{2 ′} and R ^{3 ′} are the same or different, and are each H or 8 to 8 carbon atoms.
It represents an acyl group derived from 36 saturated or unsaturated fatty acids, at least one of which is an acyl group derived from saturated or unsaturated fatty acids having 8 to 36 carbon atoms. ) The process of obtaining the amide ester compound represented by these. Step (4) A dihydroxyamide compound represented by the general formula (IV) or (VI), or an amide ester compound represented by the general formula (V) or (VIII), and a general formula (IX) R ⁴ X (IX ) (In the formula, R ⁴ and X have the same meanings as described above.) The quaternization agent represented by the formula (I) is reacted, and salt exchange is further carried out if necessary to obtain the compound represented by the general formula (I). A step of obtaining a quaternary ammonium salt. 6. A mono-form represented by the following general formula (I-1) 0 to 60% by weight, and a di-form represented by the general formula (I-2) 0 to 90.
% By weight, and a tri-form represented by the general formula (I-3) 0 to 10
A surfactant composition consisting of 0% by weight. [Chemical 6] (In the formula, R ¹ , R ⁴ , A, X, Y, Z, n and m have the same meanings as described above, R ^{2 ″} and R ^{3 ″} are the same or different and have 8 carbon atoms.
~ 36 acyl groups derived from saturated or unsaturated fatty acids. ) 7. A mono-form represented by the general formula (I-1) 0 to
The interface according to claim 6, comprising 50% by weight, 0 to 80% by weight of a di-former represented by the general formula (I-2), and 10 to 100% by weight of a tri-former represented by the general formula (I-3). Activator composition. 8. A hair cosmetic containing the quaternary ammonium salt according to claim 1. 9. A mono-form represented by the general formula (I-1) 0 to 60% by weight, and a di-form represented by the general formula (I-2) 0 to 90.
% By weight, and a tri-form represented by the general formula (I-3) 0 to 10
9. A surfactant composition comprising 0% by weight.
The hair cosmetic according to the above.