JP2002294278A - Two-hydrophobic chain/two-hydrophilic group type surfactant and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-hydrophobic chain/two-hydrophilic group type surfactant which is high in purity and can be produced at a high yield; and a detergent composition, a hair treatment composition and a softening agent composition using the two-hydrophobic chain/two-hydrophilic group type surfactant and its ammonium salt. SOLUTION: The two-hydrophobic chain/two-hydrophilic group type surfactant can be obtained by reacting the salt of a secondary amine compound with an epihalohydrin followed by reacting with a secondary amine compound or a tertiary amine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a two-chain dihydrophilic surfactant having a high purity and a high yield produced by a method characterized by a selective reaction comprising two steps, The present invention relates to a cleaning composition, a hair treatment composition and a softening composition using a hydrophilic group type surfactant and its ammonium salt.

[0002]

2. Description of the Related Art It has been reported that a two-chain, two-hydrophilic group-type surfactant has excellent interface physical properties such as a lower critical micelle concentration and an interfacial tension lowering ability than a conventional one-chain, one-hydrophilic group-type surfactant. In recent years, it has attracted attention as a highly functional surfactant. Since such excellent interface properties can reduce the amount of surfactant used, it is expected to be very high in the future such as reduction of environmental load.

A report on a two-chain dihydrophilic surfactant is disclosed in JP-A-10-330785, which describes a structure in which two molecules of an amide group of a fatty acid amide ethyl ether sulfate anionic surfactant are linked by a methylene chain. Are disclosed. However, in this reaction, an organic solvent such as acetone must be used in order to suppress the decomposition of the acid chloride as an intermediate material, and further, the yield of the acylation reaction with the acid chloride is extremely low. Also,
JP-A-8-301747 discloses a compound in which an amino group is linked by a carbonyl group by a condensation reaction of fatty acid amidomethylethanolamine and urea. However, this reaction requires ancillary equipment for collecting ammonia generated in the condensation reaction with urea,
It also has the disadvantage of low product purity and yield.

[0004] On the other hand, a method for producing a two-chain dihydrophilic surfactant using epihalohydrin at the junction of two molecules is described as follows.
J. Am. Oil. Chem. Soc. 73, 67 (1
996); Am. Oil. Chem. So
c. 73, 907 (1996) discloses a method for synthesizing a two-chain dihydrophilic surfactant from the reaction of a tertiary amine compound and epichlorohydrin. A purification process is required to remove the tertiary amine compound. Further, Japanese Unexamined Patent Publication No.
No. 103646 discloses a method in which two imidazoline rings are linked with epichlorohydrin under a reaction condition that maintains an imidazoline ring structure, and then the imidazoline ring is hydrolyzed under basic conditions to form an amidoamine, which is further induced into an anionic surfactant. However, the compound obtained by hydrolysis of the imidazoline ring contains by-products other than the intended amidoamine, and has a problem that the yield is low.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a two-chain dihydrophilic surfactant which can be produced with high purity and a high yield, the obtained two-chain dihydrophilic surfactant and its ammonium salt. An object of the present invention is to provide a cleaning composition, a hair treatment composition and a softening composition using the same.

[0006]

The present invention provides: (A) a two-chain dihydrophilic compound obtained by reacting a salt of a secondary amine compound with epihalohydrin and then reacting with a secondary or tertiary amine compound. Base surfactant. (B) The two-chain dihydrophilic surfactant according to the above (A), wherein the secondary amine compound or the tertiary amine compound is represented by the formula (1).

[0007]

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[0008] (wherein R ¹ CO represents an aliphatic acyl group having 10 to 22 carbon atoms, R ^2, R ³ represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms or a hydrogen atom,, R ⁴ Represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4.) (C) After reacting a salt of a secondary amine compound with epihalohydrin, the secondary amine compound or An ammonium salt of a two-chain dihydrophilic surfactant obtained by reacting a triamine compound and further reacting with a quaternizing agent. (D) A detergent composition containing the two-chain two-hydrophilic surfactant of (A) or (C) or an ammonium salt thereof in an amount of 0.1% by weight or more. (E) A hair treatment composition comprising the double-chain two-hydrophilic surfactant (A) or (C) or an ammonium salt thereof in an amount of 0.1% by weight or more. (F) A softener composition comprising the two-chain dihydrophilic surfactant of (A) or (C) or an ammonium salt thereof in an amount of 0.1% by weight or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The two-chain dihydrophilic surfactant of the present invention comprises reacting a salt of a secondary amine compound with epihalohydrin in a first step, and then reacting a secondary amine compound or a tertiary amine in a second step. It is obtained by reacting an amine compound. In the first step, a salt of a tertiary amine compound having an alkylhalide group derived from epihalohydrin at a terminal is obtained by opening the epoxy ring of the epihalohydrin and adding it to the salt of the secondary amine compound. The salt of the secondary amine compound is
Obtained by neutralizing the secondary amine compound. The acid used for the neutralization is preferably a monovalent inorganic acid such as hydrochloric acid or nitric acid, and more preferably hydrochloric acid in consideration of the effect on the reaction step with epihalohydrin and the purification step of the two-chain dihydrophilic surfactant. The amount of epihalohydrin to be used is preferably in the range of 1.00 to 1.05 moles, more preferably 1.02 to 1.03 times, based on the salt of the secondary amine compound.
It is twice the mole. If the amount of epihalohydrin used is more than 1.05 mole, by-products increase, and if it is less than 1.00 mole, unreacted salts of the secondary amine compound remain. It is not preferable because it decreases.
The reaction temperature is usually from 10 to 70 ° C., preferably from 30 to 5 ° C., because epihalohydrin is a highly reactive compound and reacts quickly with the secondary amine compound.
0 ° C.

When the secondary amine compound is reacted with epihalohydrin as it is without neutralizing the secondary amine compound to form a salt of the secondary amine compound, the produced tertiary amine compound reacts due to its own basicity. Side reactions other than the intended ring-opening addition reaction, such as the reaction with an alkylhalide derived from epihalohydrin in the system to form a polycondensate, undesirably lower the purity and yield. In the method of the present invention, by reacting the salt of the secondary amine compound with epihalohydrin, the generated tertiary amine compound is converted into a salt, so that side reactions such as polycondensation can be suppressed, and the purity and yield are high and the purity is high. A salt of a triamine compound can be obtained.

In the second step, following the ring-opening addition reaction of epihalohydrin in the first step, a secondary amine compound or a tertiary amine compound is added to the reaction solution, and an intermediate tertiary amine is added.
A nucleophilic substitution reaction is performed on the alkyl halide group of the salt of the amine compound. The amount of the secondary amine compound or the tertiary amine compound to be used is preferably in the range of 0.96 to 0.99 times, more preferably 0.97 to 0.9, mol per mol of the salt of the tertiary amine compound as an intermediate. It is 98 times mol. Reaction temperature is 6
0-110 ° C is preferred, and more preferably 80-90 ° C
It is. When the reaction temperature is higher than 110 ° C., the alkyl halide of the salt of the tertiary amine compound as an intermediate is hydrolyzed,
If the temperature is lower than 60 ° C., the reaction hardly proceeds, which is not preferable. A base to which an alkalizing agent such as sodium hydroxide or potassium hydroxide is added to increase the nucleophilic reactivity of the secondary amine compound or the tertiary amine compound and, in the case of the secondary amine compound, to involve dehydrohalogenation. The reaction is carried out under neutral conditions.

In the method for producing a two-chain dihydrophilic surfactant of the present invention, the first step and the second step can be carried out continuously in one reaction vessel. The solvent is not particularly limited as long as it is a solvent that is compatible with water, but it is preferable that the solvent be used only with water in consideration of applications to lifestyle-related products such as cosmetics and toiletry products.

The secondary amine compound or tertiary amine compound used in the present invention includes an amide group, an ester group, and an ether group which become a hydrophobic group when a desired two-chain dihydrophilic surfactant is synthesized. And a secondary or tertiary amine compound having an alkyl group or an alkenyl group, and a functional group serving as a hydrophilic group. As the secondary amine compound, for example, in an alkylaminoalkanol,
Alkyl amino methanol, alkyl amino ethanol, alkyl amino propanol, alkyl amino butanol, fatty acid amide alkyl amino alkanol, fatty acid amide methyl amino methanol, fatty acid amide methyl amino ethanol, fatty acid amide methyl amino propanol, fatty acid amide methyl amino butanol,
Fatty acid amidoethylamino methanol, fatty acid amidoethylaminoethanol, fatty acid amidoethylaminopropanol, fatty acid amidoethylaminobutanol, fatty acid amidopropylaminomethanol, fatty acid amidopropylaminoethanol, fatty acid amidopropylaminopropanol, fatty acid amidopropylaminobutanol,
Fatty acid amide butyl amino methanol, fatty acid amide butyl amino ethanol, fatty acid amide butyl amino propanol, fatty acid amide butyl amino butanol, fatty acid ester amino alkanol, fatty acid ester methyl amino methanol, fatty acid ester methyl amino ethanol, fatty acid ester methyl amino propanol, fatty acid Ester methyl amino butanol, fatty acid ester ethyl amino methanol, fatty acid ester ethyl amino ethanol, fatty acid ester ethyl amino propanol, fatty acid ester ethyl amino butanol, fatty acid ester propyl amino methanol, fatty acid ester propyl amino ethanol, fatty acid ester propyl amino propanol, fatty acid ester propyl Aminobutanol, fatty acid ester Butylamino methanol, fatty acid ester butylaminoethanol, fatty acid ester butylaminopropanol, fatty acid ester butylaminobutanol are alkyl ether aminoalkanols, alkyl ether methyl amino methanol, alkyl ether methyl amino ethanol, alkyl ether methyl amino propanol, alkyl ether Methylamino butanol, alkyl ether ethyl amino methanol, alkyl ether ethyl amino ethanol, alkyl ether ethyl amino propanol, alkyl ether ethyl amino butanol, alkyl ether propyl amino methanol, alkyl ether propyl amino ethanol, alkyl ether propyl amino propanol, alkyl ether propyl amino Butanol, alkyl ether butylamino methanol, alkylether butylamino ethanol, alkyl ether butyl aminopropanol, alkyl ether butylamino butanol.

Examples of the tertiary amine compound include alkyl-type tertiary amine compounds such as aminoalkanoldimethylamine, alkyldiethylamine, alkyldipropylamine, alkyldibutylamine, alkylmethylethylamine, alkylethylpropylamine, alkyldimethanolamine. Alkyldiethanolamine,
Fatty acid amide alkyl type tertiary amine compounds include fatty acid amide methyl dimethylamine, fatty acid amide ethyl dimethylamine, fatty acid amide propyl dimethylamine, fatty acid amide butyl dimethylamine, fatty acid amide methyl dimethanol amine, fatty acid amide ethyl dimethanol amine, fatty acid amide Propyl dimethanolamine, fatty acid amide butyl dimethanolamine, fatty acid amide methyl diethanolamine, fatty acid amide ethyl diethanolamine, fatty acid amide propyl diethanolamine, fatty acid amide butyl diethanolamine, fatty acid amide methyl dipropanolamine, fatty acid amide ethyl dipropanolamine, fatty acid amide propyldiethyl Propanolamine, fatty acid amide butyl dipropanolamine, fatty acid amide Ludibutanolamine, fatty acid amidoethyldibutanolamine, fatty acid amidopropyldibutanolamine, and fatty acid amidobutyldibutanolamine are fatty acid ester-type tertiary amine compounds. Fatty acid ester methyldimethylamine, fatty acid ester ethyldimethylamine, fatty acid ester propyl Dimethylamine, fatty acid ester butyldimethylamine, fatty acid ester methyldimethanolamine, fatty acid ester ethyldimethanolamine, fatty acid ester propyldimethanolamine, fatty acid ester butyldimethanolamine, fatty acid ester methyldiethanolamine, fatty acid ester ethyldiethanolamine, fatty acid ester propyl Diethanolamine, fatty acid ester butyldiethanolamine, fatty acid ester Ludipropanolamine, fatty acid ester ethyldipropanolamine, fatty acid ester propyldipropanolamine, fatty acid ester butyldipropanolamine, fatty acid ester methyldibutanolamine, fatty acid ester ethyldibutanolamine, fatty acid ester propyldibutanolamine, fatty acid ester butyldibutylamine When butanolamine is an alkyl ether type tertiary amine compound, alkyl ether methyl dimethylamine, alkyl ether ethyl dimethylamine, alkyl ether propyl dimethylamine, alkyl ether butyl dimethylamine, alkyl ether methyl dimethanolamine, alkyl ether ethyl dimethanolamine , Alkyl ether propyl dimethanolamine, alkyl ether butyl dimetha Nolamine, alkyl ether methyl diethanolamine, alkyl ether ethyl diethanolamine, alkyl ether propyl diethanolamine, alkyl ether butyl diethanolamine, alkyl ether methyl dipropanolamine, alkyl ether ethyl dipropanolamine, alkyl ether propyl dipropanolamine, alkyl ether butyl dipropanolamine, Examples thereof include alkyl ether methyl dibutanolamine, alkyl ether ethyl dibutanolamine, alkyl ether propyl dibutanolamine, and alkyl ether butyl dibutanolamine.

Preferred secondary amine compounds or tertiary amine compounds are amidoalkyl type secondary amine compounds or tertiary amine compounds represented by the formula (1).

[0016]

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[0017] (wherein R ¹ CO represents an aliphatic acyl group having 10 to 22 carbon atoms, R ^2, R ³ represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms or a hydrogen atom,, R ⁴ Represents an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4.) In the secondary amine compound or the tertiary amine compound represented by the formula (1), R ¹ CO is It is an aliphatic acyl group having 10 to 22 carbon atoms, specifically, saturated aliphatic groups such as a decyloyl group, an undecyloyl group, a dodecyloyl group, a tetradecyloyl group, a hexadecyloyl group, an octadecyloyl group, an eicosiroyl group, a docosiroyl group and an isostearyl group. Unsaturated aliphatic acyl groups such as an acyl group and an octadecenyloyl group, and coconut oil aliphatic acyl groups and tallow aliphatic acyl groups which are mixtures thereof Mixed aliphatic acyl group such as hardened beef tallow fatty acyl group. R ² has 1 to 4 carbon atoms
And specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. When R ³ and R ⁴ are secondary amine compounds, R ³ is a hydrogen atom, and R ⁴ is a hydroxyalkyl group having 1 to ⁴ carbon atoms, specifically, a hydroxymethyl group, a hydroxyethyl group, A propyl group and a hydroxybutyl group; in the case of a tertiary amine compound, each is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, Examples include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.

Particularly preferred are fatty acid amidoalkylaminoalkanols which are fatty acid residues having 10 to 22 carbon atoms, such as amidoethylaminoethanol decanoate, amidoethylaminoethanol undecanoate, amidoethylaminoethanol dodecanoate, tetradecane Amide ethylaminoethanol, amide ethylaminoethanol hexadecanoate, amide ethylaminoethanol octadecanoate, amide ethylaminoethanol eicodecanoate, amide ethylaminoethanol docosadecanoate, amide ethylaminoethanol isostearate and the like. Diamine compounds, secondary amine compounds having an unsaturated aliphatic acyl such as octadecenoic acid amidoethylaminoethanol, and coconut which is a mixture thereof Fatty acid amide-ethylamino ethanol, tallow fatty acid amide-ethylamino ethanol, secondary amine compounds with mixed aliphatic acyl group such as hardened beef tallow fatty acid amide-ethylamino ethanol.

By performing the above-mentioned production method using these secondary amine compounds, a two-chain dihydrophilic surfactant represented by the formula (2) can be obtained.

[0020]

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(Wherein R ¹ CO and R ⁵ CO represent an aliphatic acyl group having 10 to 22 carbon atoms which may be the same or different, and R ² and R ⁶ represent an alkyl group having 1 to 4 carbon atoms or hydroxyalkyl In the present invention, by selecting a secondary amine compound or a tertiary amine compound used in each of the two steps,
It is possible to provide a two-chain, two-hydrophilic group type surfactant having two hydrophobic groups and two hydrophilic groups different from each other or having the same structure. The two-chain dihydrophilic surfactants neutralize a tertiary amine in the molecule with an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or an organic acid such as formic acid, acetic acid, propionic acid, methyl halide, diethyl sulfate or the like. By quaternizing with a cationizing agent, a bisammonium salt can be obtained.

The two-chain dihydrophilic surfactant and its ammonium salt of the present invention can be used in combination with an anionic surfactant, a zwitterionic surfactant and a nonionic surfactant to form a detergent composition, A hair treatment composition and a softening composition can be obtained. Examples of anionic surfactants that can be used in combination include, for example, alkyl sulfate-type anionic surfactants, polyoxyethylene alkyl ether sulfate-type anionic surfactants, and polyoxyethylene amide ether sulfate-type anionic surfactants. Surfactants, acylmethyltaurine-type anionic surfactants, acylamino acid-type anionic surfactants, sulfosuccinic acid-type anionic surfactants and the like can be mentioned. Examples of the amphoteric surfactant include alkyl betaine-type amphoteric surfactants, amidoalkyl betaine-type amphoteric surfactants, imidazolinium betaine-type amphoteric surfactants, and alkyl iminodiacetic acid-type amphoteric surfactants. Can be Examples of the nonionic surfactant include a polyoxyethylene alkyl ether type nonionic surfactant, a polyoxyethylene fatty acid ester type nonionic surfactant, a sucrose ester type nonionic surfactant, and a polyoxyalkylene. Sucrose ester type nonionic surfactant, sorbitan ester type nonionic surfactant, polyoxyethylene sorbitan ester type nonionic surfactant, polyglycerin fatty acid ester type nonionic surfactant, polyoxyethylene cured castor Oil-type nonionic surfactants and alkyl glycoside-type nonionic surfactants are exemplified.

In the case of the detergent composition, by using the two-chain dihydrophilic surfactant and the ammonium salt thereof according to the present invention, the detergent composition has a suitable viscosity, good detergency, and excellent usability. Agent composition is obtained. Among the two-chain dihydrophilic surfactants and ammonium salts thereof of the present invention, a two-chain dihydrophilic surfactant represented by the formula (2) is preferable,

[0024]

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(Wherein R ¹ CO and R ⁵ CO represent an aliphatic acyl group having 10 to 22 carbon atoms which may be the same or different, and R ² and R ⁶ represent an alkyl group having 1 to 4 carbon atoms or hydroxyalkyl Or a hydrogen atom.) In view of the low-temperature stability of the detergent composition, the aliphatic acyl group is a dodecyloyl group, a tetradecyloyl group, a hexadecyloyl group, or a mixed aliphatic acyl group of these two-chain dihydrophilic groups. Base surfactants are particularly preferred.

The two-chain dihydrophilic surfactant and the ammonium salt thereof according to the present invention have two cationic functional groups in one molecule. Therefore, the hair treatment composition has a negatively charged hair surface. It is easy to be adsorbed on the skin, and has good finger passage during washing and rinsing, and shows excellent conditioning effect after drying. The softener composition can also impart flexibility to clothing, and the hydroxyl group in the molecule provides appropriate water absorption, so that it is possible to simultaneously impart flexibility and water absorption. Among the two-chain dihydrophilic surfactants and the ammonium salts thereof according to the present invention, the two-chain dihydrophilic surfactant represented by the formula (2):

[0027]

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(Wherein R ¹ CO and R ⁵ CO represent the same or different aliphatic acyl groups having 10 to 22 carbon atoms, and R ² and R ^{6 each} represent an alkyl group having 1 to 4 carbon atoms or hydroxyalkyl Or a hydrogen atom.) A two-chain, two-hydrophilic surfactant in which the aliphatic acyl group is a hexadecyloyl group, an otadecyloyl group, an octadecenyloyl group, or a mixed aliphatic acyl group thereof is preferable, and ammonium salts thereof are preferred. Salts are particularly preferred.

The amount of the two-chain dihydrophilic surfactant and its ammonium salt to be added to the detergent composition, the hair treatment composition and the softener composition according to the present invention may vary depending on the performance required for each composition. Although not so, it is usually 0.1 to 40% by weight. When the amount is less than 0.1% by weight, it is difficult to exhibit performance such as viscosity and feeling of use.

The above-mentioned cleaning composition, hair treatment composition and softening composition may contain, if desired, components generally incorporated, for example, higher alcohols such as cetanol and stearyl alcohol, glycerin, ethylene glycol, propylene glycol, and the like. Polyhydric alcohols such as 1,3-butanediol, oils such as squalane, jojoba oil, olive oil, castor oil, lanolin, lecithin, cellulose ether type cationic polymer compounds, cationic polyvinylpyrrolidone derivatives, cationic Polyacrylic acid derivatives, cationic polyamide derivatives, polydimethyldiallylammonium chloride, copolymers of dimethyldiallylammonium chloride and acrylamide, cationic polymer compounds such as alkyl polyethyleneimine, highly polymerized methylpolysiloxane, dimethylsiloxane Silicone derivatives such as xan-methyl (polyoxyethylene) siloxane copolymer, pearlizing agents such as ethylene glycol distearate, styrene polymer, preservatives such as paraoxybenzoate, sodium benzoate, phenoxyethanol, and 5-methyl- 2-isopropylcyclohexanol, tonic such as pepper tincture, ethylenediaminetetraacetate, citric acid, chelating agent such as trisodium nitrilotriacetate,
Ultraviolet absorbers such as benzophenone derivatives and benzotriazole derivatives, other dyes, fragrances and the like can be contained to such an extent that the effects of the present invention are not impaired.

[0031]

EFFECT OF THE INVENTION The two-chain dihydrophilic surfactant and its ammonium salt of the present invention, which can be obtained with high purity and high yield, can be used in detergent compositions, hair treatment compositions and softener compositions.

[0032]

EXAMPLES The present invention will be specifically described with reference to examples.

Example 1 In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 86.0 g of water and 43.0 g (0.1 ml) of amidoethylethanolamine dodecanoate were added.
50 mol) and neutralized with 15.6 g (0.150 mol) of 35% hydrochloric acid while stirring at 40 ° C. to convert the amidoamine into a hydrochloride. While maintaining the liquid temperature at 40 ° C., 14.2 g (0.154 mol) of epichlorohydrin (molecular weight 92.5) was added dropwise. The thin layer chromatogram showed that the spot of dodecanoamidoethylethanolamine disappeared, that no oxirane oxygen was detected, and that only free chlorine from hydrochloric acid used for neutralization was detected.
It was confirmed that epichlorohydrin only undergoes ring-opening addition reaction of the epoxy ring. Thereafter, 86.0 g of water and 43.0 g of dodecanoamidoethylethanolamine (0.1
50 mol) and 25.0 g (0.300 mol) of 48% NaOH, and reacted at 85 ° C. for 2 hours. After the completion of the reaction, the reaction solution was transferred to a separatory funnel, and the lower aqueous layer was removed to obtain 235.9 g of a reaction product. The reaction product was purified by column chromatography to obtain 77.4 g (82% yield) of an epichlorohydrin conjugate of two molecules of dodecanoamidoethylethanolamine (compound A). ¹ H
-The following structure was confirmed from the NMR spectrum (see FIG. 1) and the IR spectrum (see FIG. 2) (Compound A).
The analysis of total amine value, tertiary amine value and hydroxyl value was carried out by the following method. Total amine value: A.0.CS Official Method Tf 1a-64 Tertiary amine value: A.0.CS Official Method Tf 2a-64 Hydroxyl value: Standard oil and fat analysis test method (edited by The Japan Oil Chemists' Society)
2.3.6.2-1996

[0034]

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[0035] ¹ H-NMR spectrum (CDCl _3, internal standard, TMS) 0.87ppm (6H, C H 3 CH 2 -), 1.25ppm (32H, CH 3 (C H 2) 8 -) 1.61ppm _{(4H, -C H 2 CH 2} CO-) 2.17ppm (4H, -CH 2 C H 2 CO-) 2.48ppm (4H,> NC H 2 CHOH-) 2.58ppm (4H, -CONHC H 2 _{CH 2 N <) 2.70ppm (4H} ,> NC H 2 CH 2 OH) 3.24~3.39ppm (4H, -CONHCH 2 C
_{H 2 N <) 3.57ppm (4H} ,> NCH 2 C H 2 OH) 3.75ppm (1H,> NCH 2 C H OHCH 2 N <) IR spectrum (KBr, tablets) 1635cm ^-1, 1536cm ^-1, 1467cm ^-1 , 1
060 cm ^-1 (analytical value) Total amine value 178.4 Tertiary amine value 174.8 Hydroxyl value 249.1

Example 2 86.0 g of water and 43.0 g (0.150 mol) of amidoethylethanolamine dodecanoate were charged into the same apparatus as in Example 1, and stirred at 40 ° C. with 35% hydrochloric acid.
Neutralized with 6 g (0.150 mol) to convert the amidoamine to the hydrochloride. While maintaining the liquid temperature at 40 ° C., 14.2 g (0.154 mol) of epichlorohydrin was added dropwise. Since the thin-layer chromatogram showed the disappearance of the spot of dodecanoamidoethylethanolamine, the absence of oxirane oxygen, and the detection of only free chlorine from the hydrochloric acid used for neutralization, epichlorohydrin caused the opening of the epoxy ring. It was confirmed that only a cycloaddition reaction was occurring. Then, 102.8 g of water, 51.4 g (0.150 mol) of hexadecanoamidoethylethanolamine, 48% Na
OH 25.0 g (0.300 mol) was charged in order,
For 2 hours. After the completion of the reaction, the reaction solution was transferred to a separatory funnel, and the lower aqueous layer was removed to obtain 256.9 g of a reaction product. The reaction product was purified by column chromatography, and 81.2 g (79% yield) of an epichlorohydrin conjugate (compound B) of amidoethylethanolamine dodecanoate and amidoethylethanolamine hexadecanoate was obtained.
Obtained. ^The following structure was confirmed from the ¹ H-NMR spectrum and the IR spectrum. The analysis was performed in the same manner as in Example 1. (Compound B)

[0037]

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[0038] ¹ H-NMR spectrum (CDCl _3, internal standard, TMS) 0.87ppm (6H, C H 3 CH 2 -), 1.26ppm (40H, CH 3 (C H 2) 8 -, CH 3 ( C
_{H 2) 12 -) 1.60ppm (} 4H, - (CH 2) 8 C H 2 CH 2 CO-,
_{- (CH 2) 12 C H} 2 CH 2 CO-) 2.18ppm (4H, -CH 2 C H 2 CO-) 2.47ppm (4H,> NC H 2 CHOH-) 2.57ppm (4H, -CONHC _{H 2 CH 2 N <) 2.71ppm} (4H,> NC H 2 CH 2 OH) 3.25~3.40ppm (4H, -CONHCH 2 C
_{H 2 N <) 3.56ppm (4H} ,> NCH 2 C H 2 OH) 3.77ppm (1H,> NCH 2 C H OHCH 2 N <) IR spectrum (KBr, tablets) 1636cm ^-1, 1534cm ^-1, 1465cm ^-1 , 1
061 cm ^-1 (analytical value) Total amine value 163.8 Tertiary amine value 160.5 Hydroxyl value 233.4

Example 3 In a device similar to that of Example 1, 102.8 g of water and 51.4 g (0.1%) of amidoethylethanolamine hexadecanoate were added.
50 mol) and neutralized with 15.6 g (0.150 mol) of 35% hydrochloric acid while stirring at 40 ° C. to convert the amidoamine into a hydrochloride. While maintaining the liquid temperature at 40 ° C., 14.2 g (0.153 mol) of epichlorohydrin was added dropwise. Because the thin layer chromatogram showed that the spot of hexadecanoic acid amidoethylethanolamine disappeared, that no oxirane oxygen was detected, and that only free chlorine from hydrochloric acid used for neutralization was detected, epichlorohydrin caused the opening of the epoxy ring. It was confirmed that only a cycloaddition reaction was occurring. Thereafter, 102.8 g of water and 51.4 g (0.150 mol) of hexadecanoamidoethylethanolamine were added.
25.0 g (0.300 mol) of 8% NaOH was charged in this order, and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction solution was transferred to a separating funnel, and the lower aqueous layer was removed.
1.6 g were obtained. The reaction product was purified by column chromatography to obtain 96.7 g (83% yield) of an epichlorohydrin conjugate of two molecules of hexadecanoamidoethylethanolamine (compound C). ^The following structure was confirmed from the ¹ H-NMR spectrum and the IR spectrum. The analysis was performed in the same manner as in Example 1. (Compound C)

[0040]

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[0041] ¹ H-NMR spectrum (CDCl _3, internal standard, TMS) 0.87ppm (6H, C H 3 CH 2 -), 1.25ppm (48H, CH 3 (C H 2) 12 -) 1.61ppm _{(4H, -C H 2 CH 2} CO-) 2.16ppm (4H, - (CH 2) 12 CH 2 C H 2 CO
-) 2.49ppm (4H,> NC H 2 CHOH-) 2.59ppm (4H, -CONHC H 2 CH 2 N <) 2.69ppm (4H,> NC H 2 CH 2 OH) 3.23~3. 41ppm (4H, -CONHCH ₂ C
_{H 2 N <) 3.58ppm (4H} ,> NCH 2 C H 2 OH) 3.76ppm (1H,> NCH 2 C H OHCH 2 N <) IR spectrum (KBr, tablets) 1634cm ^-1, 1537cm ^-1, 1465cm ^-1 , 1
059 cm ^-1 (analytical value) Total amine value 144.3 Tertiary amine value 1141.4 Hydroxyl value 205.6

Comparative Example 1 The same apparatus as in Example 1 was charged with 86.0 g of water and 43.0 g (0.150 mol) of amidoethylethanolamine dodecanoate, and 14.2 g of epichlorohydrin (0. .153 mol) was added dropwise. In the thin layer chromatogram, the spot of dodecanoamidoethylethanolamine did not disappear. Also, although oxirane oxygen was not detected, but free chlorine was detected,
It was confirmed that epichlorohydrin undergoes ring-opening addition reaction of epoxy ring and substitution reaction by dechlorination. Then, 86.0 g of water, 43.0 g (0.150 mol) of amidoethylethanolamine dodecanoate, 48% NaOH2
5.0 g (0.300 mol) were charged in this order and reacted at 85 ° C. for 2 hours. After the completion of the reaction, the reaction solution was transferred to a separatory funnel, and the lower aqueous layer was removed to obtain 235.9 g of a reaction product. The reaction is purified by column chromatography and
39.6 g (42% yield) of an epichlorohydrin-linked compound (compound A) of dodecanoamidoethylethanolamine having a molecular weight was obtained.

Comparative Example 2 172.0 g of water and 86.0 g (0.300) of amidoethylethanolamine dodecanoate were placed in the same apparatus as in Example 1.
Mol) and stirring at 40 ° C. with 35% hydrochloric acid (1).
The mixture was neutralized with 5.6 g (0.150 mol), and half of the amidoamine charged was converted into a hydrochloride. While maintaining the liquid temperature at 40 ° C., 14.2 g (0.153 mol) of epichlorohydrin was added dropwise. In the thin layer chromatogram, the spot of dodecanoamidoethylethanolamine disappeared. Oxirane oxygen was not detected, but free chlorine was detected, confirming that epichlorohydrin had undergone a ring-opening addition reaction of the epoxy ring and a substitution reaction by dechlorination. Thereafter, 25.0 g of 48% NaOH (0.300
Mol) and reacted at 85 ° C. for 2 hours. After the completion of the reaction, the reaction solution was transferred to a separating funnel, and the lower aqueous layer was removed.
235.9 g of reaction product was obtained. The reaction product was purified by column chromatography to obtain 29.2 g (yield: 31%) of an epichlorohydrin conjugate (compound A) of two molecules of dodecanoamidoethylethanolamine.

Example 4 A 500 ml autoclave equipped with a stirrer, a thermometer and a pressure gauge was charged with the two-chain dihydrophilic surfactant (compound A) obtained in Example 1, isopropanol and methyl chloride. Quaternization was performed at 80 ° C. for 4 hours to obtain an ammonium salt solution. Example 2 and Example 3
The same procedure was applied to the two-chain two-hydrophilic group type surfactant (Compound B and Compound C) obtained in the above. Table 1 shows the amounts charged for quaternization and the analysis values of the ammonium salt solution for each.

[0045]

[Table 1]

1) 1% by weight of a residue obtained by drying 1 g of a sample at 105 ° C. for 2 hours 2) Potentiometric titrator (COM-50 manufactured by Hiranuma Sangyo Co., Ltd.)
Using 0), the silver nitrate solution was titrated to obtain Cl%. 3) AOCS Official Method Tf 1a-64

Example 5 A detergent composition was prepared using the two-chain dihydrophilic surfactant obtained in Examples 1 to 4 and its ammonium salt.
evaluated. The composition and results are shown in Table 2. The composition shown in the table indicates% by weight, and the evaluation was performed by the following method. <Evaluation method> (1) Viscosity Using a B-type viscometer (manufactured by Tokyo Keiki Seisakusho), 25
The viscosity after 100 seconds was measured under the condition of ° C., and evaluated by the following three steps. High viscosity. (6000 mPa · s or more) It is a preferable viscosity. (1500 mPa · s or more, 60
(Less than 00 mPa · s) Low viscosity. (Less than 1500 mPa · s) (2) Detergency Terg-O-tometer using an aqueous solution prepared so that the detergent composition has a concentration of 1% by weight as an effective component.
Then, the artificially-contaminated wool muslin cloth is heated at 40 ° C. and 70 rpm.
m, washing for 10 minutes. After drying the contaminated cloth, the surface reflectance was measured with a color computer, the detergency was calculated from the following equation, and evaluated in the following three steps. Detergency (%) = A / B x 100 A: (Reflectance of contaminated cloth after cleaning)-(Reflectance of contaminated cloth before cleaning) B: (Reflectance of wool muslin)-(Contamination cloth before cleaning) (Reflectance of the cleaning) Excessive cleaning power. (60% or more of detergency) Good detergency. (25% or more and less than 60% of detergency) Detergency is weak. (Less than 25% of detergency) (3) Sliminess at the time of washing Twenty women were panelists, and the sliminess at the time of washing their fingers with 5 g of the detergent composition was evaluated. A total score of 20 people was calculated with 2 points when the slimy feeling was not felt, 1 point when the slimy feeling was strong, and 0 when the slimy feeling was persistent and it took time to rinse. , Next 3
It was evaluated on a scale. There is no slimy feeling. (Total value 30 points or more) Somewhat slimy feeling. (Total value is 20 points or more and less than 30 points) A slimy feeling is strong. (Total value is less than 20 points) (4) Feeling of Skin Tightening after Washing Twenty women were panelists, and the feeling of skin tightening after washing their fingers with 5 g of the detergent composition was evaluated. The total value of the 20 subjects was calculated based on the following three grades, with 2 points when the skin was not firmly felt at all, 1 point when the skin was slightly firmed, and 0 when the skin felt very firm. . I don't feel tight. (Total value 30 points or more) There is a feeling of slight tension. (Total value 20 points or more and less than 30 points) The feeling of tightness is strong. (Total value less than 20 points) (5) Refreshing feeling after washing 20 women were panelists, and the refreshing feeling after washing hands with 5 g of the detergent composition was evaluated. The total score of the 20 people was calculated based on the following three grades, with 2 points for feeling very refreshing, 1 point for feeling not very refreshing, and 0 point for feeling not refreshing at all. did. A sufficient refreshing feeling is obtained. (Total value 30 points or more) A refreshing feeling is not obtained much. (Total 20 points or more 3
(Less than 0 point) Refreshing feeling cannot be obtained. (Less than 20 points in total)

[0048]

[Table 2]

The compounding amount represents the weight% of the active ingredient.

Example 6 A hair treatment composition was prepared using the two-chain dihydrophilic surfactant obtained in Examples 1 to 4 and its ammonium salt, and evaluated. The composition and results are shown in Table 3. The composition shown in the table indicates% by weight, and the evaluation was performed by the following method. <Evaluation method> (1) Finger penetration at the time of hair washing and rinsing Twenty women were panelists, and finger penetration at the time of hair washing and rinsing with 5 ml of the composition was evaluated. The total value of the 20 people was calculated, with 2 points when the finger felt smooth and the hair did not get caught, 1 point when the hair felt slightly caught, and 0 point when the finger felt bad, and , Next 3
It was evaluated on a scale. Good finger passing (30 points or more in total) Slightly poor finger passing (20 points or more and less than 30 points) Poor finger passing (20 points or less in total) (2) Sliminess at the time of rinsing Hair shampoo-composition 5 with women as panelists
g and the slimy feeling upon rinsing after washing the hair was evaluated. A score of +1 was given if the slimy feeling during rinsing was persistent, 0 was given if the slimy feeling was appropriate, and -1 was given if the slimy feeling was not enough. The total value was determined and evaluated in the following three stages. Persistence of slimyness (total value of 10 points or more) Good sliminess (total value of -10 points or more and less than 10 points) Insufficient sliminess (total value of less than -10 points) (3) Conditioning effect after drying Hair shampoo-composition 5 with women as panelists
g, the hair was rinsed and rinsed, and the conditioning effect was evaluated by the combability after air-drying. If the hair does not feel squeaky and the comb feels smooth,
The score is 1 when the comb feels a bit on the hair and 0 when the hair is squeezed and the comb feels poor.
The total value of 0 persons was obtained and evaluated in the following three stages. Good conditioning effect (30 points or more in total) Slightly poor conditioning effect (20 points or more and less than 30 points) Bad conditioning effect (20 points or less in total)

[0051]

[Table 3]

[0052] The compounding amount represents the weight% of the active ingredient.

Example 7 A softener composition using the two-chain dihydrophilic surfactant obtained in Examples 1 to 4 and its ammonium salt was prepared.
evaluated. The composition and results are shown in Table 4. The composition shown in the table indicates% by weight, and the evaluation was performed by the following method. <Evaluation method> (1) Flexibility test 25% by weight of di-hardened tallow dimethyl quaternary ammonium salt
Six milliliters of the solution was added to 30 liters of water, and a cotton towel washed with household detergent was rinsed with the solution for three minutes. The cotton towel was dehydrated and air-dried to obtain a standard product. The softener compositions shown in Table 4 were also rinsed with cotton towels in the same manner as the standard products. Using these cotton towels and standard cotton towels, 20 panelists performed a pairwise comparison. The evaluation criteria are as follows: When the flexibility is felt to be much better than the standard product: +2. When the flexibility is felt to be better than the standard product: +1. When the flexibility is felt to be equal to the standard product: 0. When the flexibility was felt to be worse than the standard product: -1 point When the flexibility was felt to be much worse than the standard product: -2 point. Those with a total score of 20 or more for 20 panelists were judged to be good in flexibility. (2) Water Absorption Test The softener composition shown in Table 4 was added to 30 liters of water for 6 times.
Milliliters were mixed, and a cotton towel cut into strips of 3 cm × 20 cm was rinsed with this solution for 3 minutes. The cotton towel was dried, and 2 cm of one end thereof was immersed in water, and the height of the raised water after 15 minutes was measured. 8.0
cm or more was determined to have good water absorption, and less than 8.0 cm was determined to be poor.

[0054]

[Table 4]

[0055] The compounding amount represents the weight% of the active ingredient.

In Examples 1 to 3, it is clear that the two-chain dihydrophilic surfactant of the present invention has high purity and high yield. In Comparative Example 1, the salt of the secondary amine compound was not used, and in Comparative Example 2, the reaction was carried out without a part of the secondary amine compound being a salt. I can't get it. In Example 4, it is clear that the ammonium salt of the two-chain dihydrophilic surfactant of the present invention has high purity and yield. In Example 5, by blending the two-chain two-hydrophilic group type surfactant of the present invention and its ammonium salt, there is a moderate viscosity and detergency,
Further, it can be seen that a detergent composition having excellent usability can be obtained. In Example 6, by blending the two-chain dihydrophilic surfactant of the present invention and its ammonium salt, it is excellent in finger passing during shampooing and rinsing, has a good slimy feeling during rinsing, and is dried. It can be seen that a hair treatment composition excellent in the subsequent conditioning effect can be obtained. In Example 7, it can be seen that a softener composition excellent in flexibility and water absorption can be obtained by blending the two-chain dihydrophilic surfactant and the ammonium salt thereof of the present invention.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of compound A obtained in Example 1.

FIG. 2 is an IR spectrum of Compound A obtained in Example 1.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C07C 233/36 C07C 233/36 C11D 1/62 C11D 1/62 F term (Reference) 4C083 AB012 AB052 AC072 AC402 AC641 AC642 AC691 AC692 CC38 DD27 EE06 EE28 4D077 AA09 AB10 AB11 DC15X DC45X DC48X 4H003 AB31 AD04 AE02 AE07 DA01 DA02 EB08 ED02 FA03 FA21 FA22 FA30 4H006 AA01 AA03 AB68 BN10 BU32 BV22

Claims (6)

[Claims] 1. A two-chain dihydrophilic surfactant obtained by reacting a salt of a secondary amine compound with epihalohydrin and then reacting with a secondary or tertiary amine compound. 2. The two-chain two-hydrophilic surfactant according to claim 1, wherein the secondary amine compound or the tertiary amine compound is represented by the formula (1). Embedded image (In the formula, R ¹ CO represents an aliphatic acyl group having 10 to 22 carbon atoms, R ² and R ³ represent an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrogen atom, and R ⁴ represents a carbon atom. Represents an alkyl group or hydroxyalkyl group of 1-4, and n represents an integer of 1-4.) 3. A two-chain, two-hydrophilic group obtained by reacting a salt of a secondary amine compound with epihalohydrin, then reacting a secondary amine compound or a tertiary amine compound, and further reacting with a quaternizing agent. Surfactant. 4. A detergent composition comprising the two-chain dihydrophilic surfactant of claim 1 or 3 or an ammonium salt thereof in an amount of 0.1% by weight or more. 5. A hair treatment composition comprising the surfactant of claim 1 or 3 or an ammonium salt thereof in an amount of 0.1% by weight or more. 6. A softener composition comprising the surfactant of claim 1 or 3 or an ammonium salt thereof in an amount of 0.1% by weight or more.