JPH09301937A - Novel amino acid ester salt, method for producing the same, and softener composition containing the same - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a compound suitable as a soft base material having excellent flexibility and biodegradability. An amino acid ester salt represented by the general formula (I), a method for producing the same, and a softener composition containing the same. Embedded image (In the formula, R ¹ and R ² are alkyl groups or alkenyl groups having 8 to 36 carbon atoms, R ³ and R ⁴ are alkylene groups having 2 to ⁴ carbon atoms, p
And q are numbers from 0 to 4, r is 1 or 2, and X ⁻ is an anionic group. )

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amino acid ester salt, a method for producing the same, and a softener composition containing the same.

[0002]

2. Description of the Related Art
Most of the commercially available products as a fabric softening agent 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 in that, when the residual substance after the treatment is released to the natural world such as a river, it is hardly biodegraded and accumulated.

As an improved product of such problems, N-methyl-N, N-bis [hardened beef tallow alkanoyloxyethyl] -N- (2-hydroxyethyl) ammonium methylsulfate and N, N-dimethyl-N, N are used. -Bis [alkanoyloxyethyl] ammonium chloride and the like are on the market, but these have improved biodegradability as compared with the above quaternary ammonium salts, but have satisfactory flexibility and environmental safety. It is not a good base.

Therefore, the object of the present invention is to provide excellent flexibility,
Another object of the present invention is to provide a compound suitable as a soft base having good biodegradability.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific novel amino acid ester salt is optimal for the above purpose, and completed the present invention. That is, the present invention provides an amino acid ester salt represented by the general formula (I), a method for producing the same, and a softener composition containing the same.

[0006]

Embedded image

(In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group or an alkenyl group having 8 to 36 carbon atoms, and R ³ and R ⁴ are the same or different and have the same carbon number. 2 to 4 represents an alkylene group, and p and q each represent the average number of moles of alkylene oxide added.
It is a number of 4, and p R ³ and q R ⁴ may be the same or different. r is 1 or 2 and X ⁻ is an anion group obtained by removing one hydrogen atom from an inorganic or organic acid. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

In the amino acid ester salt represented by the general formula (I) of the present invention, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group or alkenyl group having 8 to 36 carbon atoms. , Preferably a linear or branched alkyl group or alkenyl group having 12 to 22 carbon atoms, more preferably a linear alkyl group or alkenyl group having 14 to 18 carbon atoms, and R ¹ and R ² are the same. Are preferred.

R ³ and R ⁴ are the same or different and each has 2 carbon atoms.
The alkylene groups of 4 to 4 are shown, and p R ^{3 s} and q R ^{4 s} may be the same or different, but an ethylene group or a propylene group is preferable, and an ethylene group is particularly preferable. p and q each represent a number of 0 to 4, and 0 is preferable.

[0011] X ^- is show inorganic or anionic group obtained by removing one hydrogen atom from an organic acid, halogen ion, sulfonic acid ion or sulfuric acid ion preferably, Cl ^-, p-toluenesulfonate ion, methanesulfonate Ions and sulfate ions are more preferable.

Examples of the amino acid ester salt represented by the general formula (I) include the followings.

[0013]

Embedded image

The amino acid ester salt represented by the general formula (I) is produced as follows. That is, the general formula (II)

[0015]

Embedded image

The amino acid represented by the formula (wherein r has the above-mentioned meaning) is an inorganic or organic compound represented by the general formula (III) HX (III) (wherein X has the above-mentioned meaning). After neutralization with an acid, the compound of the general formula (IV) or (IV ') R ¹ O- (R ³ O) _p -H (IV) R ² O- (R ⁴ O) _q -H (IV') (formula Wherein R ¹ , R ² , R ³ , R ⁴ , p and q have the above-mentioned meanings) and are esterified with one or more of the higher alcohols or alkylene oxide adducts thereof. To be done.

Examples of the amino acid represented by the general formula (II) include aspartic acid and glutamic acid. To neutralize these amino acids, an amino acid may be made into an aqueous solution and then an inorganic or organic acid represented by the general formula (III) may be added.
(IV) or (IV ') after being dispersed in a higher alcohol represented by (IV) or alkylene oxide adduct thereof,
An inorganic or organic acid represented by II) may be added. Alternatively, it may be neutralized in a solvent used for the next esterification. The inorganic or organic acid represented by the general formula (III) used for neutralization may be any strong acid, but hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like are preferable. The addition amount of the inorganic or organic acid represented by the general formula (III) is sufficient if 1 equivalent is added to the amino acid represented by the general formula (II), but if it is added in excess, an esterification catalyst is added. It is preferable to work as. Therefore, the general formula
The addition amount of the inorganic or organic acid represented by (III) is preferably 1.0 to 1.2 equivalents, more preferably 1.0 to 1.1 equivalents, relative to the amino acid represented by the general formula (II).

Next, esterification is carried out with a higher alcohol represented by the general formula (IV) or (IV ') or an alkylene oxide adduct thereof. The higher alcohol used here or an alkylene oxide adduct thereof is octanol. , Decanol, dodecanol, tetradecanol,
Hexadecanol, octadecanol, eicosanol, docosanol, oleyl alcohol or ethylene oxide or propylene oxide adducts thereof can be used. These can use 1 type or a mixture of 2 or more types.

The esterification is carried out in the presence of a solvent such as benzene, toluene or xylene, or without a solvent.
The reaction temperature for esterification is 80 ° C to 200 ° C, preferably 80 ° C.
~ 120 ° C. The reaction is preferably carried out while distilling off the produced water, and it is also preferable to carry out the reaction under normal pressure or reduced pressure.

When a solvent is used, the amino acid ester salt represented by the general formula (I) can be obtained by distilling off the solvent after completion of the reaction. The structure of the obtained amino acid ester salt can be confirmed by infrared absorption spectrum and ¹ H-NMR spectrum.

The amino acid ester salt represented by the general formula (I) of the present invention thus obtained can be used as a softener composition by dispersing it in water. The content of the amino acid ester salt represented by the general formula (I) in the softener composition of the present invention is preferably 2 to 40% by weight. If it is 2% by weight or more, a sufficient softening effect can be obtained, and if it is 40% by weight or less, the viscosity of the composition does not increase and handling becomes good.

The softening agent composition of the present invention contains a higher alcohol, in order to further improve softening performance and storage stability.
Higher fatty acids, other viscosity modifiers, lower alcohols as storage stabilizers, and further known cation activators, nonionic activators, inorganic salts, pH adjusters, hydrotropes, fragrances, defoamers, pigments, etc., if necessary. Can be added.

In the softener composition of the present invention, the amino acid ester salt represented by the general formula (I) and other components are melt-mixed and gradually added dropwise to deionized water under stirring to form an emulsion. It can be prepared by

The softener composition of the present invention is used as a softening agent for imparting flexibility and elasticity to fibers, or as a hair cosmetic agent for imparting excellent smoothness and flexibility to hair. Can be used.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 200 ml of toluene was placed in a four-necked flask equipped with a stirrer, a dehydration tube and a thermometer, 26.6 g of aspartic acid was dispersed therein, and then 38.2 g of p-toluenesulfonic acid (monohydrate) was added. Neutralized. Next, 108.0 g of octadecanol was added, and the temperature was 105 ° C.
The esterification was carried out for 6 hours while distilling off the produced water. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 170.5 g of an amino acid ester salt represented by the following structural formula (A).

[0027]

[Chemical 6]

[0028]

[Chemical 7]

IR spectrum (KBr tablet) 1760 cm ^-1 , 1740 cm ^-1 , 1600 cm ^-1 Example 2 10% in a four-necked flask equipped with a stirrer, a dehydration tube and a thermometer.
120 g of hydrochloric acid was added, and 44.1 g of glutamic acid was added for neutralization. Next, 145.2 g of hexadecanol was added, and the temperature was raised to 120 ° C. while distilling off water at 50 torr. Esterification was carried out for 6 hours while distilling off the produced water.
After completion of the reaction, the solvent was distilled off under reduced pressure to obtain the following structural formula (B).
185.3 g of an amino acid ester salt represented by

[0030]

Embedded image

[0031]

Embedded image

[0032] IR spectrum (KBr tablet) 1740 cm ^-1, 1710 cm ^-1 Example 3 a stirrer, a dehydration tube, placed 200ml of toluene into a four-necked flask equipped with a thermometer, after dispersing the aspartic acid 26.6 g, p -Toluenesulfonic acid (monohydrate) (38.2 g) was added for neutralization. Next, add 162.3 g of ethylene oxide adduct of oleyl alcohol (average number of moles added: 3.0) at 105 ° C.
The esterification was carried out for 6 hours while distilling off the produced water. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 210.5 g of an amino acid ester salt represented by the following structural formula (C).

[0033]

Embedded image

[0034]

Embedded image

IR spectrum (KBr tablet) 1760 cm ⁻¹ , 1740 cm ⁻¹ , 1600 cm ⁻¹ Test Example The softening agent compositions containing the amino acid ester salts obtained in Examples 1 to 3 were used to give flexibility by the following method. evaluated. The results are shown in Table 1.

<Flexibility Evaluation Method> Preparation of Softening Agent Composition The amino acid ester salts obtained in Examples 1 to 3 were melted,
The mixture was added dropwise to warm water with stirring to prepare a dispersion liquid so that the concentration of the amino acid ester salt was 5% by weight to obtain a softener composition.

Treatment method 2 kg of a commercially available cotton towel is used in a 30 liter washing machine,
After repeatedly washing with a commercially available detergent attack (registered trademark, manufactured by Kao Corporation) 5 times in 3.5 ° DH hard water, 25 ml of a softening agent composition consisting of the above dispersion of the amino acid ester salt was added at the time of rinsing at 25 ° C., It was treated under stirring for 1 minute.

Softness Evaluation Method The cotton towel treated by the above method was air-dried at room temperature and then at 25 ° C.
It was left for 24 hours in a constant temperature and humidity room at 65% RH. These were evaluated for flexibility. For the evaluation, a pair of comparisons were made with a cotton towel treated as above as a soft base, which is a general dimethyldi-cured beef tallow alkylammonium chloride, as a control, and evaluated according to the following criteria.

Evaluation criteria 3; Softer than control 2; Softer than control 1; Equivalent to control 0; Control is slightly softer

[0040]

[Table 1]

As is clear from the results shown in Table 1, Example 1
In each of the cases, the ones treated with the softener composition containing the amino acid ester salt obtained in each of Examples 3 to 3 had excellent flexibility as compared with the control.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Tatezawa 1334 Minato Minato, Wakayama City, Wakayama Prefecture Research Laboratory (72) Inventor Yasunori Ota 1334 Minato Minato, Wakayama City, Wakayama Prefecture Research Laboratory, Kao Corporation (72) Inventor Katsuhisa Inoue 1334 Minato Minato, Wakayama City, Wakayama Research Institute (72) Inventor Michio Terasaka 1334 Minato Minato, Wakayama City, Wakayama Research Institute

Claims (3)

[Claims] 1. An amino acid ester salt represented by the general formula (I). Embedded image (In the formula, R ¹ and R ² are the same or different and have 8 to 8 carbon atoms.
36 represents a linear or branched alkyl group or alkenyl group, wherein R ³ and R ⁴ are the same or different and have 2 to 4 carbon atoms.
Of the alkylene group, p and q are each a number from 0 to 4 indicating the average number of added moles of alkylene oxide,
The p R ^{3 s} and the q R ^{4 s} may be the same or different. r
Is 1 or 2, X ^- is a hydrogen atom from an inorganic or organic acid.
The anion group excluding the individual is shown. ) 2. A compound of the general formula (II) (Wherein r has the above-mentioned meaning), an amino acid represented by the general formula (III) HX (III) (wherein X has the above-mentioned meaning) is an inorganic or organic acid. after sum, in the general formula (IV) or ^{(IV ') R 1 O- (} R 3 O) p -H (IV) R 2 O- (R 4 O) q -H (IV') ( wherein, R ¹ , R ² , R ³ , R ⁴ , p and q
Has the above-mentioned meaning. The method for producing an amino acid ester salt represented by the general formula (I) according to claim 1, wherein the esterification is carried out with one or more higher alcohols represented by the formula (1) or alkylene oxide adducts thereof. 3. A softener composition comprising the amino acid ester salt according to claim 1.