JPH09188654A - Surfactant and liquid softening finish composition containing the same - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a surfactant having excellent flexibility and biodegradability, which is suitable as a soft base, and a liquid soft finish composition containing the same. A quaternary ammonium salt (I),
A surfactant in which the ratio of R ¹ and R ^{2 having} a total carbon number of 32 or more is 50% by weight or more and less than 100% by weight, and a liquid softening agent composition containing the same. Embedded image (In the formula, R ¹ represents a linear alkyl group or alkenyl group having 16 to 18 carbon atoms, and R ² represents a linear alkyl group or alkenyl group having 14 to 16 carbon atoms.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surfactant comprising a specific quaternary ammonium salt and a liquid softening finish composition containing the same. More specifically,
The present invention relates to a surfactant that imparts excellent flexibility and elasticity (puffiness) to various fibers, has excellent storage stability, and has excellent biodegradability, and a liquid softener composition containing the same. Is.

[0002]

2. Description of the Related Art
The quaternary ammonium salt used as the main component of the softening agent for fibers is 2 in 1 molecule as typified by di (hardened tallow alkyl) dimethyl ammonium chloride.
It is a quaternary ammonium salt having a long-chain alkyl group. However, the quaternary ammonium salt has a problem in that, when the residue after the treatment is released into the natural environment such as a river, the quaternary ammonium salt is hardly decomposed and accumulates. As its improved products, methyl bis (hardened beef tallow alkanoyloxyethyl) 2-hydroxyethyl ammonium methyl sulfate, dimethyl bis (alkanoyloxyethyl) ammonium chloride and the like are on the market, but these are compared with the above quaternary ammonium salt. Although the biodegradability is improved, it is not a satisfactory agent in terms of flexibility and environmental safety.

Therefore, an object of the present invention is to provide a surfactant which is excellent in flexibility and biodegradability and which is suitable as a soft base, and a liquid soft finish composition containing the same.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found a surfactant most suitable for the above purpose and completed the present invention. That is, the present invention
General formula (I)

[0005]

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(Wherein R ¹ represents a linear alkyl group or alkenyl group having 16 to 18 carbon atoms, and R ² represents a linear alkyl group or alkenyl group having 14 to 16 carbon atoms). The quaternary ammonium salt of which the total carbon number of R ¹ and R ² is 32 or more is 50% by weight or more of the total.
The present invention provides a surfactant characterized by being less than 100% by weight, and a liquid softening agent composition containing the same.

[0007]

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 is a linear alkyl group or alkenyl group having 16 to 18 carbon atoms, preferably a linear alkyl group having 16 to 18 carbon atoms. It indicates an alkyl group, R ² is an alkyl or alkenyl group of a straight chain of 14-16 carbon atoms, preferably an alkyl group having a straight chain of 14-16 carbon atoms.

In the surfactant of the present invention, in the general formula (I), the proportion of the quaternary ammonium salt in which the total number of carbon atoms of R ¹ and R ² is 32 or more is from 50% by weight to 100% by weight of the whole. Is less than 70% by weight, preferably less than 70% by weight and less than 100% by weight, and more preferably 25% by weight or more of the quaternary ammonium salt having a total carbon number of R ¹ and R ² of 34 or more.
It is less than 100% by weight. If the proportion of the quaternary ammonium salt in which the total number of carbon atoms of R ¹ and R ² is 32 or more is less than 50% by weight of the whole, sufficient flexibility cannot be obtained.
Further, when the proportion of the quaternary ammonium salt having a total carbon number of R ¹ and R ² of 32 or more is 100% by weight, it is necessary to purify the raw material alcohol used, which is economically disadvantageous.

The quaternary ammonium salt of the present invention represented by the above general formula (I) (hereinafter abbreviated as quaternary ammonium salt (I)) is produced by the following method.
General formula (II)

[0011]

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The branched alcohol represented by the formula (wherein R ¹ and R ² have the same meanings as described above) is subjected to an esterification reaction using monochloroacetic acid to give a compound represented by the general formula (III)

[0013]

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(Wherein R ¹ and R ² have the same meanings as described above), and the haloester is reacted with trimethylamine to give the quaternary ammonium salt (I). obtain.

The method for producing the quaternary ammonium salt (I) will be described in detail below. First, the branched alcohol represented by the general formula (II) is 0.9 to 3.0 times mol, preferably
70-230 with 1.0-1.5 times molar monochloroacetic acid
C., preferably 100 to 150.degree. C., using a catalyst if necessary, esterification is carried out for 0.5 to 30 hours to give a compound of the general formula (I
The haloester represented by II) is obtained. If necessary, during the esterification reaction, by blowing an inert gas such as nitrogen into the reaction system or under an air stream, or by performing the reaction under reduced pressure, the reaction product water can be efficiently removed from the system. The reaction time can be shortened by distilling off.

The branched alcohol represented by the general formula (II) used here is cetyl alcohol, stearyl alcohol, hardened or uncured beef tallow alcohol, palm stearyl alcohol, and one or a mixture of two or more potassium hydroxide. It is obtained by carrying out a condensation reaction at a high temperature using an alkali catalyst such as. Examples of the catalyst used in the above esterification reaction include acid catalysts such as p-toluenesulfonic acid and sulfuric acid.

Next, the general formula (I
II) and a haloester of 0.9 to 10.0 times mol, preferably 0.95 to 2.0 times mol, of this haloester, at 30 to 120 ° C., preferably 40 to
The quaternary ammonium salt (I) can be obtained by carrying out the quaternization reaction at a temperature of 70 ° C. for 0.1 to 10 hours using a solvent if necessary. Examples of the solvent used here include methanol, ethanol, isopropanol, acetone and the like.

The quaternary ammonium salt (I) of the present invention is
NMR, IR, gel permeation chromatography (GPC)
The structure and alkyl composition can be confirmed by.

The surfactant of the present invention is the quaternary ammonium salt (I) obtained as described above, in which the total number of carbon atoms of R ¹ and R ² is 32 or more, and the proportion thereof is 50%. If it is at least wt%, it is excellent in both flexibility and odor even if it is used as a soft base without refining the reaction mixture, and it is useful as a soft base.

The liquid softening agent composition of the present invention comprises the quaternary ammonium salt (I) obtained as described above, and the total carbon number of R ¹ and R ² is 32 or more. It contains 2 to 40% by weight of a surfactant having a proportion of the primary ammonium salt of 50% or more and less than 100% by weight. When the content of this surfactant is less than 2% by weight, the softening effect desired by the present invention cannot be obtained, and when it exceeds 40% by weight, the viscosity of the composition increases and the handling property becomes poor. .

In order to further improve the softening performance and storage stability, the liquid softening and finishing composition of the present invention comprises higher alcohols, higher fatty acids, other viscosity modifiers, lower alcohols as storage stabilizers, and known compounds. A cationic activator, a nonionic activator, an inorganic salt, a pH adjuster, a hydrotrope, a fragrance, an antifoaming agent, a pigment and the like can be added as required.

The liquid softening agent composition of the present invention can be prepared by melt-mixing the above-mentioned surfactant and other components, and gradually dripping into deionized water with stirring to form an emulsion. I can.

[0023]

[Examples] The present invention will be described in more detail below with reference to examples of synthesizing the surfactant of the present invention and examples of flexibility evaluation, but the present invention is not limited to these examples.

Example 1 33 g of monochloroacetic acid and 150 g of a condensation reaction product of stearyl alcohol / cetyl alcohol = 6/4 (weight ratio) were placed in a four-necked flask equipped with a stirrer, a thermometer and a cooling tube.
The temperature was raised to 40 ° C. After the produced water was distilled off and the reaction was carried out at the same temperature for 7 hours, excess monochloroacetic acid was removed by washing with water to obtain 172 g of chloroacetic acid ester.
A 0.5 liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was charged with 100 g of the chloroacetic acid ester, 15 g of trimethylamine and 28 g of isopropyl alcohol, and the temperature was raised to 50 ° C. The reaction was terminated by stirring at the same temperature for 3 hours. After the reaction, excess trimethylamine was distilled off,
112.5 g of the desired reaction mixture was obtained. NMR spectrum,
The following structure was confirmed from the IR spectrum.

[0025]

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[0026]

[Chemical 6]

IR spectrum (KBr tablets) 1746 cm ^-1 , 1204 cm ^-1 The following composition was confirmed by GPC (measurement condition eluent: tetrahydrofuran, column: G2000H × L + G1000H × L manufactured by Tosoh Corporation).

[0028] Example 2 33 g of monochloroacetic acid and 150 g of a condensation reaction product of beef tallow alcohol were placed in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, and the temperature was raised to 140 ° C. After distilling off the produced water, the reaction was carried out at the same temperature for 7 hours, and then excess monochloroacetic acid was removed by washing with water to remove chloroacetic acid ester.
g was obtained. A 0.5 liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was charged with 100 g of the chloroacetic acid ester, 15 g of trimethylamine and 28 g of isopropyl alcohol, and the temperature was raised to 50 ° C. The reaction was terminated by stirring at the same temperature for 3 hours. After the reaction, excess trimethylamine was distilled off to obtain 112.5 g of a desired reaction mixture. NMR
The following structure was confirmed from the spectrum and IR spectrum.

[0029]

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[0030]

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IR spectrum (KBr tablets) 1746 cm ^-1 , 1206 cm ^-1 The following composition was confirmed by GPC (measurement conditions eluent: tetrahydrofuran, column: G2000H × L + G1000H × L manufactured by Tosoh Corporation).

[0032] Example 3 33 g of monochloroacetic acid and 1450 g of a condensation product of palm stearyl alcohol were placed in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, and the temperature was raised to 140 ° C. After the produced water was distilled off and the reaction was carried out at the same temperature for 7 hours, the excess monochloroacetic acid was removed by washing with water to obtain 165 g of chloroacetic acid ester. With stirrer, thermometer, pressure gauge
Add the above chloroacetic ester to a 0.5 liter autoclave.
100 g, 14.5 g of trimethylamine and 27 g of isopropyl alcohol were added and the temperature was raised to 50 ° C. The reaction was terminated by stirring at the same temperature for 3 hours. After the reaction, excess trimethylamine was distilled off to obtain 110 g of a desired reaction mixture. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0033]

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[0034]

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IR spectrum (KBr tablets) 1746 cm ^-1 , 1206 cm ^-1 The following composition was confirmed by GPC (measurement condition eluent: tetrahydrofuran, column: G2000H × L + G1000H × L manufactured by Tosoh Corporation).

[0036] Comparative Example 1 Instead of the condensation reaction product of stearyl alcohol / cetyl alcohol = 6/4 (weight ratio), stearyl alcohol /
Using a condensation reaction product of cetyl alcohol = 2/8 (weight ratio), in the same manner as in Example 1, a fourth compound having the following structural formula.
A primary ammonium salt was obtained.

[0037]

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GPC (measurement conditions: eluent: tetrahydrofuran, column: Tosoh Corp. G2000H × L + G1000H ×
The following composition was confirmed by L).

[0039] Comparative Example 2 Quaternary ammonium having the following structural formula in the same manner as in Example 1 except that the condensation reaction product of cetyl alcohol was used instead of the condensation reaction product of stearyl alcohol / cetyl alcohol = 6/4 (weight ratio). I got salt.

[0040]

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Test Examples The surfactants composed of the quaternary ammonium salts obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for flexibility by the following method. The results are shown in Table 1.

<Flexibility Evaluation Method> Preparation of Quaternary Ammonium Salt Dispersion Liquid The quaternary ammonium salt prepared in Examples and Comparative Examples was melted and added dropwise to hot water with stirring to give quaternary ammonium salt. A dispersion liquid was prepared so that the salt concentration was 5% by weight.

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

Flexibility 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 carried out using a cotton towel treated as above as a standard with dimethyldi-hardened tallow alkylammonium chloride as a soft base. The evaluation is expressed as follows.

4; considerably softer than the control 3; softer than the control 2; slightly softer than the control 1; equal to the control 0; slightly softer than the control

[0046]

[Table 1]

As is clear from the results shown in Table 1, in each case, the examples are superior in flexibility to the comparative examples.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriko Yamaguchi 1334 Minato Minato, Wakayama City, Wakayama Prefecture Kao Research Institute

Claims (4)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ represents a linear alkyl group or alkenyl group having 16 to 18 carbon atoms, and R ² represents a linear alkyl group or alkenyl group having 14 to 16 carbon atoms.) Fourth consisting of a quaternary ammonium salt and having a total carbon number of R ¹ and R ² of 32 or more
A surfactant characterized in that the proportion of the primary ammonium salt is 50% by weight or more and less than 100% by weight of the whole. 2. In the general formula (I), the proportion of quaternary ammonium salt in which the total number of carbon atoms of R ¹ and R ² is 34 or more is
The surfactant according to claim 1, which is 25% by weight or more and less than 100% by weight. 3. R ¹ is a linear alkyl group having 16 to 18 carbon atoms,
The surfactant according to claim 1, wherein R ² is a linear alkyl group having 14 to 16 carbon atoms. 4. A liquid softener composition comprising 2 to 40% by weight of the surfactant according to any one of claims 1 to 3.