JPH08245984A - Liquid cleaning agent composition - Google Patents

Abstract

PURPOSE: To provide a liquid cleaning agent composition containing a material obtained by treating a synthesized amidesulfobetaine type amphoteric surfactant with a reverse osmosis membrane, mild to skin and hair, excellent in foaming and cleaning abilities and having excellent stability at low temperatures. CONSTITUTION: This composition contains a treated product of an amidesulfobetaine type amphoteric surfactant with a reverse osmosis membrane of the formula III, which is obtained by carrying out amphoteric compound- forming reaction of (A) an amide amine compound of formula I [R<1> CO is a C8-22 saturated fatty acid residue; R<2> and R<3> are each H, methyl, ethyl or hydroxyethyl; (n) is 2 to 10] with (B) a chlorohydroxypropane sulfonate compound of the formula II (X and Y are each H, OH or SO3 , and X is H or OH when Y is SO3 and X is SO3 when Y is H or OH). Furthermore, for example, the amphoteric compound-forming reaction is preferably carried out at 60 to 90 deg.C for 1 to 6 hours in the presence of a basic compound such as sodium methylate or sodium hydroxide. Laurylamide dimethylhydroxypropylsulfobetaine can be cited as an example of the amphoteric surfactant.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is gentle on skin and hair,
The present invention relates to a liquid detergent composition having excellent foaming power / cleaning power and good low-temperature stability.

[0002]

2. Description of the Related Art In recent years, surfactants used as a base for liquid detergents such as kitchen detergents and shampoos are required to be less irritating to skin such as hands and scalp and hair. ing. Amidoamine-type amphoteric surfactants and amidobetaine-type amphoteric surfactants are widely used as one type of such mild surfactants.

It has been recently reported that amidobetaine-type amphoteric surfactants have a stimulating effect. Amidosulfobetaine, which is classified as an amidobetaine-type amphoteric surfactant, is a commonly used amidoacetic acid. It is described in JP-A-6-145698, etc. that it is more useful as a solvent having a pearly luster as it is more likely to have a viscosity in combination with other activators than betaine.

[0004]

Conventionally, amidosulfobetaine has been produced by amphoterizing an amidoamine compound with a chloro compound derived from epichlorohydrin. However, when an amphoteric reaction is carried out using a chloro compound in the presence of a base, sodium chloride is inevitably produced as a by-product and cannot be removed by an ordinary treatment operation, so that sodium chloride remains in the product.

On the other hand, shampoos containing a cationic polymer to impart a conditioning effect and kitchen detergents containing collagen have been widely used.

However, although conventional amide sulfobetaine dissolves cationic polymers and the like relatively well as compared with amidoacetate betaine as described in JP-A-52-66506, amide sulfobetaine products. Due to the effect of sodium chloride remaining inside, there is a drawback that a cationic polymer or the like is deposited during low temperature storage.

Therefore, it has a mild effect on the skin and hair,
A detergent composition excellent in foaming power / cleansing power and excellent in low temperature stability has not been known so far.

An object of the present invention is to provide a detergent composition which has a mild action on the skin and hair and which does not impair excellent detergency and foaming power and has excellent stability even at low temperatures. It is to be.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a surfactant obtained by amphoteric conversion of chlorohydroxypropane sulfonate to an amidoamine compound in the presence of a basic substance by a conventional method. It was found that the above problems can be solved by blending the above with a reverse osmosis membrane treated, and the present invention was completed.

That is, the present invention has the general formula (1)

[0011]

[Chemical 4]

(In the formula, R ¹ CO represents a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms, and R ² and R ³ are each independently selected from a hydrogen atom, a methyl group, an ethyl group and a hydroxyethyl group. Represents a substituent represented by the formula, n is 2 to 1
To the amidoamine compound represented by the general formula (2)

[0013]

Embedded image

(In the formula, X and Y are hydrogen atom, hydroxyl group, S
Represents a substituent selected from O ₃ groups, where X is Y ₃
When it is a hydrogen atom or a hydroxyl group, and when Y is a hydrogen atom or a hydroxyl group, it represents an SO ₃ group.) A general formula (3) obtained by subjecting a chlorohydroxypropane sulfonate compound represented by

[0015]

[Chemical 6]

A reverse osmosis membrane treatment product of an amidosulfobetaine type amphoteric surfactant represented by the formula (wherein R ¹ CO, R ² , R ³ , n, X and Y are the same as defined above). And a liquid detergent composition comprising:

The amide sulfobetaine represented by the general formula (3) used in the present invention has a fatty acid having 8 to 22 carbon atoms as a starting material, and amide such as dimethylaminopropylamine.
Dehydration condensation with a lower alkyldiamine containing a primary amine,
An amidoamine compound represented by the general formula (1) containing a tertiary amine is produced, and epichlorohydrin and sulfite are separately reacted to prepare chlorohydroxypropane sulfonate, which are reacted in the presence of a base and treated with a reverse osmosis membrane. It can be manufactured by

The acyl group (R in the general formulas (1) and (2)
¹ CO) is a linear or branched fatty acid having 8 to 22 carbon atoms, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, coconut oil fatty acid, For example, palm kernel oil fatty acid and beef tallow fatty acid.

Specific examples of the amidoamine compound represented by the general formula (1) include, for example, N, N-dimethylpropyllauric acid amide, N, N-dimethylpropylcoconut oil fatty acid amide and N-methyl-N-hydroxy. Examples thereof include ethylpropyl myristate amide and N, N-dimethylethyllauric acid amide.

Specific examples of the chlorohydroxypropane sulfonate compound (2) for amphoterizing the amidoamine compound represented by the general formula (1) include, for example, 3-
Examples thereof include sodium chloro-2-hydroxypropane sulfonate, sodium 2-chloro-3-hydroxypropane sulfonate, and mixtures thereof.

Amphoterization of the amidoamine compound (1) with the chlorohydroxypropane sulfonate compound (2) may be carried out according to a conventional amphoteric reaction, for example, a basic compound such as sodium methylate or sodium hydroxide. The reaction may be carried out at a temperature of 60 to 90 ° C. for 1 to 6 hours.

Examples of typical amide sulfobetaine represented by the general formula (3) include lauryl amide dimethyl hydroxypropyl sulfobetaine and cocoyl amide dimethyl hydroxypropyl sulfobetaine. However, the amidosulfobetaine used is not limited to these.

The reverse osmosis membrane used in the present invention includes, for example, a cellulose acetate membrane, a sulfonated polysulfone membrane, a polyamidated sulfone membrane and the like.

To treat the amide sulfobetaine type surfactant with these reverse osmosis membranes, the concentration of the amide sulfobetaine type surfactant is adjusted to 5 to 50%, preferably 20 to 40%. To process. If the treatment concentration is less than 5%, it will take a long time and the cost will increase, which is not preferable.
If it exceeds 50%, the viscosity of the treatment liquid increases, pressure is applied to the membrane, and the membrane may be damaged.

Other surfactants to be added to the detergent composition of the present invention include fatty acid soap, higher alcohol sulfate ester salt, polyoxyethylene higher alcohol sulfate ester salt, higher alcohol phosphate ester salt, polyoxyethylene. Higher alcohol phosphate ester salt, polyoxyethylene higher fatty acid phosphate ester salt, sulfonated higher fatty acid salt, sulfonated higher fatty acid higher alcohol ester salt, higher alcohol sulfosuccinate ester salt, acylmethyl taurine, N-long chain acyl-glutamic acid N-acyl amino acid salt such as salt, anionic surfactant such as α-olefin sulfonate, fatty acid diethanolamide,
Examples thereof include nonionic surfactants such as fatty acid alkanolamides such as fatty acid monoethanolamide and fatty acid isopropanolamide and polyoxyethylene adducts thereof, and amphoteric surfactants such as alkylbetaine / alkylamide betaine / alkylimidazolium betaine.

If necessary, cationic polymers such as cationized guar, cationized cellulose, cationized chitin and cationized chitosan, solubilizing agents such as glycols, emollients such as ester oils, hyaluronic acid,
Moisturizing agents such as chitin, chitosan, collagen and its derivatives, cell activating agents such as placenta extract, allantoin, anti-inflammatory agents such as glycyrrhizinic acid, anti-dandruff agents such as zinc pyrithione and piroctone olamine, ethylene glycol distearate, etc. Pearlescent agents and fungicides, fragrances, pigments and the like can be added.

[0027]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified,
"%" Indicates% by weight.

Production Example 1 1 mol of lauric acid (200 g) and 1.0 mol of N, N-dimethylpropylamine (102 g) were added under reduced pressure to 140-2.
Dehydration condensation was carried out at 00 ° C., and 1 mol of water was removed to obtain lauric acid N, N-dimethylpropylamide. To this, 900 ml of purified water was added, 1 mol (197 g) of sodium chlorohydroxypropanesulfonate prepared by ring-opening epichlorohydrin with sodium bisulfite and a base catalyst was added, and 7.84 g of sodium hydroxide was added as a base catalyst. After reacting at 70 to 80 ° C. for 5 hours, the mixture was cooled and adjusted to pH 7 with an aqueous hydrochloric acid solution. 36% dry residue,
Lauric acid amide hydroxypropyl sulfobetaine was obtained as a pale yellow transparent liquid having a salt content of 5.7%.

Next, after adding purified water to a solid content concentration of 30%, a reverse osmosis membrane treatment device (trade name "20 type RO / UF" in which polyamidated sulfone having a membrane cross-sectional area of 0.4 m ² is set.
Test module ": Techno Universe) pressure 2
It was circulated at 0 Kg / cm ² . Purified water was added so that the salt solution that had permeated the membrane was removed so that the amount of the treatment liquid did not decrease and the pressure on the membrane did not rise. A total amount of 2130 g of membrane permeate was taken. The water content was adjusted so that the solid content of the obtained solution was 30%. The resulting lauric acid amide hydroxypropyl sulfobetaine had a dry residue of 32%,
The salt was 0.2%.

Production Example 2 1 mol of coconut oil fatty acid (206 g, neutralization number 272) and N,
1.0 mol (102 g) of N-dimethylpropylamine was dehydrated and condensed under reduced pressure at 140 to 200 ° C. to remove 1 mol of water to obtain lauric acid N, N-dimethylpropylamide. To this, 900 ml of purified water was added, 1 mol (197 g) of sodium chlorohydroxypropanesulfonate prepared by ring-opening epichlorohydrin with sodium bisulfite and a base catalyst was added, and 7.84 g of sodium hydroxide was added as a base catalyst. 5 at 70-80 ° C
After reacting for a time, the mixture was cooled and adjusted to pH 7 with an aqueous hydrochloric acid solution. Coconut oil fatty acid amide hydroxypropylsulfobetaine was obtained as a pale yellow transparent liquid having a dry residue of 36% and a salt content of 5.7%.

Next, purified water was added to make the solid content concentration 30%, and then reverse osmosis membrane treatment was carried out according to Production Example 1 to obtain a total amount of 2520 g of the membrane permeate. The water content was adjusted so that the solid content of the obtained solution was 30%. The obtained coconut oil fatty acid amide hydroxypropyl sulfobetaine had a dry residue of 30% and salt of 0.1%.

Example 1, Comparative Examples 1-3 A transparent liquid detergent was prepared according to the formulation shown in Table 1.
The low temperature stability, skin irritation and detergency of the obtained transparent liquid detergent were examined. The results are also shown in Table 1.

[0033]

[Table 1]

(Low temperature stability) Approximately 100 g of a sample was packed in a 100 ml transparent glass bottle, left at -5 ° C for 24 hours, and visually observed for the formation of solution precipitates and the degree of dullness. ◎ …… Transparent and no dullness ○ …… Dullness but no turbidity (precipitation) × …… Precipitation occurs and opacity (skin irritation) Using ovalbumin pH7 buffer solution and sample concentration of 1 using aqueous high performance liquid chromatography % Ovalbumin denaturation rate when the sample is added to be 2%
It measured using the absorption peak of 20 nm.

[0035]

[Equation 1]

The evaluation criteria were set as follows.

⊚: Ovalbumin denaturation rate of less than 10% ◯: Ovalbumin denaturation rate of 10 to 30% Δ: Ovalbumin denaturation rate of> 30 to 50% ×: Ovalbumin denaturation rate of> 50%

(Detergency) The total concentration of the surfactant is 0.05.
The test solution was adjusted so as to be 100% and a detergency test was performed. The detergency test was performed according to JIS K-3370, and evaluated according to the following evaluation criteria.

⊚:> 60% ∘:> 40 to 60% Δ:> 20 to 40% x: 20% or less.

As is clear from the results shown in Table 1, the transparent liquid cleansing agent of the present invention has low skin irritation and excellent detergency.
Moreover, while the appearance stability at low temperature was good despite containing the cationic polymer, the cleaning agents containing betaine not subjected to reverse osmosis membrane treatment of Comparative Examples 1 and 2 were Although it was excellent in irritation and detergency, it was poor in low temperature stability, and the detergent containing the polyoxyethylene (2) lauryl ether sulfate of Comparative Example 3 was slightly irritating to the skin.

Example 2 (weakly acidic shampoo) -lauryl sulfate triethanolamine salt (30%) 33.0% -coconut oil fatty acid diethanolamide 2.0-amide sulfobetaine-type amphoteric surfactant of Production Example 1 33. 0 ・ Hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether (50%) 0.5 ・ 1,3-butylene glycol 3.0 ・ EDTA 0.2 ・ Methylparaben 0.2 ・ Propylparaben 0.1 ・ Citric acid pH = 6. Amount to be 5 ・ Amount to be 100% purified water This shampoo has good foaming and a viscosity (25 ° C) of 1
It was 500 cP. Even if this shampoo was allowed to stand at −5 ° C. for one week, there was no change in its appearance and it was extremely stable at low temperatures. The action on the skin and scalp was mild.

Example 3 (pearl luster hair shampoo) -Amidosulfobetaine-type amphoteric surfactant (30%) of Production Example 2-20.0% -N-lauroyl sarcosine sodium salt (30%) 15.0-Polyoxy Ethylene (3EO) lauryl ether sulfate sodium (27%) 21.7 ・ Cationized guar 0.5 ・ Lauric acid isopropanolamide 4.0 ・ Stearic acid monoethanolamide 1.0 ・ Ethylene glycol distearate 1.5 ・ Succinylated Carboxymethyl chitin 1.0 ・ Atelocollagen 1.0 ・ 2-Phenoxyethanol 0.5 ・ Hydroxyethanediphosphonic acid 0.2 ・ Perfume 0.3 ・ Citric acid pH = 6.5 amount ・ Purified water 100% Amount This shampoo lathers well and exhibits excellent detergency. Table 2 shows the measurement results of low temperature stability and skin irritation.

Example 4 (transparent conditioning shampoo) -Amidosulfobetaine-type amphoteric surfactant of Production Example 1 41.5% -N-lauroyl-β-alanine sodium salt (30%) 15.0-Trimethyl monostearate Ammonium chloride 7.5-Hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether (50%) 0.5-Polyoxyethylene (2EO) coconut fatty acid monoethanolamide 4.0-EDTA 0.2-Methylparaben 0.2-Citric acid pH Amount = 6.5, perfume 0.3 / purified water 100% This shampoo had good lathering and excellent detergency. Table 2 shows the measurement results of low temperature stability and skin irritation.

Example 5 (Pearl Conditioning Shampoo) -Amidosulfobetaine-type amphoteric surfactant of Production Example 17.0% -Polyoxyethylene (3EO) lauryl ether sulfate (27%) 20.0-laurylamide Propyl acetate betaine (30%) 5.0-N-lauroylmethyl-β-alanine sodium salt (30%) 20.0-Trimethylammonium chloride monostearate (50%) 8.0-Cetanol 0.5-Palm oil Fatty acid monoethanolamide 3.0 ・ Glycerin 2.0 ・ Carboxymethyl chitin 1.0 ・ Amino-modified silicone 0.3 ・ Citric acid pH = 6.5 ・ EDTA 0.2 ・ Purified water 100% This shampoo had a good lather and exhibited excellent detergency. Table 2 shows the measurement results of low temperature stability and skin irritation.

Example 6 (Body shampoo) -N-lauroylmethyl taurine (30%) 8.0% -Amidosulfobetaine type amphoteric surfactant 12.0 of Production Example 2-N-lauroyl glutamic acid triethanolamine salt ( 30%) 15.0 ・ Polyoxyethylene (5EO) coconut oil fatty acid monoethanolamide phosphate 3.0 ・ Palm oil fatty acid 5.0 ・ Amount of potassium hydroxide pH = 8.5 ・ EDTA 0.2 ・ Methylparaben 0.2 Amount of purified water to be 100% This shampoo had a good foaming property and showed excellent detergency. Table 2 shows the measurement results of low temperature stability and skin irritation.

Example 7 (Kitchen detergent) -Surface activity of Production Example 1 5.0% -Sodium α-olefin sulfonate (38%) 10.0-Lauryl dimethylamine oxide (30%) 10.0-Atelocollagen 1 0.0-Polyoxyethylene (2) lauric acid monoethanolamide 1.5-Purified water 100% -Citric acid pH = 7.0 This kitchen detergent has good foaming properties and excellent cleaning power. Indicated. Table 2 shows the measurement results of low temperature stability and skin irritation.

[0047]

[Table 2]

[0048]

EFFECTS OF THE INVENTION According to the present invention, a liquid detergent composition which is stable to the skin and hair, has sufficient foaming power and detergency, and has excellent low-temperature stability that stably dissolves other components at low temperatures. The thing can be manufactured.

Claims (1)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R ¹ CO represents a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms, and R ² and R ³ are each independently a substituent selected from a hydrogen atom, a methyl group, an ethyl group and a hydroxyethyl group. In which n represents an integer of 2 to 10) and the amidoamine compound represented by the general formula (2) (Wherein, X, Y is a hydrogen atom, a hydroxyl group, represents a substituent selected from SO ₃ group, X is, Y is a hydrogen atom or a hydroxyl group when the SO ₃ group, Y is a hydrogen atom or a hydroxyl group In the case of, a chlorohydroxypropane sulfonate compound represented by SO ₃ group) is obtained by an amphoteric reaction and represented by the general formula (3): (Wherein R ¹ CO, R ² , R ³ , n, X and Y are the same as defined above), and a liquid containing a reverse osmosis membrane treatment product of an amidosulfobetaine type amphoteric surfactant. Cleaning composition.