JPS5919596B2 - New transparent solid cleaning agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transparent solid detergent, and more specifically, a novel transparent solid detergent molded from a base consisting of a basic amino acid salt of an N-long chain acyl optically active acidic amino acid mixed with urea. This is related to drugs.

Conventional transparent solid detergents are based on fatty acid soap and contain sugar,
It is manufactured by the so-called frame drawing method, in which saccharoids or polyols such as glycerin, sorbitol, and propylene glycol are used as clarifying agents, and these are heated and dissolved in water and lower alcohols, poured into a frame, and cooled and solidified. It is customary. Although the transparent soap produced in this way is transparent, it gives a sense of luxury and has high commercial value, but it is essentially the same as ordinary opaque fatty acid soap, with the release of free fatty acids in the soap. Unavoidable disadvantages include skin irritation caused by alkali and pH increase due to hydrolysis during use, poor foaming in hard water, and generation of soap gas during use. N-long-chain acyl soaps do not have the disadvantages of fatty acid soaps, have a mild and soft feel on the skin, and have excellent shape retention and detergency. Although solid detergents based on acidic amino acid salts are commercially available, they are opaque in appearance.

Attempts have already been made to produce transparent fatty acid soap using fatty acid soap as a base and adding N long-chain acyl acidic amino acid monosodium salt as an additive (Japanese Unexamined Patent Publication No. 51-24606). Transparent solid detergents based on long-chain acyl acidic amino acid salts and with increased commercial value have not been known to date.

Therefore, in order to obtain a transparent solid detergent based on N long-chain acylamino acid salts without using fatty acid soap as a base, the present inventors discovered that N-long complex acyl-basic amino acids of optically active acidic amino acids I discovered that salt could be used and filed an application (Japanese Unexamined Patent Publication No. 55-160096, Japanese Patent Application No. 1984-66).
No. 788).

However, in this solid detergent, the length of the acyl group,
Depending on the type of amino acid, the degree of neutralization, etc., the transparency may be slightly inferior, and when left in a humid environment, there was a tendency for transparency to be impaired (hereinafter referred to as devitrification). Furthermore, the present inventors conducted extensive research to develop a transparent solid detergent based on N long-chain acylamino acid salts that have a wide range of good transparency and good devitrification resistance. The present invention was completed by discovering that a long-chain acyl acidic amino acid salt mixed with urea can be used as a base.

That is, in the present invention, urea is added to a basic amino acid salt of an N long chain acyl optically active acidic amino acid obtained by reacting 1 to 2 moles of a basic amino acid with 1 mole of an N long chain acyl optically active acidic amino acid. This is a transparent solid cleaning agent characterized by being molded using the ingredients as a base.

In the basic amino acid salt of N long-chain acyl-optically active acidic amino acid used as a base for the transparent solid detergent of the present invention, the optically active acidic amino acid is aspartic acid,
At least one type of D or L form selected from glutamic acid, cysteic acid, and homocysteic acid.

On the other hand, when the acidic amino acid component is a racemate, the transparency is poor and a good transparent solid detergent cannot be obtained. is at least one selected from lysine, arginine and ornithine, and these basic amino acids may be in either an optically active form or a racemic form, but in the case of a racemic form, transparency tends to be slightly reduced.

The degree of neutralization with basic amino acids is 1.0 equivalent to 2.0 equivalent (
N long-chain acyl (1 mol to 2 mol of basic amino acid per 1 mol of optically active acidic amino acid), and the degree of neutralization is 1.
If the amount is less than 0, clarity and foaming will be poor;
If the amount exceeds the equivalent amount, foaming may be poor, hardness may not be sufficient, and in some cases, coloring may occur over time, which is not preferable.

In the N long-chain acyl-optically active acidic amino acid monobasic amino acid salt that is the base of the transparent solid detergent of the present invention, the long-chain acyl group is a saturated or unsaturated fatty acid residue having 10 to 20 carbon atoms, In particular, saturated fatty acid residues having 10 to 16 carbon atoms and unsaturated fatty acid residues having 16 to 18 carbon atoms have excellent transparency.

The weight ratio of N long-chain acyl-optically active acidic amino acid monobasic amino acid salt and urea, which is the base of the transparent solid detergent of the present invention, is 95:5 to 50:50, preferably 90:10 to 50:50. It is 60:40.

If the urea content is less than 5% by weight, a sufficient effect in improving the transparency of the transparent solid detergent will not be observed, and if it exceeds 50% by weight, the foaming will decrease, the solid detergent will become soft, and the hygroscopicity of the product will increase. In some cases, crystals may form on the surface of the solid detergent, reducing its commercial value. The transparent solid detergent of the present invention includes polyhydric alcohols such as glycerin, diglycerin, ethylene glycol, propylene glycol, and Solpit, which are conventionally used in the production of transparent soap, and transparent solids such as monosaccharide, fructose, and sucrose. Auxiliary agents such as coloring agents, fragrances, and coloring agents can be added as appropriate.

Furthermore, for the purpose of adjusting detergency and foaming, other types of anionic surfactants, amphoteric surfactants, and nonionic surfactants may be added to the extent that they do not impair transparency. These include fatty acid soaps, higher alcohol sulfate ester salts, polyoxyethylene higher alcohol sulfate ester salts, higher alcohol phosphate esters and their salts, polyoxyethylene higher alcohol phosphate esters and their salts, polyoxyethylene higher fatty acid phosphates, Acid esters and their salts, sulfonated higher fatty acid salts, sulfonated higher fatty acid alcohol ester salts, higher alcohol sulfosuccinate ester salts, isethionic acid higher fatty acid ester salts, α-sulfo higher alcohol acetate ester salts, lauric acid diethanolamide, stearic acid Condensates of higher fatty acids and alkylolamines such as diethanolamide, lauric acid monoethanolamide, and stearic acid monoethanolamide, and their ethylene oxide adducts, polyoxyethylene higher fatty acid monoethanolamide phosphates, N long-chain acyl Acidic amino acid salt (
salts other than basic amino acid salts, such as alkali metal salts, ammonium salts, alkanolamine salts, etc.), N long-chain acyl sarcosine salts, N long-chain acyl-N-alkyl-β
- N long-chain acylamino acid salts such as alanine salts, N-acyl peptides, higher alkylaminopropionates such as lauryl aminopropionic acid, higher alkyliminodiacetates such as lauryl iminodiacetate, higher alkyl dimethyl betaines, Higher alkyl dihydroxyethyl betaine, N-alkyloyl N'-(2-hydroxyethyl)-N-carboxymethylethylenediamine salt, N-
Alkyloyl-N-(2-hydroxyethyl)-N'-
Examples include, but are not limited to, amine amide compounds such as N'-piscarboxymethylethylenediamine. The border method is mainly used to manufacture transparent soaps based on fatty acid soaps, which produce products with excellent transparency, but the machine kneading method produces only translucent products, and only a small percentage of them are available on the market. The current situation is that we can only see it.

However, a major feature of the transparent solid detergent of the present invention is that it can be obtained not only by the border line method but also by the mechanical kneading method. In order to produce the transparent solid cleaning agent that is the object of the present invention by the border line method, N long-chain acyl, optically active acidic amino acid monobasic amino acid salt, urea, etc. are added to a mixed solvent of lower alcohol such as ethanol and water. If necessary, other additives may be dissolved, the solution may be poured into a mold, cooled and solidified, and then the usual method for manufacturing border soap may be applied, which involves cutting, drying, and molding.

At this time, the mixing ratio of lower alcohol such as ethanol and water is preferably 1:0.5 to 1:3, and the nitrogen content in the solution is preferably 1:0.5 to 1:3.
The concentration of the long-chain acyl-optically active acidic amino acid monobasic amino acid salt, etc. is preferably 40 to 75% by weight (25 to 60% by weight of the mixed solvent).

Furthermore, it is preferable to heat to 70 to 85°C to ensure rapid and complete dissolution. The number of drying days when producing the transparent solid detergent targeted by the present invention using the border-line method may be about 30 to 60 days, as in the case of ordinary transparent soap. Furthermore, since the solvent evaporates during drying, the weight of the transparent solid detergent decreases.

This weight loss due to drying varies depending on the type and amount of solvent and the drying period, but 1% of the 25 to 60 parts by weight of the mixed solvent
It is 5 to 30 parts by weight. Therefore, the content of the solvent consisting essentially of water in the transparent solid cleaning agent after drying is from 10 to
It amounts to 30 parts by weight, or about 11-43% by weight. In addition, in order to produce by a mechanical kneading method, water is added to a mixture of N, long-chain acyl, optically active acidic amino acid, monobasic amino acid salt, urea, and additives as required, and the resulting mixture is mixed with a roll and/or pelletizer. After kneading in step 1, extrusion molding may be performed.

The amount of water to be added is such that the degree of neutralization by basic amino acids is 1.0~
When the amount is 1.5 equivalents, the amount may be 5 to 25% by weight, and when the amount is 1.6 to 2.0 equivalents, it may be 5 to 35% by weight. The transparent solid detergent of the present invention thus obtained has the following excellent performance and advantages.

1. Since the pH during use is weakly acidic to neutral, it can be used even by people who are unable to use soap because it is too alkaline.

2. Shows good foaming and cleaning power in hard water.

3. It is non-irritating, does not irritate the skin, and gives a moist feel to the skin when used.

4. Productivity is high because it can be manufactured not only by the frame line method but also by the machine kneading method.

The present invention will be explained in more detail below using Examples.

All "parts" in the examples are parts by weight. Each test in the examples was conducted as follows. (1) Transparency test A transparent solid detergent with a thickness of 201!L was placed on top of the type. Those with clearly legible characters smaller than 26 points were given an O, those larger than 26 points were given a Δ, and those whose point print was completely illegible were given a ×.

(2) Measurement of PH The PH of a 1% aqueous solution of each solid detergent at 40°C was measured using a glass electrode PH meter.

(3) Devitrification test After using the manufactured transparent solid detergent in the usual hand washing method, wet the surface uniformly with water so that no bubbles remain, and wash at 24℃.
It was left in an environment with relative humidity of 80% all day and night.

After that, the transparency of the surface was observed in the same manner as the transparency test, and the devitrification was evaluated. Example 4 N-mixed fatty acids with different degrees of neutralization as shown in Table 3 (15% apricot fatty acid, 85% semi-hardened beef tallow fatty acid) *Example 1 N with different degrees of neutralization as shown in Table 1 20 parts of water was added to 80 parts of a mixture of -an fatty acid acyl-L-glutamic acid-L-lysine salt and urea, and the mixture was thoroughly kneaded with a small roll, and then molded with a small soap extruder whose die was kept at 40°C.

The resulting solid detergent was measured for transparency, pH, and devitrification. The results are shown in Table 1. Of the symbols in Table 1, the upper left column indicates transparency, and the lower right column indicates transparency after the devitrification test.

From the results in Table 1, it can be seen that by blending urea into the N long-chain acyl-L-glutamic acid-L-lysine salt, the devitrification is improved and the range of transparency is expanded.

Examples 2 and 3; Comparative Examples 1 and 2 Example 1 for various N long-chain acyl optically active acidic amino acid monobasic amino acid salts shown in Table 2 as Examples 2 and 3 and Comparative Examples 1 and 2 A solid detergent was manufactured in the same manner as above, and its transparency and pH were measured.

The results are shown in Table 2. A clear solution was prepared, poured into a frame, cooled and solidified, then taken out and dried indoors for 30 days.

The loss on drying was 24.1 parts by weight. The water content of this solid detergent is therefore 34.1% by weight. Then the second
As is clear from the results in Table 4, the transparency observed when the degree of neutralization of the basic amino acid with respect to the N long-chain acyl acidic amino acid of the N long-chain acyl-optically active acidic amino acid monobasic amino acid salt is low. By incorporating urea, the decrease in transparency is prevented and the range of transparency is expanded. Example 7 below
Sample No. 11 was molded by the frame line method or by a conventional method using a foot stamping machine, and its transparency, devitrification, and pH were measured.

The results are shown in Table 3 according to Example 1. Example 5,
6: Comparative Examples 3 and 4 Various N long-chain acyl optically active acidic amino acid monobasic amino acid salts shown in Table 4 as Examples 5 and 6 and Comparative Examples 3 and 4 were treated in the same manner as in Example 4. A solid detergent was manufactured and its transparency and pH were measured.

The drying loss was 23.1 parts by weight in Example 5 and 2 parts by weight in Example 6.
It was 3.8 parts by weight. Therefore, the water content is
They are 35.0% by weight and 34.4% by weight. The results are shown in Table 4.・Water 27 parts ●Ethanol 16" ・Dye, fragrance appropriate amount Example 8 ・N-mixed fatty acid acyl-L-glutamic acid 50 parts
L-arginine salt (neutralized by 1.5 equivalents) - Urea 12" - Lauric acid diethanolamide 3" °.

23”.Ethanol 12”・Fragrance Appropriate amount Example 9 N-Myristoyl-L-glutamic acid 40 parts-L
-Arginine salt (neutralized by 1.8 equivalents)/N-stearoyl-L-glutamic acid 10''-L-lysine salt (1.
8 equivalents neutralized) ・Urea 7″ 2-Anofatty alkyl-N-carbo 2″xymethyl-N-hydroxyethylimidazolinium betaine sodium・Water 27 ・Ethanol 14″ Example 10 .N-Palmitoyl-L-glutamic acid Part 38-L
-Ornithine salt (neutralized by 1.1 equivalent)・Urea 18″
・Glycerin 4" ・Sodium fatty acid 6". Water 20". Ethanol 14" ・Fragrance Appropriate amount Example 11 N-Anofatty Acyl-L-Glutami 30 Parts Phanoic Acid-L
-Lysine salt (1.6 equivalents neutralized). N-mixed fatty acid acyl-L-glutamic acid-lysine salt (1.6 equivalents neutralized). Urea 9〃 N-lauroylsarcosine sodium 3〃. Glycerin 2″・Water 22〃・Ethanol 12〃 Example 12・N-Myristoyl-L-glutamic acid 40 parts-L-
Arginine salt (1.7 equivalents neutralized)/N-lauroyl-L-aspartic acid 18-L-ornithine salt (1
．． 9 equivalents neutralized) ・Urea 5″ ・Sugar 2″ ●Water 35″ .Dye Appropriate amountExample 13 .N-Palmitoyl-L-glutamic acid 50 parts-L-
Lysine salt (neutralized by 1.4 equivalents)/N-lauroyl-L-
Cysteic acid-5〃L-arginine salt (1.0 equivalent neutralized). N-oleoyl-L-glutamic acid-30”
L-lysine salt, urea 5″, thiourea 1″, water 9″.Fragrance appropriate amount Example 14

Claims (1)

[Claims] 1 N-long chain acyl optically active acidic amino acid obtained by reacting 1 to 2 moles of basic amino acid with 1 mole of optically active acidic amino acid N-long chain acyl optically active acidic amino acid basic amino acid salt and urea Moisture content: 5 to 3
5% by weight transparent solid cleaning agent. 2. The transparent solid detergent according to claim 1, wherein the acyl group of the N-long chain acyl-optically active acidic amino acid-basic amino acid salt is a saturated or unsaturated fatty acid residue having 10 to 20 carbon atoms. . 3 The optically active acidic amino acid of the N-long chain acyl-optically active acidic amino acid-basic amino acid salt is aspartic acid,
The transparent solid detergent according to claim 1, which is at least one L-form or D-form selected from glutamic acid, cysteic acid, and homocysteic acid. 4. The basic amino acid of the N-long chain acyl-optically active acidic amino acid-basic amino acid salt is at least one L-form or D-form selected from lysine, arginine, and ornithine, according to claim 1. Transparent solid cleaning agent. 5. The transparent solid detergent according to claim 1, wherein the weight ratio of N-long chain acyl optically active acidic amino acid monobasic amino acid salt and urea is from 95:5 to 50:50.