JPS60197611A - External agent for skin - Google Patents

Abstract

PURPOSE:An external preparation for skin that contains a specific nicotinic acid derivative, thus keeping high stability within a broad range of temperature even after storage for a long period of time, showing good action with high safety and good feel, when applied. CONSTITUTION:The objective preparation contains 1-alkyl-3-carbamidepyridinium salt of formula I (R1 is straight or branched alkyl of 3-30 carbon atoms; X is halogen) or 1-alkyl(or phenyl)-3-alkylcarbamidepyridinium salt of formula II (R2 is straight or branched alkyl of 1-30 carbon atoms, phenyl). These compounds have been classified into naturally occurring surfactant and have good surface activating action and bacteriostatic action to give an external preparation for skins of low irritation which could not be obtained from the conventional cationic surface active agent.

Description

[Detailed Description of the Invention] The purpose of the present invention is to utilize nicotinic acid derivatives, which are highly safe, have excellent surfactant functions, and have mild effects on the skin, as surfactants, bacteriostatic agents, or solid agents thereof. The present invention relates to a skin preparation for external use.

Nicotinic acid is a vitamin B, also called niacin, and is a coenzyme of nicotinamide adenine dinucleotide (oxidoreductase), which is important in maintaining life phenomena in living organisms.
N A D p
constitutes a It is also well known to be effective in treating pellagra, chronic alcoholism, chilblains, glossitis, etc.

On the other hand, alkylpyridunium salts, alkyltrimethylammonium salts, alkyldumethylbenzylammonium salts, etc. are cationic surfactants that are widely used in a wide range of fields such as rinse agents, disinfectants, softeners, and antistatic agents. However, when these are applied to the skin, they cause strong irritation, which is a side effect peculiar to surfactants, and it is not preferable to use them for purposes other than cosmetics, such as hair conditioners and treatments.

The present invention has been made in view of the current situation, and provides an external skin preparation characterized by containing a nicotinic acid derivative represented by the following general formula CAI or [B].

[A] [B':] (wherein kl is a straight chain or branched alkyl group having 8 to 30 carbon atoms, R2 is a straight chain or branched alkyl group having 1 to 30 carbon atoms and a phenyl group, and X is (Represents a halogen group.) The details of this invention will be described below.

First, 1 represented by the general formula [A] applied to this invention
-Alkyl-3-carbamide pyridinium salts and 1-alkyl-3-alkylcarbamide pyridinium salts represented by general formula [B] were investigated by the present inventor, focusing on the physiological effects of garnicotinamide. As a result, it is a coenzyme NAD+ model compound and is clearly classified as a natural surfactant. And when such compounds are present in the interfacial region, oily ingredients can be emulsified very easily, probably due to the formation of broad charge transfer complexes between the pyridinium skeleton and other formulation ingredients. However, the micelles and emulsions formed are extremely stable and have surfactant and bacteriostatic functions, making them useful for hypoallergenic lotions, emulsions, and emulsions that cannot be obtained with conventional cationic surfactants. It can be applied to external skin preparations such as creams and hair conditioners.

There are many methods for synthesizing such nicotinic acid derivatives, but for CADI, for example, a method in which nicotinic acid amide is reacted with a desired alkyl halide in a solvent such as ethanol or dimethylformamide is advantageous;
For [B], nicotinic acid is reacted with an excess chlorinating agent such as thionyl monochloride to form nicotinic acid chloride, and this is reacted with an alkylamine in a solvent such as benzene and in the presence of a base such as triethylamine. An advantageous method is to produce a 3-alkylcalcumidopyridine and then react it with a desired alkylenolide in a solvent such as ethanol. Specific examples of these methods are as follows.

[Synthesis example of Al: Dissolve 1.22 g (0.01 mol) of nicotinic acid amide in 15 ml of dimethylformamide, add 2.89 g (0.01 mol) of stearyl crophyte, react under reflux for 2 hours, and then leave to room temperature. It got cold.

The white crystals formed were suction filtered, washed with ether, and
．． 5 g of 1-stearyl-3-carbamidopyridunium chloride was obtained. On the other hand, the dimethylformamide solution of the filtrate was concentrated to several ml, heated once, and left overnight under water cooling to obtain 1.2 g of the same product. The overall yield in this synthesis example was 90%.

Synthesis example of [B]: Nicotinic acid 1.85 g (0,015 mol) +
c Add lQml of thionyl chloride and incubate at 70-80°C.
Stir for hours. After the reaction, the converted thionyl was removed by distillation, and the nicotinic acid chloride crystals were sealed and stored. −
1,000, stearylamine 2.70g (0.01mol)
was dissolved in 100 ml of benzene, and 10 ml of triethylamine was added thereto, and the nonicotinic acid chloride was added at room temperature, followed by stirring at 55 to 60°C for 2 hours. After the reaction, 40 ml of water was added, the mixture was allowed to stand on ice, and the formed crystals were filtered and recrystallized from n-hexane-benzene to give 3.2 ml of 3-stearylcarbamide pyridine.
Obtained 0g.

Obtained crystals: 1. 2 in B B g (5 mmol)
0 ml of ethanol was added, and then 2.52 g (20 mmol) of benol chloride was added thereto, and the mixture was reacted under reflux for 5 hours. After the reaction, ethanol was removed by distillation, and the resulting crystals were recrystallized using petroleum ether-benzene to obtain 2.34 g of 1-bennol-3-stearylcarbamide pyrinonium chloride.

When the skin external preparation of the present invention described above is to be used in ordinary cosmetics, known ingredients may be added as needed, and if necessary, moisturizers, thickening stabilizers, preservatives, and colorants may be added. , flavoring agents, etc. may be added. Cosmetics made in this way remain stable over a wide temperature range even when stored for long periods of time, are extremely safe for the skin, and exhibit excellent effects and feel when used. It can be said that its commercial value is extremely high.

Examples of this invention will be shown below. In addition, all compounding ratios (%) are weight %.

[Example 1] A cream rinse having the following composition was prepared.

Group 1: 1-stearyl-3-carbamidopyridunium chloride 0.4% cetostearyl anocoal 2.5 paraffin wax 1.0 isopropyl palmitate 0.5 olive oil 0.5 fragrance 0.3 preservative. , 2 2nd group: Pigment Appropriate amount of purified water The rest, that is, first, dissolve the mixture of the 1st group by heating to 80 ° C.
The 80° C. solution of the second group was added to this, homogenized using a homomixer, and then cooled. The obtained cream rinse was stable for more than 3 months in an oven test at 45°C, and was not irritating. The circulation feeling 1 was also very good. A cream rinse was prepared using a halide other than chlorine consisting of bromine, fluorine, and iodine in place of 1-stearyl-3-carbamidopyridunium chloride, but the cream rinse had the same properties. Indicated.

[Example 2] A cleansing lawn with the following composition was prepared.

The preparation procedure is the same as in Example 1.

Group 1: 1-cetyl-3-carbamidopyridunium chloride
0.8% cetostearyl alcohol 1.2 Vaseline 5.0 Liquid paraffin 11.0 Isopropyl palmitate 2.0 Fragrance 0.1 Preservative 0.2 Group 2: 1.3-Butylene glycol 5.0 Purified water 74 .7 The resulting cleansing lotion was stable for more than 3 months in an oven test at 45°C, and was non-irritating.
The usability was very good.

[Example 3] A skin cream having the composition shown below was prepared.

Group 1: 1-stearyl-3-carbamidopyrinonium chloride 1.0% cetostearyl alcohol 5.0 Squalane 10.0 Stearic acid 8.0 Beeswax 2.0 Olive oil 3.0 Fragrance 0.1 Preservative 0. 2 Group 2: 1.3-Butylene glycol 8.0 Glycerin 4.0 Purified water 58.7 The preparation procedure was exactly the same as in Example 1, and the obtained skin cream also showed excellent results in the oven test at 45°C. It was stable for more than a month, had no irritation, and had a very good feeling of use.

[Example 4] A clean nongloss cream having the composition shown below was prepared.

Group 1: 1-bare nor-3-stearyl pyridunium chloride 2.0% Cetostearyl alcohol 3.0 Liquid paraffin 35.0 Paraffin wax 2.0 Isopropyl valmitate 10.0 Group 2: Maltitol 3.0 Purified water 45.0 The preparation procedure was exactly the same as in Example 1, and the resulting cleansing cream was stable for more than 3 months in an oven test at 45°C, was non-irritating, and had no feeling of use. It was very good.

[Example 5] A lotion having the composition shown below was prepared.

Group 1: 1-lauryl-3-carbamidopyridunium chloride 0.60% fragrance 0.2゜oleyl alcohol 0.04 1.3-butylene glycol 1.00 glycerin 1
,00 Group 2: Citric acid 0.07 Purified water 97.06 That is, the aqueous solution of Group 2 was added to the solution of Group 1 and sufficiently stirred until it was uniformly and transparently dissolved. The resulting transparent lotion has a mild effect on the skin, and because it solubilizes fragrances and oils without using ethyl alcohol, which is included in regular lotions, it has a gentle effect on the skin. It was very good.

In addition, when the bacteriostatic effect was investigated for Examples 1 to 5, a remarkable effect was observed at least for miscellaneous bacteria.

Patent applicant: Iwashio Kenjibe Shoten Co., Ltd. Same agent Kama 1) Sentence 2

Claims (1)

[Scope of Claims] An external skin preparation characterized by containing a nicotinic acid derivative represented by the following general formula [A] or [B]. CAI CB] (In the formula, R1 represents a straight chain or branched alkyl group having 8 to 30 carbon atoms, Machi represents a straight chain or branched alkyl group having 1 to 30 carbon atoms and a phenyl group, and X represents a halogen group. )