KR20220095933A - Highly viscous composition containing ammonium for skin protection, its manufacturing process and its application - Google Patents

Abstract

The present invention relates to a high-viscosity or solid skin external composition having a skin protection function, and more specifically, to a technique capable of preparing a textured formulation having high viscosity without using a wax or a surfactant by using a highly viscous mixture composed of an ammonium salt and an ammonium salt solubilizer. If a sunscreen or antioxidant material is mixed and used as an external preparation for skin, the effect of alleviating skin damage caused by light can be obtained without clogging or irritating pores.

Description

Highly viscous composition containing ammonium for skin protection, its manufacturing process and its application

The present invention relates to an ultra-high-viscosity external preparation for skin having a skin photoaging inhibitory function. Surfactants and fats that may cause irritation and inflammation are not used, and polymer dispersants such as dimethicone are not used, but excellent dispersibility. It is possible to prepare a gel having

As modern life becomes more complex, the incidence of skin immune-related diseases is increasing. Skin immune diseases are symptoms caused by failure to control inflammation, and are known to be caused by various causes. Representatively, there are various light rays derived from natural or artificial light sources such as blue light, ultraviolet light, and near infrared light. Excessive light induces denaturation of nucleic acids, lipids, and proteins, resulting in signal transduction system or metabolic dysfunction.

Factors and denatured bioconstituents are often not used for carrying out normal metabolic processes, causing metabolic stress and promoting inflammation or skin aging. When chronic skin inflammation or metabolic abnormalities occur, harmful by-products such as active oxygen or aldehydes are mainly accumulated in the tissue.

Other factors that cause skin damage include fine dust such as PM2.5, metal, and the like. It is known that most of these skin damage mechanisms involve inflammation. Therefore, various studies are being conducted to alleviate skin damage by blocking UV rays or harmful substances or applying antioxidants and inflammatory control materials to the skin.

However, since most of the active ingredients show low solubility and stability in aqueous solution-based formulations, their use is limited. In the past, to solve this problem, various formulations such as fatty acids, TWEEN, SPAN, PEG, and liposomes were attempted to solve this problem, but there are limitations in that it is difficult to dissolve more than 5% and there is a problem in separation of the formulation.

On the other hand, according to recent studies, various ionic solvents can be prepared by adjusting the mixing ratio of ammonium salts and dissolution aids. It is known that it is possible to dissolve phenol, natural glycosides, polymeric carbohydrates, etc. in an amount of several to several tens of wt%. By utilizing these properties, it is not only necessary to additionally add surfactants or waxes to dissolve the physiologically active substances, but it is also possible to develop formulations composed of high-concentration physiologically active substances that were previously unavailable due to their low solubility. do.

In addition, it is known that the melting point tends to be extremely reduced in the case of such a composition. This phenomenon is also known as the eutectic state. This helps the material to be processed at lower temperatures, which helps to reduce thermal damage during processing. If used well, the stability of the formulation can be dramatically increased. For example, if an active ingredient is added to a composition in a highly viscous liquid state to form a formulation and then cooled, it is solidified in a dispersed state and it is possible to maintain the formulation semi-permanently.

Nevertheless, such ion-based dispersion technology is still being studied at a basic level such as extraction (EP3280276B1, JP6239976B2), low-temperature chemical reaction (US20140336308A1), and purification (NL2021729B1). Although limited formulation application patents for some lipid-based formulations (US6897195B2) and patents for materials containing eutectic solvents (US20140178315A1) have also been registered, it is only a concept that can be applied with existing formulations, eutectic solvents Industrial application cases utilizing the unique characteristics have not yet been reported.

Therefore, if this ionic composition technology is applied to the development of cosmetic and medical formulations, it is expected that products differentiated from existing formulations can be manufactured.

NL2021729B1 EP3280276B1 JP6239976B2 US20140336308A1 US6897195B2 US20140178315A1

Alexandre Paiva et al. (2014) Natural Deep Eutectic Solvents - Solvents for the 21st Century. ACS Sustainable Chemistry & Engineering 2;1063-1071 Food and Drug Administration Notice No. 2012-88, "Ultraviolet blocking effect measurement method and standard, 2012. 8. 24" ISO 24444:2019(en), “Cosmetics — Sun protection test methods — In vivo determination of the sun protection factor (SPF)”

The problem to be solved by the present invention is to develop an anti-photoaging composition and a composition used as a raw material for the photoaging composition, which have the effect of preventing skin damage and reducing irritation due to excessive light and/or components included in the product.

Another problem to be solved by the present invention is to develop a technology for dispersing harmful light blocking materials without using surfactants, lipids and/or polymer stabilizers.

The problem to be solved by the present invention is to develop a curing agent type or high viscosity gel formulation having a melting point of less than 40 °C.

In order to prepare a curing formulation in which a harmful light blocking material is dispersed without using a surfactant, a lipid and/or a polymer stabilizer, which is a problem to be solved by the present invention, a halogen salt of an alkyl ammonium ion and a hydrophilic organic compound A method of mixing the lozenge salt dissolution aid in a ratio of 20:1 to 1:20 was used.

At this time, in order to achieve the goal of developing a curing formulation with a melting point of 40 ° C or higher, which is another problem to be solved by the present invention, a halogen salt of an alkyl ammonium ion and a hydrophilic organic material are mixed at a temperature higher than 40 ° C. Cooling and curing technology was applied.

According to the reaction system of the present invention, a formulation technology that does not use wax has been developed for a product that applies a material that blocks ultraviolet light and blue light to the skin to protect the skin from ultraviolet rays, and prevents the pores of the skin from being blocked and inflammation. In addition to preventing the generation of triggers, it is possible to apply the anti-inflammatory material itself as a formulation material.

In this way, it is possible to commercialize a light blocking agent formulation that has good spreadability and high transparency and is easy to clean because it does not use a surfactant that causes irritation, and has less irritation. can

1 is a schematic diagram comparing the conventional surfactant-based formulation manufacturing process and the manufacturing process using the ionic composition of the present invention.
Figure 2 is a photograph comparing the properties before and after the liquefaction process for the preparation of the ionic composition in the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments and drawings described herein.

The present invention relates to an anti-photodamage formulation that can be used for cosmetics and medical purposes, and an ionic composition capable of dissolving or dispersing a photoaging agent at a concentration of 0.001 to 30% by weight, a method for preparing the ionic composition, and an ionic composition It relates to a wax-free anti-aging formulation prepared using

Preferably, the photoaging agent may be dissolved or dispersed at a concentration of 0.5 to 20% by weight, more preferably, it may be dissolved or dispersed at a concentration of 1 to 15% by weight, and most Preferably, it may be dissolved or dispersed at a concentration of 2 to 10 wt%.

The photoaging agent may be classified into a material having a property of physically blocking light or a material having a property of preventing oxidation due to light.

The photoaging agent is not particularly limited, such as organic or inorganic. However, in general, a material having a property of physically blocking light may be an inorganic photoaging agent, and a material preventing oxidation due to light may be an organic photoaging agent.

The material having the property of physically blocking light absorbs and scatters 20 to 99.99% of light in the range of 230 to 450 nm, such as TiO ₂ , ZnO, etc., when irradiated with light of 1 kWh/m ² intensity for 2 hours. Or a reflective light blocking material.

Meanwhile, the material having the property of physically blocking light may have an SPF index of 20 or more according to the evaluation of the UV blocking effect according to ISO 24444.

The material having the property of preventing oxidation due to light, such as oxalic acid, phytic acid, tannins, polyphenols, carotenoids, vitamin A, vitamin C, vitamin E, etc. )) is in the range of -0.500 to 0.800 V, and it is a component that can remove ROS (Reactive oxygen species) from the living body caused by light.

The ionic composition has a viscosity of 1000 CP or more at 25 ℃, or the melting point is characterized in that the range of 25 to 150 ℃. In this case, the ionic composition may be prepared by mixing the ammonium salt and the ammonium salt solubilizer in a molar ratio of 1:0.05 to 1:20. In the manufacturing method, the ammonium salt and the ammonium salt solubilizer are mixed at a ratio to obtain suitable conditions for use and then stirred at room temperature or, in some cases, increased to 40 to 80 ° C. and stored or stirred to convert to a high viscosity liquid. When this is cooled to below the melting point, a highly viscous gel having a unique color or a formulation having a transparent solid appearance can be obtained.

The ammonium salt and the ammonium salt solubilizer may be more preferably prepared by mixing in a molar ratio of 1:0.1 to 1:10, and most preferably, mixed in a molar ratio of 1:0.4 to 1:1 .

The composition for anti-photoaging can be obtained by heating the ionic composition above its melting point, adding it to the desired concentration to prepare the anti-photoaging material, stirring, dispensing into an appropriate container, and then cooling.

The anion constituting the ammonium salt refers to an ionic compound comprising at least one of a chlorine anion, a bromine anion, and an iodine anion in an amount of 0.1 to 35% by weight based on the total weight of the ammonium salt. for cations, phosphatidylcholine; phosphocholine; glycerophosphocholine; D-sphingosine-1-phosphocholine; D-sphinganine-1-phosphocholine; D-phytosphingosine-1-phosphocholine; sphingomyelin; betaine; choline; choline fatty acid esters; Alternatively, a material in which four hydrogens are bonded around nitrogen, or in which one or more hydrogens are substituted with a carbon group may be used. The carbon atom group means a carbon compound composed of 1 to 24 carbons, including 0 to 5 cyclic carbon structures in an unbranched or branched alkyl group, and 0 to 5 hydroxyl groups bonded to the alkyl group It contains 0 to 23 hydroxyl groups bonded to an alkyl group, 0 to 5 carboxyl groups, 0 to 5 aldehyde groups, 0 to 5 ketone groups, 0 to 0 phosphoric acid groups. It contains two and is a functional group characterized by including 0 to 5 amine groups.

That is, in the ammonium salt, 1 to 3 hydrogens may be a primary amine including a substituted or unsubstituted alkyl group, a secondary amine, a secondary amine, and a halogen salt thereof.

The ammonium salt solubilizer is, glyceraldehyde, dihydroxyacetone, erythrose, threose, erythrulose, arabinose, lyxose, ribose, xylose, arabinose, lyxose, ribose, xylose, allose, altrose, glucose, mannose, gluose, idose, galactose, fructose, galactose, , sorbose, tagatose, glycero-manno-heptose, glcero-galacto-heptose, glycero-gluco-heptose, heptulose, manno-heptulose, heptulose, allo-heptulose, and monosaccharide phosphate compounds; sucrose, lactose, maltose, trehalose, cellobiose, chitobiose, kojibiose, nigerose, isomaltose, sophorose, laminaribiose, gentiobiose, trehalulose, turanose, maltulose ibi, leucrose, isomaltulose, rucebiose, melose bin;

trisaccharides such as nigerotriose, maltotriose, melezitose, maltotirulose, raffinose, kestose, and panose;

starch, glycogen, maltodextran, beta-1,3-glucan, beta-1,4-glucan, beta-1,6-glucan and hydrolysates thereof, polysaccharides such as xylan, pectin, chitin, chitosan, and hydrolysates thereof;

aldonic acids such as glyceric acid, xylonic acid, gluconic acid, ascorbic acid, and erythorbic acid;

ulosonic acids such as neuraminic acid and ketodeoxyoctulosonic acid;

uronic acids such as glucuronic acid, galacturonic acid, and iduronic acid;

aldaric acids such as tartaric acid, mucic acid, and saccharic acid;

amino acids such as arginine, histidine, lysine, aspartic aicd, glutamic acid, serine, threonine, asparagine, glutamine, cysteine, selenocysteine, glycine, proline, alanine, valine, isoleucine, leucine, methionine, phenylalanine, tyrosine and their polymers;

organic acids such as lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, malic acid, tartaric acid, and benzoic aicd;

amines such as creatine, urea, dimethyl urea, putrescine, cadaverine, agmatine, spermidine, spermine, histamine, and tyramine;

ethylene glycol, propylene glycol, glycerol, erythritol, threitol, pentanediol, arabitol, xylitol, ribitol, hexanediol, mannitol, corbitol, galactitol, fucitol, iditol, inositol, volemitol, etc. alcohols containing a real group;

phenols and glycosides thereof, such as flavones, flavonols, flavanols, flavanones, isoflavones, catechin, hesperetin, cyanidin, daidzein, proanthocyanidin, quercetin, phenolic acid, ellagic acid, and lignans;

Terpene compounds (terpene compounds) such as sophoricoside, amino acid-2 glucoside, steviol glucoside, mogroside, asiatic acid, asiaticoside, madecassic acid, madecassoside, and glycyrrhizin and one or more of its glycosides can be selected.

The ionic composition prepared through the above composition and method is used as a cosmetic raw material such as sunscreen gel, sun stick, basic cosmetic material dispersion, basic makeup stick, color cosmetics, lipstick, lip balm, or wound reliever, burn reliever, light It can be used as a raw material for formulations for the purpose of medical or medical assistance, such as skin protection and inflammation relief, such as allergy treatment and contact dermatitis reliever. In addition, it can be used as a raw material for products for the purpose of protecting animal skin.

The composition for preventing photoaging is to prevent skin damage caused by light, and specifically, it may be to prevent skin damage caused by light, such as wrinkles, erythema, blemishes, reduced elasticity, inflammation, and dry skin. .

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited by the examples.

<Example>

In order to develop a solid sunscreen formulation in which wax is not used, an ionic composition as the basis of the formulation was prepared.

Tetraethyl ammonium chloride (TCI, Japan) powder and ascorbic acid (Daejung, Korea) powder were added in a molar ratio of 1.5:1, followed by stirring at 60°C at 100 RPM to induce liquefaction. As a result of stirring for 12 hours, it was confirmed that the mixture was converted into a transparent liquid ionic composition. Thereafter, it was confirmed that the mixture was cooled at a rate of 1 °C per minute to convert to a transparent solid phase in the range of 43 to 45 °C.

Thereafter, the ionic composition was heated to 60° C. to prepare a sunscreen formulation, and TiO ₂ (DC chemical, Korea) was added as much as 3% of the weight of the mixture while stirring at 200 RPM. The prepared sample was placed in a quartz cuvette with an optical path of 1 cm and UV transmittance at 280 nm was analyzed using a spectrophotometer. As a result, it was confirmed that 98.5% of UV was blocked.

<Comparative example>

A formulation was prepared with the same composition as in Example, but as a result of preparing the composition without inducing liquefaction by increasing the temperature, it was maintained in a powder state, making it impossible to make a formulation containing TIO ₂ .

[Experimental example]

In order to check the melting point according to the mixing ratio of tetraethyl ammonium chloride and ascorbic acid, each powder is mixed in a molar ratio of 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1 and shaken Using an incubator, the mixture was stirred at 100 RPM at 60 °C for 1 day.

The results before and after the liquefaction process are as shown in FIG. 2, and when 24 hours have elapsed after mixing, the powder was melted to obtain a composition in a transparent liquid state. Of these, a complete liquid was obtained in the test section mixed with 1.5:1 and 2:1 molar ratio, but powders that were not completely dissolved were confirmed in the remaining test sections. As a result of analyzing the temperature at which the fluidity disappears by cooling the completely molten test strips at a rate of 1 °C per minute, 43-45 °C for the 1.5:1 molar ratio and 51 to 45 °C for the 2:1 molar ratio. The freezing point was confirmed at ~55 °C. Therefore, the most advantageous composition for processing was confirmed to be a mixture of tetraethyl ammonium chloride and ascorbic acid in a ratio of 1.5:1 (see the test zone highlighted by the red square in FIG. 2 (B)).

Claims (22)

An ionic composition for an anti-photoaging composition,
In the ionic composition, 0.001 to 30% by weight of the photoaging agent is dissolved and/or dispersed based on the total weight of the photoaging composition.
The method of claim 1,
The photoaging agent is an inorganic photoaging agent and/or an organic photoaging agent.
3. The method of claim 2,
The inorganic photoaging agent is an ionic composition having an SPF index of 20 or more according to the evaluation of the UV protection effect according to ISO 24444.
3. The method of claim 2,
The organic photoaging agent has a standard redox potential (standard redox potential, E '0 (v)) of -0.500 to 0.800 V ionic composition.
According to claim 1,
The ionic composition is an ionic composition having a viscosity of 1000 CP or more at 25 ℃.
According to claim 1,
The ionic composition has a melting point of 25 to 150 ℃ ionic composition.
According to claim 1,
The ionic composition is an ionic composition comprising an ammonium salt and an ammonium salt solubilizer in a molar ratio of 1:0.05 to 1:20.
8. The method of claim 7,
The ammonium salt is an ionic composition comprising 0.1 to 35% by weight of at least one selected from the group consisting of chlorine anion, bromine anion, and iodine anion based on the total weight of the ammonium salt.
8. The method of claim 7,
The ammonium salt is phosphatidylcholine and its halogen salt; choline fatty acid esters and their halogen salts, phosphocholine and its halogen salts, glycerophosphocholine and its halogen salts, D-sphingosine-1-phosphocholine and its halogen salts, D-sphinganine-1-phosphocholine and its halogen salts; D-phytosphingosine-1-phosphocholine and its halogen salts; sphingomyelin and its halogen salts; betaine; choline; An ionic composition comprising at least one selected from the group consisting of primary amines and halogen salts thereof, secondary amines and halogen salts thereof, tertiary amines and halogen salts thereof.
8. The method of claim 7,
The ammonium salt is an ionic composition comprising 10 to 99.999% by weight based on the total weight of the ionic composition.
10. The method of claim 9,
The primary amine, secondary amine and tertiary amine are substituted with at least one hydrocarbon group,
The hydrocarbon group is a C _1-24 unbranched chain alkyl group, a branched chain alkyl group,
The hydrocarbon group includes 0 to 5 cyclic alkyl groups,
The hydrocarbon group includes 0 to 23 selected from the group consisting of a hydroxyl group and a carboxyl group,
The hydrocarbon group includes 0 to 5 selected from the group consisting of an aldehyde group and a ketone group,
The hydrocarbon group includes 0 to 12 amine groups,
The hydrocarbon group is an ionic composition comprising 0 to 2 phosphoric acid groups.
8. The method of claim 7,
The ammonium salt dissolving agent is monosaccharides and phosphoric acid compounds thereof, disaccharides, trisaccharides, polysaccharides and hydrolysates thereof, aldonic acids, urosonic acids, uronic acids, aldaric acids, amino acids and polymers thereof, organic acids, amines, C _1-12 An ionic composition comprising at least one selected from the group consisting of alcohols, flavones, flavonols, flavanols, flavanones, isoflavones, phenols and glycosides thereof, terpenes and glycosides thereof.
An anti-photoaging composition comprising the ionic composition according to claim 1 .
As a method for preparing the ionic composition according to claim 1,
forming a liquid mixture by standing or stirring a mixture of an ammonium salt and an ammonium salt solubilizer at 25 to 80°C;
cooling the liquid mixture to a melting point or less to form a gel or solid phase;
A method for producing an ionic composition comprising a.
A method for preparing the composition for photoaging according to claim 13, comprising:
heating the ionic composition above its melting point to add a photoaging agent, followed by stirring;
Cooling to form a gel or solid phase;
A method for preparing a composition for photoaging comprising a.
A cosmetic composition comprising the composition for photoaging according to claim 13 in an amount of 0.001 to 99.999% by weight based on the total weight.
17. The method of claim 16,
The cosmetic composition is a cosmetic composition that prevents skin damage caused by light.
18. The method of claim 17,
The skin damage caused by the light is at least one cosmetic composition selected from the group consisting of wrinkles, erythema, blemishes, reduced elasticity, inflammation, and dry skin.
A pharmaceutical composition comprising the composition for photoaging according to claim 13 in an amount of 0.001 to 99.999% by weight based on the total weight.
A composition for protecting animal skin comprising the composition for photoaging according to claim 13 in an amount of 0.001 to 99.999% by weight based on the total weight.
14. The method of claim 13,
The anti-photoaging composition is a stick-type formulation.
A method for preparing the composition for photoaging according to claim 21, comprising:
It is prepared by filling a stick-type container including an inner container and an outer container with a composition for preventing photoaging,
The method for producing an anti-photoaging composition, wherein the inner container includes a double container provided with a means for controlling the exposure amount of the composition for photoaging therein.

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