KR20230044050A - Sunscreen composition with enhanced moisturizing effect using hyaluronic acid complex - Google Patents

Abstract

The present invention relates to a non-irritating sunscreen cosmetic composition containing cross-linked hyaluronic acid or an acceptable salt as an active ingredient, wherein the composition according to the present invention exhibits a very excellent ultraviolet ray blocking effect, and moreover, when used together with an organic sunscreen, even a small amount shows a significantly increased UV protection effect while offsetting the skin irritation caused by the organic sunscreen.

Description

Sunscreen composition with enhanced moisturizing effect using hyaluronic acid complex}

The present invention relates to a composition containing a cross-linked hyaluronic acid or an acceptable salt thereof and having an excellent effect of preventing skin damage by a sunscreen effect.

Human skin color is determined by various factors such as the activity of melanocytes that produce melanin pigment, the distribution of blood vessels, the thickness of the skin, and the presence or absence of pigments inside and outside the body, such as carotenoids and bilirubin. The most important is melanin, a black pigment produced by the action of several enzymes such as rosinase. The formation of melanin pigment is influenced by genetic factors, physiological factors related to hormone secretion and stress, and environmental factors such as ultraviolet irradiation. Melanin is present in the skin and has an important function of protecting the body from ultraviolet rays, etc., but it is known that overproduction of melanin not only forms spots or freckles, but also promotes skin aging and plays an important role in inducing skin cancer.

Ascorbic acid, kojic acid, arbutin, hydroquinone, glutathione or derivatives thereof in order to treat or alleviate excessive melanin pigmentation caused by abnormal skin pigmentation symptoms such as melasma, freckles or pigmentation and exposure to ultraviolet rays , Substances with tyrosinase inhibitory activity have been used in cosmetics or pharmaceuticals, but their use is limited due to insufficient whitening effect, safety problems on the skin, and formulation and stability problems when blended in cosmetics.

Ultraviolet rays included in sunlight can cause blemishes or blemishes by promoting the formation of erythema or the production of melanin pigment in skin cells when excessively irradiated to the skin. Not only can it cause, but in severe cases, it can also cause skin cancer. Ultraviolet rays are divided into UV-A (320~400nm), UV-B (280~320nm), and UV-C (200~280nm) according to their wavelength. Since most ultraviolet rays are absorbed in the atmosphere, ultraviolet rays that directly affect the human body are known as UV-A and UV-B.

Sunscreen used for the purpose of preventing skin damage caused by UV rays refers to a formulation that shows a UV blocking effect by applying a special substance to a certain skin area. The UV blocking effect uses a unit called SPF (Sun Protection Factor). It indicates the degree of blocking of the product. The sun protection factor is calculated by the formula of the FDA (U.S. Food and Drug Administration). The Minimum Erythema Dose (MED) of UV-B without sunscreen and the minimum UV-B after sunscreen Indicates the ratio of erythema amount. That is, as a multiple of the degree to which the skin in its natural state blocks ultraviolet rays, the higher the value of the UV protection index, the better the effect of blocking sunlight, but the feeling of wearing on the skin deteriorates and side effects may also increase.

Sunscreens are broadly classified into organic sunscreens and inorganic sunscreens. Organic sunscreens have the advantage of excellent sunscreen effects, but they have a narrow wavelength range, are sticky and shiny, and have a bad feeling of use. Inorganic sunscreen reduces the amount of transmitted ultraviolet rays by reflecting and scattering ultraviolet rays. Skin irritation is relatively low compared to organic sunscreen agents, but it has the disadvantage of causing a heavy feeling of use and whitening. (Patent Publication No. 10-2003-0046103).

In order to compensate for the disadvantages of such sunscreens, various studies have been conducted. Specifically, the form of mixing organic sunscreens and inorganic sunscreens in an appropriate ratio is currently applied to most sunscreen products, but the fundamental disadvantages described above are exist. In addition, the form of adsorbing inorganic or polymeric particle surfaces with titanium dioxide, an inorganic blocking agent, or containing an organic blocking agent inside the particles has been supplemented in terms of skin safety, but has disadvantages in that the manufacturing process is complicated and the UV blocking efficiency is not high. Finally, there is a type that supplements the disadvantages of existing inorganic blocking agents by manufacturing titanium dioxide, zinc oxide, and silver inorganic materials into ultra-fine particles and has a high-efficiency blocking effect, but this cannot completely reduce the whitening phenomenon, and the smaller the particle size, the better It has the downside of making it worse. Since the side effects of sunscreens made of such chemical substances have become a problem, natural sunscreens that are completely harmless to the human body have been interested.

Accordingly, the present inventors discovered that cross-linked hyaluronic acid provides an excellent sunscreen effect and completed the present invention.

Hyaluronic acid is a linear polymer polysaccharide in which β-D-N-acetylglucosamine and β-D-glucuronic acid are alternately bonded. It is known that hyaluronic acid is present in connective tissues such as subcutaneous tissue and cartilage tissue of mammals, as well as in the vitreous body of the eye, the umbilical cord, and the like, and also in the capsular membrane of streptococci and bacilli. Common methods for obtaining hyaluronic acid include a method of extracting from chicken combs and umbilical cords, and a method of culturing streptococci and bacilli and then extracting and purifying them.

Natural hyaluronic acid with excellent biocompatibility does not have specificity between species and does not have tissue or organ specificity. It enhances the moisturizing power of the skin, maintains skin elasticity, reduces damage to the lower layer of the skin when skin is damaged, and collagen, the main component of the skin, It also acts as a lubricant to facilitate movement between cells. In addition, alluronic acid induces skin cell activation and is known to help cell regeneration.

Hyaluronic acid has a different weight average molecular weight depending on the length of its sugar chain, and a difference occurs in the skin area where it acts according to the weight average molecular weight. That is, the smaller the weight average molecular weight, the easier it is to penetrate the skin. Therefore, hyaluronic acid with a low weight average molecular weight acts on the dermal layer, and hyaluronic acid with a high weight average molecular weight acts on the stratum corneum, giving skin moisturizing and regenerating power.

On the other hand, when natural hyaluronic acid is used as it is, not only does it have poor mechanical properties, but it is easily decomposed and removed by an enzyme called hyaluronidase present in the body, so there are limitations in various applications. In order to compensate for the disadvantages of such natural hyaluronic acid, therefore, efforts are being made to develop structurally stable hyaluronic acid derivatives (Laurent, T.C. "The chemistry, biology and medical applications of hyaluronan and its derivatives" Portland Press Ltd ., London, 1998). Such hyaluronic acid derivatives are being developed for various purposes such as anti-adhesion agents after surgery, anti-wrinkle agents, molding aids, joint function improving agents, drug delivery systems, and cell culture scaffolds. Research is being done (F. Manna, M. Dentini, P. Desider, O. De Pita, E. Mortilla, B. Maras, Journal of European Academy of Dermatology and Venereology, 13(1999) 183-192). As one of the hyaluronic acid derivatives, the cross-linked hyaluronic acid in which hyaluronic acids are mutually covalently bonded using a cross-linking agent has excellent biocompatibility, physical stability and biodegradability, and U.S. Patent Nos. 4,716,224, 4,963,666, 5,017,229, 5,356,883 and the like disclose methods for its preparation.

According to the development of such cross-linked hyaluronic acid, the disadvantages of hyaluronic acid are complemented, and Korean Patent Publication No. 10-2018-0003443 entitled "Cosmetic composition containing hyaluronic acids having different weight average molecular weights" and Republic of Korea as cosmetics or transdermal application preparations Publication No. 10-2017-0076223 discloses "Hydrogel capsule, manufacturing method thereof, and cosmetic composition containing the same". However, they do not have any information about the UV blocking effect of cross-linked hyaluronic acid.

Accordingly, an object of the present invention is to provide a composition containing cross-linked hyaluronic acid exhibiting an excellent sunscreen effect.

In order to achieve the above technical problem, the present invention provides a sunscreen cosmetic composition without skin irritation containing crosslinked hyaluronic acid or an acceptable salt as an active ingredient.

In the sunscreen cosmetic composition according to the present invention, the crosslinking agent for the crosslinked hyaluronic acid is divinylsulfone, 1,3-butadiene diepoxide, 1,2,7,8-diepoxyoctane, 1,5-hexadiene diepoxy de, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, divinyl sulfone, epichlorhydrin, 1,4-butanediol diglycidyl ether (BDDE), 1,4-bis(2 ,3-epoxypropoxy)butane, 1,4-bisglycidyloxybutane, 1,2-bis(2,3-epoxypropoxy)ethylene and 1-(2,3-epoxypropyl)-2,3 - It may be any one or more selected from the group consisting of epoxycyclohexane.

The composition of the present invention contains cross-linked hyaluronic acid or an acceptable salt as an active ingredient, so it has an excellent sunscreen effect and is very useful as a cosmetic composition because it does not irritate the skin. It has a characteristic of exerting a remarkably increased UV blocking effect.

Hereinafter, specific details for carrying out the present invention will be described.

In order to achieve the above object, the present invention provides a cosmetic composition that contains cross-linked hyaluronic acid or an acceptable salt as an active ingredient, has excellent sunscreen effect, and does not irritate the skin. The cross-linked hyaluronic acid is widely known in the art to which the present invention belongs, and is composed of a step of conducting a cross-linking reaction between a cross-linking agent and hyaluronic acid, and a step of cutting the obtained cross-linked hyaluronic acid, and can be used without particular limitation, as a cross-linking agent. is divinylsulfone, 1,3-butadiene diepoxide, 1,2,7,8-diepoxyoctane, 1,5-hexadiene diepoxide, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether , divinylsulfone, epichlorhydrin, 1,4-butanediol diglycidyl ether (BDDE), 1,4-bis(2,3-epoxypropoxy)butane, 1,4-bisglycidyl selected from the group consisting of oxybutane, 1,2-bis(2,3-epoxypropoxy)ethylene and 1-(2,3-epoxypropyl)-2,3-epoxycyclohexane, the weight average of hyaluronic acid Molecular weight, degree of crosslinking, etc. can be appropriately determined depending on the properties of the desired product, and divinylsulfone is preferably used as a crosslinking agent.

In addition, in the present invention, "crosslinked hyaluronic acid nanoparticles" may be used. For example, the P-crosslinked hyaluronic acid nanoparticles are specifically: i) surfactant dissolved in an oil phase and ii) basic aqueous solution of hyaluronic acid. hyaluronic acid hydrogel nanoparticles characterized in that they are crosslinked hyaluronic acid hydrogel nanoparticles (PEGDG) in a w/o emulsion in which an aqueous phase in which a water-soluble crosslinking agent is dissolved is mixed.

In the present invention, cross-linked hyaluronic acid salts widely known in the art to which the present invention pertains may be used without particular limitation, and for example, sodium salts may be used.

The weight average molecular weight of the cross-linked hyaluronic acid used in the present invention is not particularly limited as long as it is known to be used in the technical field to which the present invention belongs, such as skin moisturizing, skin regeneration, skin whitening, skin elasticity improvement, and skin aging inhibition. , preferably 5,000 KDa ~ 9,000 KDa, more preferably 7,000 kDa, for this reason, if the molecular weight is too small, it is practically absorbed into the skin and it is difficult to show a sunscreen effect, and if the molecular weight is too large, the skin barrier becomes too thick, resulting in a feeling of use because it falls

Cross-linked hyaluronic acid as described above is preferably included in an amount of 0.0001 to 0.1% by weight based on the total weight of the composition, and if less than that, the effect can be exerted, and if it is included in excess, the increase in effect is limited, and the stability of the formulation is also affected. is undesirable as it can affect

In addition, the cross-linked hyaluronic acid of the present invention has a feature of showing a significant synergistic effect even in a small amount when used together with an organic sunscreen, and the organic sunscreen is octyl methoxycinnamate, octyl salicyl If it is widely known in the art to which the present invention pertains, including but not limited to, octocrylene, butylmethoxydibenzoylmethane, oxybenzone, octyltriazone, menthylantranilate, and 3,4-methylbenzylidene camphor, etc. It can be used and the usage amount is also within the normal range.

The cosmetic composition of the present invention as described above may include components commonly used in cosmetic compositions, and for example, antioxidants, stabilizers, solubilizers, vitamins, pigments and flavors, and carriers. include

Such a cosmetic composition may be prepared in any formulation conventionally prepared in the art. In one embodiment, it may be any one formulation selected from the group consisting of a high-viscosity emulsifier type, a low-viscosity emulsifier type, and a solubilizing formulation, but is not limited thereto. Depending on the formulation to be prepared, cosmetic composition ingredients commonly used in the art may be included. For example, it may be formulated into solutions, suspensions, emulsions, pastes, gels, creams, lotions, powders, emulsion foundations, wax foundations, packs, massage creams and sprays, but is not limited thereto. More specifically, it may be prepared in formulations such as softening lotion, nutrient lotion, nutrient cream, massage cream, essence, eye cream, sun lotion, sunscreen, makeup base, and BB cream. Depending on the formulation to be prepared, an aqueous phase component, an oil phase component, a surfactant, a moisturizer, a lower alcohol, a thickener, a chelating agent, a preservative, a flavoring agent, etc. may be selected and added.

Hereinafter, the present invention will be described in detail through examples and experimental examples. It is clear that the present invention is not limited by the description of the above-described embodiment.

<Preparation of Example and Comparative Example Compositions 1>

A composition according to the present invention as shown in Table 1 below was prepared using cross-linked hyaluronic acid having a weight average molecular weight of 3,000 KDa to 15,000 KDa prepared using divinylsulfone as a cross-linking agent.

The composition according to the present invention was prepared by dividing the case of containing cross-linked hyaluronic acid alone and the case of showing a synergistic effect by being contained together with an organic sunscreen widely known in the art to which the present invention belongs. Comparative example compositions include organic sunscreen It was prepared to include alone.

As the organic sunscreen, octylmethoxycinnamate and octocrylene were used. <Experimental Example 1: Measurement of UV protection factor (SPF) and UV A protection level (PA)> UV protection factor for the compositions of Examples and Comparative Examples according to the UV protection function test method among the 'Criteria and Test Methods for Functional Cosmetics' notified by the Ministry of Food and Drug Safety (SPF) and UVA protection factor (PA) were measured. The sample was applied to Transpore tape to a level of 2 mg/cm2, and after drying for 15 minutes, SPF 290 analyzer was used to measure the result. The sun protection index was summarized as the average value of three experimental values, and the results are shown in Table 2 below. As can be seen from Table 2, it was found that the sunscreen effect was remarkably superior to Comparative Examples 1 and 2 using only the organic sunscreen agent. showed a significant synergistic effect.

<Experimental Example 2: Evaluation of skin irritation>

To evaluate skin irritation, a human body patch test was conducted according to the skin safety test method standard of the Korea Food and Drug Administration. After applying each of the compositions of the examples and leaving them for 1 hour, skin irritation was evaluated according to the following criterion, and the results are shown in Table 3. (+++: strong trouble, ++: mild trouble, +: weak trouble, -: negative) As shown in Table 3 above, the composition of the present invention was found not to cause skin irritation, especially the conventional The compositions of Comparative Example containing only the organic sunscreen of induced skin irritation, but the compositions of Examples 2 and 3 containing a small amount of cross-linked hyaluronic acid showed no skin irritation.

<Preparation of Example and Comparative Example Composition 2>

Compositions according to the present invention as shown in Table 4 below were prepared using cross-linked hyaluronic acid having a weight average molecular weight of 3,000 KDa to 15,000 KDa prepared using divinylsulfone as a cross-linking agent.

In the composition of Table 4 below, the weight average amount of crosslinked hyaluronic acid was selected to be approximately 3,000 KDa in Example 4, 7,000 KDa in Example 5, 9,000 KDa in Example 6, and 12,000 KDa in Example 7. <Experimental Example 2: Measurement of UV protection factor (SPF) and UVA protection level (PA)> UV protection factor for the compositions of Examples and Comparative Examples according to the UV protection function test method among 'Criteria and Test Methods for Functional Cosmetics' notified by the Ministry of Food and Drug Safety (SPF) and UVA protection factor (PA) were measured. The sample was 2mg/cm2

It was applied on Transpore tape to a level, and after drying for 15 minutes, it was measured with an SPF 290 analyzer. The sunscreen index was summarized as the average value of three experiments, and the results are shown in Table 5 below. As can be seen from Table 5, Examples 5 to 7 showed improved effects than Example 4 of 3,000 KDa, In particular, Example 5 using 7,000 KDa showed significantly increased results, and Example 7 of 12,000 KDa showed almost similar results to Example 6.

From the above results, when cross-linked hyaluronic acid is included, there is no skin irritation and a very good sunscreen effect is shown, and when used together with an organic sunscreen agent, even a small amount offsets the skin irritation caused by the organic sunscreen agent, while remarkably increased ultraviolet rays It was confirmed that the composition showed a blocking effect and was useful as a composition for blocking ultraviolet rays.

Claims (1)

A sunscreen cosmetic composition without skin irritation, characterized in that it contains 0.0001 to 0.0004% by weight based on the total weight of the composition as an active ingredient of crosslinked hyaluronic acid or an acceptable salt.