JP2553474B2 - Skin cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to a low molecular weight acidic mucopolysaccharide and a salt thereof,
A skin cosmetic excellent in the effect of preventing skin aging (rough skin improving effect, keratin improving effect, horny layer turnover accelerating effect, beautiful skin effect, etc.) containing at least one type of alkali metal hopanthenate in combination .

(Prior Art) Aging skin is dry and rough skin that is exfoliated by keratinocytes and the connective tissue is collagen /
High elastin ratio and many wrinkles. It is said that in aging skin, the turnover of the stratum corneum is slow due to a decrease in cell metabolism, and therefore, the turnover becomes faster when the anti-aging effect is imparted to the skin. Cosmetics have been proposed.

However, although any of the conventionally proposed skin cosmetics can contribute to the modification of the skin surface, for example, to make the skin moist, smooth, etc., it has a positive effect on preventing aging skin. It was difficult to obtain an excellent skin cosmetic as expected.

In order to expect the effect of preventing skin aging, it is necessary to blend a component having a skin cell activating action or a blood circulation promoting action into a skin cosmetic, even under appropriate technical conditions, with only such technical elements, It does not exhibit the expected anti-aging effect.

That is, the skin cells take in the skin cell activating components and the nutrients of the skin cells that are exuded from the skin capillaries existing in the dermis layer, and perform normal cell metabolism.

However, in the dermis layer, along with its constituents, especially structural glycoproteins, acidic mucopolysaccharides that fill the interstices of fibrous proteins, such as hyaluronic acid, dermatan sulfate, chondroitin sulfate, heparan sulfate, and other components. Dermal matrix component composed of, or in the epidermis, basal cells,
Skin cell activating components migrate to the mesothelial material layer composed of lymph fluid, lipids and acidic mucopolysaccharide sugar filling the gaps between spiny cells, granule cells and keratinocytes, and fibroblasts etc. in the dermis. In the epidermis, the expected aging-preventing effect is exhibited only when the cells reach basal cells, spiny cells, etc., and the components are smoothly taken into each cell.

However, in aging skin, the epidermal cell layer is thinned, and the amount of components such as lymph and acidic mucopolysaccharide, which are the components that make up the matrix and mesothelial substances in the epidermal cells, is reduced, and therefore peripheral blood vessels are reduced. Skin cell activating components and skin cell nutrients exuding from the skin cannot migrate sufficiently in the matrix component layer or the mesothelial substance layer, and the uptake of the components by the cells is not sufficiently carried out, and therefore anti-aging effect is expected. It does not appear to the extent that it does.

By normalizing the composition of matrix components and mesogens that are present between the skin capillaries and skin cells, the skin cell activating components and components such as skin cell nutrients are incorporated into the skin cells smoothly. There are still no proposals for skin cosmetics.

(Disclosure of the Invention) As a result of research in view of the above-mentioned problems, the present inventor has found that, as described in Japanese Patent Application No. 62-075448, "the average molecular weight is 1000-10
The present invention has been completed as "a skin cosmetic characterized by containing at least one low-molecular weight acidic mucopolysaccharide having a molecular weight of 0000 and a salt thereof, and calcium fopanthenate."

However, as for the skin cosmetics excellent in the effect of preventing skin aging, which is the object of the present invention, as a result of further intensive studies, at least one of the specific low-molecular weight acidic mucopolysaccharides and salts thereof described later and an alkali metal fopanthenate salt. The skin cosmetics containing at least one of the
Compared with the skin cosmetics according to the invention described in No. 8, it is much more excellent in the effect of preventing skin aging, storage stability, the effect of accelerating turnover of the stratum corneum, the effect of improving rough skin, and the effect of improving keratin. The present invention has been completed by discovering that it exhibits a moisturizing effect (moist feeling), flexibility (smooth feeling), elasticity (tension), and a beautiful skin effect capable of imparting luster to the skin.

(Object of the Invention) That is, the object of the present invention is a skin cosmetic excellent in storage stability and rough skin improving effect, reforming improving effect, effect of accelerating turnover of the stratum corneum, and skin aging preventing effect such as beautiful skin effect. To provide.

(Structure of the Invention) The present invention is characterized by containing at least one kind of low molecular weight acidic mucopolysaccharide having an average molecular weight of 1,000 to 100,000 and a salt thereof, and at least one kind of alkali metal fopanthenate. Cosmetics.

(Detailed Description of the Invention) The acidic mucopolysaccharide used in the present invention, namely hyaluronic acid,
Dermatan sulfate, chondroitin sulfate, heparan sulfate and the like are known substances, and are widely distributed in the animal body by forming a matrix component in cartilage, joints, eyes, skin and other connective tissues, binding to proteins.

The low molecular weight acidic mucopolysaccharides and salts thereof used in the present invention can be obtained as follows.

(1) Low molecular weight hyaluronic acid and its salt 5 g of commercially available hyaluronic acid with an average molecular weight of 1 million
Is dispersed and dissolved in 100 ml of 0.02N hydrochloric acid aqueous solution, and the pH is 2 to 2.
The mixture was adjusted to 3 and heated to 65 ° C. in a warm bath with sufficient stirring. By changing the heating treatment time from 10 minutes to 120 minutes, hyaluronic acid having an average molecular weight of 1,000 to 100,000 can be obtained.

Then, after neutralizing with 1N-caustic soda, the solution was cooled to room temperature, and a precipitate obtained by adding 3 volumes of ethanol was washed with ethanol and dried to obtain low-molecular weight hyaluronic acid sodium salt powder. . In addition, this low molecular weight hyaluronic acid sodium salt is treated with an acid to give free hyaluronic acid, which is then treated with another basic substance, for example, potassium salt, triethanolamino salt, L-arginine salt, etc. Was prepared.

(2) Low molecular weight chondroitin sulfate and its salts, etc. 5 g of commercially available sodium chondroitin sulfate having an average molecular weight of 50,000 was dissolved in 50 ml of water, and Amberlite IR was used.
The effluent obtained by passing through a -120 (H type) resin column was heated to 75 ° C in a warm bath while being sufficiently stirred. By changing the heating treatment time from 10 minutes to 120 minutes, chondroitin sulfate having an average molecular weight of 1,000 to 100,000 can be obtained. It is then neutralized with 1N-caustic soda. After the solution was cooled to room temperature, 3 times volume of ethanol was added, the resulting precipitate was centrifuged, washed with ethanol, and dried to obtain a powder of chondroitin sulfate sodium salt. Then, this sodium chondroitin sulfate salt is treated with an acid to give free chondroitin sulfate, and then this is treated with another basic substance, for example, a salt such as a potassium salt, a triethanolamine salt or an L-arginine salt. Was prepared.

Also, low molecular weight dermatan sulfate, low molecular weight heparan sulfate, etc. were prepared in free form or their respective salts by the same treatment as in the above example of chondroitin sulfate.

The method for measuring the average molecular weight of the acidic mucopolysaccharide obtained by each treatment time was Somogyi-Nelson (Somogyi-Ne
lson) method was used.

The alkali metal hopanthenic acid is a known substance, for example, sodium salt, potassium salt, and lithium salt of hopanthenic acid.

Moreover, it can be obtained by an ordinary production method in the same manner as calcium fopanthenate.

The alkali metal salts of hopanthenic acid used in the skin cosmetics of the present invention have effects such as storage stability in skin cosmetics and the effect of accelerating turnover of aged skin, rough skin improving effect, and keratin improving effect as compared with the above-mentioned calcium hopantenate. It is presumed that all of them are excellent and have a continuous blood circulation stimulating effect to activate skin cells to exert an excellent anti-aging effect on skin, and further normalize the metabolic function of skin cells to enhance the skin beautiful effect.

The compounding amount of the alkali metal hopanthenate is 0.05 to 2.0% by weight based on the total weight of the composition of the skin cosmetic of the present invention.
(Hereinafter abbreviated as wt%), preferably 0.1
~ 1.5wt%. If the blending amount is less than 0.05 wt%, the effect aimed at by the present invention is not sufficient. On the other hand, if it exceeds 2.0 wt%, improvement in the effect commensurate with the increase cannot be expected.

In addition, the present inventor conducted various researches on the content ratio of the above-mentioned constituents contained in the skin cosmetic composition to maximize the synergistic effect, and as a result, (1) low-molecular-weight acidic mucopolysaccharides and salts thereof, ( 2) The ratio (weight ratio) of the respective contents of the alkali metal hopanthenate is (1) :( 2) = 1:
It is preferably 0.01 to 1: 1 and the excellent effect aimed at by the present invention was observed.

That is, the blood circulation accelerating agent of (2) promotes blood circulation in peripheral capillaries in the dermis adjacent to skin cells, and the skin cell activating components and skin cell nutrients contained in the blood are transferred to the dermis tissue. By stimulating the exudation and further improving the composition ratio of the substrate component that surrounds the skin cells in (1), the smooth absorption of substances such as the skin cell activation component of the skin cells is promoted, and the metabolism of the skin cells is improved. Along with promoting
The excellent water-holding ability of (1) contributed to the appropriate application and retention of water to the skin, and the effect of exhibiting a beautiful skin effect could be achieved.

Further, the blending amount of the low molecular weight acidic mucopolysaccharide and the salt thereof may be 0.01 to 2.0 wt% with respect to the total weight of the cosmetic composition. However, even if the upper limit is exceeded, it is not possible to expect an improvement in the effect commensurate with the increase.

In addition to the above, the skin cosmetics of the present invention include various oils, polyhydric alcohols, ultraviolet absorbers, dyes, fragrances, preservatives, surfactants, pigments, antioxidants, thickeners, resin-forming agents, etc. Can be appropriately blended within a range that achieves the object of the present invention.

Further, the dosage form of the skin cosmetic of the present invention can be arbitrarily prepared such as skin lotions, emulsions, creams, packs and foundations.

(Example) Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples.

In addition, storage stability test in cosmetics, rough skin improvement effect test,
Horny layer improvement effect test, stratum corneum turnover measurement test,
The sensory test (Beautiful skin effect test) is as follows.

(1) Storage stability test After storage in a temperature-controlled room at 45 ° C and 5 ° C for 3 months, the lotion (described later) has a visually opaque appearance and the emulsions (described later) also shows a separated state. And evaluated.
Good ones are indicated as ◯ ○, and bad ones are indicated as ×.

(2) Rough skin improvement effect test 20 middle-aged and elderly subjects having rough skin on the lower legs were tested for the application effect for 4 consecutive weeks. About 1 g of the sample was applied to the left lower leg test site of the test subject once a day, and the condition of the skin before and after the start of the test was evaluated according to the following criteria. The lower right leg was not coated with the sample and served as a control.

Criteria for skin dryness −: Normal ±: Minor dryness, no desquamation +: Dry, mild desquamation ++: Dry, moderate desquamation +++: Dryness, remarkable desquamation Compare the determination results of the test site before and after the test and the control site,
When the skin dryness is improved by two or more steps (for example, + →
−, ++ → ±) is valid, 1 is slightly improved when it is improved, and is invalid when there is no change. The test results were shown by the number of subjects who were valid or slightly valid.

(3) Keratin improvement (increased anti-peeling property of keratinocytes) effect test Scotch tape (Nichiban Mending Tape) was adhered to the subject's skin before and after the rough skin improvement effect test described above, and the tape was peeled off. The state of the keratinocytes adhered to was examined in detail by a scanning electron microscope, and the skin keratinocyte anti-exfoliation property was analyzed according to the following criteria to determine the keratin improving effect.

Criteria for keratin improvement effect (increased keratinocyte anti-exfoliation) Evaluation point 1: No scale is observed 2: Small scale is scattered 3: Small to medium scale is remarkable 4: Large scale is remarkable Evaluation is a test site after 4 weeks continuous application When the difference between the evaluation points of 1 and 2 was 2 points or more, it was judged as valid, 1 point as slightly valid, and 0 point as invalid. Judgment result is valid,
It is shown by the number of subjects who were slightly effective.

(4) Turnover measurement test of the stratum corneum The fluorescent dye dansyl chloride was added to white petrolatum 5 times.
Make an ointment containing 20% by weight and apply it to the skin of the forearm of 20 test subjects for 24 hours, and dansyl chloride is permeated and bonded to the stratum corneum. After that, the test sample was applied to the same site twice a day (morning and evening), the fluorescence of dansyl chloride was examined every day, and the number of days until the fluorescence disappeared was defined as the turnover of the stratum corneum of the skin.

The judgment results are shown as the average number of days of the subjects. The normal turnover of the stratum corneum is 14 to 16 days, but in aged skin it extends around 18 days. On the other hand, when the anti-aging effect appears, it is shortened to around 12 days.

(5) Sensory test (Beautiful skin effect test) Female subjects who complain of rough skin, fine wrinkles, dry skin (35-55)
20 years old, the effect of the sample was evaluated twice a day (morning and evening) after 3 consecutive months. The test results were expressed by the number of people who answered that the skin was moistened, the skin became smooth, and the skin became taut for each item of skin wettability, smoothness, and elasticity.

Comparative Examples 1 to 3 and Examples 1 to 5 [Two-layer type skin lotion] As shown in Table 1, two-layer type skin lotion bases were mixed with alkali metal hopanthenate as shown in Table 1, respectively. The skin lotion was prepared and the above-mentioned tests were carried out.

In addition, as an acidic mucopolysaccharide used in the present invention, hyaluronic acid is abbreviated as HA, and hereinafter, sodium hyaluronate (HA
-N), chondroitin sulfate (CO), chondroitin sulfate triethanolamine (CO-T), chondroitin sulfate L
-Abbreviated as arginine (CO-A), dermatan sulfate (DE), potassium dermatan sulfate (DE-K), heparan sulfate (HP), sodium heparan sulfate (HP-N).

(1) Composition (2) Preparation method (C) Component alkali metal salt of fopanthenic acid, etc. and (D) component acidic mucopolysaccharide are mixed and dissolved in the (B) component in advance, and the (A) and (B) components are uniformly mixed. After melting
The component (A) and the component (B) are mixed and dispersed by stirring, and then filled in a container. At the time of use, the contents should be evenly dispersed by shaking.

(3) Properties The results of various tests of each two-layer type skin lotion are shown in the right column of Table 1.

In all the tests, the skin cosmetics of the present invention of Examples 1-5 showed favorable results in comparison with the skin cosmetics of Comparative Example 1-3 containing the acidic mucopolysaccharide and calcium hopanthenate.

In addition, in Comparative Examples 1 to 3, in the storage stability test, the appearance of the lower aqueous phase portion became cloudy.

Comparative Example 4 and Examples 6-9 [Skin Cream] Similar to Example 1, each skin cream was prepared with the following composition and various tests were carried out. The results are shown in the right column of Table 2.

(1) Composition (2) Preparation method The alkali metal salt of fopanthenic acid as the component (C) and the acidic mucopolysaccharide as the component (D) are mixed in the component (B), and the components (A) and (B) are heated to 80 ° C, respectively. After melting by heating,
Each skin cream was prepared by mixing and stirring and cooling to 30 ° C.

(3) Characteristics As shown in Table 2, it is clear that the skin creams of Examples 6 to 9 which are the skin cosmetics of the present invention are superior to Comparative Example 4 in all of their characteristics. No abnormality was found in the compounding characteristics.

In Comparative Example 4, the appearance was separated in the storage stability test.

(Effect of the Invention) As described above, it is apparent that the skin cosmetic of the present invention provides an excellent skin cosmetic that enhances the skin function and exerts a remarkable effect in preventing skin aging.

Claims (1)

(57) [Claims] 1. A skin cosmetic comprising at least one low-molecular-weight acidic mucopolysaccharide having an average molecular weight of 1,000 to 100,000 and a salt thereof, and at least one alkali metal fopanthenic acid salt.