JP5689332B2 - Cosmetics - Google Patents

Description

  The present invention relates to a cosmetic.

One purpose of cosmetics is to prevent skin dryness, regulate moisture on the skin surface, and give the skin a moist feeling. For this reason, various components are added to the cosmetic as a moisturizing agent. Commonly used as a humectant include polyhydric alcohols such as glycerin and 1,3 butylene glycol (1,3BG) sorbitol, biological humectants such as amino acids, organic acids and hyaluronic acid.
In addition to the above, as a moisturizing agent for cosmetics, it is known that a polymer such as polyoxyalkylene glycol monoacrylate or polyoxyalkylene glycol has a moisturizing effect as a cosmetic substrate (Patent Document 1: Special). Kaihei 1-131106). In addition, polymethoxymethoxyglycol methacrylate (methyl ether methacrylate polymer) has been confirmed to have a moisturizing effect by a moisturizing test using pork skin, and a cosmetic product containing the same has been proposed (Patent Document 2: Special). No. 2003-171257). Patent Document 2 discloses a lotion in which polymethoxyethylene glycol having an average degree of polymerization of 4.5 polyoxyethylene chains is blended with O // polyethylene methacrylate having an average degree of polymerization of 22.7 in polyoxyethylene chains. A W-type emulsion is disclosed.

JP-A-01-131106 JP 2003-171257 A

Supervised by Katsuyuki Takeda et al., “Usefulness of Cosmetics: Advances in Evaluation Technology and Future Prospects”, First Printing, Yakuji Nippo Inc., March 31, 2001, 82p. 82-101

  It is an object of the present invention to provide a cosmetic product having a high moisturizing effect, which contains polymethoxypolyethylene glycol glycol methacrylate and a moisturizing agent and maintains a moisturizing effect for a long time that cannot be maintained by blending only the moisturizing agent.

The main configuration of the present invention is as follows.
(1) A cosmetic comprising polymethoxymethoxyglycol methacrylate having an average degree of polymerization of 9 and a polyoxyethylene chain.
(2) The cosmetic according to ( 1) , wherein the humectant is a polyhydric alcohol humectant.
(3) The cosmetic according to (1) or (2) , wherein the methoxypolyethylene glycol polymethacrylate contains 0.01 to 0.5 parts by weight with respect to 1 part by weight of the humectant.
(4) In ( 2) or (3) , the polyhydric alcohol humectant is one or more selected from glycerin, 1,3-butylene glycol (1,3BG), and sorbitol. Cosmetics described.

By carrying out the present invention, it was possible to realize a novel cosmetic that exhibits improved moisturizing properties when applied to the skin and exhibits an effect of extending the moisturizing time. In particular, the cosmetic composition of the present invention uses poly (methoxypolyethylene glycol) methacrylate and a polyhydric alcohol as a humectant, and further blends glycerin among the polyhydric alcohols, thereby moisturizing the skin and extending the moisturizing time. Therefore, it is possible to provide a cosmetic with high moisture retention. In addition, by combining the methoxypolyethylene glycol polymethacrylate having a polyoxyethylene chain average polymerization degree of 9 and a humectant, the moisture content of the stratum corneum can be further increased synergistically, and the amount of the humectant to be blended And the stickiness of cosmetics can be improved.
Furthermore, the cosmetic of the present invention brings about a moist feeling on the skin, and is effective in improving rough skin and preventing rough skin.

The graph which shows the test result which measured the time-dependent fluctuation | variation of the stratum corneum moisture content of Test Examples 1-6 The graph which shows the test result which measured the time-dependent fluctuation | variation of the stratum corneum moisture content of Test Examples 1, 2, and 7-10. The graph which shows the test result which measured the time-dependent fluctuation | variation of the stratum corneum moisture content of Experiment 1, 2, 10-14 The graph which shows the test result which measured the time-dependent fluctuation | variation of the stratum corneum moisture content of Test Example 1, 2, 15-24 The graph which shows the test result which measured the time-dependent fluctuation | variation of the stratum corneum water content of Test Examples 1, 2, 25 and 26

  The methoxypolyethylene glycol polymethacrylate used in the present invention can be obtained by homopolymerizing methoxypolyethylene glycol methacrylate. The best polymethacrylic acid methoxypolyethylene glycol for carrying out the present invention may be one having an average degree of polymerization of polyoxyethylene chain of 4 to 23, and more preferably an average degree of polymerization of polyoxyethylene chain of 7 to 15. Those having an average degree of polymerization of 9 are particularly preferred.

  For example, methoxypolyethylene glycol methacrylate having a polyoxyethylene chain average polymerization degree of 9 can be obtained by reacting polyethylene glycol methyl ether and methacrylic acid chloride as disclosed in Patent Document 2. Some synthetic raw materials are commercially available as reagents. NK ester M-90G (n≈9) manufactured by Shin-Nakamura Chemical Co., Ltd. and Bremer PME-400 (n≈9) manufactured by NOF Corporation can be used as monomers. About the manufacturing method of a polymer, what is necessary is just to follow the method currently disclosed by the said patent document 2, and it is obtained by making a monomer react in presence of a polymerization initiator in a solvent. The methoxypolyethylene glycol polymethacrylate as a cosmetic raw material has an average molecular weight of 1,000 to 100,000 when measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, preferably 2, 500 to 100,000, particularly preferably 3,000 to 50,000.

The moisturizing agent used in the present invention may be any component having a skin moisturizing function (wetting function) necessary for cosmetics. For example, examples of naturally-occurring components include mucopolysaccharides, collagen, organic acids, and amino acids as biological components, and glycerin, diglycerin, sorbitol, maltitol, methylgluces, trehalose, 1 , 3-butylene glycol, 1,2-pentanediol and the like.
Mucopolysaccharides include hyaluronic acid, sodium hyaluronate, acetylated hyaluronic acid, etc., organic acids such as lactic acid, sodium lactate, citric acid, sodium citrate, etc., amino acids such as valine, leucine, isoleucine, threonine, methionine, Examples include phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid, hydroxylysine, arginine, ornithine, histidine and the like.
Glycerin is widely used as a cosmetic, and concentrated glycerin for cosmetics manufactured by Lion Corporation, concentrated glycerin manufactured by Kao Corporation, and the like can be obtained and used. As a commercial product of sorbitol, sorbit D-70 manufactured by Mitsubishi Corporation Foodtech Co., Ltd. can be obtained and used. Sorbit D-70 is a mixed raw material composed of 70% by weight of sorbitol and 30% by weight of water. As commercial products of 1,3-butylene glycol, 1,3-butylene glycol manufactured by Daicel Chemical Industries, Ltd., 1,3-butylene glycol manufactured by Kyowa Hakko Bio Co., Ltd., etc. should be used. Can do. Moreover, although not illustrated here, other moisturizing ingredients than those described above can be used without any problem as long as they are provided as cosmetic raw materials.

As long as the amount of the moisturizing agent is within a range that is usually blended in cosmetics, an appropriate amount can be blended appropriately in the intended cosmetic. For example, it is preferably 0.01% by weight or more and 25% by weight or less based on the total mass of the cosmetic. If it is less than 0.01% by weight, the moisture retention as a cosmetic product may be insufficient, and if it exceeds 25% by weight, it may become sticky.
In the cosmetic of the present invention, the polymer is contained in an amount of 0.01 to 25% by weight, preferably 0.01 to 15% by weight, based on the entire cosmetic.

  Furthermore, the methoxypolyethylene glycol polymethacrylate used in the present invention can exert a more appropriate effect by blending in the range of 0.01 to 0.5 parts by weight with respect to 1 part by weight of the humectant. . When it is less than this ratio, the effect of enhancing the moisturizing effect or extending the moisturizing duration cannot be exhibited. Moreover, since the effect does not increase so much even if it exceeds this ratio, it is preferable to mix | blend in this range.

  In the cosmetic of the present invention, components usually used in cosmetics can be blended, and oils, surfactants, water-soluble polymers, organic powders, inorganic powders, fragrances, pH adjusters, preservatives, Beauty ingredients such as vitamins can be included.

  The cosmetic of the present invention is mainly applied to the skin, and includes pharmaceuticals and quasi-drugs according to the classification of the Pharmaceutical Affairs Law as long as they have an effect on moisturizing the skin.

  Examples of the dosage form of the cosmetic of the present invention include lotion, emulsion, cream, aqueous gel, pack, face wash and the like, and the emulsifier type can be either oil-in-water emulsification or water-in-oil emulsification.

  The present invention will be described more specifically with reference to test examples and examples for confirming the effects.

Test 1
A composition is prepared by mixing a moisturizing agent, which is a blending component of the cosmetic of the present invention, and poly (methoxypolyethylene methacrylate) glycol in a ratio to be blended in cosmetics, and this is directly applied to the skin to measure the moisturizing effect.
Tables 1 to 3 show the formulations of the samples used in this test. Tables 4 to 6 show the results of measuring the moisturizing effect. Moreover, among the data of Table 4-Table 6, the time-dependent change of the moisture content of a stratum corneum was graphed and shown in FIGS. 1 corresponds to Table 4, FIG. 2 corresponds to Table 5, and FIG. Sample 1 is only water, and Test Example 1 in which this was applied is a control in this test. The polymethacrylic acid methoxypolyethylene glycol used in the test was prepared in the reference examples shown below. As the moisturizing agent, a commercially available cosmetic raw material was used.

  The determination of the moisturizing effect was performed by measuring the moisture in the stratum corneum of the skin before application of the test sample and after a lapse of a certain time after application, and comparing with the value before application. The stratum corneum moisture was measured and standardized according to the following procedure.

Measuring method of stratum corneum moisture content Measuring procedure (1) Wash the inner part of the forearm with face wash and rinse with warm water for 10 seconds.
(2) Wipe off moisture from the forearm and keep it at rest in an environment of 24 ° C. and relative humidity of 25% for 20 minutes.
(3) Mark a 2.5 cm × 2.5 cm area on the left and right forearms and apply the sample. The sample is applied by placing a spatula on a precision electronic balance, weighing 10 mg of the sample, and applying the sample to an area of 2.5 cm × 2.5 cm using the spatula.
(4) Measure stratum corneum moisture before applying the sample and at the point when 30 minutes, 60 minutes or 90 minutes have elapsed after applying the sample.
In addition, the stratum corneum moisture content used SKICON-200EX by IBS which is an apparatus which measures skin surface conductance. Measurement was performed 3 or 5 times, and the value obtained by averaging the obtained conductance values was handled as the moisture content. The amount of water in the results of the following test is the amount of conductance. In order to match the standard, a value (ΔμS) obtained by subtracting the measured value before applying the sample from the measured value after applying the sample was used as a reference when evaluating the moisture retention of the sample.

Test results The water content of the stratum corneum in the control in which water (sample 1) was applied to the skin hardly changed before and after application (Test Example 1).
Even when the sample (sample 2) containing only poly (methacrylic acid) methoxypolyethylene glycol having a polymerization degree of 9 prepared by the synthesis method shown in the reference example was applied to the skin, the stratum corneum moisture content hardly changed (Test Example 2). . Therefore, it was evaluated that even when only methoxypolyethylene glycol polymethacrylate was applied to the skin, there was almost no effect (moisturizing effect) of increasing the amount of moisture in the stratum corneum. This result was different from the evaluation of the test using dry pig skin described in Prior Art Document 1. The test of Prior Art Document 1 is an in vitro test using porcine dry skin, and the present invention is a test directly applied to human skin, which reflects such a moisturizing effect of the living body itself, and thus is evaluated in this way. It was judged that As a test for the moisturizing effect of human skin, measuring methods for the stratum corneum moisture retaining effect and the stratum corneum barrier effect have been established. Although they are closely related, they are distinct effects (supervised by Katsuyuki Takeda et al., “Usefulness of Cosmetics: Advances in Evaluation Technology and Future Prospects”, 1st edition, Yakuji Nippo Inc., March 2001) 31st, 82p.82-101). In the present invention, the former stratum corneum moisture retention effect is evaluated. On the other hand, the measurement method of Prior Art Document 1 measures the water loss rate from pig skin, and is considered to be an effect that combines the water retention effect and the transpiration shielding (barrier) effect, and the measurement object is different from the present invention. Is.
On the other hand, when samples 3, 7, and 11 containing only the humectant (1,3BG, sorbitol, glycerin) were applied to the skin, the moisture content of the stratum corneum increased and the moisturizing effect was confirmed (Test Examples 3 and 7). 11).

Test example 4 in which samples 4, 8, and 12 containing polymethoxymethoxyglycol glycol (Synthesis example 1) having a polymerization degree of 9 used in the present invention and a moisturizer (1,3BG, sorbitol, glycerin) were applied to the skin , 8 and 12 have a stratum corneum water content increased and a moisturizing retention time clearly extended when the humectant was applied to the skin alone (Test Examples 3, 7, and 11).
Samples 5 and 6 containing poly (methacrylic acid) methoxypolyethylene glycol having a polymerization degree of 4.5 and a polymerization degree of 22.5 (Synthesis Example 2 and Synthesis Example 3) and a humectant (1,3BG, sorbitol, glycerin). , 9, 10, 13 and 14 were applied to the skin, the results of Test Examples 5, 6, 9, 10, 13 and 14 showed an increase in the stratum corneum moisture content compared to the control. It was inferior compared with poly (methoxypolyethylene glycol) methacrylate.
From the above test results, it was confirmed that methoxypolyethylene glycol polymethacrylate alone did not show a moisturizing effect on human skin, but enhanced moisturizing effect and prolonged moisturizing time when used in combination with a moisturizing agent. Moreover, the effect confirmed that the substance of average polymerization degree 9 was the most effective.

Test 3
Next, in Test 1, the content of the methoxypolyethylene glycol polymethacrylate having an average degree of polymerization of 9 which was excellent in the evaluation of the moisturizing property was fixed, and the blending amount of the humectant (glycerin) was 1, 5, 10, 15, 25 The moisture retention evaluation test (measuring stratum corneum moisture content) was performed while changing the weight%. Table 7 shows the formulation of the sample used in this experiment. Table 8 shows the results. Moreover, the result of having graphed the data of Table 8 similarly to Test 1 is shown in FIG.

Test results When samples 20 to 24 containing poly (methacrylic acid methoxypolyethylene glycol) with a polymerization degree of 9 and glycerin were applied to the skin, the water content of the stratum corneum increased as compared with the case where glycerin was applied to the skin alone. , Moisturizing maintenance time was extended. It was confirmed that the action of increasing the moisturizing effect of poly (methacrylic acid methoxypolyethylene glycol) is increased in the range of 0.02 to 0.5 parts by weight of poly (methacrylic acid) methoxypolyethylene glycol with respect to 1 part by weight of glycerin. .

Test 3
A moisturizing evaluation test (measurement of water content in the stratum corneum) was carried out by combining poly (methoxypolyethylene glycol) having a polymerization degree of 9 and two kinds of moisturizing agents (glycerin 5% and sorbitol 3%). Table 9 shows the formulation of the sample used in this test. Table 10 shows the results. Further, FIG. 5 shows the change with time of the water content of the stratum corneum as in Tests 1 and 2.

Test results It was confirmed that the moisturizing effect was enhanced and the moisturizing maintenance time could be extended by combining a plurality of moisturizing agents and further blending poly (methacrylic acid methoxypolyethylene glycol) having a polymerization degree of 9.

  As a result of Test 1 to Test 3, the composition containing polymethoxymethoxyglycol glycol having an average degree of polymerization of 9 polyoxyethylene chains of the present invention and a moisturizer is used to determine the moisture content of the skin stratum corneum. It has been shown to increase and extend the moisturizing time.

[Reference example]
Below, the synthesis example of the polymethacrylic acid methoxypolyethylene glycol used for this invention as a reference example is shown.

Synthesis Example 1: Polymethoxymethoxyglycol methacrylate (average degree of polymerization of polyoxyethylene chain is 9)
0.0403g of polymerization initiator azobisisobutyronitrile (AIBN) was weighed into a 100ml eggplant flask, and the inside of the flask was replaced with argon gas three times. Then, 30ml of distilled benzene was added and stirred at room temperature until AIBN was dissolved. . 5 ml of polyethylene glycol methyl ether methacrylate (average polymerization degree of PEG is 9) was added thereto, and the mixture was heated at 60 ° C. for 48 hours and then at 70 ° C. for 24 hours for polymerization. Thereafter, the polymerization was stopped and the desired product was recovered.

Synthesis Example 2: Polymethoxymethoxyglycol methacrylate (average polymerization degree of polyoxyethylene chain is 4.5)
In a 100 ml eggplant flask, 0.0306 g of polymerization initiator AIBN was weighed and the inside of the flask was replaced with argon gas three times. Then, 30 ml of distilled benzene was added and stirred at room temperature until AIBN was dissolved. To this was added 5 ml of polyethylene glycol methyl ether methacrylate (PEG has an average degree of polymerization of 4.5), and polymerization was carried out by heating at 60 ° C. for 48 hours and then at 70 ° C. for 24 hours. Thereafter, the polymerization was stopped and the desired product was recovered.

Synthesis Example 3: Polymethoxymethoxyglycol methacrylate (average degree of polymerization of polyoxyethylene chain is 22.7)
In a 100 ml eggplant flask, 0.00753 g of the polymerization initiator AIBN was weighed, and the inside of the flask was replaced with argon gas three times. Then, 30 ml of distilled benzene was added and stirred at room temperature until the AIBN was dissolved. To this was added 5 ml of polyethylene glycol methyl ether methacrylate (average polymerization degree of PEG is 22.7), and the mixture was heated at 60 ° C. for 48 hours and then at 70 ° C. for 24 hours for polymerization. Thereafter, the polymerization was stopped and the desired product was recovered.

  The molecular weight of the resulting polymethacrylic acid methoxypolyethylene glycol was measured using GPC. The molecular weight of Synthesis Example 1 was 15363 in terms of polystyrene, the number average molecular weight was 35680, and the mass average molecular weight was 35680.

  The molecular weight of Synthesis Example 2 was 13800 in terms of polystyrene and the number average molecular weight was 40400 in terms of polystyrene. The molecular weight of Synthesis Example 3 was 8300 in terms of number average molecular weight and 10,000 in terms of mass average molecular weight in terms of polystyrene.

Formulation Example 1 Lotion
(Compounding ingredients) (wt%)
1. Polymethacrylic acid methoxypolyethylene glycol of synthesis example 1
(The average degree of polymerization of the polyoxyethylene chain is 9) 1
2. Glycerin 5
3. 1,3-butylene glycol 4
4.1,2-Pentanediol 1
5. Xanthan gum 0.1
6). Trisodium citrate 0.04
7). Citric acid 0.01
8). Phenoxyethanol 0.2
9. Purified water residue

Ingredients 1-9 were mixed to prepare a lotion.
The lotion of the present invention has high moisturizing properties and was excellent in improving rough skin and preventing it.

Formulation example 2 serum
(Compounding ingredients) (wt%)
1. Polyglyceryl distearate-10 0.6
2. Polyglyceryl stearate-10 1.4
3. Olive oil 4
4). Jojoba oil 4
5. Polymethacrylic acid methoxypolyethylene glycol of synthesis example 1
(Average polymerization degree of polyoxyethylene chain is 9) 2
6). Sorbitol 8
7). Glycerin 10
8). Carboxyvinyl polymer 0.1
9. 1,2-pentanediol 1
10. Elastin 0.1
11. Hyaluronic acid 0.1
12 Collagen 0.1
13. Potassium hydroxide 0.03
14 Purified water residue

Mixing ingredients 1 to 4 heated and dissolved at 80 degrees and mixing ingredients 5 to 9, 13 and 14 heated and dissolved at 80 degrees are mixed and emulsified, stirred and cooled to 40 degrees, and components 10 to 12 are added. A cosmetic solution was prepared by stirring and cooling to the end.

The cosmetic liquid of the present invention has high moisturizing properties and was excellent in improving rough skin and preventing skin.

Claims (4)

A cosmetic comprising a moisturizer and polymethoxyethylene glycol polymethacrylate having an average degree of polymerization of 9 polyoxyethylene chains. The cosmetic according to claim 1 , wherein the humectant is a polyhydric alcohol humectant. The cosmetic according to claim 1 or 2 , wherein the polymethoxypolyethylene glycol polymethacrylate contains 0.01 to 0.5 parts by weight with respect to 1 part by weight of the humectant. The cosmetic according to claim 2 or 3 , wherein the polyhydric alcohol humectant is one or more selected from glycerin, 1,3-butylene glycol (1,3BG), and sorbitol.

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