JP2992415B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics, and more particularly, to cosmetics which are excellent in moisturizing effect and skin roughening effect on skin, while having excellent protective effect on hair based on film forming action. It will not be provided.

[0002]

2. Description of the Related Art In general, drying of the skin depends on the amount of skin secretions,
In particular, the decrease in the amount of sebum secretion and the decrease in natural moisturizing factors such as intercellular lipids and amino acids cause the barrier function of the stratum corneum to decrease,
Occurs when transepidermal water loss (hereinafter abbreviated as TEWL) increases. Therefore, a condition in which skin dryness worsens due to a decrease in skin secretions due to winter or excessive skin washing, age, constitution, and the like, and a condition in which the water content of the stratum corneum is reduced to about 10% or less is particularly called dry skin. As described above, when the skin is in a dry state, the gloss of the skin decreases, and adverse effects such as fine wrinkles appear. Similarly, a decrease in the amount of water in the hair causes the hair to lose its smoothness and to cause other problems such as a decrease in gloss.

Conventionally, in order to improve these skin conditions and hair conditions, it has been necessary to prevent a decrease in the water content of the stratum corneum and hair and to maintain a normal function. Has been studied. As a result, the proposed method has a good adhesiveness to the skin and a TE by using an occluding agent such as Vaseline ointment or water-in-oil emulsion having hydrophilicity.
A method for suppressing WL, having hygroscopicity and moisturizing power, for example, polysaccharides such as hyaluronic acid and chitin, proteins such as collagen and elastin, polyhydric alcohols such as sorbitol, ethylene glycol and glycerin, and sodium pyrrolidone carboxylate There has been a method of enhancing the hydration effect by blending a moisture absorbent and a humectant such as organic acid salts such as sodium lactate into a skin base or a hair base.
Recently, it was revealed that ceramide and sphingolipids, which are components of intercellular lipids such as the stratum corneum, play an important role in retaining water, and ceramides from synthetic and natural extracts have also been added. It is getting.

[0004]

However, none of the above-mentioned methods known in the prior art has a sufficient water retention ability, and when an occlusive agent is used, they are greasy and sticky. On the other hand, in the case of using a moisture absorbent or a humectant, a large amount must be added in order to enhance the effect, and as a result, uncomfortable feelings such as sticky feeling and slimy feeling are obtained. There is a problem of giving a feeling, and in fact, it is impossible to mix a large amount in a prescription system. Further, there is a disadvantage that the stability with respect to time and microorganisms is poor. Further, there is no single substance that has both a moisture absorbing / humidifying action and a promoting action / stabilizing action of an intercellular lipid lamellar layer such as ceramide.

The present invention has been made in view of the above circumstances, and is intended to improve the condition of skin and hair caused by dryness such as rough skin and lack of luster, and to provide moisturizing by sufficient moisture retention. It is an object of the present invention to provide a cosmetic composition having a beautiful hair effect and having almost no problem in feel.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the present inventors have found that the present inventors have found that the present inventors have found that the present invention has the same structure as a polar group of phospholipid (phosphatidylcholine), which is a main component of a biological membrane. Methacryloyloxyethyl phosphorylcholine is a copolymer having a constitutional unit is moisture-absorbing,
The present inventors have found that they have a high moisture retention function based on a moisturizing effect, and are excellent in a lamellar formation promoting / stabilizing effect and a film forming ability, and based on this, the present invention has been completed.

That is, the present invention is a cosmetic comprising a copolymer of 2-methacryloyloxyethylphosphorylcholine and a hydrophilic monomer, and in a preferred embodiment, the hydrophilic monomer is a nonionic Examples include acrylamide, vinylpyrrolidone, polyethylene glycol monomethacrylate, 2-methacryloyloxyethylmethylsulfokind, and examples of ionic substances include acrylic acid, methacrylic acid, acrylamide-2-methyl-propanesulfonic acid, and p-styrenesulfonic acid. , 3-methacryloyloxypropyl sulfonic acid, N, N-dimethylaminoethyl methacrylate,
One or more selected from N, N-diethylaminoethyl methacrylate and vinylpyridine, or the copolymer has a molecular weight of 5,000 or more, or the composition ratio of 2-methacryloyloxyethyl phosphorylcholine to the hydrophilic monomer is 3 : 97 to 45:55, or relates to a cosmetic having a copolymer content of 0.001 to 10% by weight based on the whole cosmetic.

Hereinafter, the present invention will be described in detail.

The copolymer applicable to the present invention is obtained by copolymerizing 2-methacryloyloxyethyl phosphorylcholine (hereinafter abbreviated as MPC) represented by the following general formula (I) and a hydrophilic monomer. It can be obtained by

[0010]

Embedded image

For such MPC, for example, 2-bromoethyl phosphoryl dichloride, 2-hydroxyethyl phosphoryl dichloride and 2-hydroxyethyl methacrylate are reacted to obtain 2-methacryloyloxyethyl-2'-bromoethyl phosphoric acid. This can be obtained by reacting with trimethylamine in a methanol solution. (Polymer Transactions, Vol. 35, P432-42
7, 1978)

On the other hand, hydrophilic monomers include MPC
Any copolymer may be used as long as it forms a copolymer by vinyl polymerization.Examples of nonionic ones include acrylamide, vinylpyrrolidone, polyethylene glycol monomethacrylate, 2-methacryloyloxyethylmethylsulfoxide, and the like. For example, acrylic acid, methacrylic acid, acrylamido-2-methyl-propanesulfonic acid, p-styrenesulfonic acid, 3-methacryloyloxypropylsulfonate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate , Vinyl pyridine and the like.

Next, the method for producing the copolymer may be a conventional method, and is obtained by reacting MPC and a hydrophilic monomer in a solvent in the presence of a polymerization initiator. The solvent used here may be any solvent in which MPC and the hydrophilic monomer can be dissolved, and specifically, water, methanol, ethanol, propanol, t-butanol, benzene, toluene, dimethylformamide, tetrahydrofuran,
Chloroform or a mixed solvent thereof is exemplified.
As the polymerization initiator, any ordinary radical initiator may be used, and 2,2'-azobisisobutyronitrile (AIBN), azobis (3-carboxypropionitrile) azobismalenonitrile can be used. And organic peroxides such as benzoyl peroxide, lauroyl peroxide and potassium persulfate.

Hereinafter, production examples of the copolymer according to the present invention will be described. Synthesis of MPC / methacrylic acid copolymer MPC and methacrylic acid (MAA) are dissolved in ethanol so that the molar composition of MAA is 3%, 5%, and the total monomer concentration is 1 mol / L, and AIBN is used as an initiator. 0.5 mol% with respect to The solution is placed in a glass reactor, purged with argon, and then sealed. 6
The reaction is carried out at 0 ° C. for 6 hours, and the reaction mixture is added dropwise to a large amount of diethyl ether to precipitate the polymer. The precipitate is filtered off, washed thoroughly with ether on a glass filter and dried in vacuo. The yield is about 50%. In the case of converting MAA into a sodium salt, the obtained MPC / MAA copolymer is dissolved in water, neutralized with NaOH while measuring the pH, and this is purified using a bisking dialysis membrane with pure water as an external solution. Dialyze for 5 days. 2-
Propanol is added and the solvent is azeotropically distilled off (ultrafiltration is also possible). The polymer is stored in solution.

ΔIR (cm ^-1 ) measurement 3200 to 2900 (CH ₂ , CH ₃ ), 1720 (C = O) 1100 to 1200 (C-OC), 1250 (P = O)

{Molecular Weight Measurement Copolymer Water-Methanol {80/20 (V / V)}
The solution was analyzed and measured using GPC, and as a result, it was 37,000 in terms of polyethylene glycol. From the determination of phosphorus, the molar composition ratio of MPC in the copolymer was 90.6%.

The molecular weight of the copolymer according to the present invention obtained as described above can be variously adjusted according to the purpose of use, but it may be adjusted in consideration of the touch surface, gelling ability, film forming ability and the like. , Usually 5,000 in terms of polyethylene glycol
It is 0 or more, preferably 10,000 or more. Further, the constitution ratio of the MPC to the hydrophilic monomer in the copolymer is preferably in the range of 3:97 to 45:55. That is, if the composition ratio of MPC is less than 3:97, the water retention function and the promotion and stabilization of lamella formation are undesirably reduced.

In the cosmetic of the present invention, the above copolymer is usually contained in the range of 0.001 to 10% by weight, preferably in the range of 0.01 to 3% by weight, based on the total amount of the cosmetic.

Further, the cosmetic of the present invention comprises a lotion, an emulsion,
It can be used as a skin cosmetic in the form of creams, lipsticks, foundations, etc.
It can be used as a hair cosmetic in the form of a hair cream, a hair lotion or the like. Furthermore, it can be used as a massage charge or a pack charge by utilizing the gelling ability and the film forming ability of the copolymer. In addition, these cosmetics can be manufactured according to a conventional method.

Further, in the cosmetic of the present invention, in addition to the copolymer, if necessary, a surfactant, a powder or a pigment, an antioxidant, an ultraviolet absorber, a humectant, a vitamin, a preservative, and a fragrance. And the like.

Here, an experiment was conducted to evaluate how the copolymer according to the present invention has excellent moisture absorption properties and aging-stabilized lamella formation. The contents are shown below.

Experiment 1 Hygroscopicity of MPC / methacrylic acid copolymer [Sample] (A) MPC / methacrylic acid copolymer (constitution ratio: 90/10, molecular weight: 12,000) (B) Chitosan (comparative product)

[Measurement method] A 50% ethanol solution of MPC / methacrylic acid copolymer (3% by weight) and an aqueous solution of chitosan in acetic acid (3% by weight) were prepared.
After casting on a Teflon plate of No. ^2, the solvent was volatilized at room temperature to form a film having a thickness of about 100 μm. This was placed in a desiccator adjusted to each relative humidity (60%, 80%, 95%) with a saturated salt solution, and the weight increase rate after 20 hours or less and 20 hours or less was measured. The result is shown in FIG. Weight increase rate (%) = [(weight after 48 hours−initial weight)
/ Initial weight] x 100

[Results] As is apparent from the results shown in FIG. 1, the MPC / methacrylic acid copolymer according to the present invention has higher hygroscopicity than the chitosan as a comparative product.

Experiment 2 Stability of MPC / methacrylic acid copolymer [Sample] MPC / methacrylic acid copolymer (constitution ratio: 90/10, molecular weight: 15,000)

[Measurement method] pH 4.
Each sample was dissolved at a concentration of 2% by weight in a 10% aqueous ethanol solution adjusted to 0, 6.0, 8.0, and 9.0, and 40%
It was left for 3 months at ℃ to observe its condition. At the start, no coloring or precipitation was observed, and the sample was transparent. Table 1 shows the results.

[0027]

[Table 1]

As shown in the results in Table 1, it was revealed that the MPC / methacrylic acid copolymer according to the present invention had excellent stability over time in a wide pH range.

[0029]

EXAMPLES Examples of the cosmetic of the present invention will be shown below.
The mixing ratio is% by weight.

Embodiment 1 o / w type emulsion stearic acid 1 beeswax 2 microcrystalline wax 1 MPC / methacrylic acid copolymer 3% by weight aqueous solution 30 (constituent ratio 15/85, molecular weight 35,000) propylene glycol 5 glycerin 2 ethyl alcohol 5 preservative 0. 3 Fragrance 0.3 Purified water 53.4

Embodiment 2 FIG. Lotion MPC / vinylpyrrolidone copolymer 2% by weight aqueous solution 25 (10/82, molecular weight: 20,000) glycerin 1.5 ethanol 6 propylene glycol 1.5 citric acid 0.01 sodium citrate 0.1 flavor 0.05 Purified water 65.84

Embodiment 3 FIG. Cream squalane 5 2-ethylhexanoic acid triglyceride 1 petrolatum 0.5 MPC / 2-methacryloyloxyethyl methyl sulfoxide copolymer 3% by weight aqueous solution (constituent ratio 18/82, molecular weight 20 000) 50 glycerin 3 1,3-butane Diol 4 Polyglycerin polyoxybutylene stearyl ether 2.5 Fragrance 0.2 Purified water 33.8

Embodiment 4 FIG. Hair lotion MPC / polyethylene glycol monomethacrylate copolymer 2% by weight aqueous solution (constitution ratio 35/65, molecular weight 45,000) 5 ethanol 10 glycerin 3 carboxymethyl chitin 0.01 vitamin E 0.1 pigment 0.02 purified water 81.87

Embodiment 5 FIG. Hair cream squalane 30.0 Vaseline 3.0 Beeswax 4.0 Stearic acid 4.0 Olive oil 2.0 Sorbitan monostearate 2.5 Polyoxyethylene sorbitan monostearate 2.5 Butyl paraben 0.1 MPC / acrylamide co-polymer 10% by weight aqueous solution 30 (constitution ratio 35/65, molecular weight 40,000) 1,3-butanediol 2.5 polyethylene glycol 200 1.5 triethanolamine 1.0 methyl paraben 0.1 fragrance 0.2 purified water 16.6

(Comparative Experiment) The cosmetics obtained according to the present invention and conventional cosmetics were compared in terms of the effect of improving skin roughness and the effect of protecting hair.

Experiment 3 Effect of Improving Artificial Skin Roughness [Sample] (a) Emulsion of Example 1 of the present invention (a) Conventional emulsion obtained by removing MPC / methacrylic acid copolymer (increased water) from the emulsion of Example 1 of the present invention Latex

[Experimental Method] Ten Japanese women (age 20-
The effect of the surfactant on the improvement of artificial skin roughness was measured by measuring the water content of the stratum corneum and judging skin eruption with a subject (age 37). That is, a glass cup having a diameter of 3 cm was adhered to the skin on the inner part of the forearm, 10 ml of 5% sodium dodecyl sulfate (SDS) was put therein, and the mixture was allowed to stand for 10 minutes while gently shaking. After leaving the same site for the next 20 minutes with the same processing solution, the processing solution was recovered to cause rough skin. This SD
One day after the S treatment, the emulsion of the sample (A) or (A) was applied to the treated site twice a day. FIGS. 2 and 3 show the results of measuring the horny layer water content before and after the experiment as skin surface conductance values according to the following measurement method, and the results (mean values) of skin rashes determined according to the following criteria.

1) Measurement of the water content of the stratum corneum The water content of the stratum corneum was determined according to the method of Tagami et al.
The measurement is performed using a ctance meter (Model IB-354, manufactured by IBM). At the time of measurement, the skin at the measurement site was 37 ° C.
After washing with warm water for 30 seconds, at 20 ° C and 50% relative humidity,
Five measurements are taken and the average is taken as the measured value.

2) Evaluation criteria for skin rash 0: No dry desquamation change is observed. 1: A slight drying desquamation change is recognized. (Faint desquamation or gloss) 2: A clear drying desquamation change is recognized. (The boundary of the treated part is clear, and clear desquamation is partially glossy and cracked.) (Clear luster, crack on clear desquamation)

As shown in the results of FIG. 2 and FIG. 3, the sample (A), which is an emulsion of the product of the present invention, recovers the water content of the stratum corneum (A) as compared with the sample (A), which is an emulsion of the conventional product. It has been demonstrated to have a remarkable effect on skin surface conductance) and dry eruption.

Experiment 4 Actual use test [Sample] The same emulsion as the samples (A) and (A) used in Experiment 3 was used.

[Experimental Method] Forty Japanese women (aged 20-49 years old) who complain of rough and dry skin were randomly divided into groups A and B (20 each). The emulsion of the sample (a) was used, and the emulsion of the sample (a) was used for Group B for one month. A comparison was made between groups regarding the beautiful skin effect such as moist feeling (water retention effect) and improvement of skin swelling (activation effect) after one month and the feel during use (stickiness). Table 2 shows the results.

[0043]

[Table 2]

As is evident from the results in Table 2, the sample (A), which is an emulsion of the product of the present invention, has no tactile problem similarly to the sample (A) which is an emulsion of the conventional product, while the water retention effect is obtained. It has been proved that the skin beautiful effect such as skin activating effect and the like is remarkably excellent.

Experiment 5 (Sample) (c) Hair lotion of Example 4 of the present invention (d) MPC from hair lotion of Example 4 of the present invention
/ Conventional hair lotion with removal of polyethylene glycol monomethacrylate copolymer (increased water)

[Experimental method] A bundle of 10 g (10 cm in length) of a Japanese woman's hair, which had never been subjected to a treatment such as perm or bleach, was bundled with the sample (c) or (d).
After applying a predetermined amount of the hair lotion, it was air-dried.
The evaluation was performed by five expert panelists according to the criteria shown in Table 3 below, and the average score was shown in Table 4. The evaluation items were for hair smoothness, gloss and moist feeling (moisturizing property).

[0047]

[Table 3]

[0048]

[Table 4]

As shown in the results in Table 4, the sample (c), which is a hair lotion of the product of the present invention, has a smoothness, gloss and moistness of hair which is higher than that of the sample (d), which is a hair lotion of a conventional product. It was clarified that all of the feelings were excellent.

Experiment 6 Stabilization of lamella layer A lamella is made from lecithin (EPC), which is an intercellular lipid analog, and the MPC-methacrylic acid copolymer makes the arrangement of the lamella structure composed of lecithin regular so that the molecules are tight (lamella layer). (Stabilization / promotion of formation) was examined by small-angle X-ray scattering.

[Experimental method] Lecithin and water were mixed for 90 to 6 days.
The mixture was mixed at a weight ratio of 5:10 to 35 to prepare a lamella phase as a control product. On the other hand, a part of the water of the control product was replaced with the MPC polymer and mixed to prepare a lamellar phase. Using the X-ray diffraction apparatus (JDX-3500 manufactured by JEOL), the interplanar spacing of the lamella phase was measured for the obtained lamella phase. The result is shown in FIG.
It was shown to.

[Measurement conditions]-Small-angle scattering device: DX-LSV3 manufactured by JEOL-Detector: Scintillation counter-Source: Cu wire-Voltage: 45 KV-Current: 200 mA-Measurement temperature: 22 to 24 ° C-Sample is a cell holder Measured between 4μm mylars

[Results] As shown in FIG.
Water = 90-65 / 10-35 wt.
A lamellar phase having a layered structure is formed in the range of 9 to 58 °. As water was replaced with the MPC / methacrylic acid copolymer solution, the d value decreased. The small-angle scattering peaks (not shown) qualitatively show that the addition of the MPC / methacrylic acid copolymer makes the direction and arrangement of lecithin molecules better than in the water-added system. This reflects the following: The interplanar spacing d of the lamellar liquid crystal phase is composed of a hydrophobic part (lecithin layer) da and an aqueous layer part dw. When the MPC / methacrylic acid copolymer enters the lecithin layer, the result is d.
As the value of w decreases and the value of d decreases, the MPC / methacrylic acid copolymer enters the lecithin layer and increases the molecular regularity of the lecithin layer. It is considered from this that the stabilization of the lamellar layer was increased together with the moisture absorption and retention properties of this product, and that the skin roughness in humans was suppressed.

[0054]

According to the present invention, of course, the skin-beautifying effect on the skin and the hair-beautifying effect on the hair based on the water retention function, the lamellar formation promoting / stabilizing action, the film forming ability and the like are remarkably excellent. It can be used without any stability problems.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between relative humidity and weight increase rate.

FIG. 2 is a diagram showing a relationship between the number of days and a skin conductance value.

FIG. 3 is a diagram showing the relationship between the number of days and rash.

FIG. 4 is a diagram showing a relationship between a water phase / oil phase ratio and a surface interval.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Kuroda 560 Paula-cho, Kashio-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Totsuka Laboratory Co., Ltd. (72) Inventor Norio Nakabayashi 5-6-20 Koganehara, Matsudo-shi, Chiba (56) References JP-A-54-63025 (JP, A) JP-A-3-39309 (JP) JP-A-62-126108 (JP, A) JP-A-61-289013 (JP, A) JP-A-2-196710 (JP, A) JP-A-55-75497 (JP, A) 5-177119 (JP, A) JP-A-6-122779 (JP, A) JP-A-6-157271 (JP, A) JP-A-5-70321 (JP, A) JP-A-6-157269 (JP, A A) (58) Field surveyed (Int.Cl. ⁶ , DB name) A61K 7 / 00-7/50 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A cosmetic comprising a copolymer of 2-methacryloyloxyethyl phosphorylcholine and a hydrophilic monomer. 2. The method according to claim 1, wherein the hydrophilic monomer is acrylamide, vinylpyrrolidone, polyethylene glycol monomethacrylate, 2-methacryloyloxyethyl methyl sulfokind, acrylic acid, methacrylic acid, acrylamide-2.
-Methyl-propanesulfonic acid, p-styrenesulfonic acid, 3-methacryloyloxypropylsulfonic acid,
N, N-dimethylaminoethyl methacrylate, N, N
The cosmetic according to claim 1, wherein the cosmetic is at least one selected from diethylaminoethyl methacrylate and vinylpyridine. 3. The cosmetic according to claim 1, wherein the molecular weight of the copolymer is 5,000 or more. 4. The cosmetic according to claim 1, wherein the composition ratio of 2-methacryloyloxyethyl phosphorylcholine and hydrophilic monomer in the copolymer is from 3:97 to 45:55. 5. The content of the copolymer is based on the total amount of the cosmetic.
The cosmetic according to any one of claims 1 to 4, wherein the cosmetic content is 0.001 to 10% by weight.