JP5537513B2 - Oil-in-water sunscreen cosmetics - Google Patents

Description

  The present invention relates to a UV care cosmetic. More specifically, the present invention relates to an oil-in-water emulsified cosmetic, particularly a sunscreen cosmetic, capable of obtaining a high SPF without highly blending an oil-soluble ultraviolet absorber.

  Protecting the skin from the damage of ultraviolet rays in skin care and body care is one of the important issues, and the main purpose of UV care cosmetics is to minimize the adverse effects of ultraviolet rays on the skin. Sunscreen cosmetics (sunscreen cosmetics), which is a type of UV care cosmetics, is a cosmetic that protects the skin from UV rays by cutting UVA and UVB by blending UV absorbers and UV scattering agents. (Non-Patent Document 1).

  As a base for UV care cosmetics, in particular, sunscreen cosmetics, oil-in-water emulsion bases, water-in-oil emulsion bases, oily bases and the like are generally used. Oil-in-water emulsified bases become sticky when the blending amount of oil-soluble UV absorbers is increased to increase SPF (Sun Protection Factor). In some cases, the characteristic of “use feeling” was lost.

  On the other hand, in order to achieve a high SPF while maintaining the freshness of the oil-in-water emulsion base, a water-soluble ultraviolet absorber is also added, but the influence of the salt constituting the water-soluble ultraviolet absorber As a result, the stability of the emulsion is reduced. In order to solve such problems, attempts have been made to use a highly hydrophilic surfactant (such as a fatty acid PEG glyceryl surfactant) (Patent Document 1), and to incorporate an alkylmethyl taurate (Patent Document 2). It has been done to some extent.

  Further, Patent Document 3 describes that by incorporating an extender pigment and making the total amount and ratio of the higher alcohol and the surfactant within a specific range, there is no stickiness, a fresh feeling of use, and a high SPF can be achieved. Has been. However, in order to obtain a stable preparation with good usability, it is essential to add a higher alcohol.

On the other hand, the oil-in-water type emulsifying base has a problem that the emulsified particles are destroyed when a high amount of alcohol is blended, and it is difficult to obtain a sufficiently stable base. , Lower alcohol 50% by weight or more, water, the following general formula as an emulsifier:
(In the above formula, m is 50 to 1000, n is 1 to 40, a is an integer of 5 to 50, and b is an integer of 5 to 50). An alcohol / oil-in-water emulsified composition characterized by substantially not containing other surfactant as an emulsifier is disclosed, and has the effect of giving gloss, softness and moisture to the hair and improving combing. It is described.
However, since the composition described in Patent Document 4 contains a large amount of lower alcohol, application to a general skin care base was difficult.

JP 2008-162930 A JP 2002-284638 A JP 2010-189281 A International Publication No. WO97 / 002888 Pamphlet

"New Cosmetics" 2nd edition, Takeo Mitsui, 2001, published by Nanzan Hall, pages 497-504

  The present invention can achieve high SPF without adding a high amount of oil-soluble UV absorber, which is the main cause of stickiness in sunscreen cosmetics, and without adding a water-soluble UV absorber, and is excellent in stability. Another object of the present invention is to provide an oil-in-water emulsified cosmetic.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have (A) a polyether-modified silicone, (B) a predetermined amount of extender pigment, and (C) a UV-A region. By combining and blending the ultraviolet absorber, it has been found that there is no stickiness, a fresh feeling of use, a stable and high SPF, and the present invention has been completed.

That is, the present invention
An oil-in-water sunscreen cosmetic comprising (A) a polyether-modified silicone (B) 3 to 8% by mass of an extender pigment and (C) an ultraviolet absorber having an absorption ability in the UV-A region I will provide a.

  The emulsified cosmetic composition of the present invention is not sticky and maintains the fresh feeling of use of the oil-in-water emulsion, because it does not contain a high amount of oil-soluble UV absorbers, is excellent in safety and stable. Thus, a high ultraviolet shielding effect (high SPF) can be achieved. Furthermore, after application to the skin, the phase is reversed to show excellent water resistance.

It is a figure which shows the UV spectrum measured about the composition of Example 1, 4 and Comparative example 1,2. It is a figure which shows the UV spectrum measured about the composition of Example 2, 3, 5 and the comparative example 1. FIG. It is a graph which shows the residual rate of the ultraviolet-ray protective effect after a water resistance test about the composition of Examples 3-5 and the comparative example 1.

The polyether-modified silicone (component A) in the cosmetic of the present invention is not particularly limited as long as it is a silicone derivative having a polyoxyalkylene group such as polyoxyethylene (POE) or polyoxypropylene (POP), One or more selected from those conventionally used for cosmetics and the like are preferably used.
Specific examples include cetyl dimethicone copolyol, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG / PPG-19 / 19 dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, (dimethicone / (PEG-10 / 15)) Cross polymer, Polysilicone-13 and the like.

In the present invention, a polyether-modified silicone having a molecular weight of 50,000 or more and a hydrophilic group selected from polyoxyethylene (POE) or polyoxypropylene (POP) is particularly preferable.
Among these, polyether-modified silicones represented by the following general formula are preferably used.
In said formula, m is 50-1000, Preferably it is 150-1000, and n is 1-40. Moreover, m: n is preferably 200: 1 to 5: 1, and particularly preferably 60: 1 to 15: 1.
Further, a is 5 to 50, and b is 5 to 50, and the content of these polyoxyalkylene groups in the molecule is not particularly limited, but the content of polyoxyalkylene groups exceeds 20% by weight in the total molecular weight. Things are desirable.

Although it does not specifically limit, For example, the polyether modified silicone whose HLB (Si) is 5 or more and is less than 10, less than 9, less than 8, or less than 7 is mentioned as a particularly preferable example.
In addition, HLB (Si) in this specification is a value calculated | required with the following formula.
When a polyether-modified silicone having an HLB (Si) of 5 or more is used, emulsification can be more stably performed by adding 5 to 50% by mass or less of ethanol.

  The polyether-modified silicone used in the present invention may be commercially available, for example, trade name BY11-030 (manufactured by Toray Dow Corning Silicone: 50% by mass of PEG / PPG-19 / 19 dimethicone and 50% by mass). PEG / PPG-19 / 19 Dimethicone is a polyether-modified silicone having a molecular weight of 55000 in which m = 400, n = 10, a = 19, and b = 19 in the above general formula; HLB (Si) = 7), trade name KF-6012 (manufactured by Shin-Etsu Silicone: PEG / PPG-20 / 22 butyl ether dimethicone), trade name SH3749 (manufactured by Shin-Etsu Silicone: PEG / PPG-20 / 20 dimethicone) and the like. Can be mentioned.

  The compounding quantity of the polyether modified silicone (component A) in the cosmetics of this invention is 0.1-10 mass%, Preferably it is 0.1-5 mass%, More preferably, it is 0.1-3 mass%. When the blending amount is less than 0.1% by mass, when it exceeds 10% by mass, a stable oil-in-water emulsion may not be obtained.

  The extender pigment (component B) to be blended in the cosmetic of the present invention is not particularly limited as long as it is usually used in cosmetics. An extender is an inorganic pigment that is generally used to maintain the dosage form of a product, not for the purpose of coloring. By incorporating an extender, the usability (extensibility and adhesion) of the product and gloss The color tone is adjusted.

Specific examples of the extender include talc, kaolin, mica, synthetic mica, sericite, magnesium carbonate, calcium carbonate, and talc / silica / titanium oxide composite. In the present invention, two or more extender pigments may be combined and blended. Among these, it is preferable to use one or more selected from talc, kaolin, and mica.
The extender pigment used in the present invention is preferably non-hydrophobized. Hydrophobic treated extender pigments tend to be inferior in UV protection and emulsification stability compared to non-hydrophobic treated pigments.

  The amount of the extender pigment in the cosmetic of the present invention is 3 to 8% by mass, preferably 4 to 8% by mass. If the blending amount is less than 3% by mass, the object of the present invention is not achieved. If the blending amount exceeds 8% by mass, the emulsion stability may be lowered.

An ultraviolet absorber having an absorption ability in the UV-A region blended in the cosmetic of the present invention (component C: hereinafter also simply referred to as “ultraviolet absorber”) is in the UV-A region (wavelength region of 320 to 400 nm). As long as it has absorptive capacity, it is not particularly limited and may be those conventionally used in cosmetics.
Specific examples include ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoyl benzoate, octocrylene, polysilicon-15, bisethylhexyloxyphenol methoxyphenyltriazine, oxybenzone-3, 2,4,6-tris [4- (2-ethylhexyl). Oxycarbonyl) anilino] -1,3,5-triazine, t-butylmethoxydibenzoylmethane, benzotriazole, benzylidene camphor, methyl bis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, and phenylbenzimidazole sulfonic acid It is done. These can be used by appropriately selecting one or more as required.
Among these, diethylaminohydroxybenzoyl hexyl benzoate and bisethylhexyloxyphenol methoxyphenyl triazine are preferable because they are less sticky and have a high ultraviolet absorption effect. In particular, it is preferable to mix and combine two kinds of diethylaminohydroxybenzoyl hexyl benzoate and bisethylhexyloxyphenol methoxyphenyl triazine since the ultraviolet absorption effect is further improved.

The compounding quantity of the ultraviolet absorber in the cosmetics of this invention is 5-30 mass%, Preferably it is 10-25 mass%, More preferably, it is 10-20 mass%. If the blending amount is less than 5% by mass, the object of the present invention is not achieved. If the blending amount exceeds 30% by mass, stickiness or irritation to the skin may occur.
In particular, when hexyl diethylaminohydroxybenzoyl benzoate and / or bisethylhexyloxyphenol methoxyphenyl triazine is blended as an ultraviolet absorber, the blending amount is preferably 1.1 to 5% by mass. If the blending amount is less than 1.1% by mass, it is difficult to further improve the ultraviolet absorption effect. If the blending amount exceeds 5% by mass, stickiness and irritation to the skin may occur.

  The cosmetic of the present invention may contain, in addition to the above essential components A to C, other optional components conventionally used in cosmetics as long as the effects of the present invention are not impaired. Specific examples include thickeners, humectants, oils, buffers, chelating agents, coloring materials, preservatives, and the like.

  Among these optional components, a hydrophilic thickener is preferably added to the cosmetic of the present invention. The hydrophilic thickener is not particularly limited as long as it is used in cosmetics, and examples thereof include natural water-soluble polymers, semi-synthetic water-soluble polymers, and synthetic water-soluble polymers.

  Examples of natural water-soluble polymers include arabia gum, tragacanth gum, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (gypsum extract), starch (rice, corn, potato, wheat). And plant polymers such as glycyrrhizic acid; microbial polymers such as xanthan gum, dextran, succinoglucan, and bullulan; and animal polymers such as collagen, casein, albumin, and gelatin.

  Examples of semi-synthetic water-soluble polymers include starch polymers such as carboxymethyl starch and methylhydroxypropyl starch; methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, carboxy Cellulose polymers such as sodium methylcellulose (CMC), crystalline cellulose and cellulose powder; and alginic acid polymers such as sodium alginate and propylene glycol alginate.

  Examples of synthetic water-soluble polymers include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, and carboxyvinyl polymer (carbomer); polyoxyethylene polymers such as polyethylene glycol (molecular weight 1500, 4000, 6000). Molecules; polyoxyethylene polyoxypropylene copolymer copolymer polymer; sodium polyacrylate, polyethyl acrylate, polyacrylamide, acrylic acid / alkyl methacrylate copolymer (trade name “Pemulene TR-1”), etc. Acrylic polymer; polyethyleneimine, cationic polymer and the like.

  The compounding quantity in the case of mix | blending a hydrophilic thickener with the cosmetics of this invention is 0.01-5 mass%, Preferably it is 0.1-3 mass%. If the blending amount is less than 0.01% by mass, no contribution to improving the emulsion stability may be observed. If the blending amount exceeds 5% by mass, a heavy feel may be caused during application.

  The cosmetic of the present invention can be produced according to a method conventionally used for producing an emulsion. For example, the oil phase component is mixed, the water phase component is mixed with the extender pigment, and the water phase and the oil phase are mixed and emulsified with a homomixer or the like to obtain the oil-in-water emulsion sunscreen cosmetic of the present invention. Can be obtained.

  Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to the following examples. Moreover, the compounding quantity in a following example etc. shows the mass% unless there is particular notice.

(Examples and Comparative Examples)
An emulsion composition having the composition listed in Table 1 below was prepared according to a conventional method, and the emulsion stability was evaluated. Moreover, the UV absorption spectrum about each composition was measured.

Emulsion stability evaluation method and criteria:
Attempts to prepare an oil-in-water emulsion composition with the composition listed in Table 1, and as a result of visual observation, an example in which a stable oil-in-water emulsion with small emulsion particles was obtained was “◯”, an example where emulsification was not possible It was set as “x”.

* 1) Product name BY11-030 (Toray Dow Corning Silicone: HLB (Si) = 7)

As is apparent from the results shown in Table 1, Comparative Examples 1 and 2 and a practical example containing a polyether-modified silicone and an ultraviolet absorber, and an amount of extender pigments such as talc, mica and kaolin being 8% by mass or less. The compositions of Examples 1 to 5 were excellent in emulsion stability. On the other hand, stable emulsions could not be obtained in the compositions of Comparative Example 3 in which extender pigments and the like were blended in excess (10% by mass) and Comparative Example 4 in which hydrophobized talc was blended.
On the other hand, in the compositions of Examples 1 to 5 according to the present invention, the ultraviolet absorptivity was remarkably improved as compared with Comparative Examples 1 and 2 in which no extender was blended or the blending amount was less than 3% by mass (FIG. 1). And 2).

Next, the water resistance test of the ultraviolet protection effect was implemented about the composition of the said comparative example 1 and Examples 3-5. The evaluation method is as follows.
A 2 mg / cm ² composition (Comparative Example 1 or Examples 3 to 5) was uniformly applied to a PMMA (polymethyl methacrylate) plate having a rough surface, and a spectrophotometer (U-4100 Hitachi Ltd.) was used. Absorbance was measured. Next, the PMMA plate (coated with each composition) was exposed to strong water for 15 minutes and dried sufficiently, and the absorbance was measured again. It was calculated what percentage the absorbance at a wavelength of 310 nm after the water resistance test corresponds to the absorbance at the same wavelength before the water resistance test, and the value was defined as the residual ratio (%) of the UV protection effect.
The residual rate of the UV protection effect obtained in each example is shown in the graph of FIG. In Comparative Example 1 containing no extender, the residual rate after the water resistance test was less than 50%, but in addition to polyether-modified silicone and UV absorber, extender pigments such as talc, mica and kaolin were used. In Examples 3 to 5 in which quantitative blending was performed, the residual ratio was improved to 65% to 75%.

Other embodiments of the present invention are shown below.
Example 6: Oil-in-water sunscreen cosmetic ion-exchanged water Residual ethyl alcohol 20
Dipropylene glycol 3
Acrylic acid / alkyl acrylate (C10-30) copolymer 0.5
Xanthan gum 0.1
Aminomethylpropanediol appropriate amount polyoxybutylene polyoxypropylene glycol 2
PEG / PPG-19 / 19 Dimethicone 2
Polyethylene glycol 1
Cyclopentasiloxane 2
Hydrogenated polyisobutene 3
Caprylyl Methicone 5
Octocrylene 3
t-Butylmethoxydibenzoylmethane 1
Benzotriazole 1
Oxybenzone-3 0.1
Talc 6
Chelating agent appropriate amount ethyl paraben appropriate amount perfume appropriate amount

Example 7: Oil-in-water sunscreen cosmetic ion-exchanged water Residual ethyl alcohol 15
1,3-butylene glycol 7
Carbomer 0.15
Acrylic acid / alkyl acrylate (C10-30) copolymer 0.15
Aminomethylpropanol appropriate amount polypropylene glycol 3
PEG / PPG-19 / 19 Dimethicone 1.5
Dimethicone 1.5
Cyclopentasiloxane 2
Dimethylpolysiloxane 2
Pentaerythrityl tetraethylhexanoate 3
Isododecane 2
Ethyl hexyl methoxycinnamate 5
Phenylbenzimidazolesulfonic acid 2
2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 0.3
Benzylidene camphor 0.2
Methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate
0.2
Mica 2
Kaolin 1
Chelating agent Appropriate amount Phenoxyethanol Appropriate amount

Claims (6)

(A) polyether-modified silicone,
(B) 3 to 8% by weight of hydrophobic untreated constitution Pigments,
(C) an ultraviolet absorber having absorption ability in the UV-A region ,
(D) ethyl alcohol,
(E) 1,3-butylene glycol, and
(F) An oil-in-water type sunscreen cosmetic comprising a hydrophilic thickener . The cosmetic according to claim 1, wherein the extender pigment is one or more selected from talc, kaolin, and mica. The ultraviolet absorber is ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoyl benzoate, octocrylene, polysilicon-15, bisethylhexyloxyphenol methoxyphenyltriazine, oxybenzone-3, 2,4,6-tris [4- (2- Selected from ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, t-butylmethoxydibenzoylmethane, benzotriazole, benzylidene camphor, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, and phenylbenzimidazolesulfonic acid The cosmetic according to claim 1, wherein the cosmetic is one type or two or more types. The polyether-modified silicone is cetyl dimethicone copolyol, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG / PPG-19 / 19 dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, (dimethicone / (PEG The cosmetic according to any one of claims 1 to 3, wherein the cosmetic is one type or two or more types selected from -10/15)) crosspolymers and polysilicone-13. The ultraviolet absorber, characterized in that it comprises a one or two kinds selected from diethylamino hydroxybenzoyl hexyl benzoate and bis-ethylhexyloxyphenol methoxyphenyl triazine, according to any one of claims 1 4 Cosmetics. The cosmetic according to claim 5 , wherein the amount of hexyl diethylaminohydroxybenzoyl benzoate and / or bisethylhexyloxyphenol methoxyphenyl triazine is 1.1 to 5.0% by mass.