JP5694818B2 - Sunscreen cosmetics - Google Patents

Description

    The present invention relates to a sunscreen cosmetic.

In recent years, in order to obtain a high sun protection factor (SPF) effect in the amount of sunscreen makeup, there is a tendency to add a large amount of ultraviolet scattering agent or ultraviolet absorber. Techniques of sunscreen cosmetics containing an ultraviolet scattering agent or an ultraviolet absorber have been disclosed (for example, Japanese Patent Application Laid-Open No. 10-120543, Japanese Patent Application Laid-Open No. 2002-521417).
The important ultraviolet absorption wavelength regions of sunscreen cosmetics are the UV-A region (320 to 400 nm) and the UV-B region (290 to 320 nm). The ultraviolet rays in the UV-A region darken the skin, but it was thought that sunburn occurred like the ultraviolet rays in the UV-B region and did not promote skin aging. However, in recent years, ultraviolet rays in the UV-B region stay relatively on the surface of the skin, whereas ultraviolet rays in the UV-A region reach the deep part of the skin, causing skin cancer as well as skin aging. It has been found to be a cause of triggering. In this way, there is an increasing demand for sunscreen cosmetics, particularly for UV absorption in the UV-A region. As one of the UV absorbers in the UV-A region, hexyl diethylaminohydroxybenzoyl benzoate (DHHB) is used. It has been pointed out that DHHB dissolves in oils frequently used in cosmetics, but precipitates at low temperatures and reduces the feeling of use. Further, metal oxides such as titanium oxide used as ultraviolet scattering agents cause aggregation and precipitation of sunscreen cosmetics.
It is necessary to increase the compounding amount of the surfactant in order to stably blend the UV absorber with a high concentration and multiple UV absorbers and UV scattering agents, but increase the compounding amount of the surfactant. It has been pointed out that the feeling of use worsens, such as causing stickiness. For this reason, a technique is often employed in which the storage stability is improved by reducing the amount of the surfactant added, adding the polymer compound, and increasing the viscosity of the composition. In this case, stickiness peculiar to a polymer compound may occur.

Japanese Patent Laid-Open No. 10-120543 JP 2002-521417 A

  The present invention contains two kinds of ultraviolet absorbers, DHHB, which is an ultraviolet absorber in the UV-A region, and an ultraviolet absorber in the UV-B region, and a metal oxide, and has excellent storage stability, stickiness, etc. It is an object to provide a sunscreen cosmetic that suppresses sunburn.

The main configuration of the present invention is as follows.
(1) System Ricoh emissions emulsifier is a polyether-modified silicone oil (A),
Polyglycerin-modified silicone oil (B),
Ultraviolet B wave (UV-B) absorber (C);
Diethylaminohydroxybenzoyl hexyl benzoate DHHB (D) as an ultraviolet A wave (UV-A) absorber;
Metal oxide (E) ,
Alkyl acrylate copolymer (F)
A sunscreen cosmetic characterized by containing a sunscreen.
(2) The sunscreen cosmetic according to (1), wherein the blending ratio of the polyether-modified silicone oil (A) and the polyglycerin-modified silicone oil (B) is 10: 1 to 3: 1.
(3) The sunscreen cosmetic according to (1) or (2), wherein the total content of the polyether-modified silicone oil and the polyglycerin-modified silicone oil in the sunscreen cosmetic is 4% by mass or less. .
(4) The polyether-modified silicone oil is lauryl PEG-9 polydimethylsiloxyethyl dimethicone and PEG-9 polydimethylsiloxyethyl dimethicone, and the polyglycerin-modified silicone oil is polyglyceryl-3 polydimethylsiloxyethyl dimethicone, The sunscreen cosmetic according to any one of (1) to (3).

  A sunscreen cosmetic excellent in storage stability without separation or sedimentation even when stored for 6 months at a high temperature of 40 ° C. or higher is obtained. Moreover, it has heat shock resistance accompanying temperature changes from high temperature to low temperature and from low temperature to high temperature, has no stickiness, and can realize a sunscreen cosmetic with an excellent feeling of use.

The polyether-modified silicone oil (hereinafter referred to as component (A)) which is an emulsifier of the present invention is used as an emulsifier for a water-in-oil emulsion composition. For example, the cosmetic display names are as follows. Examples include PEG-3 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-32 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, etc. it can.
Particularly preferred is lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

The polyglycerin-modified silicone oil (hereinafter referred to as component (B)), which is the second emulsifier of the present invention, is widely used as an emulsifier for water-in-oil emulsion compositions. For example, the cosmetic display name is as follows. Examples thereof include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.
Polyglyceryl-3 polydimethylsiloxyethyl dimethicone is particularly preferable. It is preferable that the polyether-modified silicone oil and the polyglycerin-modified silicone oil contain both at the same time, the blending ratio is 10: 1 to 3: 1, and the total amount is 4% by mass or less.

  When lauryl PEG-9 polydimethylsiloxyethyl dimethicone and polyglyceryl-3 polydimethylsiloxyethyl dimethicone are used as the (A) component and (B) component of the present invention, the total range is 1.3 to 2.9% by mass. Is preferable because it can provide a sunscreen cosmetic with excellent stability and no stickiness. If the blending amount is out of this range, stickiness may occur or stability may be impaired.

  Diethylaminohydroxybenzoyl hexyl benzoate DHBB (hereinafter referred to as component (D)), which is the ultraviolet A wave absorber of the present invention, is an ultraviolet absorber or ultraviolet scattering agent blended in the sunscreen cosmetic of the present invention. The blending amount can be appropriately adjusted according to the type and amount. In order to shield ultraviolet A wave reliably, 1-5 mass% is mix | blended.

  Examples of the metal oxide (hereinafter referred to as (E) component) of the present invention include inorganic powders such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and fine particle zirconium oxide. You may use what is surface-treated (coating process) with a fatty acid, silicone, etc. It is preferable to use a surface-treated (coating treatment) with silicone. These metal oxides may be used by obtaining a simple substance, or a paste-like commercial product in which the metal oxide is stably reduced in the order of particles in a volatile silicone substrate may be used. Although a metal oxide is suitably determined according to the objective of cosmetics, it is preferable to mix | blend 5-10 mass%.

Moreover, this invention mix | blends the ultraviolet absorber which also absorbs ultraviolet B waves (UV-B) other than DHHB as a (C) component according to the objective. Examples of such an ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2′-dihydroxy-4-methoxybenzophenone, and p-methoxyhydrocinnamic acid. Diethanolamine salt, paraaminobenzoic acid (hereinafter abbreviated as PABA), ethyldihydroxypropyl PABA, glyceryl PABA, homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethylhexyldimethyl PABA Ethylhexyl salicylate, 2-phenyl-benzimidazole-5-sulfate, triethanolamine salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionate 2-ethylhexyl, ethylhexyltriazone, dimethoxycinnamic acid isooctanoic acid glyceride, their polymer derivatives, silane derivatives And ethylhexyl methoxycinnamate.
By combining the UV absorber in the UV-A region and the UV absorber in the UV-B region, a high UV protection effect is exhibited in a wide UV region. In particular, when ethylhexyl methoxycinnamate is used as an ultraviolet absorber in the UV-B region, hexyl diethylaminohydroxybenzoyl benzoate dissolves without precipitating, so that it is possible to obtain a preferred sunscreen cosmetic when blended in combination. As commercial products of ethylhexyl methoxycinnamate, Pulsol MCX manufactured by DSM Nutrition Japan Co., Ltd. and Nom Coat TAB manufactured by Nisshin Oilio Group Co., Ltd. can be obtained and used. The amount of ethyl hexyl methoxycinnamate is appropriately determined, but it is preferably 2 to 10% by mass. When ethylhexyl methoxycinnamate is blended in an amount twice or more that of hexyl diethylaminohydroxybenzoylbenzoate, precipitation of hexyl diethylaminohydroxybenzoylbenzoate can be prevented.

  In the present invention, an alkyl acrylate copolymer is blended as the component (F) in addition to the above-described structure. As shown in the test results of the examples, the alkyl acrylate copolymer enhances the stability at 50 ° C., so that it is possible to obtain a sunscreen cosmetic with excellent storage stability against high temperatures and heat shock. As a commercial product of an alkyl acrylate copolymer, Matsumoto Microsphere S-100 manufactured by Matsumoto Yushi Seiyaku Co., Ltd. can be obtained and used. The blending amount of the alkyl acrylate copolymer is appropriately determined according to the blending amount of the UV absorber and the metal oxide blended at the same time, but is preferably blended by 1 to 10% by mass.

  A polyhydric alcohol can be blended in the sunscreen cosmetic of the present invention as necessary. Examples of the polyhydric alcohol include polyethylene glycol, 1,2-pentanediol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin and the like.

  In the sunscreen cosmetics of the present invention, oil agents usually used in cosmetics such as hydrocarbon oils, ester oils, waxes, silicone oils, animal and vegetable oils can be used.

When blending an oil agent, the oil agent is selected for the purpose of stably dissolving hexyl diethylaminohydroxybenzoyl benzoate, which is a UV-A absorber of component (D), which is hardly soluble and easily precipitates at low temperatures. It is preferable to blend them. Specifically, isotridecyl isononanoate, cetyl ethylhexanoate, ethylhexyl palmitate, propylene glycol dicaprylate, ditrimethylolpropane triethylhexanoate, erythyl triethylhexanoate, (isostearic acid / sebacic acid) ditrimethylolpropane, diisostearyl malate Polypropylene glycol oligoester succinate, diglyceryl tetraisostearate, triethylhexanoin, neopentyl glycol diethylhexanoate, octyldodecyl lactate, di (capryl / capric) butylene glycol, dioctyl ether, diglyceryl hydroxystearate, tri (Caprylic acid / Capric acid) Glyceryl, Dineopentanoic acid methylpentanediol, Cyclohexanedicarboxylic acid Bis ethoxy diglycol, glyceryl tri-2-ethylhexanoate, etc. diisopropyl sebacate can be exemplified. Particularly preferably, isotridecyl isononanoate, di (caprylic / capric) butylene glycol, tri (caprylic / capric) glyceryl, dineopentanoic acid methylpentanediol, cyclohexanedicarboxylic acid bisethoxydiglycol, glyceryl tri-2-ethylhexanoate, Diisopropyl sebacate.
The sunscreen cosmetic of the present invention is preferably blended with such an oil agent in a proportion of 1 to 15% by mass, preferably 1 to 10% by mass.

  The component (D) DHHB of the present invention is hardly soluble in silicone oil. For example, only 0.4% by mass of hexyl diethylaminohydroxybenzoylbenzoate is dissolved in cyclomethicone. Therefore, when blending DHHB, when blending silicone oil as an oil, DHHB is blended by combining an oil that dissolves DHHB in addition to silicone oil and an ultraviolet absorber (ethylhexyl methoxycinnamate) as described above. Precipitation at a low temperature can be prevented in advance, and a sunscreen cosmetic with excellent usability can be obtained.

    For the sunscreen cosmetics of the present invention, extender pigments, organic powders, pearl agents, inorganic pigments, organic pigments and the like can be used. For example, talc, mica, kaolin, magnesium silicate, magnesium aluminum silicate, magnesium carbonate, calcium carbonate, silica, nylon powder, polyethylene powder, styrene powder, silk powder, crystalline cellulose, starch, octenyl succinic corn starch ester aluminum, mica Examples thereof include titanium, titanium oxide, iron oxide mica titanium, zinc oxide, yellow iron oxide, black iron oxide, and bengara.

  Furthermore, in the sunscreen cosmetics of the present invention, components usually used in cosmetics, for example, antioxidants, moisturizers, fragrances, fragrances, preservatives, pH adjusters, as long as the effects of the invention are not impaired. Perfumes, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, other cosmetic ingredients, medicinal ingredients, and the like can be blended.

  Examples of the sunscreen cosmetics of the present invention include sunscreen creams, sunscreen lotions, sun care sprays, sunscreen emulsions, sunscreen mousses, liquid foundations, cream foundations, makeup bases, liquid eye shadows, liquid cheek colors, and the like. .

  Hereinafter, the present invention will be described more specifically with reference to examples and test examples for effect confirmation.

  Sunscreen cosmetics having the compositions shown in Table 1 were prepared and tested for storage stability and feeling of use (evaluation of stickiness).

[Comparative Examples, Production Methods of Example Products]
Component 1, 2, 3, 7 and a part of component 9 are mixed in advance into component 6 to make a paste (referred to as a). In a separate container, the ultraviolet absorbers of ingredients 4 and 5 are heated and dissolved and mixed. Next, components 8, 9, 10 and (a) are added and mixed by stirring to prepare an oil phase. In a separate container, ingredients 11 to 14 are stirred and mixed to prepare an aqueous phase. Add water phase to oil phase and emulsify at room temperature.
In Example 9, the alkyl acrylate copolymer (component F) in the column of component 7 is added together with components 8, 9, 10, and (a) to form an oil phase.

[Stability test]
Put the prepared sunscreen cosmetics in a jar, seal them, and store them at 5 ° C, 25 ° C, 40 ° C, 50 ° C, in a cycle (40 ° C to 5 ° C), and check for separation and sedimentation (caking) every month. Observations were made for up to 6 months and evaluated according to the following criteria.
○: No separation or sedimentation (caking) for 6 months △: No change in observation after 3 months, but either separation or sedimentation (caking) after 4 months ×: 1 There is either separation or settling (caking) within a month

[Sensory evaluation test]
Ten professional panels evaluated the feeling of use (presence or absence of stickiness) of the sunscreen cosmetics of Examples and Comparative Examples. Evaluation results were determined according to the following criteria.
○: Evaluation that 7 or more of 10 people are not sticky △: Evaluation that 4 to 6 people are not sticky out of 10 ×: Evaluation that 1 to 3 of 10 people are not sticky

[Test results]
The results are shown in Table 1, below.
The formulation of the comparative example is either 1.5 to 3% by mass of either polyether-modified silicone oil (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) or polyglycerin-modified silicone oil (polyglyceryl-3 polydimethylsiloxyethyl dimethicone). It is a prescription contained in the range. All of these formulations were separated or settled in a storage test at 40 ° C.
In the examples, the storage stability was good. However, when the total content of the polyether-modified silicone oil (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) and the polyglycerin-modified silicone oil (polyglyceryl-3 polydimethylsiloxyethyl dimethicone) exceeds 3%, the feeling of use may be inferior. Appeared (Examples 7 and 8). The upper limit of the amount of polyether-modified silicone oil (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) and polyglycerin-modified silicone oil (polyglyceryl-3 polydimethylsiloxyethyl dimethicone) as an emulsifier is around 3% in total. Estimated.
Examples 1-5 contain 2 mass% in total of polyether modified silicone oil (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) and polyglycerin modified silicone oil (polyglyceryl-3 polydimethylsiloxyethyl dimethicone). Example 6 contains 2.5 mass% in total. These were evaluated as having no separation or precipitation observed in those stored at 40 ° C. for 6 months, and 9 out of 10 people were not sticky.

  In the emulsified system using polyether-modified silicone oil (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) or polyglycerin-modified silicone oil (polyglyceryl-3 polydimethylsiloxyethyl dimethicone), the amount of other surfactants is increased. On the contrary, it was confirmed that the storage stability at 40 ° C. was impaired and the feeling of use was also made sticky (Comparative Examples 1 to 3).

  Next, even when the present invention was further stored at 50 ° C. or in a cycle (40 ° C. to 5 ° C.), a composition for improving the stability was examined. Each formulation in Table 2 was prepared in the same manner and tested for storage stability and usability.

[Production method]
In the same manner as described above, Examples 9 and 10 containing the component (F) were prepared.

〔Test results〕
The results are shown in the lower column of Table 2.

  The sunscreen cosmetics of Examples 9 and 10 containing an alkyl acrylate copolymer were stored for 6 months at 50 degrees, and had no separation or sedimentation even when stored for 6 months in a cycle (5 degrees to 40 degrees). There was no stickiness.

From the above results, it became clear that the sunscreen cosmetics excellent in both stability and usability can be provided by adopting the configuration of the present invention.
Further, it is clear that when the composition of the present invention further contains an alkyl acrylate copolymer, it is possible to provide a sunscreen cosmetic that is more suitable in an environment where a high temperature is expected, such as the interior of a leisure destination in midsummer. Became.

The prescription example of the sunscreen lotion which is one Embodiment of this invention is shown below.
[Formulation Example 1] Sunscreen Lotion (Composition) (mass%)
(1) Decamethylcyclopentasiloxane 10
(2) Stearic acid-treated fine particle tin oxide 5
(3) Silicone-treated fine particle zinc oxide 5
(4) Diethylaminohydroxybenzoyl hexyl benzoate 3
(5) Ethylhexyl methoxycinnamate 7
(6) Methyl polysiloxane 5
(7) Isotridecyl isononanoate 5
(8) Polyoxyethylene-modified silicone (KF-6038, Shin-Etsu Chemical Co., Ltd.) 1.7
(9) Polyglycerin-modified silicone (KF-6104, Shin-Etsu Chemical Co., Ltd.) 0.4
(10) Alkyl acrylate copolymer (Matsumoto Microsphere S-100 manufactured by Matsumoto Yushi) 10 (11) Glycerin 5
(12) 1,2-pentanediol 2
(13) Purified water residue (production method)
Components 2 and 3 are mixed in advance with components 8 and 9 and a part of component 1 to form a paste (referred to as a). In a separate container, the ultraviolet absorbers of ingredients 4 and 5 are heated and dissolved and mixed. Next, components 6, 7, 10 and (a) are added and mixed by stirring to prepare an oil phase. In a separate container, ingredients 11 to 13 are stirred and mixed to prepare an aqueous phase. Add water phase to oil phase and emulsify at room temperature.

The sunscreen lotion of Formulation Example 1 was excellent in storage stability and excellent in use feeling.

[Prescription Example 2] Makeup Base (Composition) (mass%)
(1) Decamethylcyclopentasiloxane 10
(2) Methylpolysiloxane 30
(3) Silicone-treated titanium oxide 7
(4) Silicone-treated iron oxide 0.5
(5) Silicone-treated zinc oxide 1
(6) Silicone treated ultramarine 2
(7) Dextrin palmitate 0.5
(8) Diethylaminohydroxybenzoyl hexyl benzoate 1
(9) Ethylhexyl methoxycinnamate 3
(10) Polyether-modified silicone (KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.) 2
(11) Polyglycerin-modified silicone (KF-6104, Shin-Etsu Chemical Co., Ltd.) 0.5
(12) Alkyl acrylate copolymer (Matsumoto Microsphere S-100 made by Matsumoto Yushi) 3
(13) Silica 2
(14) 1,3-butylene glycol 5
(15) Magnesium sulfate 2
(16) Water residue (Manufacturing method)
Ingredients 3, 5 and components 10, 11 and a part of ingredient 1 are mixed in advance to form a paste (referred to as a). In a separate container, the UV absorbers of components 8 and 9 are heated and dissolved and mixed. Next, components 2, 4, 6, 7, 12, 13, (a) are added and mixed by stirring to prepare an oil phase. In a separate container, ingredients 14-16 are stirred and mixed to prepare an aqueous phase. Add water phase to oil phase and emulsify at room temperature.

The makeup base of Formulation Example 2 was excellent in storage stability and excellent in use feeling.

Claims (4)

And Shi Ricoh emissions emulsifier is a polyether-modified silicone oil (A),
Polyglycerin-modified silicone oil (B),
Ultraviolet B wave (UV-B) absorber (C);
Diethylaminohydroxybenzoyl hexyl benzoate DHHB (D) as an ultraviolet A wave (UV-A) absorber;
Metal oxide (E) ,
Alkyl acrylate copolymer (F)
A sunscreen cosmetic characterized by containing a sunscreen.   The sunscreen cosmetic according to claim 1, wherein the blending ratio of the polyether-modified silicone oil (A) and the polyglycerin-modified silicone oil (B) is 10: 1 to 3: 1.   The sunscreen cosmetic according to claim 1 or 2, wherein the total content of the polyether-modified silicone oil and the polyglycerin-modified silicone oil in the sunscreen cosmetic is 4% by mass or less.   The polyether-modified silicone oil is lauryl PEG-9 polydimethylsiloxyethyl dimethicone and PEG-9 polydimethylsiloxyethyl dimethicone, and the polyglycerin-modified silicone oil is polyglyceryl-3 polydimethylsiloxyethyl dimethicone. The sunscreen cosmetics in any one of 1-3.