JP2010222349A - Sunscreen cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sunscreen cosmetic free from unsmoothness and rough feeling when used, also nonsticky with dry touch, thus good in touch feeling in use, further, free from leaving whiteness on the skin, excellent in makeup finish as well, and also excellent in rinsability after use. <P>SOLUTION: The sunscreen cosmetic includes: (a) isodecyl neopentanoate; (b) an ultraviolet light absorber; (c) an ultraviolet light scattering agent; and (d) a silicone oil. In this sunscreen cosmetic, it is preferable that: the (b) ingredient(s) is(are) one or more compounds selected from a p-aminobenzoic acid derivative, salicylic acid derivative, cinnamic acid derivative, β,β-diphenylacrylate derivative, benzophenone derivative, benzylidene camphor derivative, phenylbenzimidazole derivative, triazine derivative, phenylbenzotriazole derivative, anthranyl derivative, imidazoline derivative, benzalmalonate derivative, and 4,4-diarylbutadiene derivative; and the (c) ingredient(s) is(are) zinc oxide and/or titanium dioxide; besides, as (e) ingredient(s), it is more preferable that this sunscreen cosmetic also includes: one or more compounds selected from a silicone-based surfactant, glycerol or polyglycerol fatty acid esters. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an oil-in-water or water-in-oil emulsified sunscreen cosmetic. More specifically, the present invention relates to an oil-in-water type or water-in-oil type sunscreen cosmetic that is excellent in usability, formulation stability, and cleanability after use and can achieve a high SPF value.

Ultraviolet rays that reach the earth's surface include UV-A (320 to 400 nm) and UV-B (290 to 320 nm). Of these, UV-A causes erythema on the skin when exposed to excessive amounts, causing an acute inflammatory reaction. It is known to cause melanoma and then blacken, causing skin cancer. Although UV-B is weak in causing erythema, it has been clarified that the melanin pigmentation is caused by oxidizing the reduced melanin of the skin, which causes blackening or long-term exposure, which causes premature aging of the skin. Thus, as the influence of ultraviolet rays on the skin becomes clear, there is an increasing demand for sunscreen cosmetics with a high ultraviolet blocking effect. As an index for protecting the skin from ultraviolet rays, an SPF (Sun Protection Factor) value is generally used, and the higher the SPF value, the higher the sunscreen effect.
In general, sunscreen cosmetics are blended with an ultraviolet absorber or an ultraviolet scattering agent in order to obtain a high SPF value by blocking ultraviolet irradiation on the skin. Ultraviolet absorbers block ultraviolet rays by absorbing light energy, but generally the absorption band of ultraviolet absorbers is highly unfavorable in terms of safety to the skin, such as having high polarity and skin irritation. For this reason, there is no irritation to the skin, and it is used in combination with silicone oil or the like having good usability. However, when UV absorbers, which are highly polar oils, and silicone oils, which are nonpolar oils, are used together, there are problems such as poor oil phase uniformity, problems in emulsion stability, and uneven coating on the skin. Arise.
On the other hand, the ultraviolet scattering agent shields ultraviolet rays by scattering ultraviolet rays, and conventionally inorganic pigments such as zinc oxide, titanium dioxide, kaolin and calcium carbonate have been used. These are capable of shielding ultraviolet rays over a wide band, and are inactive, so that they have high skin safety and are more useful ultraviolet shielding agents.
However, although these inorganic pigments, particularly titanium dioxide and zinc oxide, have a high ultraviolet shielding effect as described above, they also have a large covering power (hiding power), so when applied to the skin, the cosmetic film becomes white and causes whitening. It becomes. For this reason, it has been proposed to use fine particles of titanium dioxide or zinc oxide (for example, see Patent Documents 1 to 3). It is known that the finer these particles, the higher the ultraviolet shielding effect, and the higher the light transmittance in the visible light part and the higher the transparency.
However, the fine particles of these inorganic pigments generally have high cohesive properties, and it is difficult to stably disperse them in a fine particle state in a blending system such as cosmetics. For this reason, the UV shielding effect and transparency are not obtained as expected. Further, since these fine particle pigments have a high refractive index of light, if they are used in a large amount, the concealing property becomes high, whitening or the like occurs, resulting in an unnatural cosmetic finish. Further, the aggregation of the particles causes problems in usability such as preventing the spreadability of the cosmetic and causing a squeaky feeling when applied to the skin.
For this reason, it is desired to provide sunscreen cosmetics that are naturally limited in the amount of these ultraviolet scattering agents and that can sufficiently exhibit the desired ultraviolet shielding effect. In order to solve this point, as a technique for obtaining an oil phase dispersant and a sunscreen cosmetic excellent in usability, a method using an isononanoic acid ester (Patent Document 4) has been found, and the inventors A method (Patent Document 5) using 2-ethylhexyl 2-ethylhexanoate has been found. However, even with this method, the uniformity of the water phase and oil phase, the emulsion stability, and the dispersibility of zinc oxide / titanium dioxide were sufficient, but only in terms of usability, spreading and spreading to the skin, In terms of smooth, non-sticky usability, it was not completely satisfactory.
On the other hand, it is known that isodecyl neopentanoate used in the present application can be used as a dispersion medium for obtaining a fine dispersion of titanium dioxide. However, when an organic ultraviolet absorber is blended to form an emulsion composition, Improvement of usability and cleanability has not been studied. (Patent Documents 6 and 7)

Japanese Examined Patent Publication No. 47-42502 JP-A-49-450 Japanese Unexamined Patent Publication No. 64-7941 JP 2000-169353 A JP 2007-145722 A Japanese National Patent Publication No. 8-507081 JP 2000-128755 A

The object of the present invention is to sufficiently exhibit the excellent ultraviolet shielding effect possessed by ultraviolet absorbers and ultraviolet scattering agents, to be well-familiar with the skin, to be non-sticky, and from the skin after use. It is an object of the present invention to provide a sunscreen cosmetic that can be easily removed (good cleanability).
More specifically, the present invention provides an emulsion composition that is stable even in a combined system of a UV absorber that is a highly polar oil and a nonpolar oil such as silicone oil that is a usability improver, Even if some titanium dioxide or zinc oxide is blended, it can be dispersed stably and uniformly, and by improving the redispersibility, it is possible to achieve a high natural SPF value with a transparent finish without white floating. The object is to provide a cosmetic material that has a good fit to the skin, spreads well and has a refreshing and non-sticky feeling.
In order to solve the above-mentioned problems, the present inventors have intensively studied, and by preparing an oil-in-water type or water-in-oil type sunscreen cosmetic using isodecyl neopentanoate, a highly polar oil is used. It has been found that the compatibility between a certain ultraviolet absorber and silicone oil which is a non-polar oil as a usability improving agent is excellent, the emulsion stability is excellent, and the dispersibility of titanium dioxide and zinc oxide is excellent. In particular, it has excellent dispersibility even for finely aggregated particles that are generally highly cohesive, and in the presence of a silicone surfactant, as a sunscreen cosmetic, stability and familiarity with the skin, good spreading, It has been found that an excellent composition can be obtained in terms of both usability such as freshness and non-stickiness. The present invention has been developed based on such knowledge.

That is, the present invention provides an oil-in-water or water-in-oil emulsion sunscreen cosmetic containing (a) isodecyl neopentanoate, (b) an ultraviolet absorber, (c) an ultraviolet scattering agent, and (d) a silicone oil. I will provide a.
In the present invention, the component (b) is a para-aminobenzoic acid derivative, a salicylic acid derivative, a cinnamic acid derivative, a β, β-diphenyl acrylate derivative, a benzophenone derivative, a benzylidene camphor derivative, a phenylbenzimidazole derivative, a triazine derivative, The sunscreen cosmetic is one or more selected from phenylbenzotriazole derivatives and 4,4-diarylbutadiene derivatives.
Moreover, this invention provides the said sunscreen cosmetics whose (c) component is zinc oxide and / or titanium dioxide.
Moreover, this invention provides the said sunscreen cosmetics whose average primary particle diameter of a zinc oxide is 5-40 nm.
Moreover, this invention provides the said sunscreen cosmetics whose average primary particle diameter of titanium dioxide is 5-30 nm.
Moreover, this invention is 1-60 mass% of (a) component, 3-20 mass% of (b) component, 0.5-50 mass% of (c) component, (d) component in cosmetics whole quantity. The sunscreen cosmetic containing 1 to 70% by mass of the sunscreen.
The present invention further provides the sunscreen cosmetic described above further comprising (e) one or more selected from silicone surfactants, glycerin or polyglycerin fatty acid esters.
In the present invention, the silicone surfactant as the component (e) is a poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, a polyoxyethylenemethylpolysiloxane copolymer, a silicone chain-branched methylpolysiloxane. Copolymer, alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer, cross-linked polyoxyethylene methyl polysiloxane, alkyl group-containing cross-linked polyoxyethylene methyl polysiloxane, branched polyglycerin-modified silicone, cross-linked The sunscreen cosmetic is one or more selected from a polyglycerin-modified silicone, an alkyl group-containing crosslinked polyglycerin-modified silicone, and an alkyl group-branched polyglycerin-modified silicone.
Moreover, this invention provides the said sunscreen cosmetics which contain 0.01-20 mass% of (e) component in cosmetics whole quantity.

According to the present invention, the ultraviolet ray shielding agent and the ultraviolet scattering agent have excellent ultraviolet shielding effects, and they are well-familiar with the skin and are not sticky, and also have excellent cleanability after use. A sunscreen cosmetic excellent in dispersibility and stability is provided.

（１）

本発明に用いられる（ａ）成分の市販品としては、ネオライト１００Ｐ［高級アルコール工業（株）社製］、AEC
Isodecyl Neopentanoate［Bermel Chemical Company社製］、Ceraphyl SLK［International
Speciality Products］、Dub VCI 10［Sterinerie Dubois Fils］等が挙げられる。 The best mode of the present invention will be described below.
Hereinafter, the present invention will be described in detail.
In the cosmetic of the present invention, isodecyl neopentanoate represented by the following formula (1) is used as the component (a).
(Chemical formula 1)

(1)

As a commercial item of the component (a) used in the present invention, Neolite 100P [manufactured by Higher Alcohol Industry Co., Ltd.], AEC
Isodecyl Neopentanoate (Bermel Chemical Company), Ceraphyl SLK [International
Specialty Products], Dub VCI 10 [Sterinerie Dubois Fils].

Conventionally, an ester of isononanoic acid having a carbon chain length of 9 or the like is generally used for improving usability such as skin familiarity. On the other hand, the present inventors have used 2-ethylhexanoic acid having a shorter carbon chain length ( Among the esters having a carbon chain length of 8), 2-ethylhexyl 2-ethylhexanoate and isononyl 2-ethylhexanoate are particularly found. These are excellent in dispersibility of zinc oxide and titanium dioxide, and can provide sunscreen cosmetics that can feel moderate “freshness” and “freshness”, but in terms of cleanability after use, The present invention solves this point.

  The blending amount of the component (a) is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly 5% by mass or more in the sunscreen cosmetic of the present invention. preferable. The upper limit is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. If the blending amount is less than 1% by mass, the effects of emulsification stability, dispersibility, and usability are not sufficiently exhibited. On the other hand, if the blending amount exceeds 60% by mass, an effect commensurate with the increase in the blending amount cannot be obtained. .

  As the ultraviolet absorber as the component (b), those generally used in cosmetics can be widely cited, and are not particularly limited, but preferably para-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives. , Β, β-diphenyl acrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranil derivatives, imidazoline derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives, etc. Is exemplified. However, it is not limited to these.

  Examples of the para-aminobenzoic acid derivative include para-aminobenzoic acid (hereinafter abbreviated as “PABA”), ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA (for example, “Escalol 507”); ISP), glyceryl PABA, PEG-25-PABA (for example, “Ubinul P25”; BASF) and the like.

Examples of the salicylic acid derivative include homosalate (for example, “Eusolex HMS”; Rona / EM Industries), ethylhexyl salicylate (for example, “Neo Heliopan (Neo)”.
Heliopan OS ”; Haarmann and Reimer), dipropylene glycol salicylate (eg“ Dipsal ”; Scher), TEA salicylate (eg“ Neo Heliopan TS ”) ; Herman & Reimer).

  Examples of the cinnamic acid derivatives include ethylhexyl methoxycinnamate (eg, “Pulsol MCX”; Hoffman-La Roche), isopropyl methoxycinnamate, isoamyl methoxycinnamate (eg, “Neo Heliopan E1000”; And Reimer), cinnoxate, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl-ethylhexanoate-dimethoxycinnamate, and the like.

  Examples of the β, β-diphenyl acrylate derivative include Octocrylene (for example, “Ubinur N539”; BASF), Etocrylene (for example, “Ubinur N35”; BASF).

Examples of the benzophenone derivative include benzophenone-1 (for example, “Ubinur 400”; BASF), benzophenone-2 (for example, “Ubinur D50”; BASF), benzophenone-3 or oxybenzone (for example, “Ubinur M40”; BASF), Benzophenone-4 (eg “Ubinur MS40”; BASF), benzophenone-5, benzophenone-6 (eg “Helisorb 11”; Norquay), benzophenone-8 (eg “Spectra-sorb”) Sorb UV-24 "; American Cyanamide (American
Cyanamid)), benzophenone-9 (for example, “Ubinur DS-49”; BASF), benzophenone-12, and the like.

  Examples of the benzylidene camphor derivatives include 3-benzylidene camphor (for example, “Mexoryl SD”; Simex), 4-methylbenzylidene camphor, benzylidene camphorsulfonic acid (for example, “Megizolyl SL”; Simex), metho Camphor sulfate (eg, “Megizolyl SO”; Simex), terephthalidene dishowosulfonic acid (eg, “Megizolyl SX”; Simex), polyacrylamide methylbenzylidene camphor (eg, “Megizolyl SW”; Simex) Is exemplified.

  Examples of the phenylbenzimidazole derivative include phenylbenzimidazole sulfonic acid (for example, “Yusolex 232”; Merck), phenyldibenzimidazole tetrasulfonate disodium (for example, “Neo Heliopan AP”; Herman & Reimer), etc. Is exemplified.

Examples of the triazine derivative include anisotriazine (for example, “Tinosorb S”; Ciba Specialty Chemicals).
Chemicals), ethylhexyltriazone (eg “Ubinur T150”; BASF), diethylhexylbutamide triazone (eg “Uvasorb HEB”; Sigma 3V (Sigma)
3V), 2,4,6-tris (diisobutyl-4′-aminobenzalmalonate) -s-triazine and the like.

Examples of the phenylbenzotriazole derivatives include Drometrizole trisiloxane (eg, “Silatrizole”; Rhodia
Chimie)), and methylene bis (benzotriazolyltetramethylbutylphenol) [for example, “Tinosorb M” (Ciba Specialty Chemicals Co., Ltd.), which is sold as a micronized form in an aqueous dispersion, Mixxim BB / 100 "(Fairmount
Chemical) and the like are sold in solid form].

Examples of the anthranyl derivative include menthyl anthranilate (for example, “Neo Heliopan MA”; Herman & Reimer).
Examples of the imidazoline derivative include ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

  Examples of the benzalmalonate derivative include polyorganosiloxane having a benzalmalonate functional group (for example, “Pulsol SLX”; Hoffman-La Roche).

  Examples of the 4,4-diarylbutadiene derivative include 1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene.

Among them, particularly preferred are ethylhexyl salicylate, ethylhexyl methoxycinnamate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, 4-methylbenzylidene camphor, terephthalylidene camphor sulfonic acid, phenylbenzimidazolesulfonic acid , Phenyldibenzimidazole tetrasulfonate disodium, anisotriazine, ethylhexyltriazone, diethylhexylbutamide triazone, 2,4,6-tris (diisobutyl-4′-aminobenzalmalonate) -s-triazine, dolometry Zoletrisiloxane, methylenebis (benzotriazolyltetramethylbutylphenol), 1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene , And mixtures thereof. (B) A component can use 1 type (s) or 2 or more types.
The blending amount of the component (b) is preferably 3% by mass or more, and more preferably 5% by mass or more, in the sunscreen cosmetic of the present invention. Moreover, it is preferable that an upper limit shall be 20 mass% or less, More preferably, it is 15 mass% or less. If the blending amount is less than 3% by mass, it is difficult to obtain a sufficient SPF value. On the other hand, if the blending amount exceeds 20% by mass, an effect commensurate with the increase in the blending amount cannot be obtained.

As the ultraviolet scattering agent as the component (c), zinc oxide and titanium dioxide are preferably used.
[Zinc oxide]
The zinc oxide used in the present invention is not particularly limited, and a wide range of zinc oxides commonly used in cosmetics can be mentioned. Preferably, it is more excellent in dispersibility, and for example, a surface treated by a known method can be used as necessary.
As a surface treatment method, silicone treatment such as methylhydrogenpolysiloxane and methylpolysiloxane; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol and the like; amino acid treatment with N-acylglutamic acid and the like; other, lecithin treatment; Metal soap treatment; fatty acid treatment; alkyl phosphate ester treatment and the like. Of these, zinc oxide subjected to silicone surface treatment is preferable.
The silicone used for the surface treatment is not particularly limited, but for example, methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa Siloxane, octamethyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethyl Siloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methylcetyloxysiloxane copolymer, dimethylsiloxa - methyl stearoxysiloxane copolymer such as various silicone oils can be exemplified. Preferably, it is methyl hydrogen polysiloxane. The use of such a silicone-treated zinc oxide is excellent in water repellency, ultraviolet shielding property, transparency, adhesion, and dispersibility, and is useful for providing an excellent sunscreen cosmetic.

  In particular, when the cosmetic of the present invention is a water-in-oil emulsified sunscreen cosmetic, zinc oxide that has been subjected to such a surface treatment is preferably used. On the other hand, in the case of oil-in-water type oxidative emulsification sunscreen cosmetics, those not subjected to such hydrophobic surface treatment are preferably used.

  The amount of silicone used for the surface treatment of zinc oxide is usually about 1 to 20% by mass, preferably 2 to 14% by mass, more preferably 2 to 10% by mass, per 100% by mass of the silicon-treated zinc oxide. It is 2-5 mass% especially. The method for treating silicon oxide with zinc oxide is not particularly limited, and a conventionally known method can be selected as appropriate.

  Specific examples of zinc oxide used in the present invention include MZ-300 (no surface treatment agent, particle size 30 to 40 nm, manufactured by Teika), MZ-303S (methicone treatment, particle size 30 to 40 nm, taker) MZ-303M (dimethicone treatment, particle size 30-40 nm, manufactured by Teika Co., Ltd.), MZ-500 (no surface treatment agent, particle size 20-30 nm, manufactured by Teika Co., Ltd.), MZ- 505S (methicone treatment, particle size 20-30 nm, manufactured by Teika), MZ-505M (dimethicone treatment, particle size 20-30 nm, manufactured by Teica), MZ-700 (no surface treatment agent, particle size 10) -20 nm, manufactured by Teika Co., Ltd.), MZ-707S (methicone treatment, particle size 10-20 nm, manufactured by Teika Co., Ltd.), FINEX-25 (no surface treatment agent, particle size 60 nm, manufactured by Sakai Chemical Co., Ltd.) , FINE -25LP (dimethicone treatment, particle size 60 nm, manufactured by Sakai Chemical Co., Ltd.), FINEX-50 (no surface treatment agent, particle size 20 nm, manufactured by Sakai Chemical Co., Ltd.), FINEX-50LP (dimethicone treatment, particle size 20 nm, Sakai Chemical Co., Ltd.), FINEX-75 (no surface treatment agent, particle size 10 nm, Sakai Chemical Co., Ltd.). However, it is not limited to these examples.

  In general, the zinc oxide used in the present invention preferably has an average primary particle size of 40 nm or less, more preferably 30 nm or less. This is because when the average primary particle diameter greatly exceeds 40 nm, there is a tendency to cause white floating or white remaining. The lower limit of the average primary particle size is not particularly limited, but the smaller the particle size, the higher the cost. Therefore, in consideration of economy, it may be 5 nm or more, and preferably 10 nm or more.

In the present invention, the average primary particle diameter is not particularly limited and means the diameter of primary particles measured by a method generally used for zinc oxide and titanium dioxide, and specifically, a transmission electron microscope. From the photograph, it is obtained as an arithmetic average of the major axis and the minor axis of the particle.
The form of the particles is not particularly limited, and may be in the form of primary particles or an aggregated secondary aggregate. Further, the shape such as a spherical shape, an elliptical shape, and a crushed shape is not particularly limited.

A more preferred embodiment of the silicone-treated zinc oxide in the present invention is dimethylhydrogenpolysiloxane-treated zinc oxide (1 to 5 mass% surface treatment) having an average primary particle size of 5 to 40 nm.

[titanium dioxide]
As titanium dioxide used for this invention, what is normally used for cosmetics can be widely mentioned, without being restrict | limited in particular. The crystal form of titanium dioxide is not particularly limited, and may be any of anatase, rutile or brookite.
Preferably, the ultraviolet shielding power is higher, and examples thereof include those that have been subjected to a surface treatment in order to enhance the ultraviolet scattering effect. As such a surface treatment method, any treatment usually used in cosmetics can be used without any particular limitation. Examples of such treatment include a method of adsorbing fats and oils on the surface of titanium dioxide, Fatty acid treatment method in which titanium dioxide that has been esterified or etherified using a functional group such as a hydroxyl group is treated with a fatty acid, in the above method, an aluminum salt of a fatty acid such as aluminum stearate or zinc stearate instead of the fatty acid And metal soap treatment using zinc salt, silicone treatment using methylpolysiloxane or methylhydrogenpolysiloxane instead of fatty acid, and treatment with fluorine compound having perfluoroalkyl group instead of fatty acid It is done.

  Preferred is aluminum stearate treated titanium dioxide treated with aluminum stearate. Although the ratio of the aluminum stearate contained in the aluminum stearate-treated titanium dioxide is not particularly limited, it may be 1 to 20% by mass. Moreover, as a ratio of titanium dioxide, 80-99 mass% is mentioned as a preferable compounding quantity.

  In particular, when the cosmetic composition of the present invention is a water-in-oil type emulsion sunscreen cosmetic composition, titanium dioxide having such a surface treatment is preferably used. On the other hand, in the case of oil-in-water type oxidative emulsification sunscreen cosmetics, those not subjected to such hydrophobic surface treatment are preferably used.

As specific examples of titanium dioxide used in the present invention, Taipei CR-50 (rutile type, aluminum oxide treatment, particle size 25 nm, manufactured by Ishihara Sangyo Co., Ltd.), Bayer titanium R-KB-1 (rutile type, zinc oxide treatment) , Aluminum oxide treatment, silicon dioxide treatment, particle size 30-40 nm, manufactured by Bayer), Typek TTO-M-1 (rutile type, zirconium oxide, aluminum oxide treatment, particle size 10-25 nm, manufactured by Ishihara Sangyo Co., Ltd.) , Taipei TTO-D-1 (rutile type, zirconium oxide treatment, aluminum oxide treatment, particle size 20-3 nm, manufactured by Ishihara Sangyo Co., Ltd.), Taipei A-100 (anatase type, surface untreated, particle size 0.4 μm) , Manufactured by Ishihara Sangyo Co., Ltd.), Kronos KA-10 (anatase type, untreated, particle size 0.3 to 0.5 μm, manufactured by Titanium Industry Co., Ltd.), Kronos KA-15 (anatase type, untreated, particle size 0.3 to 0.5 μm, manufactured by Titanium Industry Co., Ltd.), Kronos KA-20 (anatase type, aluminum oxide treatment, particle size 0.3 to 0.5 μm) , Manufactured by Titanium Industry Co., Ltd.), Kronos KA-30 (anatase type, untreated, particle size 0.2-0.4 μm, manufactured by Titanium Industry Co., Ltd.), Kronos KA-35 (anatase type, untreated, grain) 0.2 to 0.4 μm in diameter, manufactured by Titanium Industry Co., Ltd.), Kronos KA-80 (anatase type, aluminum oxide treatment, silicon dioxide treatment, particle size 0.3 to 0.5 μm, manufactured by Titanium Industry Co., Ltd.) , Kronos KR-310 (rutile type, untreated, particle size 0.3 to 0.5 μm, manufactured by Titanium Industry Co., Ltd.), Kronos KR-380 (rutile type, aluminum oxide treatment, silicon dioxide treatment, particle size 0. 3 to 0.5 μm, h Manufactured by Co., Ltd.), Kronos KR-460 (rutile type, aluminum oxide treatment, particle size 0.2 to 0.4 μm, manufactured by Titanium Industry Co., Ltd.), Kronos KR-480 (rutile type, aluminum oxide treatment, Silicon dioxide treatment, particle size 0.2 to 0.4 μm, manufactured by Titanium Industry Co., Ltd., Kronos KR-270 (rutile type, zinc oxide treatment, aluminum oxide treatment, particle size 0.2 to 0.4 μm, titanium industry Manufactured by Titanics JR-301 (rutile type, aluminum oxide treatment, particle size 0.3 μm, manufactured by Teica Co., Ltd.), Titanics JR-403 (rutile type, aluminum oxide treatment, silicon dioxide treatment, grain) Diameter 0.25 μm, manufactured by Teika Co., Ltd.), Titanics JR-405 (rutile type, aluminum oxide treatment, particle size 0.21 μm, manufactured by Teica Co., Ltd.), Titanics JR-60 0A (rutile type, aluminum oxide treatment, particle size 0.25 μm, manufactured by Teika Co., Ltd.), Titanics JR-605 (rutile type, aluminum oxide treatment, particle size 0.25 μm, manufactured by Teica Co., Ltd.), Titanics JR-600E (rutile type, aluminum oxide treatment, particle size 0.27 μm, manufactured by Teika Co., Ltd.), Titanic JR-603 (rutile type, aluminum oxide treatment, zirconium oxide treatment, particle size 0.28 μm, Teika Co., Ltd.) )), Titanics JR-805 (rutile type, aluminum oxide, silicon dioxide treatment, particle size 0.29 μm, manufactured by Teica), Titanics JR-806 (rutile type, aluminum oxide treatment, silicon dioxide treatment) Particle size 0.25 μm, manufactured by Teika Co., Ltd.), Titanics JR-701 (rutile type, aluminum oxide treatment, silicon dioxide) , Zinc oxide treatment, particle size 0.27 μm, manufactured by Teica Co., Ltd.), Titanic JRNC (rutile type, aluminum oxide treatment, silicon dioxide treatment, zirconium oxide treatment, manufactured by Teika Co., Ltd.), Titanics JR-800 (Rutile type, aluminum oxide treatment, silicon dioxide treatment, manufactured by Teika Co., Ltd.), Titanics JR (rutile type, untreated, particle size 0.27 μm, manufactured by Teika Co., Ltd.), Titanics JA-1 (anatase type) , Untreated, particle size 0.18 μm, manufactured by Teica Co., Ltd.), Titanics JA-C (anatase type, untreated, particle size 0.18 μm, manufactured by Teica Co., Ltd.), Titanics JA-3 (anatase type) , Untreated, particle size 0.18 μm, manufactured by Teika Co., Ltd.), Titanics JA-4 (anatase type, aluminum oxide treatment, particle size 0.18 μm, manufactured by Teika Co., Ltd.), Chi Nicks EN-5 (anatase type, untreated, particle size 0.18 .mu.m, manufactured by Tayca Corporation), and the like. However, it is not limited to these examples, and titanium dioxide may be prepared in the form of fine particles in order to enhance the ultraviolet scattering effect. Although it does not restrict | limit as fine particle titanium dioxide, Preferably an average primary particle diameter is 30 nm or less, More preferably, a 20 nm or less thing can be mentioned. When the average primary particle diameter greatly exceeds 30 nm, it tends to cause white floating and white remaining. The lower limit of the average primary particle size is not particularly limited, but it becomes more expensive as the particle size becomes smaller. Therefore, in view of economy, it may be 5 nm or more, and preferably 10 nm or more.

The total blending amount of the component (c) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 3% by mass or more in the sunscreen cosmetic of the present invention. Moreover, it is preferable that an upper limit shall be 50 mass% or less, More preferably, it is 40 mass% or less. When the blending amount is less than 0.5% by mass, it is difficult to obtain a sufficient SPF value. On the other hand, even if blending exceeds 50% by mass, an effect commensurate with the increase in the blending amount cannot be obtained, and formulation tends to be difficult It is in. In particular, when zinc oxide or titanium dioxide is used as the component (c), an excessive amount is not preferable because it causes problems in terms of usability such as spreading on the skin and whitening, and stability.

  In addition, when mix | blending zinc oxide as a (c) component, it is preferable to mix | blend in 5-40 mass%. Moreover, when mix | blending titanium dioxide, it is preferable to mix | blend in 0.5-10 mass%.

Examples of the silicone oil as the component (d) include those generally used in cosmetics. Specific examples include methylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and the like. be able to. Preferred examples include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. However, it is not limited to these examples. (D) 1 type (s) or 2 or more types can be used for a component.

The blending amount of component (d) is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more in the sunscreen cosmetic of the present invention. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. When the blending amount is less than 1% by mass, there is a tendency to become. On the other hand, even if the blending amount exceeds 70% by mass, an effect commensurate with the increase in the blending amount cannot be obtained, and stickiness is caused, which deteriorates the UV protection effect. Will be allowed to.

  The cosmetic of the present invention comprises the above components (a) to (d) as essential components, and further, as a component (e), from the viewpoint of improving usability and stability, a silicone surfactant, glycerin or polyglycerin fatty acid. You may mix | blend 1 type, or 2 or more types chosen from ester.

[Silicone surfactant]
The silicone surfactant is not particularly limited. For example, a nonionic silicone surfactant in which a siloxane skeleton is modified with a polyether group, an epoxy polyether group, a hydroxyl group, an amino group, an epoxy group, or the like; Examples include, but are not limited to, cationic silicone surfactants in which the siloxane skeleton is modified with an ammonium base; amphoteric silicone surfactants in which the siloxane skeleton is modified with a sulfobetaine group.

  By using a silicone-based surfactant having a modified group introduced into the polysiloxane chain, the dispersibility and stability of titanium dioxide and zinc oxide in the preparation are significantly improved compared to the use of 2-ethylhexanoic acid ester alone. In addition, a cosmetic material excellent in formulation can be prepared.

  Preferably, polyether-modified silicone surfactants can be mentioned in that the polarity can be adjusted over a wide range from hydrophilic to lipophilic. Among them, poly (oxyethylene / oxypropylene) methyl polysiloxane copolymer, polyoxyethylene methyl polysiloxane copolymer, silicone chain branched methyl polysiloxane copolymer, alkyl chain branched polyoxyethylene methyl polysiloxane copolymer Copolymer, alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer, cross-linked polyoxyethylene methyl polysiloxane, alkyl group-containing cross-linked polyoxyethylene methyl polysiloxane, branched polyglycerin-modified silicone, cross-linked poly Preferable examples include glycerin-modified silicone, alkyl group-containing crosslinked polyglycerin-modified silicone, and alkyl group-branched polyglycerin-modified silicone.

Examples of the poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer include PEG / PPG-20 / 22 butyl ether dimethicone (“KF-6012”; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG / PPG-20 / 20. Dimethicone (“BY22-008M”; manufactured by Toray Dow Corning Silicone), lauryl PEG / PPG-18 methicone (“5200
Formulation Aid "; manufactured by Toray Dow Corning Co., Ltd.), PEG / PPG-19 / 19 dimethicone (" 5330 Fluid "; manufactured by Toray Dow Corning Co., Ltd.), PEG / PPG-15 / 15 dimethicone (" 5330
Fluid "; manufactured by Toray Dow Corning Co., Ltd.).

  Examples of the polyoxyethylene methylpolysiloxane copolymer include PEG-11 methyl ether dimethicone (“KF-6011”; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-9 dimethicone (“KF-6013”; Shin-Etsu Chemical Co., Ltd.). ), PEG-3 ("KF-6015"; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-9 methyl ether dimethicone ("KF-6016"; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-10 dimethicone ( "KF-6017"; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-11 methyl ether dimethicone ("KF-6018"; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-9 dimethicone ("KF-6019"; Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd.), PEG-12 dimethicone (“SH3771M”, “SH3772M”, “SH3773M”, “SH3775M”, etc.) Dow Corning Co., Ltd.), and the like.

  Examples of the silicone chain branched methylpolysiloxane copolymer include PEG-9 polydimethylsiloxyethyl dimethicone (“KF-6028”; manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the alkyl chain branched polyoxyethylene methyl polysiloxane copolymer include PEG / PPG-10 / 3 oleyl ether dimethicone (“KF-6026”; manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer include lauryl PEG-9 polydimethylsiloxyethyl dimethicone (“KF-6038”; manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the crosslinked polyoxyethylene methylpolysiloxane include dimethicone (dimethicone / (PEG-10 / 15)) crosspolymer (“KSG-210”; manufactured by Shin-Etsu Chemical Co., Ltd.), cyclomethicone / PEG-12 dimethicone dimethicone cross. Polymer ("9011 silicone elastomer blend"; manufactured by Toray Dow Corning Silicone Co., Ltd.).

  Examples of the alkyl group-containing crosslinked polyoxyethylene methylpolysiloxane include mineral oil, PEG-15 lauryl dimethicone cross polymer (“KSG-310”, manufactured by Shin-Etsu Chemical Co., Ltd.), isododecane, PEG-15 lauryl dimethicone cross polymer ( “KSG-320”; manufactured by Shin-Etsu Chemical Co., Ltd.), trioctanoin / PEG-15 lauryl dimethicone cross polymer (“KSG-330”; manufactured by Shin-Etsu Chemical Co., Ltd.), squalane / PEG-15 lauryl dimethicone cross Examples include polymers and PEG-10 lauryl dimethicone crosspolymer (“KSG-340”; manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the branched polyglycerin-modified silicone include polyglyceryl-3 disiloxane dimethicone (“KF-6100”; manufactured by Shin-Etsu Chemical Co., Ltd.), polyglyceryl-3 polydimethylsiloxyethyl dimethicone (“KF-6104”; Shin-Etsu Chemical ( Etc.).

  Examples of the crosslinked polyglycerin-modified silicone include dimethicone / (dimethicone / polyglycerin-3) crosspolymer (“KSG-710”; manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the alkyl group-containing crosslinked polyglycerin-modified silicone include mineral oil (lauryl dimethicone / polyglycerin 3) crosspolymer (“KSG-810”; manufactured by Shin-Etsu Chemical Co., Ltd.), isododecane (lauryl dimethicone / polyglycerin 3). ) Crosspolymer (“KSG-820; manufactured by Shin-Etsu Chemical Co., Ltd.”), trioctanoin (lauryl dimethicone / polyglycerin 3) crosspolymer (“KSG-830”; manufactured by Shin-Etsu Chemical Co., Ltd.), squalane -(Lauryl dimethicone / polyglycerin 3) crosspolymer ("KSG-840"; manufactured by Shin-Etsu Chemical Co., Ltd.)

Examples of the alkyl group-branched polyglycerin-modified silicone include lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (“KF-6105”; manufactured by Shin-Etsu Chemical Co., Ltd.).

Among them, poly (oxyethylene / oxypropylene) methyl polysiloxane copolymer, alkyl chain branched poly (oxyethylene / oxypropylene) methyl polysiloxane copolymer, silicone chain / alkyl chain branched poly (oxyethylene / oxypropylene) ) A methylpolysiloxane copolymer is preferably used.

[Glycerin or polyglycerol fatty acid esters]
Examples of glycerin or polyglycerin fatty acid esters include glyceryl undecylate, glyceryl myristate, glyceryl stearate, self-emulsifying glyceryl stearate, glyceryl isostearate, glyceryl oleate, glyceryl oliveate, glyceryl dioleate, stearic acid Polyglyceryl-2, polyglyceryl-2 oleate, polyglyceryl-2 dioleate, polyglyceryl-2 isostearate, polyglyceryl-2 diisostearate, polyglyceryl-2 triisostearate, polyglyceryl-4 stearate, polyglyceryl-4 oleate, tristearin polyglyceryl -4, polyglyceryl pentaoleate 4, polyglyceryl laurate-6, polyglyceryl-6 myristate, Polyglyceryl 6-oleate, polyglyceryl oleate-6, polyglyceryl tristearate, polyglyceryl tetrabehenate, polyglyceryl pentastearate, polyglyceryl pentaoleate, polyglyceryl-6 polyricinoleate, polyglyceryl laurate 10, polyglyceryl-10 myristate, polyglyceryl-10 stearate, polyglyceryl isostearate, polyglyceryl-10 oleate, polyglyceryl-10 linoleate, polyglyceryl-10 distearate, polyglyceryl-10 diisostearate, polyglyceryl tristearate , Polyglyceryl trioleate-10, polyglyceryl pentastearate-10, pentahydroxystearic acid poly Lyceryl-10, polyglyceryl-10 pentaisostearate, polyglyceryl pentaoleate-10, polyglyceryl-10 heptearate, polyglyceryl-10 heptaoleate, polyglyceryl-10 decastearate, polyglyceryl-10 decaisostearate, polyglyceryl decaoleate 10, decamademia nut fatty acid polyglyceryl-10, polyricinoleate polyglyceryl-10, and the like.

  The cosmetics of the present invention can take any emulsification form of oil-in-water emulsification or water-in-oil emulsification. In the case of an oil-in-water emulsion sunscreen cosmetic, polyoxyethylene methylpolysiloxane copolymer, glycerin or polyglycerin fatty acid esters are preferably used as the component (e). In the case of a water-in-oil emulsified sunscreen cosmetic, as the component (e), an alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer, a silicone chain branched polyoxyethylene methyl polysiloxane copolymer Polyoxyethylene methyl polysiloxane copolymer and the like are preferably used.

The blending amount of the component (e) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass in the sunscreen cosmetic of the present invention. That's it. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. If the blending amount is less than 0.01% by mass, the cosmetics tend to be less stable. On the other hand, if the blending amount greatly exceeds 20% by mass, the sticky feeling tends to occur and the usability tends to deteriorate.

  In addition to the above components, other components that are usually used in cosmetics can be appropriately blended in the cosmetic of the present invention as necessary. Examples of such components include water-soluble polymers, oil-soluble polymers, waxes, alcohols, hydrocarbon oils, fatty acids, higher alcohols, fatty acid esters, drugs, and the like. However, it is not limited to these examples.

  Examples of the water-soluble polymer include homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as “AMPS”). The copolymer is a copolymer composed of a comonomer such as vinyl pyrrolidone, acrylic acid amide, sodium acrylate, or hydroxyethyl acrylate. That is, an AMPS homopolymer, a vinylpyrrolidone / AMPS copolymer, a dimethylacrylamide / AMPS copolymer, an acrylic amide / AMPS copolymer, a sodium acrylate / AMPS copolymer, and the like are exemplified.

  Furthermore, carboxyvinyl polymer, ammonium polyacrylate, sodium polyacrylate, sodium acrylate / alkyl acrylate / sodium methacrylate / alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, Glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar etc. Illustrated.

  Examples of the oil-soluble polymer include trimethylsiloxysilicic acid, alkyl-modified silicone, polyamide-modified silicone, dimethicone crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, polymethylsilsesquioxane, and the like.

  Examples of waxes include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, jojoballow and the like.

  Examples of alcohols include lower alcohols such as ethanol and isopropanol, higher alcohols such as isostearyl alcohol, octyldodecanol, and hexyldecanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polybutylene glycol. Examples thereof include monohydric alcohols.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.

  Examples of the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidonic acid and the like.

  Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, aralkyl alcohol, batyl alcohol, chimyl alcohol, carnervir alcohol, ceryl alcohol, coryranyl alcohol, myricyl alcohol, lacteryl alcohol, elayl Illustrative examples include zircyl alcohol, isostearyl glyceryl ether, octyl alcohol, triacontyl alcohol, ceralkyl alcohol, cetostearyl alcohol, oleyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, and octyl decanol.

  Examples of fatty acid esters include myristyl myristate, cetyl palmitate, cholesteryl stearate, beeswax fatty acid 2-octyldodecyl, and the like.

  Examples of the drug include salts of L-ascorbic acid and derivatives thereof, glycyrrhizic acid and derivatives thereof such as dicarylum glycyrrhizinate and monoammonium glycyrrhizinate, glycyrrhetinic acid and derivatives thereof such as stearyl glycyrrhetinate, allantoin, tranexamic acid and derivatives thereof And salts of alkoxysalicylic acid and its derivatives, glutathione and its derivatives, allantoin, azulene and the like.

The oil-in-water type or water-in-oil type emulsified sunscreen cosmetics of the present invention include milky products and creamy products. These products can be manufactured by a conventional method by mixing the above-described essential components and components usually blended in cosmetics.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a following example. In addition, all compounding quantities are shown by the mass%.

Prior to the examples, the test method and evaluation method used in the present invention will be described.

(Examples 1-18 and comparative examples)
Sunscreen cosmetic compositions were prepared according to the formulations shown in Tables 1 to 3 below. Examples 1 to 9 (Table 1) are oil-in-water emulsified types, and Examples 10 to 18 (Table 2) are water-in-oil emulsified types. In Table 3, Comparative Examples 1 and 7 are oil-in-water types, and Comparative Examples 2 to 6, 8, and 9 are water-in-oil emulsification types.

About the sunscreen cosmetics (samples) obtained in Examples 1 to 18 and Comparative Examples 1 to 9, sunscreen effect, dispersibility immediately after preparation, and stability (temperature stability, transport stability) by severe tests, respectively. Evaluation was performed according to the following evaluation criteria. In addition, 20 monitors were asked to use each cosmetic, and a questionnaire was conducted on five items, ie, spread / coating comfort, feeling of roughness, white residue, stickiness, and moist feeling, and the feeling of use was evaluated from the results. The results are shown in Tables 1 to 3, respectively.

[Sunscreen effect]
The SPF value of each sample was measured according to the “SPF measurement method standard” (established in 2000) formulated by the Japan Cosmetic Industry Association.
(Evaluation criteria)
A: SPF value of 50 or more and / or PA ++
○: SPF value of 30 or more and less than 50 and / or PA ++
Δ: SPF value of 20 or more and less than 30 and / or PA +
X: SPF value less than 20

[Dispersibility immediately after production]
After each sample was prepared, a part of the preparation was taken on a slide glass, and the dispersion of the powder was observed visually and with a microscope.
(Evaluation criteria)
A: Good. No agglomeration of powder is observed. ○: Slightly good. Aggregates of powder less than 1 mm are observed Δ: Slightly inferior A powder aggregate of 1 to 2 mm is observed. X: Inferior. Aggregates of powder of 2 mm or more are observed

[Stability by severe test]
(1) Temperature stability Each sample is filled in a glass bottle and a plastic container and stored for 1 month under the temperature conditions of 0 ° C, 25 ° C, 40 ° C and 50 ° C. Odor, sedimentation aggregation of powder, specific gravity, viscosity, emulsified state) and redispersibility of the powder after shaking (number of shaking necessary for dispersion, dispersibility, specific gravity, viscosity) were observed.

(2) Rolling stability Each sample is filled in a screw tube, and a rolling tester performs a rolling test for 5 hours at a speed of 30 rotations / minute, and the degree of change of each sample (presence of discoloration, smell, Sedimentation aggregation of powder, specific gravity, viscosity, emulsified state) and redispersibility of powder after rolling test (number of shaking necessary for dispersion, dispersibility, specific gravity, viscosity) were observed.
(Evaluation criteria)
(I) Degree of change in preparation ◎: Good. ○ in a state almost the same as that at the time of manufacture: slightly good. Discoloration / odor change, sedimentation and aggregation of powder, change in specific gravity, change in viscosity, and separation of sample are slightly observed. Δ: Slightly inferior. Discoloration / odor change, sedimentation and aggregation of powder, change in specific gravity, change in viscosity, and separation of sample are clearly observed x: Inferior. Discoloration / odor change, powder sedimentation aggregation, specific gravity change, viscosity change, and sample separation are remarkably observed.

(Ii) Redispersibility of powder after shaking A: Good. It quickly recovers to almost the same state as at the time of manufacture. ○: Slightly good. Although the number of times of shaking is required, it recovers to a state close to that at the time of manufacture. When the number of shaking is increased, recovery is performed, but it is slightly worse than the state at the time of manufacture. Regardless of the number of shakes, no recovery was observed, and the redispersibility of the powder was extremely poor.

[Usage feeling]
Based on the results of the questionnaire, the following five criteria (elongation / coating comfort, rough feeling, white residue, stickiness, moist feeling) were evaluated.
(Evaluation criteria)
◎: Among 20 people, 15 or more responded as good. ○: Among 20 people, 10-14 answered as good. △: Among 20 people, 5-9 answered good. ×: Among 20 people. Less than 4 responded good

[Cleanability]
Each monitor evaluated the detergency of each sample using a cleansing agent 6 hours after application to the skin.
(Evaluation criteria)
◎: Among 20 people, 15 or more responded that the detergency was good. ○: Among 20 people, 10-14 replied that the detergency was good. △: Among 20 people, 5-9 were good detergency. ×: Less than 4 out of 20 responded that the cleanability was good

(* 1) Hydrophobized zinc oxide: Zinc oxide treated with methylhydrogenpolysiloxane “SS-Activox
C80 ”; Showa Denko Co., Ltd. (* 2) Hydrophobized titanium dioxide: Aluminum stearate-treated titanium dioxide“ MT-014 ”; Teika Co., Ltd. (* 3) Polyoxyethylene methyl polysiloxane co-polymer Combined: PEG-11 methyl ether dimethicone (“KF-6011”, HLB value = 14.5; manufactured by Shin-Etsu Chemical Co., Ltd. (* 4) Glyceryl monostearate: “Nikkor MGS-ASEV”, HLB value = 6.0; Nikko Chemicals Co., Ltd. (* 5) alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer:
Lauryl PEG-9 polydimethylsiloxyethyl dimethicone “KF-6038”, HLB value = 3.0; manufactured by Shin-Etsu Chemical Co., Ltd. (* 6) polyglyceryl-2 diisostearate: “Saracos 42V”; Nisshin Oilio Co., Ltd. (* 7) Dimethylpolysiloxane: "SH200cs-5cs"; manufactured by Toray Dow Corning Silicone Co., Ltd.

As is apparent from the results of Tables 1 to 3, the oil-in-water type or water-in-oil type emulsion sunscreen cosmetics of the present invention containing the components (a) to (d) are compared with the cosmetics of Comparative Examples, The dispersibility and stability were significantly superior, and accordingly, the sunscreen effect and usability were excellent.

The cosmetic of the present invention had good skin spread, no squeaky or rough feeling at the time of use, a smooth feel, no stickiness, and excellent usability. Furthermore, there was no white residue on the skin, the cosmetic finish was excellent, and the washability after use was also excellent.

These effects are unique effects obtained by using isodecyl neopentanoate as the ester oil, as can be seen from the comparison between Examples and Comparative Examples.

Below, the other prescription example of this invention is shown.
[Example 19] Oil-in-water emulsified sunscreen cosmetic (cream type)]
(Compounding ingredients) (mass%)
(Water phase)
(1) 1,3-butylene glycol 7.0
(2) Zinc oxide 5.0
Product name: “Nanofine-K-LP”; manufactured by Sakai Chemical Co., Ltd. (3) disodium edetate 0.05
(4) Triethanolamine 1.0
(5) 2,2′-methylenebis [6- (2H-benzotriazol-2-yl)
-(1,1,3,3-tetramethylbutyl) phenol]
Product name: “Tinosorb M”; Ciba Specialty Chemicals 3.0
(6) Ion exchange water Residue (oil phase)
(7) 4-Methylbenzylidene camphor 2.0
Product name: “NEO HELIOPAN MBC”; manufactured by Simrise (8) Octyl salicylate 3.0
Product name: “NEO HELIOPAN OS”; manufactured by Simrise (9) Isodecyl neopentanoate 10.0
(10) Decamethylcyclopentasiloxane 10.0
(11) Vaseline 5.0
(12) Stearyl alcohol 3.0
(13) Stearic acid 3.0
(14) Glyceryl monostearate 3.0
(15) Polyethyl acrylate 1.0
(16) Glutathione appropriate amount (17) Paraben appropriate amount (18) Fragrance appropriate amount

(Manufacturing method)
The oil phase part and the water phase part are each heated to 70 ° C. and dissolved. In the water phase part, the titanium dioxide is sufficiently dispersed, and the oil phase part is added and emulsified using a homogenizer. The emulsion was cooled using a heat exchanger. The obtained oil-in-water emulsified sunscreen cosmetics had no squeaky or rough feeling at the time of use, and also had a smooth feel, non-stickiness and excellent use feeling. Furthermore, there was no white residue on the skin, and the cosmetic finish was excellent. Furthermore, it was excellent in cleanability after use. The SPF measurement described above also showed SPF value of 22, and PA + value.

[Example 20 Oil-in-water type emulsion sunscreen cosmetic (milky lotion type)]
(Mixed component) (mass%)
(Water phase)
(1) Dipropylene glycol 6.0
(2) Ethanol 3.0
(3) Hydroxyethyl cellulose 0.3
(4) Phenylbenzimidazolesulfonic acid 1.5
Product name: “NEO HELIOPAN HYDRO”; manufactured by Simrise (5) Benzylidene camphor sulfonic acid 1.5
Product name: “Mexoryl SL”; manufactured by Chimex (6) Zinc oxide 3.0
Product name: “Zinc Oxide neutral”, particle size 40 nm, manufactured by Symrise (7) Titanium dioxide 3.0
Product name: “STR-100C”; manufactured by Sakai Chemical Co., Ltd.
(8) Residual ion exchange water (oil phase)
(9) Isodecyl neopentanoate 4.0
(10) 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy]
Phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine 0.5
Product name: “Tinosorb S”; Ciba Specialty Chemicals (Ciba)
(11) Ethylhexyl methoxycinnamate 2.0 manufactured by Specialty Chemicals)
Product name: “Parsol MCX”; (12) 4-tert-butyl-4′-methoxybenzoylmethane manufactured by Hoffmann-La-Roche, Inc. 1.0
Product name: “Palsol 1789”; Hoffmann-La-Roche (13) Benzophenone-3 1.0
Product name: “Uvinul M40”; BASF (14) oleyl oleate 5.0
(15) Dimethylpolysiloxane (6 mPa · s) 3.0
Product name: “KF-96A-6”; Shin-Etsu Chemical Co., Ltd. (16) Vaseline 0.5
(17) Cetyl alcohol 1.0
(18) Sorbitan sesquioleate
0.8
(19) Tocopherol appropriate amount (20) perfume appropriate amount (production method)
The oil phase part and the water phase part are heated to 70 ° C. and dissolved. In the water phase part, the titanium dioxide is sufficiently dispersed, and the oil phase part is added and emulsified using a homogenizer. The emulsion was cooled using a heat exchanger.

The obtained oil-in-water emulsified sunscreen cosmetics had no squeaky or rough feeling at the time of use, and also had a smooth feel, non-stickiness and excellent use feeling. Furthermore, there was no white residue on the skin, and the cosmetic finish was excellent. Furthermore, it was excellent in cleanability after use. The SPF measurement described above also showed an SPF value of 25 and a value of PA ++.

[Example 21: Water-in-oil type emulsion sunscreen cosmetic (cream type)]
(Mixed component) (mass%)
(Water phase)
(1) 1,3-butylene glycol 5.0
(2) Residual ion exchange water (oil phase)
(3) Isodecyl neopentanoate 15.0
(4) Octocrylene 5.0
Product name: “NEO HELIOPAN 303”; manufactured by Simrise (5) Butylmethoxydibenzoylmethane 3.0
Product name: “NEO HELIOPAN”; manufactured by Simrise (6) 3- (4′-methylbenzylidene) -dl-camphor 3.0
Product name: “Eusolex 6300”; Merck (7) Hydrophobic treatment (alumina / fatty acid soap treatment) Titanium dioxide 3.0
Product name: “TTO-S-4”; manufactured by Ishihara Sangyo Co., Ltd. (8) Glycerin diisostearate 3.0
(9) Organically modified montmorillonite 1.5
(10) Decamethylcyclopentasiloxane 10.0
(11) Paraben proper amount (12) Fragrance proper amount (Manufacturing method)
The oil phase part and the water phase part are each heated to 70 ° C. and dissolved. In the oil phase part, the aqueous phase part is added while sufficiently dispersing titanium dioxide and performing a homogenizer treatment.

The obtained water-in-oil emulsified sunscreen cosmetics had no squeaky or rough feeling at the time of use, had a smooth feel, was not sticky, and had excellent use feeling. Furthermore, there was no white residue on the skin, and the cosmetic finish was excellent. Furthermore, it was excellent in cleanability after use. The SPF measurement described above also showed an SPF value of 40 and a PA ++ value.

[Example 22: Water-in-oil type emulsion sunscreen cosmetic (cream type)]
(Mixed component) (mass%)
(Water phase)
(1) 1,3-butylene glycol 2.0
(2) Glycerin 2.0
(3) Residual ion exchange water (oil phase)
(4) Isodecyl neopentanoate 23.0
(5) Isoamyl-p-methoxycinnamate 2.0
Product name: “NEO HELIOPAN E1000”; manufactured by Simrise (6) 2,4-bis-{[4- (2-ethylhexyloxy) -2-
Hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-
Triazine 3.0
Product name: “Tinosorb S”; Ciba Specialty Chemicals
(Made by Specialty Chemicals)
(7) 3- (4′-Methylbenzylidene) -dl-camphor 3.0
Product name: “Eusolex 6300” (Merck)
(8) Hydrophobic treatment (fatty acid soap treatment) Titanium dioxide 3.0
Product name: “MT-014”; manufactured by Teika Co., Ltd. (9) PEG-9 Polydimethylsiloxyethyl dimethicone 3.0
Product name: “KF-6028”; manufactured by Shin-Etsu Chemical Co., Ltd.)
(10) Dimethicone / (Dimethicone / polyglycerin-3) crosspolymer 1.5
Product name: “KSG-710”; manufactured by Shin-Etsu Chemical Co., Ltd. (11) Decamethylcyclopentasiloxane 5.0
(12) Dimethylpolysiloxane 5.0
(13) Paraben proper amount (14) Fragrance proper amount (Manufacturing method)
The oil phase part and the water phase part are each heated to 70 ° C. and dissolved. In the oil phase part, the aqueous phase part is added while sufficiently dispersing titanium dioxide and performing a homogenizer treatment.

The obtained water-in-oil emulsified sunscreen cosmetics had no squeaky or rough feeling at the time of use, had a smooth feel, was not sticky, and had excellent use feeling. Furthermore, there was no white residue on the skin, and the cosmetic finish was excellent. Furthermore, it was excellent in cleanability after use. The SPF measurement described above also showed an SPF value of 50 and a PA ++ value.

[Example 23: Water-in-oil emulsified sunscreen cosmetic (emulsion type)]
(Mixed component)
(mass%)
(Water phase)
(1) 1,3-butylene glycol 5.0
(2) Dipropylene glycol 2.0
(3) Residual ion exchange water (oil phase)
(4) Isodecyl neopentanoate 4.0
(5) Etocrylene 5.0
Product name: “Uvinul N35”; BASF (6) ethylhexyl methoxycinnamate 5.0
Product name: “NEO HELIOPAN AV” (Symrise)
(7) 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl)
Propane-1,3-dione 5.0
Product name: “Eusolex 9020” (Merck)
(8) Hydrophobic treatment (dimethicone treatment) zinc oxide 5.0
Product name: “MT-FINEX-50LP”; manufactured by Sakai Chemical Co., Ltd. (9) Hydrophobized (alumina / dimethicone) titanium dioxide 2.0
Product name: “SAS-015”; (10) PEG-3 dimethicone 1.0 manufactured by Miyoshi Kasei Co., Ltd.
Product name: “KF-6015”; manufactured by Shin-Etsu Chemical Co., Ltd. (11) PEG-11 methyl ether dimethicone 2.5
Product name: “KF-6018”; manufactured by Shin-Etsu Chemical Co., Ltd. (12) Decamethylcyclopentasiloxane 2.0
(13) Dimethylpolysiloxane 2.0
(14) Paraben proper amount (15) Fragrance proper amount (Manufacturing method)
The oil phase part and the water phase part are each heated to 70 ° C. and dissolved. In the oil phase part, the aqueous phase part is added while sufficiently dispersing titanium dioxide and performing a homogenizer treatment.

The obtained water-in-oil emulsified sunscreen cosmetics had no squeaky or rough feeling at the time of use, had a smooth feel, was not sticky, and had excellent use feeling. Furthermore, there was no white residue on the skin, and the cosmetic finish was excellent. Furthermore, it was excellent in cleanability after use. The SPF measurement described above also showed an SPF value of 40 and a PA ++ value.

Example 24. Oil-in-water emulsified skin cosmetic (cream type)
(Compounding ingredients)
(Water phase)
(1) Dipropylene glycol 5.0
(2) Glycerin 2.0
(3) Zinc oxide 5.0
Product name: “Nanofine-K-LP”; manufactured by Sakai Chemical Co., Ltd. (4) Disodium edetate 0.05
(5) Triethanolamine 1.0
(6) 2,2′-methylenebis [6- (2H-benzotriazol-2-yl)
-(1,1,3,3-tetramethylbutyl) phenol] 1.0
Product name: “Tinosorb M”; Ciba Specialty Chemicals (7) Ion-exchanged water Residual (8) Green tea extract 0.1

(Oil phase)
(8) 4-Methylbenzylidene camphor 2.0
Product name: “NEO HELIOPAN MBC”; manufactured by Simrise (9) Octyl salicylate 3.0
Product name: “NEO HELIOPAN OS”; manufactured by Simrise (10) Isodecyl neopentanoate 8.0
(11) Dimethicone 1.5 mPa · s 5.0
(12) α-olefin oligomer 3.0
(13) Behenyl alcohol 1.0
(14) Stearyl alcohol 0.5
(15) Glyceryl monostearate 3.0
(16) PEG-40 stearate 0.5
(17) (Dimethylacrylamide / acryloyldimethyltaurine sodium)
Cross polymer 0.5
(18) Paraben appropriate amount (18) Perfume appropriate amount

(Manufacturing method)
The oil phase part and the water phase part are each heated to 70 ° C. and dissolved. In the water phase part, the titanium dioxide is sufficiently dispersed, and the oil phase part is added and emulsified using a homogenizer. The emulsion was cooled using a heat exchanger. The obtained oil-in-water emulsified sunscreen cosmetics were free from squeaks and roughness during use, had a smooth feel, were not sticky, and were excellent in use feeling. Furthermore, there was no white residue on the skin, and the cosmetic finish was excellent. Furthermore, it was excellent in cleanability after use. Moreover, SPF value 20 and the value of PA + were shown by SPF measurement mentioned above.

Claims (9)

(A) isodecyl neopentanoate, (b) an ultraviolet absorber, (c) an ultraviolet scattering agent,
(D) Oil-in-water type or water-in-oil type emulsion sunscreen cosmetics containing silicone oil.
(B) component is a para-aminobenzoic acid derivative, salicylic acid derivative, cinnamic acid derivative, β, β-diphenyl acrylate derivative, benzophenone derivative, benzylidene camphor derivative, phenylbenzimidazole derivative, triazine derivative, phenylbenzotriazole derivative, The sunscreen cosmetic according to claim 1, wherein the sunscreen cosmetic is one or more selected from anthranyl derivatives, imidazoline derivatives, benzalmalonate derivatives, and 4,4-diarylbutadiene derivatives.
The sunscreen cosmetic according to claim 1 or 2, wherein the component (c) is zinc oxide and / or titanium dioxide.
The sunscreen cosmetic according to claim 3, wherein the average primary particle diameter of zinc oxide is 5 to 40 nm.
The sunscreen cosmetic according to claim 3, wherein the average primary particle diameter of titanium dioxide is 5 to 30 nm.
In the total amount of the cosmetic, (a) component is 1 to 60 mass%, (b) component is 3 to 20 mass%, (c) component is 0.5 to 50 mass%, and (d) component is 1 to 70 mass%. % Sunscreen cosmetics according to any one of claims 1 to 5.
Furthermore, the sunscreen cosmetics in any one of Claims 1-6 containing 1 type (s) or 2 or more types chosen from (e) silicone type surfactant, glycerol, or polyglycerol fatty acid ester.
(E) A silicone surfactant as a component is a poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, a polyoxyethylenemethylpolysiloxane copolymer, a silicone chain-branched methylpolysiloxane copolymer, an alkyl Chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer, cross-linked polyoxyethylene methyl polysiloxane, alkyl group-containing cross-linked polyoxyethylene methyl polysiloxane, branched polyglycerin-modified silicone, cross-linked polyglycerin-modified silicone The sunscreen cosmetic according to claim 7, which is one or more selected from alkyl group-containing crosslinked polyglycerin-modified silicone and alkyl group-branched polyglycerin-modified silicone.
The sunscreen cosmetic according to claim 7 or 8, comprising 0.1 to 10% by mass of the component (e) in the total amount of the cosmetic.