JP2009091307A - Ultraviolet-absorbing powder and cosmetic comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet-absorbing powder which can be compounded in a cosmetic in any amount, has excellent ultraviolet ray absorbability and further exhibits good sense of use in a state of high safety and high stability, and to provide a cosmetic formulated therewith. <P>SOLUTION: The ultraviolet-absorbing powder comprises spherical polymer particles and, included therein, a slightly soluble ultraviolet absorber having solubility in decamethylcyclopentasiloxane of ≤0.1 g/g of decamethylcyclopentasiloxane at 0°C. The cosmetic comprises the ultraviolet-absorbing powder. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ultraviolet absorbing powder characterized in that a slightly soluble ultraviolet absorber is encapsulated in a spherical polymer powder, and a cosmetic containing the same.

  The sun rays that reach the surface of the earth contain about 6% of ultraviolet rays of about 290 to 400 nm in all wavelengths, which are considered to cause great damage to human skin. Further, among the ultraviolet rays reaching the ground surface, the wavelength region of 290 to 320 nm is classified as UV-B, and the wavelength region of 320 to 400 nm is classified as UV-A. UV-B mainly causes an acute reaction and causes sunburn, aging and skin cancer, and UV-A causes a chronic reaction and causes suntan and skin aging.

  In such a situation, development of ultraviolet protection materials is actively performed in order to reduce the influence of ultraviolet rays. Examples of the material using the ultraviolet scattering effect include inorganic oxides having a high refractive index such as titanium dioxide and zinc oxide. In addition, examples of materials using ultraviolet absorption include organic substances such as benzophenone derivatives and paraaminobenzoic acid derivatives.

  Titanium dioxide, zinc oxide and the like using the ultraviolet light scattering effect are blended in many sunscreen preparations because of their relatively high light stability and high safety to the human body. However, when blended in a large amount, the whiteness due to the application is conspicuous, and the feeling of use is further reduced.

  On the other hand, benzophenone derivatives and paraaminobenzoic acid derivatives utilizing ultraviolet absorption can effectively protect a specific wavelength region with a small amount. However, denaturation due to photodegradation is a problem.

  As one method for reducing the sensitization and improving the stability of an organic ultraviolet absorber, it has been proposed to disperse the organic ultraviolet absorber in the resin. For example, Patent Document 1 describes that a powdered product obtained from a core-shaped ultraviolet absorber-encapsulated non-film-forming vinyl resin emulsion having small pores inside is blended in a sunscreen cosmetic. .

  However, since the above powder has small pores, when a compatible oil component coexists when blended with a sunscreen, the UV absorber dispersed inside the resin elutes into the oil component, reducing skin irritation. There was concern that the effect would decrease.

  On the other hand, in Patent Document 2, a core material made of a (meth) acrylic resin and / or a styrene resin containing an organic ultraviolet absorber in order to suppress elution of the ultraviolet absorber from the powdered product. And a surface layer portion made of a (meth) acrylic resin and / or a styrene resin that does not contain an organic ultraviolet absorber.

  In this method, the effect of suppressing the elution of the ultraviolet absorber can be expected by using a double structure, but the problem of cost increase due to an increase in the number of manufacturing steps is great. Furthermore, when the oil component coexisting with the powdered product is compatible with the ultraviolet absorber, it is not possible to completely eliminate the concern that the oil component penetrates from the surface layer into the core material and the ultraviolet absorber is eluted out of the powder. .

  On the other hand, diethylaminohydroxybenzoylhexylbenzoate is described in Patent Document 3 and hydroxyphenyl-triazine is described in Patent Document 4 as a poorly soluble ultraviolet absorber for oils, and is blended in cosmetics.

JP 62-93220 A JP-A-7-291837 JP 2000-319628 A JP-A-9-188666

  As a result of intensive studies in view of the above-described background art, the present inventor has incorporated a sparingly soluble UV absorber into a cosmetic particle by encapsulating a sparingly soluble UV absorber in a cosmetic blended oil component in the polymer particles at the polymerization stage. It has been found that it can be contained in a large amount in the cosmetic, exhibits an excellent ultraviolet absorption effect in the cosmetic, and exhibits a good feeling of use in a highly safe and stable state.

  On the other hand, in cosmetic preparations, conventionally, a large amount of dissolved oil must be blended in order to sufficiently dissolve the hardly soluble ultraviolet absorber. Therefore, there is a problem that the range of preparation of the preparation is limited. However, by blending the ultraviolet absorbing powder according to the present invention into cosmetics, it has become possible to expand the range of cosmetic preparations.

  Furthermore, it is possible to prepare cosmetic preparations even with oils that are incompatible with poorly soluble UV absorbers, and as a result, it is possible to suppress elution of UV absorbers and achieve high safety and stability. As a result, the present invention has been completed.

  It is an object of the present invention to maintain an excellent feeling of use in a state of being superior in UV absorption characteristics and high in safety and stability as compared with a powder obtained by combining a conventional UV absorber and a resin, and further a cosmetic. An object of the present invention is to provide a UV-absorbing powder capable of expanding the range of preparation of a preparation and a cosmetic containing the same.

  That is, in the present invention, a spherical polymer particle encapsulates a hardly soluble ultraviolet absorber having a solubility of 0 g at 0 ° C. with respect to decamethylcyclopentasiloxane in an amount of 0.1 g / g or less per 1 g of decamethylcyclopentasiloxane. The present invention provides an ultraviolet absorbing powder characterized by the above.

  The present invention also provides the above ultraviolet absorbing powder, wherein the ultraviolet absorbing powder has an average particle size of 0.1 μm to 100 μm.

  Furthermore, the present invention provides the above ultraviolet absorbing powder, wherein the hardly soluble ultraviolet absorber is contained in an amount of 0.1 to 50% by mass based on the total amount of the ultraviolet absorbing powder.

  In addition, the present invention is characterized in that the spherical polymer particles are made of one or more resins selected from the group consisting of polystyrene resin, (meth) acrylic resin, nylon resin, silicone resin, and polyethylene resin. The above ultraviolet absorbing powder is provided.

  Furthermore, the present invention provides the above-mentioned ultraviolet absorbing powder, wherein the hardly soluble ultraviolet absorber is an amino-substituted hydroxybenzophenone derivative and / or a bis (resorcinyl) triazine derivative.

  Moreover, this invention provides the cosmetics characterized by mix | blending said ultraviolet-absorbing powder.

  Furthermore, this invention provides said cosmetics characterized by mix | blending said ultraviolet-absorbing powder 0.1-30 mass% with respect to cosmetics whole quantity.

  In the present invention, the cosmetic is an emulsified cosmetic or a solid cosmetic, and the content of an oil component that is soluble in the ultraviolet absorber blended in the cosmetic is based on the total amount of the cosmetic. The cosmetic is characterized by being 5% by mass or less.

  Furthermore, the present invention provides that the hardly soluble ultraviolet absorber is 2,4-bis-{[4- (2-ethylhexyloxy) -2hydroxy] phenyl} -6- (4-methoxyphenyl)-(1,3, 5) It provides a cosmetic as described above, which is triazine.

  The present invention also provides the cosmetic described above, wherein the hardly soluble ultraviolet absorber is 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester.

  According to the present invention, the powdered polymer particles can contain a large amount of an ultraviolet absorber that is sparingly soluble in the oil contained in the cosmetic. This ultraviolet absorbing powder exhibits an excellent ultraviolet absorber in cosmetics, and can maintain a good feeling of use in a highly safe and stable state. Moreover, even if it is a small amount in the cosmetic, it has an excellent ultraviolet absorption effect, so that the amount can be reduced to a level that does not whiten during application.

  In the conventional cosmetics, in order to sufficiently dissolve the poorly soluble ultraviolet absorber, a large amount of dissolved oil must be blended, and there is a problem that the range of preparation of the cosmetic preparation is limited. However, by blending the ultraviolet absorbing powder according to the present invention, it is possible to expand the range of cosmetic preparation preparation.

  When it is desired to add a poorly soluble ultraviolet absorber, it is possible to prepare a cosmetic preparation using an oil that is poorly compatible with the poorly soluble ultraviolet absorber. As a result, it is possible to provide a cosmetic that suppresses elution of the ultraviolet absorber and can realize high safety and stability.

  Hereinafter, this embodiment will be described in detail.

The hardly soluble ultraviolet absorber used in the present invention is one having a solubility in decamethylcyclopentasiloxane at 0 ° C. of 0.1 g / g or less per 1 g of decamethylcyclopentasiloxane.
Preferred are amino-substituted hydroxybenzophenone derivatives and / or bis (resorcinyl) triazine derivatives. For example, the following poorly soluble ultraviolet absorbers described in Patent Document 3 (Japanese Patent Laid-Open No. 2000-319628) can be preferably used.

〔式中、不定項目は互いに独立に以下の意味を有する：Ｒ¹及びＲ²は、水素原子、Ｃ₁〜Ｃ₂₀−アルキル、Ｃ₂〜Ｃ₁₀−アルケニル、Ｃ₃〜Ｃ₁₀−シクロアルキル、Ｃ₃〜Ｃ₁₀−シクロアルケニルであるが、この場合、置換基Ｒ¹及びＲ²は、これらと結合している窒素原子と一緒になって５員環又は６員環を形成していてもよく；Ｒ³及びＲ⁴は、Ｃ₁〜Ｃ₂₀−アルキル、Ｃ₂〜Ｃ₁₀−アルケニル、Ｃ₃〜Ｃ₁₀−シクロアルキル、Ｃ₃〜Ｃ₁₀−シクロアルケニル、Ｃ₁〜Ｃ₁₂−アルコキシ、Ｃ₁〜Ｃ₂₀−アルコキシカルボニル、Ｃ₁〜Ｃ₁₂−アルキルアミノ、Ｃ₁〜Ｃ₁₂−ジアルキルアミノ、アリール、ヘテロアリールであるが、ニトリル基、カルボキシレート基、スルホネート基又はアンモニウム基からなるグループから選択された水溶性する置換基で置換されていてもよく；Ｘは、水素原子、ＣＯＯＲ⁵、ＣＯＮＲ⁶Ｒ⁷であり；Ｒ⁵〜Ｒ⁷は、水素原子、Ｃ₁〜Ｃ₂₀−アルキル、Ｃ₂〜Ｃ₁₀−アルケニル、Ｃ₃〜Ｃ₁₀−シクロアルキル、Ｃ₃〜Ｃ₁₀−シクロアルケニル、−（Ｙ−Ｏ）_o−Ｚ、アリールであり；Ｙは、−（ＣＨ₂）₂−、−（ＣＨ₂）₃−、−（ＣＨ₂）₄−、−ＣＨ（ＣＨ₃）−ＣＨ₂−であり；Ｚは、−ＣＨ₂−ＣＨ₃、−ＣＨ₂−ＣＨ₂−ＣＨ₃、−ＣＨ₂−ＣＨ₂−ＣＨ₂−ＣＨ₃、−ＣＨ（ＣＨ₃）−ＣＨ₃であり；ｍは、０〜３であり；ｎは、０〜４であり；ｏは、１〜２０である〕

[Wherein the indefinite items have the following meanings independently of each other: R ¹ and R ² are a hydrogen atom, C ₁ -C ₂₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₃ -C ₁₀ -cycloalkyl; , C ₃ -C ₁₀ -cycloalkenyl, in which the substituents R ¹ and R ² together with the nitrogen atom bound thereto form a 5- or 6-membered ring. It is good; R ³ and R ^4, C ₁ ~C ₂₀ - alkyl, C ₂ ~C ₁₀ - alkenyl, C ₃ ~C ₁₀ - cycloalkyl, C ₃ ~C ₁₀ - cycloalkenyl, C ₁ ~C ₁₂ - alkoxy, C ₁ -C ₂₀ - alkoxycarbonyl, C ₁ -C ₁₂ - alkylamino, C ₁ -C ₁₂ - dialkylamino, aryl, and heteroaryl, nitrile group, a carboxylate group, a sulphonate group or an ammonium group Selected from the group May be substituted with a substituent of the water-soluble; X is a hydrogen atom, a ^{COOR 5, CONR 6 R 7;} R 5 ~R 7 is hydrogen atom, C ₁ -C ₂₀ - alkyl, C ₂ ~ C ₁₀ - alkenyl, C ₃ ~C ₁₀ - cycloalkyl, C ₃ ~C ₁₀ - _{cycloalkenyl, - (Y-O) o} -Z, aryl; Y _{is, - (CH 2) 2 -} , - ( CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH (CH ₃ ) —CH ₂ —; Z represents —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₃ , —CH _2. -CH ₂ -CH ₂ -CH _3, be _{-CH (CH 3) -CH 3;} m is an 0 to 3; n is an 0 to 4; o is 1 to 20]

式中、Ｒ₁およびＲ₂は互いに独立的にＣ₃−Ｃ₁₈アルキル、Ｃ₂−Ｃ₁₈アルケニル、式−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−Ｔ₁の基であるか；またはＲ₁およびＲ₂は式（４ａ）の基であり

〔式中、Ｒ₁₂は直接結合、直鎖または枝分かれＣ₁−Ｃ₄アルキレン基または式−Ｃ_m1Ｈ_2m1−または−Ｃ_m1Ｈ_2m1−Ｏ−の基であり；Ｒ₁₃、Ｒ₁₄およびＲ₁₅は互いに独立的にＣ₁−Ｃ₁₈アルキル、Ｃ₁−Ｃ₁₈アルコキシまたは次式の基であり

（式中、Ｒ₁₆はＣ₁−Ｃ₅アルキルであり；ｍ₁は１乃至４である）、ｐ₁は０または１乃至５の数である；Ａ₁は（１ｂ）、（１ｃ）または（１ｄ）の基である

〔式中、Ｒ₃は水素、Ｃ₁−Ｃ₁₀アルキル、−（ＣＨ₂ＣＨＲ₅−Ｏ）_n1−Ｒ₄または−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−Ｔ₁の基であり；Ｒ₄は水素、Ｍ、Ｃ₁−Ｃ₅アルキルまたは式

の基である（Ｒ₅は水素またメチルであり；Ｔ₁は水素またＣ₁−Ｃ₈アルキルであり；Ｑ₁はＣ₁−Ｃ₁₈アルキルであり；Ｍは金属陽イオンであり；ｍ₂は１乃至４であり；ｎ₁は１乃至１６である）〕。 Moreover, the following hardly soluble ultraviolet absorber described in patent document 4 (Unexamined-Japanese-Patent No. 9-188666) can be used preferably.

In which R ₁ and R ₂ are independently of each other a group of C ₃ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, formula —CH ₂ —CH (OH) —CH ₂ —OT ₁ ; Or R ₁ and R ₂ are groups of formula (4a)

[Wherein R ₁₂ is a direct bond, a linear or branched C ₁ -C ₄ alkylene group or a group of the formula —C _m1 H _2m1 — or —C _m1 H _2m1 —O—; R ₁₃ , R ₁₄ and R ₁₅ are independently of each other C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or a group of the formula

Wherein R ₁₆ is C ₁ -C ₅ alkyl; m ₁ is 1 to 4; p ₁ is 0 or a number from 1 to 5; A ₁ is (1b), (1c) or It is a group of (1d)

[Wherein R ₃ is hydrogen, C ₁ -C ₁₀ alkyl, — (CH ₂ CHR ₅ —O) _n1 —R ₄ or —CH ₂ —CH (OH) —CH ₂ —O—T ₁ . R ₄ is hydrogen, M, C ₁ -C ₅ alkyl or formula

(R ₅ is hydrogen or methyl; T ₁ is hydrogen or C ₁ -C ₈ alkyl; Q ₁ is C ₁ -C ₁₈ alkyl; M is a metal cation; m ₂ Is 1 to 4; n ₁ is 1 to 16)].

In the present invention, the solubility of decamethylcyclopentasiloxane at 0 ° C. is 0.1 g / g or less per 1 g of decamethylcyclopentasiloxane, and this is an oil component that can be blended in cosmetics. For example, the ultraviolet absorbent is not limited to the above-described ultraviolet absorbent, and the poorly soluble ultraviolet absorbent may be appropriately selected and included in the spherical polymer particles.
As a specific hardly soluble ultraviolet absorber, it is preferable to use an amino-substituted hydroxybenzophenone derivative and / or a bis (resorcinyl) triazine derivative. More specifically, 2,4-bis-{[4- (2-ethylhexyloxy) -2hydroxy] phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine and / or 2 -[4- (Diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester. The UV-absorbing powder containing these hardly soluble UV absorbers exhibits a very excellent UV-A absorption effect when blended in cosmetics.

  The method for producing the ultraviolet absorbing powder in which the hardly soluble ultraviolet absorber is encapsulated in the spherical polymer particles is not limited. Encapsulation is not a state in which a poorly soluble ultraviolet absorber is unevenly distributed on the surface of spherical polymer particles, but is uniformly dispersed in a polymer matrix, or a so-called core having a polymer as a shell and a poorly soluble ultraviolet absorber as a core. It means a shell structure.

As a method for producing a powder in which a poorly soluble ultraviolet absorber is encapsulated in a polymer, a method of encapsulating from a monomer by emulsion polymerization or suspension polymerization and pulverizing, and a powder encapsulated by kneading in a pre-synthesized polymer It is divided roughly into the method of making it.
As an embodiment of a method for producing from a monomer, an acrylic copolymer production method described in JP-A No. 2001-151626 can be mentioned. When suspension polymerization of (meth) acrylate monomer, ethyl acrylate monomer, and polyfunctional vinyl monomer mixture, the poorly soluble UV absorber to be encapsulated in the monomer is dissolved and polymerized to encapsulate the hardly soluble UV absorber. Spherical resin powder is obtained.
An organic ultraviolet absorber described in Patent Document 2 (Japanese Patent Laid-Open No. 7-291837) is preliminarily dissolved in a monomer that forms a (meth) acrylic resin or a styrene resin, and then dispersed in an aqueous medium for polymerization. A core part made of a (meth) acrylic resin or a styrene resin containing an organic ultraviolet absorber by performing a reaction and then adding an additional monomer to the aqueous medium for polymerization, and the core material By taking a structure having a (meth) acrylic resin or a surface layer made of a styrene resin that does not contain an organic ultraviolet absorber formed on the surface of the portion, the elution of the ultraviolet absorber can be suitably suppressed it can.
In addition to the above, there is no particular limitation as long as it is a method capable of producing spherical polymer particles capable of encapsulating a poorly soluble ultraviolet absorber, such as emulsion polymerization, soap-free polymerization, dispersion polymerization, and seed polymerization.
As a method of encapsulating from a monomer, a suspension polymerization method is preferable because the production cost is low and spherical particles of about 10 μm can be easily produced.
Further, as a uniform method for producing from a polymer, a resin composition in which fine particles made of a water-insoluble thermoplastic resin described in JP-A-2006-328208 are dispersed in a matrix made of a water-soluble material. A method of obtaining true spherical thermoplastic resin fine particles having high sphericity by cooling and solidifying under specific conditions and then washing with water is mentioned. In the above production method, it is possible to encapsulate by dispersing or dissolving an ultraviolet absorber in a water-insoluble thermoplastic resin, and in particular, a combination that undergoes phase separation during polymerization from monomers is dispersed by kneading. Can be included.

  The average particle diameter of the ultraviolet absorbing powder is preferably 0.1 μm to 100 μm. More preferably, it is 1-20 micrometers. If the average particle size is too small, the dispersibility in the preparation will deteriorate, and the UV protection ability cannot be exhibited effectively. Conversely, if the average particle size is too large, the UV absorbing powder will uniformly cover the skin. Will not be possible and UV protection will be reduced.

It is preferable that 0.1-50 mass% of a hardly soluble ultraviolet absorber is contained with respect to the total amount of the ultraviolet absorbing powder. More preferably, it is 1-30 mass%. If the blending amount of the poorly soluble UV absorber is too low, it is necessary to blend a large amount of powder in order to exert the UV protection ability. Conversely, if the blending amount of the sparingly soluble UV absorber is too high, Inclusion becomes difficult.
This content is adjusted by the mixing amount of the monomer and the ultraviolet absorber or the mixing amount of the polymer and the ultraviolet absorber in the polymerization system for producing the ultraviolet absorbing powder.

  The spherical polymer particles are preferably made of one or more resins selected from the group consisting of polystyrene resin, (meth) acrylic resin, nylon resin, silicone resin, and polyethylene resin. Particularly preferred are polystyrene resin and methacrylic resin.

  The above ultraviolet absorbing powder is preferably used in a cosmetic. The form which cosmetics can take is not specifically limited, For example, various forms, such as powder form, cream form, stick form, pencil form, liquid form, etc., can be taken. As products, it is possible to provide various cosmetics such as makeup foundation, foundation, white powder, blusher, lipstick, mascara, eye shadow, eyeliner, cream, milky lotion and lotion. These cosmetics can be produced by a known method using components that can be usually added to cosmetics together with the ultraviolet absorbing powder of the present invention.

  The blending amount of the ultraviolet absorbing powder in the cosmetic can be freely selected depending on various uses, dosage forms, and product forms of the cosmetic. Usually, it is possible to make it contain in the range of about 0.1-30 mass% with respect to a composition. Preferably, it is 1-15 mass% with respect to cosmetics whole quantity. If the blending amount is too low, ultraviolet rays cannot be effectively protected. Conversely, if the blending amount is too high, other blending components in the preparation are limited.

The cosmetic of the present invention is preferably an emulsified cosmetic or a solid cosmetic. Solid cosmetics include lipstick, mascara, eye shadow, solid foundation and the like. Furthermore, it is preferable that content of the oil component which has solubility with respect to the ultraviolet absorber mix | blended in the said cosmetics is 5 mass% or less with respect to cosmetics whole quantity.
UV absorbers are often used in sunscreen preparations, but sunscreen preparations currently contain a large amount of silicone oil to improve water resistance and sebum resistance. However, since most of the UV absorbers are hydrocarbon-based and have a lot of oil with high polarity, in order to ensure solubility, the oil component that dissolves the UV absorber at the expense of water resistance and sebum resistance. In many cases, it was added.
However, as in the present invention, a slightly soluble ultraviolet absorber is encapsulated in a polymer to form a spherical powder, so that it becomes possible to highly blend a poorly soluble ultraviolet absorber without adding a soluble oil component. It is possible to provide a sunscreen formulation that is excellent in sebum and smooth to use.

  In many cases, such as solid foundations and funnels, the oil content in the preparation is 10% by mass or less, and the blending of the oil component that dissolves the poorly soluble ultraviolet absorber is also limited. However, by simply replacing the ultraviolet absorbing powder of the present invention with a conventionally blended spherical powder, a high ultraviolet absorbing effect can be realized without a decrease in usability.

  In addition to the above-mentioned essential components, the cosmetics of the present invention are other components usually used in cosmetics, such as oils (liquid fats, solid fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils). ), Powder component, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water-soluble polymer, thickener, film agent, ultraviolet absorber, sequestering agent, Lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant auxiliaries, fragrances, water, etc. are appropriately blended as necessary, It can be produced by a conventional method according to the intended dosage form.

The oil component that can be blended in the cosmetic of the present invention is not limited. For example, vegetable oils such as olive oil and castor oil; waxes such as beeswax, candelilla wax and tree wax; hydrocarbons such as liquid paraffin, squalane, petrolatum and paraffin wax; higher alcohols such as cetanol, stearyl alcohol and behenyl alcohol; dimethicone, Silicone oils such as phenylmethicone, alkylmethicone, cyclomethicone; fluorinated oils such as perfluoropolyether, perfluorodecalin, perfluorooctane; ester oils such as long chain fatty acid esters, dicarboxylic acid diesters, glycerin fatty acid esters, triglycerides; Lanolin and the like can be mentioned.
In consideration of compatibility with the hardly soluble ultraviolet absorber, the effects of the present invention are preferably exhibited when blending silicone oil, fluorine-based oil, low-polarity oil, or the like.

  The present invention will be described more specifically with reference to examples. The present invention is not limited only to the following examples.

"Example 1"
1% by weight of partially saponified PVA aqueous solution (degree of saponification 87.3%) 100 parts by weight 2.25 parts by weight of styrene 0.25 parts by weight divinylbenzene 0.05 parts by weight 2-2′azobisisobutyronitrile 2,4-bis-{[4- (2-ethylhexyloxy) -2hydroxy] phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine (trade name Tinosorb S, manufactured by Ciba Geigy ) 0.5 part by weight was dissolved with a homomixer (trade name: TK homomixer, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 3000 r.p. p. m for 2 minutes. This was transferred to a flask, bubbled with argon gas for 30 minutes, stirred at 250 rpm, reacted at 80 ° C. for 6 hours, and then completed polymerization at 90 ° C. for 1 hour. After centrifuging the mixed solution, decantation was repeated, and the separated powder was vacuum-dried at 50 ° C. for 12 hours and pulverized in an agate mortar to obtain an ultraviolet absorbing powder.

"Example 2"
1% by weight of partially saponified PVA aqueous solution (degree of saponification 87.3%) 100 parts by weight 2.25 parts by weight of styrene 0.25 parts by weight divinylbenzene 0.05 parts by weight 2-2′azobisisobutyronitrile , 2- [4- (Diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester (trade name ubinal A +, manufactured by BASF) 0.75 parts by weight of a homomixer (trade name TK homomixer, special machine) Kogyo Co., Ltd.) p. m for 2 minutes. This was transferred to a flask, bubbled with argon gas for 30 minutes, stirred at 250 rpm, reacted at 80 ° C. for 6 hours, and then completed polymerization at 90 ° C. for 1 hour. After centrifuging the mixed solution, decantation was repeated, and the separated powder was vacuum-dried at 50 ° C. for 12 hours and pulverized in an agate mortar to obtain an ultraviolet absorbing powder.

"Comparative Example 1"
1% by weight of partially saponified PVA aqueous solution (degree of saponification 87.3%) 100 parts by weight 2.25 parts by weight of styrene 0.25 parts by weight divinylbenzene 0.05 parts by weight 2-2′azobisisobutyronitrile Was dissolved with a homomixer (trade name: TK homomixer, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 3000 r.p. p. m for 2 minutes. This was transferred to a flask, bubbled with argon gas for 30 minutes, stirred at 250 rpm, reacted at 80 ° C. for 6 hours, and then completed polymerization at 90 ° C. for 1 hour. After centrifuging the mixture, decantation was repeated, and the separated powder was vacuum-dried at 50 ° C. for 12 hours and pulverized in an agate mortar to obtain polystyrene powder.

"Test Example 1 Transparency and UV protection effect"
The transmittance of the above ultraviolet absorbing powder was measured by the following method to evaluate the transparency in the visible region and the ultraviolet protective effect.
That is, 2 parts by weight of powder was sufficiently pulverized and dispersed with 3 rollers in 3 parts by weight of silicone oil, and the obtained dispersion was further diluted with silicone oil to a powder concentration of 5% by weight. This dispersion was applied to quartz glass with a film thickness of 10 μm and dried at room temperature for 30 minutes. About the formed coating film, the transmittance | permeability of 280-800 nm was measured with the spectrophotometer, and the following reference | standard evaluated.

<Evaluation criteria for transparency in the visible range>
◎: Transmittance at 450 nm is 90% or more ○: Transmittance at 450 nm is 85% or more and less than 90% Δ: Transmittance at 450 nm is 80% or more and less than 85% X: Transmittance at 450 nm is less than 80%

<Evaluation criteria for UV protection effect>
UV-A protective property ◎: Transmittance at 360 nm is less than 50% ○: Transmittance at 360 nm is 50% or more and less than 75% Δ: Transmittance at 360 nm is 75% or more and less than 90% X: Transmittance at 360 nm The transmittance is 90% or more and the UV-B protective property ◎: The transmittance at 280 nm is less than 50% ○: The transmittance at 280 nm is 50% or more and less than 75% Δ: The transmittance at 280 nm is 75% or more and less than 90% × : The transmittance at 280 nm is 90% or more.

  Examples of cosmetics containing ultraviolet absorbing powder are shown below.

Example 3: W / O type emulsion type sunscreen oil phase part (1) Silicone oil 29.0% by mass
(2) Octyl methoxycinnamate 5.0
(3) 4-tertbutyl-4′methoxybenzoylmethane 1.0
(4) Oxybenzone 3.0
(5) Glycerin diisostearate 2.0
(6) Organically modified montmorillonite 0.5
(7) Preservative appropriate amount (8) perfume appropriate amount powder part (9) silicone-treated zinc oxide 10.0
(10) UV-absorbing powder of Example 1 15.0
Aqueous phase (11) Purified water 28.5
(12) 1,3-butylene glycol 5.0
(Manufacturing method)
The oil phase part and the water phase part are heated to 70 ° C. and dissolved. After adding the powder part to the oil phase part and dispersing with a homomixer, the aqueous phase heated to 70 ° C. is gradually added to the oil phase in which the powder is dispersed while stirring with a homomixer and emulsified. A W / O type emulsion type sunscreen was obtained.

  The W / O type emulsion type sunscreen obtained in Example 3 showed a smooth feeling of use and a high UV protection effect.

Comparative Example 2: W / O type emulsion type sunscreen oil phase part (1) Silicone oil 29.0% by mass
(2) Octyl methoxycinnamate 5.0
(3) 4-tertbutyl-4′methoxybenzoylmethane 1.0
(4) Oxybenzone 3.0
(5) Glycerin diisostearate 2.0
(6) Organically modified montmorillonite 0.5
(7) Preservative Appropriate amount (8) Fragrance Appropriate amount (9) Slightly soluble ultraviolet absorber used in Example 1 (Tinosorb S)
2.5
Powder part (10) Silicone-treated zinc oxide 10.0
(11) Spherical powder 12.5
Aqueous phase (12) Purified water 28.5
(13) 1,3-butylene glycol 5.0
(Manufacturing method)
The oil phase part and the water phase part are heated to 70 ° C. and dissolved. After adding the powder part to the oil phase part and dispersing with a homomixer, the aqueous phase heated to 70 ° C. is gradually added to the oil phase in which the powder is dispersed while stirring with a homomixer and emulsified. A W / O type emulsion type sunscreen was obtained.

  The W / O type emulsion type sunscreen obtained in Comparative Example 2 was found to be rough due to the poorly soluble UV absorber, and felt rough during use.

Example 4: Solid-use foundation powder part (1) Silicone-treated talc 15.50% by mass
(2) Silicone-treated mica 40.0
(3) Silicone-treated titanium dioxide 15.0
(4) Silicone-treated ultrafine titanium dioxide 5.0
(5) Silicone-treated Bengala 1.0
(6) Silicone-treated yellow iron oxide 3.0
(7) Silicone-treated black iron oxide 0.2
(8) Zinc stearate 0.1
(9) UV absorbing powder of Example 2 5.0
(10) Ethylparaben Appropriate amount of oil phase (11) Squalane 4.0
(12) Solid paraffin 0.5
(13) Dimethylpolysiloxane 4.0
(14) Glycerin triisooctanoate 5.0
(15) Octyl methoxycinnamate 1.0
(16) Antioxidant (Vitamin E) Appropriate amount (17) Fragrance Appropriate amount (Manufacturing method)
(1) to (7) are pulverized and mixed with a pulverizer, and the remaining powder parts (8) to (10) are added and mixed well. The oil phase components (11) to (17) were uniformly blended into the powder part, and then pulverized and mixed with a pulverizer. Furthermore, it compression-molded to the inside plate through the sieve, and obtained the target solid-use combination foundation.

  The solid amphibious foundation obtained in Example 4 showed smooth usability and high UV protection effect.

Comparative Example 3: Solid amphibious foundation powder part (1) Silicone-treated talc 15.50% by mass
(2) Silicone-treated mica 40.0
(3) Silicone-treated titanium dioxide 15.0
(4) Silicone-treated ultrafine titanium dioxide 5.0
(5) Silicone-treated Bengala 1.0
(6) Silicone-treated yellow iron oxide 3.0
(7) Silicone-treated black iron oxide 0.2
(8) Zinc stearate 0.1
(9) Spherical resin powder 3.85
(10) Ethylparaben proper amount oil phase part (11) solid paraffin 0.5
(12) Squalane 4.0
(13) Trimethylolpropane triisostearate 4.0
(14) Glycerin triisooctanoate 5.0
(15) Octyl methoxycinnamate 1.0
(16) Slightly soluble UV absorber (Ubinal A +) used in Example 2
1.15
(17) Antioxidant (Vitamin E) Appropriate amount (18) Fragrance Appropriate amount (Manufacturing method)
(1) to (7) are pulverized and mixed with a pulverizer, and the remaining powder parts (8) to (10) are added and mixed well. The oil phase components (11) to (18) were uniformly blended into the powder part, and then pulverized and mixed with a pulverizer. Furthermore, it compression-molded to the inside plate through the sieve, and obtained the target solid-use combination foundation.

  Although the solid amphibious foundation obtained by Comparative Example 3 showed a high UV protection effect, it deteriorated over time when applied to the skin with a decrease in usability due to the oil used to dissolve the poorly soluble UV absorber. The makeup collapse was seen.

Example 5: Solid white powder powder part (1) Talc 48.0
(2) Sericite 15.0
(3) Kaolin 10.0
(4) Titanium dioxide 5.0
(5) Zinc myristate 5.0
(6) Magnesium carbonate 5.0
(7) UV absorbing powder of Example 2 5.0
(8) Coloring pigment Appropriate amount of oil phase (9) Squalane 3.0
(10) Glycerin triisooctanoate 2.0
Others (11) Preservatives and antioxidants Appropriate amount (12) Fragrance Appropriate amount
Mix talc and colored pigment in a blender. Add the remaining powder to this, mix well, add oil and preservatives, adjust the color, spray fragrance, and mix evenly. After this is pulverized by a pulverizer, it is compression molded into an intermediate dish.

  The white powder obtained in Example 5 showed smooth usability and UV protection effect.

Comparative Example 4: Solid white powder powder part (1) Talc 48.0
(2) Sericite 15.0
(3) Kaolin 10.0
(4) Titanium dioxide 5.0
(5) Zinc myristate 5.0
(6) Magnesium carbonate 5.0
(7) Spherical powder 3.85
(8) Coloring pigment Appropriate amount of oil phase (9) Squalane 2.85
(10) Triisooctanoic acid glycerin 1
(11) Slightly soluble ultraviolet absorber (Ubinal A +) used in Example 2
1.15
Others (12) Preservatives and antioxidants Appropriate amount (13) Fragrance Appropriate amount (Manufacturing method)
Mix talc and colored pigment in a blender. Add the remaining powder to this, mix well, add oil and preservatives, adjust the color, spray fragrance, and mix evenly. After this is pulverized by a pulverizer, it is compression molded into an intermediate dish.

  Since the white powder obtained in Comparative Example 4 contained a small amount of oil, the hardly soluble UV absorber could not be dissolved, so that it was confirmed that it was rough and rough when used.

  ADVANTAGE OF THE INVENTION According to this invention, the ultraviolet-absorbing powder which can mix | blend a small amount of ultraviolet absorber hardly soluble with respect to the oil component mix | blended with cosmetics in the inside of a powder polymer particle can be provided. This ultraviolet absorbing powder exhibits an excellent ultraviolet absorber in cosmetics, and can maintain a good feeling of use in a highly safe and stable state. In addition, since it has an excellent ultraviolet absorption effect, the blending amount can be made small so as not to become white at the time of coating.

  In the conventional cosmetics, in order to sufficiently dissolve the poorly soluble ultraviolet absorber, a large amount of dissolved oil must be blended, and there is a problem that the range of preparation of the cosmetic preparation is limited. However, by blending the ultraviolet absorbing powder according to the present invention, it is possible to expand the range of cosmetic preparation preparation.

  In addition, according to the present invention, it is possible to prepare a cosmetic preparation even with an oil component that is poorly compatible with a poorly soluble ultraviolet absorber, and as a result, the elution of the ultraviolet absorber is suppressed, and high safety is achieved. Cosmetics that can achieve stability can be provided.

It is a photograph figure by the scanning electron microscope (SEM) of the ultraviolet-absorption powder of the manufacture example 1 of this invention. It is a photograph figure by the scanning electron microscope (SEM) of the ultraviolet-absorbing powder of the manufacture example 2 of this invention.

Claims (10)

  Ultraviolet rays characterized in that spherical polymer particles encapsulate a hardly soluble ultraviolet absorber having a solubility in decamethylcyclopentasiloxane at 0 ° C. of 0.1 g / g or less per 1 g of decamethylcyclopentasiloxane. Absorbing powder.   The ultraviolet absorbing powder according to claim 1, wherein the ultraviolet absorbing powder has an average particle size of 0.1 to 100 µm.   The ultraviolet absorbing powder according to claim 1 or 2, wherein the hardly soluble ultraviolet absorber is contained in an amount of 0.1 to 50% by mass based on the total amount of the ultraviolet absorbing powder.   The spherical polymer particles are made of one or more resins selected from the group consisting of polystyrene resin, (meth) acrylic resin, nylon resin, silicone resin, and polyethylene resin. The ultraviolet absorbing powder according to any one of the above.   The ultraviolet absorbing powder according to any one of claims 1 to 4, wherein the hardly soluble ultraviolet absorber is an amino-substituted hydroxybenzophenone derivative and / or a bis (resorcinyl) triazine derivative.   A cosmetic comprising the ultraviolet absorbing powder according to any one of claims 1 to 5.   The cosmetic according to claim 6, wherein the ultraviolet absorbing powder is blended in an amount of 0.1 to 30% by mass based on the total amount of the cosmetic.   The cosmetic is an emulsified cosmetic or a solid cosmetic, and the content of oil having solubility with respect to the ultraviolet absorber blended in the cosmetic is 5% by mass or less based on the total amount of the cosmetic. The cosmetic according to claim 7, wherein:   The hardly soluble ultraviolet absorber is 2,4-bis-{[4- (2-ethylhexyloxy) -2hydroxy] phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine. The cosmetic according to claim 9.   10. The cosmetic according to claim 9, wherein the hardly soluble ultraviolet absorber is 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester.

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