JP7509542B2 - Composition containing ultraviolet wavelength conversion material - Google Patents
Composition containing ultraviolet wavelength conversion material Download PDFInfo
- Publication number
- JP7509542B2 JP7509542B2 JP2019239802A JP2019239802A JP7509542B2 JP 7509542 B2 JP7509542 B2 JP 7509542B2 JP 2019239802 A JP2019239802 A JP 2019239802A JP 2019239802 A JP2019239802 A JP 2019239802A JP 7509542 B2 JP7509542 B2 JP 7509542B2
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- Prior art keywords
- weight
- wavelength conversion
- ultraviolet
- vitamin
- composition
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- DLISVLVFJRCVJM-UHFFFAOYSA-N zinc oxygen(2-) phosphane Chemical compound [O--].P.[Zn++] DLISVLVFJRCVJM-UHFFFAOYSA-N 0.000 claims description 18
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Images
Landscapes
- Cosmetics (AREA)
Description
本発明は，細胞賦活作用を有する、紫外線波長変換物質を含有する組成物に関する。 The present invention relates to a composition containing an ultraviolet wavelength conversion substance that has a cell activation effect.
紫外線は体内にフリーラジカルを生成することにより、皮脂の酸化や細胞ＤＮＡの傷害を引き起こすとされている。紫外線のこのような作用による皮膚に対する弊害としては，例えば，皮膚癌，光老化，しみ，しわ，炎症といった悪影響があり，健康や美容の観点からも好ましくない。紫外線の利用としては殺菌効果を目的とするもの等が存在するものの，紫外線による弊害とのバランスを考えると，紫外線を積極的に利用するよりもむしろ防御することに焦点が当てられているのが現状である。 UV rays are believed to generate free radicals in the body, which can cause the oxidation of sebum and damage to cellular DNA. The harmful effects of UV rays on the skin include skin cancer, photoaging, age spots, wrinkles, and inflammation, and are undesirable from the standpoint of health and beauty. Although UV rays are used for the purpose of sterilization, considering the balance with the harmful effects of UV rays, the current situation is that the focus is on defense against UV rays rather than actively using them.
よって，紫外線から肌を防御するための方策が数多く取られている。例えば，日焼け止め剤の使用や，日光に当たらないような屋内での活動，UVカット加工された帽子や衣類，紫外線カットフィルムの使用などが挙げられる。 Therefore, many measures are taken to protect the skin from UV rays. For example, this includes using sunscreen, staying indoors to avoid exposure to sunlight, using hats and clothing with UV protection, and using UV-blocking film.
例えば特許文献１１の実施例には蛍光性酸化亜鉛を含む油性蛍光化粧料の記載があるが、分散剤の濃度が0.8％と低く、また細胞賦活効果を奏するための紫外線波長変換物質の記載はない。 For example, Patent Document 11 describes an oil-based fluorescent cosmetic that contains fluorescent zinc oxide in the examples, but the concentration of the dispersant is low at 0.8%, and there is no mention of an ultraviolet wavelength conversion substance to achieve a cell activation effect.
本発明の課題は，紫外線を利用した細胞賦活作用を有する新規な組成物の提供にある。 The objective of the present invention is to provide a novel composition that utilizes ultraviolet light to activate cells.
本発明者らは，紫外線を皮膚に対し有用に利用できるよう鋭意研究を行った。その結果，細胞賦活作用に優れた、紫外線波長変換物質を含有する組成物に想到した。 The inventors of the present invention have conducted extensive research into how to utilize ultraviolet light effectively on the skin. As a result, they have come up with the idea of a composition containing an ultraviolet wavelength conversion substance that has excellent cell activation effects.
本願は，以下の発明を提供する。
(1)（Ａ）紫外線波長変換物質、（Ｂ）分散剤、（Ｃ）紫外線吸収剤及び／又は紫外線散乱剤、並びに（Ｄ）油分を含み、前記（Ｂ）分散剤の配合量が１質量％以上である、組成物。
(2)前記（Ａ）紫外線波長変換物質が無機紫外線波長変換物質である、(1)に記載の組成物。
(3)前記無機紫外線波長変換物質が酸化亜鉛蛍光体またはチタン酸マグネシウム蛍光体である、(2)に記載の組成物。
(4)前記（Ａ）紫外線波長変換物質が有機紫外線波長変換物質である、 (1)に記載の組成物。
(5)前記有機紫外線波長変換物質がフィコシアニンである、(4)に記載の組成物。
(6)前記（Ａ）紫外線波長変換物質として無機紫外線波長変換物質と有機紫外線波長変換物質の双方が含まれる、(1)～(4)のいずれか１項に記載の組成物。
(7)前記（Ｂ）分散剤が、ＰＥＧ－１０ジメチコン、ビスブチルジメチコンポリグリセリル－３、ＰＥＧ－ポリジメチルポリシロキサンエチルジメチコン、ラウリルＰＥＧ－ポリジメチルポリシロキサンエチルジメチコン、セチルＰＥＧ／ＰＰＧ－１０／ジメチコン、イソステアリン酸、ジイソステアリン酸ポリグリセリル－２、カルボキシデシルトリシロキサン、ＰＥＧ－１２ジメチコン及びモノステアリン酸ポリオキシエチレンソルビタンからなる群から選ばれる１又は複数種である、(1)～(6)のいずれか１項に記載の組成物。
(8)ポリメタクリル酸メチル、シリカ、タルク、スターチ及びポリウレタンからなる群から選ばれる1又は複数種の粉末を含む、(1)～(7)のいずれか１項に記載の組成物。
(9)油中水型組成物である、(1)～(8)のいずれか１項に記載の組成物。
(10)日焼け止め化粧料である、(1)～(9)のいずれか１項に記載の組成物。
(11)蛍光強度増大効果を示す、(1)～(10)のいずれか１項に記載の組成物。
(12)細胞賦活効果を示す、(1)～(11)のいずれか１項に記載の組成物。
The present application provides the following inventions.
(1) A composition comprising: (A) an ultraviolet wavelength conversion substance; (B) a dispersant; (C) an ultraviolet absorber and/or an ultraviolet scattering agent; and (D) an oil component, wherein the blending amount of the (B) dispersant is 1 mass% or more.
(2) The composition according to (1), wherein the (A) ultraviolet wavelength conversion material is an inorganic ultraviolet wavelength conversion material.
(3) The composition according to (2), wherein the inorganic ultraviolet wavelength conversion material is a zinc oxide phosphor or a magnesium titanate phosphor.
(4) The composition according to (1), wherein the (A) ultraviolet wavelength conversion material is an organic ultraviolet wavelength conversion material.
(5) The composition according to (4), wherein the organic ultraviolet wavelength conversion substance is phycocyanin.
(6) The composition according to any one of (1) to (4), wherein the (A) ultraviolet wavelength conversion material contains both an inorganic ultraviolet wavelength conversion material and an organic ultraviolet wavelength conversion material.
(7) The composition according to any one of (1) to (6), wherein the dispersant (B) is one or more selected from the group consisting of PEG-10 dimethicone, bisbutyldimethicone polyglyceryl-3, PEG-polydimethylpolysiloxane ethyl dimethicone, lauryl PEG-polydimethylpolysiloxane ethyl dimethicone, cetyl PEG/PPG-10/dimethicone, isostearic acid, polyglyceryl-2 diisostearate, carboxydecyltrisiloxane, PEG-12 dimethicone, and polyoxyethylenesorbitan monostearate.
(8) The composition according to any one of (1) to (7), further comprising one or more kinds of powder selected from the group consisting of polymethyl methacrylate, silica, talc, starch, and polyurethane.
(9) The composition according to any one of (1) to (8), which is a water-in-oil type composition.
(10) The composition according to any one of (1) to (9), which is a sunscreen cosmetic.
(11) The composition according to any one of (1) to (10), which exhibits a fluorescence intensity enhancing effect.
(12) The composition according to any one of (1) to (11), which exhibits a cell activation effect.
本発明に係る紫外線波長変換物質は，紫外線を有効活用して皮膚細胞を賦活させることに適しており，皮膚に好ましい作用を奏することができ、本発明の組成物の成分組成は紫外線波長変換物質が紫外線を可視光（蛍光）に変換するために適している。従来，紫外線は皮膚に好ましくないため，皮膚をなるべく紫外線に当てないような対策を採るのが当分野の技術常識である。一方，本発明は紫外線波長変換物質が紫外線を逆に利用して細胞を賦活することにより、皮膚に好ましい作用を与えるという知見に基づいており，非常に驚くべきものである。従って，本発明に係る組成物は，これまで美容や健康上の理由よりなるべく紫外線を避けていた者であっても積極的に外出する気分になれるといった生活の質の向上にもつながることもある。 The ultraviolet wavelength conversion substance according to the present invention is suitable for effectively utilizing ultraviolet light to activate skin cells and can exert a favorable effect on the skin, and the component composition of the composition of the present invention is suitable for the ultraviolet wavelength conversion substance to convert ultraviolet light into visible light (fluorescence). Conventionally, ultraviolet light is not good for the skin, so it is common technical knowledge in this field to take measures to avoid exposing the skin to ultraviolet light as much as possible. On the other hand, the present invention is based on the finding that the ultraviolet wavelength conversion substance exerts a favorable effect on the skin by using ultraviolet light in the opposite way to activate cells, which is very surprising. Therefore, the composition according to the present invention can improve the quality of life by making even those who have avoided ultraviolet light as much as possible for beauty or health reasons feel more comfortable going outside.
以下、本発明を具体的な実施の形態に即して詳細に説明する。但し、本発明は以下の実施の形態に束縛されるものではなく、本発明の趣旨を逸脱しない範囲において、任意の形態で実施することが可能である。 The present invention will be described in detail below with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and can be implemented in any form without departing from the spirit of the present invention.
なお、本開示で引用する特許公報、特許出願公開公報、及び非特許文献等は、何れもその全体が援用により、あらゆる目的において本開示に組み込まれるものとする。 All patent publications, patent application publications, and non-patent literature cited in this disclosure are hereby incorporated by reference in their entirety into this disclosure for all purposes.
本開示において、数値に対して適用された場合の「～」とは、規定された基準値以上で、かつ規定された基準値以下の範囲に入る値の範囲を指す。 In this disclosure, when applied to a numerical value, "to" refers to a range of values that is equal to or greater than the specified reference value and is equal to or less than the specified reference value.
（Ａ）紫外線波長変換物質
本発明の組成物は，紫外線波長変換物質を有効成分として含有する。紫外線波長変換物質とは，入射光に含まれる紫外線の波長を変換して前記紫外線の波長よりも長い波長の出射光を放出する物質を指す。
(A) Ultraviolet Wavelength Conversion Material The composition of the present invention contains an ultraviolet wavelength conversion material as an active ingredient. The ultraviolet wavelength conversion material refers to a material that converts the wavelength of ultraviolet rays contained in incident light and emits outgoing light with a wavelength longer than that of the ultraviolet rays.
紫外線は，UVA，UVB，UVC等を含んでもよい。ある実施形態では，紫外線は，200nm～400nmにピーク波長を有する光である。また，例えば太陽光といった入射光に紫外線が含まれていてもよい。あるいは，入射光が紫外線であってもよく，人工的に生成された紫外線を用いてもよい。 The ultraviolet light may include UVA, UVB, UVC, etc. In one embodiment, the ultraviolet light is light having a peak wavelength between 200 nm and 400 nm. The ultraviolet light may also be included in the incident light, e.g., sunlight. Alternatively, the incident light may be ultraviolet light, or artificially generated ultraviolet light may be used.
紫外線波長変換物質により放出される出射光は，紫外線よりも波長が長く，好ましくは500nm～700nmにピーク波長を有する。出射光は，例えば，限定されないものの，510nm，520nm，530nm，540nm，550nm，560nm，570nm，580nm，590nm，600nm，610nm，620nm，630nm，640nm，650nm，660nm，670nm，680nm，690nm，700nm，あるいはこれらの数値の任意の範囲内に1又は複数のピークを有してもよいし，あるいは，赤色光，橙色光，緑色光，青色光等であってもよい。ある実施形態では，紫外線波長変換物質は，200nm～400nmの励起光で励起した際に発する光の主波長が500nm～700nmを示す。 The emitted light emitted by the ultraviolet wavelength conversion material has a longer wavelength than ultraviolet light, and preferably has a peak wavelength of 500 nm to 700 nm. The emitted light may have one or more peaks, for example, but not limited to, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm, 600 nm, 610 nm, 620 nm, 630 nm, 640 nm, 650 nm, 660 nm, 670 nm, 680 nm, 690 nm, 700 nm, or within any range of these values, or may be red light, orange light, green light, blue light, etc. In one embodiment, the ultraviolet wavelength conversion material exhibits a dominant wavelength of 500 nm to 700 nm when excited with excitation light of 200 nm to 400 nm.
紫外線波長変換物質の例として，以下の成分が挙げられる：アロフィコシアニン，C-フィコシアニン（LinaBlueなど），R-フィコシアニン，フィコエリスロシアニン，B-フィコエリスリン，b-フィコエリスリン，C-フィコエリスリン，R-フィコエリスリンなどのフィコビリ蛋白；ビタミンA，βカロテン，ビタミンK，ビタミンB1，ビタミンB2，ビタミンB6，ビタミンB12，葉酸，ナイアシン，リコピン，クチナシ，ベニバナ，ウコン，コチニール，シソ，赤キャベツ，フラボノイド，カロテノイド，キノイド，ポルフィリン類，アントシアニン類，ポリフェノール類などの天然由来又は合成成分；赤色401号，赤色227号，赤色504号，赤色218号，橙色205号P，黄色4号，黄色5号，緑色201号，ピラニンコンク，青色1号，塩酸2,4-ジアミノフェノキシエタノール，アリズリンパープルSS，紫色401号，黒色401号，へリンドンピンク，黄色401号，ベンチジンエローG，青色404号，赤色104号，メタアミノフェノールなどの色素；無機化合物にドープし蛍光を持たせた蛍光体，例えば，特許第6424656号に記載の非晶質シリカ粒子と，セリウムと，リン及び／又はマグネシウムとを含む青色蛍光体および特許第6361416号に記載のアルカリ土類金属硫化物とガリウム化合物との混晶物にユーロピウムを賦活した化合物を含む赤色蛍光体，国際公開第2018/004006号に記載の酸化亜鉛の蛍光体，特開2018-131422号に記載の酸化亜鉛の蛍光体；特開平5-117127号に記載の無機蛍光体;等が挙げられる（以下、酸化亜鉛に由来する蛍光体を「酸化亜鉛蛍光体」という。例えば、LumateG）。ある実施形態では，無機蛍光体は，ZnO：Zn，Zn１+ｚ，ZnO1-ｘのように表すことができる酸化亜鉛を国際公開第2018/004006号に記載の，例えば硫化亜鉛，硫酸亜鉛等の硫化塩及び／又は硫酸塩といった硫黄含有化合物でドープした蛍光体，MgTiO3，Mg2TiO4といったチタン酸マグネシウムをマンガンでドープしたチタン酸マグネシウムの蛍光体（以下、チタン酸マグネシウムに由来する蛍光体を「チタン酸マグネシウム蛍光体」という。例えば、LumateR），及びCa(H2PO4)2，CaHPO4，Ca3(PO4)2といったリン酸カルシウムをセリウムでドープしたリン酸カルシウム蛍光体から選択される1種又は複数種の蛍光体である。 Examples of UV-converting substances include phycobiliproteins such as allophycocyanin, C-phycocyanin (e.g., LinaBlue), R-phycocyanin, phycoerythrocyanin, B-phycoerythrin, b-phycoerythrin, C-phycoerythrin, and R-phycoerythrin; vitamin A, beta-carotene, vitamin K, vitamin B1, vitamin B2, vitamin B6, and vitamin B12. Natural or synthetic ingredients such as folic acid, niacin, lycopene, gardenia, safflower, turmeric, cochineal, perilla, red cabbage, flavonoids, carotenoids, quinoids, porphyrins, anthocyanins, and polyphenols; Red No. 401, Red No. 227, Red No. 504, Red No. 218, Orange No. 205 P, Yellow No. 4, Yellow No. 5, Green No. 201, Pyranine Concentrate, Blue No. 1, 2,4-Diaminophenol Hydrochloride Dyes such as xyethanol, alizurin purple SS, purple No. 401, black No. 401, herringbone pink, yellow No. 401, benzidine yellow G, blue No. 404, red No. 104, and meta-aminophenol; phosphors doped with inorganic compounds to give them fluorescence, such as the blue phosphor containing amorphous silica particles, cerium, phosphorus, and/or magnesium described in Japanese Patent No. 6424656 and the red phosphor containing a compound in which a mixed crystal of an alkaline earth metal sulfide and a gallium compound is activated with europium described in Japanese Patent No. 6361416, zinc oxide phosphors described in International Publication No. 2018/004006, zinc oxide phosphors described in Japanese Patent Publication No. 2018-131422, inorganic phosphors described in Japanese Patent Publication No. 5-117127, and the like (hereinafter, phosphors derived from zinc oxide are referred to as "zinc oxide phosphors"; for example, Lumate G). In one embodiment, the inorganic phosphor is one or more phosphors selected from phosphors in which zinc oxide, which can be represented as ZnO:Zn, Zn1 +z , ZnO1 -x, is doped with a sulfur-containing compound, e.g., zinc sulfide, zinc sulfate, or other sulfide salt and/or sulfate salt, as described in WO 2018/004006; magnesium titanate phosphors in which magnesium titanate, e.g. , MgTiO3 , Mg2TiO4 , is doped with manganese (hereinafter, phosphors derived from magnesium titanate are referred to as "magnesium titanate phosphors"; e.g., LumateR); and calcium phosphate phosphors in which calcium phosphate, e.g., Ca( H2PO4 ) 2 , CaHPO4 , Ca3 ( PO4 ) 2 , is doped with cerium.
紫外線波長変換物質は，動物，植物，藻類等の天然物から抽出などの方法により得ても，化学的な合成といった人工的な方法により得てもよい。例えば，フィコビリ蛋白は，スピルリナ（Spirulina platensis）などの藍藻類，チノリモ（Porphyridium purpureum）などの紅藻類といった藻類を，例えば特許第4048420号，特許第4677250号，特許第3303942号等に記載の方法で抽出することにより調製してもよい。酸化亜鉛蛍光体は，例えば国際公開第2018/004006号，特開2018-131422号，特開平5-117127号に記載の方法により製造してもよい。チタン酸マグネシウム蛍光体は，特開2017-88719号に記載の方法により製造してもよい。リン酸カルシウム蛍光体は，国際公開第2018/117117号に記載の方法により製造してもよい。 The ultraviolet wavelength conversion substance may be obtained by a method such as extraction from natural products such as animals, plants, and algae, or by an artificial method such as chemical synthesis. For example, phycobiliprotein may be prepared by extracting algae such as blue-green algae such as Spirulina platensis and red algae such as Porphyridium purpureum by a method such as that described in Patent No. 4048420, Patent No. 4677250, Patent No. 3303942, etc. Zinc oxide phosphor may be produced by a method such as that described in International Publication No. 2018/004006, JP 2018-131422, and JP 5-117127. Magnesium titanate phosphor may be produced by a method described in JP 2017-88719. Calcium phosphate phosphor may be produced by a method described in International Publication No. 2018/117117.
これらの紫外線波長変換物質は，本発明の波長変換効果を損なわない限り，上で例示した成分から構成されてもよく，含まれていてもよく，単体で使用しても複数種を混合してもよい。例えば，上記フィコビリ蛋白や無機物蛍光体に他の紫外線波長変換物質，例えば，ビタミンB（ビタミンB1，ビタミンB2，ビタミンB6，ビタミンB12等）を混合し相乗的な効果を目指してもよい。しかしながら，これらの成分は例示であり本発明の波長変換効果を奏するいかなる物質も使用可能である。 As long as the wavelength conversion effect of the present invention is not impaired, these ultraviolet wavelength conversion substances may be composed of or contain the components exemplified above, and may be used alone or in combination with multiple types. For example, the above phycobiliproteins or inorganic phosphors may be mixed with other ultraviolet wavelength conversion substances, such as vitamin B (vitamin B1, vitamin B2, vitamin B6, vitamin B12, etc.), to achieve a synergistic effect. However, these components are merely examples, and any substance that provides the wavelength conversion effect of the present invention may be used.
また，本発明の組成物における紫外線波長変換物質の含有量は本発明の波長変換効果を損なわない限り特に限定されず，紫外線波長変換物質の種類や紫外線波長変換物質を含む組成物の用途により適宜決定できる。例えば，0.01～99.99重量％，0.1％～99.9重量％等の範囲内で任意である。 The content of the ultraviolet wavelength conversion substance in the composition of the present invention is not particularly limited as long as it does not impair the wavelength conversion effect of the present invention, and can be appropriately determined depending on the type of ultraviolet wavelength conversion substance and the application of the composition containing the ultraviolet wavelength conversion substance. For example, it can be any content within the range of 0.01 to 99.99% by weight, 0.1% to 99.9% by weight, etc.
本発明の一態様としては、組成物における紫外線波長変換物質は酸化亜鉛蛍光体（例えば、ＬｕｍａｔｅＧ）であり、本発明の組成物での好ましい酸化亜鉛蛍光体の含有量は、組成物全体に対して０．１重量％以上であり、好ましくは１．０質量％以上、より好ましくは１．５重量％以上であり、さらに好ましくは２重量％以上であり、また、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.01～99.99重量％，0.1～99.9重量％、0.1～50重量％、0.1～40重量％、0.1～30重量％、0.1～20重量％、0.1～10重量％または1～10重量％である。 In one embodiment of the present invention, the ultraviolet wavelength conversion material in the composition is a zinc oxide phosphor (e.g., Lumate G), and the content of the zinc oxide phosphor in the composition of the present invention is preferably 0.1% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more, and even more preferably 2% by weight or more, and is preferably 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, and is 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, or 1 to 10% by weight, based on the total composition.
本発明の一態様としては、組成物における紫外線波長変換物質は酸化チタン酸マグネシウム蛍光体（例えば、ＬｕｍａｔｅＲ）であり、本発明の組成物での好ましいチタン酸マグネシウム蛍光体の含有量は、組成物全体に対して０．１重量％以上であり、好ましくは１．０質量％以上、より好ましくは１．５重量％以上であり、さらに好ましくは２重量％以上であり、また、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.01～99.99重量％，0.1～99.9重量％、0.1～50重量％、0.1～40重量％、0.1～30重量％、0.1～20重量％、0.1～10重量％または1～10重量％である。 In one embodiment of the present invention, the ultraviolet wavelength conversion material in the composition is a magnesium titanate oxide phosphor (e.g., LumateR), and the content of the magnesium titanate phosphor in the composition of the present invention is preferably 0.1% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more, even more preferably 2% by weight or more, and 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, or 1 to 10% by weight, based on the total composition.
本発明の一態様としては、組成物における紫外線波長変換物質はフィコシアニン（例えば、ＬｉｎａＢｌｕｅ）であり、本発明の組成物での好ましいフィコシアニンの含有量は、組成物全体に対して０．００００１重量％以上であり、好ましくは０．０００１質量％以上であり、また、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.00001～99.99重量％，0.0001～99.9重量％、0.0001～50重量％、0.0001～40重量％、0.0001～30重量％、0.0001～20重量％、0.0001～10重量％、0.0001～5重量％である。 In one embodiment of the present invention, the ultraviolet wavelength conversion substance in the composition is phycocyanin (e.g., LinaBlue), and the preferred content of phycocyanin in the composition of the present invention is 0.00001% by weight or more, preferably 0.0001% by mass or more, and 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, and is 0.00001 to 99.99% by weight, 0.0001 to 99.9% by weight, 0.0001 to 50% by weight, 0.0001 to 40% by weight, 0.0001 to 30% by weight, 0.0001 to 20% by weight, 0.0001 to 10% by weight, or 0.0001 to 5% by weight.
細胞賦活とは，限定されないものの，ヒトを含む動物の細胞，例えば，皮膚の線維芽細胞及び/又は角化細胞の新陳代謝やターンオーバーの促進，機能の向上，増殖の促進，酸化の抑制，疲労や外部刺激に対する耐性の向上，機能や活性の低下の抑制などが挙げられる。皮膚の細胞が賦活されると，しわ，シミ，皮膚老化，光老化等の予防・改善といった効果が期待される。 Cell activation includes, but is not limited to, the promotion of metabolism and turnover of animal cells, including human cells, such as skin fibroblasts and/or keratinocytes, improving function, promoting proliferation, inhibiting oxidation, improving resistance to fatigue and external stimuli, and inhibiting decline in function and activity. Activating skin cells is expected to have effects such as preventing and improving wrinkles, age spots, skin aging, photoaging, etc.
細胞賦活効果の測定は，例えば実施例のように，Alamar Blueを用いて生細胞の生存率、還元能力や増殖を測定することで行ってもよいし，その他の色素アッセイ，ミトコンドリア膜電位異存的色素アッセイ，細胞内チトクロームｃアッセイ、エラスターゼ切断色素アッセイ，ATP，ADEアッセイ，解糖フラックスと酸素消費アッセイ等任意の方法が使用できる。 The cell activation effect can be measured, for example, by measuring the viability, reducing capacity, and proliferation of live cells using Alamar Blue as in the Examples, or any other method can be used, such as other dye assays, mitochondrial membrane potential-dependent dye assays, intracellular cytochrome c assays, elastase cleavage dye assays, ATP, ADE assays, glycolytic flux and oxygen consumption assays, etc.
蛍光強度の測定は、例えば実施例のように，基体表面に組成物の塗膜を形成し、紫外線を照射したときの蛍光強度を、分光蛍光強度計を用いて測定することができる。基体としてポリメタクリル酸メチル（ＰＭＭＡ）、ナイロン、又はアクリル板等の樹脂基板、ガラスや石英等の無機物板を用いることができ、例えば、表面にＶ字形状の溝を設けたＰＭＭＡ板（「Ｓプレート」ともいう：特許第４４５３９９５号参照）等を用いることができる。蛍光強度の測定は特定の単一波長の蛍光値でもよく、特定の波長領域の積算値でもよい。 Fluorescence intensity can be measured, for example, as in the examples, by forming a coating of the composition on the surface of a substrate and irradiating it with ultraviolet light, and then measuring the fluorescence intensity using a spectrofluorometer. As the substrate, a resin substrate such as polymethylmethacrylate (PMMA), nylon, or acrylic plate, or an inorganic plate such as glass or quartz can be used, and for example, a PMMA plate with a V-shaped groove on the surface (also called an "S plate": see Patent No. 4453995) can be used. The fluorescence intensity can be measured as the fluorescence value of a specific single wavelength, or as the integrated value of a specific wavelength range.
（Ｂ）分散剤
本発明の組成物は，分散剤を含有する。分散剤とは、水相または油相中に分散された粒子の表面に吸着することで、水性または油性媒体中に均一に分散せしめることのできる物質を指す。 本発明で使用し得る分散剤は、紫外線波長変換物質の機能を損なわない限り特に限定されず、油系の分散剤が好ましく、油系の分散剤としては、非イオン性界面活性剤、カチオン界面活性剤、アニオン界面活性剤、シリコーン系界面活性剤、脂肪酸等が挙げられる。本発明においては、特に、化粧品、医薬品に通常使用される、非イオン性界面活性剤、シリコーン系界面活性剤及び／又は脂肪酸の使用が好ましい。
(B) Dispersant The composition of the present invention contains a dispersant. A dispersant refers to a substance that can be adsorbed to the surface of particles dispersed in an aqueous or oily phase, thereby dispersing the particles uniformly in an aqueous or oily medium. The dispersant that can be used in the present invention is not particularly limited as long as it does not impair the function of the ultraviolet wavelength conversion material, and is preferably an oil-based dispersant. Examples of the oil-based dispersant include nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, fatty acids, etc. In the present invention, it is particularly preferable to use nonionic surfactants, silicone-based surfactants, and/or fatty acids that are commonly used in cosmetics and pharmaceuticals.
本発明の組成物に含まれる好ましい分散剤としては、ＰＥＧ－１０ジメチコン、ビスブチルジメチコンポリグリセリル－３、ＰＥＧ－ポリジメチルポリシロキサンエチルジメチコン、ラウリルＰＥＧ－ポリジメチルポリシロキサンエチルジメチコン、セチルＰＥＧ／ＰＰＧ－１０／ジメチコン、イソステアリン酸、ジイソステアリン酸ポリグリセリル－２、カルボキシデシルトリシロキサン、ＰＥＧ－１２ジメチコン、もしくはモノステアリン酸ポリオキシエチレンソルビタンまたはこれらの2以上の組み合わせがあげられる。 Preferred dispersants included in the compositions of the present invention include PEG-10 dimethicone, bis-butyl dimethicone polyglyceryl-3, PEG-polydimethylpolysiloxane ethyl dimethicone, lauryl PEG-polydimethylpolysiloxane ethyl dimethicone, cetyl PEG/PPG-10/dimethicone, isostearic acid, polyglyceryl-2 diisostearate, carboxydecyl trisiloxane, PEG-12 dimethicone, or polyoxyethylene sorbitan monostearate, or a combination of two or more of these.
本発明の組成物に含まれる分散剤の好ましい例としては、紫外線波長変換物質の機能を亢進することから、ＰＥＧ－１０ジメチコン、ビスブチルジメチコンポリグリセリル-3、PEG-9ポリジメチルポリシロキシエチルジメチコン、ラウリルPEG-9ポリジメチルポリシロキシエチルジメチコン、セチルPEG/PPG-10/1ジメチコン、イソステアリン酸、もしくはカルボキシデシルトリシロキサン、またはこれらの2以上の組み合わせがあげられる。 Preferred examples of dispersants contained in the composition of the present invention, which enhance the function of the ultraviolet wavelength conversion substance, include PEG-10 dimethicone, bisbutyldimethicone polyglyceryl-3, PEG-9 polydimethylpolysiloxyethyl dimethicone, lauryl PEG-9 polydimethylpolysiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, isostearic acid, or carboxydecyltrisiloxane, or a combination of two or more of these.
また，本発明の組成物における分散剤の含有量は本発明の波長変換効果を損なわない限り特に限定されず，紫外線波長変換物質の種類や紫外線波長変換物質を含む組成物の用途により適宜決定できる。例えば，0.01～99.99重量％，0.1％～99.9重量％等の範囲内で任意である。 The content of the dispersant in the composition of the present invention is not particularly limited as long as it does not impair the wavelength conversion effect of the present invention, and can be appropriately determined depending on the type of ultraviolet wavelength conversion substance and the application of the composition containing the ultraviolet wavelength conversion substance. For example, it can be any content within the range of 0.01 to 99.99% by weight, 0.1% to 99.9% by weight, etc.
本発明の組成物における好ましい分散剤の含有量は、組成物全体に対して０．１重量％以上であり、好ましくは０．８％よりも多く、０．９％質量以上、より好ましくは１．０質量％以上、さらに好ましくは１．５重量％以上、または２重量％以上であり、また、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.01～99.99重量％，0.1～99.9重量％、0.1～50重量％、0.1～40重量％、0.1～30重量％、0.1～20重量％、0.1～10重量％、0.5～10重量％、1～10重量％、1.5～10重量％または0.8～3重量％である。 The preferred content of the dispersant in the composition of the present invention is 0.1% by weight or more, preferably more than 0.8%, 0.9% by weight or more, more preferably 1.0% by weight or more, even more preferably 1.5% by weight or more, or 2% by weight or more, and is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and is 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, 0.5 to 10% by weight, 1 to 10% by weight, 1.5 to 10% by weight, or 0.8 to 3% by weight, based on the total composition.
本発明の一態様としては、組成物における分散剤はＰＥＧ－１０ジメチコンであり、組成物における分散剤の含有量は、組成物全体に対して、０．１重量％以上であり、好ましくは０．８％よりも多く、０．９％質量以上、より好ましくは１．０質量％以上、さらに好ましくは１．５重量％以上、または２重量％以上であり、また、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.01～99.99重量％，0.1～99.9重量％、0.1～50重量％、0.1～40重量％、0.1～30重量％、0.1～20重量％、0.1～10重量％、0.5～10重量％、1～10重量％、1.5～10重量％または0.8～3重量％である。 In one embodiment of the present invention, the dispersant in the composition is PEG-10 dimethicone, and the content of the dispersant in the composition is 0.1% by weight or more, preferably more than 0.8%, 0.9% by weight or more, more preferably 1.0% by weight or more, even more preferably 1.5% by weight or more, or 2% by weight or more, and is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, and is 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, 0.5 to 10% by weight, 1 to 10% by weight, 1.5 to 10% by weight, or 0.8 to 3% by weight, based on the total composition.
本発明の一態様としては、組成物における分散剤はビスブチルジメチコンポリグリセリル-3、PEG-9ポリジメチルポリシロキシエチルジメチコン、ラウリルPEG-9ポリジメチルポリシロキシエチルジメチコン、セチルPEG/PPG-10/1ジメチコン、イソステアリン酸及びカルボキシデシルトリシロキサンの群から選択される1以上の分散剤とＰＥＧ－１０ジメチコンの組み合わせであり、組成物におけるＰＥＧ－１０ジメチコンの含有量は、組成物全体に対して、０．１重量％以上であり、好ましくは１．０質量％以上、より好ましくは１．５重量％以上であり、さらに好ましくは２重量％以上であり、また、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.01～99.99重量％，0.1～99.9重量％、0.1～50重量％、0.1～40重量％、0.1～30重量％、0.1～20重量％、0.1～10重量％、0.5～10重量％、1～10重量％、1.5～10重量％または0.8～3重量％であり、組み合わせの各分散剤の含有量は、組成物全体に対して０．１重量％以上であり、好ましくは１．０質量％以上、より好ましくは１．５重量％以上であり、さらに好ましくは２重量％以上であり、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下であり、また組成物全体に対して0.1～50重量％、0.1～40重量％、0.1～30重量％、0.1～20重量％、0.1～10重量％、0.5～10重量％、1～10重量％、1.5～10重量％または0.8～3重量％である。 In one embodiment of the present invention, the dispersant in the composition is a combination of one or more dispersants selected from the group consisting of bisbutyldimethicone polyglyceryl-3, PEG-9 polydimethylpolysiloxyethyl dimethicone, lauryl PEG-9 polydimethylpolysiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, isostearic acid, and carboxydecyltrisiloxane, and PEG-10 dimethicone. The content of PEG-10 dimethicone in the composition is 0.1% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more, even more preferably 2% by weight or more, and 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and 0.01 to 99. 99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, 0.5 to 10% by weight, 1 to 10% by weight, 1.5 to 10% by weight, or 0.8 to 3% by weight, and the content of each dispersant in the combination is 0.1% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more, based on the total weight of the composition; More preferably, it is 2% by weight or more, 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, and is 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, 0.5 to 10% by weight, 1 to 10% by weight, 1.5 to 10% by weight, or 0.8 to 3% by weight relative to the total composition.
（C）紫外線吸収剤及び／又は紫外線散乱剤
紫外線吸収剤及び紫外線散乱剤は、入射する紫外線を吸収または散乱させるため、紫外線波長変換物質の機能を間接的に阻害してしまうと考えられるが、驚くべきことに、本発明の組成物は，紫外線吸収剤及び／又は紫外線散乱剤を含有することができ、紫外線波長変換物質の機能を発揮することができる。
(C) Ultraviolet absorbing agent and/or ultraviolet scattering agent Ultraviolet absorbing agents and ultraviolet scattering agents absorb or scatter incident ultraviolet light, and are therefore thought to indirectly inhibit the function of the ultraviolet wavelength conversion material. However, surprisingly, the composition of the present invention can contain an ultraviolet absorbing agent and/or ultraviolet scattering agent, and can exhibit the function of an ultraviolet wavelength conversion material.
紫外線吸収剤とは、紫外線を吸収し、熱や赤外線などのエネルギーに変化させて放出させる物質を指す。本発明で使用し得る紫外線吸収剤は、直接的に紫外線波長変換物質の機能を損なわない限り特に限定されず、たとえば、サリチル酸ホモメンチル、サリチル酸エチルヘキシル、ホモサレート、サリチル酸トリエタノールアミン等のサリチル酸系紫外線吸収剤；
パラメトキシケイ皮酸２－エチルヘキシル、ジパラメトキシケイ皮酸モノ－２－エチルヘキサン酸グリセリル、２，５－ジイソプロピルケイ皮酸メチル、２，４，６－トリス［４－（２－エチルへキシルオキシカルボニル）アニリノ］－１，３，５－トリアジン（以下、「エチルヘキシルトリアゾン」とも呼ぶ。）、トリメトキシケイ皮酸メチルビス（トリメチルシロキシ）シリルイソペンチル、パラメトキシケイ皮酸イソプロピル・ジイソプロピルケイ皮酸エステル混合物、ｐ－メトキシハイドロケイ皮酸ジエタノールアミン塩等のケイ皮酸系紫外線吸収剤；
２－フェニル－ベンズイミダゾール－５－硫酸、４－イソプロピルジベンゾイルメタン、４－ｔｅｒｔ－ブチル－４'－メトキシジベンゾイルメタン等のベンゾイルメタン系紫外線吸収剤；
オクトクリレン、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸２－エチルヘキシル、１－（３，４－ジメトキシフェニル）－４，４－ジメチル－１，３－ペンタンジオン、シノキサート、メチル－Ｏ－アミノベンゾエート、３－（４－メチルベンジリデン）カンフル、オクチルトリアゾン、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン及びメチレンビスベンゾトリアゾリルテトラメチルブチルフェノールが挙げられ、これらから選ばれる１種または２種以上を組成物中に含むことができる。
The ultraviolet absorbent refers to a substance that absorbs ultraviolet rays, converts them into energy such as heat or infrared rays, and then releases them. The ultraviolet absorbent that can be used in the present invention is not particularly limited as long as it does not directly impair the function of the ultraviolet wavelength conversion substance, and examples thereof include salicylic acid-based ultraviolet absorbents such as homomenthyl salicylate, ethylhexyl salicylate, homosalate, and triethanolamine salicylate;
cinnamic acid-based ultraviolet absorbers such as 2-ethylhexyl paramethoxycinnamate, glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate, methyl 2,5-diisopropylcinnamate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine (hereinafter also referred to as "ethylhexyl triazone"), methyl bis(trimethylsiloxy)silylisopentyl trimethoxycinnamate, a mixture of isopropyl paramethoxycinnamate and diisopropyl cinnamate, and diethanolamine p-methoxyhydrocinnamate;
Benzoylmethane-based ultraviolet absorbers such as 2-phenyl-benzimidazole-5-sulfuric acid, 4-isopropyldibenzoylmethane, and 4-tert-butyl-4'-methoxydibenzoylmethane;
Examples of the benzotriazolidine dibenzoate include octocrylene, 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidinepropionate, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, cinoxate, methyl-O-aminobenzoate, 3-(4-methylbenzylidene)camphor, octyl triazone, diethylaminohydroxybenzoylhexyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine, and methylene bisbenzotriazolyl tetramethylbutylphenol. One or more selected from these may be contained in the composition.
本発明の組成物に含まれる（各）紫外線吸収剤の含有量は、入射光に含まれる紫外線を吸収しすぎないために、組成物全体に対して、２０重量％以下であり、好ましくは１５重量％以下、より好ましくは１０重量％以下であり、さらに好ましくは５重量％以下である。 The content of the (each) ultraviolet absorber in the composition of the present invention is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on the total composition, in order not to absorb too much ultraviolet light contained in incident light.
本発明の組成物は，紫外線散乱剤を含有してもよい。紫外線散乱剤とは、紫外線を反射・散乱させて皮膚等を紫外線から防御することができる物質を指す。本発明で使用し得る紫外線散乱剤の材料としては、酸化チタン、成分（Ａ）以外の酸化亜鉛、酸化鉄、酸化ジルコニウム、酸化アルミニウム等が挙げられる。また、紫外線散乱剤としてこれらの材料を微粒子化したものや、複合化したものが挙げられる。紫外線散乱剤は、好ましくは、酸化チタンおよび成分（Ａ）以外の酸化亜鉛から選択される１種または２種以上を含む。 The composition of the present invention may contain an ultraviolet scattering agent. The ultraviolet scattering agent refers to a substance that can reflect and scatter ultraviolet rays to protect the skin, etc. from ultraviolet rays. Examples of ultraviolet scattering agent materials that can be used in the present invention include titanium oxide, zinc oxide other than component (A), iron oxide, zirconium oxide, aluminum oxide, etc. Furthermore, examples of ultraviolet scattering agents include those in which these materials are made into fine particles or composites. The ultraviolet scattering agent preferably contains one or more types selected from titanium oxide and zinc oxide other than component (A).
紫外線散乱剤として用いられる酸化チタンおよび酸化亜鉛は、化粧料に通常用いられている酸化チタンおよび酸化亜鉛であってよい。好ましくはより分散性に優れたもの、たとえば必要に応じて公知の方法で表面を表面処理、具体的には疎水化処理したものを組成物中に含有することができる。 The titanium oxide and zinc oxide used as the UV scattering agent may be the titanium oxide and zinc oxide that are commonly used in cosmetics. Preferably, the titanium oxide and zinc oxide have better dispersibility, for example, the surface of which has been treated, specifically hydrophobized, by a known method as necessary, may be contained in the composition.
表面処理の方法としては、メチルハイドロゲンポリシロキサン、メチルポリシロキサン等のシリコーン処理；パーフルオロアルキルリン酸エステル、パーフルオロアルコール等によるフッ素処理；Ｎ－アシルグルタミン酸等によるアミノ酸処理；オクチルトリエトキシシラン、オクチルトリメトキシシラン等のアルキルアルコキシシラン処理；その他、レシチン処理；金属石鹸処理；脂肪酸処理；アルキルリン酸エステル処理等が挙げられる。なかでも、表面をシリコーン処理した酸化亜鉛が好ましく用いられる。 Surface treatment methods include silicone treatment with methylhydrogenpolysiloxane, methylpolysiloxane, etc.; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol, etc.; amino acid treatment with N-acylglutamic acid, etc.; alkylalkoxysilane treatment with octyltriethoxysilane, octyltrimethoxysilane, etc.; lecithin treatment; metal soap treatment; fatty acid treatment; alkyl phosphate ester treatment, etc. Among these, zinc oxide with a silicone-treated surface is preferably used.
表面処理に用いられるシリコーンは制限されないが、たとえばメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロゲンポリシロキサン、メチルシクロポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、オクタメチルトリシロキサン、テトラデカメチルヘキサシロキサン、ジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン・メチル（ポリオキシプロピレン）シロキサン共重合体、ジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体、ジメチルシロキサン・メチル（ポリオキシプロピレン）シロキサン共重合体、ジメチルシロキサン・メチルセチルオキシシロキサン共重合体、ジメチルシロキサン・メチルステアロキシシロキサン共重合体等の各種シリコーン油を挙げることができる。好ましくは、メチルハイドロゲンポリシロキサンやメチルポリシロキサンである。 The silicone used for the surface treatment is not limited, but examples include various silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane-methyl(polyoxyethylene)siloxane-methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane-methyl(polyoxyethylene)siloxane copolymer, dimethylsiloxane-methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane-methylcetyloxysiloxane copolymer, and dimethylsiloxane-methylstearoxysiloxane copolymer. Methylhydrogenpolysiloxane and methylpolysiloxane are preferred.
本発明の組成物に含まれる（各）紫外線散乱剤の含有量は、入射光に含まれる紫外線を散乱しすぎないために、組成物全体に対して、３０重量％以下であり、好ましくは２０重量％以下、より好ましくは１５重量％以下であり、さらに好ましくは１０重量％以下である。 The content of the (each) ultraviolet scattering agent in the composition of the present invention is 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, based on the total composition, in order not to scatter the ultraviolet rays contained in the incident light too much.
（Ｄ）油分
本発明の組成物は，油分を含有する。油分とは、本発明の組成物の成分である、水と相分離する疎水性の物質を指す。本発明で使用し得る油分は、特に限定されず、例えば、炭化水素油、エステル油、シリコーン油、液体油脂、固体油脂及び高級アルコールの少なくとも一種以上を含む。
(D) Oil The composition of the present invention contains an oil. The oil refers to a hydrophobic substance that is a component of the composition of the present invention and undergoes phase separation from water. The oil that can be used in the present invention is not particularly limited, and includes, for example, at least one of hydrocarbon oil, ester oil, silicone oil, liquid oil, solid oil, and higher alcohol.
炭化水素油としては、流動パラフィン、テトライソブタン、水添ポリデセン、オレフィンオリゴマー、イソドデカン、イソヘキサデカン、スクワラン、水添ポリイソブテン等が挙げられる。 Examples of hydrocarbon oils include liquid paraffin, tetraisobutane, hydrogenated polydecene, olefin oligomer, isododecane, isohexadecane, squalane, hydrogenated polyisobutene, etc.
エステル油としては、セバシン酸ジイソプロピル、パルミチン酸オクチル、イソオクタン酸セチル（２－エチルヘキサン酸セチル）、トリエチルヘキサノイン、ジカプリン酸ネオペンチルグリコール、トリイソステアリン、リンゴ酸ジイソステアリル、ジピバリン酸ＰＰＧ－３、コハク酸ジ２－エチルヘキシル、２－エチルヘキサン酸２－エチルヘキシル、オクタカプリル酸ポリグリセリル－６、トリ（カプリル酸／カプリン酸）グリセリル等が挙げられる。 Ester oils include diisopropyl sebacate, octyl palmitate, cetyl isooctanoate (cetyl 2-ethylhexanoate), triethylhexanoin, neopentyl glycol dicaprate, triisostearin, diisostearyl malate, PPG-3 dipivalate, di-2-ethylhexyl succinate, 2-ethylhexyl 2-ethylhexanoate, polyglyceryl-6 octacaprylate, and tri(caprylic/capric acid)glyceryl.
シリコーン油としては、ジメチコン、アミノ変性ポリシロキサン、ポリエーテル変性ポリシロキサン、アルキル変性ポリシロキサン、フッ素変性ポリシロキサン等が挙げられる。 Examples of silicone oils include dimethicone, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane.
液体油脂としては、アボカド油、ツバキ油、マカデミアナッツ油、ミンク油、オリーブ油、ヒマシ油、ホホバ油、トリグリセリン、トリオクタン酸グリセリン等が挙げられる。 Liquid oils include avocado oil, camellia oil, macadamia nut oil, mink oil, olive oil, castor oil, jojoba oil, triglycerin, and glycerin trioctanoate.
固体油脂としては、ヤシ油、硬化ヤシ油、パーム油、牛脂、羊脂、モクロウ、硬化ヒマシ油等が挙げられる。 Examples of solid fats and oils include coconut oil, hardened coconut oil, palm oil, beef tallow, mutton tallow, Japan wax, and hardened castor oil.
高級アルコールとしては、イソステアリルアルコール、オレイルアルコール、ブチレングリコールとプロピレングリコールの共重合体（例えば、ＰＢＧ／ＰＰＧ-9/1コポリマー）等が挙げられる。 Examples of higher alcohols include isostearyl alcohol, oleyl alcohol, and copolymers of butylene glycol and propylene glycol (e.g., PBG/PPG-9/1 copolymer).
本発明の組成物に含まれる油分全体の含有量は、組成物全体に対して、１０重量％以上であり、好ましくは１５重量％以上、より好ましくは２０重量％以上であり、さらに好ましくは２５重量％以上である。 The total oil content of the composition of the present invention is 10% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more, and even more preferably 25% by weight or more, based on the total composition.
（任意成分）
本発明の組成物は、本発明の効果に影響を及ぼさない範囲で、各種成分を適宜配合することができる。各種成分としては、化粧料に通常配合し得るような添加成分、例えば、粘土鉱物（ジメチルジステアリルアアンモニウムヘクトライト等）、粉末（ポリメタクリル酸メチル、架橋型シリコーン・網状型シリコーンブロック共重合体、シリカ、疎水化タルクを包含するタルク、トウモロコシデンプン等のスターチ、疎水化処理ポリウレタンを包含するポリウレタン等）、キレート剤、香料、保湿剤（グリセリン、ジプロピレングリコール等）、防腐剤、油相固化剤（トリ酢酸テトラステアリン酸スクロース、パルミチン酸デキストリン、パルミチン酸、（ベヘン酸／エイコサン二酸）グリセル、Ｎ－ラウロイルL-グルタミン酸ジブチルアミド、ポリアミド‐８等）、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤、保湿剤、水溶性高分子、シリコーン化多糖類等の皮膜形成剤、金属イオン封鎖剤、低級アルコール、多価アルコール、各種抽出液、糖、アミノ酸、有機アミン、高分子エマルジョン、ｐＨ調整剤、皮膚栄養剤、ビタミン、医薬品、医薬部外品、化粧品等に適用可能な水溶性薬剤、酸化防止剤、緩衝剤、酸化防止助剤、噴射剤、有機系粉末、顔料、染料、色素、水、酸成分、アルカリ成分等を挙げることができる。これらの任意成分は、油相中及び水相中に適宜配合することができる。さらに，本発明の効果を高めるために，他の細胞賦活化剤等を含有または併用してもよい。
(Optional ingredients)
The composition of the present invention may be appropriately blended with various ingredients within the range that does not affect the effects of the present invention. Examples of the various ingredients include additives that can be normally blended in cosmetics, such as clay minerals (dimethyl distearyl ammonium hectorite, etc.), powders (polymethyl methacrylate, crosslinked silicone/network silicone block copolymers, silica, talc including hydrophobized talc, starch such as corn starch, polyurethane including hydrophobized polyurethane, etc.), chelating agents, fragrances, moisturizing agents (glycerin, dipropylene glycol, etc.), preservatives, oil phase solidifying agents (sucrose tetrastearate triacetate, dextrin palmitate, palmitic acid, (behenic acid/eicosadioic acid) glycol, etc.), and the like. Examples of the components include lysel, N-lauroyl L-glutamic acid dibutylamide, polyamide-8, etc.), anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizing agents, water-soluble polymers, film-forming agents such as silicone-modified polysaccharides, sequestering agents, lower alcohols, polyhydric alcohols, various extracts, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, water-soluble drugs applicable to medicines, quasi-drugs, cosmetics, etc., antioxidants, buffers, antioxidant assistants, propellants, organic powders, pigments, dyes, colorants, water, acid components, and alkaline components. These optional components can be appropriately blended in the oil phase and the aqueous phase. Furthermore, in order to enhance the effects of the present invention, other cell activators, etc. may be contained or used in combination.
本発明の組成物の一態様としては、油中水型組成物がある。本発明の油中水型組成物は通常の製造方法に従って製造することができる。
具体的には、以下の手順により本実施形態における組成物が得られる。すなわち、紫外線吸収剤、紫外線散乱剤および適宜他の油性成分を混合して油相を調製し、油相に分散する場合には（Ａ）紫外線波長変換物質、（Ｂ）分散剤を混合する。つづいて、適宜他の水溶性成分を混合して水相を調製し、水相に分散する場合には（Ａ）紫外線波長変換物質、（Ｂ）分散剤を混合する。前記水相を油相に添加し、撹拌することにより、組成物を得る。
One embodiment of the composition of the present invention is a water-in-oil composition. The water-in-oil composition of the present invention can be produced according to a conventional production method.
Specifically, the composition of this embodiment is obtained by the following procedure. That is, an ultraviolet absorbing agent, an ultraviolet scattering agent, and other oily components are mixed to prepare an oil phase, and when dispersing in the oil phase, (A) an ultraviolet wavelength conversion substance and (B) a dispersant are mixed. Next, other water-soluble components are mixed as appropriate to prepare an aqueous phase, and when dispersing in the aqueous phase, (A) an ultraviolet wavelength conversion substance and (B) a dispersant are mixed. The aqueous phase is added to the oil phase and stirred to obtain a composition.
本発明の組成物の一態様としては、粉末を含む油中水型組成物がある。粉末としては、例えば、ポリメタクリル酸メチル、架橋型シリコーン・網状型シリコーンブロック共重合体、シリカ、疎水化タルクを包含するタルク、トウモロコシデンプン等のスターチ、疎水化処理ポリウレタンを包含するポリウレタン等があり、
本発明の粉末を含む油中水型組成物は通常の製造方法に従って製造することができる。
One embodiment of the composition of the present invention is a water-in-oil type composition containing a powder. Examples of the powder include polymethyl methacrylate, crosslinked silicone/network silicone block copolymer, silica, talc including hydrophobized talc, starch such as corn starch, polyurethane including hydrophobized polyurethane, etc.
The water-in-oil composition containing the powder of the present invention can be produced according to a conventional production method.
本発明の組成物としては、化粧下地、サンスクリーンクリーム等の日焼け止め化粧料等に使用される組成物が含まれる。また、剤型としては、たとえば乳液類、クリーム類等とすることができる。 The composition of the present invention includes compositions used in makeup bases, sunscreen cosmetics such as sunscreen creams, etc. The formulation may be, for example, a milky lotion, a cream, etc.
本発明の組成物は、皮膚、中でも頭髪を除く皮膚、好ましくは顔、身体、手足等のいずれかに適用、好ましくは塗布することにより、使用することができる。たとえば、本実施形態の組成物を皮膚に適用、好ましくは塗布することにより、紫外線を防御して皮膚への悪影響を抑制するだけにとどまらず、皮膚細胞を賦活して肌に自然で好ましい外観を与えることも可能となる。 The composition of the present invention can be used by applying, preferably coating, the skin, particularly the skin excluding hair, preferably the face, body, hands, feet, etc. For example, applying, preferably coating, the composition of the present embodiment to the skin not only protects against ultraviolet rays and suppresses adverse effects on the skin, but also activates skin cells to give the skin a natural and desirable appearance.
次に実施例によって本発明を更に詳細に説明する。なお，本発明はこれにより限定されるものではない。 The present invention will now be described in more detail with reference to examples. Note that the present invention is not limited to these examples.
実験１：各種紫外線波長変換物質の細胞賦活効果
実験１－１：紫外線波長変換物質の調製
紫外線波長変換物質を以下のように調製した。
（１）B-フィコエリスリン
B-フィコエリスリン（B-phycoerythrin）は，チノリモ（Porphiridium Cruentum）抽出物から得られ，吸収スペクトルは305nmにピーク波長を有し，発光スペクトルは570nmおよび610nmにピーク波長を有していた。
（２）C-フィコシアニン
C-フィコシアニン（C-phycocyanin）は，スピルリナ（Spirulina platensis）抽出物から得られ，吸収スペクトルは350nmにピーク波長を有し，発光スペクトルは640nmおよび700nmにピーク波長を有していた。DIC社製のLinablueを使用した。
（３）酸化亜鉛蛍光体
堺化学工業株式会社製のLumate Gを使用した。Lumate Gは，国際公開第2018/004006号に記載のようにZnOを硫黄含有化合物でドープした酸化亜鉛蛍光体であり，吸収スペクトルは365nmにピーク波長を有し，発光スペクトルは510nmにピーク波長を有していた。
（４）チタン酸マグネシウム蛍光体
堺化学工業株式会社製のLumate Rを使用した。Lumate Rは，MgTiO3をマンガンでドープしたチタン酸マグネシウム蛍光体であり，吸収スペクトルは365nmにピーク波長を有し，発光スペクトルは660～680nmの帯域にピーク波長を有していた。
（１）～（２）の紫外線波長変換物質を水に溶解し，1％及び5％の濃度の溶液を調製した。
（３）～（４）の紫外線波長変換物質はアルコールに分散し5％及び10％の分散液を調整した。
Experiment 1: Cell activation effects of various ultraviolet wavelength conversion substances Experiment 1-1: Preparation of ultraviolet wavelength conversion substance Ultraviolet wavelength conversion substances were prepared as follows.
(1) B-phycoerythrin
B-phycoerythrin was obtained from an extract of Porphiridium Cruentum, and its absorption spectrum had a peak wavelength at 305 nm, and its emission spectrum had peak wavelengths at 570 nm and 610 nm.
(2) C-phycocyanin
C-phycocyanin was obtained from an extract of Spirulina platensis, and its absorption spectrum had a peak wavelength at 350 nm, and its emission spectrum had peak wavelengths at 640 nm and 700 nm. Linablue manufactured by DIC was used.
(3) Zinc oxide phosphor Lumate G manufactured by Sakai Chemical Industry Co., Ltd. was used. Lumate G is a zinc oxide phosphor in which ZnO is doped with a sulfur-containing compound as described in International Publication No. 2018/004006, and its absorption spectrum had a peak wavelength at 365 nm and its emission spectrum had a peak wavelength at 510 nm.
(4) Magnesium titanate phosphor Lumate R manufactured by Sakai Chemical Industry Co., Ltd. was used. Lumate R is a magnesium titanate phosphor in which MgTiO3 is doped with manganese, and its absorption spectrum has a peak wavelength at 365 nm, and its emission spectrum has a peak wavelength in the 660 to 680 nm band.
The ultraviolet wavelength conversion substances (1) and (2) were dissolved in water to prepare solutions with concentrations of 1% and 5%.
The ultraviolet wavelength conversion substances (3) and (4) were dispersed in alcohol to prepare 5% and 10% dispersions.
実験１－２：細胞試料の調製
細胞試料を以下のように調製した。
1. Kurabo社から購入したヒト皮膚線維芽細胞およびヒト皮膚角化細胞を使用した。液体窒素で保存されていた細胞懸濁液（1mL）を湯浴（37℃）にかけ小さな氷ペレットが残る程度に解凍し，次いで9mLの温培地で希釈した。
2. 希釈物を穏やかに混合してからT75フラスコに移し，37℃で一晩インキュベートした。
3. 翌日，培地を10mLの新鮮培地に交換した。
4. 培地を定期的に交換し（線維芽細胞では2日に1回，角化細胞では2～3日に1回），細胞の増殖を継続した。その間，顕微鏡を用いて細胞を観察し，細胞が正しい形態で増殖していることを確認した。
5. 細胞が約80％のコンフルエントに達してから，細胞を継代した。細胞の継代は，10mLの温PBSで細胞を1回洗浄してから，5mLの温トリプシンをT75フラスコに加え，トリプシン溶液でフラスコの底面をカバーし1分間室温においてから吸引することにより行った。
6. 線維芽細胞では（最大）2分間，角化細胞では（最大）7分間，フラスコを37℃のオーブン内に静置した。顕微鏡を用いて細胞を観察し，細胞が小さく楕円形であることを確認した。
7. その後，T75フラスコの側面を軽く叩いて細胞を遊離させた。顕微鏡を用いて細胞を観察し，細胞が自由に動いていることを確認した。
8. 線維芽細胞は，5mLの温FGM（10％血清含有）に再懸濁し，滅菌50mLファルコンチューブに移した。フラスコをさらに5mLの温FGMで洗い流してファルコンチューブに加えることにより確実に全ての細胞を移すようにした。
9. 細胞を10,000rpmで5分間遠心し（4℃），細胞ペレットを乱さないよう注意しながら上清を除去した。
10. 細胞の種類に応じ，線維芽細胞は2×104cells/well（500μL），角化細胞は4×104cells/well（500μL）の濃度でFGMまたはKGMに再懸濁し，24ウェルプレートにプレーティングした。
11. 24ウェルプレートに細胞を播種し，培地を定期的に交換し（線維芽細胞では2日に1回，角化細胞では2～3日に1回），60～70％のコンフルエント（実験の種類により異なる）に達するまで細胞を増殖させた。（注：線維芽細胞は，2×104cells/wellの細胞密度だと24時間で所望のコンフルエンシーに達するはずである。細胞密度が，例えば1×104cells/well等と低い場合，線維芽細胞が所望のコンフルエンシーに達するのに48時間かかる。）
12. 照射の24時間前に，サプリメント無添加の培地（角化細胞の場合）または低濃度の血清を含有する（0.5％FCS）培地（線維芽細胞の場合）に変更した。
Experiment 1-2: Preparation of cell samples Cell samples were prepared as follows.
1. Human skin fibroblasts and human skin keratinocytes purchased from Kurabo Co., Ltd. Cell suspension (1 mL) stored in liquid nitrogen was thawed in a water bath (37°C) until a small ice pellet remained, and then diluted with 9 mL of warm medium.
2. The dilutions were mixed gently and then transferred to T75 flasks and incubated overnight at 37°C.
3. The next day, the medium was replaced with 10 mL of fresh medium.
4. The medium was changed periodically (once every 2 days for fibroblasts and once every 2-3 days for keratinocytes) to allow the cells to continue growing. During this time, the cells were observed under a microscope to confirm that they were growing with the correct morphology.
5. When the cells reached approximately 80% confluence, they were passaged by washing the cells once with 10 mL of warm PBS, adding 5 mL of warm trypsin to a T75 flask, covering the bottom of the flask with the trypsin solution, leaving it at room temperature for 1 minute, and then aspirating.
6. The flasks were placed in a 37°C oven for 2 minutes (max) for fibroblasts and 7 minutes (max) for keratinocytes. The cells were observed under a microscope to confirm that they were small and oval in shape.
7. The cells were then loosened by gently tapping the side of the T75 flask and observed under a microscope to confirm that the cells were moving freely.
8. Fibroblasts were resuspended in 5mL of warm FGM (containing 10% serum) and transferred to a sterile 50mL Falcon tube. The flask was rinsed with an additional 5mL of warm FGM and added to the Falcon tube to ensure all cells were transferred.
9. The cells were centrifuged at 10,000 rpm for 5 minutes (4°C) and the supernatant was removed, being careful not to disturb the cell pellet.
10. Depending on the type of cells, fibroblasts were resuspended in FGM or KGM at a concentration of 2 x 10 4 cells/well (500 μL) and keratinocytes were resuspended at a concentration of 4 x 10 4 cells/well (500 μL) and plated in a 24-well plate.
11. Seed the cells in 24-well plates and grow them with regular medium changes (every 2 days for fibroblasts, every 2-3 days for keratinocytes) until they reach 60-70% confluency (depending on the type of experiment). (Note: fibroblasts should reach the desired confluency in 24 hours at a cell density of 2x104 cells/well. If the cell density is lower, e.g., 1x104 cells/well, it will take 48 hours for fibroblasts to reach the desired confluency.)
12. 24 hours before irradiation, the medium was changed to supplement-free (for keratinocytes) or to medium containing low concentrations of serum (0.5% FCS) (for fibroblasts).
実験１－３：紫外線の照射
1. 照射の少なくとも30分前にソーラーシミュレータの電源を入れてランプをウォームアップした。ソーラーシミュレータは，UG11フィルターを使用する設定にした。UG11フィルターは，UVBのみを通過させ他の波長光をカットするフィルターである。UG11フィルターを通過したUV光は300nm～385nmにピーク波長を有していた。
2. 温度制御プレートをオンにして33℃に設定した。
3. 実験１－２で調製した細胞を温PBSで1回洗浄した。
4. 各ウェルに0.5mLの温めたMartinez溶液(145mM NaCl, 5.5mM KCl, 1.2mM MgCl2.6H2O, 1.2mM NaH2PO4.2H2O, 7.5mM HEPES, 1mM CaCl2, 10mM D-グルコース)を加えた。
5. 図１に示すように，細胞ウェルをプレート上に載置し，更にその上に，実験１－１で調製した紫外線波長変換物質（１）～（４）を含む溶液を24ウェルプレートの各穴に0.4ml注入し，細胞入りのウェルを覆うように載置し，紫外線波長変換物質の溶液が細胞溶液と直接触れずに，UV光が紫外線波長変換物質の溶液を通過して細胞溶液に照射されるようにした。
6. 合計が100mJ/cm2の線量になるよう照射を行った。また，対照として，細胞ウェルの上に紫外線波長変換物質のプレートを載せず細胞に直接UV光を照射した試料と，細胞にUV光を照射せず暗所で培養した試料を作成した。
7. 照射後，Martinezを温めたKGM（サプリメント無添加）またはFGM（0.5％FCS含有）と交換し，プレートを37℃のインキュベータに戻した。
Experiment 1-3: UV irradiation
1. The solar simulator was turned on to warm up the lamp at least 30 minutes before irradiation. The solar simulator was set to use the UG11 filter. The UG11 filter is a filter that passes only UVB and blocks other wavelengths of light. The UV light that passed through the UG11 filter had a peak wavelength of 300nm to 385nm.
2. The temperature control plate was turned on and set to 33°C.
3. The cells prepared in Experiment 1-2 were washed once with warm PBS.
4. 0.5 mL of warmed Martinez solution (145 mM NaCl, 5.5 mM KCl, 1.2 mM MgCl2.6H2O, 1.2 mM NaH2PO4.2H2O , 7.5 mM HEPES, 1 mM CaCl2 , 10 mM D - glucose) was added to each well.
5. As shown in Figure 1, the cell wells were placed on a plate, and 0.4 ml of the solution containing the ultraviolet wavelength conversion substances (1) to (4) prepared in Experiment 1-1 was poured into each well of the 24-well plate, and the wells containing the cells were then placed so as to cover them. This was done so that the solution of the ultraviolet wavelength conversion substance did not come into direct contact with the cell solution, and UV light was irradiated onto the cell solution through the solution of the ultraviolet wavelength conversion substance.
6. The total dose was 100 mJ/ cm2 . As controls, a sample was prepared in which the cells were directly irradiated with UV light without placing a plate of UV wavelength conversion material on the cell well, and a sample was prepared in which the cells were cultured in the dark without being irradiated with UV light.
7. After irradiation, the Martinez was replaced with warmed KGM (no supplements) or FGM (containing 0.5% FCS) and the plates were returned to the 37°C incubator.
実験１－４：細胞活性の測定
実験１－３の後インキュベータ内で48時間保持した細胞を用いて，以下の方法により活性を測定した。
1. 培地（サプリメント無添加のKGM培地または0.5％FCS含有FGM培地）に10％Alamar Blueを添加し37℃に温めた（溶液は暗所で保持）。
2. ウェル内の培地を500μLの上記10％Alamar Blue溶液に交換し，プレートを37℃のインキュベータに戻し約3時間保持した。対照のウェルも同様にインキュベータ内で保持した。これらの溶液を光から保護するため暗所で保持した。
3. 3時間後，100μLのアリコートを採取し，黒色の96ウェルプレートに移した。
4. 蛍光測定器 (OPwave+, Ocean Photonics)を用いて544nm/590nmでの蛍光測定値を読み取った。
Experiment 1-4: Measurement of cell activity After Experiment 1-3, cells were kept in an incubator for 48 hours and their activity was measured by the following method.
1. Culture medium (KGM medium without supplements or FGM medium containing 0.5% FCS) was added with 10% Alamar Blue and warmed to 37°C (the solution was kept in the dark).
2. The medium in the wells was replaced with 500 μL of the above 10% Alamar Blue solution, and the plate was returned to the 37°C incubator for approximately 3 hours. The control wells were also kept in the incubator. These solutions were kept in the dark to protect them from light.
3. After 3 hours, a 100 μL aliquot was removed and transferred to a black 96-well plate.
4. Fluorescence measurements were taken at 544 nm/590 nm using a fluorometer (OPwave+, Ocean Photonics).
結果を図２に示す。UVを照射すると照射しない対照に比べて細胞活性が低下していた。しかし，紫外線波長変換物質を通してUVを照射した細胞の活性は，照射しない対照に比べていずれの紫外線波長変換物質でも上昇していた。以上の結果より，UV照射により細胞活性は低下するものの，紫外線波長変換物質を用いると細胞活性低下が抑制されることがわかった。 The results are shown in Figure 2. Cell activity was reduced when exposed to UV light compared to the non-irradiated control. However, the activity of cells exposed to UV light through a UV wavelength conversion substance was increased for all UV wavelength conversion substances compared to the non-irradiated control. These results show that although UV irradiation reduces cell activity, the use of a UV wavelength conversion substance can suppress the reduction in cell activity.
実施例２：紫外線波長変換物質の濃度およびUVの強度の違いによる細胞活性への影響
紫外線波長変換物質としてC-フィコシアニンを使用し0％，0.4％，2％となるように添加した溶液入りのプレートで細胞培養物を覆い，0，10，25，50，75，100mJ/cm2の線量でUVを照射した以外は実験１と同じ方法を行った。
Example 2: Effects of different concentrations of ultraviolet wavelength conversion substance and UV intensity on cell activity The same method as in Experiment 1 was used, except that the cell culture was covered with a plate containing a solution containing 0%, 0.4%, or 2% C-phycocyanin as an ultraviolet wavelength conversion substance, and UV was irradiated at doses of 0, 10, 25, 50, 75, and 100 mJ/ cm2 .
結果を図３に示す。紫外線波長変換物質を用いない場合，UV照射量が上がるほど細胞活性は低下した。しかし，0.4％のC-フィコシアニンを添加するとUV照射しても細胞活性の低下は抑制されており，2％のC-フィコシアニンを添加するとUV照射をしない場合よりも細胞活性がむしろ亢進されていた。以上の結果より，UV照射により細胞活性は低下するものの，紫外線波長変換物質を用いると濃度依存的に細胞活性低下が抑制されるのみならず，細胞活性が亢進されることがわかった。 The results are shown in Figure 3. When no ultraviolet wavelength conversion substance was used, the higher the UV irradiation dose, the lower the cell activity. However, when 0.4% C-phycocyanin was added, the lowering of cell activity was suppressed even with UV irradiation, and when 2% C-phycocyanin was added, cell activity was actually enhanced compared to when no UV irradiation was used. These results show that, although UV irradiation reduces cell activity, the use of an ultraviolet wavelength conversion substance not only suppresses the lowering of cell activity in a concentration-dependent manner, but also enhances cell activity.
実施例３：UV照射により低下した細胞活性の回復
図４に示すように，紫外線波長変換物質を使用せずに照射量が400mJ/cm2となるまでUV照射を行い細胞活性を一旦低下させた後に，紫外線波長変換物質としてC-フィコシアニンを0％，0.4％，2％となるように添加した溶液入りのプレートで細胞培養物を覆い，0，10，25，50，75，100，200mJ/cm2の線量になるまでUVを照射した以外は実験１と同じ方法を行った。
Example 3: Restoration of cell activity reduced by UV irradiation As shown in Fig. 4, the same method as in Experiment 1 was used except that, after UV irradiation was performed without using an ultraviolet wavelength conversion substance until the irradiation dose reached 400 mJ/ cm2 to reduce cell activity, the cell culture was covered with a plate containing a solution containing 0%, 0.4%, and 2% C-phycocyanin as an ultraviolet wavelength conversion substance, and UV irradiation was performed until the dose reached 0, 10, 25, 50, 75, 100, and 200 mJ/ cm2 .
結果を図５に示す。紫外線波長変換物質を使用せずUV照射により一旦活性が低下した細胞であっても，紫外線波長変換物質を用いてUV照射を施すことにより細胞活性が回復したことがわかる。また，この効果は，C-フィコシアニンが0.4％の濃度であっても2％の場合と同等であり，0.4％でも十分な細胞賦活効果があることが示唆される。一方，紫外線波長変換物質を用いずにUV照射を行った場合，細胞活性はUV線量依存的に低下した。 The results are shown in Figure 5. It can be seen that even in cells whose activity had once decreased due to UV irradiation without the use of an ultraviolet wavelength conversion substance, cellular activity was restored by UV irradiation using an ultraviolet wavelength conversion substance. Furthermore, this effect was the same even at a concentration of 0.4% C-phycocyanin as at 2%, suggesting that even at 0.4%, sufficient cell activation is achieved. On the other hand, when UV irradiation was performed without the use of an ultraviolet wavelength conversion substance, cellular activity decreased in a UV dose-dependent manner.
以上，ヒト皮膚線維芽細胞についての結果を示したが，角化細胞についても同様の結果が見られた（データ示さず）。これらの結果により，紫外線波長変換物質はUV照射による細胞活性の低下を抑制するのみならず，UV光を利用して細胞を賦活する効果があることがわかった。皮膚の細胞が賦活されると，しわ，シミ，皮膚老化，光老化等の予防・改善が期待される。 The above results were shown for human skin fibroblasts, but similar results were also seen for keratinocytes (data not shown). These results demonstrate that UV wavelength conversion substances not only suppress the decline in cell activity caused by UV exposure, but also have the effect of activating cells using UV light. Activating skin cells is expected to help prevent and improve wrinkles, age spots, skin aging, photoaging, and more.
前記実施例1～3により、紫外線波長変換物質が紫外線を波長変換し、発光した可視光（主波長が500nm～700nmの蛍光）が線維芽細胞や角質細胞等の皮膚の細胞を賦活するものと考えられた。そこで、以下紫外線波長変換物質を含む種々の組成物を製造して、紫外線照射時の発光する蛍光量について評価を行った。 From the above Examples 1 to 3, it was believed that the ultraviolet wavelength conversion substance converts the wavelength of ultraviolet light, and the emitted visible light (fluorescence with a dominant wavelength of 500 nm to 700 nm) activates skin cells such as fibroblasts and keratinocytes. Therefore, various compositions containing the ultraviolet wavelength conversion substance were produced as described below, and the amount of fluorescence emitted when irradiated with ultraviolet light was evaluated.
蛍光量の測定は、組成物をSプレート（特許第４４５３９９５号参照）に２mg/cm2で塗布し、乾燥させて組成物の塗膜を調製した。得られた塗膜に所定波長の紫外線を照射し、所定波長領域の蛍光積算値を分光蛍光光度計RF-5300PC（島津製作所）を用いて測定した。紫外線波長変換物質がLumateGの場合は365nmの紫外線で照射し、400-600nmの蛍光積算値を同様に測定した。紫外線波長変換物質がLumateRの場合は340nmの紫外線で照射し、550-800nmの蛍光積算値を同様に測定した。紫外線波長変換物質がLinaBlueの場合は350nmの紫外線で照射し、550-800nmの蛍光積算値を同様に測定した。 The amount of fluorescence was measured by applying the composition to an S plate (see Patent No. 4453995) at 2 mg/ cm2 and drying to prepare a coating film of the composition. The obtained coating film was irradiated with ultraviolet light of a predetermined wavelength, and the fluorescence integrated value in a predetermined wavelength region was measured using a spectrofluorophotometer RF-5300PC (Shimadzu Corporation). When the ultraviolet wavelength conversion material was LumateG, it was irradiated with ultraviolet light of 365 nm, and the fluorescence integrated value at 400-600 nm was measured in the same manner. When the ultraviolet wavelength conversion material was LumateR, it was irradiated with ultraviolet light of 340 nm, and the fluorescence integrated value at 550-800 nm was measured in the same manner. When the ultraviolet wavelength conversion material was LinaBlue, it was irradiated with ultraviolet light of 350 nm, and the fluorescence integrated value at 550-800 nm was measured in the same manner.
実施例４：紫外線吸収剤／紫外線散乱剤共存下での紫外線波長変換物質の機能
表１に記載の組成の組成物（処方例U1、U2）を通常の製造方法に従って製造した。処方例U1、U2は紫外線波長変換物質である酸化亜鉛蛍光体（LumateG）を含み、処方例U2は更に紫外線吸収剤（オクトクリレン、サリチル酸エチルヘキシル及びホモサレート）及び紫外線散乱剤（微粒子酸化亜鉛）を含む。処方例U1の蛍光積算値が25624に対し、処方例U2の蛍光積算値3570と低下したものの、紫外線波長変換物質は、紫外線吸収剤／紫外線散乱剤共存下でも波長変換機能を有していることが分かった。
Example 4: Function of ultraviolet wavelength conversion material in the presence of ultraviolet absorber/ultraviolet scattering agent Compositions (prescription examples U1 and U2) with the composition shown in Table 1 were manufactured according to a normal manufacturing method. Prescription examples U1 and U2 contain zinc oxide phosphor (Lumate G), which is an ultraviolet wavelength conversion material, and prescription example U2 further contains ultraviolet absorbers (octocrylene, ethylhexyl salicylate, and homosalate) and an ultraviolet scattering agent (fine particle zinc oxide). Although the fluorescence integrated value of prescription example U1 was 25624 and that of prescription example U2 was 3570, which was lower, it was found that the ultraviolet wavelength conversion material has a wavelength conversion function even in the presence of ultraviolet absorber/ultraviolet scattering agent.
実施例５：紫外線波長変換物質酸化亜鉛蛍光体の効果
表２に記載の組成の組成物（処方例Ｇ１～Ｇ６）を通常の製造方法に従って製造した。いずれの処方例も紫外線波長変換物質である酸化亜鉛蛍光体（LumateG）を含む。Ｇ１～Ｇ６の各処方例の蛍光積算値はそれぞれ、669、2230、4273、16116、23515、43316であり、酸化亜鉛蛍光体は組成物に含めても用量依存的に波長変換機能を有していることが分かった。
Example 5: Effect of zinc oxide phosphor as ultraviolet wavelength conversion material Compositions (formulation examples G1 to G6) having the composition shown in Table 2 were produced according to a normal production method. All formulation examples contain zinc oxide phosphor (Lumate G), which is an ultraviolet wavelength conversion material. The fluorescence integrated values of formulation examples G1 to G6 were 669, 2230, 4273, 16116, 23515, and 43316, respectively, and it was found that zinc oxide phosphor has a wavelength conversion function in a dose-dependent manner even when included in the composition.
実施例６：紫外線波長変換物質チタン酸マグネシウム蛍光体の効果
表３に記載の組成の組成物（処方例Ｒ１～Ｒ５）を通常の製造方法に従って製造した。いずれの処方例も紫外線波長変換物質であるチタン酸マグネシウム蛍光体（LumateR）を含む。Ｒ１～Ｒ５の各処方例の蛍光積算値はそれぞれ、4986、7537、5797、5488、8746であり、チタン酸マグネシウム蛍光体は組成物に含めても用量依存的に波長変換機能を有していることが分かった。
Example 6: Effect of magnesium titanate phosphor as ultraviolet wavelength conversion material Compositions (formulation examples R1 to R5) having the composition shown in Table 3 were produced according to a normal production method. All formulation examples contain magnesium titanate phosphor (LumateR), which is an ultraviolet wavelength conversion material. The fluorescence integrated values of formulation examples R1 to R5 were 4986, 7537, 5797, 5488, and 8746, respectively, and it was found that magnesium titanate phosphor has a wavelength conversion function in a dose-dependent manner even when included in the composition.
実施例７：紫外線波長変換物質C-フィコシアニンの効果
表４に記載の組成の組成物（処方例L１～L５）を通常の製造方法に従って製造した。いずれの処方例も紫外線波長変換物質であるC-フィコシアニン（LinaBlue）を含む。L１～L５の各処方例の蛍光積算値はそれぞれ、6308、11937、9287、5608、3946であり、C-フィコシアニンは組成物に含めても波長変換機能を有しており、紫外線波長変換効果はＬｉｎａＢｌｕｅが0.5％～3％の濃度で最適な、ベルシェイプな用量依存性であることが分かった。
Example 7: Effect of ultraviolet wavelength conversion substance C-phycocyanin The compositions (formulation examples L1 to L5) shown in Table 4 were produced according to a conventional manufacturing method. All formulation examples contain C-phycocyanin (LinaBlue), an ultraviolet wavelength conversion substance. The fluorescence integrated values of formulation examples L1 to L5 were 6308, 11937, 9287, 5608, and 3946, respectively, and it was found that C-phycocyanin has a wavelength conversion function even when included in the composition, and the ultraviolet wavelength conversion effect is bell-shaped dose-dependent, with LinaBlue at a concentration of 0.5% to 3% being optimal.
実施例８：分散剤PEG-10ジメチコンの効果
表５に記載の組成の組成物（処方例Ｄ１～Ｄ４）を通常の製造方法に従って製造した。いずれの処方例も紫外線波長変換物質である酸化亜鉛蛍光体（LumateG）を含む。Ｄ１～Ｄ４の各処方例の蛍光積算値はそれぞれ、3570、4015、5657、6500であり、分散剤PEG-10ジメチコンは用量依存的に酸化亜鉛蛍光体の波長変換機能を亢進し、また別の分散剤ラウリルPEG-9ポリジメチルポリシロキシエチルジメチコンと組み合わせることにより、さらに波長変換機能を高めることが分かった。
Example 8: Effect of dispersant PEG-10 dimethicone Compositions (formulation examples D1 to D4) having the composition shown in Table 5 were produced according to a normal production method. All formulation examples contain zinc oxide phosphor (Lumate G), which is an ultraviolet wavelength conversion material. The fluorescence integrated values of formulation examples D1 to D4 were 3570, 4015, 5657, and 6500, respectively, and it was found that the dispersant PEG-10 dimethicone enhances the wavelength conversion function of the zinc oxide phosphor in a dose-dependent manner, and that the wavelength conversion function is further enhanced by combining it with another dispersant, lauryl PEG-9 polydimethylpolysiloxyethyl dimethicone.
表６に記載の組成の組成物（処方例Ｍ１～Ｍ１０）を通常の製造方法に従って製造した。いずれの処方例も紫外線波長変換物質である酸化亜鉛蛍光体LumateGを含む。Ｍ１～Ｍ１０の各処方例の蛍光積算値はそれぞれ、4294、5685、6779、7412、7608、7016、4309、7305、3633、1531であり、分散剤PEG-10ジメチコンにビスブチルジメチコンポリグリセリル-3、PEG-9ポリジメチルポリシロキシエチルジメチコン、ラウリルPEG-9ポリジメチルポリシロキシエチルジメチコン、セチルPEG/PPG-10/1ジメチコン、イソステアリン酸またはカルボキシデシルトリシロキサンを組み合わせることにより、PEG-10ジメチコンのみと比較して、酸化亜鉛蛍光体の波長変換機能を高めることが分かった。
表７に記載の組成の組成物（処方例Ｐ１～Ｐ７）を通常の製造方法に従って製造した。いずれの処方例も紫外線波長変換物質である酸化亜鉛蛍光体（LumateG）を含む。Ｍ１～Ｍ１０の各処方例の蛍光積算値はそれぞれ、19133、21805、19486、23191、21689、21788、22552であり、組成物に各種粉末を含めても酸化亜鉛蛍光体の波長変換機能を抑制せず、シリカ粉末などでは酸化亜鉛蛍光体の波長変換機能を高めることが分かった。このことから、粉末を含む油中水型の組成物も細胞賦活剤として製造可能であると考えられた。
実施例１１：チトクロームｃ含量への効果
前記実施例1～３にて、波長変換された可視光がAlamarBlueアッセイでミトコンドリア呼吸鎖からの電子受容による還元能力を亢進することがわかった。チトクロームｃはミトコンドリアの電子伝達系に関与する分子であり、還元剤であるＮＤＨ分子の生産に重要な機能を果たす。そこで、次に本発明の組成物が細胞のチトクロームｃの細胞内濃度に影響するかについて検討した。
Example 11: Effect on cytochrome c content In the above Examples 1 to 3, it was found that wavelength-converted visible light enhances the reduction ability by electron acceptance from the mitochondrial respiratory chain in the AlamarBlue assay. Cytochrome c is a molecule involved in the mitochondrial electron transport system and plays an important role in the production of NDH molecules, which are reducing agents. Therefore, next, we investigated whether the composition of the present invention affects the intracellular concentration of cytochrome c in cells.
本発明の組成物を24well plateに0.1g/wellずつ塗布・分注し、乾燥させた。ヒト皮膚由来線維芽細胞（ＳｃｉｅｎＣｅｌｌ Ｒｅｓｅａｒｃｈ Ｌａｂ．＃2320）を24well プレートに1x105 cells/wellの密度で播種し、ＤＭＥＭ培地で（Thermo Fisher, #11965-092）3日間培養した。細胞をＰＢＳによる洗浄後に、1ｍＬのＰＢＳを添加した。乾燥させた組成物を含む24well plateを細胞を含む24well plateに重ね、約70ｃｍ離れた距離から人工太陽ライト（セリック社、XC-500BF）により最大出力量で40分間照射した。なお、すべての細胞プレートは20℃の蓄熱材の上に設置することにより、温度上昇を防止した。照射時間経過後に、ＰＢＳを除去し、0.3ｍＬの細胞抽出液（ＲＩＰＡ buffer:50mM Tris-HCl(pH8.0), 150mM NaCl, 0.5%(w/v) Sodium Deoxycholate, 0.1%(w/v)SDS, 1.0%(w/v)NP-40 substitute, 1mM PMSF）を加え、ピペッティングにより細胞を完全に溶解した。細胞溶解液を4℃、10000×gで10分間遠心し、上清中のチトクロームcを測定した(Proteintech Group社、KE00079)。 The composition of the present invention was applied and dispensed at 0.1 g/well on a 24-well plate and dried. Human skin-derived fibroblasts (ScienCell Research Lab. #2320) were seeded on a 24-well plate at a density of 1x10 5 cells/well and cultured in DMEM medium (Thermo Fisher, #11965-092) for 3 days. After washing the cells with PBS, 1 mL of PBS was added. The 24-well plate containing the dried composition was placed on top of the 24-well plate containing the cells, and irradiated with an artificial solar light (Cerric, XC-500BF) at maximum output from a distance of about 70 cm for 40 minutes. All cell plates were placed on a heat storage material at 20°C to prevent temperature rise. After the irradiation time had elapsed, the PBS was removed, and 0.3 mL of cell extract (RIPA buffer: 50 mM Tris-HCl (pH 8.0), 150 mM NaCl, 0.5% (w/v) sodium deoxycholate, 0.1% (w/v) SDS, 1.0% (w/v) NP-40 substitute, 1 mM PMSF) was added, and the cells were completely lysed by pipetting. The cell lysate was centrifuged at 4°C and 10,000 x g for 10 minutes, and cytochrome c in the supernatant was measured (Proteintech Group, KE00079).
太陽光照射前後で細胞の外観に影響は見られなかった。組成物を介しない細胞でのチトクロームc含量が、3782pg/mLに対し、紫外線波長変換機能の高かった、処方例M4及びM5のチトクロームc含量は、それぞれ、5150pg/mL、5448pg/mLであり、細胞内のチトクロームｃの含量を高めていることが分かった。 No effect was observed on the appearance of the cells before and after exposure to sunlight. The cytochrome c content in cells without the composition was 3782pg/mL, while the cytochrome c contents of formulations M4 and M5, which had a high UV wavelength conversion function, were 5150pg/mL and 5448pg/mL, respectively, demonstrating that the composition increased the amount of cytochrome c in the cells.
以上，本発明の組成物の実施の形態について説明してきた。しかしながら，本発明はこれらに限定されるものではなく，発明の趣旨を逸脱しない範囲で適宜変更可能である。 The above describes the embodiments of the composition of the present invention. However, the present invention is not limited to these, and can be modified as appropriate without departing from the spirit of the invention.
Claims (9)
前記（Ａ）紫外線波長変換物質が、フィコビリ蛋白、ビタミンＡ、ビタミンＫ、ビタミンＢ１、ビタミンＢ２、ビタミンＢ６、ビタミンＢ１２、葉酸、酸化亜鉛蛍光体、及びチタン酸マグネシウム蛍光体からなる群から選ばれる少なくとも一種を含み、
前記（Ｂ）分散剤が、ＰＥＧ－１０ジメチコン、ビスブチルジメチコンポリグリセリル－３、ＰＥＧ－９ポリジメチルシロキシエチルジメチコン、セチルＰＥＧ／ＰＰＧ－１０／１ジメチコン、イソステアリン酸、及びカルボキシデシルトリシロキサンからなる群から選ばれる少なくとも一種を含む、
組成物。 (A) an ultraviolet wavelength conversion substance, (B) a dispersant, (C) an ultraviolet absorbing agent and/or an ultraviolet scattering agent, and (D) an oil component, the blending amount of the (B) dispersant being 1% by weight or more,
the ultraviolet wavelength converting substance (A) contains at least one selected from the group consisting of phycobiliprotein, vitamin A , vitamin K, vitamin B1, vitamin B2, vitamin B6, vitamin B12, folic acid, a zinc oxide phosphor, and a magnesium titanate phosphor;
The (B) dispersant contains at least one selected from the group consisting of PEG-10 dimethicone, bisbutyl dimethicone polyglyceryl-3, PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, isostearic acid, and carboxydecyl trisiloxane.
Composition.
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| JP7794889B2 (en) | 2026-01-06 |
| JP2024096356A (en) | 2024-07-12 |
| JP2021107369A (en) | 2021-07-29 |
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