JP6887832B2 - Topical skin or cosmetics - Google Patents
Topical skin or cosmetics Download PDFInfo
- Publication number
- JP6887832B2 JP6887832B2 JP2017045954A JP2017045954A JP6887832B2 JP 6887832 B2 JP6887832 B2 JP 6887832B2 JP 2017045954 A JP2017045954 A JP 2017045954A JP 2017045954 A JP2017045954 A JP 2017045954A JP 6887832 B2 JP6887832 B2 JP 6887832B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- acid
- extract
- humus
- skin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002537 cosmetic Substances 0.000 title claims description 60
- 230000000699 topical effect Effects 0.000 title 1
- 239000000843 powder Substances 0.000 claims description 71
- 239000003864 humus Substances 0.000 claims description 65
- 239000000284 extract Substances 0.000 claims description 56
- -1 methylolhexyl lactone Chemical class 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 41
- 239000002689 soil Substances 0.000 claims description 37
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000004021 humic acid Substances 0.000 claims description 29
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 20
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 20
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Landscapes
- Cosmetics (AREA)
Description
本発明は、皮膚外用剤又は化粧料に関するものである。 The present invention relates to an external preparation for skin or a cosmetic.
近年、皮膚外用剤や化粧料には、太陽光線中の紫外線を遮断し、紫外線による悪影響から肌を守る効果を付与することが強く求められてきており、酸化亜鉛や酸化チタン等の金属酸化物粉体や有機紫外線吸収剤を含有することにより、高い紫外線防御効果をもつ皮膚外用剤や化粧料が開発されている。また、皮膚外用剤や化粧料において、高い紫外線防御効果を発揮するためには化粧膜の均一性に優れることが重要な品質の一つであり、様々な検討がなされてきた。
例えば、化粧膜の均一性を向上させる技術としては、有機紫外線吸収剤と水溶性増粘剤、特定の親水性非イオン界面活性剤及び親油性界面活性剤を用いる技術(特許文献1参照)等が知られている。
In recent years, there has been a strong demand for skin external preparations and cosmetics to block ultraviolet rays in the sun's rays and to impart the effect of protecting the skin from the adverse effects of ultraviolet rays, and metal oxides such as zinc oxide and titanium oxide have been strongly required. Skin external preparations and cosmetics having a high UV protection effect have been developed by containing powders and organic UV absorbers. Further, in skin external preparations and cosmetics, excellent uniformity of the cosmetic film is one of the important qualities in order to exert a high ultraviolet protection effect, and various studies have been conducted.
For example, as a technique for improving the uniformity of a decorative film, a technique using an organic ultraviolet absorber, a water-soluble thickener, a specific hydrophilic nonionic surfactant, and a lipophilic surfactant (see Patent Document 1) and the like. It has been known.
一方、腐植土は、地上植物、大型・微細藻類などの植物(広義)や魚介類およびその他無機物が、海、沼、池や湖の底部に堆積したものやこれが地表に隆起したもの、また森林の地表部に堆積したもの等のように植物(広義)などやこれを含む堆積物が、長い年月の間に嫌気性微生物等により分解、有機化を受けたものである。この腐植土の抽出物は、フルボ酸、フミン酸などの腐植土壌特有の構成物質のほか、脂肪酸、有機酸、アミノ酸、タンパク質、ミネラル等が含まれていることが知られており、皮膚外用剤や化粧料への含有が検討されてきた(特許文献2参照)。また、腐植土抽出物又はその成分であるフミン質(フルボ酸、フミン酸等)は、I型アレルギー抑制作用、抗菌・殺菌、ウイルス不活化等が見出され、皮膚外用剤や化粧料における有効成分として利用することが検討されてきており近年注目を集めている(特許文献2、3参照)。 On the other hand, humus soil is terrestrial plants, plants such as large and microalgae (in a broad sense), seafood and other inorganic substances deposited on the bottom of the sea, swamps, ponds and lakes, uplifted on the ground surface, and forests. Plants (in a broad sense) and sediments containing them, such as those deposited on the surface of the sea, have been decomposed and organicized by anaerobic microorganisms over a long period of time. This humus extract is known to contain fatty acids, organic acids, amino acids, proteins, minerals, etc., in addition to constituents peculiar to humic acid such as fulvic acid and humic acid. And their inclusion in cosmetics has been studied (see Patent Document 2). In addition, humic acid extract or its component humic acid (fulvic acid, humic acid, etc.) has been found to have type I allergy-suppressing action, antibacterial / bactericidal action, virus inactivation, etc., and is effective in external skin preparations and cosmetics. It has been studied to be used as an ingredient and has been attracting attention in recent years (see Patent Documents 2 and 3).
しかしながら、腐植土抽出物特有の構成成分であるフミン質は、分子内に多数の極性基を有するため、製剤に含有した際にべたつきが強く、延展性に欠け、化粧膜の均一性を損なってしまうという課題があり、皮膚外用剤や化粧料の紫外線防御効果を低下させてしまう原因となる場合があった。また、特定の親水性界面活性剤及び親油性界面活性剤等を用いる技術(特許文献1参照)では、化粧膜の均一性を向上させるために界面活性剤の含有量を増やすと、界面活性剤由来のべたつきが出てしまい、満足のいく滑らかな伸び広がりが得られていなかった。
このため、腐植土抽出物を含有しながらも、滑らかに伸び広がり、紫外線防御効果に優れる皮膚外用剤や化粧料の開発が望まれていた。
However, since humic acid, which is a constituent component peculiar to humus extract, has a large number of polar groups in the molecule, it is strongly sticky when contained in a pharmaceutical product, lacks spreadability, and impairs the uniformity of the cosmetic film. There is a problem that it is removed, which may cause a decrease in the ultraviolet protection effect of external preparations for skin and cosmetics. Further, in the technique using a specific hydrophilic surfactant, lipophilic surfactant, etc. (see Patent Document 1), when the content of the surfactant is increased in order to improve the uniformity of the cosmetic film, the surfactant is used. The origin was sticky, and a satisfactory and smooth spread was not obtained.
Therefore, it has been desired to develop an external preparation for skin and a cosmetic which spreads smoothly and has an excellent ultraviolet protection effect while containing a humus extract.
発明者は誠意検討の結果、優れた延展性を有し、均一な付着性を有する平均粒子径5〜30μmの球状粉体を含有させることで、腐植土抽出物を含有していても、滑らかに伸び広がり、紫外線防御効果にも優れる皮膚外用剤又は化粧料が得られることを見出し、本発明を完成するに至った。 As a result of sincere examination, the inventor has made it smooth even if it contains a humus extract by containing a spherical powder with an average particle size of 5 to 30 μm, which has excellent spreadability and uniform adhesion. It has been found that an external preparation for skin or a cosmetic having an excellent UV protection effect can be obtained, and the present invention has been completed.
すなわち、本発明は、次の成分(A)〜(C);
(A)腐食土抽出物
(B)有機紫外線吸収剤及び/又は金属酸化物粉体
(C)平均粒子径が5〜30μmの球状粉体
を含有する皮膚外用剤又は化粧料、
That is, the present invention describes the following components (A) to (C);
(A) Corrosive soil extract (B) Organic UV absorber and / or metal oxide powder (C) Skin external preparation or cosmetic containing spherical powder with an average particle size of 5 to 30 μm.
前記成分(A)腐植土抽出物が、水性溶媒抽出物である皮膚外用剤又は化粧料、 The component (A) humus extract is an aqueous solvent extract for external use on the skin or cosmetics.
前記成分(A)腐植土抽出物が、エキス分濃度が0.5質量%となるように水に溶解または懸濁したときにフミン質を100mg/L以上含有するものである皮膚外用剤又は化粧料、 A skin external preparation or cosmetic containing 100 mg / L or more of humic acid when the humus extract of the component (A) is dissolved or suspended in water so that the extract concentration is 0.5% by mass. Fee,
前記成分(A)腐植土抽出物が、エキス分濃度が0.5質量%となるように水に溶解または懸濁したときにフルボ酸を0.1〜100mg/L含有するものである皮膚外用剤又は化粧料、 For external use on the skin, the component (A) humus extract contains 0.1 to 100 mg / L of fulvic acid when dissolved or suspended in water so that the extract concentration is 0.5% by mass. Agent or cosmetic,
前記成分(C)の平均粒子径が5〜15μmである皮膚外用剤又は化粧料、 A skin external preparation or cosmetic having an average particle size of the component (C) of 5 to 15 μm.
前記成分(C)がシリコーン系樹脂粉体、アクリル系樹脂粉体、無水ケイ酸粉体から選ばれる1種又は2種以上である皮膚外用剤又は化粧料、 A skin external preparation or cosmetic in which the component (C) is one or more selected from silicone-based resin powder, acrylic-based resin powder, and silicic anhydride powder.
前記成分(A)と前記成分(C)の含有質量比が(A):(C)=1:1〜1:100000である皮膚外用剤又は化粧料、 A skin external preparation or cosmetic having a mass ratio of the component (A) to the component (C) of (A) :( C) = 1: 1 to 1: 100,000.
前記皮膚外用剤又は化粧料が乳化物である皮膚外用剤又は化粧料を提供するものである。 It provides a skin external preparation or cosmetic in which the skin external preparation or cosmetic is an emulsion.
本発明は皮膚外用剤又は化粧料に関し、更に詳細には、滑らかな伸び広がり、化粧膜の均一性に優れ、高い紫外線防御効果を有するものである。 The present invention relates to an external preparation for skin or a cosmetic, and more specifically, it has a smooth spreading and spreading, an excellent uniformity of a cosmetic film, and a high ultraviolet protection effect.
本発明の詳細について以下に説明する。なお、本明細書において、「〜」はその前後の数値を含む範囲を意味するものとする。 Details of the present invention will be described below. In addition, in this specification, "~" means the range including the numerical values before and after it.
本発明において、成分(B)の金属酸化物粉体及び成分(C)の球状粉体の平均粒子径の測定方法は、走査型電子顕微鏡を用いて、任意の視野の粒子10個について、粒子径を測定した結果から算出する。 In the present invention, the method for measuring the average particle size of the metal oxide powder of the component (B) and the spherical powder of the component (C) is to use a scanning electron microscope to measure 10 particles in an arbitrary field of view. Calculated from the result of measuring the diameter.
本発明に用いられる成分(A)は、腐植土抽出物である。本発明で使用する腐植土抽出物の腐植土は、特に限定されず、産地、状態を問わずいずれのものも使用することができる。具体的には、この腐植土として、例えば、森林、河川、湖沼、海洋などを起源とするものを使用することが可能であり、この腐植土とは、そこで生息していた地上植物、大型・微細藻類などの植物(広義)などやこれを含む堆積物が、嫌気性微生物などにより分解、合成、有機化を受けたものである。このうち、海洋でできた堆積物を起源とする腐植土、より好ましくは海洋でできた堆積物が隆起してなったような日本列島由来の腐植土であり、さらに九州由来の腐植土が好ましい。この腐植土の腐植の程度も特に限定されず、腐植が進行し、高分子有機化合物であるフルボ酸やフミン酸が含まれるものが好ましい。 The component (A) used in the present invention is a humus extract. The humus soil of the humus soil extract used in the present invention is not particularly limited, and any humus soil can be used regardless of the place of origin or condition. Specifically, as this humus soil, for example, those originating from forests, rivers, lakes, marshes, oceans, etc. can be used, and this humus soil is the above-ground plants that inhabited there, large-scale, and so on. Plants such as microalgae (in a broad sense) and sediments containing them are decomposed, synthesized, and organicized by anaerobic microorganisms. Of these, humus soil originating from sediments formed in the ocean, more preferably humus soil derived from the Japanese archipelago in which sediments formed in the ocean are uplifted, and humus soil derived from Kyushu is more preferable. .. The degree of humus of this humus soil is not particularly limited, and those in which humus progresses and contains high molecular weight organic compounds such as fulvic acid and humic acid are preferable.
本発明で使用する腐植土抽出物は、抽出手段にて腐植土を溶媒に接触させて効果のある成分を抽出し、回収することによって得られる。さらに、不要物除去や除菌のため、ろ過手段を行うのが好ましい。得られた腐植土抽出物は、必要に応じて、希釈、濃縮や乾燥を行うことができ、また不純物の除去のため分離や精製等を行ってもよい。腐植土抽出物の形態としては、特に限定されず、例えば、固体状、半固体状や液状が挙げられる。具体的には、例えば、溶液、懸濁液、濃縮液、エマルジョン、スラリー、粉末、顆粒および固形などの状態が挙げられる。また腐植土抽出物は、特に記載した場合を除き、腐植土から抽出操作によって得られる、組成物または腐食土特有の成分をいう。腐植土抽出物は、フミン質、フミン酸またはフルボ酸であり得る。 The humus extract used in the present invention is obtained by bringing the humus soil into contact with a solvent by an extraction means to extract an effective component and recover it. Further, it is preferable to use a filtration means for removing unnecessary substances and sterilizing bacteria. The obtained humus soil extract can be diluted, concentrated or dried, if necessary, and may be separated or purified to remove impurities. The form of the humus extract is not particularly limited, and examples thereof include a solid state, a semi-solid state, and a liquid state. Specific examples include states such as solutions, suspensions, concentrates, emulsions, slurries, powders, granules and solids. Further, the humus soil extract refers to a composition or a component peculiar to corroded soil obtained from humus soil by an extraction operation, unless otherwise specified. The humus extract can be humic acid, humic acid or fulvic acid.
好適な腐植土抽出物を製造する方法の一例として、腐植土に、抽出溶媒を加えて混合攪拌後、有効成分を分離することによって腐植土抽出物を得ることが挙げられる。 As an example of a method for producing a suitable humus extract, an extraction solvent is added to the humus, the mixture is stirred and then the active ingredient is separated to obtain the humus extract.
抽出手段としては、特に限定されず、固液抽出、液液抽出、浸漬、煎出、浸出、還流抽出、超臨界流体抽出、超音波抽出、マイクロ波抽出、混合攪拌等が挙げられる。これらを適宜組み合わせてもよい。また、分離手段としては、特に限定されず、例えば、ろ過分離手段や遠心分離手段などが挙げられる。これらを単独で又は組み合わせて使用してもよい。ろ過分離手段としては、自然ろ過、減圧ろ過および加圧ろ過などが挙げられる。このとき、セルロースフィルター、ガラス繊維フィルター、メンブランフィルターなどのろ材を用い、必要に応じてセライト、砂利および活性炭などのろ過助剤を用いる。孔径は特に限定されず、例えば0.1〜1μmが好適である。これらを適宜組み合わせてもよい。なお、腐植土抽出物は、除菌用フィルターを用いてろ過されているものが、腐植土が熱変性されず、また不溶性物質などが除去されているので、好ましい。
また、抽出に先立って行う腐植土の乾燥や前処理の有無および方法に特に限定はない。
The extraction means is not particularly limited, and examples thereof include solid-liquid extraction, liquid-liquid extraction, immersion, brewing, leaching, reflux extraction, supercritical fluid extraction, ultrasonic extraction, microwave extraction, and mixed stirring. These may be combined appropriately. The separation means is not particularly limited, and examples thereof include filtration separation means and centrifugal separation means. These may be used alone or in combination. Examples of the filtration separation means include natural filtration, reduced pressure filtration and pressurized filtration. At this time, a filter medium such as a cellulose filter, a glass fiber filter, or a membrane filter is used, and if necessary, a filtration aid such as Celite, gravel, or activated carbon is used. The pore size is not particularly limited, and for example, 0.1 to 1 μm is preferable. These may be combined appropriately. The humus extract is preferably filtered using a sterilization filter because the humus is not heat-denatured and insoluble substances and the like are removed.
In addition, there is no particular limitation on the presence or absence and method of drying and pretreating the humus soil prior to extraction.
抽出溶媒としては、特に限定されず、水性溶媒又は油性溶媒のいずれも使用してもよい。水性溶媒としては、水(温泉水、海洋深層水などのミネラル分を含む水や精製水等);直鎖、分岐鎖又は環状のアルコール類;アセトン、メチルエチルケトンなどのケトン類;酢酸メチル、酢酸エチルなどのエステル類;テトラヒドロフラン、ジエチルエーテルなどの鎖状および環状エーテル類;ポリエチレングリコールなどのポリエーテル類等が挙げられ、油性溶媒としては、スクワラン、ヘキサン、シクロヘキサン、石油エーテルなどの炭化水素類;トルエンなどの芳香族炭化水素類;ジクロロメタン、クロロホルム、ジクロロエタンなどのハロゲン化炭化水素類等が挙げられる。なお、これらは単独又は2種以上組み合わせた混合溶媒として使用してもよい。 The extraction solvent is not particularly limited, and either an aqueous solvent or an oil solvent may be used. Aqueous solvents include water (hot spring water, water containing minerals such as deep ocean water, purified water, etc.); linear, branched or cyclic alcohols; ketones such as acetone and methyl ethyl ketone; methyl acetate, ethyl acetate. Esters such as; chain and cyclic ethers such as tetrahydrofuran and diethyl ether; polyethers such as polyethylene glycol and the like; examples of the oily solvent include hydrocarbons such as squalane, hexane, cyclohexane and petroleum ether; toluene. Aromatic hydrocarbons such as; halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane and the like. These may be used alone or as a mixed solvent of two or more kinds.
本発明者の検討によると、腐植土抽出物に含まれる成分のうち、目的の効果が高い成分の一つがフルボ酸であると考えられることから、腐植土抽出物の抽出溶媒は、フルボ酸が溶解可能であることが好ましい。具体的には水性溶媒、すなわち水を含む溶媒が好ましく、水又は水とアルコール類との混液がより好ましい。 According to the study of the present inventor, among the components contained in the humus extract, one of the components having a high desired effect is considered to be fulvic acid. Therefore, fulvic acid is used as the extraction solvent for the humus extract. It is preferably soluble. Specifically, an aqueous solvent, that is, a solvent containing water is preferable, and water or a mixed solution of water and alcohols is more preferable.
ここで、アルコール類は、一価又は多価アルコール類のいずれでもよく、一価アルコール類としては、例えば、メタノール、エタノールおよびプロパノールなどが挙げられ、多価アルコール類としては、例えば、エチレングリコール、プロピレングリコール、1,3−ブチレングリコール、1,2−ペンタンジオール、グリセリンおよびジプロピレングリコールなどが挙げられる。アルコール類のうち、例えば、エタノールおよび1,3−ブチレングリコールなどの炭素数1〜5の低級アルコール類が好ましく、このうち低級一価アルコール類が好ましく、このうちさらにエタノールが好ましい。 Here, the alcohols may be either monohydric or polyhydric alcohols, examples of the monohydric alcohols include methanol, ethanol and propanol, and examples of the polyhydric alcohols include ethylene glycol and the like. Examples thereof include propylene glycol, 1,3-butylene glycol, 1,2-pentanediol, glycerin and dipropylene glycol. Among the alcohols, for example, lower alcohols having 1 to 5 carbon atoms such as ethanol and 1,3-butylene glycol are preferable, of which lower monohydric alcohols are preferable, and ethanol is more preferable.
水又は水とアルコール類との混液を100容量%とした場合に、アルコール類の含有量は、0〜90容量%であり、好ましくは0〜70容量%、より好ましくは0〜50容量%、さらに好ましくは0〜20容量%であると好適である。 When water or a mixed solution of water and alcohols is taken as 100% by volume, the content of alcohols is 0 to 90% by volume, preferably 0 to 70% by volume, and more preferably 0 to 50% by volume. More preferably, it is 0 to 20% by volume.
溶媒の使用量は、特に限定されず、例えば、腐植土(乾燥状態)100kgに対して、腐植土成分の抽出効率および作業効率の点で、100〜1000Lとするのが好ましく、200〜600Lとするのがより好ましい。 The amount of the solvent used is not particularly limited, and is preferably 100 to 1000 L, preferably 200 to 600 L, for 100 kg of humus soil (dry state) in terms of extraction efficiency and work efficiency of the humus soil component. It is more preferable to do so.
抽出期間は、特に限定されず、好ましくは1日〜3年間であり、より好ましくは10日〜1.5年間である。このときの腐植土と抽出溶媒との混合攪拌は、特に限定されず、例えば、0.5〜48時間程度行えばよい。これにより腐植土と抽出溶媒が接触し、有効成分を抽出しやすくなる。また、連続又は不連続に混合攪拌を行えばよい。例えば、混合撹拌した後、さらに一定期間混合攪拌する若しくは一定期間混合攪拌後放置するか、又は放置して熟成させるのが、抽出効率の点で、好適である。混合攪拌後に放置することで腐植土が沈降し、分離の際に有利であるため、好ましい。例えば、抽出期間内(例えば1日〜3年間)、連続又は不連続に混合攪拌を行う;1時間〜7日間混合攪拌後、1〜60日間(好適には20〜40日間)放置する;引き続き1〜20日間(好適には3〜9日間)混合攪拌した後、1日〜3年間(好適には6ヶ月〜2年間)放置するなどが挙げられる。 The extraction period is not particularly limited, and is preferably 1 day to 3 years, more preferably 10 days to 1.5 years. The mixing and stirring of the humus soil and the extraction solvent at this time is not particularly limited, and may be performed, for example, for about 0.5 to 48 hours. As a result, the humus soil and the extraction solvent come into contact with each other, and the active ingredient can be easily extracted. Further, the mixing and stirring may be performed continuously or discontinuously. For example, it is preferable in terms of extraction efficiency that the mixture is mixed and stirred for a certain period of time, mixed and stirred for a certain period of time and then left to stand, or left to stand for aging. It is preferable to leave the humus soil after mixing and stirring because it is advantageous for separation. For example, during the extraction period (for example, 1 to 3 years), the mixture is stirred continuously or discontinuously; after the mixture is stirred for 1 to 7 days, it is left to stand for 1 to 60 days (preferably 20 to 40 days); After mixing and stirring for 1 to 20 days (preferably 3 to 9 days), the mixture may be left for 1 to 3 years (preferably 6 to 2 years).
抽出温度は、特に限定されず、好ましくは低温〜高温(例えば、0〜100℃程度)、より好ましくは低温(例えば、0〜9℃程度)〜常温(例えば、10〜40℃程度)とするのが、腐植土を熱変性させないために、好適である。 The extraction temperature is not particularly limited, and is preferably low temperature to high temperature (for example, about 0 to 100 ° C.), more preferably low temperature (for example, about 0 to 9 ° C.) to normal temperature (for example, about 10 to 40 ° C.). Is suitable because it does not heat-denature the humus.
なお、乾燥としては、天日乾燥、自然乾燥、風乾燥、熱乾燥、凍結乾燥などが挙げられ、腐植土が熱変性しない乾燥であれば好適である。このとき、腐植土が微粉砕できる程度に乾燥するのが望ましく、粉砕することによって腐植土の抽出効率が向上するので、好適である。 Examples of the drying include sun drying, natural drying, air drying, heat drying, freeze drying and the like, and it is preferable if the humus soil is not heat-denatured. At this time, it is desirable that the humus soil is dried to such an extent that it can be finely pulverized, and pulverization improves the extraction efficiency of the humus soil, which is preferable.
腐植土抽出物には、フルボ酸、フミン酸などの腐植土壌特有の構成物質(フミン質など)や、脂肪酸、有機酸、アミノ酸、タンパク質、ミネラルなどが含まれている。 The humus extract contains constituent substances (humic acid, etc.) peculiar to humic soil such as fulvic acid and humic acid, and fatty acids, organic acids, amino acids, proteins, minerals and the like.
腐植土抽出物には、エキス分濃度が0.5質量%となるように水に溶解もしくは懸濁したときに、フミン質が、少なくとも0.1mg/L以上、好ましくは10mg/L以上、より好ましくは100mg/L以上、さらに好ましくは100〜1000mg/L、さらに好ましくは200〜700mg/L、さらに好ましくは350〜650mg/L含まれているのが好適である。ここで、フミン質(腐植質)とは、例えば、植物成分などが土壌中に分解、縮合して生成する高分子物質を指す。ここで、フミン質は、鉱泉試験法(衛生試験法・注解2002、日本薬学会)の腐植質についての試験法で定量することができる。試験法詳細は、下記のとおりである。 The humic acid extract contains at least 0.1 mg / L or more, preferably 10 mg / L or more of humic acid when dissolved or suspended in water so that the extract concentration becomes 0.5% by mass. It is preferably contained in an amount of 100 mg / L or more, more preferably 100 to 1000 mg / L, further preferably 200 to 700 mg / L, still more preferably 350 to 650 mg / L. Here, humic acid (humic acid) refers to, for example, a polymer substance produced by decomposing and condensing plant components and the like in soil. Here, humic acid can be quantified by the test method for humic acid of the mineral spring test method (sanitary test method / commentary 2002, Pharmaceutical Society of Japan). The details of the test method are as follows.
試料VmL(腐植質として約20mg以上含む。)を正確にとり、孔径0.45μmメンブランフィルター(あらかじめデシケーター(シリカゲル)で乾燥し、秤量しておく。)を用いて吸引ろ過し、少量の水で洗浄した後、ろ液および洗浄液を合わせ、HCl10mLを加えてよくかき混ぜ、一昼夜放置する。これをメンブランフィルターでろ過する。ろ過に際しては、上清をまず静かに吸引ろ過し、最後に沈殿部を追加する。ろ過し終わったら沈殿を水でよく洗う。ろ液はいくらか着色しているのが普通である。フルボ酸が多いときは着色が著しい。ろ過後、フィルター部分をはがして、パラフィン紙に包んでデシケーター(シリカゲル)中で恒量になるまで乾燥する(一昼夜放置)。メンブランフィルターの重量を差し引いて腐植質の量を求め、試料中の含量を計算する。腐植質は灰分を含むので、メンブランフィルターをるつぼに移し、少量のメチルアルコールを加えて燃やし、さらに灰化して灰分を求め、先の重量から差し引く。 Accurately take sample VmL (containing about 20 mg or more as humus), suction filter using a 0.45 μm membrane filter (previously dried with a desiccator (silica gel) and weighed), and wash with a small amount of water. After that, combine the filtrate and washing solution, add 10 mL of HCl, stir well, and leave it for a whole day and night. This is filtered with a membrane filter. For filtration, the supernatant is first gently suction-filtered, and finally a precipitate is added. After filtering, wash the precipitate thoroughly with water. The filtrate is usually somewhat colored. When there is a lot of fulvic acid, coloring is remarkable. After filtration, peel off the filter part, wrap it in paraffin paper, and dry it in a desiccator (silica gel) until it reaches a constant weight (leave it for a whole day and night). The amount of humus is calculated by subtracting the weight of the membrane filter, and the content in the sample is calculated. Since the humus contains ash, transfer the methanol filter to a crucible, add a small amount of methyl alcohol to burn it, and then incinerate it to obtain ash, which is subtracted from the previous weight.
フミン質(腐植質)(mg/L)=((A−B)−C)/D×100
A:フィルター部分の重量(mg)
B:メンブランフィルターの重量(mg)
C:灰分の重量(mg)
D:試料採取量(ml)
Huminic acid (humus) (mg / L) = ((AB) -C) / D × 100
A: Weight of filter part (mg)
B: Weight of membrane filter (mg)
C: Weight of ash (mg)
D: Sample collection amount (ml)
本発明者の検討によると、水を溶媒として得た腐植土抽出物に目的の効果が十分に見られたので、目的の効果が高い成分の一つは、フミン質の中でもフルボ酸であると考えられている。したがって、有効成分として用いる腐植土抽出物にはフルボ酸が多く含まれていることが好ましく、具体的には、固形分濃度が0.5質量%となるように水に溶解もしくは懸濁したときに、フルボ酸が、好ましくは0.1〜100mg/L、より好ましくは1〜50mg/L、さらに好ましくは5〜50mg/L含まれているのが好適である。ここで、フルボ酸は、植物などが微生物により分解される最終生成物である腐植物質のうち、酸によって沈殿しない無定形高分子有機酸を指す。フルボ酸は、重金属などを吸着、放出するキレート作用を有し得る。 According to the study by the present inventor, the desired effect was sufficiently observed in the humus extract obtained by using water as a solvent. Therefore, one of the components having a high desired effect is fulvic acid among the humic acids. It is considered. Therefore, it is preferable that the humus extract used as an active ingredient contains a large amount of fulvic acid, and specifically, when it is dissolved or suspended in water so that the solid content concentration becomes 0.5% by mass. Fulvic acid is preferably contained in an amount of 0.1 to 100 mg / L, more preferably 1 to 50 mg / L, and even more preferably 5 to 50 mg / L. Here, fulvic acid refers to an amorphous high molecular weight organic acid that is not precipitated by an acid among humic substances that are the final products of plants and the like being decomposed by microorganisms. Fulvic acid may have a chelating action that adsorbs and releases heavy metals and the like.
腐植土抽出物には、エキス分濃度が0.5質量%となるように水に溶解もしくは懸濁したときに、フミン酸が、好ましくは0.2mg/L以上、より好ましくは2mg以上、さらに好ましくは3mg/L以上、さらに好ましくは4mg/L以上含まれているのが好適である。いずれの場合であっても、腐植土抽出物中のフミン酸は、好ましくは30mg/L以下とすることができ、20mg以下としてもよく、1.6mg/L以下としてもよい。また、フミン酸は、腐植物質のうち酸性領域で沈殿し、アル
カリ性領域で可溶であるものを指す。詳細な化学構造は不明であるが、多価フェノール形の芳香族化合物と含チッ素化合物との縮合物であり、フェノール性水酸基およびカルボキシル基を有するとされている。
In the humus extract, humic acid is preferably 0.2 mg / L or more, more preferably 2 mg or more, and further, when dissolved or suspended in water so that the extract concentration becomes 0.5% by mass. It is preferably contained in an amount of 3 mg / L or more, more preferably 4 mg / L or more. In any case, the amount of humic acid in the humus extract can be preferably 30 mg / L or less, 20 mg or less, or 1.6 mg / L or less. Humic acid refers to humic acid that precipitates in the acidic region and is soluble in the alkaline region. Although the detailed chemical structure is unknown, it is a condensate of a polyhydric phenolic aromatic compound and a nitrogen-containing compound, and is said to have a phenolic hydroxyl group and a carboxyl group.
フミン酸:フルボ酸の混合割合は、特に限定されず、好ましくは1:10〜10:1とするのが好適である。フミン酸およびフルボ酸の定量方法は、「Soil Science and Plant Nutrition, 38巻, 23-30頁(Kuwatsuka S et al. 1992); Soil Science and
Plant Nutrition, 40巻, 601-608頁(Watanabe A. et al. 1994);Humic Substances Research, 1巻, 18-28頁(Watanabe A. et al. 2004)」等の参考文献に従って行えばよい。測定法により定量値が異なる場合は、フルボ酸の定量値がより高い測定法を採用することが好ましい。
The mixing ratio of humic acid: fulvic acid is not particularly limited, and is preferably 1:10 to 10: 1. A method for quantifying humic acid and fulvic acid is described in "Soil Science and Plant Nutrition, Vol. 38, pp. 23-30 (Kuwatsuka S et al. 1992); Soil Science and
Plant Nutrition, Vol. 40, pp. 601-608 (Watanabe A. et al. 1994); Humic Substances Research, Vol. 1, pp. 18-28 (Watanabe A. et al. 2004) ”. When the quantified value differs depending on the measuring method, it is preferable to adopt the measuring method having a higher quantified value of fulvic acid.
腐植土抽出物のpHは、酸性領域、好ましくはpH1〜6、より好ましくはpH2〜5とするのが、薬理活性および安定性の点で、好適である。このとき、エキス分濃度0.1〜1質量%水溶液とし、20℃で適宜pH調整剤にて調整してもよい。pH調整剤としては、通常使用されるものであれば特に限定されず、例えば、塩酸、硫酸、硝酸、炭酸、リン酸などの無機酸類;クエン酸、酢酸、乳酸、コハク酸、グリコール酸、アスコルビン酸、リンゴ酸、フマル酸、酒石酸、尿素、ε−アミノカプロン酸、ピロリドンカルボン酸などの有機酸類;グリシンベタイン、リジンベタインなどのベタイン類;水酸化ナトリウム、水酸化カリウム、水酸化カルシウムなどの金属水酸化物(アルカリ金属水酸化物およびアルカリ土類金属水酸化物など)などの無機アルカリ類;グアニジン、2−アミノ−2−メチルプロパンなどの有機アミン類;アンモニア、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、イソプロパノールアミン、ジイソプロパノールアミンなどのアルカノールアミン;アルギニン、リジンなどの塩基性アミノ酸など、およびこれらの組み合わせが挙げられる。 The pH of the humus extract is preferably in the acidic range, preferably pH 1 to 6, more preferably pH 2 to 5, from the viewpoint of pharmacological activity and stability. At this time, an aqueous solution having an extract concentration of 0.1 to 1% by mass may be prepared and adjusted appropriately with a pH adjuster at 20 ° C. The pH adjuster is not particularly limited as long as it is usually used, and for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, carbonic acid, and phosphoric acid; citric acid, acetic acid, lactic acid, succinic acid, glycolic acid, and ascorbin. Organic acids such as acids, malic acid, fumaric acid, tartaric acid, urea, ε-aminocaproic acid, pyrrolidonecarboxylic acid; betaines such as glycine betaine and lysine betaine; metallic water such as sodium hydroxide, potassium hydroxide and calcium hydroxide. Inorganic alkalis such as oxides (alkali metal hydroxides and alkaline earth metal hydroxides, etc.); Organic amines such as guanidine, 2-amino-2-methylpropane; ammonia, monoethanolamine, diethanolamine, triethanol Alkanoylamines such as amines, isopropanolamines and diisopropanolamines; basic amino acids such as arginine and lysine, and combinations thereof.
本発明に使用される成分(A)腐植土抽出物の含有量は、特に限定されないが、皮膚外用剤又は化粧料全量中、エキス分として0.00001〜1質量%(以下、質量%は単に、「%」と略す)であることが好ましく、0.0001〜0.1%とするのが効用の点等でより好ましい。 The content of the component (A) humus extract used in the present invention is not particularly limited, but 0.00001 to 1% by mass (hereinafter, mass% is simply mass%) as the extract content in the total amount of the external preparation for skin or cosmetics. , "%"), And more preferably 0.0001 to 0.1% in terms of utility and the like.
本発明に用いられる成分(B)は、有機紫外線吸収剤及び/又は金属酸化物粉体であれば特に限定されず、皮膚外用剤又は化粧料に使用できるものであれば、いずれのものも使用できる。 The component (B) used in the present invention is not particularly limited as long as it is an organic ultraviolet absorber and / or a metal oxide powder, and any component (B) that can be used as an external preparation for skin or cosmetics is used. it can.
有機紫外線吸収剤としては、例えば、ベンゾフェノン系、PABA系、ケイ皮酸系、サリチル酸系、シリコーン系等が挙げられ、これらを1種または2種以上組み合わせて用いることができる。具体的には、2−[4−(ジエチルアミノ)−2−ヒドロキシベンゾイル]安息香酸ヘキシルエステル、オキシベンゾン、4−tert−4’−メトキシジベンゾイルメタン、2,4−ビス−[{4−(2−エチルヘキシルオキシ−2−ヒドロキシ}−フェニル]−6−(4−メトキシフェニル)−1,3,5−トリアジン、2−ヒドロキシ−4−メトキシベンゾフェノン、サリチル酸−2−エチルヘキシル、パラジヒドロキシプロピル安息香酸エチル、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、2,2’−メチレンビス[6−(2H−ベンゾトリアゾール−2イル)−4−(1,1,3,3−テトラメチルブチル)フェノール]、(1,3,5)−トリアジン−2,4−ビス[{4−(2−エチルヘキシロキシ)−2−ヒドロキシ}−フェニル]−6−(4−メトキシフェニル)−1,3,5−トリアジン、ジメチコジエチルベンザルマロネート、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸及びそのナトリウム塩、ポリシリコーン−15等が挙げられ、これらを1種または2種以上組み合わせて用いることができる。 Examples of the organic ultraviolet absorber include benzophenone type, PABA type, cinnamic acid type, salicylic acid type, silicone type and the like, and one type or a combination of two or more of these can be used. Specifically, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, oxybenzone, 4-tert-4'-methoxydibenzoylmethane, 2,4-bis- [{4- (2). -Ethylhexyloxy-2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2-hydroxy-4-methoxybenzophenone, -2-ethylhexyl salicylate, ethyl paradihydroxypropyl benzoate , 2-Ethylhexyl dimethoxybenzidioxoimidazolidine propionate, 2,2'-methylenebis [6- (2H-benzotriazol-2yl) -4- (1,1,3,3-tetramethylbutyl) phenol], (1,3,5) -Triazine-2,4-bis [{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5- Examples thereof include triazine, dimethicodiethylbenzalmalonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, polysilicone-15, etc., and these may be used alone or in combination of two or more. it can.
金属酸化物粉体としては、例えば、酸化亜鉛、酸化チタン、酸化セリウム、酸化アルミニウム等が挙げられ、皮膚外用剤又は化粧料に一般的に使用されるものであれば、球状、板状、針状等の形状、煙霧状、微粒子、顔料級等の粒子径、多孔質、無孔質等の粒子構造等により特に限定されず、これらを1種または2種以上組み合わせて用いることができる。金属酸化物粉体の平均粒子径は15〜1000nmのものが、高い紫外線防御効果が得られる等の点から好ましく、更に25〜850nmのものがそれらの効果が特に顕著であるためより好ましい。これらの粉体は、公知の表面処理方法、例えば、無水ケイ酸処理、アルミナ処理、水酸化アルミニウム処理、フッ素化合物処理、シリコーン処理、シリコーン樹脂処理、ペンダント処理、シランカップリング剤処理、チタンカップリング剤処理、シラン処理、油剤処理、N−アシル化リジン処理、ポリアクリル酸処理、金属石鹸処理、アクリル樹脂処理、金属酸化物粉体処理等の方法で表面処理していてもよい。
金属酸化物粉体の市販品としては、例えばFINEX−50(堺化学工業社製)、ZnO−350(住友大阪セメント社製)、酸化亜鉛FZO−50(石原産業社製)、微粒子酸化亜鉛MZ−500(テイカ社製)、TIPAQUE CR−50(石原産業社製)、TIPAQUE A−100(石原産業社製)、TITANIX JR−800(テイカ社製)、MICRO TITANIUM DIOXIDE MT−500SA(テイカ社製)等が挙げられ、これらを1種または2種以上組み合わせて用いることができる。
Examples of the metal oxide powder include zinc oxide, titanium oxide, cerium oxide, aluminum oxide, and the like, and if they are generally used for skin external preparations or cosmetics, they are spherical, plate-shaped, or needle-shaped. It is not particularly limited by the shape such as shape, the particle size such as fumes, fine particles, pigment grade, etc., and the particle structure such as porous and non-porous, and these can be used alone or in combination of two or more. The average particle size of the metal oxide powder is preferably 15 to 1000 nm from the viewpoint of obtaining a high ultraviolet protection effect, and more preferably 25 to 850 nm because these effects are particularly remarkable. These powders are subjected to known surface treatment methods such as silicon dioxide treatment, alumina treatment, aluminum hydroxide treatment, fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, and titanium coupling. Surface treatment may be performed by a method such as agent treatment, silane treatment, oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, and metal oxide powder treatment.
Commercially available metal oxide powders include, for example, FINEX-50 (manufactured by Sakai Chemical Industry Co., Ltd.), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), zinc oxide FZO-50 (manufactured by Ishihara Sangyo Co., Ltd.), and fine particle zinc oxide MZ. -500 (manufactured by Teika), TIPAQUE CR-50 (manufactured by Ishihara Sangyo), TIPAQUE A-100 (manufactured by Ishihara), TITANIX JR-800 (manufactured by Teika), MICRO TITANIUM DIOXIDE MT-500SA (manufactured by Teika) ), Etc., and these can be used alone or in combination of two or more.
本発明に使用される成分(B)有機紫外線吸収剤及び/又は金属酸化物粉体の含有量は、特に限定されないが、皮膚外用剤又は化粧料全量に対して、0.5〜40%であると、高い紫外線防御効果が得られる等の点で好ましく、1.5〜30%とするとそれらの効果が特に顕著であるためより好ましい。 The content of the component (B) organic ultraviolet absorber and / or metal oxide powder used in the present invention is not particularly limited, but is 0.5 to 40% with respect to the total amount of the external preparation for skin or cosmetics. If there is, it is preferable in that a high ultraviolet protection effect can be obtained, and if it is 1.5 to 30%, those effects are particularly remarkable, which is more preferable.
本発明の成分(C)平均粒子径5〜30μmの球状粉体は、通常皮膚外用剤又は化粧料に使用される球状の粉体であれば、多孔質、無孔質、中空、多層等の粒子構造等により特に限定されず、有機粉体、無機粉体等が挙げられる。具体的には、オルガノポリシロキサンエラストマー、メチルシロキサン網状重合体、架橋型シリコーン・網状型シリコーンブロック共重合体、ポリアクリル酸アルキル、ポリエチレン、ポリスチレン、ナイロン、ウレタン、ウール、シルク、結晶セルロース、N−アシルリジン等の有機粉体、無水ケイ酸、炭酸カルシウム等の無機粉体等が挙げられ、これらを1種又は2種以上用いることができる。これらの球状粉体の中でも、オルガノポリシロキサンエラストマー、メチルシロキサン網状重合体、架橋型シリコーン・網状型シリコーンブロック共重合体等のシリコーン系樹脂粉体、ポリアクリル酸アルキル等のアクリル系樹脂粉体、無水ケイ酸粉体等の正電荷を帯びていない球状粉体の場合、フミン質との相互作用が少なく、球状粉体本来の優れた延展性と均一な付着性等に、より優れるため、より好ましい。それらの中でも、オルガノポリシロキサンエラストマー、メチルシロキサン網状重合体、架橋型シリコーン・網状型シリコーンブロック共重合体、ポリアクリル酸アルキル、無水ケイ酸の球状粉体が特に好ましく、これらを1種または2種以上組み合わせて用いることができる。市販品としては、オルガノポリシロキサンエラストマーであるトレフィルE505、E506、E701(何れも、東レ・ダウコーニング・シリコーン社製)等、メチルシロキサン網状重合体であるトスパール2000B*(東芝シリコーン社製)等、架橋型シリコーン・網状型シリコーンブロック共重合体であるSP−100、101、102、105、300(何れも信越化学工業社製)等、ポリアクリル酸アルキルであるマツモトマイクロスフェアーM−101、305(何れも、松本油脂製薬社製)、ガンツパールGM−2800(アイカ工業社製)等、無水ケイ酸であるCHIFFONSIL P−3R(日揮触媒化成社製)、シリカマイクロビード BA−1(日揮触媒化成社製)等が挙げられる。 The spherical powder having an average particle diameter of 5 to 30 μm of the component (C) of the present invention may be porous, non-porous, hollow, multi-layered or the like as long as it is a spherical powder usually used for external preparations for skin or cosmetics. The particle structure and the like are not particularly limited, and examples thereof include organic powder and inorganic powder. Specifically, organopolysiloxane elastomer, methylsiloxane reticulated polymer, crosslinked silicone / reticulated silicone block copolymer, alkylpolyacrylate, polyethylene, polystyrene, nylon, urethane, wool, silk, crystalline cellulose, N- Examples thereof include organic powders such as acylidine, inorganic powders such as silicic anhydride and calcium carbonate, and one or more of these can be used. Among these spherical powders, silicone-based resin powders such as organopolysiloxane elastomers, methylsiloxane reticulated polymers, crosslinked silicone / reticulated silicone block copolymers, and acrylic resin powders such as alkyl polyacrylates. In the case of non-positively charged spherical powder such as silicic anhydride powder, there is little interaction with the fuminaceous material, and the excellent spreadability and uniform adhesion inherent in the spherical powder are more excellent. preferable. Among them, organopolysiloxane elastomers, methylsiloxane reticulated polymers, crosslinked silicone / reticulated silicone block copolymers, alkyl polyacrylates, and spherical powders of silicic acid anhydride are particularly preferable, and one or two of these are particularly preferable. The above can be used in combination. Commercially available products include Trefil E505, E506, and E701 (all manufactured by Toray Dow Corning Silicone), which are organopolysiloxane elastomers, and Tospearl 2000B * (manufactured by Toshiba Silicone), which is a methylsiloxane reticulated polymer. Matsumoto Microsphere M-101, 305, which is an alkyl polyacrylate, such as SP-100, 101, 102, 105, 300 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), which are cross-linked silicone / reticulated silicone block copolymers. (All manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), Ganzpearl GM-2800 (manufactured by Aika Kogyo Co., Ltd.), etc. (Manufactured by Kaseisha) and the like.
また、成分(C)の平均粒子径5〜30μmの球状粉体は、公知の表面処理方法、例えば、無水ケイ酸処理、アルミナ処理、水酸化アルミニウム処理、フッ素化合物処理、シリコーン処理、シリコーン樹脂処理、ペンダント処理、シランカップリング剤処理、チタンカップリング剤処理、シラン処理、油剤処理、N−アシル化リジン処理、ポリアクリル酸処理、金属石鹸処理、アクリル樹脂処理、金属酸化物処理等の方法で表面処理していてもよい。 Further, the spherical powder having an average particle diameter of 5 to 30 μm of the component (C) is treated with known surface treatment methods such as silicic anhydride treatment, alumina treatment, aluminum hydroxide treatment, fluorine compound treatment, silicone treatment, and silicone resin treatment. , Pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, silane treatment, oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, metal oxide treatment, etc. The surface may be treated.
成分(C)の平均粒子径は、5〜30μmであり、より好ましくは5〜15μmである。平均粒子径が5μm未満の場合、満足のいく延展性及び滑らかな伸び広がりが得られず、平均粒子径が30μmを超える場合は、満足のいく化粧膜の均一な付着性が得られず、紫外線防御効果を低下させてしまう原因となる場合がある。 The average particle size of the component (C) is 5 to 30 μm, more preferably 5 to 15 μm. If the average particle size is less than 5 μm, satisfactory ductility and smooth spreading and spreading cannot be obtained, and if the average particle size exceeds 30 μm, satisfactory uniform adhesion of the cosmetic film cannot be obtained, and ultraviolet rays are not obtained. It may cause a decrease in the protective effect.
本発明に使用される成分(C)の平均粒子径5〜30μmの球状粉体の含有量は、特に限定されないが、皮膚外用剤又は化粧料全量に対して、0.0001〜50%が好ましく、0.001〜40%がより好ましく、0.1〜20%が特に好ましい。この範囲であると、滑らかな伸び広がりと紫外線防御効果により優れる等の点で、より好ましい。 The content of the spherical powder having an average particle size of 5 to 30 μm of the component (C) used in the present invention is not particularly limited, but is preferably 0.0001 to 50% with respect to the total amount of the external preparation for skin or cosmetics. , 0.001 to 40%, more preferably 0.1 to 20%. This range is more preferable in terms of smooth spread and spread and excellent UV protection effect.
本発明においては、特に限定されないが、成分(A)と成分(C)の含有質量比が(A):(C)=1:1〜1:100000であることが好ましく、1:10〜1:10000であることがより好ましい。この範囲であると、滑らかな伸び広がりと紫外線防御効果により優れる等の点で、より好ましい。 In the present invention, although not particularly limited, the content mass ratio of the component (A) to the component (C) is preferably (A) :( C) = 1: 1 to 1: 100,000, preferably 1: 10 to 1. : 10000 is more preferable. This range is more preferable in terms of smooth spread and spread and excellent UV protection effect.
本発明の皮膚外用剤又は化粧料は、上記の成分(A)〜(C)の他に、通常皮膚外用剤又は化粧料に使用される成分、油性成分、無機顔料、有機顔料及び色素等の粉体およびそれらのシリコーン処理物やフッ素化合物処理物、界面活性剤、繊維、多価アルコール、水溶性高分子、水溶性皮膜形成性樹脂、保湿剤等の水性成分、糖類、酸化防止剤、消泡剤、美容成分、防腐剤、香料等を本発明の効果を妨げない範囲で含有することができる。 In addition to the above-mentioned components (A) to (C), the skin external preparation or cosmetic of the present invention includes components usually used for skin external preparations or cosmetics, oily components, inorganic pigments, organic pigments, pigments and the like. Aqueous components such as powders and their silicone-treated products and fluorine compound-treated products, surfactants, fibers, polyhydric alcohols, water-soluble polymers, water-soluble film-forming resins, moisturizers, sugars, antioxidants, erasing agents. Foaming agents, beauty ingredients, preservatives, fragrances and the like can be contained within a range that does not interfere with the effects of the present invention.
油性成分としては、通常皮膚外用剤又は化粧料に用いられる油であれば特に制約なく使用することができ、動物油、植物油、合成油等の起源や半固形油、液体油、揮発性油等の性状を問わず、炭化水素類、油脂類、エステル油類、脂肪酸類、高級アルコール類、フッ素系油類等を使用することができる。具体的には、流動パラフィン、スクワラン、ワセリン、ポリイソブチレンの炭化水素類、オリーブ油、ミンク油、マカデミアナッツ油等の油脂類、イソオクタン酸セチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、ミリスチン酸オクチルドデシル、ジオクタン酸ネオペンチルグリコール、トリ(カプリル酸/カプリン酸)グリセリル、ホホバ油、トリ2−エチルヘキサン酸グリセリル、リンゴ酸ジイソステアリル等のエステル類、イソステアリン酸、オレイン酸等の脂肪酸類、オレイルアルコール、イソステアリルアルコール等の高級アルコール類、パーフルオロデカン、パーフルオロオクタン、パーフルオロポリエーテル等のフッ素系油剤類、油溶性美容成分等が挙げられる。 As the oily component, any oil usually used for external skin preparations or cosmetics can be used without particular limitation, and the origin of animal oils, vegetable oils, synthetic oils, etc., semi-solid oils, liquid oils, volatile oils, etc. Regardless of the properties, hydrocarbons, oils and fats, ester oils, fatty acids, higher alcohols, fluorine-based oils and the like can be used. Specifically, liquid paraffin, squalane, vaseline, hydrocarbons of polyisobutylene, fats and oils such as olive oil, mink oil, macadamia nut oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, dioctanoic acid. Neopentyl glycol, tri (caprylic acid / capric acid) glyceryl, jojoba oil, glyceryl tri2-ethylhexanoate, esters such as diisostearyl malate, fatty acids such as isostearic acid and oleic acid, oleyl alcohol, isostearyl Examples thereof include higher alcohols such as alcohol, fluorine-based oils such as perfluorodecane, perfluorooctane, and perfluoropolyether, and oil-soluble beauty ingredients.
粉体成分としては、皮膚外用剤又は化粧料に一般に使用される粉体として用いられる成分(B)、(C)以外の粉体であれば、板状、針状等の形状、煙霧状、微粒子、顔料級等の粒子径、多孔質、無孔質等の粒子構造等により特に限定されず、無機粉体類、光輝性粉体類、有機粉体類、色素粉体類、金属粉体類、複合粉体類等が挙げられる。具体的に例示すれば、酸化鉄、カーボンブラック、酸化クロム、水酸化クロム、紺青、群青等の有色無機顔料、タルク、白雲母、金雲母、紅雲母、黒雲母、合成雲母、絹雲母(セリサイト)、合成セリサイト、硫酸バリウム、カオリン、炭化珪素、ベントナイト、スメクタイト、珪ソウ土、ケイ酸アルミニウム、メタケイ酸アルミニウムマグネシウム、ケイ酸カルシウム、ケイ酸バリウム、ケイ酸マグネシウム、炭酸マグネシウム、ヒドロキシアパタイト、窒化ホウ素等の白色体質粉体、酸化チタン被覆雲母、酸化チタン被覆オキシ塩化ビスマス、酸化鉄雲母チタン、紺青処理雲母チタン、カルミン処理雲母チタン、オキシ塩化ビスマス、魚鱗箔、ポリエチレンテレフタレート・アルミニウム・エポキシ積層末、ポリエチレンテレフタレート・ポリオレフィン積層フィルム末、ポリエチレンテレフタレート・ポリメチルメタクリレート積層フィルム末等の光輝性粉体、ステアリン酸亜鉛、N−アシルリジン等の有機低分子性粉体、シルク粉末、セルロース粉末、デキストリン粉末等の天然有機粉体、赤色201号、赤色202号、赤色205号、赤色226号、赤色228号、橙色203号、橙色204号、青色404号、黄色401号等や、赤色3号、赤色104号、赤色106号、橙色205号、黄色4号、黄色5号、緑色3号、青色1号等のジルコニウム、バリウム又はアルミニウムレーキ等の有機顔料粉体あるいは更にアルミニウム粉、金粉、銀粉等の金属粉体、微粒子酸化チタン被覆雲母チタン、微粒子酸化亜鉛被覆雲母チタン、硫酸バリウム被覆雲母チタン、酸化チタン含有二酸化珪素、酸化亜鉛含有二酸化珪素等の複合粉体、ナイロン、ポリエステル、レーヨン、セルロース等の繊維等が挙げられる。これらはフッ素化合物、シリコ−ン油、粉体、油剤、ゲル化剤、界面活性剤等で表面処理されていてもよい。これらの粉体は、1種又は2種以上を用いることができ、更に複合化したものを用いても良い。 As the powder component, if it is a powder other than the components (B) and (C) generally used as a powder for external use on the skin or cosmetics, it has a plate-like shape, a needle-like shape, a smoke-like shape, etc. It is not particularly limited by the particle size such as fine particles and pigment grade, and the particle structure such as porous and non-porous, and is not particularly limited. Inorganic powders, glittering powders, organic powders, pigment powders, metal powders, etc. Classes, composite powders and the like. Specifically, colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, dark blue, and ultramarine, talc, white mica, gold mica, red mica, black mica, synthetic mica, and silk mica (seri). Site), synthetic sericite, barium sulfate, kaolin, silicon carbide, bentonite, smectite, silica soil, aluminum silicate, aluminum magnesium metasilicate, calcium silicate, barium silicate, magnesium silicate, magnesium carbonate, hydroxyapatite, White constitution powder such as boron nitride, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide mica, dark blue treated mica titanium, carmine treated mica titanium, bismuth oxychloride, fish scale foil, polyethylene terephthalate / aluminum / epoxy laminate Glitter powder such as powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder, organic low molecular weight powder such as zinc stearate, N-acylidine, silk powder, cellulose powder, dextrin powder. Natural organic powders such as red 201, red 202, red 205, red 226, red 228, orange 203, orange 204, blue 404, yellow 401, etc., red 3, red Organic pigment powders such as zirconium, barium or aluminum lake such as 104, red 106, orange 205, yellow 4, yellow 5, green 3 and blue 1, or aluminum powder, gold powder, silver powder and the like. Composite powders such as metal powder, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, nylon, polyester, rayon, cellulose, etc. Examples include fibers. These may be surface-treated with a fluorine compound, silicone oil, powder, oil agent, gelling agent, surfactant or the like. As these powders, one kind or two or more kinds can be used, and a composite one may be used.
界面活性剤としては、皮膚外用剤又は化粧料一般に用いられている界面活性剤であればいずれのものも使用でき、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤等が挙げられる。
水性成分としては、水に可溶な成分であれば何れでもよく、水の他に、例えば、プロピレングリコール、1,3−ブチレングリコール、ジプロピレングリコール、グリセリン、ジグリセリン、ポリグリセリン、アロエベラ、ウイッチヘーゼル、ハマメリス、キュウリ、レモン、ラベンダー、ローズ水等の植物抽出液が挙げられる。
酸化防止剤としては、例えばトコフェロール、アスコルビン酸等、美容成分としては例えばビタミン類、消炎剤、生薬等、防腐剤としては、例えばパラオキシ安息香酸エステル、フェノキシエタノール、1,2−ペンタジオール等が挙げられる。
As the surfactant, any of the surfactants generally used for external skin or cosmetics can be used, and nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Examples include surfactants.
The aqueous component may be any component soluble in water, and in addition to water, for example, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, polyglycerin, aloe vera, witch. Examples thereof include plant extracts such as hazel, hamamelis, cucumber, lemon, lavender, and rose water.
Examples of antioxidants include tocopherol, ascorbic acid, etc., cosmetic ingredients include, for example, vitamins, anti-inflammatory agents, crude drugs, etc., and preservatives include, for example, paraoxybenzoic acid ester, phenoxyethanol, 1,2-pentadiol and the like. ..
本発明の皮膚外用剤又は化粧料は常法に従って製造することができ、例えば、成分(A)、(B)に界面活性剤や他の油剤等を加え、90℃に加熱して均一に混合し、予め他の水性成分等と混合された成分(A)に加えることによって得ることができる。 The external preparation for skin or cosmetic of the present invention can be produced according to a conventional method. For example, a surfactant or other oil agent is added to the components (A) and (B), and the mixture is heated to 90 ° C. and uniformly mixed. It can be obtained by adding it to the component (A) previously mixed with another aqueous component or the like.
本発明の皮膚外用剤又は化粧料の性状は、特に限定されず、液状、ゲル状、クリーム状、半固形状、固形状、スティック状、パウダー状等のいずれであってもよい。 The properties of the external preparation for skin or cosmetics of the present invention are not particularly limited, and may be any of liquid, gel, cream, semi-solid, solid, stick, powder and the like.
本発明の皮膚外用剤又は化粧料としては、医薬品等の皮膚外用剤や化粧料等を挙げることでができ、例えば、外用固形剤、外用液剤、スプレー剤、軟膏剤、クリーム剤、ゲル剤、貼付剤等や、乳液、化粧水、パック化粧料、洗顔料、マッサージ用化粧料、ヘア用化粧料、日焼け止め料、ボディパウダー、ボディクリーム等のボディ用化粧料、日中用美容液等の美容液、アイクリーム等の目周り用化粧料、リップエッセンス、リップクリーム等の口唇ケア用化粧料、ファンデーション、下地、コンシーラー、白粉、アイシャドウ、頬紅、口紅、マスカラ、アイブロウ等のメーキャップ製剤等が挙げられる。一方、本発明の皮膚外用剤又は化粧料の剤型としては、水系、O/W乳化系、W/O乳化系、油性系、粉体系が挙げられ、特に、成分(B)の有機紫外線吸収剤及び/又は金属酸化物粉体を高含有させることができ、高い紫外線防御効果を得られる等の点でO/W乳化系、W/O乳化系が好適に用いられる。 Examples of the skin external preparation or cosmetic of the present invention include skin external preparations such as pharmaceuticals and cosmetics. For example, external solid preparations, external liquid preparations, sprays, ointments, creams, gels, etc. Patches, milky lotions, lotions, pack cosmetics, wash pigments, massage cosmetics, hair cosmetics, sunscreens, body powders, body creams and other body cosmetics, daytime beauty liquids, etc. Beauty liquid, eye cream and other eye care cosmetics, lip essence, lip cream and other lip care cosmetics, foundation, foundation, concealer, white powder, eye shadow, cheek red, lipstick, mascara, eyebrow and other makeup preparations, etc. Can be mentioned. On the other hand, examples of the dosage form of the external preparation for skin or cosmetics of the present invention include water-based, O / W emulsifying, W / O emulsifying, oil-based, and powder-based, and in particular, organic ultraviolet absorption of the component (B). The O / W emulsification system and the W / O emulsification system are preferably used in that the agent and / or the metal oxide powder can be contained in a high content and a high ultraviolet protection effect can be obtained.
以下に製造例及び実施例をあげて本発明を詳細に説明する。尚、これらは本発明を何ら限定するものではない。
[製造例1:腐植土抽出物の製造]
地中(九州地方海岸付近土壌)から採取した腐食土壌を乾燥させた後、微粉砕した。この粉砕物5kgと、精製水20リットルを2時間混合攪拌し、さらに常温(10〜30℃程度)で7日間撹拌し、20日間静置した。静置後、メンブランフィルター(孔径0.45μm)を用いてろ過し、腐植土抽出物水溶液(原液)を得た。このときのpH(20℃)は3.0であった。また、この乾燥エキス分(エキス分濃度)は0.4%であった。この原液に含まれるフミン質の総量は350mg/L(乾燥エキス分5g/水1Lの水溶液換算としたとき、438mg/L)であり、フミン酸およびフルボ酸の含有量は、それぞれ4mg/Lおよび6.7mg/L(乾燥エキス分5g/水1Lの水溶液換算としたとき、それぞれ5mg/Lおよび8.4mg/L)であった。以下の実施例では乾燥エキス分をそのまま用いた。
The present invention will be described in detail below with reference to production examples and examples. It should be noted that these do not limit the present invention in any way.
[Production example 1: Production of humus soil extract]
Corroded soil collected from the ground (soil near the coast of the Kyushu region) was dried and then finely pulverized. 5 kg of this pulverized product and 20 liters of purified water were mixed and stirred for 2 hours, further stirred at room temperature (about 10 to 30 ° C.) for 7 days, and allowed to stand for 20 days. After standing, it was filtered using a membrane filter (pore size 0.45 μm) to obtain an aqueous solution of humus extract (stock solution). The pH (20 ° C.) at this time was 3.0. The dry extract content (extract concentration) was 0.4%. The total amount of humic acid contained in this stock solution is 350 mg / L (438 mg / L when converted to an aqueous solution of 5 g of dry extract / 1 L of water), and the contents of humic acid and fulvic acid are 4 mg / L and 4 mg / L, respectively. It was 6.7 mg / L (5 mg / L and 8.4 mg / L, respectively, when converted to an aqueous solution of 5 g of dry extract / 1 L of water). In the following examples, the dried extract was used as it was.
フミン酸およびフルボ酸の定量方法は、上述の参考文献Soil Science and Plant Nutrition, 38巻, 23-30頁(Kuwatsuka S et al. 1992); Soil Science and Plant Nutrition, 40巻, 601-608頁(Watanabe A. et al. 1994);Humic Substances Reseacrh, 1巻, 18-28頁(Watanabe A. et al. 2004)にしたがって行った。 For methods of quantifying humic acid and fulvic acid, see References Soil Science and Plant Nutrition, Vol. 38, pp. 23-30 (Kuwatsuka S et al. 1992); Soil Science and Plant Nutrition, Vol. 40, pp. 601-608 ( Watanabe A. et al. 1994); Humic Substances Reseacrh, Vol. 1, pp. 18-28 (Watanabe A. et al. 2004).
実施例1〜8及び比較例1〜4:W/O乳化系リキッドファンデーション
下記表1に示す処方のW/O乳化系リキッドファンデーションを調製し、イ.滑らかな伸び広がり、ロ.紫外線防御効果について下記評価方法により評価した。その結果も併せて表1に示す。
Examples 1 to 8 and Comparative Examples 1 to 4: W / O emulsifying liquid foundation The W / O emulsifying liquid foundation having the formulation shown in Table 1 below was prepared. Smooth expansion and spread, b. The UV protection effect was evaluated by the following evaluation method. The results are also shown in Table 1.
(評価方法)
下記イの項目について、各試料について専門パネル20名による使用テストを行った。パネル各人が下記評価基準1にて7段階に評価し評点をつけ、パネル全員の評点合計からその平均値を算出し、下記判定基準1により判定した。
下記ロの項目については、各試料をポリメチルメタクリレート板に、厚さ50μmで塗布し、24時間室温にて乾燥後、SPF アナライザー UV−2000S(Labsphere社製)にてSPF値を3回測定し、下記判定基準2により判定した。
(評価項目)
イ.滑らかな伸び広がり
ロ.紫外線防御効果
(Evaluation method)
For the following items (a), each sample was tested for use by 20 specialized panels. Each panel member evaluated and scored on a 7-point scale according to the following evaluation criteria 1, calculated the average value from the total score of all the panels, and judged according to the following criteria 1.
Regarding the items in (b) below, each sample was applied to a polymethylmethacrylate plate at a thickness of 50 μm, dried at room temperature for 24 hours, and then the SPF value was measured three times with an SPF analyzer UV-2000S (manufactured by Labsphere). , Judgment was made according to the following criteria 2.
(Evaluation item)
I. Smooth expansion and spread b. UV protection effect
<評価基準1>
(評点):(評価)
6 :非常に良い
5 :良い
4 :やや良い
3 :普通
2 :やや悪い
1 :悪い
0 :非常に悪い
<判定基準1>
(判定):(評点の平均点)
◎ :5点を超える
○ :3.5点を超え5点以下
△ :1点を超え3.5点以下
× :1点以下
<判定基準2>
(判定):(SPF測定結果(N=3)の平均値)
◎ :25を超える
○ :20を超え25以下
× :20以下
<Evaluation Criteria 1>
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad <Criteria 1>
(Judgment): (Average score)
◎: Over 5 points
◯: Over 3.5 points and 5 points or less
△: More than 1 point and less than 3.5 points
×: 1 point or less
<Criteria 2>
(Judgment): (Average value of SPF measurement result (N = 3))
◎: More than 25 ○: More than 20 and less than 25 ×: More than 20
(製造方法)
A:成分(1)〜(11)をロールミルにて均一に混合分散する。
B:Aに成分(12)〜(22)を加え、均一に混合する。
C:Bに成分(23)〜(29)を加えて乳化する
D:Cを容器に充填する。
(Production method)
A: Ingredients (1) to (11) are uniformly mixed and dispersed by a roll mill.
B: Add components (12) to (22) to A and mix uniformly.
The container is filled with D: C to be emulsified by adding the components (23) to (29) to C: B.
表1の結果から明らかなように、本発明の実施例1〜8のW/O乳化系リキッドファンデーションは、比較例1〜4に比べ、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
一方、成分(C)が含有されていない比較例1では、べたつきが強く、滑らかな伸び広がりに欠け、化粧膜が均一でないため、紫外線防御効果にも欠け、満足のいくものが得られなかった。また、粉体等の分散性を向上させるために、成分(C)を含有させる代わりに、分散剤の含有量を増やした比較例2では、分散剤由来のべたつきがでてしまい、滑らかに伸び広がらず、化粧膜が均一でないため、紫外線防御効果についても満足のいくものが得られなかった。成分(C)の代わりに平均粒子径が45μmの球状粉体を用いた比較例3では、伸び広がりには優れるものの平均粒子径が大きいためムラになりやすく、化粧膜の均一性に劣るため、紫外線防御効果に欠け、満足のいくものが得られなかった。成分(C)の代わりに形状が楕円お椀状である粉体を用いた比較例4では、延展性に欠けるため、満足のいく滑らかな伸び広がりが得られず、化粧膜が均一でないため、紫外線防御効果も十分ではなく、満足のいくものが得られなかった。
As is clear from the results in Table 1, the W / O emulsified liquid foundations of Examples 1 to 8 of the present invention have a smooth spread and spread and an excellent UV protection effect as compared with Comparative Examples 1 to 4. It was.
On the other hand, in Comparative Example 1 in which the component (C) was not contained, the stickiness was strong, the smooth spread and spread was lacking, and the cosmetic film was not uniform, so that the UV protection effect was also lacking, and a satisfactory one could not be obtained. .. Further, in Comparative Example 2 in which the content of the dispersant was increased instead of containing the component (C) in order to improve the dispersibility of the powder or the like, stickiness derived from the dispersant appeared and the powder spread smoothly. Since it did not spread and the cosmetic film was not uniform, a satisfactory UV protection effect could not be obtained. In Comparative Example 3 in which a spherical powder having an average particle size of 45 μm was used instead of the component (C), although it was excellent in spreading and spreading, it was prone to unevenness due to the large average particle size, and the uniformity of the decorative film was inferior. It lacked the UV protection effect, and I could not obtain a satisfactory one. In Comparative Example 4 in which a powder having an elliptical bowl shape was used instead of the component (C), a satisfactory smooth spread and spread could not be obtained due to lack of ductility, and the cosmetic film was not uniform, so that ultraviolet rays were emitted. The protective effect was not sufficient, and I was not satisfied with it.
実施例9〜16及び比較例5〜8:O/W乳化系日焼け止め
下記表2に示す処方のO/W乳化系日焼け止めを調製し、イ.滑らかな伸び広がり、ロ.紫外線防御効果について下記評価方法により評価した。その結果も併せて表2に示す。
Examples 9 to 16 and Comparative Examples 5 to 8: O / W emulsifying sunscreens The O / W emulsifying sunscreens having the formulations shown in Table 2 below were prepared. Smooth expansion and spread, b. The UV protection effect was evaluated by the following evaluation method. The results are also shown in Table 2.
(評価方法)
下記イの項目について、各試料について専門パネル20名による使用テストを行った。パネル各人が上記評価基準1にて7段階に評価し評点をつけ、パネル全員の評点合計からその平均値を算出し、上記判定基準1により判定した。
下記ロの項目については、各試料をポリメチルメタクリレート板に、厚さ50μmで塗布し、24時間室温にて乾燥後、SPF アナライザー UV−2000S(Labsphere社製)にてSPF値を3回測定し、下記判定基準3により判定した。
(評価項目)
イ.滑らかな伸び広がり
ロ.紫外線防御効果
(Evaluation method)
For the following items (a), each sample was tested for use by 20 specialized panels. Each panel member evaluated the evaluation criteria 1 on a 7-point scale and gave a score, and the average value was calculated from the total score of all the panels, and the evaluation was made according to the above criteria 1.
Regarding the items in (b) below, each sample was applied to a polymethylmethacrylate plate at a thickness of 50 μm, dried at room temperature for 24 hours, and then the SPF value was measured three times with an SPF analyzer UV-2000S (manufactured by Labsphere). , Judgment was made according to the following criteria 3.
(Evaluation item)
I. Smooth expansion and spread b. UV protection effect
<判定基準3>
(判定):(SPF測定結果(N=3)の平均値)
◎ :55を超える
○ :50を超え55以下
× :50以下
<Criteria 3>
(Judgment): (Average value of SPF measurement result (N = 3))
◎: More than 55 ○: More than 50 and less than 55 ×: More than 50
(製造方法)
A:成分(1)〜(19)を均一に混合分散する。
B:成分(20)〜(27)を70℃で均一に混合溶解する。
C:AにBを加えて乳化する
D:Cを容器に充填する。
(Production method)
A: Ingredients (1) to (19) are uniformly mixed and dispersed.
B: Ingredients (20) to (27) are uniformly mixed and dissolved at 70 ° C.
C: Add B to A and emulsify D: C is filled in a container.
表2の結果から明らかなように、本発明の実施例9〜16のO/W乳化系日焼け止めは、比較例5〜8に比べ、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
一方、成分(C)が含有されていない比較例5では、べたつきが強く、滑らかな伸び広がりに欠け、化粧膜が均一でないため、紫外線防御効果にも欠け、満足のいくものが得られなかった。また、粉体等の分散性を向上させるために、成分(C)を含有させる代わりに、分散剤の含有量を増やした比較例6では、分散剤由来のべたつきがでてしまい、滑らかに伸び広がらず、化粧膜が均一でないため、紫外線防御効果についても満足のいくものが得られなかった。成分(C)の代わりに平均粒子径が45μmの球状粉体を用いた比較例7では、伸び広がりには優れるものの粒子径が大きいためムラになりやすく、化粧膜の均一性に劣るため、紫外線防御効果に欠け、満足のいくものが得られなかった。成分(C)の代わりに形状が楕円お椀状である粉体を用いた比較例8では、延展性に欠けるため、満足のいく滑らかな伸び広がりが得られず、化粧膜が均一でないため、紫外線防御効果も十分ではなく、満足のいくものが得られなかった。
As is clear from the results in Table 2, the O / W emulsified sunscreens of Examples 9 to 16 of the present invention have a smooth spread and spread and an excellent UV protection effect as compared with Comparative Examples 5 to 8. It was.
On the other hand, in Comparative Example 5 in which the component (C) was not contained, the stickiness was strong, the smooth spread and spread was lacking, and the cosmetic film was not uniform, so that the UV protection effect was also lacking, and a satisfactory one could not be obtained. .. Further, in Comparative Example 6 in which the content of the dispersant was increased instead of containing the component (C) in order to improve the dispersibility of the powder or the like, stickiness derived from the dispersant appeared and the powder spread smoothly. Since it did not spread and the cosmetic film was not uniform, a satisfactory UV protection effect could not be obtained. In Comparative Example 7 in which a spherical powder having an average particle size of 45 μm was used instead of the component (C), although it was excellent in spreading and spreading, it was prone to unevenness due to the large particle size, and the uniformity of the decorative film was inferior. It lacked a protective effect, and I was not satisfied with it. In Comparative Example 8 in which a powder having an elliptical bowl shape was used instead of the component (C), a satisfactory smooth spread and spread could not be obtained due to lack of ductility, and the cosmetic film was not uniform, so that ultraviolet rays were emitted. The protective effect was not sufficient, and I was not satisfied with it.
実施例17:O/W乳化系日中用美容液
(成分) (%)
(1)精製水 残量
(2)カルボキシビニルポリマー*22 0.2
(3)グリセリン 8
(4)ポリオキシエチレングリセリン(26E.O.) 5
(5)ポリオキシプロピレンメチルグルコシド 3
(6)ジプロピレングリコール 8
(7)メチルパラベン 0.3
(8)加水分解ヒアルロン酸 0.01
(9)加水分解コラーゲン 0.01
(10)(アスコルビル/トコフェリル)リン酸K 0.01
(11)腐植土抽出物*16 10
(12)水酸化ナトリウム 1.5
(13)赤227 0.0005
(14)黄色4 0.0005
(15)架橋型シリコーン・網状型シリコーンブロック共重合体*23 3
(16)ステアリン酸 2
(17)ステアリン酸グリセリル 0.5
(18)セテアリルアルコール 1.5
(19)パラメトキシケイ皮酸2−エチルヘキシル 7
(20)ポリシリコーン−15*24 3
(21)天然ビタミンE 0.1
(22)香料 0.1
*22:CARBOPOL 980(LUBRIZOL ADOVANCED MATERIALS社製)
*23:KSP−102(信越化学工業社製) 平均粒子径30μm
*24:PARSOL SLX(DSM NUTRITIONAL PRODUCTS社製)
(製造方法)
A:成分(1)〜(14)を均一に混合する。
B:成分(15)〜(22)を70℃で均一に混合溶解する。
C:AにBを加えて乳化する
D:Cを容器に充填する。
実施例17のO/W乳化系日中用美容液は、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
Example 17: O / W emulsifying daytime beauty essence (ingredient) (%)
(1) Remaining amount of purified water (2) Carboxyvinyl polymer * 22 0.2
(3) Glycerin 8
(4) Polyoxyethylene glycerin (26EO) 5
(5) Polyoxypropylene methylglucoside 3
(6) Dipropylene glycol 8
(7) Methylparaben 0.3
(8) Hydrolyzed hyaluronic acid 0.01
(9) Hydrolyzed collagen 0.01
(10) (Ascorbyl / Tocopheryl) K 0.01
(11) Humus soil extract * 16 10
(12) Sodium hydroxide 1.5
(13) Red 227 0.0005
(14) Yellow 4 0.0005
(15) Cross-linked silicone / reticulated silicone block copolymer * 23 3
(16) Stearic acid 2
(17) Glyceryl stearate 0.5
(18) Cetearyl alcohol 1.5
(19) 2-ethylhexyl paramethoxycinnamate 7
(20) Polysilicone-15 * 24 3
(21) Natural Vitamin E 0.1
(22) Fragrance 0.1
* 22: CARBOPOL 980 (manufactured by LUBRIZOL ADOVANCED MATERIALS)
* 23: KSP-102 (manufactured by Shin-Etsu Chemical Co., Ltd.) Average particle size 30 μm
* 24: PARSOL SLX (manufactured by DSM NUTRITIONAL PRODUCTS)
(Production method)
A: Ingredients (1) to (14) are uniformly mixed.
B: Ingredients (15) to (22) are uniformly mixed and dissolved at 70 ° C.
C: Add B to A and emulsify D: C is filled in a container.
The O / W emulsified daytime beauty essence of Example 17 was excellent in smooth spread and spread and UV protection effect.
実施例18:O/W乳化系クリーム
(成分) (%)
(1)N−ステアロイル−N−メチルタウリンナトリウム 2
(2)グリセリン 5
(3)1,3−ブチレングリコール 15
(4)ポリエチレングリコール*25 5
(5)エデト酸二ナトリウム 0.05
(6)リン酸一水素ナトリウム 0.1
(7)テアニン 0.5
(8)腐植土抽出物*16 20
(9)精製水 残量
(10)キサンタンガム 0.2
(11)(ジフェニルジメチコン/ビニルジフェニルジメチコン/
シルセスキオキサン)クロスポリマー*26 2
(12)無水ケイ酸*27 1
(13)ベヘニルアルコール 3
(14)グリセリン脂肪酸エステル*28 2
(15)パラメトキシケイ皮酸2−エチルヘキシル 5
(16)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 2
(17)ジカプリン酸プロピレングリコール 10
(18)トリメリト酸トリトリデシル 3
(19)N−ラウロイル−L−グルタミン酸ジ
(フィトステリル・2−オクチルドデシル) 5
(20)ジリノール酸ジ(フィトステリル/イソステアリル/セチル/
ステアリル/ベヘニル) 5
(21)水添ポリイソブテン*29 3
(22)オリーブ果実油 2
(23)香料 0.2
*25:PEG−1500(東邦化学工業社製)
*26:KSP−300(信越化学工業社製) 平均粒子径5μm
*27:HCS 160M5(日揮触媒化成社製) 平均粒子径5μm
*28:サンファクト GMR−90(太陽化学社製)
*29:パールリーム 24(日油社製)
(製造方法)
A:成分(1)〜(10)を70℃で均一に混合溶解する。
B:成分(11)〜(23)を80℃で均一に混合溶解する。
C:AにBを加えて乳化する
D:Cを容器に充填する。
実施例18のO/W乳化系クリームは、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
Example 18: O / W emulsifying cream (ingredient) (%)
(1) Sodium N-stearoyl-N-methyltaurine 2
(2) Glycerin 5
(3) 1,3-butylene glycol 15
(4) Polyethylene glycol * 255
(5) Disodium edetate 0.05
(6) Sodium monohydrogen phosphate 0.1
(7) Theanine 0.5
(8) Humus extract * 16 20
(9) Remaining amount of purified water (10) Xanthan gum 0.2
(11) (Diphenyldimethicone / Vinyldiphenyldimethicone /
Silsesquioxane) Crosspolymer * 26 2
(12) Silicic anhydride * 27 1
(13) Behenyl alcohol 3
(14) Glycerin fatty acid ester * 28 2
(15) 2-ethylhexyl paramethoxycinnamate 5
(16) Bisethylhexyloxyphenol methoxyphenyl triazine 2
(17) Propylene Glycol Dicaprate 10
(18) Tritridecyl trimeritoate 3
(19) Di (phytosteryl 2-octyldodecyl) N-lauroyl-L-glutamic acid 5
(20) Dilinolate (phytosteryl / isostearyl / cetyl /
Stearyl / Behenyl) 5
(21) Hydrogenated polyisobutene * 29 3
(22) Olive fruit oil 2
(23) Fragrance 0.2
* 25: PEG-1500 (manufactured by Toho Chemical Industry Co., Ltd.)
* 26: KSP-300 (manufactured by Shin-Etsu Chemical Co., Ltd.) Average particle size 5 μm
* 27: HCS 160M5 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) Average particle size 5 μm
* 28: Sunfact GMR-90 (manufactured by Taiyo Kagaku Co., Ltd.)
* 29: Pearl Dream 24 (manufactured by NOF CORPORATION)
(Production method)
A: Ingredients (1) to (10) are uniformly mixed and dissolved at 70 ° C.
B: Ingredients (11) to (23) are uniformly mixed and dissolved at 80 ° C.
C: Add B to A and emulsify D: C is filled in a container.
The O / W emulsifying cream of Example 18 was excellent in smooth spreading and spreading and UV protection effect.
実施例19:W/O乳化系リップエッセンス
(成分) (%)
(1)パルミチン酸デキストリン 5
(2)リンゴ酸ジイソステアリル 15
(3)トリイソステアリン酸ポリグリセリル−2 残量
(4)ワセリン 10
(5)ポリブテン*30 25
(6)ジフェニルジメチコン*31 5
(7)パラメトキシケイ皮酸2−エチルヘキシル 7
(8)ジメチコン*32 3
(9)流動パラフィン*33 5
(10)ジブチルヒドロキシトルエン 0.1
(11)メントール 0.5
(12)カンファ― 0.5
(13)l−メンチルグリセリルエーテル 0.5
(14)セージ葉エキス 0.01
(15)セイヨウハッカエキス 0.01
(16)ジプロピレングリコール 3
(17)無水ケイ酸*34 3
(18)酸化チタン被覆雲母*35 0.5
(19)腐植土抽出物*16 15
*30:日石ポリブテン HV−1900F(JX日鉱日石エネルギー社製)
*31:KF−54(信越化学工業社製)
*32:KF−96−100CS(信越化学工業社製)
*33:KLEAROL WHITE MINERAL OIL(SONNEBORN社製)
*34:シリカマイクロビード P−1505(日揮触媒化成社製) 平均粒子径10μm
*35:FLAMENCO RED 420C(BASF社製)
(製造方法)
A:成分(1)〜(10)を70℃で均一に混合溶解する。
B:成分(11)〜(16)を均一に混合溶解する。
C:A、B、成分(17)〜(18)を均一に混合する。
D:Cに成分(19)を加えて乳化する。
E:Dを60℃で容器に充填する。
実施例19のW/O乳化系リップエッセンスは、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
Example 19: W / O emulsifying lip essence (ingredient) (%)
(1) Dextrin palmitate 5
(2) Diisostearyl malate 15
(3) Polyglyceryl triisostearate-2 Remaining amount (4) Vaseline 10
(5) Polybutene * 30 25
(6) Diphenyldimethicone * 31 5
(7) 2-ethylhexyl paramethoxycinnamate 7
(8) Dimethicone * 32 3
(9) Liquid paraffin * 335
(10) Dibutylhydroxytoluene 0.1
(11) Menthol 0.5
(12) Conference 0.5
(13) l-menthylglyceryl ether 0.5
(14) Sage leaf extract 0.01
(15) Mentha extract 0.01
(16) Dipropylene glycol 3
(17) Silicic anhydride * 34 3
(18) Titanium oxide coated mica * 35 0.5
(19) Humus extract * 16 15
* 30: Nippon Oil Polybutene HV-1900F (manufactured by JX Nippon Oil Energy Co., Ltd.)
* 31: KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 32: KF-96-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 33: KLEAROL WHITE MINERAL OIL (manufactured by SONNEBORN)
* 34: Silica microbead P-1505 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) Average particle size 10 μm
* 35: FLAMENCO RED 420C (manufactured by BASF)
(Production method)
A: Ingredients (1) to (10) are uniformly mixed and dissolved at 70 ° C.
B: Ingredients (11) to (16) are uniformly mixed and dissolved.
C: A, B and components (17) to (18) are uniformly mixed.
D: C is emulsified by adding component (19).
E: D is filled in a container at 60 ° C.
The W / O emulsifying lip essence of Example 19 had a smooth spreading and spreading effect and was excellent in UV protection effect.
実施例20:油性系リップクリーム
(成分) (%)
(1)ポリエチレン*36 5
(2)合成ワックス*37 5
(3)ミツロウ*38 5
(4)エチルヘキサン酸セチル 残量
(5)ジイソステアリン酸ポリグリセリル−2 5
(5)ワセリン 10
(6)ヘキサ(ヒドロキシステアリン酸/ステアリン酸/ロジン酸)
ジペンタエリスリチル 10
(7)シア脂 10
(8)マカデミアナッツ脂肪酸フィトステリル 5
(9)パラメトキシケイ皮酸2−エチルヘキシル 5
(10)ポリシリコーン−1 クロスポリマー*39 5
(11)腐植土抽出物*16 3
*36:PERFORMALENE 500(ニューフェーズテクノロジー社製)
*37:CIREBELLE 108(CIREBELLE社製)
*38:WHITE BEES WAX(三木化学社製)
*39:KSP−411(信越化学工業社製) 平均粒子径12μm
(製造方法)
A:成分(1)〜(9)を加熱溶解し、成分(10)〜(11)を加え均一に混合する。
B:Aを80℃で容器に充填し、冷却固化する。
実施例20の油性系リップクリームは、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
Example 20: Oil-based lip balm (ingredient) (%)
(1) Polyethylene * 365
(2) Synthetic wax * 375
(3) Beeswax * 385
(4) Remaining amount of cetyl ethylcaproate (5) Polyglyceryl diisostearate-25
(5) Vaseline 10
(6) Hexa (hydroxystearic acid / stearic acid / rosin acid)
Dipentaerythrityl 10
(7) Shea fat 10
(8) Macadamia nut fatty acid phytosteryl 5
(9) 2-ethylhexyl paramethoxycinnamate 5
(10) Polysilicone-1 crosspolymer * 395
(11) Humus extract * 16 3
* 36: PERFORMALENE 500 (manufactured by New Phase Technology)
* 37: CIREBELLE 108 (manufactured by CIREBELLE)
* 38: WHITE BEES WAX (manufactured by Miki Chemical Co., Ltd.)
* 39: KSP-411 (manufactured by Shin-Etsu Chemical Co., Ltd.) Average particle size 12 μm
(Production method)
A: The components (1) to (9) are heated and dissolved, and the components (10) to (11) are added and mixed uniformly.
B: A is filled in a container at 80 ° C. and cooled and solidified.
The oil-based lip balm of Example 20 had a smooth spreading and spreading effect and was excellent in UV protection effect.
実施例21:O/W乳化系下地
(成分) (%)
(1)パーフルオロオクチルトリエトキシシラン
2%処理微粒子酸化チタン*40 10
(2)酸化チタン*41 3
(3)ベンガラ 0.1
(4)黄酸化鉄 0.5
(5)黒酸化鉄 0.02
(6)ポリシリコーン−22※42 5
(7)モノオレイン酸ポリエチレンソルビタン(20E.O) 1
(8)セスキオレイン酸ソルビタン 0.5
(9)レシチン 0.3
(10)1,3−ブチレングリコール 5
(11)ポリオキシエチレンメチルグルコシド 2
(12)グリセリン 5
(13)カルボキシビニルポリマー※43 0.5
(14)アルカリゲネス産生多糖体 0.5
(15)精製水 残量
(16)腐植土抽出物※16 20
(17)トリエタノールアミン 0.5
(18)パラメトキシケイ皮酸2−エチルヘキシル 8
(19)流動パラフィン※44 3
(20)ジメチコン※45 2
(21)セトステアリルアルコール 0.3
(22)ベヘニルアルコール 0.2
(23)ステアリン酸グリセリル 0.3
※40:TTO−51(A)(石原産業社製)平均粒子径0.02μm
※41:ST−730EC(チタン工業社製)平均粒子径0.5μm
※42:KSP−441(信越化学工業社製) 平均粒子径12μm
※43:CARBOPOL 940(LUBRIZOL ADOVANCED MATERIALS社製)
※44:ハイコール K−350(カネダ社製)
※45:KF−96L 2CS(信越化学工業社製)
(製造方法)
A:成分(1)〜(12)を均一に混合分散する。
B:A及び成分(13)〜(17)を均一に混合分散する。
C:成分(18)〜(23)を80℃で均一に混合溶解する。
D:BにCを加えて乳化する
E:Dを容器に充填する。
実施例21のO/W乳化系下地は、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
Example 21: O / W emulsifying base (ingredient) (%)
(1) Perfluorooctyltriethoxysilane 2% treated fine particle titanium oxide * 40 10
(2) Titanium oxide * 41 3
(3) Bengala 0.1
(4) Yellow iron oxide 0.5
(5) Black iron oxide 0.02
(6) Polysilicone-22 * 425
(7) Polyethylene sorbitan monooleate (20EO) 1
(8) Sorbitan sesquioleate 0.5
(9) Lecithin 0.3
(10) 1,3-butylene glycol 5
(11) Polyoxyethylene methylglucoside 2
(12) Glycerin 5
(13) Carboxyvinyl polymer * 43 0.5
(14) Alcaligenes-producing polysaccharide 0.5
(15) Remaining amount of purified water (16) Humus extract * 16 20
(17) Triethanolamine 0.5
(18) 2-ethylhexyl paramethoxycinnamate 8
(19) Liquid paraffin * 44 3
(20) Dimethicone * 45 2
(21) Setostearyl alcohol 0.3
(22) Behenyl alcohol 0.2
(23) Glyceryl stearate 0.3
* 40: TTO-51 (A) (manufactured by Ishihara Sangyo Co., Ltd.) Average particle size 0.02 μm
* 41: ST-730EC (manufactured by Titan Kogyo Co., Ltd.) Average particle size 0.5 μm
* 42: KSP-441 (manufactured by Shin-Etsu Chemical Co., Ltd.) Average particle size 12 μm
* 43: CARBOPOL 940 (manufactured by LUBRIZOL ADOVANCED MATERIALS)
* 44: HYCOAL K-350 (manufactured by Kaneda)
* 45: KF-96L 2CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Ingredients (1) to (12) are uniformly mixed and dispersed.
B: A and components (13) to (17) are uniformly mixed and dispersed.
C: Ingredients (18) to (23) are uniformly mixed and dissolved at 80 ° C.
E: D to be emulsified by adding C to D: B is filled in a container.
The O / W emulsified base of Example 21 was excellent in smooth spreading and spreading and UV protection effect.
実施例22:軟膏
(成分) (%)
(1)ステアリルアルコール 18.0
(2)モクロウ 20.0
(3)ポリオキシエチレン(20モル)モノオレイン酸エステル 0.3
(4)トコフェロール 0.1
(5)ワセリン 40.0
(6)パラメトキシケイ皮酸2−エチルヘキシル*6 0.5
(7)テトライソステアリン酸ペンタエリスリチル 1.0
(8)無水ケイ酸*13 0.5
(9)精製水 残量
(10)グリセリン 10.0
(11)腐植土抽出物※16 0.5
(製造方法)
A:成分(1)〜(8)を70℃で均一に混合する。
B:成分(9)〜(11)を70℃に加温する。
C:AにBを加え乳化し、軟膏を得た。
実施例22の軟膏は、滑らかな伸び広がり、紫外線防御効果に優れたものであった。
Example 22: Ointment (ingredient) (%)
(1) Stearyl alcohol 18.0
(2) Japan wax 20.0
(3) Polyoxyethylene (20 mol) monooleic acid ester 0.3
(4) Tocopherol 0.1
(5) Vaseline 40.0
(6) 2-ethylhexyl paramethoxycinnamate * 6 0.5
(7) Pentaerythrityl tetraisostearate 1.0
(8) Silicic anhydride * 13 0.5
(9) Remaining amount of purified water (10) Glycerin 10.0
(11) Humus extract * 16 0.5
(Production method)
A: Ingredients (1) to (8) are uniformly mixed at 70 ° C.
B: Ingredients (9) to (11) are heated to 70 ° C.
C: B was added to A and emulsified to obtain an ointment.
The ointment of Example 22 had a smooth spreading and spreading effect and was excellent in UV protection effect.
Claims (7)
(A)腐食土抽出物
(B)有機紫外線吸収剤及び/又は金属酸化物粉体
(C)平均粒子径が5〜30μmの球状粉体(但し、ポリメチルシルセスキオキサン、(HDI/トリメチロールヘキシルラクトン)クロスポリマー、又はポリアクリル酸アルキルを除く)
を含有する皮膚外用剤又は化粧料。 The following components (A) to (C);
(A) Corrosive soil extract (B) Organic UV absorber and / or metal oxide powder (C) Spherical powder with an average particle size of 5 to 30 μm ( however, polymethylsilsesquioxane, (HDI / tri) (Excluding methylolhexyl lactone) crosspolymer or alkyl polyacrylate )
A skin external preparation or cosmetic containing.
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