JP5084021B2 - Sunscreen cosmetics - Google Patents

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JP5084021B2
JP5084021B2 JP2007253489A JP2007253489A JP5084021B2 JP 5084021 B2 JP5084021 B2 JP 5084021B2 JP 2007253489 A JP2007253489 A JP 2007253489A JP 2007253489 A JP2007253489 A JP 2007253489A JP 5084021 B2 JP5084021 B2 JP 5084021B2
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聖子 鈴木
絵美 赤羽
正直 亀井
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Shin Etsu Chemical Co Ltd
Kose Corp
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本発明は、日焼け止め化粧料に関する。さらに詳しくは、分散媒として揮発性オルガノポリシロキサンを用い、有機系紫外線吸収剤の存在下、これに表面処理金属酸化物微粒子を分散剤で分散させてなる、保存時の分散安定性に優れた日焼け止め化粧料に関する。   The present invention relates to a sunscreen cosmetic. More specifically, volatile organopolysiloxane is used as a dispersion medium, and surface-treated metal oxide fine particles are dispersed with a dispersant in the presence of an organic ultraviolet absorber, which has excellent dispersion stability during storage. Related to sunscreen cosmetics.

紫外線による肌への悪影響を防ぐために、金属酸化物の微粒子や有機系紫外線吸収剤を配合した日焼け止め化粧料が開発され、一般的に使用されている。すなわち、紫外線のうち皮膚の黒化をもたらす、長波長紫外線領域(320〜400nm)を効果的に防御し、かつ可視部の透明性が高い素材として酸化亜鉛など金属酸化物の微粒子が日焼け止め化粧料に一般的に配合されている。また、皮膚に紅斑を引き起こす中波長紫外線領域(280〜320nm)を防御するために、有機系紫外線吸収剤が一般的に配合されている。更に、金属酸化物の微粒子と有機系紫外線吸収剤とを一緒に配合した日焼け止め化粧料も良く知られている。   In order to prevent the adverse effects of UV rays on the skin, sunscreen cosmetics containing metal oxide fine particles and organic UV absorbers have been developed and are generally used. In other words, fine particles of metal oxides such as zinc oxide as sunscreen makeup effectively protect the long-wavelength ultraviolet region (320-400 nm), which causes skin darkening among ultraviolet rays, and are highly transparent in the visible region. Generally blended into the ingredients. Moreover, in order to protect the medium wavelength ultraviolet region (280-320 nm) which causes erythema on the skin, an organic ultraviolet absorber is generally blended. Furthermore, sunscreen cosmetics in which metal oxide fine particles and an organic ultraviolet absorber are blended together are well known.

上記の金属酸化物微粒子は、化粧料中に分散させて配合使用するが、凝集力が強いため安定に分散させることは困難である。紫外線防御力を増加させるべく粒子を小さくすればするほど、この傾向が強くなる。そのため、安定に分散させる手段として、粒子の表面を処理してその分散性を高める方法、また微粒子を良好に分散させる分散性能がよい分散剤などが種々提案されている。微粒子を表面処理してその分散性を高める方法に関しては、金属酸化物微粒子を表面処理剤で処理して疎水化する技術、例えば、ジメチコン・メチコンコポリマーで表面処理する技術(特許文献1)、有機基及び粒子との反応性基を有する特定のシリコーンで粉体を表面処理する技術(特許文献2)などが提案されている。また粉体を分散させる分散剤に関しては、無機化合物の微粉末を特定のHLBを持つポリエーテル変性メチルポリシロキサンで分散させる技術 (特許文献3)、油相へ粉体を分散させる分散剤として、メタクリル酸含有アクリルシリコーンを用いた水中油型乳化化粧料(特許文献4)などが提案されている。更に、各種油剤に対して優れた乳化性能を有するシリコーン化合物として、アルキル基及びポリオキシアルキレン基共変性シリコーンが提案されている(特許文献5)。   The metal oxide fine particles are blended and used in cosmetics, but it is difficult to stably disperse because of their strong cohesive strength. This tendency becomes stronger as the particles are made smaller to increase the UV protection. For this reason, as means for stably dispersing, various methods have been proposed, such as a method for treating the surface of the particles to increase the dispersibility, and a dispersing agent with good dispersion performance for dispersing fine particles. Regarding the method of surface-treating fine particles to improve their dispersibility, a technique of treating metal oxide fine particles with a surface treatment agent to make them hydrophobic, for example, a technique of surface-treating with dimethicone / methicone copolymer (Patent Document 1), organic A technique (Patent Document 2) for surface-treating powder with a specific silicone having a group and a reactive group with particles has been proposed. As for the dispersant for dispersing the powder, a technique for dispersing fine powder of an inorganic compound with a polyether-modified methylpolysiloxane having a specific HLB (Patent Document 3), as a dispersant for dispersing the powder in an oil phase, An oil-in-water emulsified cosmetic using a methacrylic acid-containing acrylic silicone (Patent Document 4) has been proposed. Furthermore, alkyl group and polyoxyalkylene group co-modified silicones have been proposed as silicone compounds having excellent emulsifying performance for various oils (Patent Document 5).

特開2003−95655号公報JP 2003-95655 A 特開2001−72891号公報JP 2001-72891 A 特開平10−167946号公報JP-A-10-167946 特開2005−247722号公報JP 2005-247722 A 特開2001−39819号公報JP 2001-39819 A

上記のように、日焼け止め化粧料について、金属酸化物微粒子を安定に分散させる技術が種々提案されているが、溶媒、分散剤、表面処理金属酸化物微粒子、有機系紫外線吸収剤などの配合成分の組み合わせによっては、金属酸化物微粒子の凝集を阻止することが困難で、経時的に金属酸化物微粒子の凝集や沈降、バルクのゲル化がおこり、保存時の分散安定性を確保することが難しい。本発明は、分散媒として揮発性オルガノポリシロキサンを用い、有機系紫外線吸収剤の存在下、これに表面処理金属酸化物微粒子を分散剤で分散させた日焼け止め化粧料について、保存時の分散安定性に優れた日焼け止め化粧料を提供することを目的とする。   As described above, various techniques for stably dispersing metal oxide fine particles have been proposed for sunscreen cosmetics. However, compounding components such as a solvent, a dispersant, surface-treated metal oxide fine particles, and an organic ultraviolet absorber Depending on the combination of the above, it is difficult to prevent the aggregation of metal oxide fine particles, and over time, the metal oxide fine particles aggregate, settle, and bulk gel, and it is difficult to ensure dispersion stability during storage. . The present invention uses a volatile organopolysiloxane as a dispersion medium, and in the presence of an organic ultraviolet absorber, a sunscreen cosmetic in which surface-treated metal oxide fine particles are dispersed with a dispersant. An object of the present invention is to provide an excellent sunscreen cosmetic.

本発明者らは、上記課題を解決するために鋭意検討を行った結果、分散媒として揮発性オルガノポリシロキサンを用い、有機系紫外線吸収剤の存在下、これに表面処理金属酸化物微粒子を分散剤で分散させた日焼け止め化粧料において、金属酸化物微粒子の表面処理剤及び分散剤として共にシリコーン化合物を用い、且つこれらのシリコーン化合物に、それぞれ特定のシリコーン化合物を選択し、組み合わせることによって、経時で粉体の凝集や沈降、系のゲル化が起こらない効果を発揮させ得ることを見出し、本発明を完成した。   As a result of intensive studies to solve the above problems, the present inventors used volatile organopolysiloxane as a dispersion medium, and dispersed surface-treated metal oxide fine particles in the presence of an organic ultraviolet absorber. In sunscreen cosmetics dispersed with an agent, a silicone compound is used as both the surface treatment agent and the dispersant for the metal oxide fine particles, and specific silicone compounds are selected and combined with these silicone compounds, respectively. Thus, the inventors have found that the effect of preventing the aggregation and sedimentation of the powder and the gelation of the system can be exhibited, and the present invention has been completed.

すなわち、本発明は、(a)揮発性オルガノポリシロキサン10〜55質量%、(b)シリコーン系分散剤0.1〜20質量%、(c)シリコーン表面処理金属酸化物微粒子1〜50質量%、及び(d)有機系紫外線吸収剤0.1〜25質量%を含有する日焼け止め化粧料であって、前記成分(b)のシリコーン系分散剤が次式の一般式(1)で表されるシリコーン化合物であり、前記成分(c)のシリコーン表面処理金属酸化物微粒子が次式の一般式(2)で表されるシリコーン化合物で表面処理された金属酸化物微粒子であることを特徴とする日焼け止め化粧料である。 That is, the present invention comprises (a) volatile organopolysiloxane 10 to 55 % by mass , (b) silicone-based dispersant 0.1 to 20% by mass , (c) silicone surface-treated metal oxide fine particles 1 to 50% by mass. And (d) a sunscreen cosmetic containing 0.1 to 25% by mass of an organic ultraviolet absorber, wherein the silicone dispersant of the component (b) is represented by the following general formula (1): The silicone surface-treated metal oxide fine particles of the component (c) are metal oxide fine particles surface-treated with a silicone compound represented by the following general formula (2): It is a sunscreen cosmetic.

Figure 0005084021
Figure 0005084021

Figure 0005084021
Figure 0005084021

上記成分(b)のシリコーン系分散剤の配合量は0.1〜20質量%が好ましい。成分(c)のシリコーン表面処理金属酸化物微粒子の配合量は、1〜50質量%が好ましく、この金属酸化物微粒子は、酸化亜鉛微粒子又は酸化チタン微粒子が好ましい。また、成分(d)の有機系紫外線吸収剤の配合量は、0.1〜25質量%が好ましく、この有機系紫外線吸収剤としては、パラメトキシケイ皮酸2−エチルヘキシルが好ましい。また、この日焼け止め化粧料の剤型は、油中水型が好ましい。   As for the compounding quantity of the silicone type dispersing agent of the said component (b), 0.1-20 mass% is preferable. The amount of the silicone surface-treated metal oxide fine particles as the component (c) is preferably 1 to 50% by mass, and the metal oxide fine particles are preferably zinc oxide fine particles or titanium oxide fine particles. Further, the blending amount of the organic ultraviolet absorber as the component (d) is preferably 0.1 to 25% by mass, and as this organic ultraviolet absorber, 2-ethylhexyl paramethoxycinnamate is preferable. Moreover, the dosage form of the sunscreen cosmetic is preferably a water-in-oil type.

分散媒として揮発性オルガノポリシロキサンを用い、有機系紫外線吸収剤の存在下、これに表面処理金属酸化物微粒子を分散剤で分散させた日焼け止め化粧料においては、有機系紫外線吸収剤の存在によって、系の経時でのゲル化が生じ易く、また金属酸化物微粒子の凝集や沈降が起こるなどの問題があった。ところが、分散剤として前記の一般式(1)で表されるシリコーン化合物を用い、更に金属酸化物微粒子の表面処理剤として前記の一般式(2)で表されるシリコーン化合物を用いた本発明の日焼け止め化粧料は、経時での金属酸化物微粒子の凝集や沈降、系のゲル化がおこらず、保存時の安定性に優れている。更に、日焼け止め化粧料においては、金属酸化物微粒子の分散が悪いと、紫外線遮蔽効果が充分でないだけでなく、肌に塗布したとき白浮きが目立つものとなるが、本発明の日焼け止め化粧料は、高分散のため、肌に塗布しても白浮きしない効果を有する。   In sunscreen cosmetics in which volatile organopolysiloxane is used as a dispersion medium and surface-treated metal oxide fine particles are dispersed with a dispersant in the presence of an organic UV absorber, the presence of the organic UV absorber However, there are problems such that gelation of the system with time tends to occur and metal oxide fine particles aggregate and settle. However, the silicone compound represented by the general formula (1) is used as a dispersant, and the silicone compound represented by the general formula (2) is used as a surface treatment agent for metal oxide fine particles. Sunscreen cosmetics are excellent in stability during storage without aggregation or sedimentation of metal oxide fine particles and gelation of the system over time. Further, in the sunscreen cosmetics, if the dispersion of the metal oxide fine particles is poor, not only the ultraviolet shielding effect is not sufficient, but also whitening becomes conspicuous when applied to the skin, but the sunscreen cosmetics of the present invention. Is highly dispersed and has the effect of not whitening even when applied to the skin.

本発明の日焼け止め化粧料の各成分について説明する。
本発明に使用する成分(a)の揮発性オルガノポリシロキサンは、金属酸化物微粒子の分散媒である。日焼け止め化粧料では、従来から、金属酸化物微粒子の分散媒として揮発性オルガノポリシロキサンが一般に用いられている。揮発性オルガノポリシロキサンとしては、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、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、メチルトリメチコンなどであり、これらは単独又は2種以上組み合わせて配合してもよい。なかでも、揮発速度や粉体の濡れ性から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、デカメチルテトラシロキサンが特に好ましい。
成分(a)の日焼け止め化粧料への配合量は、10〜55質量%が好ましい。10質量%未満の場合、安定な日焼け止め化粧料を得るためには必然的に他の油分の配合量が多くなり、そのためさっぱりした使用感といった揮発性シリコーン配合のメリットが得られにくくなる。55質量%を越えると塗布中のなじみが遅くなり、使用感が油っぽくなるため好ましくない。
Each component of the sunscreen cosmetic of the present invention will be described.
The component (a) volatile organopolysiloxane used in the present invention is a dispersion medium of metal oxide fine particles. In sunscreen cosmetics, volatile organopolysiloxanes are generally used as a dispersion medium for metal oxide fine particles. Volatile organopolysiloxanes include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, methyltrimethicone, etc. You may mix | blend individually or in combination of 2 or more types. Of these, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane are particularly preferable from the viewpoint of volatilization rate and powder wettability.
As for the compounding quantity to the sunscreen cosmetics of a component (a), 10-55 mass% is preferable. When the amount is less than 10% by mass, the amount of other oils is inevitably increased in order to obtain a stable sunscreen cosmetic, and therefore, it is difficult to obtain the merit of volatile silicone formulation such as a refreshed feeling of use. If it exceeds 55% by mass, the familiarity during application becomes slow and the feeling of use becomes oily, which is not preferable.

本発明で使用する成分(b)のシリコーン系分散剤は、前記一般式(1)で表されるシリコーン化合物である。この一般式(1)で表されるシリコーン化合物は、前記の特許文献5に記載されたシリコーン化合物の一種である。一般式(1)で表されるシリコーン化合物は、主鎖に直鎖のメチルポリシロキサンを持ち、そのメチル基の一部を、炭素数8〜14のアルキル基、ポリオキシエチレン基、及びメチルポリシロキサン基で置換した構造を持つ。炭素数8〜14のアルキル基は有機系紫外線吸収剤との相溶性を調整するために分子中に導入されている。このアルキル基は特にラウリル基が好ましい。また、ポリオキシエチレン基は、粉体との吸着点となることを期待して分子中に導入されている。そして、主鎖の長さや、炭素数8〜14のアルキル基、ポリオキシエチレン基、メチルポリシロキサン基の導入量によって、粉体への吸着性や揮発性オルガノポリシロキサンもしくは、有機系紫外線吸収剤への相溶性に違いがある。本発明では、一般式(1)で表されるシリコーン化合物について、主鎖の長さ、並びに、炭素数8〜14のアルキル基、ポリオキシエチレン基及びメチルポリシロキサン基の導入量を決めるx,y,z,p,a及びbを特定の範囲にすることにより、これらの機能を最大限に発揮させて、優れた分散性能を持たせたものである。   The silicone-based dispersant of component (b) used in the present invention is a silicone compound represented by the general formula (1). The silicone compound represented by the general formula (1) is a kind of silicone compound described in Patent Document 5. The silicone compound represented by the general formula (1) has a linear methylpolysiloxane in the main chain, and a part of the methyl group is substituted with an alkyl group having 8 to 14 carbon atoms, a polyoxyethylene group, and methylpolysiloxane. It has a structure substituted with a siloxane group. The alkyl group having 8 to 14 carbon atoms is introduced into the molecule in order to adjust the compatibility with the organic ultraviolet absorber. This alkyl group is particularly preferably a lauryl group. Moreover, the polyoxyethylene group is introduced into the molecule in the hope of becoming an adsorption point with the powder. Depending on the length of the main chain and the amount of alkyl group having 8 to 14 carbon atoms, polyoxyethylene group, and methylpolysiloxane group, the adsorptivity to the powder and the volatile organopolysiloxane or organic ultraviolet absorber There is a difference in compatibility. In the present invention, for the silicone compound represented by the general formula (1), x, which determines the length of the main chain and the introduction amount of an alkyl group having 8 to 14 carbon atoms, a polyoxyethylene group, and a methylpolysiloxane group By setting y, z, p, a, and b to specific ranges, these functions are exhibited to the maximum to provide excellent dispersion performance.

成分(b)の日焼け止め化粧料への配合量は、0.1〜20質量%が好ましく、より好ましくは1〜10質量%である。0.1質量%未満の場合には分散性が悪く、金属酸化物微粒子の凝集、沈降が起きる。また20質量%を超えると経時での系のゲル化がおきやすくなるとともに、べたつきを感じるため好ましくない。   0.1-20 mass% is preferable, and, as for the compounding quantity to the sunscreen cosmetics of a component (b), More preferably, it is 1-10 mass%. When the amount is less than 0.1% by mass, the dispersibility is poor and the metal oxide fine particles are aggregated and settled. On the other hand, if it exceeds 20% by mass, gelation of the system with time tends to occur and stickiness is felt, which is not preferable.

本発明で使用する成分(c)のシリコーン表面処理金属酸化物微粒子は、前記の一般式(2)で表されるシリコーン化合物で表面処理された金属酸化物微粒子である。上記一般式(2)で表されるシリコーン化合物は、前記特許文献2に記載されたシリコーン化合物の一種である。一般式(2)で表されるシリコーン化合物は主鎖に直鎖のメチルポリシロキサンを持ち、そのメチル基の一部を、炭素数4〜12のアルキル基、トリエトキシシラン基、及びメチルポリシロキサン基で置換した構造を持つ。炭素数4〜12のアルキル基は一般式(2)の化合物で表面処理された粉体と有機系紫外線吸収剤との濡れ性を調整するために分子中に導入されている。このアルキル基はヘキシル基が特に好ましい。また、トリエトキシシラン基は金属酸化物微粒子の表面への反応性基として分子中に導入されている。そして、炭素数4〜12のアルキル基及びメチルポリシロキサン基の導入量によって、一般式(2)の化合物で表面処理される粉体の濡れ性が変り、初期の分散性や保存安定性を左右する因子となりえる。本発明では、一般式(2)で表されるシリコーン化合物のW,X,Y,Z及びnを特定の範囲にすることによって、金属酸化物微粒子の表面処理剤としての機能を最大限に発揮させ、且つ前記一般式(1)のシリコーン系分散剤によって良好に分散しえる表面処理金属酸化物微粒子を得たものである。   The silicone surface-treated metal oxide fine particles of the component (c) used in the present invention are metal oxide fine particles surface-treated with the silicone compound represented by the general formula (2). The silicone compound represented by the general formula (2) is a kind of silicone compound described in Patent Document 2. The silicone compound represented by the general formula (2) has a linear methylpolysiloxane in the main chain, and part of the methyl group is an alkyl group having 4 to 12 carbon atoms, a triethoxysilane group, and a methylpolysiloxane. It has a structure substituted with a group. The alkyl group having 4 to 12 carbon atoms is introduced into the molecule in order to adjust the wettability between the powder surface-treated with the compound of the general formula (2) and the organic ultraviolet absorber. This alkyl group is particularly preferably a hexyl group. The triethoxysilane group is introduced into the molecule as a reactive group on the surface of the metal oxide fine particles. And the wettability of the powder surface-treated with the compound of the general formula (2) varies depending on the introduction amount of the alkyl group having 4 to 12 carbon atoms and the methylpolysiloxane group, and the initial dispersibility and storage stability are affected. Can be a factor. In the present invention, by making W, X, Y, Z and n of the silicone compound represented by the general formula (2) into a specific range, the function as a surface treating agent for the metal oxide fine particles is maximized. And surface-treated metal oxide fine particles that can be satisfactorily dispersed by the silicone-based dispersant of the general formula (1).

上記の金属酸化物微粒子は、レーザー回析法による1次粒子径が1μm以下、好ましくは0.1μm以下の大きさのものが好ましい。また、金属酸化物微粒子は、酸化亜鉛微粒子、酸化チタン微粒子が好ましく使用される。この金属酸化物微粒子は、シリカやアルミナなどで処理した金属酸化物微粒子であってもよい。ここに、1次粒子径とは、1次粒子の平均粒子径のことである。1次粒子径1μm以下の酸化亜鉛微粒子の市販品としては、例えば堺化学工業(株)製のFINEX−50、住友大阪セメント(株)製のZnO−350、石原産業(株)製の酸化亜鉛FZO−50、テイカ(株)製の微粒子酸化亜鉛MZ−500等が挙げられる。酸化チタン微粒子の市販品としては堺化学工業(株)製のSTR−60、STR−100、テイカ(株)製のMT−500Bなどが挙げられる。   The metal oxide fine particles preferably have a primary particle diameter of 1 μm or less, preferably 0.1 μm or less as measured by a laser diffraction method. As the metal oxide fine particles, zinc oxide fine particles and titanium oxide fine particles are preferably used. The metal oxide fine particles may be metal oxide fine particles treated with silica or alumina. Here, the primary particle diameter is the average particle diameter of the primary particles. Examples of commercially available zinc oxide fine particles having a primary particle diameter of 1 μm or less include FINEX-50 manufactured by Sakai Chemical Industry Co., Ltd., ZnO-350 manufactured by Sumitomo Osaka Cement Co., Ltd., and zinc oxide manufactured by Ishihara Sangyo Co., Ltd. Examples thereof include FZO-50, fine particle zinc oxide MZ-500 manufactured by Teika Corporation. Examples of commercially available titanium oxide fine particles include STR-60 and STR-100 manufactured by Sakai Chemical Industry Co., Ltd. and MT-500B manufactured by Teika Co., Ltd.

前記の一般式(2)で表されるシリコーン化合物による金属酸化物微粒子の表面処理は、方法そのものは、従来公知の方法で行える。すなわち、例えば、(i)一般式(2)で表されるシリコーン化合物を含有させた水或いは有機溶剤から選択される媒体中に金属酸化物微粒子を分散させて表面処理する方法、(ii)金属酸化物微粒子と一般式(2)で表されるシリコーン化合物を混合した後、ボールミル、ジェットミルなどの粉砕機を用いて表面処理する方法、(iii)一般式(2)で表されるシリコーン化合物の溶剤溶液に金属酸化物微粒子を分散させて、金属酸化物微粒子表面にシリコーン化合物を吸着させ、その後乾燥、焼結させる方法などで行う。金属酸化物微粒子に対する表面処理剤(シリコーン化合物)の量は、0.1〜12質量%が好ましく、より好ましくは3〜8質量%である。また、成分(c)の日焼け止め化粧料への配合量は、好ましくは1〜50質量%、より好ましくは、5〜35質量%である。1質量%未満では紫外線防御効果を十分に得ることができない。また50質量%を超えて配合すると、沈降しやすくなるなど保存安定性上好ましくない上に、粉っぽい使用感になり好ましくない。   The surface treatment of the metal oxide fine particles with the silicone compound represented by the general formula (2) can be performed by a conventionally known method. That is, for example, (i) a method in which metal oxide fine particles are dispersed in a medium selected from water or an organic solvent containing a silicone compound represented by the general formula (2), and (ii) a metal. A method in which oxide fine particles and a silicone compound represented by the general formula (2) are mixed and then surface-treated using a pulverizer such as a ball mill or a jet mill; (iii) a silicone compound represented by the general formula (2) The metal oxide fine particles are dispersed in the above solvent solution, the silicone compound is adsorbed on the surface of the metal oxide fine particles, and then dried and sintered. 0.1-12 mass% is preferable and, as for the quantity of the surface treating agent (silicone compound) with respect to metal oxide microparticles | fine-particles, More preferably, it is 3-8 mass%. Moreover, the compounding quantity to the sunscreen cosmetics of a component (c) becomes like this. Preferably it is 1-50 mass%, More preferably, it is 5-35 mass%. If it is less than 1% by mass, a sufficient ultraviolet protective effect cannot be obtained. Moreover, when it exceeds 50 mass%, it is not preferable in terms of storage stability because it tends to settle, and it is not preferable because it gives a powdery feeling.

本発明で使用する成分(d)の有機系紫外線吸収剤は、一般に化粧料に用いられているものであり、例えば、ケイ皮酸誘導体、パラ−アミノ安息香酸誘導体、サリチル酸誘導体、β,β−ジフェニルアクリラート誘導体、ベンゾフェノン誘導体、ベンジリデンショウノウ誘導体、フェニルベンゾイミダゾール誘導体、フェニルベンゾトリアゾール誘導体、アントラニル誘導体、イミダゾリン誘導体、ベンザルマロナート誘導体、4,4−ジアリールブタジエン誘導体等である。そのうち、特に好ましいものはケイ皮酸誘導体である。   The organic ultraviolet absorber of component (d) used in the present invention is generally used in cosmetics. For example, cinnamic acid derivatives, para-aminobenzoic acid derivatives, salicylic acid derivatives, β, β- Examples thereof include diphenyl acrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, phenylbenzotriazole derivatives, anthranyl derivatives, imidazoline derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives, and the like. Of these, cinnamic acid derivatives are particularly preferred.

上記ケイ皮酸誘導体としては、例えば、パラメトキシケイ皮酸2−エチルヘキシル(例えば「ユビヌルMC80」;BASF社製)、メトキシケイ皮酸イソプロピル、メトキシケイ皮酸イソアミル(例えば「ネオ・ヘリオパンE1000」;ハーマン・アンド・レイマー社製)、シンノキサート、DEAメトキシシンナマート、メチルケイ皮酸ジイソプロピル、グリセリル−エチルヘキサノアート−ジメトキシシンナマートなどが用いられる。そのうち、特に好ましいものはパラメトキシケイ皮酸2−エチルヘキシルである。   Examples of the cinnamic acid derivative include 2-methoxyhexyl paramethoxycinnamate (eg, “Ubinur MC80”; manufactured by BASF), isopropyl methoxycinnamate, and isoamyl methoxycinnamate (eg, “Neo Heliopan E1000”). Herman & Reimer), cinnoxate, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl-ethylhexanoate-dimethoxycinnamate, and the like. Of these, 2-ethylhexyl paramethoxycinnamate is particularly preferred.

成分(d)の日焼け止め化粧料への配合量は、好ましくは、0.1〜25質量%、より好ましくは、3〜20質量%である。本発明においては、分散剤として前記の一般式(1)で表されるシリコーン化合物を用い、更に金属酸化物微粒子の表面処理剤として前記の一般式(2)で表されるシリコーン化合物を用いたため、中波長紫外部領域(280〜320nm)を効率よく防御すべく、有機系紫外線吸収剤を3質量%以上配合する系であっても、高い日焼け止め効果を発揮しつつ、なおかつ経時での凝集や沈降、系のゲル化がおこらず、保存時の安定性に優れている。   The amount of the component (d) to be added to the sunscreen cosmetic is preferably 0.1 to 25% by mass, more preferably 3 to 20% by mass. In the present invention, the silicone compound represented by the general formula (1) is used as a dispersant, and the silicone compound represented by the general formula (2) is used as a surface treatment agent for metal oxide fine particles. In order to efficiently protect the mid-wavelength ultraviolet region (280 to 320 nm), even if it is a system containing 3% by mass or more of an organic ultraviolet absorber, it exhibits a high sunscreen effect and also aggregates over time. No sedimentation or gelation of the system, and excellent stability during storage.

本発明の日焼け止め化粧料は、必要に応じて他の成分を併用して、常法により調製することができる。例えば、液状、乳液状、クリーム状、ゲル状、ペースト状など種々の形態にて実施することができる。また、この化粧料の剤型は、例えば油中水型、油性(実質的に水を含まない)、水中油型などが挙げられるが、中でも油中水型が好ましい。また本発明の日焼け止め化粧料は、日焼け止め乳液、日焼け止めクリーム、化粧下地、ファンデーション、日焼け止めリップバームなどの製品にて実施することができる。   The sunscreen cosmetic of the present invention can be prepared by a conventional method using other components in combination as necessary. For example, it can be carried out in various forms such as liquid, emulsion, cream, gel, and paste. Examples of the cosmetic dosage form include a water-in-oil type, an oily (substantially free of water), and an oil-in-water type. Among these, a water-in-oil type is preferable. Moreover, the sunscreen cosmetics of the present invention can be implemented in products such as sunscreen emulsions, sunscreen creams, makeup bases, foundations, sunscreen lip balms and the like.

本発明の日焼け止め化粧料は、上記成分の他、本発明の効果を損なわない範囲で、化粧品に一般に使用される成分を配合することができる。このような成分としては、例えば、水、油脂、ロウ、炭化水素、脂肪酸、アルコール、エステル系オイル、エーテル系オイル、シリコーン系オイル、フッ素化合物等の油剤原料、成分(c)以外の粉体原料、金属石鹸、界面活性剤、成分(b)以外のシリコーン系界面活性剤、多価アルコール、酸化防止剤、高分子化合物、香料、防腐剤、保湿剤、pH調整剤、美容成分、色素、香料などが挙げられる。   The sunscreen cosmetic of the present invention can be blended with components generally used in cosmetics in addition to the above components, as long as the effects of the present invention are not impaired. Examples of such components include water, fats and oils, waxes, hydrocarbons, fatty acids, alcohols, ester oils, ether oils, silicone oils, fluorine compounds and other oil agent raw materials, and powder raw materials other than component (c). , Metal soaps, surfactants, silicone surfactants other than component (b), polyhydric alcohols, antioxidants, polymer compounds, fragrances, preservatives, moisturizers, pH adjusters, cosmetic ingredients, pigments, fragrances Etc.

本発明を実施例、比較例により詳細に説明する。配合量については特記しない限り、質量%で示す。まず、実施例及び比較例で用いるシリコーン系分散剤及びシリコーン表面処理金属酸化物について説明する。
A.実施例及び比較例で用いるシリコーン系分散剤及びその製造例
1.実施例で用いるシリコーン系分散剤及びその製造例(製造例1)
反応器に、下記平均組成式(1−1)で示されるオルガノハイドロジェンポリシロキサン560質量部と、下記平均組成式(1−2)で示されるオルガノポリシロキサン210質量部及びイソプロピルアルコール480質量部を混合し、塩化白金酸2質量%のイソプロピルアルコール溶液0.2質量部を加え、溶剤の還流下3時間反応させた。更に、1−ドデセン460質量部を添加し、溶剤の還流下3時間反応を継続させた後、下記平均組成式(1−3)で示されるポリオキシエチレンモノアリルエーテル380質量部を添加し、更に6時間加熱還流することによって反応を完結させた。次いで、0.01N塩酸水溶液を200質量部添加し、60〜70℃で加熱することで未反応のポリオキシアルキレンのアリルエーテル基を加水分解処理した。反応液を減圧下で加熱して溶剤を溜去した後、ろ過を行い下記平均組成式(1−4)で示されるオルガノポリシロキサンを得た。この生成物は、淡黄色透明な液体であり、粘度は、1120mm/s(25℃)、屈折率は1.4401(25℃)であった。
The present invention will be described in detail with reference to examples and comparative examples. Unless otherwise specified, the amount is shown in mass%. First, the silicone-based dispersant and the silicone surface-treated metal oxide used in Examples and Comparative Examples will be described.
A. Silicone-based dispersant used in Examples and Comparative Examples and Production Example 1 Silicone dispersants used in the examples and production examples thereof (Production Example 1)
In the reactor, 560 parts by mass of an organohydrogenpolysiloxane represented by the following average composition formula (1-1), 210 parts by mass of an organopolysiloxane represented by the following average composition formula (1-2) and 480 parts by mass of isopropyl alcohol Were mixed, 0.2 parts by mass of an isopropyl alcohol solution containing 2% by mass of chloroplatinic acid was added, and the mixture was reacted for 3 hours under reflux of the solvent. Furthermore, after adding 460 parts by mass of 1-dodecene and continuing the reaction for 3 hours under reflux of the solvent, 380 parts by mass of polyoxyethylene monoallyl ether represented by the following average composition formula (1-3) was added, The reaction was completed by further refluxing for 6 hours. Subsequently, 200 mass parts of 0.01N hydrochloric acid aqueous solution was added, and the allyl ether group of the unreacted polyoxyalkylene was hydrolyzed by heating at 60-70 degreeC. The reaction solution was heated under reduced pressure to distill off the solvent, followed by filtration to obtain an organopolysiloxane represented by the following average composition formula (1-4). This product was a pale yellow transparent liquid, the viscosity was 1120 mm 2 / s (25 ° C.), and the refractive index was 1.4401 (25 ° C.).

Figure 0005084021
Figure 0005084021

Figure 0005084021
Figure 0005084021

2.比較例で用いるシリコーン系分散剤及びその製造例(比較製造例1〜5)
製造例1の各原料の質量比を変えた以外は、製造例1と同様にして比較製造例1〜5のオルガノポリシロキサンを得た。原料の比率、物性は表1に記す。
2. Silicone dispersants used in comparative examples and production examples thereof (comparative production examples 1 to 5)
Except having changed the mass ratio of each raw material of manufacture example 1, it carried out similarly to manufacture example 1, and obtained organopolysiloxane of comparative manufacture examples 1-5. The ratio of raw materials and physical properties are shown in Table 1.

Figure 0005084021
Figure 0005084021

B.実施例及び比較例で用いるシリコーン表面処理酸化亜鉛粒子及びその製造例
1.表面処理に用いるシリコーンの製造例(製造例2)
反応器に下記平均組成式(2−1)で示されるオルガノハイドロジェンポリシロキサン1200質量部とトルエン920質量部を仕込み、塩化白金酸0.5質量%のトルエン溶液3質量部を加えた。次いで、前記平均組成式(1−2)で表されるオルガノポリシロキサン1330質量部と1−ヘキセン180質量部の混合物を滴下し、さらにビニルトリエトキシシラン380質量部を滴下しながら溶剤の還流下に6時間反応させた。反応物を減圧下で加熱して溶剤を溜去し、下記平均組成(2−2)で表されるオルガノポリシロキサンを得た。この生成物は、淡褐色透明な液体であり、粘度が47mm/s(25℃)、屈折率は1.4121(25℃)であった。
B. Silicone surface-treated zinc oxide particles used in Examples and Comparative Examples and production examples thereof 1. Production examples of silicone used in surface treatment (Production Example 2)
The reactor was charged with 1200 parts by mass of an organohydrogenpolysiloxane represented by the following average composition formula (2-1) and 920 parts by mass of toluene, and 3 parts by mass of a toluene solution of 0.5% by mass of chloroplatinic acid was added. Subsequently, a mixture of 1330 parts by mass of the organopolysiloxane represented by the above average composition formula (1-2) and 180 parts by mass of 1-hexene was dropped, and further 380 parts by mass of vinyltriethoxysilane was dropped while the solvent was refluxed. For 6 hours. The reaction product was heated under reduced pressure to distill off the solvent, and an organopolysiloxane represented by the following average composition (2-2) was obtained. This product was a light brown transparent liquid with a viscosity of 47 mm 2 / s (25 ° C.) and a refractive index of 1.4121 (25 ° C.).

Figure 0005084021
Figure 0005084021

Figure 0005084021
Figure 0005084021

2.表面処理に用いるシリコーンの製造例(製造例3)
製造例2の各原料の質量比を変えた以外は、製造例2と同様にして製造例3のオルガノポリシロキサンを得た。原料の比率及び物性は表2に記す。
2. Production example of silicone used for surface treatment (Production Example 3)
The organopolysiloxane of Production Example 3 was obtained in the same manner as Production Example 2 except that the mass ratio of each raw material of Production Example 2 was changed. The raw material ratio and physical properties are shown in Table 2.

Figure 0005084021
Figure 0005084021

3.酸化亜鉛微粒子の表面処理
あらかじめ熱乾燥処理した未処理の平均粒径20〜30nmの酸化亜鉛微粒子(テイカ社製MZ−500)50質量部を反応器に仕込み、製造例2又は製造例3で得たシリコーン化合物2.5質量部をヘキサン100質量部に希釈した溶液を徐々に加えながら攪拌した。更に、昇温してヘキサンを留去し、150℃にて3時間攪拌することにより焼き付け処理を行い、その後粉体を窒素気流下で室温に戻し、シリコーン表面処理酸化亜鉛微粒子を得た。なお、シリコーン表面処理酸化チタン微粒子も同様の表面処理で得た。
3. Surface Treatment of Zinc Oxide Fine Particles 50 parts by mass of untreated zinc oxide fine particles having an average particle diameter of 20 to 30 nm (MZ-500 manufactured by Teika Co., Ltd.) previously charged in a reactor were obtained in Production Example 2 or Production Example 3. The solution was prepared by gradually adding a solution obtained by diluting 2.5 parts by mass of the silicone compound to 100 parts by mass of hexane. Further, the temperature was raised and hexane was distilled off, followed by baking at 150 ° C. for 3 hours. Then, the powder was returned to room temperature under a nitrogen stream to obtain silicon surface-treated zinc oxide fine particles. Silicone surface-treated titanium oxide fine particles were also obtained by the same surface treatment.

実施例1〜4及び比較例1〜8. W/O型日焼け止め化粧料
表3に示す組成の日焼け止め料(W/O型エマルション)を、下記の製造方法にて調製し、初期の分散性及び経時安定性(保存安定性)について、下記に示す方法により評価を行った。その結果も併せて表3に示す。
Examples 1-4 and Comparative Examples 1-8. W / O-type sunscreen cosmetics Sunscreens (W / O-type emulsions) having the compositions shown in Table 3 were prepared by the following production method, and the initial dispersibility and stability over time (storage stability) were: Evaluation was performed by the method shown below. The results are also shown in Table 3.

Figure 0005084021
Figure 0005084021

(製造方法)
イ:成分1〜12を、規格瓶に入れ、ジルコニアビーズを成分1〜12の合計質量の2倍質量加えペイントシェイカーで15時間混合分散し、ジルコニアビーズを取り除いて粉体分散物を得た。
ロ:イで得た粉体分散物をデスパーズミルで攪拌しながら、成分13〜16を順次入れ、10分間混合した。
ハ:ロに成分17〜19をデスパーで攪拌しながら加え10分間乳化してW/O型の日焼け止め料を得た。
(Production method)
A: Components 1 to 12 were put in a standard bottle, zirconia beads were added twice the total mass of components 1 to 12, and mixed and dispersed for 15 hours with a paint shaker, and the zirconia beads were removed to obtain a powder dispersion.
(B) While stirring the powder dispersion obtained in (a) with a desperse mill, ingredients 13 to 16 were sequentially added and mixed for 10 minutes.
C: Components 17 to 19 were added to B while stirring with a desper and emulsified for 10 minutes to obtain a W / O type sunscreen.

(評価)
表3における初期の分散性及び経時安定性の評価は以下の如くして行った。
1.初期の分散性は製造直後に、日焼け止め化粧料の200μlを石英板に滴下し、6milのドクターブレードを用いて薄膜を引き、可視部(750nm)から紫外部(250nm)までの透過スペクトルを測定し、下記の評価基準より判定した。
[評価基準]
360nmにおける透過率が低いほど粉体の凝集が少なく高分散していると判断して評価を行った。
[判定]360nmにおける透過率
◎:20%未満
○:20%以上〜30%未満
△:30%以上〜40%未満
×:40%以上
(Evaluation)
The initial dispersibility and stability over time in Table 3 were evaluated as follows.
1. The initial dispersibility is that immediately after production, 200 μl of sunscreen cosmetic is dropped onto a quartz plate, a thin film is drawn using a 6 mil doctor blade, and the transmission spectrum from the visible part (750 nm) to the ultraviolet part (250 nm) is measured. And it judged from the following evaluation criteria.
[Evaluation criteria]
The evaluation was carried out by judging that the lower the transmittance at 360 nm, the less the powder agglomerates and the higher the dispersion.
[Determination] Transmittance at 360 nm ◎: Less than 20% ○: 20% to less than 30% Δ: 30% to less than 40% x: 40% or more

2.経時安定性は、5℃、50℃、室温の各条件下にて1ヶ月保存した後、状態を目視により観察し、下記の基準により判定した。
[評価基準]
ゲル化もしくは、分離の有無を判定した。
[判定]
◎:ゲル化は見られず、さらさらしている
○:ゲル化の程度が低く、若干のとろみがある
△:ゲル化が見られ、傾けても流れないが、手で振ると流動性が出る
×:ゲル化していて、逆さにしても動かず、手で振ってもゲルが崩れない
××:粉体が沈降し分離している
2. Stability over time was determined by the following criteria by observing the state visually after storing for 1 month at 5 ° C., 50 ° C., and room temperature.
[Evaluation criteria]
The presence or absence of gelation or separation was determined.
[Judgment]
◎: Gelation is not seen and freezing ○: The degree of gelation is low and there is a slight thickening △: Gelation is seen and does not flow even when tilted, but fluidity appears when shaken by hand ×: Gelled, does not move even when inverted, and gel does not collapse even when shaken by hand. XX: Powder settles and separates.

表3の結果から明らかなように、実施例1〜4の日焼け止め化粧料は、初期の分散性が高く、また50℃、室温、5℃に1ヶ月間保存した後の分散性が良く、系のゲル化や粉体の沈降が起きておらず、経時の分散安定性に優れた日焼け止め化粧料であった。一方、金属酸化物微粒子の表面処理剤として、本発明の一般式(2)で表されるシリコーン化合物に代えて、ジメチコン・メチコンコポリマー(比較例1)又はメチコン(比較例2)を用いた日焼け止め化粧料は、初期の分散は良いものの、経時で系のゲル化が起き、経時分散安定性が悪かった。また未表面処理の酸化亜鉛微粒子を用いた比較例3の日焼け止め化粧料では、初期における分散性が悪く、経時の分散安定性も悪かった。また、分散剤として、本発明の一般式(1)で表されるシリコーン化合物に代えて、主鎖の長さ、並びに、ラウリル基、ポリオキシエチレン基及びメチルポリシロキサン基の導入量を決めるx,y,z,p及びbが、本発明の範囲内にないシリコーン化合物(比較製造例1〜5)を用いた比較例4〜8の日焼け止め化粧料は、初期の分散性は良好なものの、経時で系のゲル化が起き、経時分散安定性が悪かった。 As is clear from the results in Table 3, the sunscreen cosmetics of Examples 1 to 4 have high initial dispersibility, and good dispersibility after storage at 50 ° C., room temperature and 5 ° C. for 1 month, It was a sunscreen cosmetic that did not cause system gelation or powder settling and was excellent in dispersion stability over time. On the other hand, as a surface treatment agent for metal oxide fine particles, sunburn using dimethicone / methicone copolymer (Comparative Example 1) or methicone (Comparative Example 2) instead of the silicone compound represented by the general formula (2) of the present invention. The stop cosmetics had good initial dispersion, but the gelation of the system occurred with time, and the dispersion stability with time was poor. Further, the sunscreen cosmetic of Comparative Example 3 using unsurface-treated zinc oxide fine particles had poor initial dispersibility and poor temporal dispersion stability. Further, in place of the silicone compound represented by the general formula (1) of the present invention as a dispersant, the length of the main chain and the introduction amount of lauryl group, polyoxyethylene group and methylpolysiloxane group are determined x , Y, z, p and b are sunscreen cosmetics of Comparative Examples 4 to 8 using a silicone compound (Comparative Production Examples 1 to 5) not within the scope of the present invention, although the initial dispersibility is good The gelation of the system occurred over time, and the dispersion stability over time was poor.

実施例5. O/W型日焼け止め乳液
成分 (%)
(1)製造例2のシリコーン5%処理酸化亜鉛微粒子 10.0
(2)ビニルピロリドン変成アクリル-シリコーン共重合体(注3) 2.0
(3)デカメチルシクロペンタシクロシロキサン 10.0
(4)製造例1のシリコーン化合物 3.0
(5)PEG11メチルエーテルジメチコン 2.0
(6)ミツロウ 2.0
(7)スクワラン 6.0
(8)メチルポリシロキサン(10CS) 5.0
(9)ソルビタンセスキオレイン酸エステル 4.0
(10)ポリオキシエチレン・メチルポリシロキサン共重合体(注4) 1.0
(11)パラメトキシケイ皮酸2−エチルヘキシル 8.0
(12)1,3−ブチレングリコール 8.0
(13)防腐剤 適量
(14)精製水 残量
(15)香料 適量
(注3) KP−545(信越化学工業(株)製)
(注4) KF−6017(信越化学工業(株)製)
Example 5 FIG. O / W type sunscreen latex Ingredient (%)
(1) Silicone 5% treated zinc oxide fine particles of Production Example 2 10.0
(2) Vinylpyrrolidone-modified acrylic-silicone copolymer (Note 3) 2.0
(3) Decamethylcyclopentacyclosiloxane 10.0
(4) Silicone compound of Production Example 1 3.0
(5) PEG11 methyl ether dimethicone 2.0
(6) Beeswax 2.0
(7) Squalane 6.0
(8) Methylpolysiloxane (10CS) 5.0
(9) Sorbitan sesquioleate ester 4.0
(10) Polyoxyethylene / methylpolysiloxane copolymer (Note 4) 1.0
(11) 2-Ethylhexyl paramethoxycinnamate 8.0
(12) 1,3-butylene glycol 8.0
(13) Preservative appropriate amount (14) Purified water Remaining amount (15) Fragrance appropriate amount (Note 3) KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(製造方法)
イ:成分(1)〜(4)を15時間ペイントシェイカーにかけ均一に混合分散した。これに(5)〜(11)を加熱溶解し、70℃にした。
ロ:(12)〜(14)を加熱溶解して70℃にし、これをイに添加して10分間乳化混合した。
ハ:ロを冷却後、(15)を添加混合して日焼け止め乳液を得た。
上記のようにして得られたO/W型日焼け止め乳液は、製造直後も高い分散性を示し、保存安定性にも優れる化粧料であった。
(Production method)
A: Components (1) to (4) were put on a paint shaker for 15 hours and mixed and dispersed uniformly. (5) to (11) were dissolved in this by heating to 70 ° C.
B: (12) to (14) were dissolved by heating to 70 ° C., and this was added to A and emulsified and mixed for 10 minutes.
C: After cooling, (15) was added and mixed to obtain a sunscreen emulsion.
The O / W-type sunscreen emulsion obtained as described above was a cosmetic that showed high dispersibility immediately after production and excellent storage stability.

実施例6. O/W型クリームファンデーション
成分 (%)
(1)デカメチルテトラシロキサン 10.0
(2)パラメトキシケイ皮酸2−エチルヘキシル 5.0
(3)製造例3のシリコーン7%処理酸化亜鉛微粒子 8.0
(4)製造例1のシリコーン化合物 5.0
(5)ステアリン酸 5.0
(6)親油型モノステアリン酸グリセリン 2.5
(7)セトステアリルアルコール 1.5
(8)ベヘニルアルコール 1.0
(9)モノラウリル酸イソプロピレングリコール 2.5
(10)ミリスチン酸イソプロピル 6.0
(11)精製水 残量
(12)トリエタノールアミン 1.2
(13)ソルビトール 3.0
(14)パラオキシ安息香酸メチル 適量
(15)製造例2のシリコーン7%処理酸化チタン微粒子 5.0
(16)カオリン 5.0
(17)黒酸化鉄 1.0
(18)ベンガラ 2.5
(19)黄酸化鉄 2.0
(20)ベントナイト 0.2
Example 6 O / W cream foundation ingredients (%)
(1) Decamethyltetrasiloxane 10.0
(2) 2-Ethylhexyl paramethoxycinnamate 5.0
(3) Silicone 7% -treated zinc oxide fine particles of Production Example 3 8.0
(4) Silicone compound of Production Example 1 5.0
(5) Stearic acid 5.0
(6) Lipophilic glyceryl monostearate 2.5
(7) cetostearyl alcohol 1.5
(8) Behenyl alcohol 1.0
(9) Isopropylene glycol monolaurate 2.5
(10) Isopropyl myristate 6.0
(11) Purified water remaining amount (12) Triethanolamine 1.2
(13) Sorbitol 3.0
(14) Methyl paraoxybenzoate Appropriate amount (15) Silicone 7% treated titanium oxide fine particles of Production Example 2 5.0
(16) Kaolin 5.0
(17) Black iron oxide 1.0
(18) Bengala 2.5
(19) Yellow iron oxide 2.0
(20) Bentonite 0.2

(製造方法)
イ:(1)〜(4)をペイントシェイカーにて均一に混合分散した。
ロ:(15)〜(19)を室温にて混合した。
ハ:(20)に(11)の一部を加えてよく膨潤させた。次に、(11)の残部と(12)〜(14)を加えて溶解させた。このものにイ及びロの混合物を加え70℃で混合した(水相)。
ニ:(5)〜(10)を70℃で溶解した(油相)。
ホ:ハで得た(水相)に、ニで得た(油相)を加えて10分間乳化し、乳化終了後、35℃まで撹拌冷却した。
上記のようにして得られたO/W型クリームファンデーションは、製造直後の粉体分散性が高く、経時でのゲル化がおこらない、保存安定性に優れたものであった。
(Production method)
A: (1) to (4) were uniformly mixed and dispersed with a paint shaker.
B: (15) to (19) were mixed at room temperature.
C: Part of (11) was added to (20) and allowed to swell well. Next, the remainder of (11) and (12) to (14) were added and dissolved. To this, the mixture of A and B was added and mixed at 70 ° C. (aqueous phase).
D: (5) to (10) were dissolved at 70 ° C. (oil phase).
(E) The (oil phase) obtained in (ii) was added to the (water phase) obtained in (c) and emulsified for 10 minutes. After the emulsification, the mixture was stirred and cooled to 35 ° C.
The O / W cream foundation obtained as described above had high powder dispersibility immediately after production, did not gel with time, and had excellent storage stability.

実施例7. W/O型リキッドファンデーション
成分 (%)
(1)製造例3のシリコーン5%処理酸化亜鉛微粒子 10.0
(2)製造例1のシリコーン化合物 5.0
(3)デカメチルシクロペンタシロキサン 20.0
(4)アクリル−シリコーン系グラフト共重合体(注5) 5.0
(5)トリ−2−エチルヘキサン酸グリセリル 3.0
(6)ジカプリン酸プロピレングリコール 3.0
(7)ジ−2−エチルヘキサン酸ネオペンチルグリコール 3.0
(8)ショ糖脂肪酸エステル 0.5
(9)有機変性ベントナイト 1.0
(10)パラメトキシケイ皮酸2−エチルヘキシル 7.0
(11)酸化チタン 9.0
(12)ベンガラ 0.6
(13)黄色酸化鉄 2.1
(14)黒酸化鉄 0.15
(15)タルク 5.0
(16)球状PMMA粉体 0.5
(17)ヘプタオレイン酸デカグリセリル 1.0
(18)セスキオレイン酸ソルビタン 1.0
(19)ポリオキシエチレン・
メチルポリシロキサン共重合体(注6) 1.0
(20)ポリオキシエチレン・
アルキル変性シリコーン(注7) 1.0
(21)合成ケイ酸ナトリウム・マグネシウム(注8) 0.3
(22)エタノール 1.5
(23)防腐剤 微量
(24)プロピレングリコール 5.0
(25)精製水 残量
(注5):KP−545:信越化学工業(株)製
(注6):KF6017:信越化学工業(株)製
(注7):アビルEM−90:ゴールドシュミット社製
(注8):ラポナイトXLS:ラポナイト社製
Example 7 W / O Liquid Foundation Ingredient (%)
(1) Silicone 5% treated zinc oxide fine particles of Production Example 3 10.0
(2) Silicone compound of Production Example 1 5.0
(3) Decamethylcyclopentasiloxane 20.0
(4) Acrylic-silicone graft copolymer (Note 5) 5.0
(5) Glyceryl tri-2-ethylhexanoate 3.0
(6) Propylene glycol dicaprate 3.0
(7) Di-2-ethylhexanoic acid neopentyl glycol 3.0
(8) Sucrose fatty acid ester 0.5
(9) Organically modified bentonite 1.0
(10) 2-Methylhexyl paramethoxycinnamate 7.0
(11) Titanium oxide 9.0
(12) Bengala 0.6
(13) Yellow iron oxide 2.1
(14) Black iron oxide 0.15
(15) Talc 5.0
(16) Spherical PMMA powder 0.5
(17) Decaglyceryl heptaoleate 1.0
(18) Sorbitan sesquioleate 1.0
(19) Polyoxyethylene
Methyl polysiloxane copolymer (Note 6) 1.0
(20) Polyoxyethylene
Alkyl-modified silicone (Note 7) 1.0
(21) Synthetic sodium silicate / magnesium (Note 8) 0.3
(22) Ethanol 1.5
(23) Preservative Trace amount (24) Propylene glycol 5.0
(25) Purified water remaining
(Note 5): KP-545: manufactured by Shin-Etsu Chemical Co., Ltd.
(Note 6): KF6017: Shin-Etsu Chemical Co., Ltd.
(Note 7): Avil EM-90: Gold Schmidt
(Note 8): LAPONITE XLS: manufactured by LAPONITE

(製造方法)
イ:成分(1)〜(3)をマイクロフルイダイザー(マイクロフルイディクス社製)=高圧ホモジナイザーで均一に分散した。
ロ:(4)〜(8)、(10)、(17)〜(20)を加熱して溶解し、均一に混合し放冷した。
ハ:ロに成分(9)、(11)〜(16)を加え、ロールミルにて均一混合した。
ニ:イにハを加え、均一に混合した。
ホ:成分(21)〜(25)を均一混合した。
ヘ:ニにホを攪拌しながら加え、乳化し、脱泡後、広口瓶に充填してリキッドファンデーションとした。
上記のようにして得られたW/O型リキッドファンデーションは、製造初期の粉体の分散性に優れ、その安定性においても、経時でのゲル化や粉体の凝集は見られず優れたものであった。
(Production method)
A: Components (1) to (3) were uniformly dispersed with a microfluidizer (manufactured by Microfluidics) = high pressure homogenizer.
B: (4) to (8), (10), (17) to (20) were heated and dissolved, mixed uniformly, and allowed to cool.
C: Components (9) and (11) to (16) were added to (b) and mixed uniformly with a roll mill.
D: C was added to A and mixed uniformly.
E: Components (21) to (25) were uniformly mixed.
F: Added to Ni while stirring, emulsified, defoamed, and filled into a wide-mouthed bottle to obtain a liquid foundation.
The W / O type liquid foundation obtained as described above is excellent in the dispersibility of the powder at the initial stage of manufacture, and also excellent in stability, without gelation or aggregation of the powder over time. Met.

実施例8. 日焼け止めリップバーム
(成分) (%)
(1)ポリエチレンワックス 2.0
(2)セレシン 1.0
(3)マイクロクリスタリンワックス 5.0
(4)リンゴ酸ジイソステアリル 9.0
(5)トリイソステアリン酸ポリグリセリル 残量
(6)ワセリン 10.0
(7)ポリブテン 10.0
(8)重質流動イソパラフィン 9.0
(9)2−エチルヘキサン酸セチル 16.0
(10)ドデカメチルシクロヘキサシロキサン 10.0
(11)製造例1のシリコーン化合物 3.0
(12)製造例2のシリコーン5%処理酸化亜鉛微粒子 7.0
(13)パラメトキシケイ皮酸2−エチルヘキシル 7.0
(14)防腐剤 0.1
(15)香料 0.1
Example 8 FIG. Sunscreen lip balm (ingredient) (%)
(1) Polyethylene wax 2.0
(2) Ceresin 1.0
(3) Microcrystalline wax 5.0
(4) Diisostearyl malate 9.0
(5) Polyglyceryl triisostearate remaining amount (6) Vaseline 10.0
(7) Polybutene 10.0
(8) Heavy liquid isoparaffin 9.0
(9) Cetyl 2-ethylhexanoate 16.0
(10) Dodecamethylcyclohexasiloxane 10.0
(11) Silicone compound of Production Example 1 3.0
(12) Silicone 5% -treated zinc oxide fine particles of Production Example 2 7.0
(13) 2-Ethylhexyl paramethoxycinnamate 7.0
(14) Preservative 0.1
(15) Fragrance 0.1

(製造方法)
イ:(10)〜(13)を15時間ビーズミル処理し分散させた。
ロ:(1)〜(9)、(14)、(15)を加え、これをローラーで混合分散した
ハ:ロを加熱溶解後、イを加え均一に混合した。
ニ:ハを容器に充填し、急冷して日焼け止めリップバームを得た。
上記のようにして得られた日焼け止めリップバームは、金属酸化物微粒子の分散性がよく、50℃、室温、5℃に1ヶ月間保存した後も経時での変化がないものであった。
(Production method)
A: (10) to (13) were dispersed by bead milling for 15 hours.
B: After adding (1) to (9), (14) and (15) and mixing and dispersing this with a roller, the mixture was heated and dissolved, and then added and mixed uniformly.
D: Ha was filled into a container and rapidly cooled to obtain a sunscreen lip balm.
The sunscreen lip balm obtained as described above had good dispersibility of the metal oxide fine particles and did not change with time even after storage at 50 ° C., room temperature and 5 ° C. for 1 month.

Claims (4)

(a)揮発性オルガノポリシロキサン10〜55質量%、(b)シリコーン系分散剤0.1〜20質量%、(c)シリコーン表面処理金属酸化物微粒子1〜50質量%、及び(d)有機系紫外線吸収剤0.1〜25質量%を含有する日焼け止め化粧料であって、前記成分(b)のシリコーン系分散剤が次式の一般式(1)で表されるシリコーン化合物であり、前記成分(c)のシリコーン表面処理金属酸化物微粒子が次式の一般式(2)で表されるシリコーン化合物で表面処理された金属酸化物微粒子であることを特徴とする日焼け止め化粧料。
Figure 0005084021
Figure 0005084021
(A) 10 to 55% by mass of volatile organopolysiloxane, (b) 0.1 to 20% by mass of silicone dispersant, (c) 1 to 50% by mass of silicone surface-treated metal oxide fine particles , and (d) organic A sunscreen cosmetic containing 0.1 to 25% by mass of an ultraviolet absorber, wherein the silicone dispersant of the component (b) is a silicone compound represented by the following general formula (1): A sunscreen cosmetic, wherein the silicone surface-treated metal oxide fine particles of component (c) are metal oxide fine particles surface-treated with a silicone compound represented by the following general formula (2):
Figure 0005084021
Figure 0005084021
成分(c)のシリコーン表面処理金属酸化物微粒子の金属酸化物微粒子が、酸化亜鉛微粒子又は酸化チタン微粒子である請求項1記載の日焼け止め化粧料。   The sunscreen cosmetic according to claim 1, wherein the metal oxide fine particles of the silicone surface-treated metal oxide fine particles of component (c) are zinc oxide fine particles or titanium oxide fine particles. 成分(d)の有機系紫外線吸収剤が、パラメトキシケイ皮酸2−エチルヘキシルである請求項1又は2記載の日焼け止め化粧料。   The sunscreen cosmetic according to claim 1 or 2, wherein the organic ultraviolet absorber of component (d) is 2-ethylhexyl paramethoxycinnamate. 剤型が、油中水型である請求項1〜3のいずれかに記載の日焼け止め化粧料。   The sunscreen cosmetic according to any one of claims 1 to 3, wherein the dosage form is a water-in-oil type.
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