JP3885811B2

JP3885811B2 - Cosmetics containing flaky metal oxide

Info

Publication number: JP3885811B2
Application number: JP2004263432A
Authority: JP
Inventors: 和宏堂下; 浩司横井
Original assignee: Nippon Sheet Glass Co Ltd
Current assignee: Nippon Sheet Glass Co Ltd
Priority date: 2004-09-10
Filing date: 2004-09-10
Publication date: 2007-02-28
Anticipated expiration: 2016-03-22
Also published as: JP2004339243A

Description

本発明は、フレーク状金属酸化物、特に発色性、安定性、安全性に優れ、かつ伸展性や触感が良好な、種々の色調を発現する着色剤に適したフレーク状金属酸化物を配合した化粧料に関する。 The present invention blends flake-shaped metal oxides, particularly flake-shaped metal oxides that are excellent in color development, stability and safety, and have good extensibility and tactile sensation, and are suitable for colorants that express various colors. Concerning cosmetics.

今まで、化粧品用着色剤として金微粒子を用いる試みがなされてきた。その例として、表面上に金微粒子を固定したマイカやタルク等の体質顔料を配合した化粧料（特開平１−２１５８６５号公報）、金コロイドで染色したタンパク質や絹フィブロイン粉末を配合した化粧料（特開平３−９００１２号公報、特開平３−７７８０６号公報）、金微粒子を固定した金属酸化物粉体を配合した化粧料（特公平５−８７０４５号公報）等が挙げられる。
特開平１−２１５８６５号公報特開平３−９００１２号公報特開平３−７７８０６号公報特公平５−８７０４５号公報 Until now, attempts have been made to use fine gold particles as cosmetic colorants. For example, cosmetics containing body pigments such as mica and talc with gold fine particles fixed on the surface (Japanese Patent Laid-Open No. 1-215865), cosmetics containing protein dyed with gold colloid and silk fibroin powder ( JP-A-3-9-10012 and JP-A-3-77806), and cosmetics (Japanese Patent Publication No. 5-87045) containing a metal oxide powder in which gold fine particles are fixed.
JP-A-1-215865 Japanese Patent Laid-Open No. 3-90012 JP-A-3-77806 Japanese Patent Publication No. 5-87045

これら金微粒子を固定した粉体は、赤紫〜紫色系統の鮮やかな色を発現し、化粧料として使用されている。しかしながら、化粧品基材のオイル成分や皮膚上の油脂分に触れることにより色がくすんだり、さらに担体表面の金微粒子の脱落や凝集により色あせや変色を起こしたり、すり潰して粉砕するときの強い圧力により金微粒子が変形し変色して色ムラを起こしたりする場合があった。 The powder in which the gold fine particles are fixed expresses a bright purple-purple color and is used as a cosmetic. However, the color becomes dull by touching the oil component of the cosmetic base material and oils and fats on the skin, and further, fading or discoloration occurs due to the dropping or agglomeration of gold fine particles on the surface of the carrier, or due to strong pressure when grinding and crushing In some cases, the gold fine particles are deformed and discolored to cause color unevenness.

また、製造方法によっては、鮮やかな色とはならず、褐色や灰色等の、化粧料としては好ましくない発色になりがちで、鮮やかな発色には製造工程の厳密な管理やノウハウが必要であり、手間がかかるなどの問題もあった。さらに、得られた金微粒子固定粉体の中には、媒体に均一分散させることが難しく、また一度分散させても、経時的に凝集していわゆる「だま」になったり、むらになる場合があった。特に、化粧料として多量配合した場合は、上記問題が顕著になり、さらに、すべりが悪くなって肌上での伸展性（のび）が悪くなるといった難点があった。 Also, depending on the manufacturing method, it may not be vivid colors, and it tends to be unfavorable for cosmetics such as brown and gray. Vivid color development requires strict management and know-how in the manufacturing process. There were also problems such as taking time and effort. Further, in the obtained gold fine particle fixed powder, it is difficult to uniformly disperse in the medium, and even if dispersed once, it may aggregate over time to become a so-called “dull” or uneven. there were. In particular, when a large amount is blended as a cosmetic, the above-mentioned problem becomes remarkable, and further, there is a problem that the slippage is worsened and the extensibility (spreading) on the skin is worsened.

本発明は上記の従来技術に鑑み、鮮やかな発色性と安定性、均一着色性を有し、かつ伸展性（のび）が良好で触感に優れた、金微粒子を含有するフレークを配合した高品質な化粧料を提供するものである。 In view of the above-mentioned conventional technology, the present invention has high quality blended with flakes containing gold fine particles having vivid color developability, stability, uniform colorability, good extensibility (extended) and excellent touch feeling. Providing cosmetics.

本課題を解決するため、本発明者らは、加水分解および縮重合が可能な有機金属化合物と水を含む溶液に、金コロイドまたは金化合物を添加し、これを基材上、好ましくは表面が平滑な基板上に塗布し、乾燥して基材から剥離させた後、熱処理すれば、簡単かつ効率的に、発色性、安定性に優れた金微粒子分散含有フレーク状金属酸化物が製造できることを見いだし、本発明に到った。 In order to solve this problem, the present inventors added a colloidal gold or gold compound to a solution containing an organometallic compound capable of hydrolysis and polycondensation and water, and this was added to the substrate, preferably the surface. If it is applied on a smooth substrate, dried and peeled off from the base material, and then heat-treated, it is possible to produce a flaky metal oxide containing gold fine particles dispersed in a simple and efficient manner with excellent color development and stability. As a result, the present invention has been reached.

すなわち、本発明は、フレーク状金属酸化物着色剤を配合した化粧料であって、前記フレーク状金属酸化物着色剤は酸化珪素、酸化チタン、酸化アルミニウムおよび酸化ジルコニウムからなる群より選ばれる少なくとも一種の金属酸化物を主成分とし、前記フレーク状金属酸化物着色剤は０．１〜２μｍの平均厚みおよび５〜１５０のアスペクト比を有し、そして１〜３００ｎｍの粒径を有する金微粒子が前記フレーク状金属酸化物着色剤の内部に分散した状態で０．０１〜３０質量％含有されている、フレーク状金属酸化物着色剤を配合した化粧料である。 That is, the present invention is a cosmetic containing a flaky metal oxide colorant, wherein the flaky metal oxide colorant is at least one selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide and zirconium oxide. a metal oxide as a main component, the flaky metal oxide colorants have a mean aspect ratio of thickness and 5 to 150 of 0.1-2 .mu.m, and the gold fine particles having a particle size of 1~300nm It is a cosmetic compounded with a flaky metal oxide colorant that is contained in an amount of 0.01 to 30 % by mass in a dispersed state inside the flaky metal oxide colorant.

本発明の化粧料に配合する着色剤であるフレーク状金属酸化物中の金微粒子の粒径（棒状の場合はその長さ）は、１ｎｍ以上、３００ｎｍ以下である。粒径が１ｎｍより小さいと、金微粒子による発色効果が低下し、鮮やかな発色が認められない。また、粒径が３００ｎｍより大きいと、光の散乱の効果が大きくなり濁った色調となる。そして金微粒子の形状は特に限定されない。球状、卵型状、棒状、板状等何でも良い。また本発明における金微粒子は、後述するが、金コロイド溶液から由来するものであるか、または加熱により金属酸化物中で析出した金微粒子である。 The particle size of gold fine particles in the flaky metal oxide which is a colorant to be blended in the cosmetic of the present invention (the length in the case of a rod-like shape) is 1 nm or more and 300 nm or less. When the particle size is smaller than 1 nm, the color development effect by the gold fine particles is lowered, and vivid color development is not recognized. On the other hand, when the particle diameter is larger than 300 nm, the effect of light scattering is increased, resulting in a cloudy color tone. The shape of the gold fine particles is not particularly limited. Any shape such as a spherical shape, an oval shape, a rod shape, or a plate shape may be used. As will be described later, the gold fine particles in the present invention are derived from a gold colloid solution, or are gold fine particles precipitated in a metal oxide by heating.

本発明におけるフレーク状金属酸化物中の金含有量は、０．０１質量％以上、３０質量％以下である。より好ましい含有量は０．２〜２５質量％である。金の含有量が０．０１質量％より少ないと、発色効果が充分でなくなる。含有量が３０質量％より多くなっても、着色濃度はそれほど濃くならず、コスト高となる。このフレーク状金属酸化物を配合した化粧料のうち、比較的に薄い着色を必要とするパウダーファンデーション、スキンクリーム、ハンドクリーム、メイクアップベース等用としてはフレーク状金属酸化物中の金含有量は比較的に小さく、例えば０．２〜３質量％が好ましい場合が多く、比較的に濃い着色を必要とするネイルエナメル、アイシャドー、口紅等用にはフレーク状金属酸化物中の金含有量は比較的に大きく、例えば３〜２５質量％が好ましい場合が多い。ただし配合によっては、他の着色剤との兼ね合いで前記好ましい範囲を逸脱する場合もある。 The gold content in the flaky metal oxide in the present invention is 0.01% by mass or more and 30% by mass or less. A more preferable content is 0.2 to 25% by mass. When the gold content is less than 0.01% by mass, the coloring effect is not sufficient. Even if the content is more than 30% by mass, the coloring density is not so high and the cost is increased. Among the cosmetics containing this flaky metal oxide, the gold content in the flaky metal oxide is for powder foundations, skin creams, hand creams, makeup bases, etc. that require relatively light coloring. The content of gold in the flaky metal oxide is relatively small, for example, 0.2 to 3% by mass is often preferred, and for nail enamel, eye shadow, lipstick and the like that require relatively dark coloring, In many cases, it is relatively large, for example, 3 to 25% by mass is preferable. However, depending on the blending, there may be cases where it deviates from the above preferred range in consideration of other colorants.

本発明におけるフレーク状金属酸化物のマトリックスは、酸化珪素、酸化チタン、酸化アルミニウム、酸化ジルコニウムからなる群より選ばれる少なくとも一種からなる。
本発明におけるフレーク状金属酸化物マトリックスは、非晶質、結晶質、非晶質と結晶質の混合体の何れでもよい。非晶質、結晶質等のいずれになるかは主としてフレーク状金属酸化物マトリックスの組成および熱処理条件によって決められ、酸化チタン、酸化アルミニウム、または酸化ジルコニウム単独からなる金属酸化物は結晶質になることが多く、酸化珪素単独またはこれと、酸化チタン、酸化アルミニウム、または酸化ジルコニウムとの混合物からなるフレーク状金属酸化物は、非晶質または、非晶質と結晶質の混合体になることが多い。好ましくは、非晶質、特にガラス状態であることが、フレーク状金属酸化物粉体の触感が特に良いので、望まれる。 The matrix of flaky metal oxide in the present invention comprises at least one selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide, and zirconium oxide.
The flaky metal oxide matrix in the present invention may be any of amorphous, crystalline, and a mixture of amorphous and crystalline. Whether it is amorphous or crystalline is mainly determined by the composition of the flaky metal oxide matrix and the heat treatment conditions, and the metal oxide consisting of titanium oxide, aluminum oxide, or zirconium oxide alone is crystalline. In many cases, a flaky metal oxide composed of silicon oxide alone or a mixture thereof with titanium oxide, aluminum oxide, or zirconium oxide is often amorphous or a mixture of amorphous and crystalline. . Preferably, it is amorphous, particularly in the glass state, since the feel of the flaky metal oxide powder is particularly good.

本発明におけるフレーク状金属酸化物の製造方法は、特に限定されないが、第一の製法として、加水分解および縮重合が可能な有機金属化合物と水を含む溶液に、金コロイドを添加し、これを基材上、好ましくは表面が平滑な基板上に塗布し、乾燥して基材から剥離させた後、熱処理して製造する方法が挙げられる。第二の製法は、加水分解および縮重合が可能な有機金属化合物と水を含む溶液に、塩化金酸、塩化金酸ナトリウム、シアン化金、シアン化金カリウム、三塩化ジエチルアミン金酸等の金化合物を添加し、これを基材上、好ましくは表面が平滑な基板上に塗布し、乾燥して基材から剥離させた後、熱処理、紫外線照射等により金微粒子を金属酸化物マトリックス中に析出させる方法である。これらの方法が特に優れた特性を有する金微粒子分散含有フレーク状金属酸化物を得ることができるので好ましい。 The method for producing the flaky metal oxide in the present invention is not particularly limited. As a first production method, a colloidal gold is added to a solution containing an organometallic compound capable of hydrolysis and polycondensation and water, and this is added. Examples of the method include a method of coating on a substrate, preferably a substrate having a smooth surface, drying and peeling off the substrate, and then heat-treating. In the second production method, a solution containing an organometallic compound capable of hydrolysis and polycondensation and water is added to a solution of gold such as chloroauric acid, sodium chloroaurate, gold cyanide, potassium cyanide cyanide, diethylamineauric acid trichloride. A compound is added, applied onto a base material, preferably a substrate with a smooth surface, dried and peeled off from the base material, and then gold fine particles are precipitated in the metal oxide matrix by heat treatment, ultraviolet irradiation, etc. It is a method to make it. These methods are preferred because a flaky metal oxide containing gold fine particles dispersed and having particularly excellent characteristics can be obtained.

本発明に用いる加水分解および縮重合が可能な有機金属化合物は、加水分解、脱水縮合を行うものであれば基本的にはどんな化合物でも良いが、アルコキシル基を有する金属アルコキシドが好ましい。具体的には、Ｓｉ、Ｔｉ、Ａｌ、Ｚｒ等のメトキシド、エトキシド、プロポキシド、ブトキシド等が、単体あるいは混合体として用いられる。 The organometallic compound capable of hydrolysis and polycondensation used in the present invention may be basically any compound as long as it undergoes hydrolysis and dehydration condensation, but a metal alkoxide having an alkoxyl group is preferred. Specifically, methoxide such as Si, Ti, Al, and Zr, ethoxide, propoxide, butoxide, and the like are used alone or as a mixture.

上記有機金属化合物を含む溶液の有機溶媒は、実質的に上記有機金属化合物を溶解すれば基本的に何でも良いが、メタノール、エタノール、プロパノール、ブタノール等のアルコール類が最も好ましい。場合によっては、溶媒を必要としないこともある。 The organic solvent in the solution containing the organometallic compound may be basically anything as long as it substantially dissolves the organometallic compound, but alcohols such as methanol, ethanol, propanol and butanol are most preferred. In some cases, no solvent is required.

上記有機金属化合物の加水分解には水が必要である。これは、酸性、中性、塩基性の何れでも良いが、加水分解を促進するためには、塩酸、硝酸、硫酸等で酸性にした水を用いるのが好ましい。酸の添加量は特に限定されないが、有機金属化合物に対してモル比で０．００１〜２が良い。添加酸量が、モル比で０．００１より少ないと、有機金属化合物の加水分解の促進が充分でなく、またモル比で２より多くても、もはや加水分解促進の効果が向上せず、酸が過剰となり好ましくない。 Water is required for hydrolysis of the organometallic compound. This may be acidic, neutral or basic, but in order to promote hydrolysis, it is preferable to use water acidified with hydrochloric acid, nitric acid, sulfuric acid or the like. Although the addition amount of an acid is not specifically limited, 0.001-2 are preferable by molar ratio with respect to an organometallic compound. When the amount of added acid is less than 0.001 in molar ratio, the promotion of hydrolysis of the organometallic compound is not sufficient, and when the molar ratio is more than 2, the effect of promoting hydrolysis is no longer improved. Is excessively undesirable.

また、この添加する水は、上記第一の製法を用いる場合における金コロイドの分散安定化のためにも必要である。水の添加量は、溶液の１０質量％以上、８０質量％以下が良い。ただしここで言う水分量は、上記コロイド中に含まれているものと、新たに添加する水の総計である。水添加量が、溶液の１０質量％より少ないと、上記コロイドが安定に存在できなくなる傾向が強く、好ましくない。また、水添加量が、溶液の８０質量％より多いと、溶液中の固形分換算濃度が低くなりすぎて、フレークの収率が低くなり、好ましくない。 The added water is also necessary for stabilizing the dispersion of the gold colloid in the case of using the first production method. The amount of water added is preferably 10% by mass or more and 80% by mass or less of the solution. However, the amount of water referred to here is the total of water contained in the colloid and newly added water. If the amount of water added is less than 10% by mass of the solution, the above colloid tends not to exist stably, which is not preferable. Moreover, when there are more water addition amounts than 80 mass% of a solution, the solid content conversion density | concentration in a solution will become low too much, and the yield of flakes will become low, and is unpreferable.

その他、上記溶液の特性を変化させるために、有機増粘剤等を添加しても良い。しかし、この添加量が多いと、最終段階の加熱で炭化することがあるので、添加量は１０質量％以下にとどめるべきである。 In addition, an organic thickener or the like may be added to change the characteristics of the solution. However, if this addition amount is large, carbonization may occur by heating in the final stage, so the addition amount should be limited to 10% by mass or less.

上記製法のうち、金コロイドを添加する上記第一の製法では、上記コロイドを上記有機金属化合物と水を含む溶液中に、均一に分散することができ、最終的に得られるフレーク状金属酸化物中の金微粒子の形状や大きさを制御することが比較的容易で、様々な特性を有するものが簡単に製造できる。上記金コロイドは、公知の方法で製造できる。例えば、塩化金酸、塩化金酸ナトリウム、シアン化金、シアン化金カリウム、三塩化ジエチルアミン金酸等の金化合物水溶液を、クエン酸、クエン酸ナトリウム、アスコルビン酸、ホルムアルデヒド、ヒドラジン、水素化ホウ素ナトリウム等の公知の還元剤で処理することにより金コロイドが得られる。また、還元剤を使用する代わりに上記金化合物水溶液に紫外線を照射することによっても得られる。 Of the above production methods, in the first production method in which gold colloid is added, the colloid can be uniformly dispersed in a solution containing the organometallic compound and water, and finally obtained flaky metal oxide It is relatively easy to control the shape and size of the gold fine particles therein, and those having various characteristics can be easily manufactured. The gold colloid can be produced by a known method. For example, an aqueous gold compound solution such as chloroauric acid, sodium chloroaurate, gold cyanide, potassium gold cyanide, diethylamineauric acid trichloride, citric acid, sodium citrate, ascorbic acid, formaldehyde, hydrazine, sodium borohydride A gold colloid can be obtained by treatment with a known reducing agent such as It can also be obtained by irradiating the gold compound aqueous solution with ultraviolet light instead of using a reducing agent.

上記金コロイド作製前の金化合物水溶液または金コロイド分散液に、安定性向上の目的で、界面活性剤や有機高分子を添加してもよい。界面活性剤は、一般に使用されているものなら何でも使用でき、特に限定されないが、例えば、塩化ステアリルトリメチルアンモニウム、臭化ジドデシルジメチルアンモニウム、塩化ヘキサデシルトリメチルアンモニウム等の陽イオン性界面活性剤、ビス（２-エチルヘキシル）スルホコハク酸ナトリウム、セチル硫酸ナトリウム、 N-アシル-Ｌ-グルタミン酸ナトリウム等の陰イオン性界面活性剤、ポリオキシエチレンセシルエーテル、モノラウリン酸ポリエチレングリコール、セスキオレイン酸ソルビタン等の非イオン性界面活性剤、ラウリルジメチルアミノ酢酸ベタイン、 β-ラウリルアミノプロピオン酸ナトリウム、２-アルキル-Ｎ-カルボキシメチル-Ｎ-ヒドロキシエチルイミダゾリニウムベタイン等の両イオン性界面活性剤等が挙げられる。このうち、水溶液中で負に帯電している金コロイドをより強く安定化させるので、上記陽イオン性界面活性剤が特に好ましく用いられる。 For the purpose of improving stability, a surfactant or an organic polymer may be added to the gold compound aqueous solution or gold colloid dispersion before the gold colloid is produced. As the surfactant, any commonly used surfactant can be used, and is not particularly limited. For example, a cationic surfactant such as stearyltrimethylammonium chloride, didodecyldimethylammonium bromide, hexadecyltrimethylammonium chloride, bis Anionic surfactants such as (2-ethylhexyl) sodium sulfosuccinate, sodium cetyl sulfate, sodium N-acyl-L-glutamate, nonionics such as polyoxyethylene cecil ether, polyethylene glycol monolaurate, sorbitan sesquioleate Surfactants, amphoteric surfactants such as betaine lauryldimethylaminoacetate, sodium β-laurylaminopropionate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine That. Among these, the cationic surfactant is particularly preferably used because it more strongly stabilizes the negatively charged gold colloid in the aqueous solution.

上記界面活性剤の添加量は、金化合物水溶液または金コロイドに対して０．００１〜１０質量％が好ましい。０．００１質量％より少ないと、金コロイドの安定化効果が小さすぎ、また１０質量％より多くても、後述の金コロイド粒子形状制御の目的を除き、安定化に対する効果はあまり向上しなくなる。界面活性剤のより好ましい添加量は０．１〜５質量％である。 The amount of the surfactant added is preferably 0.001 to 10% by mass with respect to the gold compound aqueous solution or gold colloid. If the amount is less than 0.001% by mass, the stabilizing effect of the colloidal gold is too small. If the amount is more than 10% by mass, the effect on the stabilization is not so improved except for the purpose of controlling the shape of the colloidal gold particles described later. A more preferable addition amount of the surfactant is 0.1 to 5% by mass.

上記有機高分子は、特に限定されないが、ゼラチン、デキストリン、可溶性デンプン、エチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルセルロース、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール等が用いられる。 The organic polymer is not particularly limited, and gelatin, dextrin, soluble starch, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol and the like are used.

上記有機高分子の添加量は、金化合物水溶液または金コロイドに対して０．０１〜１０質量％が好ましい。０．０１質量％より少ないと金コロイドの安定化効果が小さすぎ、また１０質量％より多くても、安定化に対する効果はあまり向上しなくなる。上記有機高分子のより好ましい添加量は０．２〜５質量％である。 The amount of the organic polymer added is preferably 0.01 to 10% by mass with respect to the gold compound aqueous solution or gold colloid. If it is less than 0.01% by mass, the stabilizing effect of the colloidal gold is too small, and if it is more than 10% by mass, the effect on stabilization is not improved so much. A more preferable addition amount of the organic polymer is 0.2 to 5% by mass.

上記金コロイドの作製前の金化合物水溶液に、金コロイドの粒子形状制御のために、多量の界面活性剤を添加してもよい。界面活性剤は、濃度に応じ様々な集合状態を取り、この影響で金コロイドの粒子形状が、球状の他、卵型状、棒状、板状等の種々形状となる。界面活性剤の種類は、特に限定されず、上記種々界面活性剤を使用することができるが、特に塩化ステアリルトリメチルアンモニウム、臭化ジドデシルジメチルアンモニウム、塩化ヘキサデシルトリメチルアンモニウム等の陽イオン性界面活性剤が、水溶液中で負に帯電した金コロイド粒子との相互作用が強いので、金コロイド粒子形状制御がより容易であり、特に好ましい。例えば塩化ヘキサデシルトリメチルアンモニウム２５質量％溶液中では棒状の金微粒子が生じるが、この界面活性剤を添加しない場合には球状の金微粒子となる。 In order to control the particle shape of the gold colloid, a large amount of a surfactant may be added to the gold compound aqueous solution before the preparation of the gold colloid. Surfactants take various aggregation states depending on the concentration, and as a result, the particle shape of the gold colloid becomes various shapes such as an oval shape, a rod shape, and a plate shape in addition to a spherical shape. The type of surfactant is not particularly limited, and the above-mentioned various surfactants can be used. In particular, cationic surfactants such as stearyltrimethylammonium chloride, didodecyldimethylammonium bromide, hexadecyltrimethylammonium chloride, and the like. Since the agent has a strong interaction with the negatively charged gold colloid particles in an aqueous solution, the shape control of the gold colloid particles is easier and particularly preferable. For example, rod-shaped gold fine particles are produced in a 25% by weight hexadecyltrimethylammonium chloride solution, but when this surfactant is not added, spherical gold fine particles are formed.

上記金コロイド粒子形状制御のための界面活性剤の添加量は、界面活性剤の種類により異なるが、概ね金コロイド作製前の溶液に対して１０〜５０質量％が好ましい。１０質量％より少ないと、顕著な金コロイド粒子形状制御効果が認められず、５０質量％より多くても形状制御の観点からは特に添加量に見合う効果は得られない。 The addition amount of the surfactant for controlling the shape of the colloidal gold particles varies depending on the type of the surfactant, but is generally preferably 10 to 50% by mass with respect to the solution before producing the gold colloid. When the amount is less than 10% by mass, a remarkable effect of controlling the shape of the colloidal gold particles is not recognized.

このような、多量の界面活性剤と金化合物を含んだ溶液を上記公知の方法で処理し、金化合物を還元して、種々の粒子形状の金コロイドが得られる。 Such a solution containing a large amount of a surfactant and a gold compound is treated by the above-mentioned known method, and the gold compound is reduced to obtain gold colloids having various particle shapes.

上記種々方法で作製できる金コロイドは、金の濃度が０．００１〜５質量％であり、１〜３００ｎｍの粒径で、球状の他、卵型状、棒状、板状等の種々粒子形状を有する。この金コロイドを、上記有機金属化合物と水を含む溶液中に添加し、均一な溶液を得た後、これを基材上、好ましくは表面が平滑な基板上に塗布し、乾燥して基材から剥離させた後、熱処理して、１〜３００ｎｍ大の金微粒子が０．０１〜３０質量％含有したフレーク状金属酸化物を製造することができる。 The colloidal gold that can be produced by the above various methods has a gold concentration of 0.001 to 5% by mass, a particle size of 1 to 300 nm, and various particle shapes such as an oval shape, a rod shape, and a plate shape in addition to a spherical shape. Have. The colloidal gold is added to a solution containing the organometallic compound and water to obtain a uniform solution, which is then coated on a substrate, preferably a substrate having a smooth surface, and dried to form a substrate. Then, it is heat-treated to produce a flaky metal oxide containing 0.01 to 30% by mass of gold fine particles having a size of 1 to 300 nm.

上記製法のうち、加水分解および縮重合が可能な有機金属化合物と水を含む溶液に、金化合物を添加する第二の製法では、熱処理または紫外線照射によって金属酸化物マトリックス中に、金微粒子を析出させる。この方法では、金コロイドを作製する手間がかからないので、工程上有利であり、容易に金微粒子含有量の高いフレーク状金属酸化物を作製することができる。 Among the above production methods, in the second production method in which a gold compound is added to a solution containing an organometallic compound capable of hydrolysis and condensation polymerization and water, gold fine particles are precipitated in the metal oxide matrix by heat treatment or ultraviolet irradiation. Let Since this method does not require time and effort for producing a gold colloid, it is advantageous in terms of the process, and a flaky metal oxide having a high gold fine particle content can be easily produced.

上記第一及び第二の製法において、金微粒子の金属酸化物前駆体（ゲル）マトリックス中での親和性や安定性を増加させ、結果として金微粒子の金属酸化物マトリックス中での含有率を向上させる方法として、３−アミノプロピルトリエトキシシラン、Ｎ-（２-アミノエチル）-３-アミノプロピルトリメトキシシラン、Ｎ-（２-アミノエチル）-３-アミノプロピルメチルジメトキシシラン、１，３-ビス（３-アミノプロピル）-１，１，３，３テトラメチルジシロキサン、３-アミノプロピルトリス（トリメチルシロキシ）シラン等のアミノシランを上記有機金属化合物と金コロイド（または金化合物）を含む溶液に添加混合しても良い。 In the first and second production methods described above, the affinity and stability of the gold fine particles in the metal oxide precursor (gel) matrix are increased, and as a result, the content of the gold fine particles in the metal oxide matrix is improved. 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 1,3- Aminosilane such as bis (3-aminopropyl) -1,1,3,3 tetramethyldisiloxane and 3-aminopropyltris (trimethylsiloxy) silane is added to a solution containing the organometallic compound and gold colloid (or gold compound). It may be added and mixed.

上記アミノシランの添加量は、特に限定されないが、有機金属化合物に対してモル比で０．０１〜１．５が良い。添加酸量が、モル比で０．０１より少ないと、金微粒子の金属酸化物マトリックス中への固定効果が充分でなく、またモル比で１．５より多いと、上記溶液がゲル化する傾向が強くなり、フレーク化が難しくなるので好ましくない。 Although the addition amount of the said aminosilane is not specifically limited, 0.01-1.5 are good by molar ratio with respect to an organometallic compound. If the amount of added acid is less than 0.01 by molar ratio, the effect of fixing the gold fine particles in the metal oxide matrix is not sufficient, and if the molar ratio is more than 1.5, the solution tends to gel. Is unfavorable because it becomes strong and flaking becomes difficult.

上記の金微粒子（または金化合物）、加水分解および縮重合が可能な有機金属化合物、水、有機溶媒を含む塗布溶液の好ましい配合比は，金微粒子（または金化合物）を基準にして次の通りである。
金微粒子（または金化合物）１質量部
加水分解および縮重合が可能な有機金属化合物５〜４０質量部
水１０〜８０質量部
酸０．００００９〜１０質量部
有機溶媒１〜５０質量部 A preferable blending ratio of the above-mentioned gold fine particles (or gold compound), an organometallic compound capable of hydrolysis and condensation polymerization, water, and an organic solvent is as follows based on the gold fine particles (or gold compound). It is.
Gold fine particle (or gold compound) 1 part by mass Organometallic compound capable of hydrolysis and condensation polymerization 5-40 parts by mass Water 10-80 parts by mass Acid 0.00009-10 parts by mass Organic solvent 1-50 parts by mass

本発明で使用する塗布基板は金属、ガラスあるいはプラスチック等の材質で、表面が平滑なものを用いる。このような基板に、上記の有機金属化合物を含む液体を塗布し、０．０６〜５０μｍの薄い膜とする。この膜が乾燥すると収縮するが、基板は収縮しないので、膜に亀裂が発生し、フレーク状となる。基板と膜との剥離が起きるためには、基板と膜との間に強い結合等の相互作用が少ない状態が好ましい。 The coated substrate used in the present invention is made of a material such as metal, glass or plastic and has a smooth surface. A liquid containing the above organometallic compound is applied to such a substrate to form a thin film of 0.06 to 50 μm. When this film dries, it shrinks, but the substrate does not shrink, so the film cracks and becomes flakes. In order for peeling between the substrate and the film, a state where there is little interaction such as strong bonding between the substrate and the film is preferable.

上記基板表面に膜を形成する技術は、公知の技術を用いればよく、例えば、上記の有機金属化合物を含む液体に基板を浸漬した後、引き上げる方法や、基板上に上記液体を滴下し、基板を高速で回転させる方法、基板上に上記液体を吹き付ける方法、ロールコーターを用いる方法、カーテンコーターを用いる方法等が用いられる。 As a technique for forming a film on the substrate surface, a known technique may be used. For example, after the substrate is immersed in a liquid containing the organometallic compound, the substrate is pulled up, or the liquid is dropped on the substrate, And a method of spraying the liquid on the substrate, a method of using a roll coater, a method of using a curtain coater, and the like.

基板上に塗布し、乾燥して基材から剥離させたフレークは、ついで熱処理する。熱処理に関しては、その方法に特に制限はない。焼結温度および時間については、マトリックスのゲルからガラスまたは結晶への転移を確実にし、かつ金微粒子が安定に存在したり、析出したりするために、高い温度で所定時間加熱することが好ましく、通常は３００〜１２００℃で５分間〜５時間加熱する。使用する目的によっては、たとえばフレーク状粉体の機械的強度が要求されず、かつそのフレーク状粉体内にすでに金微粒子が分散しているときには、乾燥後の熱処理を行わなくてもよい場合がある。 The flakes coated on the substrate, dried and peeled off from the substrate are then heat treated. Regarding the heat treatment, there is no particular limitation on the method. With respect to the sintering temperature and time, it is preferable to heat at a high temperature for a predetermined time in order to ensure the transition from the gel of the matrix to the glass or crystal, and the gold fine particles exist stably or precipitate, Usually, it heats at 300-1200 degreeC for 5 minutes-5 hours. Depending on the purpose of use, for example, when the mechanical strength of the flaky powder is not required and the gold fine particles are already dispersed in the flaky powder, it may not be necessary to perform heat treatment after drying. .

また、上記製法のうち、加水分解および縮重合が可能な有機金属化合物と水を含む溶液に金化合物を添加する上記第二の製法では、上記熱処理または紫外線照射によって金属酸化物マトリックス中に、金微粒子を析出させる。紫外線照射に関しても、その方法に特に制限はない。一般に使用される水銀灯やキセノンランプを用い、１分間〜１００時間照射する。照射時期は、上記溶液を基板に塗布する前後や乾燥前後、フレーク状ゲル回収前後等いつでも良い。 In the second production method, in which the gold compound is added to a solution containing an organometallic compound capable of hydrolysis and polycondensation and water, the metal oxide matrix is subjected to heat treatment or ultraviolet irradiation in the metal oxide matrix. Deposit fine particles. There is no particular limitation on the method for ultraviolet irradiation. Irradiation is performed for 1 minute to 100 hours using a commonly used mercury lamp or xenon lamp. The irradiation time may be any time before and after applying the solution to the substrate, before and after drying, and before and after collecting the flaky gel.

フレーク状金属酸化物の厚みは、溶液あるいは製膜条件等によって変化するが、概ね０．０５μｍから５μｍの間である。５μｍより厚いと、製膜後の自由表面と基板付近との乾燥速度の差が大きくなりすぎ、基板に平行な方向での膜間剥離が発生するようになる。逆に０．０５μｍより薄いと、基板と膜との付着力が大きくなりすぎ、膜が基板から剥離しなくなる。本発明の化粧料に配合するフレーク状金属酸化物着色剤の厚みは０．１〜２μｍである。この範囲の厚みを持つフレーク状粉体は、良好な触感を有する。さらに好ましくは、０．１〜１μｍである。この範囲のフレーク状粉体は、特に良好な触感を有し、非常に伸びが良い。 The thickness of the flaky metal oxide varies depending on the solution or film forming conditions, but is generally between 0.05 μm and 5 μm. If it is thicker than 5 μm, the difference in drying speed between the free surface after film formation and the vicinity of the substrate becomes too large, and film separation occurs in a direction parallel to the substrate. On the contrary, if it is thinner than 0.05 μm, the adhesion force between the substrate and the film becomes too large, and the film does not peel from the substrate. The thickness of the flaky metal oxide colorant blended in the cosmetic of the present invention is 0.1 to 2 μm. The flaky powder having a thickness in this range has a good feel. More preferably, it is 0.1-1 micrometer. The flaky powder in this range has particularly good tactile sensation and very good elongation.

本発明におけるフレーク状金属酸化物のアスペクト比は５〜１５０である。この範囲のアスペクト比を持つフレーク状粉体は、ムラがなく、滑らかな触感や伸展性（のび）が得られる。より好ましいアスペクト比は１０〜１００である。 The aspect ratio of the flaky metal oxide in the present invention is 5 to 150. The flaky powder having an aspect ratio in this range has no unevenness and provides a smooth feel and extensibility. A more preferable aspect ratio is 10 to 100.

本発明におけるフレーク状金属酸化物の粒径は、２〜１５０μｍであることが好ましく、この範囲の粒径を持つフレーク状粉体は、ムラがなく、滑らかな触感や伸展性（のび）が得られる。より好ましい粒径は５〜８０μｍである。 The particle size of the flaky metal oxide in the present invention is preferably 2 to 150 μm, and the flaky powder having a particle size in this range has no unevenness and has a smooth feel and extensibility. It is done. A more preferable particle size is 5 to 80 μm.

本発明におけるフレーク状金属酸化物は、金微粒子の大きさ、形状、金属酸化物の種類等により、色調が異なり、赤色、赤紫色、紫色、青紫色、青色等の様々な発色を示す。例えば金微粒子が１００ｎｍ以上の大きさになると、マトリックスにもよるが、青色系統の色になりやすく、またマトリックスの誘電率が高くなると、金微粒径が数十ｎｍであっても、紫色〜青色系統の色となる。通常の金コロイドの大きさ（数十ｎｍ以下）で低誘電率マトリックス中であれば赤色系統の色になりやすい。また金微粒子のアスペクト比が大きくなるにしたがって赤色から次第に青色に変化する傾向にある。 The flaky metal oxide in the present invention has a different color tone depending on the size and shape of the gold fine particles, the type of the metal oxide, and the like, and exhibits various colors such as red, red purple, purple, blue purple, and blue. For example, when the gold fine particle has a size of 100 nm or more, although it depends on the matrix, it tends to be a blue color, and when the matrix has a high dielectric constant, even if the gold fine particle size is several tens of nm, the purple to The color is blue. If it is a normal gold colloid size (several tens of nm or less) and in a low dielectric constant matrix, it tends to have a red color. Further, there is a tendency to gradually change from red to blue as the aspect ratio of the gold fine particles increases.

このフレーク状金属酸化物着色剤を配合した本発明の化粧料は、金微粒子の凝集や脱落等の経時変化がなく、金微粒子と油脂やオイル成分との直接的な接触がないので、鮮やかな発色性と安定性、均一着色性を有する。また、熱処理温度によっては、金属酸化物の硬度が充分高いので、外圧や外力によって金微粒子が変形することもなく、色ムラや変色がない。さらに、金微粒子分散含有フレーク状金属酸化物が、互いに凝集することもなく、その表面が平滑であり、良好なすべり性を示すことから、伸展性（のび）が良く、使用触感に優れた製品となる。 The cosmetic of the present invention containing this flaky metal oxide colorant has no change over time such as aggregation and dropping off of the gold fine particles, and there is no direct contact between the gold fine particles and the oil or oil component. It has color development and stability, and uniform colorability. Further, depending on the heat treatment temperature, the hardness of the metal oxide is sufficiently high, so that the gold fine particles are not deformed by external pressure or external force, and there is no color unevenness or discoloration. Furthermore, the flaky metal oxide containing gold fine particles is not agglomerated with each other, its surface is smooth, and it exhibits good sliding properties. Therefore, it has excellent extensibility and feel in use. It becomes.

本発明で言う化粧料には、上記金微粒子分散含有フレーク状金属酸化物着色剤の他、必要に応じ、通常用いられている顔料等を併用しても、何等差し支えない。例えば、酸化チタン、酸化亜鉛、酸化ジルコニウム、黄色酸化鉄、黒色酸化鉄、弁柄、群青、紺青、酸化クロム、水酸化クロム等の無機顔料、雲母チタン、オキシ塩化ビスマス等の真珠光沢顔料、タール色素、天然色素、シリカビーズ、ナイロン、アクリル等のプラスチックビーズ等の粉体、タルク、カオリン、マイカ、セリサイト、その他の雲母類、炭酸マグネシウム、炭酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、クレー類等が例示される。 In the cosmetic referred to in the present invention, in addition to the above-mentioned gold fine particle dispersion-containing flaky metal oxide colorant, a pigment or the like that is usually used may be used in combination as required. For example, titanium oxide, zinc oxide, zirconium oxide, yellow iron oxide, black iron oxide, petal, inorganic pigments such as ultramarine, bitumen, chromium oxide, chromium hydroxide, pearlescent pigments such as titanium mica, bismuth oxychloride, tar Powders such as pigments, natural pigments, silica beads, plastic beads such as nylon and acrylic, talc, kaolin, mica, sericite, other mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, clays, etc. Illustrated.

上記金微粒子分散含有フレーク状金属酸化物着色剤の配合量としては、その目的とする化粧料の種類により異なるが、顔料等の固体成分に対して１〜８０質量％の範囲で用いられ、特に２〜５０質量％の範囲が好ましい。これ以下の含有量では、着色効果が顕著に発揮されない、発色が良くない等の問題点があり、逆に上限より多くのフレーク状金属酸化物を添加しても、着色効果は上がらず、他の顔料成分が減少し、色調を整えたり、皮膚への付着性を上げることが困難になる。 The compounding amount of the gold fine particle dispersion-containing flaky metal oxide colorant is different depending on the type of cosmetic intended, but is used in a range of 1 to 80% by mass with respect to solid components such as pigments. The range of 2-50 mass% is preferable. If the content is less than this, there is a problem that the coloring effect is not exhibited remarkably, the color development is not good, and conversely, even if more flaky metal oxide is added than the upper limit, the coloring effect does not increase, other It is difficult to adjust the color tone and improve the adhesion to the skin.

また、本発明で用いる金微粒子分散含有フレーク状金属酸化物着色剤の化粧料中での分散性を向上させたり、感触を良くするために、このフレーク状金属酸化物の表面処理を施して、改質することは何等差し支えない。例えば、メチルハイドロジェンポリシロキサン、反応性アルキルポリシロキサン、金属石鹸の他、水素添加レシチン、アシルアミノ酸、アシル化コラーゲンのアルミニウム、マグネシウム、カルシウム、チタン、亜鉛、ジルコニウム、鉄より選ばれた金属塩等の、いわゆる疎水化剤で表面処理を行うと、フレーク状金属酸化物の表面は親水性から疎水性に変わるため、化粧料の調合時に添加する油剤との馴染みが良くなり、感触の良い化粧料となる。 In addition, in order to improve the dispersibility of the gold fine particle dispersion-containing flaky metal oxide colorant used in the present invention in cosmetics, in order to improve the feel, surface treatment of this flaky metal oxide, There is no problem with the modification. For example, methyl hydrogen polysiloxane, reactive alkyl polysiloxane, metal soap, hydrogenated lecithin, acylamino acid, acylated collagen aluminum, magnesium, calcium, titanium, zinc, zirconium, iron, etc. When the surface treatment is performed with a so-called hydrophobizing agent, the surface of the flaky metal oxide changes from hydrophilic to hydrophobic, so that the familiarity with the oil added during the preparation of the cosmetic is improved, and the cosmetics with a good feel. It becomes.

本発明で言う化粧料としては、口紅、アイシャドー、パウダーファンデーション、ネイルエナメル、眉墨、アイライナー等のメイクアップ化粧品の他、石鹸、クレンジングクリーム、コールドクリーム、スキンクリーム、スキンミルク、スキンローション、ミルキーローション、Ｔゾーンエッセンス、エッセンスパウダー、パック、ハンドクリーム、メイクアップベース、シェービングフォーム、シェービングクリーム、ベビーオイル等の洗浄用化粧品、基礎化粧品やヘアートニック、ヘアーリキッド、ヘアートリートメント、ヘアークリーム、ヘアーオイル、シャンプー、リンス、ヘアースプレー等の頭髪用化粧品にも用いることができる。 Cosmetics referred to in the present invention include makeup cosmetics such as lipstick, eye shadow, powder foundation, nail enamel, eyebrow, eyeliner, etc., soap, cleansing cream, cold cream, skin cream, skin milk, skin lotion, milky Lotion, T Zone Essence, Essence Powder, Pack, Hand Cream, Makeup Base, Shaving Foam, Shaving Cream, Baby Oil and other Cosmetics for Washing, Basic Cosmetics and Hair Tonic, Hair Liquid, Hair Treatment, Hair Cream, Hair Oil, It can also be used for hair cosmetics such as shampoos, rinses and hair sprays.

本発明の化粧料は、金微粒子の凝集や脱落等の経時変化がなく、金微粒子と油脂やオイル成分との直接的な接触がないので、鮮やかな発色性と色調安定性、均一着色性を有する。また、外圧や外力によって金微粒子が変形することもなく、色ムラや変色がなく、透明感、光沢感が良く、さらに、金微粒子分散含有フレーク状金属酸化物着色剤が、互いに凝集することもなく、その表面が平滑であり、良好なすべり性を示すことから、伸展性（のび）が良く、付着性（つき）が良く、使用触感に優れた各種化粧料製品となる。 The cosmetic of the present invention has no change over time such as aggregation and dropping off of the gold fine particles, and there is no direct contact between the gold fine particles and the fats and oils, so that vivid color development, color stability, and uniform colorability are achieved. Have. In addition, the gold fine particles are not deformed by external pressure or external force, there is no color unevenness or discoloration, the transparency and glossiness are good, and the flaky metal oxide colorant containing the gold fine particle dispersion may aggregate together. Since the surface is smooth and exhibits good sliding properties, it becomes various cosmetic products having good extensibility (adhesion), good adhesion (stickiness), and excellent touch feeling.

以下に実施例を示す。
［製造例１］
水１３００ｍｌおよび１質量％の塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）水溶液２００ｍｌを混合し、加熱沸騰させた。これに１質量％のクエン酸水溶液５００ｍｌを添加した後、ただちにポリビニルアルコール（重合度５０）１２ｇを添加し、暫く加熱沸騰させて、赤紫色の金コロイド（金０．１２５質量％）を得た。動的光散乱法で、金コロイドの粒径を測定したところ、平均粒径は約１０ｎｍであった。 Examples are shown below.
[Production Example 1]
1300 ml of water and 200 ml of a 1% by mass aqueous solution of chloroauric acid (HAuCl ₄ .4H ₂ O) were mixed and heated to boiling. After adding 500 ml of a 1% by mass citric acid aqueous solution to this, 12 g of polyvinyl alcohol (polymerization degree 50) was immediately added and heated to boiling for a while to obtain a red-purple gold colloid (gold 0.125% by mass). . When the particle size of the gold colloid was measured by the dynamic light scattering method, the average particle size was about 10 nm.

この金コロイド１６００ｍｌと０．８Ｎ硝酸１００ｍｌ、シリコンテトラメトキシド９８０ｍｌ、エタノール６００ｍｌ、２-プロパノール６００ｍｌを混合し、５０℃で約１５時間養生して塗布液とした。
この液に、表面を研磨して平滑にした厚さ０．５ｍｍのステンレス板を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥して、塗布されたゲル膜を剥離しフレーク状とし、１０００℃で１時間焼結した。この焼結フレークをジェットミルで粉砕、分級して、平均粒径約１０μｍとして、桃色のフレーク状シリカ粉体を得た。 1600 ml of this gold colloid, 100 ml of 0.8N nitric acid, 980 ml of silicon tetramethoxide, 600 ml of ethanol and 600 ml of 2-propanol were mixed and cured at 50 ° C. for about 15 hours to obtain a coating solution.
A stainless steel plate having a thickness of 0.5 mm, which had been polished and smoothed, was immersed in this liquid, and the liquid was pulled up at a speed of 30 cm / min and applied to the surface. This was dried at 150 ° C., the applied gel film was peeled off to form a flake, and sintered at 1000 ° C. for 1 hour. The sintered flakes were pulverized and classified by a jet mill to obtain a pink flake silica powder having an average particle size of about 10 μm.

このフレーク状粉体をＸ線回折により調べた結果、マトリックスはガラス状態のシリカであった。焼結後のフレークの化学分析の結果、金の含有量は、約０．５質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約１０ｎｍの球状金微粒子が、シリカガラスマトリックス中に凝集することなく分散しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、表面は非常に平滑であり、厚みは約０．６μｍであった。 As a result of examining this flaky powder by X-ray diffraction, the matrix was silica in a glass state. As a result of chemical analysis of the flakes after sintering, the gold content was about 0.5% by mass. When flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 10 nm were dispersed in the silica glass matrix without agglomeration. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

このフレーク状粉体を手に取り触感を調べたところ、非常に滑らかな感触であった。また、乳鉢を用いて、このフレーク状粉体をすりつぶしても、変色は認められなかった。また、別にこのフレーク状粉体にひまし油を少量添加し、かき混ぜたが、やはり顕著な色の変化はなかった。 When this flake powder was picked up and examined for tactile sensation, it was very smooth. Moreover, even if this flaky powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flaky powder and stirred, but there was no noticeable color change.

［比較製造例１］
水１６００ｍｌ、０．８Ｎ硝酸１００ｍｌ、シリコンテトラメトキシド９８０ｍｌ、エタノール６００ｍｌ、２-プロパノール６００ｍｌを混合し、５０℃で約１５時間養生して塗布液とした。
この液に、表面を研磨して平滑にした厚さ０．５ｍｍのステンレス板を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥して、塗布されたゲル膜を剥離しフレーク状とし、１０００℃で１時間焼結した。この焼結フレークをジェットミルで粉砕、分級して、平均粒径約１０μｍとして、フレーク状シリカガラス粉体を得た。 [Comparative Production Example 1]
1600 ml of water, 100 ml of 0.8N nitric acid, 980 ml of silicon tetramethoxide, 600 ml of ethanol, and 600 ml of 2-propanol were mixed and cured at 50 ° C. for about 15 hours to obtain a coating solution.
A stainless steel plate having a thickness of 0.5 mm, which had been polished and smoothed, was immersed in this liquid, and the liquid was pulled up at a speed of 30 cm / min and applied to the surface. This was dried at 150 ° C., the applied gel film was peeled off to form a flake, and sintered at 1000 ° C. for 1 hour. The sintered flakes were pulverized and classified with a jet mill to obtain a flake-like silica glass powder having an average particle size of about 10 μm.

このフレーク状シリカガラス粉体１００ｇを３０００ｍｌの水に分散させ、炭酸ナトリウムを加えてｐＨを約１１に調整した。この懸濁液を攪拌しながら、０．１質量％の塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）水溶液１０００ｍｌをゆっくりと滴下した。滴下後、数時間攪拌し、フレークを濾過、水洗して、１５０℃で乾燥後、３００℃で１時間熱処理して桃色のフレーク状粉体を得た。 100 g of this flaky silica glass powder was dispersed in 3000 ml of water, and sodium carbonate was added to adjust the pH to about 11. While stirring this suspension, 1000 ml of a 0.1% by mass aqueous solution of chloroauric acid (HAuCl ₄ .4H ₂ O) was slowly added dropwise. After dropping, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 150 ° C., and heat-treated at 300 ° C. for 1 hour to obtain a pink flake powder.

このフレーク状粉体をＸ線回折により調べた結果、マトリックスはガラス状態であった。化学分析の結果、金の含有量は、約０．５質量％であった。透過型電子顕微鏡でフレークを観察したところ、約２０ｎｍの直径の球状金微粒子が、シリカガラス表面上に付着しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、厚みは約０．６μｍであった。 As a result of examining the flaky powder by X-ray diffraction, the matrix was in a glass state. As a result of chemical analysis, the gold content was about 0.5% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 20 nm were adhered on the silica glass surface. When the flakes were observed with a scanning electron microscope, the thickness was about 0.6 μm.

このフレーク状粉体を手に取り触感を調べたところ、少し抵抗を感じるものの滑らかな感触であった。乳鉢を用いて、このフレーク状粉体をすりつぶしたところ、一部赤褐色や灰青色に変色した。また、別にこのフレーク状粉体にひまし油を少量添加し、かき混ぜたところ、全体が少し黒っぽくくすんだ。 When this flake-like powder was picked up and examined for tactile sensation, although it felt a little resistance, it was smooth. When this flaky powder was ground using a mortar, it partially turned reddish brown or grayish blue. In addition, when a small amount of castor oil was added to the flaky powder and stirred, the whole became a little darker.

［実施例１及び比較例１］
以下の表１〜３に示す配合でパウダーファンデーションを作製した。 [Example 1 and Comparative Example 1]
Powder foundations were prepared with the formulations shown in Tables 1 to 3 below.

［表１］
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
成分-１配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
製造例１で作製した本発明のフレーク１５.８
タルク７３.５
酸化チタン（一次粒径２００〜２５０ｎｍ）３.８
微粒子酸化チタン（一次粒径３０〜５０ｎｍ）１.９
ステアリン酸マグネシウム２.９
黄色酸化鉄０.８
黒色酸化鉄０.１
シルクパウダー０.５
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− [Table 1]
--------------------------------
Ingredient-1 amount (% by mass)
--------------------------------
The flakes of the present invention produced in Production Example 1 15.8
Talc 73.5
Titanium oxide (primary particle size 200-250 nm) 3.8
Fine particle titanium oxide (primary particle size 30-50nm) 1.9
Magnesium stearate 2.9
Yellow iron oxide 0.8
Black iron oxide 0.1
Silk powder 0.5
--------------------------------

［表２］
−−−−−−−−−−−−−−−−−−−−−−−
成分-２配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−
スクワラン０.５
セスキオレイン酸ソルビタン０.１
−−−−−−−−−−−−−−−−−−−−−−− [Table 2]
-----------------------
Component-2 blending amount (mass%)
-----------------------
Squalane 0.5
Sorbitan sesquioleate 0.1
-----------------------

［表３］
−−−−−−−−−−−−−−−−−−−−−−−
成分-３配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−
香料０.１
−−−−−−−−−−−−−−−−−−−−−−− [Table 3]
-----------------------
Ingredient-3 Blending amount (% by mass)
-----------------------
Fragrance 0.1
-----------------------

成分-１をヘンシェルミキサーを用いて、５分間撹拌した。これに、７０℃にて均一に溶融した成分-２を滴下しながら、撹拌混合を行った。さらに、成分-３を添加後、１分間撹拌混合し、アトマイザーにより粉砕して製品-１（実施例１）を得た。 Ingredient-1 was stirred for 5 minutes using a Henschel mixer. The mixture was stirred and mixed while dropwise adding Component-2 uniformly melted at 70 ° C. Further, after component-3 was added, the mixture was stirred and mixed for 1 minute, and pulverized with an atomizer to obtain product-1 (Example 1).

成分-１中の製造例１で作製した金微粒子分散含有フレーク状シリカガラス（厚み０．６μｍ、粒径１０μｍ、金含有量０．５質量％）の代わりに、比較製造例１で作製した金微粒子被覆フレーク状シリカガラス（厚み０．６μｍ、粒径１０μｍ、金含有量０．５質量％）を添加した以外は、上記と全く同じ方法で製品-２（比較例１）を得た。 Gold produced in Comparative Production Example 1 instead of the flaky silica glass containing gold fine particles dispersed in Production Example 1 in Component-1 (thickness 0.6 μm, particle size 10 μm, gold content 0.5 mass%) Product-2 (Comparative Example 1) was obtained in exactly the same manner as above except that fine particle-coated flaky silica glass (thickness 0.6 μm, particle size 10 μm, gold content 0.5 mass%) was added.

これらをパネラー２０名に１０日間使用させ、最高点を５点とする１〜５点の５段階法にて、評価した官能テストの結果を表４に示す。 Table 4 shows the results of the sensory test evaluated by a five-step method of 1 to 5 points, in which 20 panelists were used for 10 days and the maximum was 5 points.

［表４］
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
項目本発明の粉体（製品-１）比較の粉体（製品-２）
（実施例１）（比較例１）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
のび４.８４.０
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
つき４.４３.５
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
透明感４.７２.４
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
光沢感４.５２.８
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
色感４.８２.２
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
性能持続性４.１３.２
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ [Table 4]
==================================
Item Powder of the present invention (Product-1) Comparative powder (Product-2)
(Example 1) (Comparative Example 1)
----------------------------------
Nobit 4.8 4.0
----------------------------------
4.4 3.4 3.5
----------------------------------
Transparency 4.7 2.4
----------------------------------
Glossiness 4.5 2.8
----------------------------------
Color 4.8 2.2
----------------------------------
Performance sustainability 4.1 3.2
==================================

このように、本発明の化粧料は、のびやつき（付着性）が良く、透明感、光沢感が良好で、発色に優れ、色あせしにくいことが確認された。 Thus, it was confirmed that the cosmetics of the present invention have good spread and adhesion (adhesiveness), good transparency and gloss, excellent color development, and are not easily faded.

［製造例２］
水５００ｍｌに塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）２０９ｇを溶解させ、これにシリコンテトラメトキシド４９０ｍｌ、１Ｎ塩酸１００ｍｌ、エタノール６００ｍｌ、３-アミノプロピルトリエトキシシラン３６８ｇを添加し混合した。別に、チタンイソプロポキシド３５６ｇを２-プロパノール１０００ｍｌに溶解させた溶液を準備し、これを、先に調製した塩化金酸とシリコンテトラメトキシドを含む溶液に、ゆっくりと添加し混合した。この混合液を６０℃で約２０時間養生して塗布液とした。 [Production Example 2]
In 500 ml of water, 209 g of chloroauric acid (HAuCl ₄ .4H ₂ O) was dissolved, and 490 g of silicon tetramethoxide, 100 ml of 1N hydrochloric acid, 600 ml of ethanol and 368 g of 3-aminopropyltriethoxysilane were added and mixed. Separately, a solution in which 356 g of titanium isopropoxide was dissolved in 1000 ml of 2-propanol was prepared, and this was slowly added to and mixed with the previously prepared solution containing chloroauric acid and silicon tetramethoxide. This mixed solution was cured at 60 ° C. for about 20 hours to obtain a coating solution.

この液に、ポリイミドフィルム板（宇部興産製、商品名ユーピレックス）を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥し、その後、上記塗布基板を多量の水中に入れ、水中で基板表面のゲル膜を剥離させフレーク状とした。水中のフレークを濾過によって回収し、１２０℃で乾燥させてフレーク状ゲルを得た。その後、このフレーク状ゲルを８５０℃で３時間焼結し、ジェットミルで粉砕、分級して、平均粒径約１０μｍとして、紫外線吸収能を有する青紫色フレーク状粉体を得た。 A polyimide film plate (product name: Upilex, manufactured by Ube Industries, Ltd.) was immersed in this liquid and pulled up at a speed of 30 cm / min to apply the liquid to the surface. This was dried at 150 ° C., and then the coated substrate was placed in a large amount of water, and the gel film on the surface of the substrate was peeled off in water to form a flake. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel. Thereafter, this flaky gel was sintered at 850 ° C. for 3 hours, pulverized and classified with a jet mill, and a blue-violet flaky powder having an average particle size of about 10 μm and an ultraviolet absorbing ability was obtained.

このフレーク状粉体をＸ線回折等により調べた結果、マトリックスはガラス状態のシリカ-チタニア２成分が主であり、アナターゼ型酸化チタンの結晶が混在しているのが認められた。焼結後のフレークの化学分析の結果、金の含有量は約２０質量％、酸化チタン含有量約２０質量％、酸化珪素含有量約６０質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約３０ｎｍの球状金微粒子が、凝集することなくフレーク中に分散しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、表面は非常に平滑であり、厚みは約０．７μｍであった。 As a result of examining the flaky powder by X-ray diffraction or the like, it was found that the matrix was mainly composed of two components of silica-titania in a glassy state and crystals of anatase type titanium oxide were mixed. As a result of chemical analysis of the sintered flakes, the gold content was about 20 mass%, the titanium oxide content was about 20 mass%, and the silicon oxide content was about 60 mass%. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 30 nm were dispersed in the flakes without agglomeration. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.7 μm.

［比較製造例２］
水１６００ｍｌ、６Ｎ塩酸２００ｍｌ、シリコンテトラメトキシド４９０ｍｌ、エタノール６００ｍｌ、３-アミノプロピルトリエトキシシラン３６８ｇを添加し混合した。別に、チタンイソプロポキシド３５６ｇを２-プロパノール５００ｍｌに溶解させた溶液を準備し、これを、先に調製した溶液に、ゆっくりと添加し混合した。この混合液を６０℃で約２０時間養生して塗布液とした。 [Comparative Production Example 2]
1600 ml of water, 200 ml of 6N hydrochloric acid, 490 ml of silicon tetramethoxide, 600 ml of ethanol and 368 g of 3-aminopropyltriethoxysilane were added and mixed. Separately, a solution in which 356 g of titanium isopropoxide was dissolved in 500 ml of 2-propanol was prepared, and this was slowly added to the previously prepared solution and mixed. This mixed solution was cured at 60 ° C. for about 20 hours to obtain a coating solution.

この液に、ポリイミドフィルム板（宇部興産製、商品名ユーピレックス）を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥し、その後、多量の水中に基板ごと入れ、水中でゲル膜を剥離させフレーク状とした。水中のフレークを濾過によって回収し、１２０℃で乾燥させてフレーク状ゲル粉体を得た。 A polyimide film plate (product name: Upilex, manufactured by Ube Industries, Ltd.) was immersed in this liquid and pulled up at a speed of 30 cm / min to apply the liquid to the surface. This was dried at 150 ° C., and then placed in a large amount of water together with the substrate, and the gel film was peeled off in water to form flakes. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel powder.

このフレーク状ゲル粉体１００ｇを３０００ｍｌの水に分散させ、アンモニアを加えてｐＨを約１２に調整した。この懸濁液を攪拌しながら、３質量％の塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）水溶液１７４３ｍｌをゆっくりと滴下した。滴下後、数時間攪拌し、フレークを濾過、水洗して、１５０℃で乾燥後、８５０℃で３時間熱処理して灰青色のフレーク状粉体を得た。 100 g of this flaky gel powder was dispersed in 3000 ml of water, and ammonia was added to adjust the pH to about 12. While stirring this suspension, 1743 ml of a 3% by mass aqueous solution of chloroauric acid (HAuCl ₄ .4H ₂ O) was slowly added dropwise. After dropping, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 150 ° C., and then heat treated at 850 ° C. for 3 hours to obtain a grayish blue flake powder.

このフレーク状粉体をＸ線回折等により調べた結果、マトリックスはガラス状態のシリカ-チタニア２成分が主であり、アナターゼ型酸化チタンの結晶が混在しているのが認められた。燒結後のフレークの化学分析の結果、金の含有量は約１４質量％、酸化チタン含有量約２１質量％、酸化珪素含有量約６５質量％であった。透過型電子顕微鏡でフレークを観察したところ、一次粒径が約５０ｎｍの球状金微粒子が、シリカガラス表面上に付着しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、厚みは約０．７μｍであった。 As a result of examining the flaky powder by X-ray diffraction or the like, it was found that the matrix was mainly composed of two components of silica-titania in a glassy state and crystals of anatase type titanium oxide were mixed. As a result of chemical analysis of the flakes after sintering, the gold content was about 14% by mass, the titanium oxide content was about 21% by mass, and the silicon oxide content was about 65% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a primary particle diameter of about 50 nm were adhered on the silica glass surface. When the flakes were observed with a scanning electron microscope, the thickness was about 0.7 μm.

このフレーク状粉体を手に取り触感を調べたところ、あまり良い感触ではなかった。乳鉢を用いて、このフレーク状粉体をすりつぶしたところ、一部褐色や黒色に変色した。また、別にこのフレーク状粉体にひまし油を少量添加し、かき混ぜたところ、全体が黒っぽくくすんだ。 When this flake powder was picked up and examined for touch, it was not very good. When this flaky powder was ground using a mortar, it partially turned brown or black. In addition, when a small amount of castor oil was added to the flaky powder and stirred, the whole became darker.

［実施例２及び比較例２］
以下の表５〜７に示す配合でネイルエナメルを作製した。 [Example 2 and Comparative Example 2]
Nail enamels were prepared with the formulations shown in Tables 5-7 below.

［表５］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-４配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
ニトロセルロース１５.０
フタル酸系アルキド樹脂１２.０
フタル酸ジブチル４.０
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 5]
------------------------
Ingredient-4 Blending amount (% by mass)
------------------------
Nitrocellulose 15.0
Phthalic acid alkyd resin 12.0
Dibutyl phthalate 4.0
------------------------

［表６］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-５配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
酢酸ブチル２５.０
酢酸エチル７.０
トルエン２４.０
２−プロパノール６.０
エタノール２.０
１−ブタノール２.０
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 6]
------------------------
Ingredient-5 Blending amount (% by mass)
------------------------
Butyl acetate 25.0
Ethyl acetate 7.0
Toluene 24.0
2-propanol 6.0
Ethanol 2.0
1-butanol 2.0
------------------------

［表７］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-６配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
製造例２で作製した本発明のフレーク３.０
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 7]
------------------------
Ingredient-6 Blending amount (% by mass)
------------------------
Flakes of the present invention produced in Production Example 2 3.0
------------------------

成分-４と成分-５を混合し溶解させた。これに、成分-６を添加し、撹拌混合を行ない、製品-３（実施例２）を得た。
成分-６である製造例２で作製した本発明のフレークのかわりに比較製造例２で作製したフレークを使用した以外は、前記と同様の方法により、製品-４（比較例２）を得た。
上記製品をパネラー２０名に１０日間使用させ、最低点を１点、最高点を５点とする５段階法にて、評価した官能テストの結果を表８に示す。 Ingredient-4 and ingredient-5 were mixed and dissolved. Ingredient-6 was added thereto, and the mixture was stirred and mixed to obtain product-3 (Example 2).
Product-4 (Comparative Example 2) was obtained by the same method as described above except that the flakes produced in Comparative Production Example 2 were used instead of the flakes of the present invention produced in Production Example 2 as Component-6. .
Table 8 shows the results of sensory tests evaluated by a five-step method in which the above products were used by 20 panelists for 10 days, with the lowest score being 1 point and the highest score being 5 points.

［表８］
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
項目本発明の化粧料（製品-３）比較の化粧料（製品-４）
（実施例２）（比較例２）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
のび４.８３.５
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
つき４.４２.８
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
塗布性４.２２.９
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
光沢感４.９３.１
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
仕上り感４.７２.５
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
色感４.６１.３
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
均一性４.５１.８
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ [Table 8]
==================================
Item Cosmetics of the present invention (Product-3) Comparative cosmetics (Product-4)
(Example 2) (Comparative example 2)
----------------------------------
Nobit 4.8 3.5
----------------------------------
4.4 2.8
----------------------------------
Application property 4.2 2.9
----------------------------------
Glossiness 4.9 3.1
----------------------------------
Finished feeling 4.7 2.5
----------------------------------
Color sensation 4.6 1.3
----------------------------------
Uniformity 4.5 1.8
==================================

このように、本発明の化粧料は、のび（伸展性）やつき（付着性）に優れ、均一に塗布し易く、透明感、光沢感が良好で、発色が良く、仕上り感に優れることが確認された。 As described above, the cosmetic of the present invention is excellent in spreading (extensibility) and sticking (adhesiveness), easy to apply uniformly, excellent in transparency and gloss, good in color, and excellent in finish. confirmed.

［製造例３］
アルミニウムｓｅｃ-ブトキシド５００ｇ、０．０３Ｎ塩酸３６００ｍｌを混合し、８５℃で８時間加熱しゾルを得た。このゾルを室温に冷やしてから、塩化金酸を２４ｇ添加し溶解させ塗布液とした。この液に、ポリエーテルエーテルケトンフィルム板（住友化学製、商品名エスペックス-ＫＣ）を浸漬して、４０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥し、５００Ｗ高圧水銀灯の光を３０分間照射してマトリックス中に金微粒子を析出させた。 [Production Example 3]
Aluminum sec-butoxide 500 g and 0.03N hydrochloric acid 3600 ml were mixed and heated at 85 ° C. for 8 hours to obtain a sol. After cooling the sol to room temperature, 24 g of chloroauric acid was added and dissolved to obtain a coating solution. A polyether ether ketone film plate (manufactured by Sumitomo Chemical Co., Ltd., trade name ESPEX-KC) was immersed in this liquid, and the liquid was pulled up at a speed of 40 cm / min and applied to the surface. This was dried at 150 ° C., and irradiated with light from a 500 W high-pressure mercury lamp for 30 minutes to precipitate gold fine particles in the matrix.

その後、上記塗布基板を３質量％ヒドラジン水溶液中に入れ、液中で基板表面の膜を剥離させフレーク状とした。液中のフレークを濾過によって回収し、２００℃で乾燥させた後、１２００℃で１時間焼結し、ジェットミルで粉砕、分級して、平均粒径約１０μｍとして、紫色フレーク状粉体を得た。 Thereafter, the coated substrate was placed in a 3% by mass hydrazine aqueous solution, and the film on the surface of the substrate was peeled off in the liquid to form a flake. The flakes in the liquid are collected by filtration, dried at 200 ° C., sintered at 1200 ° C. for 1 hour, pulverized and classified with a jet mill to obtain a purple flaky powder having an average particle size of about 10 μm. It was.

このフレーク状粉体をＸ線回折等により調べた結果、マトリックスはα-アルミナの結晶であるのが認められた。化学分析の結果、金の含有量は約１０質量％であった。透過型電子顕微鏡でフレークを観察したところ、約２０ｎｍ大の卵型状金微粒子が、凝集することなくフレーク中に分散しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、表面は平滑であり、厚みは約０．７μｍであった。 As a result of examining the flaky powder by X-ray diffraction or the like, it was found that the matrix was α-alumina crystals. As a result of chemical analysis, the gold content was about 10% by mass. When the flakes were observed with a transmission electron microscope, it was observed that egg-shaped gold fine particles having a size of about 20 nm were dispersed in the flakes without agglomeration. When the flakes were observed with a scanning electron microscope, the surface was smooth and the thickness was about 0.7 μm.

このフレーク状粉体を手に取り触感を調べたところ、滑らかな感触であった。また、乳鉢を用いて、このフレーク状粉体をすりつぶしても、変色は認められなかった。また、別にこのフレーク状粉体にひまし油を少量添加し、かき混ぜたが、やはり顕著な色の変化はなかった。 When this flake powder was picked up and examined for tactile feel, it was a smooth feel. Moreover, even if this flaky powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flaky powder and stirred, but there was no noticeable color change.

［比較製造例３］
アルミニウムｓｅｃ-ブトキシド５００ｇ、０．０３Ｎ塩酸３６００ｍｌを混合し、８５℃で８時間加熱しゾルを得た。このゾルを室温に冷やし塗布液とした。この液に、ポリエーテルエーテルケトンフィルム板（住友化学製、商品名エスペックス-ＫＣ）を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥し、その後、３質量％ヒドラジン水溶液中でゲル膜を剥離させフレーク状とした。液中のフレークを濾過によって回収し、１２０℃で乾燥させてフレーク状粉体を得た。 [Comparative Production Example 3]
500 sec of aluminum sec-butoxide and 3600 ml of 0.03N hydrochloric acid were mixed and heated at 85 ° C. for 8 hours to obtain a sol. This sol was cooled to room temperature to obtain a coating solution. A polyether ether ketone film plate (manufactured by Sumitomo Chemical Co., Ltd., trade name ESPEX-KC) was immersed in this liquid, and the liquid was pulled up at a speed of 30 cm / min and applied to the surface. This was dried at 150 ° C., and then the gel film was peeled off in a 3% by mass hydrazine aqueous solution to form a flake. The flakes in the liquid were collected by filtration and dried at 120 ° C. to obtain a flaky powder.

このフレーク状粉体１００ｇを３０００ｍｌの水に分散させ、ヒドラジンを加えてｐＨを約１０に調整した。この懸濁液を攪拌しながら、１質量％の塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）水溶液２１００ｍｌをゆっくりと滴下した。滴下後、数時間攪拌し、フレークを濾過、水洗して、２００℃で乾燥後、１２００℃で１時間熱処理して紫色のフレーク状粉体を得た。 100 g of this flaky powder was dispersed in 3000 ml of water, and hydrazine was added to adjust the pH to about 10. While stirring this suspension, 2100 ml of a 1% by mass aqueous solution of chloroauric acid (HAuCl ₄ .4H ₂ O) was slowly added dropwise. After dropping, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 200 ° C., and then heat treated at 1200 ° C. for 1 hour to obtain a purple flaky powder.

このフレーク状粉体をＸ線回折等により調べた結果、マトリックスはα-アルミナの結晶であるのが認められた。化学分析の結果、金の含有量は約１０質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約２０ｎｍの球状金微粒子が、フレーク表面上に付着しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、厚みは約０．７μｍであった。 As a result of examining the flaky powder by X-ray diffraction or the like, it was found that the matrix was α-alumina crystals. As a result of chemical analysis, the gold content was about 10% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 20 nm were adhered on the surface of the flakes. When the flakes were observed with a scanning electron microscope, the thickness was about 0.7 μm.

［実施例３及び比較例３］
次に、以下の表９〜１１に示す配合でアイシャドーを作製した。 [Example 3 and Comparative Example 3]
Next, eye shadows were prepared according to the formulations shown in Tables 9 to 11 below.

［表９］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-７配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
製造例３で作製した本発明のフレーク１３.５
タルク４０.０
マイカ２１.０
雲母チタン１０.３
ステアリン酸亜鉛８.６
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 9]
------------------------
Ingredient-7 Blending amount (% by mass)
------------------------
The flakes 13.5 of the present invention produced in Production Example 3
Talc 40.0
Mica 21.0
Mica titanium 10.3
Zinc stearate 8.6
------------------------

［表１０］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-８配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
スクワラン１.０
セスキオレイン酸ソルビタン１.０
流動パラフィン３.０
ワセリン１.５
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 10]
------------------------
Ingredient-8 Blending amount (% by mass)
------------------------
Squalane 1.0
Sorbitan sesquioleate 1.0
Liquid paraffin 3.0
Vaseline 1.5
------------------------

［表１１］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-９配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
香料０.１
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 11]
------------------------
Ingredient-9 blending amount (% by mass)
------------------------
Fragrance 0.1
------------------------

成分-７をヘンシェルミキサーを用いて、５分間撹拌した。これに、７０℃にて均一に混合した成分-８を滴下しながら、撹拌混合を行った。さらに、成分-９を添加後、１分間撹拌混合し、粉砕したものを圧縮成形して、製品-５（実施例３）を得た。 Ingredient-7 was stirred for 5 minutes using a Henschel mixer. To this, stirring and mixing were performed while adding Component-8 uniformly mixed at 70 ° C. Further, after component-9 was added, the mixture was stirred and mixed for 1 minute, and the pulverized product was compression molded to obtain product-5 (Example 3).

成分-７中の製造例３で作製した本発明のフレークのかわりに、比較製造例３で作製したフレークを使用した以外は、前記と同様の方法により、製品-６（比較例３）を得た。 Product-6 (Comparative Example 3) was obtained by the same method as described above except that the flakes produced in Comparative Production Example 3 were used instead of the flakes of the present invention produced in Production Example 3 in Component-7. It was.

上記製品をパネラー２０名に１０日間使用させ、最低点１、最高点を５点とする５段階法にて、評価した官能テストの結果を表１２に示す。 Table 12 shows the results of the sensory test evaluated by a five-step method in which the above-mentioned product was used by 20 panelists for 10 days and the lowest score was 1 and the highest score was 5.

［表１２］
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
項目本発明の化粧料（製品-５）比較の化粧料（製品-６）
（実施例３）（比較例３）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
のび４.５３.８
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
つき４.３３.７
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
ぼかし易さ４.２３.２
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
光沢感４.０３.９
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
仕上り感４.５３.４
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
色感４.６２.８
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ [Table 12]
==================================
Item Cosmetics of the present invention (Product-5) Comparative cosmetics (Product-6)
(Example 3) (Comparative Example 3)
----------------------------------
Nobit 4.5 3.8
----------------------------------
4.3 4.3 3.7
----------------------------------
Ease of blur 4.2 3.2
----------------------------------
Glossiness 4.0 3.9
----------------------------------
Finished feeling 3.4 3.4
----------------------------------
Color sensation 4.6 2.8
==================================

このように、本発明の化粧料は、のび（伸展性）やつき（付着性）に優れ、ぼかし易く、発色が良く、仕上り感に優れることが、確認された。 As described above, it was confirmed that the cosmetic of the present invention was excellent in spreading (extensibility) and sticking (adhesiveness), easy to blur, good color development, and excellent in finishing feeling.

［製造例４］
水５００ｍｌにヒドロキシエチルセルロース５ｇ、塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）３１ｇを溶解させ、これにシリコンテトラメトキシド４９０ｍｌ、１Ｎ塩酸１００ｍｌ、エタノール６００ｍｌ、３-アミノプロピルトリエトキシシラン１８４ｇを添加し混合した。別に、ジルコニウムイソプロポキシド５５ｇを２-プロパノール５００ｍｌに溶解させた溶液を準備し、これを、先に調製した塩化金酸とシリコンテトラメトキシドを含む溶液に、ゆっくりと添加し混合した。この混合液を６０℃で約１５時間養生した。 [Production Example 4]
In 500 ml of water, 5 g of hydroxyethyl cellulose and 31 g of chloroauric acid (HAuCl ₄ · 4H ₂ O) are dissolved, and 490 ml of silicon tetramethoxide, 100 ml of 1N hydrochloric acid, 600 ml of ethanol, and 184 g of 3-aminopropyltriethoxysilane are added and mixed. did. Separately, a solution in which 55 g of zirconium isopropoxide was dissolved in 500 ml of 2-propanol was prepared, and this was slowly added to and mixed with the previously prepared solution containing chloroauric acid and silicon tetramethoxide. This mixture was cured at 60 ° C. for about 15 hours.

この液に、５００Ｗ高圧水銀灯の光を５時間照射し、液中に金微粒子を生成させ、さらに５０℃で５時間養生して塗布液とした。この液に、ポリイミドフィルム板（宇部興産製、商品名ユーピレックス）を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥し、その後、多量の水中に基板ごと入れ、水中でゲル膜を剥離させフレーク状とした。水中のフレークを濾過によって回収し、１２０℃で乾燥させてフレーク状ゲルを得た。その後、このフレーク状ゲルを５００℃で３時間焼結し、ジェットミルで粉砕、分級して、平均粒径約１５μｍとして、光沢感ある赤紫色フレーク状粉体を得た。 This solution was irradiated with light from a 500 W high-pressure mercury lamp for 5 hours to form gold fine particles in the solution, and further cured at 50 ° C. for 5 hours to obtain a coating solution. A polyimide film plate (product name: Upilex, manufactured by Ube Industries, Ltd.) was immersed in this liquid and pulled up at a speed of 30 cm / min to apply the liquid to the surface. This was dried at 150 ° C., and then placed in a large amount of water together with the substrate, and the gel film was peeled off in water to form flakes. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel. Thereafter, the flaky gel was sintered at 500 ° C. for 3 hours, pulverized and classified by a jet mill, and a glossy red-purple flaky powder having an average particle size of about 15 μm was obtained.

このフレーク状粉体をＸ線回折等により調べた結果、マトリックスはシリカ-ジルコニア２成分のガラス状態であるのが認められた。化学分析の結果、金の含有量は約５質量％、酸化ジルコニウム含有量約７質量％、酸化珪素含有量約８８質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約５ｎｍの球状金微粒子が、フレーク中に単分散しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、表面は非常に平滑であり、厚みは約０．６μｍであった。 As a result of examining the flaky powder by X-ray diffraction or the like, it was confirmed that the matrix was in a glass state of two components of silica-zirconia. As a result of chemical analysis, the gold content was about 5% by mass, the zirconium oxide content was about 7% by mass, and the silicon oxide content was about 88% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 5 nm were monodispersed in the flakes. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

このフレーク状粉体を手に取り触感を調べたところ、非常に滑らかな感触であった。また、乳鉢を用いて、このフレーク状粉体をすりつぶしても、変色は認められなかった。また、別にこのフレーク状粉体にひまし油を少量添加し、かき混ぜたところ、色がより鮮やかに変化するのが認められた。これはフレークに存在する微細な孔にひまし油が含浸して微細な孔による光散乱が減少するためと考えられる。 When this flake powder was picked up and examined for tactile sensation, it was very smooth. Moreover, even if this flaky powder was ground using a mortar, no discoloration was observed. In addition, when a small amount of castor oil was added to the flaky powder and stirred, it was recognized that the color changed more vividly. This is thought to be because castor oil is impregnated into fine pores existing in the flakes and light scattering by the fine pores is reduced.

［比較製造例４］
水５００ｍｌ、６Ｎ塩酸２００ｍｌ、シリコンテトラメトキシド６１３ｍｌ、エタノール６００ｍｌを添加し混合した。別に、ジルコニウムイソプロポキシド５５ｇを２-プロパノール５００ｍｌに溶解させた溶液を準備し、これを、先に調製した溶液に、ゆっくりと添加し混合した。この混合液を６０℃で約２０時間養生して塗布液とした。 [Comparative Production Example 4]
500 ml of water, 200 ml of 6N hydrochloric acid, 613 ml of silicon tetramethoxide, and 600 ml of ethanol were added and mixed. Separately, a solution in which 55 g of zirconium isopropoxide was dissolved in 500 ml of 2-propanol was prepared, and this was slowly added to and mixed with the previously prepared solution. This mixed solution was cured at 60 ° C. for about 20 hours to obtain a coating solution.

この液に、ポリイミドフィルム板（宇部興産製、商品名ユーピレックス）を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥し、その後、多量の水中に基板ごと入れ、水中でゲル膜を剥離させフレーク状とした。水中のフレークを濾過によって回収し、１２０℃で乾燥させてフレーク状ゲルを得た。その後、このフレーク状ゲルを５００℃で３時間焼結し、ジェットミルで粉砕、分級して、平均粒径約１５μｍとした。 A polyimide film plate (product name: Upilex, manufactured by Ube Industries, Ltd.) was immersed in this liquid and pulled up at a speed of 30 cm / min to apply the liquid to the surface. This was dried at 150 ° C., and then placed in a large amount of water together with the substrate, and the gel film was peeled off in water to form flakes. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel. Thereafter, the flaky gel was sintered at 500 ° C. for 3 hours, pulverized and classified by a jet mill, and the average particle size was about 15 μm.

このフレーク状粉体１００ｇを３０００ｍｌの水に分散させ、ヒドラジンを加えてｐＨを約１０に調整した。この懸濁液を攪拌しながら、１質量％の塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）水溶液１１５０ｍｌをゆっくりと滴下した。滴下後、数時間攪拌し、フレークを濾過、水洗して、２００℃で乾燥後、５００℃で３時間熱処理して赤紫色のフレーク状粉体を得た。 100 g of this flaky powder was dispersed in 3000 ml of water, and hydrazine was added to adjust the pH to about 10. While stirring this suspension, 1150 ml of a 1% by mass aqueous solution of chloroauric acid (HAuCl ₄ .4H ₂ O) was slowly added dropwise. After dropping, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 200 ° C., and heat-treated at 500 ° C. for 3 hours to obtain a reddish purple flake-like powder.

このフレーク状粉体をＸ線回折等により調べた結果、マトリックスはシリカ-ジルコニア２成分のガラス状態であるのが認められた。化学分析の結果、金の含有量は約５質量％、酸化ジルコニウム含有量約７質量％、酸化珪素含有量約８８質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約５ｎｍの球状金微粒子が、フレーク表面上に付着しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、厚みは約０．６μｍであった。 As a result of examining the flaky powder by X-ray diffraction or the like, it was confirmed that the matrix was in a glass state of two components of silica-zirconia. As a result of chemical analysis, the gold content was about 5% by mass, the zirconium oxide content was about 7% by mass, and the silicon oxide content was about 88% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 5 nm were adhered on the surface of the flakes. When the flakes were observed with a scanning electron microscope, the thickness was about 0.6 μm.

このフレーク状粉体を手に取り触感を調べたところ、少し抵抗を感じるが良い感触であった。乳鉢を用いて、このフレーク状粉体をすりつぶしたところ、色が濃い部分と薄い部分にわかれ、色ムラとなった。また、別にこのフレーク状粉体にひまし油を少量添加し、かき混ぜたところ、色調が濃くなったが、全体が少し黒っぽくくすんだ。 When this flake-like powder was picked up and examined for tactile sensation, it was a good feeling although it felt a little resistance. When this flaky powder was crushed using a mortar, it was divided into a dark portion and a light portion, resulting in uneven color. In addition, when a small amount of castor oil was added to this flaky powder and stirred, the color became darker, but the whole became darker.

［実施例４及び比較例４］
以下の表１３〜１５に示す配合で口紅を作製した。 [Example 4 and Comparative Example 4]
Lipsticks were prepared with the formulations shown in Tables 13 to 15 below.

［表１３］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-１０配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
ひまし油３５.０
ミリスチン酸オクチルドデシル１９.０
ミリスチン酸イソプロピル５.４
ラノリン５.５
みつろう２.７
キャンデリラろう６.６
カルナウバろう０.９
セレシン７.２
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 13]
------------------------
Ingredient-10 Blending amount (% by mass)
------------------------
Castor oil 35.0
Octyldodecyl myristate 19.0
Isopropyl myristate 5.4
Lanolin 5.5
Beeswax 2.7
Candelilla 6.6
Carnauba wax 0.9
Ceresin 7.2
------------------------

［表１４］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-１１配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
製造例４で作製した本発明のフレーク１２.１
二酸化チタン５.５
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 14]
------------------------
Ingredient-11 Blending amount (% by mass)
------------------------
Flakes of the present invention produced in Production Example 4 12.1
Titanium dioxide 5.5
------------------------

［表１５］
−−−−−−−−−−−−−−−−−−−−−−−−−
成分-１２配合量（質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−
香料０.１
−−−−−−−−−−−−−−−−−−−−−−−−− [Table 15]
------------------------
Ingredient-12 Blending amount (% by mass)
------------------------
Fragrance 0.1
------------------------

成分-１０を混合して８５℃に加熱溶融した。この溶融物に成分-１１を添加して、撹拌混合を行った。さらに、成分-１２を添加、撹拌混合し、型に流し込み、冷却して、棒状に成形して製品-７（実施例４）を得た。
成分-１１中の製造例４で作製した本発明のフレークのかわりに、比較製造例４で作製したフレークを使用した以外は、前記と同様の方法により、製品-８（比較例４）を得た。
上記製品をパネラー２０名に１０日間使用させ、最低点を１点、最高点を５点とする５段階法にて、評価した官能テストの結果を表１６に示す。 Ingredient-10 was mixed and heated to 85 ° C and melted. Component-11 was added to the melt and stirred and mixed. Further, Component-12 was added, stirred and mixed, poured into a mold, cooled, and formed into a rod shape to obtain Product-7 (Example 4).
Product-8 (Comparative Example 4) was obtained in the same manner as described above except that the flakes produced in Comparative Production Example 4 were used instead of the flakes of the present invention produced in Production Example 4 in Component-11. It was.
Table 16 shows the results of the sensory test evaluated by a five-step method in which the above-mentioned product was used by 20 panelists for 10 days, with the lowest point being 1 point and the highest point being 5 points.

［表１６］
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
項目本発明の化粧料（製品-７）比較の化粧料（製品-８）
（実施例４）（比較例４）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
のび４.５４.０
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
つき４.５３.８
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
光沢感４.３４.０
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
仕上り感４.６３.５
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
色感４.７２.７
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
化粧もち３.９３.３
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ [Table 16]
==================================
Item Cosmetics of the present invention (Product-7) Comparative cosmetics (Product-8)
(Example 4) (Comparative Example 4)
----------------------------------
Nobit 4.5 4.0
----------------------------------
4.5 3.8
----------------------------------
Glossiness 4.3 4.0
----------------------------------
A feeling of finish 4.6 3.5
----------------------------------
Color sensation 4.7 2.7
----------------------------------
Makeup mochi 3.9 3.3
==================================

このように、本発明の化粧料は、のび（伸展性）やつき（付着性）に優れ、光沢感が良好で、発色が良く、仕上り感及び化粧もちの良いことが、確認された。 As described above, it was confirmed that the cosmetic of the present invention was excellent in spread (extensibility) and stickiness (adhesiveness), had a good gloss feeling, had good color development, and had a finished feeling and a long lasting makeup.

［実施例５］
２質量％の塩化金酸（ＨＡｕＣｌ₄・４Ｈ₂Ｏ）水溶液２０００ｍｌにポリビニルアルコール（重合度３００）８０ｇを添加し溶解させ、これを加熱沸騰させて５質量％のクエン酸水溶液５００ｍｌを添加し、暫く加熱沸騰させ、褐色の金コロイド（金０．７４質量％）を得た。動的光散乱法で、金コロイドの粒径を測定したところ、平均粒径は約１１０ｎｍであった。 [Example 5]
Polyvinyl alcohol (degree of polymerization 300) 80 g is added to 2000 ml of ₂ % by mass chloroauric acid (HAuCl ₄ .4H ₂ O) aqueous solution, dissolved, heated and boiled, 500 ml of 5% by mass citric acid aqueous solution is added, The mixture was heated and boiled for a while to obtain a brown gold colloid (gold 0.74% by mass). When the particle size of the gold colloid was measured by a dynamic light scattering method, the average particle size was about 110 nm.

この金コロイド１１００ｍｌと６Ｎ硝酸２００ｍｌ、シリコンテトラメトキシド８５８ｍｌ、Ｎ-（２-アミノエチル）-３-アミノプロピルトリメトキシシラン１８５ｇ、エタノール６００ｍｌ、２-プロパノール６００ｍｌを混合し、４０℃で約５時間養生して塗布液とした。 1100 ml of this gold colloid, 200 ml of 6N nitric acid, 858 ml of silicon tetramethoxide, 185 g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 600 ml of ethanol, and 600 ml of 2-propanol are mixed at 40 ° C. for about 5 hours. Cured to make a coating solution.

この液に、表面をクロムメッキした厚さ０．５ｍｍのステンレス板を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを２００℃で乾燥して、塗布されたゲル膜を剥離しフレーク状とし、１０００℃で１時間焼結した。この焼結フレークをジェットミルで粉砕、分級して、平均粒径約２０μｍとして、赤みがかった茶褐色のフレーク状粉体を得た。 A stainless steel plate having a thickness of 0.5 mm whose surface was chrome-plated was immersed in this liquid, and the liquid was pulled up at a speed of 30 cm / min and applied to the surface. This was dried at 200 ° C., the applied gel film was peeled off to form a flake, and sintered at 1000 ° C. for 1 hour. The sintered flakes were pulverized and classified with a jet mill to obtain a reddish brown flaky powder having an average particle size of about 20 μm.

このフレーク状粉体をＸ線回折により調べた結果、マトリックスはガラス状態のシリカであった。燒結後のフレークの化学分析の結果、金の含有量は、約２質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約１００ｎｍの球状金微粒子が、凝集することなくシリカガラスマトリックス中に分散しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、表面は非常に平滑であり、厚みは約０．６μｍであった。 As a result of examining this flaky powder by X-ray diffraction, the matrix was silica in a glass state. As a result of chemical analysis of the flakes after sintering, the gold content was about 2% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 100 nm were dispersed in the silica glass matrix without agglomeration. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

このフレークを用いて、実施例１に示した方法で、パウダリーファンデーションを作製したところ、のびやつき（付着性）が良く、独特の色調を持ち、発色に優れ、色あせしにくい化粧料が得られた。 Using this flake, a powdery foundation was prepared by the method shown in Example 1. As a result, a cosmetic with good spread and adhesion (adhesiveness), a unique color tone, excellent color development, and hardly faded was obtained. It was.

［実施例６］
３０質量％の塩化ヘキサデシルトリメチルアンモニウム水溶液２０００ｍｌに塩化金酸を１２ｇ添加し、溶解させた。この溶液に、２００Ｗの高圧水銀灯の光を５０時間照射し、金微粒子を生成させ、赤紫色の金コロイド（金０．２９質量％）を得た。透過型電子顕微鏡観察によれば、この金コロイド中には、直径が約２０〜３０ｎｍの球状の金微粒子と、幅約２０〜３０ｎｍ、長さ約１００〜２００ｎｍの棒状の金微粒子が混在していた。 [Example 6]
12 g of chloroauric acid was added to 2000 ml of 30% by mass hexadecyltrimethylammonium chloride aqueous solution and dissolved. This solution was irradiated with light of a 200 W high-pressure mercury lamp for 50 hours to produce gold fine particles, and a red-purple gold colloid (gold 0.29% by mass) was obtained. According to the transmission electron microscope observation, this gold colloid contains spherical gold fine particles having a diameter of about 20 to 30 nm and rod-shaped gold fine particles having a width of about 20 to 30 nm and a length of about 100 to 200 nm. It was.

この金コロイド１７４２ｍｌに、モノラウリン酸ポリエチレングリコール５２ｇを溶解させ、さらに０．８Ｎ硝酸１００ｍｌ、シリコンテトラメトキシド９８０ｍｌ、エタノール６００ｍｌ、２-プロパノール６００ｍｌを混合し、５０℃で約１５時間養生して塗布液とした。 In 1742 ml of this gold colloid, 52 g of polyethylene glycol monolaurate is dissolved, and further 100 ml of 0.8N nitric acid, 980 ml of silicon tetramethoxide, 600 ml of ethanol, and 600 ml of 2-propanol are mixed and cured at 50 ° C. for about 15 hours. It was.

この液に、表面を研磨して平滑にした厚さ０．５ｍｍのステンレス板を浸漬して、３０ｃｍ／ｍｉｎの速度で引き上げその表面に液を塗布した。これを１５０℃で乾燥して、塗布されたゲル膜を剥離しフレーク状とし、１０００℃で１時間焼結した。この焼結フレークをジェットミルで粉砕、分級して、平均粒径約３０μｍとして、淡赤紫色のフレーク状粉体を得た。 A stainless steel plate having a thickness of 0.5 mm, which had been polished and smoothed, was immersed in this liquid, and the liquid was pulled up at a speed of 30 cm / min and applied to the surface. This was dried at 150 ° C., the applied gel film was peeled off to form a flake, and sintered at 1000 ° C. for 1 hour. The sintered flakes were pulverized and classified with a jet mill to obtain a light reddish purple flake powder having an average particle size of about 30 μm.

このフレーク状粉体をＸ線回折により調べた結果、マトリックスはガラス状態のシリカであった。燒結後のフレークの化学分析の結果、金の含有量は、約１．２質量％であった。透過型電子顕微鏡でフレークを観察したところ、直径が約２０ｎｍの球状の金微粒子と、幅約２０〜３０ｎｍ、長さ約１００〜２００ｎｍの棒状の金微粒子が混在してシリカガラスマトリックス中に凝集することなく分散しているのが観察された。また走査型電子顕微鏡でフレークを観察したところ、表面は非常に平滑であり、厚みは約０．６μｍであった。 As a result of examining this flaky powder by X-ray diffraction, the matrix was silica in a glass state. As a result of chemical analysis of the flakes after sintering, the gold content was about 1.2% by mass. When the flakes were observed with a transmission electron microscope, spherical gold fine particles having a diameter of about 20 nm and rod-shaped gold fine particles having a width of about 20 to 30 nm and a length of about 100 to 200 nm were mixed and aggregated in the silica glass matrix. Dispersion was observed without any problems. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

Claims

フレーク状金属酸化物着色剤を配合した化粧料であって、前記フレーク状金属酸化物着色剤は酸化珪素、酸化チタン、酸化アルミニウムおよび酸化ジルコニウムからなる群より選ばれる少なくとも一種の金属酸化物を主成分とし、前記フレーク状金属酸化物着色剤は０．１〜２μｍの平均厚みおよび５〜１５０のアスペクト比を有し、そして１〜３００ｎｍの粒径を有する金微粒子が前記フレーク状金属酸化物着色剤の内部に分散した状態で０．０１〜３０質量％含有されている、フレーク状金属酸化物着色剤を配合した化粧料。 A cosmetic comprising a flaky metal oxide colorant, wherein the flaky metal oxide colorant mainly comprises at least one metal oxide selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide and zirconium oxide. and components, the flaky metal oxide colorants have a mean aspect ratio of thickness and 5 to 150 of 0.1-2 .mu.m, and gold particles the flaky metallic oxide having a particle size of 1~300nm colored Cosmetics containing a flaky metal oxide colorant which is contained in an amount of 0.01 to 30 % by mass in a dispersed state inside the agent .

前記フレーク状金属酸化物着色剤は、（１）加水分解および縮重合が可能な、珪素、チタン、アルミニウムおよびジルコニウムからなる群より選ばれる少なくとも一種の金属の有機化合物、（２）金化合物、および（３）水を含む溶液を基材上に塗布し、乾燥して基材から剥離させた後、熱処理することによって得られるものである請求項１記載の化粧料。The flaky metal oxide colorant comprises (1) an organic compound of at least one metal selected from the group consisting of silicon, titanium, aluminum and zirconium, which can be hydrolyzed and polycondensed, (2) a gold compound, and (3) The cosmetic according to claim 1, wherein the cosmetic is obtained by applying a solution containing water on a substrate, drying it and separating it from the substrate, followed by heat treatment.

前記フレーク状金属酸化物着色剤は、（１）加水分解および縮重合が可能な、珪素、チタン、アルミニウムおよびジルコニウムからなる群より選ばれる少なくとも一種の金属の有機化合物、（２）金化合物、および（３）水を含む溶液を基材上に塗布し、乾燥して基材から剥離させ、ここにおいて前記塗布前の溶液、前記基材上の塗布膜、乾燥後の塗布膜または剥離後の膜に紫外線を照射することによって得られるものである請求項１記載の化粧料。 The flaky metal oxide colorant comprises (1) an organic compound of at least one metal selected from the group consisting of silicon, titanium, aluminum and zirconium, which can be hydrolyzed and polycondensed, (2) a gold compound, and (3) A solution containing water is applied onto a substrate, dried and peeled off from the substrate, wherein the solution before coating, the coating film on the substrate, the coating film after drying or the film after peeling The cosmetic according to claim 1, wherein the cosmetic is obtained by irradiating the skin with ultraviolet rays .

前記フレーク状金属酸化物着色剤を化粧料の全固体成分に対して１〜８０質量％配合した請求項１〜３のいずれか１項に記載の化粧料。 Cosmetics of any one of Claims 1-3 which mix | blended 1-80 mass% of said flaky metal oxide coloring agents with respect to all the solid components of cosmetics.

前記化粧料がパウダーファンデーション、スキンクリーム、ハンドクリームまたはメイクアップベースであり、前記フレーク状金属酸化物着色剤を化粧料の全固体成分に対して０．２〜３質量％配合した請求項１〜３のいずれか１項に記載の化粧料。 The cosmetic powder foundation, a skin cream, hand cream or makeup base, the flaky metal oxide colorant cosmetic of claim 1 blended 0.2-3% by weight, based on the total solid component 4. The cosmetic according to any one of 3 above.

前記化粧料がネイルエナメル、アイシャドーまたは口紅であり、前記フレーク状金属酸化物着色剤を化粧料の全固体成分に対して３〜２５質量％配合した請求項１〜３のいずれか１項に記載の化粧料。 The cosmetic is nail enamel, eye shadow or lipstick, and the flaky metal oxide colorant is blended in an amount of 3 to 25% by mass based on the total solid components of the cosmetic. Cosmetics described.

前記フレーク状金属酸化物着色剤が非晶質またはガラス状である請求項１〜６のいずれか１項に記載の化粧料。 The cosmetic according to any one of claims 1 to 6 , wherein the flaky metal oxide colorant is amorphous or glassy.