JPH08239310A - Flaky powder, its production, and cosmetic formulated therewith - Google Patents

Abstract

PURPOSE: To obtain metal oxide flaky powder suitable for formulation as a colorant in cosmetics, safe to human body, excellent in light resistance, bleed resistance, heat resistance, etc., containing an organic pigment with high opacifying power. CONSTITUTION: The objective metal oxide flaky powder contains 0.5-40wt.% of an organic pigment (esp. pref. Red #226, Red #202, Red #203, Red #204). The metal oxide is pref. selected from silica, titania, alumina and zirconia. The flaky powder is obtained by the following process: a solution comprising water, an organic solvent, organic pigment and hydrolyzable organometallic compound subject to polycondensation is applied on a smooth-surfaced substrate, and the resultant film is peeled off and then heated at 80-250 deg.C for 5min to 24h. For the flaky powder, the organic pigment lies included and immobilized by the inorganic oxide; therefore, the organic pigment is seldom leached or eliminated from the flakes. The other objective cosmetic formulated with the flaky powder is excellent in perspiration resistance, etc.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、フレーク状粉体、特に
着色剤として化粧料中に配合するに適した色素含有フレ
ーク状粉体、およびその製造方法、ならびにそのフレー
ク状粉体を配合した化粧料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flake powder, particularly a pigment-containing flake powder suitable for being incorporated into cosmetics as a coloring agent, a method for producing the same, and the flake powder. Regarding cosmetics.

【０００２】[0002]

【従来の技術】従来、化粧料用着色剤として、タール系
合成色素や天然色素等が使用されている。これら着色剤
を、化粧料基剤中にそのまま添加混合した場合、時とし
て分散が不完全で、色ムラや色ブツが観察されることが
あり好ましくなかった。さらに、色素添加量が多くなる
と、皮膚や爪等に色素が強く付着し、処方時に共に配合
される他の無機系顔料（例えば弁柄）との色分かれを生
じ、メークアップ効果を阻害する問題があった。また、
使用感触も重く、伸ばしにくい欠点も有していた。よっ
て、色素配合量に制限があり、高彩度の化粧料を得にく
かった。2. Description of the Related Art Conventionally, tar-based synthetic pigments and natural pigments have been used as colorants for cosmetics. When these colorants were directly added to and mixed with the cosmetic base, the dispersion was sometimes incomplete, and color unevenness and color spots were sometimes observed, which was not preferable. Furthermore, when the amount of pigment added increases, the pigment adheres strongly to the skin, nails, etc., causing color separation with other inorganic pigments (for example, Benji) that are also compounded at the time of prescription, which hinders the make-up effect. was there. Also,
It was heavy to use and had the drawback of being difficult to stretch. Therefore, there is a limit to the amount of the pigment compounded, and it has been difficult to obtain a highly saturated cosmetic product.

【０００３】また、上記色素をタルクやマイカ等の無機
顔料と混合して、無機顔料表面に色素を付着させて色素
の分散性を向上させることも行われてきた。しかしなが
ら、この場合には、色素の鮮明さが低下するという欠点
を有し、また、化粧料の製造工程、例えば粉砕による剪
断力により、容易に無機顔料から色素が脱離し、色分か
れが生じる。It has also been carried out to improve the dispersibility of the dye by admixing the dye with an inorganic pigment such as talc or mica to adhere the dye to the surface of the inorganic pigment. However, in this case, there is a drawback that the vividness of the pigment is lowered, and the pigment is easily detached from the inorganic pigment due to the shearing force in the manufacturing process of the cosmetic, for example, the crushing, so that color separation occurs.

【０００４】一方、再生フィブロイン微粉末を酸性染料
で染色した着色顔料を化粧料に配合することも提案され
ている（例えば、特開昭６１−３７７１５）。この方法
により、ある程度の耐光性、耐ブリード性の向上は認め
られるものの充分ではなく、また、染色効率が悪い、色
素によっては高濃度に染色することが難しい、配合化粧
料使用時に色素が脱離する場合がある等の問題があっ
た。On the other hand, it has also been proposed to blend a coloring pigment obtained by dyeing regenerated fibroin fine powder with an acid dye into a cosmetic (for example, JP-A-61-37715). Although some improvement in light resistance and bleeding resistance is recognized by this method, it is not sufficient, and the dyeing efficiency is poor, it is difficult to dye at high concentration depending on the dye, and the dye is detached when using the combined cosmetic. There was a problem such as sometimes.

【０００５】また、従来から化粧料に繁用されているタ
ール系合成色素は、発癌性、アレルギー性等、人体への
有害性が問題となってから、化粧品として使用許可され
ている法定色素が年々減少していく傾向にあり、より安
全性の高い色素の開発が望まれている。アレルギー性の
低減方法としては、原料の精製や、色素の有機溶媒等に
よる洗浄（例えば、特開昭５７−１９２４６８、特開昭
５９−７４１６４）、水溶液を活性炭処理後レーキ化す
る方法（例えば特公平４−５１５８８）等が開示されて
いる。これら方法で、処理された色素は、安全性が向上
しているものの、製造工程が増えコスト高となる、精製
や不純物除去を完全に行うには、非常に手間がかかる等
の問題点があった。In addition, the tar-based synthetic pigments that have been frequently used in cosmetics have been the legal pigments that are licensed for use as cosmetics since they pose a problem of carcinogenicity, allergenicity and other harmful effects on the human body. There is a tendency to decrease year by year, and the development of more safe dyes is desired. As a method for reducing allergenicity, a method of purifying a raw material, washing a dye with an organic solvent or the like (for example, JP-A-57-192468, JP-A-59-74164) or a method in which an aqueous solution is treated with activated carbon and then laked (for example, Japanese Patent Publication No. 4-51588) is disclosed. Although the dyes treated by these methods have improved safety, there are problems that the number of manufacturing steps increases and the cost becomes high, and that complete purification and impurity removal are extremely troublesome. It was

【０００６】より安全性の高い色素として、天然色素が
あるが、これは耐光性、耐ブリード性、耐熱性等に劣
り、ｐＨによる色相の変動が大きい等の問題点があっ
た。Natural dyes are one of the safer dyes, but they have problems in that they are inferior in light resistance, bleeding resistance, heat resistance and the like, and the hue varies greatly depending on pH.

【０００７】本発明者らは 、先に、 酸性染料を含有す
るフレーク体の製造法について出願した（特願平６−１
９８１１３）。この方法では、加水分解および脱水縮合
可能な有機金属化合物、例えばシリコンテトラメトキシ
ドのような金属アルコキシド、および酸性染料を含む溶
液を、表面が平滑な基板上に塗布し、これを剥離するこ
とにより、有機色素を含有するフレーク体が得られる。
このフレーク体は、色調に優れているものの、透明感が
高すぎ、必ずしも着色性、発色特性や隠蔽性が、充分で
はなく、化粧料に対する多様なニーズに対応するには不
充分であった。＄The present inventors previously applied for a method for producing a flake body containing an acid dye (Japanese Patent Application No. 6-1).
98113). In this method, a solution containing an organic metal compound capable of being hydrolyzed and dehydrated and condensed, for example, a metal alkoxide such as silicon tetramethoxide, and an acid dye is applied on a substrate having a smooth surface, and then the solution is peeled off. A flake body containing an organic dye is obtained.
Although the flakes have an excellent color tone, they are too transparent, and their coloring properties, coloring properties and hiding properties are not sufficient, and they are insufficient to meet various needs for cosmetics. $

【発明が解決しようとする課題】本発明は上記の従来技
術に鑑み、人体に安全で皮膚刺激がなく、非アレルギー
性、耐光性、耐ブリード性、耐熱性、耐水性、耐汗性、
付着性、伸展性、分散性、肌に対する感触、色調に優
れ、着色性、隠蔽性が特に優れた着色フレーク状粉体配
合の化粧料を提供するものである。SUMMARY OF THE INVENTION In view of the above-mentioned prior art, the present invention is safe for human body, does not cause skin irritation, and is non-allergenic, light resistance, bleed resistance, heat resistance, water resistance, sweat resistance,
It is intended to provide a cosmetic containing a colored flake powder which is excellent in adhesiveness, spreadability, dispersibility, touch to the skin, color tone, and particularly excellent in colorability and hiding power.

【０００８】[0008]

【課題を解決するための手段】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、水、有機溶媒を含む溶液に、有機顔料を添加、
分散し、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、有機顔料を含有した、優れた特
性を有する着色フレーク状粉体が製造できることを見い
だし本発明に至った。すなわち本発明は、有機顔料を
０．５〜４０重量％含有する金属酸化物フレーク状粉体
である。[Means for Solving the Problem] In order to solve this problem,
The present inventors added an organic pigment to a solution containing an organometallic compound capable of hydrolysis and polycondensation, water, and an organic solvent,
Dispersing, coating this on a substrate, preferably a substrate having a smooth surface, drying and peeling from the substrate, and then heat-treating, easily and efficiently, containing an organic pigment, excellent It was found that a colored flake powder having characteristics could be produced, and the present invention was completed. That is, the present invention is a metal oxide flake powder containing 0.5 to 40% by weight of an organic pigment.

【０００９】本発明の金属酸化物フレーク状粉体は次の
ようにして製造される。加水分解および縮重合が可能な
有機金属化合物、水、有機溶媒を含む溶液中に有機顔料
を分散させ、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、着色フレーク状粉体が製造
できる。The metal oxide flake powder of the present invention is manufactured as follows. An organic pigment is dispersed in a solution containing an organic metal compound capable of hydrolysis and polycondensation, water, and an organic solvent, and this is applied onto a substrate, preferably a substrate having a smooth surface, and dried to obtain a substrate. If the colored flaky powder is produced, the colored flaky powder can be produced easily and efficiently by peeling it from the substrate and then heat treating it.

【００１０】このように、有機顔料を添加分散すること
により、染料を添加した場合よりも、濃色で隠蔽性のあ
る着色フレーク状粉体が得られる。As described above, by adding and dispersing the organic pigment, a colored flake powder having a darker color and hiding power than that obtained by adding a dye can be obtained.

【００１１】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としては、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、シリコン、
チタン、アルミニウム、ジルコニウム等のメトキシド、
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。得られるフレーク状粉体
の組成は、金属酸化物、例えば純粋なシリカ、珪酸塩
系、チタン酸塩系、アルミン酸系、ジルコニウム酸塩系
の非晶質のものである。得られる着色フレーク状粉体の
使用上の安全性安心感から、上記金属エトキシドが、さ
らに好ましく用いられる。これは、得られる着色フレー
ク状粉体中に残留している有機残基が、何等かの分解促
進を受けた場合でも、分解生成物がエタノールであれ
ば、化粧料使用上差し支えないことによる。The hydrolyzable and polycondensable organometallic compound used in the present invention is preferably a metal alkoxide having an alkoxyl group. Specifically, silicon,
Methoxide such as titanium, aluminum, zirconium,
Ethoxide, propoxide, butoxide and the like are used alone or as a mixture. The composition of the obtained flake powder is a metal oxide such as pure silica, silicate type, titanate type, aluminate type, zirconate type amorphous. The above metal ethoxide is more preferably used from the viewpoint of safety and security in using the obtained colored flake powder. This is because even if the organic residue remaining in the obtained colored flake powder is subjected to some decomposition promotion, if the decomposition product is ethanol, there is no problem in using cosmetics.

【００１２】上記着色フレーク状粉体中の有機顔料とし
ては、昭和４１年８月３１日厚生省令第３０号による有
機顔料（通称法定色素）群から選定するのが、化粧品と
して使用する上で好ましく、赤色２０２号、赤色２０３
号、赤色２０４号、赤色２０５号、赤色２０６号、赤色
２０７号、赤色２０８号、赤色２１９号、赤色２２０
号、赤色２２１号、赤色２２６号、赤色２２８号、だい
だい色２０３号、だいだい色２０４号、黄色２０５号、
青色２０４号、赤色４０４号、赤色４０５号、だいだい
色４０１号、黄色４０１号、青色４０４号等が例示され
る。これら有機顔料のうち、汎用性を考慮すると、赤色
２２６号、赤色２０２号、赤色２０３号、赤色２０４号
の使用が好ましく、実際、これら有機顔料を用いて作製
した着色フレーク状粉体は、色調や発色がより優れてい
る。本発明では、上記有機顔料の一種または二種以上混
合して使用するものである。The organic pigment in the colored flake powder is preferably selected from the group of organic pigments (commonly known as legal dyes) according to the Ordinance No. 30 of the Ministry of Health and Welfare on August 31, 1941 for cosmetic use. , Red No. 202, Red 203
No., Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. 208, Red No. 219, Red No. 220
No., Red 221, Red 226, Red 228, Day 203, Day 204, Yellow 205,
Blue No. 204, Red No. 404, Red No. 405, Daidai No. 401, Yellow No. 401, Blue No. 404, etc. are exemplified. Among these organic pigments, in consideration of versatility, it is preferable to use Red 226, Red 202, Red 203, and Red 204. In fact, colored flake powders produced using these organic pigments have different color tones. And the color development is better. In the present invention, one kind or a mixture of two or more kinds of the above organic pigments is used.

【００１３】これら有機顔料を、加水分解および縮重合
が可能な有機金属化合物、水、有機溶媒を含む溶液に添
加し、分散工程を経て均一な溶液とする。有機顔料は後
述のようにフレーク状粉体中の有機顔料含有量が、０．
５〜４０重量％になるように前記溶液中に含有させる。These organic pigments are added to a solution containing an organometallic compound capable of being hydrolyzed and polycondensed, water, and an organic solvent, and a uniform solution is obtained through a dispersion process. As described below, the organic pigment has an organic pigment content of 0.
It is contained in the solution so as to be 5 to 40% by weight.

【００１４】上記の有機顔料、加水分解および縮重合が
可能な有機金属化合物、水、有機溶媒を含む溶液の好ま
しい配合比は，有機顔料を基準にして次の通りである。 有機顔料 １重量部 加水分解および縮重合が可能な有機金属化合物 ５〜３５重量部 水 １０〜７５重量部 有機溶媒 １〜５０重量部The preferred blending ratio of the above-mentioned organic pigment, a solution containing an organic metal compound capable of hydrolysis and polycondensation, water, and an organic solvent is as follows based on the organic pigment. Organic pigment 1 part by weight Organometallic compound capable of hydrolysis and polycondensation 5 to 35 parts by weight Water 10 to 75 parts by weight Organic solvent 1 to 50 parts by weight

【００１５】有機顔料の分散は、公知の技術によって行
えば良く、ホモジナイザー、ディスパーザー、サンドグ
ラインダーミル、ボールミル、ローラーミル、高速イン
ペラーミル、ペッブルミル、アトライター、コロイドミ
ル等の分散機の使用が例示される。しかし、有機顔料の
種類によっては、これら分散機が必ずしも必要ではな
く、単に攪拌を行うだけでも、実用上差し支えない分散
状態が得られる場合もある。The organic pigment may be dispersed by a known technique, and examples thereof include the use of a homogenizer, a disperser, a sand grinder mill, a ball mill, a roller mill, a high speed impeller mill, a pebble mill, an attritor, a colloid mill and the like. To be done. However, depending on the type of organic pigment, these dispersers are not always necessary, and there are cases in which a dispersed state that is practically acceptable will be obtained by simply stirring.

【００１６】上記有機顔料の分散時に、界面活性剤や分
散剤を添加しても良い。使用する界面活性剤や分散剤
は、特に限定されないが、上記着色フレーク状粉体が、
化粧料として使用されることを考慮すると、化粧品原料
基準記載の物質を用いるのが好ましい。ステアリン酸セ
ッケンや各種の金属セッケン、ポリオキシエチレンアル
キルエーテル、ポリオキシエチレン脂肪酸エステル、ソ
ルビタン脂肪酸エステル、ジアルキルスルホコハク酸
塩、ステアリン酸、グリセリン、各種油脂等が例示され
る。A surfactant or a dispersant may be added when the above organic pigment is dispersed. The surfactant or dispersant used is not particularly limited, but the colored flake powder is
Considering the fact that they are used as cosmetics, it is preferable to use the substances listed in the standards for cosmetic raw materials. Examples thereof include stearic acid soaps, various metal soaps, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, dialkylsulfosuccinates, stearic acid, glycerin, and various oils and fats.

【００１７】上記有機顔料の分散は、加水分解および縮
重合が可能な有機金属化合物と水と有機溶媒の混合溶媒
中で行うのが、工程が単純で好ましいが、この最終分散
工程前に、予め有機顔料を適当な溶媒中に分散させてお
いても良い。Dispersion of the above organic pigment is preferably carried out in a mixed solvent of an organic metal compound capable of hydrolysis and polycondensation, water and an organic solvent, since the process is simple, but before this final dispersion process, The organic pigment may be dispersed in a suitable solvent.

【００１８】上記有機金属化合物を含む溶液中に添加す
る有機溶媒は、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好ましい。
得られる着色フレーク状粉体の使用上の安全性安心感か
ら、エタノールが、さらに好ましく用いられる。しかし
前記有機金属化合物の加水分解反応で発生するアルコー
ルで十分な場合には、溶媒は特に用いなくても良い。ま
た、有機顔料の分散性向上の観点から、アセトン、キシ
レン、酢酸ブチル等の各種有機溶媒を、最終的に得られ
る溶液の均一性が損なわれない程度添加しても良い。た
だし、この時は、得られた着色フレーク状粉体中にこれ
ら溶媒が残留しないように、充分乾燥する必要がある。The organic solvent added to the solution containing the organometallic compound may be basically any solvent as long as it substantially dissolves the organometallic compound, but alcohols such as methanol, ethanol, propanol and butanol are preferred.
Ethanol is more preferably used from the viewpoint of safety and security in use of the obtained colored flake powder. However, if the alcohol generated by the hydrolysis reaction of the organometallic compound is sufficient, the solvent need not be used. From the viewpoint of improving the dispersibility of the organic pigment, various organic solvents such as acetone, xylene and butyl acetate may be added to such an extent that the homogeneity of the finally obtained solution is not impaired. However, at this time, it is necessary to dry sufficiently so that these solvents do not remain in the obtained colored flake powder.

【００１９】上記有機金属化合物の加水分解を促進する
ために、塩酸、硝酸、硫酸等の酸を添加するのが好まし
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。In order to accelerate the hydrolysis of the organometallic compound, it is preferable to add an acid such as hydrochloric acid, nitric acid or sulfuric acid. The amount of the acid added is not particularly limited, but a molar ratio of 0.001 to 2 with respect to the organometallic compound is preferable. The amount of added acid is
If the molar ratio is less than 0.001, the promotion of hydrolysis of the organometallic compound is not sufficient, and if the molar ratio is more than 2, the effect of promoting hydrolysis is no longer improved and the acid becomes excessive, which is not preferable. .

【００２０】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、乾燥剥離工程の歩留りが低下することがあ
るので、添加量は１０重量％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 the amount of addition is large, the yield of the dry peeling process may decrease, so the amount of addition should be limited to 10% by weight or less.

【００２１】上記有機金属化合物を含む溶液中に、例え
ば紫外線遮蔽効果の付与を目的として、酸化チタン、酸
化セリウム、酸化亜鉛等の金属酸化物微粒子を添加して
も良い。金属酸化物微粒子の添加については、特に限定
されないが、１）上記有機顔料と同時に行い、分散する
方法、２）金属酸化物粉体を予め水やアルコール等の溶
媒に分散させておき、上記有機顔料と別に添加分散を行
う方法等が例示される。さらに好ましくは、水やアルコ
ール等を分散媒とする金属水酸化物コロイド、含水金属
酸化物コロイド、金属酸化物コロイド等を添加するの
が、金属酸化物等の微粒子の分散安定性が高く、製造工
程が簡略化されるので良い。Fine particles of metal oxides such as titanium oxide, cerium oxide and zinc oxide may be added to the solution containing the organometallic compound for the purpose of imparting an ultraviolet shielding effect. The addition of the metal oxide fine particles is not particularly limited, but 1) a method in which the metal oxide powder is dispersed at the same time as the organic pigment and 2) a metal oxide powder is previously dispersed in a solvent such as water or alcohol, Examples include a method of adding and dispersing separately from the pigment. More preferably, a metal hydroxide colloid having water or alcohol as a dispersion medium, a hydrous metal oxide colloid, a metal oxide colloid, etc. is added, because the dispersion stability of fine particles such as metal oxide is high, It is good because the process is simplified.

【００２２】本発明で使用する基板は金属、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溶
液を塗布し、０．２〜５０μｍ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
用の少ない状態が好ましい。The substrate used in the present invention is made of a material such as metal, glass or plastic and has a smooth surface. A solution containing the above organometallic compound is applied to such a substrate to form a thin film of 0.2 to 50 μm. When this film dries, it contracts, but the substrate does not contract, so cracks occur in the film, and the film becomes flakes. In order for the substrate and the film to be separated from each other, it is preferable that there is little interaction such as strong bonding between the substrate and the film.

【００２３】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（ディ
ップコーティング法）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（スピンコーティング
法）、基板上に上記液体を吹き付ける方法（スプレーコ
ーティング法）、回転するロールに上記液体を付着さ
せ、これを基板に接触させる方法（ロールコーティング
法）、上記液体をスリット状ノズルから押しだし基板上
に塗布する方法（ダイコーティング法）、上記液体をス
リットから自然落下させて基板上に塗布する方法（カー
テンコーティング法）等が用いられる。本発明では、上
記液体中に分散させた有機顔料粒子が有効かつ均一に塗
膜中に含ませるため、上記方法のうち、スプレーコーテ
ィング法、ロールコーティング法、ダイコーティング
法、カーテンコーティング法が好ましく用いられる。As a technique for forming a film on the surface of the substrate, a known technique may be used. For example, a method of dipping the substrate in a liquid containing the above-mentioned organometallic compound and then pulling it up (dip coating method), or Drop the above liquid on,
A method of rotating the substrate at a high speed (spin coating method), a method of spraying the liquid on the substrate (spray coating method), a method of attaching the liquid to a rotating roll and bringing the liquid into contact with the substrate (roll coating method), A method in which the liquid is pushed out from a slit-shaped nozzle and applied on the substrate (die coating method), a method in which the liquid is naturally dropped from the slit and applied on the substrate (curtain coating method), and the like are used. In the present invention, since the organic pigment particles dispersed in the liquid are effectively and uniformly contained in the coating film, the spray coating method, the roll coating method, the die coating method, and the curtain coating method are preferably used among the above methods. To be

【００２４】熱処理に関しては、その方法に特に制限は
ない。熱処理温度および時間は、溶媒や酸の除去を確実
にし、かつ有機顔料の分解が起こらない条件が好まし
く、通常は８０〜２５０℃で５分間〜２４時間加熱す
る。有機顔料の分解を抑制する目的で、減圧下で熱処理
を行う場合もある。There is no particular limitation on the method of heat treatment. The heat treatment temperature and time are preferably conditions under which removal of the solvent and acid is ensured and decomposition of the organic pigment does not occur, and heating is usually performed at 80 to 250 ° C. for 5 minutes to 24 hours. Heat treatment may be performed under reduced pressure for the purpose of suppressing the decomposition of the organic pigment.

【００２５】このようにして得られた着色フレーク状粉
体の厚みは、溶液あるいは製膜条件等によって変化する
が、概ね０．１〜５μｍであり、化粧料配合用としては
好ましくは０．３〜１．０、特に好ましくは０．４〜
０．９μｍ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
０．１μｍ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。また着色フレー
ク状粉体の粒径は平均粒径が１〜１００μｍであり、化
粧料配合用としては好ましくは３〜５０μｍ、特に好ま
しくは７〜４０μｍの大きさに粉砕・分級される。The thickness of the colored flake powder thus obtained varies depending on the solution or film forming conditions, but is generally 0.1 to 5 μm, and is preferably 0.3 for cosmetics. ~ 1.0, particularly preferably 0.4 ~
It is 0.9 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 peeling between films occurs in a direction parallel to the substrate. On the other hand, when the thickness is less than 0.1 μm, the adhesive force between the substrate and the film becomes too large and the film does not peel off from the substrate. The particle diameter of the colored flake powder is 1 to 100 μm, and for blending with cosmetics, it is preferably 3 to 50 μm, and particularly preferably 7 to 40 μm.

【００２６】本発明の着色フレーク状粉体中の有機顔料
含有量は、０．５重量％以上、４０重量％以下、より好
ましくは３〜３０重量％である。０．５％より少ないと
有機顔料による着色効果が小さくなり、着色の色調が良
くない等の理由で好ましくない。また、４０％より多い
と、フレーク状粉体表面に露出する有機顔料が顕著に認
められるようになり、非アレルギー性、伸展性（の
び）、分散性、肌に対する感触等の特性が劣化するの
で、好ましくない。The content of the organic pigment in the colored flake powder of the present invention is 0.5% by weight or more and 40% by weight or less, more preferably 3 to 30% by weight. If it is less than 0.5%, the coloring effect by the organic pigment becomes small and the color tone of coloring is not good, which is not preferable. On the other hand, when it is more than 40%, the organic pigment exposed on the surface of the flaky powder becomes noticeable, and the properties such as non-allergenicity, extensibility (spreading), dispersibility, and touch to the skin are deteriorated. , Not preferable.

【００２７】本発明の有機顔料含有フレーク状粉体を配
合した化粧料は、無機酸化物によって有機顔料が内包固
定化されているので、有機顔料がフレークから溶出した
り、脱離したりすることがほとんどなく、耐ブリード
性、耐水性、耐汗性に優れた安定な製品となる。また、
有機顔料が皮膚に直接触れないので、非アレルギー性が
向上しており、また皮膚や爪等を染めることがなく、さ
らにフレーク形状であることから、有機顔料が汗腺や毛
穴に詰まることがなく、皮膚刺激がない安全な製品とな
る。In the cosmetic containing the organic pigment-containing flake powder of the present invention, the organic pigment is encapsulated and fixed by the inorganic oxide, so that the organic pigment may be eluted or detached from the flakes. It is a stable product with almost no bleed resistance, water resistance, and sweat resistance. Also,
Since the organic pigment does not come into direct contact with the skin, non-allergenicity is improved, and it does not stain the skin, nails, etc., and since it has a flake shape, the organic pigment does not clog sweat glands and pores, It is a safe product with no skin irritation.

【００２８】また、無機酸化物中に有機顔料が含有され
ていることにより、有機顔料の安定性が向上しており、
耐光性、耐熱性が高く、鮮やかな発色を有する好ましい
色調の製品となる。さらに、有機顔料含有フレーク状粉
体が、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）、
分散性、付着性が良く、使用触感に優れた製品となる。Further, since the organic pigment is contained in the inorganic oxide, the stability of the organic pigment is improved,
The product has high light resistance and heat resistance, and has a preferable color tone with vivid color. Further, the organic pigment-containing flake-like powder does not aggregate with each other, its surface is smooth, and exhibits good slipperiness, so that extensibility (spreading),
The product has good dispersibility and adhesion, and is excellent in touch feeling.

【００２９】本発明で言う化粧料には、上記有機顔料含
有フレーク状粉体の他、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、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 cosmetics of the present invention, in addition to the above-mentioned organic pigment-containing flake powder, pigments that are usually used may be used in combination, if necessary. For example, titanium oxide, zinc oxide, zirconium oxide, yellow iron oxide,
Inorganic pigments such as black iron oxide, rouge, ultramarine blue, dark blue, chromium oxide and chromium hydroxide, pearlescent pigments such as mica titanium and bismuth oxychloride, powders such as silica beads, plastic beads such as nylon and acrylic, talc , Kaolin, mica, sericite, other mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, clays and the like.

【００３０】上記有機顔料含有フレーク状粉体の配合量
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重量％の範囲で
用いられ、特に２〜５０重量％の範囲が好ましい。これ
以下の含有量では、使用触感が改善されない、発色が良
くない等の問題点があり、逆に上限より多くの有機顔料
含有フレーク状粉体を添加しても、着色効果は上がら
ず、他の成分が減少し、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 blending amount of the above-mentioned organic pigment-containing flake powder varies depending on the kind of the intended cosmetic, but it is used in the range of 1 to 80% by weight with respect to the solid component such as pigment, and particularly 2 The range of ˜50% by weight is preferred. If the content is less than this, there is a problem that the feeling of use is not improved, color development is not good, and conversely, the addition of more organic pigment-containing flake powder than the upper limit does not improve the coloring effect, It becomes difficult to adjust the color tone and improve the adhesion to the skin.

【００３１】また、本発明で用いる有機顔料含有フレー
ク状粉体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、このフレーク状粉体の表面処理を施し
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、フレーク状ガラス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 order to improve the dispersibility of the organic pigment-containing flake powder used in the present invention in cosmetics and to improve the touch, the flaky powder is surface-treated and modified. You can do anything. For example, methyl hydrogen polysiloxane, reactive alkyl polysiloxane, metal soap, hydrogenated lecithin, acyl amino acid, acylated collagen metal salt selected from aluminum, magnesium, calcium, titanium, zinc, zirconium, iron, etc. When surface treatment is performed with a so-called hydrophobizing agent, the surface of the flake-shaped glass changes from hydrophilic to hydrophobic, so that it becomes more familiar with the oil agent added when formulating the cosmetic composition, resulting in a cosmetic product with a good feel. .

【００３２】[0032]

【実施例】以下に実施例を示す。 実施例−１及び比較例−１ エタノール３２０ｍｌ、シリコンテトラエトキシド１４
８０ｍｌ、純水１２００ｍｌ、０．８Ｎ硝酸２００ｍｌ
を混合し、３０℃で５時間攪拌して、均一な液（Ａ液）
を得た。一方、別に、赤色２０２号（リソールルビンＢ
ＣＡ）４４ｇを、１０００ｍｌの純水に添加し、超音波
を照射しながら激しく攪拌して、赤色２０２号分散液
（Ｂ液）を得た。Ａ液を攪拌しながらＢ液を添加し、さ
らに循環式のサンドミルを用いて赤色２０２号の分散を
行った。その後、５０℃で約２０時間養生して塗布液と
した。この液を径２ｍｍのノズルから霧状に噴霧し、表
面を研磨して平滑にした厚さ０．５ｍｍのステンレス板
表面に液を塗布した。これを１５０℃で約２分乾燥し
て、塗布されたゲル膜を剥離させ、フレーク状とし、１
２０℃で２４時間熱処理した。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、厚みは約０．６
μｍであった。窒素吸着法によりこのフレークの表面積
を測定したところ、比表面積が約２０ｍ²／ｇ であり、
直径８ｎｍ以下の細孔を有する多孔質体であった。フレ
ーク中の赤色２０２号含有量は、約１０重量％であっ
た。Examples are shown below. Example-1 and Comparative Example-1 320 ml of ethanol, silicon tetraethoxide 14
80 ml, pure water 1200 ml, 0.8N nitric acid 200 ml
Were mixed and stirred at 30 ° C for 5 hours to obtain a uniform liquid (liquid A).
I got On the other hand, separately, Red No. 202 (Resor Rubin B
CA) (44 g) was added to 1000 ml of pure water, and the mixture was vigorously stirred while being irradiated with ultrasonic waves to obtain a red No. 202 dispersion liquid (B liquid). Solution B was added while stirring solution A, and red No. 202 was dispersed using a circulating sand mill. After that, the coating liquid was cured at 50 ° C. for about 20 hours. This liquid was sprayed in a mist form from a nozzle having a diameter of 2 mm, and the liquid was applied to the surface of a stainless steel plate having a thickness of 0.5 mm whose surface was polished and smoothed. This is dried at 150 ° C for about 2 minutes to peel off the applied gel film to form flakes.
It heat-processed at 20 degreeC for 24 hours. When the flakes were observed with a scanning electron microscope, the surface was smooth and the thickness was about 0.6.
μm. When the surface area of this flake was measured by the nitrogen adsorption method, the specific surface area was about 20 m ² / g,
It was a porous body having pores with a diameter of 8 nm or less. The content of Red No. 202 in the flakes was about 10% by weight.

【００３３】この熱処理フレークをジェットミルで粉
砕、分級して、平均粒径約１４μｍの鮮やかな赤色フレ
ーク状粉体（粉体Ａ）を得た。このフレーク状粉体は、
互いに凝集することがなく、滑り性があって、独特の優
れた触感を有していた。水及び油に対する有機顔料溶出
を観察したところ、有機顔料の溶出はほとんど認められ
なかった。The heat-treated flakes were crushed by a jet mill and classified to obtain a bright red flake powder (powder A) having an average particle diameter of about 14 μm. This flake powder is
They did not aggregate with each other, had slipperiness, and had a unique and excellent tactile sensation. When the elution of the organic pigment with respect to water and oil was observed, almost no elution of the organic pigment was observed.

【００３４】赤色２２６号（ヘリンドンピンクＣＮ）１
３５ｇ、純水１０００ｍｌ、エタノール１００ｍｌ、モ
ノステアリン酸ポリオキシエチレングリセリン（日本油
脂株式会社製ノニオンＳ−１０）２ｇを混合し、サンド
ミルを用いて分散を行い、赤色の分散液を得た。一方、
別にシリコンテトラエトキシド１４８０ｍｌ、０．１Ｎ
硝酸１６００ｍｌを混合して、超音波照射を３０分間行
い、その後５０℃で約１０時間養生した。この液と、先
の赤色２２６号分散液を混合し、超音波照射を５分間行
い、さらに５０℃で約２時間養生して、塗布液を得た。
先述の方法でフレーク化、熱処理、粉砕分級を行い、赤
色２２６号含有量約２５％、厚み約０．７μｍ、平均粒
径約１５μｍの赤色フレーク状粉体（粉体Ｂ）を得た。
このフレーク状粉体は、互いに凝集することがなく、滑
り性があって、独特の優れた触感を有していた。また、
窒素吸着法によりこのフレーク状粉体の表面積を測定し
たところ、比表面積が約２０ｍ²／ｇ であり、直径８ｎ
ｍ以下の細孔を有する多孔質体であった。水及び油に対
する有機顔料溶出を観察したところ、有機顔料の溶出は
ほとんど認められなかった。Red No. 226 (Herringdon Pink CN) 1
35 g, 1000 ml of pure water, 100 ml of ethanol, and 2 g of polyoxyethylene glycerin monostearate (Nonion S-10 manufactured by NOF CORPORATION) were mixed and dispersed using a sand mill to obtain a red dispersion liquid. on the other hand,
Separately, silicon tetraethoxide 1480 ml, 0.1N
The mixture was mixed with 1600 ml of nitric acid, irradiated with ultrasonic waves for 30 minutes, and then cured at 50 ° C. for about 10 hours. This solution was mixed with the red color No. 226 dispersion described above, ultrasonic irradiation was carried out for 5 minutes, and further aged at 50 ° C. for about 2 hours to obtain a coating solution.
Flake formation, heat treatment, and pulverization classification were performed by the above-mentioned method to obtain red flake powder (powder B) having a red No. 226 content of about 25%, a thickness of about 0.7 μm, and an average particle size of about 15 μm.
The flaky powder did not aggregate with each other, had slipperiness, and had a unique and excellent tactile sensation. Also,
When the surface area of this flake powder was measured by the nitrogen adsorption method, the specific surface area was about 20 m ² / g and the diameter was 8 n.
It was a porous body having pores of m or less. When the elution of the organic pigment with respect to water and oil was observed, almost no elution of the organic pigment was observed.

【００３５】次に以下の配合で口紅を作製した。 成分−１ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 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 ７．２Next, a lipstick was prepared with the following composition. Component-1 Blending amount (% by weight) ---------------------------------- Castor oil 35.0 Myristic acid Octyldodecyl 19.0 Isopropyl myristate 5.4 Lanolin 5.5 Beeswax 2.7 Candelilla wax 6.6 Carnauba wax 0.9 Ceresin 7.2

【００３６】 成分−２ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 上記赤色２０２号含有フレーク状粉体（粉体Ａ） ７．５ 上記赤色２２６号含有フレーク状粉体（粉体Ｂ） ４．６ 二酸化チタン ５．５Component-2 blending amount (% by weight) -------------------------------------------- The above red 202 No.-containing flake powder (Powder A) 7.5 The above red No. 226-containing flake powder (Powder B) 4.6 Titanium dioxide 5.5

【００３７】 成分−３ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 香料 ０．１ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Component-3 Blending amount (% by weight) ----------------------------------..-- Perfume 0. 1 ------------------------------------------------

【００３８】成分−１を混合して８５℃に加熱溶融し
た。この溶融物に成分−２を添加して、撹拌混合を行っ
た。さらに、成分−３を添加、撹拌混合し、型に流し込
み、冷却して、棒状に成形して口紅製品−１（実施例−
１）を得た。Component-1 was mixed and heated to 85 ° C. and melted. Component-2 was added to this melt, and the mixture was stirred and mixed. Furthermore, component-3 is added, mixed with stirring, poured into a mold, cooled, and molded into a stick shape to obtain a lipstick product-1 (Example-
1) was obtained.

【００３９】 成分−４ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 赤色２０２号 ０．８ 赤色２２６号 １．０ マイカ １０．３ 二酸化チタン ５．５Component-4 Amount of compounding (% by weight) ----------------------------------------- Red No. 202 0.8 Red No. 226 1.0 Mica 10.3 Titanium dioxide 5.5

【００４０】成分−２の代わりに成分−４を使用した以
外は、前記と同様の方法により、口紅製品−２（比較例
−１）を得た。Lipstick product-2 (Comparative Example-1) was obtained in the same manner as described above except that Component-4 was used instead of Component-2.

【００４１】上記製品をパネラー２０名に５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１に示す。The above product is used by 20 panelists for 5 days, and the minimum point is 1 point and the maximum point is 5 points.
The results of the sensory tests evaluated are shown in Table 1.

【００４２】[0042]

【表１】 表１ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 項目 本発明の化粧料（口紅製品−１） 比較の化粧料（口紅製品−２） （実施例−１） （比較例−１） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− のび ４．７ ３．０ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− つき ４．５ ３．８ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 光沢感 ４．３ ３．１ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 仕上り感 ３．９ ２．２ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 色感 ４．６ ４．０ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 化粧もち ３．７ ３．３ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝[Table 1] Table 1 =================================== Item The cosmetics of the present invention (lipstick products -1) Comparative Cosmetic (Lipstick Product-2) (Example-1) (Comparative Example-1) --------------- ------------- No. 4.7 3.0 -------------------------------------------- --- Adhesiveness 4.5 3.8 --------------------------------------------- Glossiness 4.3 3. 1 ----------------------------------------- Finishing feeling 3.9 2.2 --- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Color Sensitivity 4.6 4.0 −−−−−−−−−−−−− −−−−−−−− ------------------------ Makeup mochi 3.7 3.3 ============================ ========

【００４３】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。なお、赤色２０２号含有フレーク状粉体（粉体Ａ）
および赤色２２６号含有フレーク状粉体（粉体Ｂ）は、
化粧料に配合された後に色がより鮮やかに変化するのが
認められた。これは粉体Ａおよび粉体Ｂが有する微細な
孔にひまし油等の油性成分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。As described above, it was confirmed that the cosmetic composition of the present invention is excellent in spreadability (extendability) and stickiness (adhesion), has a good glossy feeling, has a good color development, and has a good finished feeling and makeup lasting. It was In addition, red No. 202-containing flake powder (powder A)
And the red 226-containing flake powder (powder B) is
It was observed that the color changed more vividly after being incorporated into the cosmetic. It is considered that this is because the fine pores of the powder A and the powder B are impregnated with an oily component such as castor oil to reduce light scattering due to the fine pores.

【００４４】実施例−２及び比較例−２ 赤色２２６号９．１ｇ、赤色２０３号（レーキレッド
Ｃ）０．６ｇ、黄色２０５号（ベンチジンイエロー）
５．０ｇ、グリセリン２ｇ、１−ブタノール５０ｍｌ、
エタノール３４０ｍｌ、純水２０００ｍｌ、シリコンテ
トラエトキシド１４８０ｍｌ、０．８Ｎ硝酸２００ｍｌ
をサンドミルを用いて混合し、５０℃で約２０時間養生
して塗布液とした。実施例−１記載の方法でフレーク
化、熱処理、粉砕分級を行い、有機顔料含有量約３．５
％、厚み約０．６μｍ、平均粒径約１０μｍの紅色フレ
ーク状粉体（粉体Ｃ）を得た。このフレーク状粉体は、
互いに凝集することがなく、滑り性があって、独特の優
れた触感を有していた。上記フレーク状粉体の少量を、
水及び油に各々添加して、有機顔料溶出を観察したとこ
ろ、有機顔料の溶出はほとんど認められなかった。Example-2 and Comparative Example-2 Red 226 No. 9.1 g, Red No. 203 (Rake Red C) 0.6 g, Yellow No. 205 (Bentzine Yellow)
5.0 g, glycerin 2 g, 1-butanol 50 ml,
Ethanol 340 ml, pure water 2000 ml, silicon tetraethoxide 1480 ml, 0.8N nitric acid 200 ml
Were mixed using a sand mill and cured at 50 ° C. for about 20 hours to obtain a coating liquid. Flake formation, heat treatment, and pulverization classification were carried out by the method described in Example-1, and the organic pigment content was about 3.5.
%, A thickness of about 0.6 μm, and an average particle size of about 10 μm were obtained as red flake powder (powder C). This flake powder is
They did not aggregate with each other, had slipperiness, and had a unique and excellent tactile sensation. A small amount of the above flake powder,
When elution of the organic pigment was observed by adding it to water and oil, elution of the organic pigment was hardly observed.

【００４５】以下の配合でネイルエナメルを作製した。 成分−５ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 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 ４．０Nail enamel was prepared with the following formulation. Component-5 Blending amount (% by weight) -------------------------------------------- Nitrocellulose 15.0 Phthal Acid-based alkyd resin 12.0 Dibutyl phthalate 4.0

【００４６】 成分−６ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 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 ２．０Component-6 Blending amount (% by weight) -------------------------------- Butyl acetate 25 0.0 Ethyl acetate 7.0 Toluene 24.0 2-Propanol 6.0 Ethanol 2.0 1-Butanol 2.0

【００４７】 成分−７ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 上記有機顔料含有フレーク状粉体（粉体Ｃ） ３．０ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Component-7 Blending amount (% by weight) ------------------------------------ Containing flake powder (powder C) 3.0 ---------------------------------------------

【００４８】成分−５と成分−６を混合し溶解させた。
これに、成分−７を添加し、撹拌混合を行ない、ＮＥ製
品−１（実施例−２）を得た。Component-5 and component-6 were mixed and dissolved.
Component-7 was added to this, and the mixture was stirred and mixed to obtain NE product-1 (Example-2).

【００４９】 成分−８ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 赤色２２６号 ０．０６５ 赤色２０３号 ０．００４ 黄色２０５号 ０．０３６ マイカ ２．８９５Ingredient -8 blending amount (% by weight) --------------------------------------- Red No. 226 0.065 Red No. 203 0.004 Yellow No. 205 0.036 Mica 2.895

【００５０】成分−７の代わりに成分−８を使用した以
外は、前記と同様の方法により、ＮＥ製品−２（比較例
−２）を得た。NE product-2 (Comparative Example-2) was obtained by the same method as described above except that Component-8 was used instead of Component-7.

【００５１】上記製品をパネラー２０名に５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２に示す。The above product is used by 20 panelists for 5 days, and the minimum point is 1 point and the maximum point is 5 points.
The results of the sensory tests evaluated are shown in Table 2.

【００５２】[0052]

【表２】 表２ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 項目 本発明の化粧料（ＮＥ製品−１） 比較の化粧料（ＮＥ製品−２） （実施例−２） （比較例−２） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− のび ４．８ ２．５ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− つき ４．３ ３．９ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 塗布性 ４．５ １．４ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 光沢感 ４．７ ３．０ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 仕上り感 ４．５ １．２ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 色感 ４．５ １．７ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 均一性 ４．６ １．３ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝[Table 2] Table 2 ==================================== Item The cosmetic of the present invention (NE product -1) Comparative cosmetics (NE product-2) (Example-2) (Comparative example-2) ----------------------------------- ------------ No. 4.8 2.5 --------------------------------------- --- Tsuki 4.3 3.9 ----------------------------------------------- Applicability 4.5 1 .. 4 ---------------------------------------- Glossiness 4.7 3.0 ----- −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Finishing feeling 4.5 1.2 −−−−−−−−−−−−− −−−−−−− −−−−−−−−−−−−−−−− Color Sensitivity 4.5 1.7 −−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−− Uniformity 4.6 1.3 =================================== ==

【００５３】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 composition of the present invention is excellent in spreadability (extendability) and stickiness (adhesion), is easy to apply uniformly, has a good transparency and glossiness, has a good color development, and gives a finished feeling. It was confirmed to be excellent.

【００５４】実施例−３及び比較例−３ 市販の含水酸化チタンコロイド ＴｉＯ（ＯＨ）2（商品
名：チタニアゾルＣＳ−Ｎ、石原産業株式会社製、二酸
化チタン換算含有量約３０重量％、粒子径３０〜６０ｎ
ｍ、水分散）１２０ｍｌ、０．２規定の硝酸１９００ｍ
ｌ、シリコンテトラエトキシド１６３０ｍｌ、エタノー
ル１４００ｍｌを混合し、３５℃で約５０時間養生し
た。この液に、だいだい色２０３号（パーマネントオレ
ンジ）１２ｇと赤色２２８号（パーマネントレッド）１
２ｇを添加混合し、サンドミルを用いて、有機顔料を均
一に分散させ、さらに５０℃で１０時間養生して、塗布
液とした。実施例−１記載の方法でフレーク化を行い、
得られたフレークを、減圧（約１Ｐａ）下、１５０℃、
２４時間の熱処理を施した。さらに、実施例−１記載の
方法で粉砕分級を行い、有機顔料含有量約５重量％（だ
いだい色２０３号含有量約２．５重量％、赤色２２８号
含有量約２．５重量％）、二酸化チタン含有量約９．５
重量％、厚み約０．７μｍ、平均粒径約１２μｍの黄橙
色フレーク状粉体（粉体Ｄ）を得た。このフレーク状粉
体をＸ線回折法で調べたところ、アナターゼ型二酸化チ
タンが検出されたのみであり、マトリックスは非晶質状
態であった。透過型電子顕微鏡でフレークを観察したと
ころ、直径が３０〜６０ｎｍの二酸化チタン微粒子が、
マトリックス中に平均的に分散して位置しているのが観
察された。このフレーク状粉体は、互いに凝集すること
がなく、滑り性があって、独特の優れた触感を有してい
た。上記フレーク状粉体の少量を、水及び油に各々添加
して、有機顔料の溶出を観察したところ、有機顔料の溶
出はほとんど認められなかった。Example-3 and Comparative Example-3 Commercially available hydrous titanium oxide colloid TiO (OH) 2 (trade name: Titania sol CS-N, manufactured by Ishihara Sangyo Co., Ltd., content of titanium dioxide equivalent about 30% by weight, particle diameter) 30-60n
m, water dispersion) 120ml, 0.2N nitric acid 1900m
1, 1630 ml of silicon tetraethoxide and 1400 ml of ethanol were mixed and aged at 35 ° C. for about 50 hours. In this liquid, 12 g of Daidai No. 203 (Permanent Orange) and 1 of Red No. 228 (Permanent Red)
2 g were added and mixed, the organic pigment was uniformly dispersed using a sand mill, and further cured at 50 ° C. for 10 hours to obtain a coating liquid. Flaking is performed by the method described in Example-1,
The obtained flakes are treated under reduced pressure (about 1 Pa) at 150 ° C.,
Heat treatment was performed for 24 hours. Further, pulverization and classification were carried out by the method described in Example-1, and the organic pigment content was about 5% by weight (daidai No. 203 content was about 2.5% by weight, red No. 228 content was about 2.5% by weight), Titanium dioxide content of about 9.5
A yellow-orange flake powder (powder D) having a weight% of about 0.7 μm and an average particle size of about 12 μm was obtained. When the flaky powder was examined by an X-ray diffraction method, only anatase type titanium dioxide was detected and the matrix was in an amorphous state. Observation of the flakes with a transmission electron microscope revealed that titanium dioxide fine particles with a diameter of 30 to 60 nm were
It was observed that they were evenly distributed and located in the matrix. The flaky powder did not aggregate with each other, had slipperiness, and had a unique and excellent tactile sensation. When a small amount of the above flake powder was added to water and oil respectively and the elution of the organic pigment was observed, almost no elution of the organic pigment was observed.

【００５５】このフレークをビニル系樹脂（硬化後の屈
折率が約１．５）中に約１０重量％混入分散させた塗料
を基板の上に塗布乾燥して、約０．１５ｍｍ厚みのフィ
ルムとして、分光光度計で透過率を測定したところ、波
長３５０ｎｍ以下の紫外線透過率が５％以下であり、紫
外線を有効に遮蔽する着色フレーク状粉体であることが
確認された。A coating in which about 10% by weight of the flakes is mixed and dispersed in a vinyl resin (having a refractive index after curing of about 1.5) is applied on a substrate and dried to form a film having a thickness of about 0.15 mm. When the transmittance was measured with a spectrophotometer, it was confirmed that the ultraviolet ray transmittance at a wavelength of 350 nm or less was 5% or less, and the powder was a colored flake powder that effectively shielded ultraviolet rays.

【００５６】次に以下の配合でパウダーファンデーショ
ンを作製した。 成分−９ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 上記有機顔料含有フレーク状粉体（粉体Ｄ） ３．７ タルク ７７．９ マイカ ９．０ 二酸化チタン ５．４ ステアリン酸マグネシウム ２．８ シルクパウダー ０．５Next, a powder foundation was prepared with the following composition. Component-9 Blending amount (% by weight) -------------------------------------------- The above organic pigment-containing flakes Powder (Powder D) 3.7 Talc 77.9 Mica 9.0 Titanium dioxide 5.4 Magnesium stearate 2.8 Silk powder 0.5

【００５７】 成分−１０ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− スクワラン ０．５ セスキオレイン酸ソルビタン ０．１Ingredient -10 Blending amount (wt%) --------------- Squalane 0. 5 Sorbitan sesquioleate 0.1

【００５８】 成分−１１ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 香料 ０．１ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Component-11 Blending amount (% by weight) -------------------------..-- Perfume 0. 1 ------------------------------------------------

【００５９】成分−９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−１０を滴下しながら、撹拌混合を行った。さらに、
成分−１１を添加後、１分間撹拌混合し、アトマイザー
により粉砕して粉製品−１（実施例−３）を得た。Component-9 was mixed with a Henschel mixer.
Stir for 5 minutes. Stirring and mixing were performed while dripping the component-10 uniformly melted at 70 ° C. further,
After adding Component-11, the mixture was stirred and mixed for 1 minute and pulverized with an atomizer to obtain a powdered product-1 (Example-3).

【００６０】 成分−１２ 配合量（重量％） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− だいだい色２０３号 ０．１ 赤色２２８号 ０．１ タルク ８０．４ マイカ ９．７ 二酸化チタン ５．５ ステアリン酸マグネシウム ２．９ シルクパウダー ０．６Component-12 Blending amount (% by weight) -------------------------------------- No. 0.1 Red No. 228 0.1 Talc 80.4 Mica 9.7 Titanium dioxide 5.5 Magnesium stearate 2.9 Silk powder 0.6

【００６１】成分−１２をヘンシェルミキサーを用い
て、１０分間撹拌した。これに、７０℃ にて均一に溶
融した成分−１０を滴下しながら、撹拌混合を行った。
さらに、成分−１１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粉製品−２（比較例−３）を得
た。Component-12 was stirred using a Henschel mixer for 10 minutes. Stirring and mixing were carried out while dropwise adding Component-10, which was uniformly melted at 70 ° C.
Further, after adding Component-11, the mixture was stirred and mixed for 1 minute and pulverized with an atomizer to obtain a powder product-2 (Comparative Example-3).

【００６２】これら製品試料を、３００Ｗキセノンラン
プで約１５ｃｍの距離から１００時間照射して、照射前
後の色調の変化を色彩色差計（ミノルタカメラ株式会社
製ＣＲ−３００）を用いて測定した。その結果、粉製品
−１（実施例−３）では色差ΔＥが２．４であり、粉製
品−２（比較例−３）では１２．６であった。よって、
本発明の化粧料は、耐光性に優れている。These product samples were irradiated with a 300 W xenon lamp from a distance of about 15 cm for 100 hours, and the change in color tone before and after irradiation was measured using a color difference meter (CR-300 manufactured by Minolta Camera Co., Ltd.). As a result, the color difference ΔE was 2.4 for powder product-1 (Example-3) and 12.6 for powder product-2 (Comparative Example-3). Therefore,
The cosmetic of the present invention has excellent light resistance.

【００６３】上記製品を（女性）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３に示す。The above product was given to 20 (female) panelists for 10 persons.
Table 3 shows the results of the sensory test evaluated by a five-stage method in which the sample was used for a day and the minimum score was 1 and the maximum score was 5.

【００６４】[0064]

【表３】 表３ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 項目 本発明の化粧料（粉製品−１） 比較の化粧料（粉製品−２） （実施例−３） （比較例−３） −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− のび ４．６ １．９ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− つき ４．４ ３．４ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 光沢感 ４．５ ２．２ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 色感 ４．４ ３．９ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 化粧もち ４．７ ２．６ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝[Table 3] Table 3 ==================================== Item Cosmetics of the present invention (powder products -1) Comparative cosmetics (powdered product-2) (Example-3) (Comparative example-3) ------------------------------------------------------------------------------------------ ------------ No. 4.6 4.6 1.9 --------------------------------------------------------------------------------------------------------------------------------------- --- Tint 4.4 3.4 ------------------------------------ Glossiness 4.5 2 .. 2 ---------------------------------------- Color Sensitivity 4.4 3.9 ----- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Makeup Mochi 4.7 2.6 ============ =========== =============

【００６５】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、化粧もちの良いことが、確認された。As described above, it was confirmed that the cosmetics of the present invention are excellent in spreadability (extendability) and stickiness (adhesion), have a good glossy feeling, have a good color development, and have a good makeup lasting.

【００６６】[0066]

【発明の効果】以上の本発明の詳細な説明及び実施例、
比較例で明らかなように、本発明の有機顔料含有フレー
ク状粉体は、無機酸化物によって有機顔料が内包固定化
されているので、有機顔料がフレークから溶出したり、
脱離したりすることがほとんどなく、これを配合した化
粧料は耐ブリード性、耐水性、耐汗性に優れた安定な製
品となる。また、有機顔料が皮膚に直接触れないので、
非アレルギー性が向上しており、また皮膚や爪等を染め
ることがなく、さらにフレーク形状であることから、有
機顔料が汗腺や毛穴に詰まることがなく、皮膚刺激がな
い安全な製品となる。また、無機酸化物中に有機顔料が
含有されていることにより、有機顔料の安定性が向上し
ており、耐光性、耐熱性が高く、鮮やかな発色を有する
好ましい色調の製品となる。さらに、有機顔料含有フレ
ーク状粉体が、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）、分散性、付着性が良く、使用触感に優れた製
品となる。The above detailed description and embodiments of the present invention,
As is clear in Comparative Examples, the organic pigment-containing flake powder of the present invention has an organic pigment encapsulated and fixed by an inorganic oxide, so that the organic pigment is eluted from the flakes,
Almost no detachment occurs, and a cosmetic composition containing this is a stable product with excellent bleed resistance, water resistance, and sweat resistance. Also, since the organic pigment does not touch the skin directly,
Since it has improved non-allergenicity, does not stain the skin and nails, and has a flake shape, the organic pigment does not clog the sweat glands and pores, and is a safe product without skin irritation. Further, since the organic pigment is contained in the inorganic oxide, the stability of the organic pigment is improved, the light resistance and heat resistance are high, and a product having a vivid color and a preferable color tone is obtained. Furthermore, since the organic pigment-containing flake powder does not aggregate with each other and its surface is smooth and exhibits good slipperiness, it has good extensibility (spreading), dispersibility, adhesiveness, and touch feeling. It will be an excellent product.

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 有機顔料を０．５〜４０重量％含有する
金属酸化物フレーク状粉体。1. A metal oxide flake powder containing 0.5 to 40% by weight of an organic pigment. 【請求項２】 前記有機顔料が、昭和４１年８月３１日
厚生省令第３０号記載の赤色２２６号、赤色２０２号、
赤色２０３号、および赤色２０４号から選ばれる少なく
とも一種である請求項１記載のフレーク状粉体。2. The organic pigments are Red No. 226, Red No. 202 described in Ordinance No. 30 of the Ministry of Health and Welfare on August 31, 1941.
The flake powder according to claim 1, which is at least one selected from Red No. 203 and Red No. 204. 【請求項３】 前記金属酸化物が、シリカ、チタニア、
アルミナ、およびジルコニアからなる群から選ばれた少
なくとも１種である請求項１または２記載のフレーク状
粉体。3. The metal oxide is silica, titania,
The flake powder according to claim 1 or 2, which is at least one selected from the group consisting of alumina and zirconia. 【請求項４】 加水分解および縮重合可能な有機金属化
合物、有機顔料、水、および有機溶媒を含む溶液を、表
面が平滑な基板上に塗布し、これを剥離し、８０〜２５
０℃で５分間〜２４時間加熱することを特徴とする金属
酸化物フレーク状粉体の製造方法。4. A solution containing a hydrolyzable and polycondensable organometallic compound, an organic pigment, water, and an organic solvent is applied onto a substrate having a smooth surface, and the substrate is peeled off to obtain a layer of 80 to 25.
A method for producing a metal oxide flake powder, which comprises heating at 0 ° C. for 5 minutes to 24 hours. 【請求項５】 請求項１から３記載のフレーク状粉体を
配合してなる化粧料。5. A cosmetic comprising the flaky powder according to any one of claims 1 to 3.