JP2003213156A - Colored pearl glossy flake pigment - Google Patents
Colored pearl glossy flake pigmentInfo
- Publication number
- JP2003213156A JP2003213156A JP2002008163A JP2002008163A JP2003213156A JP 2003213156 A JP2003213156 A JP 2003213156A JP 2002008163 A JP2002008163 A JP 2002008163A JP 2002008163 A JP2002008163 A JP 2002008163A JP 2003213156 A JP2003213156 A JP 2003213156A
- Authority
- JP
- Japan
- Prior art keywords
- pearlescent
- pigment
- hydrotalcite
- flake
- double hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、粉体における滑り
感と塗布層における視覚効果や被覆保護効果が有用性を
もち、加えて人体無害性が要求されるメイクアップ化粧
品などの分野で着色料となる着色真珠光沢フレーク顔料
とその製造法および該フレーク顔料を配合して得られる
化粧料に係るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a usefulness in terms of a slippery feeling in powder and a visual effect and a coating protecting effect in a coating layer, and in addition, it is a coloring agent in the field of make-up cosmetics and the like in which harmlessness to the human body is required. The present invention relates to a colored pearlescent flake pigment, a method for producing the same, and a cosmetic obtained by blending the flake pigment.
【０００２】[0002]
【従来の技術】マイカ系真珠光沢顔料において、酸化チ
タンや酸化ジルコニウムなど高屈折率の無色金属酸化物
被覆層による干渉色に選択吸収による着色を重畳させる
ため、酸化鉄のような無機着色成分を被覆層に添加した
り、無機または有機着色料を粒子表面に被覆することに
よって、ゴールド色や紺青色やカルミン色の着色真珠光
沢顔料が開発され、特殊塗装やメイクアップ化粧品の分
野で活用されている。2. Description of the Related Art In mica pearlescent pigments, an inorganic coloring component such as iron oxide is added in order to superimpose the coloring by selective absorption on the interference color of a coating layer of a colorless metal oxide having a high refractive index such as titanium oxide or zirconium oxide. By adding it to the coating layer or coating the surface of the particles with an inorganic or organic coloring agent, gold, dark blue or carmine colored pearlescent pigments have been developed and used in the fields of special coating and makeup cosmetics. There is.
【０００３】[0003]
【発明が解決しようとする課題】従来技術において、無
機着色成分による着色は色相が限られる上に彩度も低
く、有機顔料による着色は人体無害性と耐溶出性の点か
ら適用できる色素が限られる。本発明では、食品衛生法
または薬事法で食品、医薬品、医薬部外品および化粧品
用に規定されたアニオン性タール色素を用いて、赤、
黄、青にわたる色相で彩度の高い着色真珠光沢フレーク
顔料を提供する。In the prior art, coloring with an inorganic coloring component has a limited hue and low saturation, and coloring with an organic pigment limits the dyes that can be applied from the viewpoints of harmlessness to human body and elution resistance. To be In the present invention, food, pharmaceuticals, quasi-drugs and cosmetics using the anionic tar dye defined by the Food Sanitation Law or Pharmaceutical Affairs Law, red,
Provided is a colored pearlescent flake pigment having a high saturation in a hue ranging from yellow and blue.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、アニオン
性タール色素をハイドロタルサイト型無機層状複水酸化
物の層間に導入して不溶化した着色組成物（ハイドロタ
ルサイト型着色組成物と称する）を、タルク、マイカ、
セリサイト、カオリン等の無機フレーク状粒子の表面に
均一な被覆層として生成させる方法を見出し、新規な着
色フレーク顔料を開発した（特開2001-234090）。この
方法を真珠光沢無機フレーク粒子に適用することによっ
て、本発明に至った。Means for Solving the Problems The inventors of the present invention have introduced a coloring composition (hydrotalcite-type coloring composition and Talc, mica,
A method for forming a uniform coating layer on the surface of inorganic flake particles such as sericite and kaolin was found, and a novel colored flake pigment was developed (JP 2001-234090). The present invention was achieved by applying this method to pearlescent inorganic flake particles.
【０００５】即ち、本発明が提供するのは、真珠光沢無
機フレーク状粒子表面にハイドロタルサイト型着色組成
物の被覆層を有することを特徴とする着色真珠光沢フレ
ーク顔料であり、また、その製造法として、真珠光沢無
機フレーク状粒子を含有する水性懸濁液中で可溶アニオ
ン色素と複数の可溶性金属塩と中和用塩基とを反応させ
て、該真珠光沢無機フレーク状粒子表面上にハイドロタ
ルサイト型着色組成物を析出生成させることを特徴とす
る方法であり、さらに、該着色真珠光沢フレーク顔料を
含有することを特徴とする化粧料である。That is, the present invention provides a colored pearlescent flake pigment characterized by having a coating layer of a hydrotalcite type coloring composition on the surface of pearlescent inorganic flake particles, and the production thereof. As a method, a soluble anionic dye, a plurality of soluble metal salts, and a neutralizing base are reacted in an aqueous suspension containing pearlescent inorganic flake-like particles, and hydrolyzed onto the surface of the pearlescent inorganic flake-like particles. A method characterized by depositing and forming a talcite-type coloring composition, and a cosmetic characterized by containing the colored pearlescent flake pigment.
【０００６】[0006]
【発明の実施の形態】ハイドロタルサイト型着色組成物
とは、マグネシウム、カルシウム、亜鉛等の二価金属イ
オン（Ｍ）とアルミニウムのような三価金属イオン
（Ｍ’）から形成させるハイドロタルサイト型層状複水
酸化物［Ｍ1-x Ｍ'x (ＯＨ)2 ］(Ａn-)x/n・m Ｈ2Ｏ
（0.2≦ｘ≦0.33）において、層間アニオン（Ａn- ）と
して色素アニオンを導入して得られる層状の結晶構造を
もった着色組成物であり、これを生成させるには大別し
て３種の方法がある。第１は、Ａn- がＣl-であるＣl形
ハイドロタルサイトをアニオン色素水溶液に接してアニ
オン交換させるイオン交換法である。第２は、ＣＯ3形
ハイドロタルサイトを約500℃で焼成し、脱水・脱炭酸
させて一旦無定形酸化物としたのち、水溶液中で色素ア
ニオンと反応させ、アニオン交換された形でハイドロタ
ルサイト構造を再生させる再構築法である。第３は、前
記組成式に従う複数の金属塩溶液と色素溶液および中和
当量の塩基溶液を適宜の方法で混合して、色素アニオン
形ハイドロタルサイトを析出させる直接生成法である。
それぞれの方法によって到達される色素含有量を前記組
成式による理論量と比較し百分率として表わすと、赤色
201号の場合、第１の方法では75％まで、第２の方法で
は45％までであるのに対し、第３の方法では95％以上で
色素アニオンを含有するハイドロタルサイト型着色組成
物が得られる（久保、辻：色材協会誌，69［10］，667
−677頁（1996年））。本発明のためにはいずれの方法
も採用しうるが、濃色の着色フレーク顔料を得る目的に
は、この直接生成法が最も適している。BEST MODE FOR CARRYING OUT THE INVENTION A hydrotalcite-type coloring composition is a hydrotalcite formed from a divalent metal ion (M) such as magnesium, calcium or zinc and a trivalent metal ion (M ') such as aluminum. Type layered double hydroxide [M 1-x M'x (OH) 2 ] (A n- ) x / n · m H 2 O
(0.2 ≦ x ≦ 0.33), a coloring composition having a layered crystal structure obtained by introducing a dye anion as an interlayer anion (A n− ). To produce this, there are roughly three methods. There is. First, A n-it is Cl - ion exchange method in which anion exchange against the Cl form hydrotalcite anionic dye solution is. Second, after burning the CO 3 type hydrotalcite at about 500 ° C, dehydrating and decarboxylating it to form an amorphous oxide, it is reacted with the dye anion in an aqueous solution, and the anion exchanged form of hydrotalcite is used. It is a reconstruction method that reproduces the site structure. The third is a direct production method in which a dye anion type hydrotalcite is precipitated by mixing a plurality of metal salt solutions according to the above composition formula, a dye solution and a neutralization equivalent amount of a base solution by an appropriate method.
When the dye content reached by each method is compared with the theoretical amount according to the above composition formula and expressed as a percentage, red color is obtained.
In the case of No. 201, in the first method, up to 75%, and in the second method, up to 45%, whereas in the third method, a hydrotalcite-type coloring composition containing 95% or more of a dye anion is used. Obtained (Kubo, Tsuji: Journal of Coloring Materials, 69 [10], 667
-677 (1996)). Although either method may be employed for the present invention, this direct production method is most suitable for the purpose of obtaining a dark colored flake pigment.
【０００７】本発明の製法で使用される金属塩として
は、人体無害性の観点から、二価金属に対してはマグネ
シウム、カルシウム、亜鉛等の塩化物、硫酸塩、硝酸塩
等が、三価金属に対してはアルミニウムの塩化物、硫酸
塩、硝酸塩等およびアルミン酸ナトリウムが用いられ
る。中和に用いる塩基物質としては、水酸化ナトリウム
やアンモニアや尿素等を用いうるが、炭酸ナトリウムは
ＣＯ3形ハイドロタルサイトを優先して生成させるため
不可である。アニオン色素としては、食用黄色４号(Tar
trazine)，黄色５号(Sunset Yellow FCF)，青色１号(Br
illiant Blue FCF)，赤色３号(Erythrosine)，赤色104
号(Floxine B)，赤色201号(Lithol Rubin B)等の、食品
衛生法または薬事法で規定された食品、医薬品、医薬部
外品および化粧品用タール色素の中から選ばれる可溶性
アニオン色素が用いられる。From the viewpoint of harmlessness to the human body, the metal salts used in the production method of the present invention include chlorides such as magnesium, calcium, zinc, etc., sulfates, nitrates, etc., and trivalent metals. For aluminum, aluminum chloride, sulfate, nitrate, etc. and sodium aluminate are used. As the basic substance used for neutralization, sodium hydroxide, ammonia, urea and the like can be used, but sodium carbonate is not possible because CO 3 type hydrotalcite is preferentially produced. As an anionic dye, food yellow No. 4 (Tar
trazine), Yellow 5 (Sunset Yellow FCF), Blue 1 (Br
illiant Blue FCF), Red No. 3 (Erythrosine), Red 104
No. (Floxine B), Red No. 201 (Lithol Rubin B), and other soluble anion dyes selected from tar dyes for foods, pharmaceuticals, quasi-drugs, and cosmetics specified by the Food Sanitation Law or Pharmaceutical Affairs Law are used. To be
【０００８】製造工程においては、前記の原料物質をそ
れぞれ水に溶解し（赤色201号のように溶解度の低いも
のは懸濁させ）、アニオン色素の種類に応じて２種ない
し４種、あるいは５種（尿素を添加する場合）の別個の
溶液としたのち、最終的にはこれらを真珠光沢無機フレ
ーク状粒子を分散させた懸濁液と合して一つに混合す
る。反応槽中にはフレーク粒子懸濁液および色素溶液と
予め混合できる原料溶液とを入れ、よく攪拌しつつこの
中にその他の原料溶液を滴下混合する。予め混合できる
原料溶液の組み合わせは、各原料の反応性などを考慮し
て決められる。青色１号のように耐酸性および耐塩基性
を欠く色素に対しては、反応槽中で色素溶液のｐＨを終
始中性域に保つために、金属塩溶液と中和塩基溶液を同
時滴下することも必要になる。赤色201号のように耐塩
基性の大きな色素においては、アルミン酸ナトリウム溶
液あるいは中和塩基溶液と予め混合しておくことができ
る。滴下混合終了後80℃以上に加温熟成することによ
り、徐々にハイドロタルサイト型着色組成物が真珠光沢
無機フレーク状粒子表面に生成する。生成速度は原料物
質および混合方法によって異なり、半日から数日であ
る。In the manufacturing process, each of the above-mentioned raw materials is dissolved in water (suspended ones having low solubility such as Red No. 201 are suspended), and 2 to 4 or 5 depending on the type of anionic dye. After a separate solution of seeds (if urea is added), they are finally combined with a suspension of pearlescent inorganic flake particles in a single mixture. A flake particle suspension and a raw material solution that can be mixed with the dye solution in advance are placed in the reaction tank, and the other raw material solutions are dropped and mixed therein while being well stirred. The combination of raw material solutions that can be mixed in advance is determined in consideration of the reactivity of each raw material. For dyes lacking acid and base resistance, such as Blue No. 1, a metal salt solution and a neutralizing base solution are added dropwise at the same time in order to keep the pH of the dye solution in a neutral range throughout the reaction tank. You also need that. In the case of a dye having a large base resistance such as Red No. 201, it can be mixed in advance with a sodium aluminate solution or a neutralized base solution. After completion of the dropwise mixing, the hydrotalcite-type coloring composition is gradually formed on the surface of the pearlescent inorganic flake-like particles by heating and aging at 80 ° C. or higher. The production rate depends on the raw materials and the mixing method, and is from half a day to several days.
【０００９】前述の方法で真珠光沢無機フレーク状粒子
表面をハイドロタルサイト型着色組成物で被覆すること
ができるが、被覆物の性状には用いる原料と中和方法に
よって顕著な差異が生ずる。金属塩化物を原料として用
い水酸化ナトリウムで中和する方法では微粒子集合体に
よる被覆となり、粒子表面の平滑性が失われる。同じ原
料で水酸化ナトリウムの６分の１〜全部を尿素に替える
と、均一で平滑な被覆が得られる。The surface of the pearlescent inorganic flake particles can be coated with the hydrotalcite-type coloring composition by the above-mentioned method. However, the properties of the coating material are significantly different depending on the raw material used and the neutralization method. In the method in which metal chloride is used as a raw material and is neutralized with sodium hydroxide, the particles are covered with a fine particle aggregate and the smoothness of the particle surface is lost. If one-sixth of all sodium hydroxide is replaced by urea with the same raw material, a uniform and smooth coating is obtained.
【００１０】[0010]
【作用】ハイドロタルサイト型着色組成物が雲母系の真
珠光沢無機フレーク状粒子表面に析出し被覆するという
作用について、次のような説明を与えることができる。
真珠光沢無機フレーク状粒子の表面層をなす金属酸化物
は、下地の粘土鉱物の結晶構造に対しある程度の方位性
をもって生成している。このため、ブルーサイト(Mg(O
H)2)型平面６角網状層によって粘土鉱物の構造との整合
性をもつハイドロタルサイト型構造は、この金属酸化物
層とも酸素イオンの配置を介して整合しうる。このこと
によって、原料混合溶液からのハイドロタルサイト型構
造の生成は該フレーク粒子表面で容易となるが、その核
生成が表面上の各所で同時多発的に起れば、被覆は微粒
子集合体となって表面平滑性を失うに至る。中和塩基の
一部もしくは全部を尿素に置き換えて添加することは、
核生成速度を遅らせランダムな核生成を抑制する効果を
もち、その結果平滑な表面被覆が形成されるものと推定
される。The following explanation can be given for the action of the hydrotalcite-type coloring composition depositing and coating on the surface of the mica-based pearlescent inorganic flake particles.
The metal oxide forming the surface layer of the pearlescent inorganic flake particles is generated with a certain degree of orientation with respect to the crystal structure of the underlying clay mineral. Therefore, the brucite (Mg (O
The hydrotalcite-type structure, which is compatible with the structure of the clay mineral by the H) 2 ) type plane hexagonal net-like layer, can also be matched with this metal oxide layer through the arrangement of oxygen ions. This facilitates the formation of the hydrotalcite-type structure from the mixed solution of the raw materials on the surface of the flake particles, but if the nucleation of the flake particles occurs at multiple points on the surface at the same time, the coating forms a fine particle aggregate. And the surface smoothness is lost. Replacing part or all of the neutralizing base with urea and adding
It has the effect of slowing the nucleation rate and suppressing random nucleation, and as a result, it is presumed that a smooth surface coating is formed.
【００１１】[0011]
【実施例】次に、本発明の具体的態様を示すために、代
表的な実施例及び配合例を挙げるが、本発明の技術的範
囲を限定するものではない。EXAMPLES Next, typical examples and formulation examples will be given to show specific embodiments of the present invention, but the technical scope of the present invention is not limited thereto.
【００１２】実施例１
赤色201号（純度92.5％）11.6g、0.5N-NaOH 620mLおよ
びパールマイカ（日本光研工業(株)、色：シルバー、粒
度：5-30μm、TiO2被覆率：38％）50.0gを2Lの三角フラ
スコ中にとり、煮沸して脱炭酸した水に溶解して全量1,
000mLの均一な分散液とする。 別にZnCl2 13.6gとAlCl3
・6H2O 12.1gとを水に溶解して300mLとした溶液を作
り、上記の分散液中に攪拌しつつ室温で１時間かけて滴
下混合する。水を加えて全量を1,500mLとしたのち室温
でさらに1時間攪拌を続け、次いで100℃に加温して24時
間還流しつつ攪拌する。この熟成によってパールマイカ
粒子表面にハイドロタルサイト型着色組成物が生成し、
赤色が鮮明化する。熟成終了後室温まで冷却し、生成物
を濾過して濾液が殆ど無色になるまで水で繰り返し洗浄
を行ったのち、50℃で乾燥する。この方法により赤色真
珠光沢フレーク顔料73.3gを得た。生成物は乾燥時に凝
集する傾向を示し、走査型電子顕微鏡観察によれば、フ
レーク粒子表面に微細析出物の集積が見られた。 Example 1 Red No. 201 (purity 92.5%) 11.6 g, 0.5 N-NaOH 620 mL and pearl mica (Nippon Koken Kogyo KK, color: silver, particle size: 5-30 μm, TiO 2 coverage: 38 %) 50.0 g in a 2 L Erlenmeyer flask and dissolved in water that has been boiled and decarbonated to give a total volume of 1.
Make a uniform dispersion of 000 mL. Separately, 13.6 g ZnCl 2 and AlCl 3
・ 6H 2 O (12.1 g) was dissolved in water to prepare a 300 mL solution, and the mixture was added dropwise to the above dispersion liquid while stirring at room temperature for 1 hour. Water is added to bring the total volume to 1,500 mL, and stirring is continued at room temperature for another hour, then heated to 100 ° C. and stirred for 24 hours under reflux. By this aging, hydrotalcite-type coloring composition is generated on the surface of pearl mica particles,
The red color becomes clear. After completion of aging, the mixture is cooled to room temperature, the product is filtered, repeatedly washed with water until the filtrate becomes almost colorless, and then dried at 50 ° C. This method gave 73.3 g of red pearlescent flake pigment. The product showed a tendency to aggregate when dried, and accumulation of fine precipitates was observed on the surface of the flake particles by scanning electron microscope observation.
【００１３】実施例２
黄色４号（純度89.4％）10.0g、0.5N-NaOH 620mLおよび
パールマイカ（メルク・ジャパン(株）、色：シルバ
ー、粒度：10-60μm、TiO2被覆率：29％）50.0gを2Lの
三角フラスコ中にとり、煮沸して脱炭酸した水を用いて
全量 1,000mLの均一な分散液とする。別にMgCl2・6H2O
20.3gとAlCl3・6H2O 12.1gとを水に溶解して300mLとし
た溶液を作り、上記の分散液中に攪拌しつつ室温で1時
間かけて滴下混合する。以下、実施例１と同様に行っ
て、黄色真珠光沢フレーク顔料72.6gが得られ、同様の
粒子性状を示した。 Example 2 Yellow No. 4 (purity 89.4%) 10.0 g, 0.5N-NaOH 620 mL and pearl mica (Merck Japan KK, color: silver, particle size: 10-60 μm, TiO 2 coverage: 29% ) Transfer 50.0g into a 2L Erlenmeyer flask and use water that has been decarbonated to boil to make a uniform dispersion of 1,000mL. Separately MgCl 2 6H 2 O
20.3 g and AlCl 3 .6H 2 O 12.1 g were dissolved in water to make a solution of 300 mL, and the solution was added dropwise to the above dispersion liquid while stirring at room temperature for 1 hour. Thereafter, the same procedure as in Example 1 was carried out to obtain 72.6 g of a yellow pearlescent flake pigment, which showed similar particle properties.
【００１４】実施例３
黄色５号（純度91.6％）12.4g、0.5N-NaOH 620mLおよび
パールマイカ（メルク・ジャパン(株）、色：シルバ
ー、粒度：10-60μm、TiO2被覆率：29％）50.0gを2Lの
三角フラスコ中にとり、煮沸して脱炭酸した水を用いて
全量1,000mLの均一な分散液とする。別にMgCl2・6H2O 2
0.3gとAlCl3・6H2O 12.1gとを水に溶解して300mLとした
溶液を作り、上記の分散液中に攪拌しつつ室温で1時間
かけて滴下混合する。以下、実施例１と同様に行って、
橙色真珠光沢フレーク顔料72.1gが得られ、同様の粒子
性状を示した。 Example 3 Yellow No. 5 (purity 91.6%) 12.4 g, 0.5 N-NaOH 620 mL and pearl mica (Merck Japan KK, color: silver, particle size: 10-60 μm, TiO 2 coverage: 29% ) Take 50.0g in a 2L Erlenmeyer flask and make a uniform dispersion of 1,000mL in total by boiling and decarbonating water. Separately MgCl 2 .6H 2 O 2
0.3 g and 12.1 g of AlCl 3 .6H 2 O are dissolved in water to make a solution of 300 mL, and the solution is added dropwise to the above dispersion liquid while stirring at room temperature for 1 hour. Thereafter, the same procedure as in Example 1 is performed,
72.1 g of orange pearlescent flake pigment was obtained, showing similar particle properties.
【００１５】実施例４
青色１号（純度91.6％）21.6gとパールマイカ（エンゲ
ルハード社、色：シルバー、平均粒子径：28μm、TiO2
被覆率：17％）50.0 gを2Lの三角フラスコ中にとり、煮
沸して脱炭酸した水に溶解して全量300mLの均一な分散
液とする。別にMgCl2・6H2O 20.3gを水に溶解して300mL
とした溶液とAlCl3・6H2O 12.1gを水に溶解して300mLと
した溶液を作り、１N-NaOH溶液 300mLとともに、３溶液
同時的に上記の分散液中に攪拌しつつ室温で１時間かけ
て滴下混合する。水を加えて全量を1,500mLとしたのち
室温でさらに1時間攪拌を続け、次いで100℃に加温して
24時間還流しつつ攪拌する。この熟成によってパールマ
イカ粒子表面にハイドロタルサイト型着色組成物が生成
し、青色が鮮明化する。以下、実施例１と同様に行っ
て、青色真珠光沢フレーク顔料72.2gが得られ、同様の
粒子性状を示した。 Example 4 21.6 g of Blue No. 1 (purity 91.6%) and pearl mica (Engelhard, color: silver, average particle size: 28 μm, TiO 2
Coverage: 17%) Take 50.0 g in a 2 L Erlenmeyer flask and dissolve it in water that has been boiled and decarbonated to make a uniform dispersion of 300 mL in total. 300mL of MgCl 2 · 6H 2 O 20.3g was dissolved in water separately
And AlCl 3 6H 2 O 12.1g were dissolved in water to make a 300mL solution, and together with 1N-NaOH solution 300mL, 3 solutions were simultaneously stirred in the above dispersion for 1 hour at room temperature. Pour and mix dropwise. Add water to bring the total volume to 1,500 mL, continue stirring at room temperature for another hour, and then heat to 100 ° C.
Stir at reflux for 24 hours. By this aging, a hydrotalcite-type coloring composition is produced on the surface of the pearl mica particles, and the blue color becomes clear. Thereafter, the same procedure as in Example 1 was carried out to obtain 72.2 g of a blue pearlescent flake pigment, which showed similar particle properties.
【００１６】実施例５
赤色201号（純度92.5％）11.6g、0.5N-NaOH 300mL、パ
ールマイカ（エンゲルハード社、平均粒子径：28μm、T
iO2被覆率：17％）50.0g、MgCl2・6H2O 20.3g、AlCl3・
6H2O 12.1gおよび尿素41.9gを2Lの三角フラスコ中にと
り、全量 1,500mLの均一な分散液とする。次いで100℃
に加温して24時間還流しつつ攪拌する。尿素の分解とと
もに中和反応が進行し、パールマイカ粒子表面にハイド
ロタルサイト型着色組成物が生成して、赤色が鮮明化す
る。以下、実施例１と同様に行って、赤色真珠光沢フレ
ーク顔料73.3gを得た。生成物は乾燥時の凝集が少な
く、実施例１よりも滑り感の良い粉体が得られた。走査
型電子顕微鏡観察によれば、フレーク粒子表面は析出物
により均一に被覆されていた。 Example 5 Red No. 201 (purity 92.5%) 11.6 g, 0.5 N-NaOH 300 mL, pearl mica (Engelhard Co., average particle size: 28 μm, T
iO 2 coverage: 17%) 50.0g, MgCl 2・ 6H 2 O 20.3g, AlCl 3・
Dispense 12.1 g of 6H 2 O and 41.9 g of urea into a 2 L Erlenmeyer flask to make a uniform dispersion with a total volume of 1,500 mL. Then 100 ° C
Warm up and stir under reflux for 24 hours. A neutralization reaction proceeds with the decomposition of urea, a hydrotalcite-type coloring composition is formed on the surface of the pearl mica particles, and the red color becomes clear. Thereafter, the same procedure as in Example 1 was carried out to obtain 73.3 g of a red pearlescent flake pigment. The product was less agglomerated upon drying, and a powder having a slippery feel better than that of Example 1 was obtained. According to scanning electron microscope observation, the surface of the flake particles was uniformly covered with the precipitate.
【００１７】実施例６
黄色４号（純度89.4％）10.0g、パールマイカ（エンゲ
ルハード社、平均粒子径：28μm、TiO2被覆率：17％）5
0.0g、ZnCl2 13.6g、AlCl3・6H2O 12.1gおよび尿素41.9
gを2Lの三角フラスコ中にとり、全量 1,500mLの均一な
水分散液とする。以下、実施例５と同様に行って、黄色
真珠光沢フレーク顔料67.8gを得た。生成物は乾燥時の
凝集が少なく、実施例２よりも滑り感の良い粉体が得ら
れた。 Example 6 Yellow No. 4 (purity 89.4%) 10.0 g, pearl mica (Engelhard, average particle size: 28 μm, TiO 2 coverage: 17%) 5
0.0g, ZnCl 2 13.6g, AlCl 3 · 6H 2 O 12.1g and urea 41.9
Transfer g to a 2 L Erlenmeyer flask to make a uniform aqueous dispersion with a total volume of 1,500 mL. Then, the same procedure as in Example 5 was carried out to obtain 67.8 g of a yellow pearlescent flake pigment. The product was less agglomerated during drying, and a powder having a slippery feel as compared with Example 2 was obtained.
【００１８】実施例７
黄色５号（91.6 %）12.4g、パールマイカ（日本光研工
業(株）、色：シルバー、粒度：5-30μm、TiO2被覆率：
38 %）50.0g、MgCl2・6H2O 20.3g、AlCl3・6H2O 12.1g
および尿素41.9gを2Lの三角フラスコ中にとり、全量 1,
500mLの均一な水分散液とする。以下、実施例５と同様
に行って、橙色真珠光沢フレーク顔料73.1gを得た。生
成物は乾燥時の凝集が少なく、実施例３よりも滑り感の
良い粉体が得られた。 Example 7 Yellow No. 5 (91.6%) 12.4 g, pearl mica (Nihon Koken Kogyo KK, color: silver, particle size: 5-30 μm, TiO 2 coverage:
38%) 50.0g, MgCl 2 · 6H 2 O 20.3g, AlCl 3 · 6H 2 O 12.1g
And 41.9 g of urea in a 2 L Erlenmeyer flask, the total amount 1,
Make 500 mL of uniform water dispersion. Thereafter, the same procedure as in Example 5 was carried out to obtain 73.1 g of an orange pearlescent flake pigment. The product was less agglomerated during drying, and a powder having a slippery feel as compared with Example 3 was obtained.
【００１９】実施例８
青色１号（純度91.6％）21.6gとパールマイカ（エンゲ
ルハード社、平均粒子径：28μm、TiO2被覆率：17％）5
0.0g、ZnCl2 13.6g、AlCl3・6H2O 12.1gおよび尿素41.9
gを2Lの三角フラスコ中にとり、全量 1,500mLの均一な
水分散液とする。次いで100℃に加温して24時間還流し
つつ攪拌する。尿素の分解とともに中和反応が進行し、
パールマイカ粒子表面にハイドロタルサイト型着色組成
物が生成して、青色が鮮明化する。以下、実施例５と同
様に行って、濃青色真珠光沢フレーク顔料79.2gを得
た。生成物は乾燥時の凝集が少なく、実施例４よりも滑
り感の良い粉体が得られた。 Example 8 21.6 g of Blue No. 1 (purity 91.6%) and pearl mica (Engelhard Co., average particle size: 28 μm, TiO 2 coverage: 17%) 5
0.0g, ZnCl 2 13.6g, AlCl 3 · 6H 2 O 12.1g and urea 41.9
Transfer g to a 2 L Erlenmeyer flask to make a uniform aqueous dispersion with a total volume of 1,500 mL. Then, the mixture is heated to 100 ° C. and stirred under reflux for 24 hours. The neutralization reaction proceeds with the decomposition of urea,
A hydrotalcite-type coloring composition is formed on the surface of the pearl mica particles, and the blue color becomes clear. Thereafter, the same procedure as in Example 5 was carried out to obtain 79.2 g of a dark blue pearlescent flake pigment. The product was less agglomerated during drying, and a powder having a slippery feel as compared with Example 4 was obtained.
【００２０】実施例９
青色１号（純度91.6％）21.6gとパールマイカ（エンゲ
ルハード社、平均粒子径：28μm、TiO2被覆率：17％）5
0.0g、ZnCl2 3.40g、AlCl3・6H2O 3.03gおよび尿素10.5
gを2Lの三角フラスコ中にとり、全量 1,500mLの均一な
水分散液とする。以下、実施例８と同様に行って、滑り
感がより良い青色真珠光沢フレーク顔料56.4gを得た。 Example 9 21.6 g of Blue No. 1 (purity 91.6%) and pearl mica (Engelhard Co., average particle size: 28 μm, TiO 2 coverage: 17%) 5
0.0g, ZnCl 2 3.40g, AlCl 3 · 6H 2 O 3.03g and urea 10.5
Transfer g to a 2 L Erlenmeyer flask to make a uniform aqueous dispersion with a total volume of 1,500 mL. Thereafter, the same procedure as in Example 8 was carried out to obtain 56.4 g of a blue pearlescent flake pigment having a better sliding feeling.
【００２１】実施例１０
青色１号（純度91.6％）1.35gとパールマイカ（エンゲ
ルハード社、平均粒子径：28μm、TiO2被覆率：17％）5
0.0g、ZnCl2 0.85g、AlCl3・6H2O 0.76gおよび尿素2.62
gを2Lの三角フラスコ中にとり、全量 1,500mLの均一な
水分散液とする。以下、実施例８と同様に行って、滑り
感がより良く、真珠光沢がより明瞭な淡青色真珠光沢フ
レーク顔料50.8gを得た。 Example 10 1.35 g of Blue No. 1 (purity 91.6%) and pearl mica (Engelhard, average particle size: 28 μm, TiO 2 coverage: 17%) 5
0.0g, ZnCl 2 0.85g, AlCl 3 · 6H 2 O 0.76g and urea 2.62
Transfer g to a 2 L Erlenmeyer flask to make a uniform aqueous dispersion with a total volume of 1,500 mL. Thereafter, the same procedure as in Example 8 was carried out to obtain 50.8 g of a pale blue pearlescent flake pigment having a better slippery feel and a clearer pearlescence.
【００２２】実施例１１
実施例５で得られた着色真珠光沢フレーク顔料を用い
て、次の処方により口紅を調製した。
油分：マイクロクリスタリンワックス １０部
セレシン １０部
トリイソオクタン酸グリセリル １０部
ワセリン １０部
トリイソグリセリン酸グリセリル ２０部
粉体：二酸化チタン ２部
本発明顔料（実施例５） １８部
製法：ワックスと油剤を加熱融解して均一に混ぜる。こ
れに粉体を加えホモミキサーで均一に分散したのち、型
に流し込み急冷し、スティック状とする。 Example 11 Using the colored pearlescent flake pigment obtained in Example 5, a lipstick was prepared according to the following formulation. Oil: Microcrystalline wax 10 parts Ceresin 10 parts Glyceryl triisooctanoate 10 parts Vaseline 10 parts Glyceryl triisoglycerate 20 parts Powder: Titanium dioxide 2 parts Pigment of the present invention (Example 5) 18 parts Manufacturing method: heating wax and oil agent Thaw and mix evenly. Powder is added to this and uniformly dispersed with a homomixer, then poured into a mold and rapidly cooled to form a stick.
【００２３】[0023]
【発明の効果】干渉色による真珠光沢とタール色素によ
る鮮明な着色を併せ持つ新規な着色真珠光沢フレーク顔
料を創製し、化粧料や人体無害性を要求される塗装の用
途で有用な着色料となる可能性をもたらす。EFFECTS OF THE INVENTION A novel colored pearlescent flake pigment having both pearly luster due to interference color and vivid coloring with tar dye is created, and becomes a useful colorant for cosmetics and coating applications requiring human harmlessness. Bring the possibilities.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１４年３月２７日（２００２．３．２
７）[Submission date] March 27, 2002 (2002.3.2)
7)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【特許請求の範囲】[Claims]
【請求項７】色素アニオンを結晶構造層間に含有するハ
イドロタルサイト型層状複水酸化物を真珠光沢無機フレ
ーク状粒子表面に被覆層として有することを特徴とする
着色真珠光沢フレーク顔料を含有することを特徴とする
化粧料。
─────────────────────────────────────────────────────
7. A colored pearlescent flake pigment comprising a hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers as a coating layer on the surface of pearlescent inorganic flake particles. Cosmetics characterized by: ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１４年１２月４日（２００２．１２．
４）[Submission date] December 4, 2002 (2002.12.
4)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２０】実施例９
青色１号（純度９１．６％）５．４ｇとパールマイカ
（エンゲルハード社、平均粒子径：２８μｍ、ＴｉＯ２
被覆率：１７％）５０．０ｇ、ＺｎＣｌ２３．４０ｇ、
ＡｌＣｌ３・６Ｈ２Ｏ ３．０３ｇおよび尿素１０．５
ｇを２Ｌの三角フラスコ中にとり、全量１，５００ｍＬ
の均一な水分散液とする。以下、実施例８と同様に行っ
て、滑り感がより良い青色真珠光沢フレーク顔料５６．
４ｇを得た。 Example 9 5.4 g of Blue No. 1 (purity 91.6%) and pearl mica (Engelhard Co., average particle size: 28 μm, TiO 2
Coverage: 17%) 50.0 g, ZnCl 2 3.40 g,
AlCl 3 .6H 2 O 3.03 g and urea 10.5
g in a 2 L Erlenmeyer flask and the total volume is 1,500 mL
To make a uniform aqueous dispersion. Thereafter, the same procedure as in Example 8 is carried out to obtain a blue pearlescent flake pigment 56.
4 g was obtained.
フロントページの続き (72)発明者 石井孝定 愛知県宝飯郡小坂井町大字伊奈字南山新田 258−８ Ｆターム(参考） 4C083 AB242 AB431 AB432 AC012 AC422 AC792 CC11 CC13 DD11 FF01 4J037 AA26 AA27 AA29 CA09 CA10 CA18 CB28 DD10 EE03 EE19 EE28 EE43 FF02 Continued front page (72) Inventor Takasada Ishii Minamiyama Nitta, Ina, Kozai-cho, Hohan-gun, Aichi 258-8 F-term (reference) 4C083 AB242 AB431 AB432 AC012 AC422 AC792 CC11 CC13 DD11 FF01 4J037 AA26 AA27 AA29 CA09 CA10 CA18 CB28 DD10 EE03 EE19 EE28 EE43 FF02
Claims (7)
イドロタルサイト型層状複水酸化物を真珠光沢無機フレ
ーク状粒子表面に被覆層として有することを特徴とする
着色真珠光沢フレーク顔料。1. A colored pearlescent flake pigment comprising a hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers as a coating layer on the surface of pearlescent inorganic flake particles.
ク、マイカ、セリサイト、カオリンから選ばれる天然粘
土鉱物または人造の粘土鉱物に屈折率の高い金属酸化物
を被覆した無機フレーク状粒子であることを特徴とする
請求項１に記載の顔料2. The pearlescent inorganic flake particles are inorganic flake particles obtained by coating a natural clay mineral selected from talc, mica, sericite and kaolin or an artificial clay mineral with a metal oxide having a high refractive index. The pigment according to claim 1, characterized in that
がマグネシウム、カルシウム、亜鉛の二価金属から選ば
れる少なくとも１種とアルミニウムとの複水酸化物であ
ることを特徴とする請求項１に記載の顔料3. The hydrotalcite-type layered double hydroxide is a double hydroxide of at least one selected from divalent metals of magnesium, calcium and zinc and aluminum. Described pigment
法で規定された食品、医薬品、医薬部外品および化粧品
用タール色素の中から選ばれる可溶性アニオン色素に由
来するアニオンであることを特徴とする請求項１に記載
の顔料4. The anion derived from a soluble anion dye selected from food, pharmaceutical, quasi drug and cosmetic tar dyes specified by the Food Sanitation Law or the Pharmaceutical Affairs Law. The pigment according to claim 1.
イドロタルサイト型層状複水酸化物を被覆層として真珠
光沢無機フレーク状粒子の表面上に有する着色真珠光沢
フレーク顔料の製造法であって、真珠光沢無機フレーク
状粒子を含有する水性懸濁液中で可溶性アニオン色素と
該層状複水酸化物の原料となる複数の可溶性金属塩と中
和用塩基とを反応させ、該真珠光沢無機フレーク状粒子
表面上に該ハイドロタルサイト型層状複水酸化物を析出
生成させることを特徴とする着色真珠光沢フレーク顔料
の製造法5. A method for producing a colored pearlescent flake pigment, which comprises a hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers as a coating layer on the surface of pearlescent inorganic flake particles. In an aqueous suspension containing pearlescent inorganic flake particles, a soluble anionic dye, a plurality of soluble metal salts as raw materials for the layered double hydroxide, and a neutralizing base are reacted to form a pearlescent inorganic flake A method for producing a colored pearlescent flake pigment, which comprises depositing and forming the hydrotalcite-type layered double hydroxide on the particle surface.
部が尿素であることを特徴とする請求項５に記載の製造
法。6. The method according to claim 5, wherein at least a part or all of the neutralizing base is urea.
イドロタルサイト型層状複水酸化物を真珠光沢無機フレ
ーク状粒子表面に被覆層として有することを特徴とする
着色真珠光沢フレーク顔料を含有することを特徴とする
化粧料。7. A colored pearlescent flake pigment comprising a hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers as a coating layer on the surface of pearlescent inorganic flake particles. Cosmetics characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002008163A JP2003213156A (en) | 2002-01-17 | 2002-01-17 | Colored pearl glossy flake pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002008163A JP2003213156A (en) | 2002-01-17 | 2002-01-17 | Colored pearl glossy flake pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003213156A true JP2003213156A (en) | 2003-07-30 |
Family
ID=27646503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002008163A Pending JP2003213156A (en) | 2002-01-17 | 2002-01-17 | Colored pearl glossy flake pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003213156A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257176A (en) * | 2005-03-16 | 2006-09-28 | Daito Kasei Kogyo Kk | Dissolution-resistant pigment of colored, glossy glass flake and cosmetic blended with the same |
| KR100743674B1 (en) | 2006-08-28 | 2007-07-30 | 한국화학연구원 | The pearlescent pigments with large aspect ratio and preparation method them |
| WO2007116769A1 (en) | 2006-03-27 | 2007-10-18 | Nippon Sheet Glass Company, Limited | Brightening pigment with gold tone and cosmetic preparation, coating material, ink, or resin composition each containing the same |
| WO2007117004A1 (en) | 2006-04-07 | 2007-10-18 | Nippon Sheet Glass Company, Limited | Photoluminescent pigment, method for production of the pigment, and cosmetic, coating, ink or resin composition comprising the pigment |
| JP2007297621A (en) * | 2006-04-21 | 2007-11-15 | Merck Patent Gmbh | Pigment |
| JP2008024916A (en) * | 2006-05-24 | 2008-02-07 | Merck Patent Gmbh | Particle |
| JP2008088068A (en) * | 2006-09-29 | 2008-04-17 | Kose Corp | Cosmetic used for eyelash or eyebrow |
| WO2008130040A1 (en) | 2007-04-18 | 2008-10-30 | Nippon Sheet Glass Company, Limited | Photoluminescent pigment and cosmetic composition using the same |
| JP2008266479A (en) * | 2007-04-23 | 2008-11-06 | Daito Kasei Kogyo Kk | Dissolution-resistant colored spherical cellulose pigment, and cosmetic containing the same |
| US8273171B2 (en) | 2006-08-29 | 2012-09-25 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
| US8440014B2 (en) | 2007-04-27 | 2013-05-14 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
| US9045643B2 (en) | 2006-04-21 | 2015-06-02 | Nippon Sheet Glass Company Limited | Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment |
| US9168393B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9168394B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9168209B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9469808B2 (en) * | 2014-06-17 | 2016-10-18 | City University Of Hong Kong | Loaded particles and the method of preparing thereof |
| JP2020125255A (en) * | 2019-02-04 | 2020-08-20 | 花王株式会社 | Lip cosmetic |
-
2002
- 2002-01-17 JP JP2002008163A patent/JP2003213156A/en active Pending
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257176A (en) * | 2005-03-16 | 2006-09-28 | Daito Kasei Kogyo Kk | Dissolution-resistant pigment of colored, glossy glass flake and cosmetic blended with the same |
| WO2007116769A1 (en) | 2006-03-27 | 2007-10-18 | Nippon Sheet Glass Company, Limited | Brightening pigment with gold tone and cosmetic preparation, coating material, ink, or resin composition each containing the same |
| WO2007117004A1 (en) | 2006-04-07 | 2007-10-18 | Nippon Sheet Glass Company, Limited | Photoluminescent pigment, method for production of the pigment, and cosmetic, coating, ink or resin composition comprising the pigment |
| JP2007297621A (en) * | 2006-04-21 | 2007-11-15 | Merck Patent Gmbh | Pigment |
| US9045643B2 (en) | 2006-04-21 | 2015-06-02 | Nippon Sheet Glass Company Limited | Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment |
| JP2008024916A (en) * | 2006-05-24 | 2008-02-07 | Merck Patent Gmbh | Particle |
| KR100743674B1 (en) | 2006-08-28 | 2007-07-30 | 한국화학연구원 | The pearlescent pigments with large aspect ratio and preparation method them |
| WO2008026829A1 (en) * | 2006-08-28 | 2008-03-06 | Korea Research Institute Of Chemical Technology | Pearlescent pigments with large aspect ratio and a method of their preparation |
| US8287636B2 (en) | 2006-08-28 | 2012-10-16 | Korea Research Institute Of Chemical Technology | Pearlescent pigments with large aspect ratio and a method of their preparation |
| US8273171B2 (en) | 2006-08-29 | 2012-09-25 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
| JP2008088068A (en) * | 2006-09-29 | 2008-04-17 | Kose Corp | Cosmetic used for eyelash or eyebrow |
| WO2008130040A1 (en) | 2007-04-18 | 2008-10-30 | Nippon Sheet Glass Company, Limited | Photoluminescent pigment and cosmetic composition using the same |
| JP5154547B2 (en) * | 2007-04-18 | 2013-02-27 | 日本板硝子株式会社 | Bright pigment and cosmetic composition using the same |
| US9107834B2 (en) | 2007-04-18 | 2015-08-18 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
| JP2008266479A (en) * | 2007-04-23 | 2008-11-06 | Daito Kasei Kogyo Kk | Dissolution-resistant colored spherical cellulose pigment, and cosmetic containing the same |
| US8440014B2 (en) | 2007-04-27 | 2013-05-14 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
| US9168393B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9168394B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9168209B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9469808B2 (en) * | 2014-06-17 | 2016-10-18 | City University Of Hong Kong | Loaded particles and the method of preparing thereof |
| JP2020125255A (en) * | 2019-02-04 | 2020-08-20 | 花王株式会社 | Lip cosmetic |
| JP7158303B2 (en) | 2019-02-04 | 2022-10-21 | 花王株式会社 | lip cosmetics |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2003213156A (en) | Colored pearl glossy flake pigment | |
| TWI313700B (en) | Five-layered pigments | |
| TWI345579B (en) | Lustrous black interference pigments | |
| JP4647494B2 (en) | Black bright pigment and cosmetics, coating composition, resin composition and ink composition containing the same | |
| JP4137383B2 (en) | High light diffusion pigment mixture | |
| TW460548B (en) | Pigment mixture | |
| TW200806753A (en) | Pigment | |
| JP2005314649A (en) | Interference pigment | |
| JP2004292815A (en) | Silver pigment | |
| CN101935022B (en) | Plate-type bismuth oxychloride crystal with controllable shape and preparation method thereof | |
| JP6694397B2 (en) | α-Al2O3 flakes | |
| US7708823B2 (en) | Semi-transparent interference pigments containing tin | |
| JP2001234090A (en) | Color flake pigment and method for producing the same | |
| JP6486959B2 (en) | Effect pigments | |
| US6837925B2 (en) | Coloring pearlescent flake pigment, manufacturing method of the same and cosmetic product containing the same | |
| JP2006257176A (en) | Dissolution-resistant pigment of colored, glossy glass flake and cosmetic blended with the same | |
| JPH0687720A (en) | Cosmetic containing flaky silica blended therein | |
| JP2003261421A (en) | Composite powder, makeup cosmetic with the same formulated therewith, and method for producing composite powder | |
| JP4786011B2 (en) | Iron oxide-bismuth compound composite pigment and cosmetic containing the same | |
| JP2922148B2 (en) | Novel pearlescent pigments and coating compositions, cosmetics, inks and plastics containing the pigments | |
| JP3911315B2 (en) | High saturation orange pearl pigment | |
| JP2003277646A (en) | Colored flake pigment having elution resistance | |
| JPH04108716A (en) | Cosmetic | |
| JPS6327419A (en) | Makeup cosmetic | |
| JP5038009B2 (en) | Elution-resistant colored spherical cellulose pigment and cosmetic containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050329 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050426 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20050620 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20050719 |