JPS6119666A - Production of colored pearlescent pigment - Google Patents
Production of colored pearlescent pigmentInfo
- Publication number
- JPS6119666A JPS6119666A JP13941584A JP13941584A JPS6119666A JP S6119666 A JPS6119666 A JP S6119666A JP 13941584 A JP13941584 A JP 13941584A JP 13941584 A JP13941584 A JP 13941584A JP S6119666 A JPS6119666 A JP S6119666A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- pearlescent pigment
- titanium dioxide
- black
- iron
- 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
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
Abstract
Description
【発明の詳細な説明】
本発明は、改良された着色真珠光沢顔料の製造法に関す
るもので、着色剤（酸化鉄）と真珠光沢顔料（二酸化チ
タン被覆雲母）とが強固に固着し、外観と感触に＆れ且
つ色分れを生じない着色真珠光沢顔料を提供せんとする
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing colored pearlescent pigments, in which the coloring agent (iron oxide) and the pearlescent pigment (titanium dioxide-coated mica) are firmly bonded to each other, and the appearance is improved. To provide a colored pearlescent pigment that is pleasant to the touch and does not cause color separation.
従来、一般に提供されている灰色から黒灰色を呈する黒
色系真珠光沢顔料は、四三酸化鉄を含有する酸化鉄層か
弱い力で真珠光沢顔料粒子の表面に付着しているか、も
しくは酸化鉄と真珠光沢顔料が混合された状態のもので
あり、これらのものは色分れが激しく、机上に塗布した
り、あるいは水中に分散させた場合には、酸化鉄と真珠
光沢顔料とが完全に分離してしまうという現象が起る。Conventionally, generally available black pearlescent pigments exhibiting a gray to blackish-gray color have either an iron oxide layer containing triiron tetroxide attached to the surface of pearlescent pigment particles with a weak force, or a combination of iron oxide and pearls. These are mixtures of lustrous pigments, and these pigments have severe color separation, and when applied on a desk or dispersed in water, the iron oxide and pearlescent pigments are completely separated. This phenomenon occurs.
例えば、この様な黒色系真珠光沢顔料を化粧料に使用し
た場合には、酸化鉄と真珠光沢顔料との色分れが容易に
生じ、酸化鉄が机上に付着し、化粧料の塗布膜がく丁ん
で見え、且つ真珠光沢顔料が浮いて見え、化粧料として
の品質低下の原因となっている。更に、この様な黒色系
真珠光沢顔料と他の着色真珠光沢顔料とを混合使用した
場合には、通常の混合、粉砕の工程中で容易に色分れし
、外観色と塗布色が一致しないという問題も引起してい
た。For example, when such a black pearlescent pigment is used in cosmetics, color separation between the iron oxide and the pearlescent pigment easily occurs, and the iron oxide adheres to the surface of the desk, causing the coating film of the cosmetic to deteriorate. It looks grainy and the pearlescent pigments appear floating, causing a decline in quality as a cosmetic. Furthermore, when such a black pearlescent pigment is mixed with other colored pearlescent pigments, the colors easily separate during the normal mixing and crushing process, and the external color and the applied color do not match. This also caused the problem.
上記のような黒色系真珠光沢顔料のもつ問題点を解決せ
んとする試みも一部にはなされてきた。例えば、特開昭
４９−１２８０２７号においては、二酸化チタン被覆雲
母の水分散液中に酸化剤を含有させておき、これに塩基
と鉄（ｎ）塩の水溶液を添加して、黒色系の真珠光沢顔
料を得る方法が既に開示されている。然しなから、この
方法では、鉄（ＩＩ）塩→水酸化鉄→四三酸化鉄に至る
反応プロセスが、過剰な酸化剤の存在の為、余りにも急
激に進行すること、及び四三酸化鉄粒子が、他の酸化鉄
例えば酸化第二鉄（Ｆｅ２０３）粒子などと比較して大
きな粒子径を肩するものである為、均−且つ強固な被覆
を得ることが困難であるなどの問題点を有していた。Some attempts have been made to solve the problems of black pearlescent pigments as described above. For example, in JP-A No. 49-128027, an oxidizing agent is contained in an aqueous dispersion of titanium dioxide-coated mica, and an aqueous solution of a base and an iron (n) salt is added to produce black pearls. A method for obtaining luster pigments has already been disclosed. However, in this method, the reaction process leading to iron (II) salt → iron hydroxide → triiron tetroxide proceeds too rapidly due to the presence of an excess oxidizing agent, and Since the particles have a larger particle size than other iron oxides, such as ferric oxide (Fe203) particles, there are problems such as difficulty in obtaining a uniform and strong coating. had.
一方、淡いレンガ色から赤色を呈する赤色系真珠光沢顔
料も既に提供され、しかも上記の黒色系真珠光沢顔料と
比較して製造は容易であり。On the other hand, red pearlescent pigments that exhibit a pale brick-red to red color have already been provided, and they are easier to manufacture than the above-mentioned black pearlescent pigments.
且つ真珠光沢顔料粒子の表面を、酸化第二鉄を主成分と
する微細な酸化鉄屑が被覆したものである為、色分れの
問題も少ないと言われていた。In addition, since the surface of the pearlescent pigment particles is coated with fine iron oxide dust containing ferric oxide as a main component, it is said that there is less problem of color separation.
しかし、逆に真珠光沢顔料粒子の表面を微細な酸化鉄層
が緻密に被覆したものであるが故に、真珠光沢顔料が本
来有していた独特の感触やすべり感が失なわれる結果と
なっていた。また、近年化粧料においては、マイルドな
外観を有するものが好まれるようになり、鮮やかでスパ
ークルな外観を有する従来の赤色系真珠光沢顔料を如何
に改良するかが、技術者にとっての課題であった。However, on the contrary, because the surface of the pearlescent pigment particles is densely coated with a fine iron oxide layer, the unique feel and smoothness that the pearlescent pigment originally had has been lost. Ta. In addition, in recent years, cosmetics with a mild appearance have become preferred, and a challenge for engineers has been how to improve the conventional red pearlescent pigments, which have a bright and sparkling appearance. Ta.
そこで本発明者は、前記従来の着色真珠光沢 ”顔
料及びその製造法が抱える問題点ｔ？解決せんと鋭意研
究したところ、二酸化チタン被覆雲母の粒子表面に先ず
水酸化鉄の状態から沈着を起こさせて着色剤と真珠光沢
顔料との結合力を高めた後１次いで四三酸化鉄の状態で
沈着させ、最後に酸化剤の働きで水酸化鉄を四三酸化鉄
に変換させるという反応プロセスを経ると、二酸化チタ
ン被覆雲母の粒子表面に四三酸化鉄を有効且つ強固に被
覆した黒色系真珠光沢顔料が得られること、更には得ら
れた黒色系真珠光沢顔料を焼成等の熱処理により、四三
酸化鉄１ｉｌ−酸化第二鉄に変換することで従来にない
赤色系真珠光沢顔料が得られることを見出し、本発明の
完成に至った。Therefore, the present inventor conducted intensive research to solve the problems faced by the conventional colored pearlescent pigments and their manufacturing method, and found that iron hydroxide was first deposited on the surface of titanium dioxide-coated mica particles. After increasing the binding strength between the coloring agent and the pearlescent pigment, the pigment is deposited in the form of triiron tetroxide, and finally, the reaction process is carried out to convert the iron hydroxide into triiron tetroxide using the action of an oxidizing agent. As a result, a black pearlescent pigment is obtained in which the particle surface of titanium dioxide-coated mica particles is effectively and firmly coated with triiron tetroxide. It was discovered that an unprecedented red pearlescent pigment could be obtained by converting iron trioxide to 1 il of ferric oxide, leading to the completion of the present invention.
本発明は、二酸化チタン被覆雲母を水中に分散させ、こ
の分散液に塩基を加えてｐＨを調整し、これと同時に酸
化剤と鉄（ＩＩ）塩とを含有する水溶液を徐々に加え、
二酸化チタン被覆雲母粒子の表面に四三酸化鉄（Ｆｅ５
０４）の沈殿を生ぜしめ被覆することを特徴とする黒色
系の着色真珠光沢顔料の製造法に関するものであり、更
には得られた黒色系の着色真珠光沢顔料を、大気中で５
００〜１０００℃の範囲で熱処理することを特徴とする
赤色系の着色真珠光沢顔料の製造法に関するものである
。The present invention involves dispersing titanium dioxide-coated mica in water, adding a base to this dispersion to adjust the pH, and at the same time gradually adding an aqueous solution containing an oxidizing agent and an iron (II) salt.
Triiron tetroxide (Fe5
The present invention relates to a method for producing a black colored pearlescent pigment characterized by forming a precipitate and coating the obtained black colored pearlescent pigment.
The present invention relates to a method for producing a red colored pearlescent pigment, which is characterized by heat treatment in the range of 00 to 1000°C.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に適用される二酸化チタン被覆雲母は市販品で良
く、粒子径も二酸化チタン被扱量も特に制限がない。本
発明では、先ず、この二酸化チタン被覆雲母を水中に分
散させ、加熱する。The titanium dioxide-coated mica applied to the present invention may be a commercially available product, and there are no particular restrictions on the particle size or the amount of titanium dioxide to be treated. In the present invention, first, this titanium dioxide-coated mica is dispersed in water and heated.
この時、二酸化チタン被覆雲母の分散量は、４０重量−
以下とし、好ましくは１〜２０重量％、特に好ましくは
２〜１０重量％の範囲を選択すると良い。４０重量％を
超えると、分散系はスラリー状を呈し、均一な品質のも
のが得られないし、逆に余りに少ない分散量では工業的
メリ゛ットが失なわれることになる。また、加熱温度と
しては、反応速度との関連から５０〜１００℃の範囲が
好ましい。更に１分散液中に空気が存在すると、生成し
た四三酸化鉄が酸化第二鉄に酸化されてしまい、且つ反
応系のコントロールが困難となる為、予め窒素ガスを吹
き込み酸素を追い出しておくと良い。At this time, the amount of dispersed mica coated with titanium dioxide is 40 weight -
It is preferable to select the following range, preferably 1 to 20% by weight, particularly preferably 2 to 10% by weight. If the amount exceeds 40% by weight, the dispersion system becomes slurry-like and uniform quality cannot be obtained, and on the other hand, if the amount of dispersion is too small, industrial advantages will be lost. Further, the heating temperature is preferably in the range of 50 to 100°C in view of the reaction rate. Furthermore, if air is present in the dispersion, the generated triiron tetroxide will be oxidized to ferric oxide, and it will be difficult to control the reaction system, so it is recommended to blow nitrogen gas in advance to drive out oxygen. good.
次に、塩・基例えば水酸化アンモニウム（Ｎｆ（４０１
（）水酸化ナトリウム（ＮａＯＨ） 、水酸化リチウム
（ＬｉＯＨ）、水酸化カリウム（ＫＯＨ）等の水溶液を
添加して、分散液のｐＨ値を７１２ｔＦｆましくは９−
１１に調整する。この時、特にＮＨ４ＯＨを使用すると
、生成する塩例えば（ＮＨ４ン２ＳＯ４がＮＨ４ＯＨと
の緩衝剤として働き、ｐＨが非常に良くコントロールさ
れ有利である。Next, a salt/base such as ammonium hydroxide (Nf(401
() Add an aqueous solution of sodium hydroxide (NaOH), lithium hydroxide (LiOH), potassium hydroxide (KOH), etc. to adjust the pH value of the dispersion to 712 tFf or 9-
Adjust to 11. At this time, it is particularly advantageous to use NH4OH because the generated salts, such as (NH4-2SO4) act as a buffer with NH4OH, and the pH can be controlled very well.
そして、ｐＨ調整後は塩基と同時に、塩化第一鉄、硫酸
第一鉄、リン酸第−鉄などの鉄（Ｊｉ）塩と硝酸塩例え
ば硝酸カリウム、硝酸ナトリウム、硝酸アンモニウム等
や塩素酸塩例えば塩素酸カリウム、塩素酸ナトリウム、
塩素酸アンモニウム等などの比較的緩和な作用を有する
酸化剤とと溶解させた水溶液を、分散液に徐々に滴下す
る。この時、鉄（ＩＩ）塩は水系中で不安定である為、
硫酸、塩酸、硝酸等の酸を添加液中に加え、ｐｌｌを酸
性化し鉄［有］）塩の安定化を図ることが好ましい。ま
た、この被覆形成中は、塩基を滴下し続けることによシ
ｐＨを７−１２の間で一定に保ち。After pH adjustment, at the same time as a base, iron (Ji) salts such as ferrous chloride, ferrous sulfate, and ferrous phosphate, nitrates such as potassium nitrate, sodium nitrate, ammonium nitrate, and chlorates such as potassium chlorate are added. , sodium chlorate,
An aqueous solution in which an oxidizing agent having a relatively mild action such as ammonium chlorate is dissolved is gradually dropped into the dispersion. At this time, since iron (II) salt is unstable in an aqueous system,
It is preferable to add an acid such as sulfuric acid, hydrochloric acid, or nitric acid to the additive solution to acidify the pll and stabilize the iron salt. During the coating formation, the pH was kept constant between 7 and 12 by continuing to drop a base.
更に窒素ガスを吹き込みながら温度も５０〜１００℃の
範囲に維持して撹拌を玩けることが大切でろる。Furthermore, it is important to maintain the temperature within the range of 50 to 100°C while stirring while blowing nitrogen gas.
上記の様なプロセスを経ることによシ、分散液は滴下の
始めより灰色を呈し、途中までは先ず水酸化鉄（Ｆｅ（
ｏＨ）ｚ）が沈着、その後急ＫｇＭ三酸化鉄が沈着し始
め、分散液は黒灰色を呈するようになる。その後も、反
応攪拌を維持して所望の着色度に至った時点で反応を終
了し、以後は常法に従がい、顔料を水洗、口過する。こ
の場合、水洗にあたっては、生、成吻中に含まれている
アンモニアや硫酸などの添加物乃至は生成不純物の痕跡
がなくなるまで水洗を行なうのが良い。得られた口過物
を、減圧下、１３０℃以下で乾燥すると黒色系の着色真
珠光沢顔料が得られるもので・ある。By going through the above process, the dispersion becomes gray from the beginning of dropping, and until the middle of the drop, it becomes iron hydroxide (Fe(
oH)z) is deposited, then rapidly KgM iron trioxide begins to deposit, and the dispersion becomes blackish-gray. Thereafter, the reaction is continued to be stirred, and the reaction is terminated when the desired degree of coloring is reached.Then, the pigment is washed with water and passed through the mouth according to a conventional method. In this case, it is preferable to wash with water until there are no traces of additives such as ammonia or sulfuric acid contained in the raw or proboscis, or of produced impurities. When the obtained mouthwash is dried under reduced pressure at 130° C. or lower, a black colored pearlescent pigment is obtained.
ここで、黒色系の着色真珠光沢顔料の色味（着色度）は
、添加する鉄（ＩＩ）塩と酸化剤の量を変化 ４
することにより任意にコントロールし得る。例えば、二
酸化チタン被覆雲母重量に対して、四三酸化鉄の被覆量
が５Ｍ量チ位では未だ銀色を呈するが、被覆量の増加と
ともに黒みが強くなり、２０重′ｉｉｋ％を超えると殆
ど黒色を呈する。Here, the color (degree of coloring) of the black colored pearlescent pigment is determined by changing the amount of iron (II) salt and oxidizing agent added.
It can be controlled arbitrarily by doing this. For example, when the coating amount of triiron tetroxide is 5M relative to the weight of titanium dioxide-coated mica, the color still appears silver, but as the coating amount increases, the blackness becomes stronger, and when it exceeds 20% by weight, it becomes almost black. exhibits.
しかし、２５重量％全超えるとつやが消失し始め、真珠
光沢顔料から単なる黒色顔料へと近づいてゆく。従って
、例えば化粧料等に黒色真珠光沢顔料として用いたい場
合には、被覆量が２０〜２５重量％の範囲のものを使用
するのが実用的である。However, when the total amount exceeds 25% by weight, the luster begins to disappear and the pearlescent pigment approaches a simple black pigment. Therefore, when it is desired to use it as a black pearlescent pigment in cosmetics, for example, it is practical to use one with a coating amount in the range of 20 to 25% by weight.
次に％得られた黒色系の着色真珠光沢顔料を大気中で５
００〜１０００℃の温度範囲で熱処理をすると、四三酸
化鉄が酸化第二鉄に変換し、赤色系の着色真珠光沢顔料
となる、この赤色系の着色真珠光沢顔料の色味（着色度
）は、当然の如く、元の黒色系の着色真珠光沢顔料にお
ける四三酸化鉄の被覆量と相関関係を有し、淡いレンガ
色（赤褐色）から濃い赤色へと変化する。Next, 5% of the obtained black colored pearlescent pigment was added to the atmosphere.
When heat-treated in the temperature range of 00 to 1000°C, triiron tetroxide is converted to ferric oxide and becomes a red colored pearlescent pigment.The color (degree of coloration) of this red colored pearlescent pigment Naturally, there is a correlation with the amount of triiron tetroxide covered in the original black colored pearlescent pigment, and the color changes from pale brick color (reddish brown) to deep red.
しか［７ながら、前述の様に真珠光沢顔料の持つ独特な
感触やすベシ感などの官能特性をそのまま維持し、且つ
マイルドな外観を呈するものとしては、二酸化チタン被
ｉｆｉ母重量に対して、酸化第二鉄の被覆量が１Ｕ〜１
５重量−の範囲のものが実用的である。However, as mentioned above, as a pearlescent pigment that maintains the sensory characteristics such as the unique feel and sticky feeling, and exhibits a mild appearance, it is necessary to The amount of ferric iron covered is 1U~1
5 weight range is practical.
以下、更に具体的に製造例をもって示す。More specific examples of production will be shown below.
製造例 １
原料の二酸化チタン被覆雲母（粒径１０〜６５ｊ１ｍ、
二酸化チタン被覆量３０条）１０Ｆを蒸留水２００ｍｇ
中に懸濁させる。懸濁液に、窒素ガスを吹き込み、撹拌
し２ながら８０℃に加熱し、２０チアンモニア水を滴下
し、ｐＨを１０付近に調整する。続い、て、硫酸第一鉄
５６．１ｔ、濃硫酸０．７２ｍ１．および硝酸カリウム
５．３ｔを蒸留水１８０ｍ／！中に溶解した溶液の全量
を徐々に滴下する。ｐＨ化ナタン被梼雲母上に層を形成
し、次第に黒色を滞びてくる。反応中は、温度を８０℃
に保ち、窒素ガスを吹き込みながら撹拌を続ける。メ応
終了後、濾過、水洗し、１００℃付近で乾燥させる。こ
の顔料の組成は、Ｆｅ３０４５０％、ＴｉＯ２ｉ５チ、
雲母３５チである。Production example 1 Raw material titanium dioxide coated mica (particle size 10-65j1m,
Titanium dioxide coating amount: 30 pieces) 10F with 200mg of distilled water
suspend in it. Nitrogen gas is blown into the suspension, heated to 80° C. while stirring, and 20 thiammonium water is added dropwise to adjust the pH to around 10. Next, 56.1 tons of ferrous sulfate and 0.72 ml of concentrated sulfuric acid were added. and potassium nitrate 5.3t with distilled water 180m/! Gradually drop the entire amount of the solution dissolved in the solution. A layer is formed on the pH-adjusted nathanum mica, and the color gradually becomes black. During the reaction, keep the temperature at 80°C.
Continue stirring while blowing nitrogen gas. After the reaction is completed, it is filtered, washed with water, and dried at around 100°C. The composition of this pigment is Fe30450%, TiO2i5%,
Mica is 35 cm.
製造例 ２
製造例１と同様にして、黒色の顔料を作った後、このも
のを大気中６００℃で焼成して赤色の顔料を得た。この
生成物は、つやがあり、真珠光沢はもたないが、元の二
酸化チタン被覆雲母の感触をもつ、非常にすべり感のあ
る顔料である。Production Example 2 A black pigment was prepared in the same manner as in Production Example 1, and then fired in the atmosphere at 600°C to obtain a red pigment. The product is a glossy, non-pearlescent, but very slippery pigment with the feel of the original titanium dioxide coated mica.
製造例 ５
原料の二酸化チタン核種雲母（粒径１０〜３５μｍ）、
二酸化チタン被覆量６０チ）１０ｆを蒸留水２０〇−中
に懸濁させる。懸濁液に窒素ガスを吹き込み、攪拌しな
がら８０℃に加熱し、２０チ水酸化ナトリウム水溶液を
滴下し、ｐＨを１０付近に調整する。引き続き、同時に
、塩化第１鉄６水塩１α１４ｔ１濃塩酸０．４０ｔｎＩ
Ｖおよび硝酸アンモニウム１．３８ｆを蒸留水６０ｄ中
に溶解した溶液を徐々に滴下する。ｐＨ値は、２０チ水
酸化タン被覆雲母上に層を形成し、次第に黒色を滞びて
くる。反応中は、温度を８０℃に保ち、窒素ガスを吹き
込みながら攪拌を続ける。反応終了後、濾過、水洗し１
００℃付近で、減圧下で乾燥させる。この顔料の組成は
、Ｆｅ３Ｏ４２５ｆｂ。Production example 5 Raw material titanium dioxide nuclide mica (particle size 10 to 35 μm),
Suspend 10 f of titanium dioxide (60 g) in 200 g of distilled water. Nitrogen gas is blown into the suspension, heated to 80° C. with stirring, and aqueous sodium hydroxide solution is added dropwise to adjust the pH to around 10. Subsequently, at the same time, ferrous chloride hexahydrate 1α14t1 concentrated hydrochloric acid 0.40tnI
A solution of V and 1.38 f of ammonium nitrate dissolved in 60 d of distilled water is gradually added dropwise. The pH value forms a layer on the 20 tungsten hydroxide coated mica and gradually becomes black. During the reaction, the temperature is maintained at 80° C. and stirring is continued while blowing nitrogen gas. After the reaction is complete, filter and wash with water 1
Dry at around 00°C under reduced pressure. The composition of this pigment is Fe3O425fb.
ＴｉＯ２２２％、ＭｉＣａ ５５％である。このものは
、黒色で更につやもあシ、全く色分れをしない顔料であ
った。TiO222%, MiCa 55%. This pigment was black, glossy, and had no color separation at all.
製造例 ４〜１０
製造例１と同様にして、硫酸第１鉄、硫酸、硝酸カリウ
ムを含む水溶液の滴下量を下記の表−１のように変化さ
せ、銀灰色〜黒色を呈する顔料を作成した。Production Examples 4 to 10 In the same manner as Production Example 1, the amount of the aqueous solution containing ferrous sulfate, sulfuric acid, and potassium nitrate dropped was varied as shown in Table 1 below, and pigments exhibiting a silvery gray to black color were created.
表−１
製造例 １１
製造例５で得られた黒色系の顔料を大気中８００℃で焼
成して赤色系の顔料を得た。このものは、もとの二酸化
チタン被覆雲母の官能特性をそのまま有し、キラキラし
たスパークルな感じが抑えられたつやのある顔料であっ
た。Table 1 Production Example 11 The black pigment obtained in Production Example 5 was fired at 800°C in the air to obtain a red pigment. This pigment had the sensory properties of the original titanium dioxide-coated mica, and was a glossy pigment with a suppressed sparkle feel.
次に、本発明の方法で作製した黒色系真珠光沢顔料と市
販品の黒色系真珠光沢顔料との比較評価を行なった。即
ち、製造例５（銀灰色）及び製造例７（黒灰色）で得ら
れた本発明に係る黒色系真珠光沢顔料とメルク社＃、コ
ロロナ・／ぞツチナ・シルツク−（銀灰色）及びマリン
クロット社製、スペクトラパールＢＫＷ （黒灰色）の
市販品の黒色系真珠光沢顔料とを用い、先ず各試料をそ
れぞれ粉砕機にかけ、６，０００ｒｐｍの条件で粉砕し
、次いで粉砕物を水中に懸濁し、ディスパーで分散させ
、その後遠心分離機Ｋかけ、３．０００ｒｐｍの条件下
で層が分離するかどうかをみた。その結果、市販品２品
はみごとに分離したが、本発明の方法で作製し九ものは
、分離することはなかった。Next, a comparative evaluation was performed between the black pearlescent pigment produced by the method of the present invention and a commercially available black pearlescent pigment. That is, the black pearlescent pigment according to the present invention obtained in Production Example 5 (silver gray) and Production Example 7 (black gray), Merck & Co. #, Kororona/Zotina Schiltsk (silver gray) and Mallinckrodt Co. Using a commercially available black pearlescent pigment, Spectra Pearl BKW (black gray), each sample was first ground in a grinder at 6,000 rpm, and then the ground product was suspended in water and ground in a disper. The mixture was dispersed and then centrifuged at 3,000 rpm to see if the layers would separate. As a result, two commercial products were successfully separated, but nine products prepared by the method of the present invention were not separated.
一方、本発明の方法に係る着色真珠光沢顔料を配合した
化粧料（後記便用例１及び２）を評価したところ、市販
化粧料の場合に問題となったくすみがなくなシ、外観色
と塗布色が一致し、化粧料として非常に良い品質のもの
でめった。On the other hand, when cosmetics containing colored pearlescent pigments according to the method of the present invention were evaluated (Examples 1 and 2 below), it was found that the dullness that was a problem with commercially available cosmetics was eliminated, and the appearance color and application were improved. The colors match and the quality is very good for cosmetics, which is rare.
ここで本発明方法の特徴を述べるならば、下記の如くと
なる。Here, the characteristics of the method of the present invention are as follows.
１）四三酸化鉄は、二酸化チタン被覆買置表面に沈殿を
生ずるが、このものは塗布とか分散等の物理的な力で簡
単［ｆｋ４１離してしまい、強固な１−として被稜する
ことは困難視されていたが、本発明の方法により強固な
被覆が可能となった。1) Triiron tetroxide forms a precipitate on the titanium dioxide coated surface, but this can be easily removed by physical force such as coating or dispersion. Although it was thought to be difficult, the method of the present invention has made it possible to provide a strong coating.
２）更に、混合顔料の製造工程では、顔料粉砕機による
粉砕が行なわれ、この時、従来の着色真珠光沢顔料は着
色剤と真珠光沢顔料が分離してしまうが、本発明の方法
で得られた着色真珠光沢顔料は、そのようなことがない
。2) Furthermore, in the manufacturing process of mixed pigments, pulverization is performed using a pigment pulverizer, and at this time, in conventional colored pearlescent pigments, the colorant and pearlescent pigment separate, but in the process of the present invention, the colorant and pearlescent pigment are separated. This is not the case with colored pearlescent pigments.
３）本発明の方法で得られた着色真珠光沢顔料は、元の
真珠光沢顔料としての感触、例えばのびの軽さ、拡がり
易さ、むらにならない等の感触をそのまま維持したもの
である。3) The colored pearlescent pigment obtained by the method of the present invention maintains the feel of the original pearlescent pigment, such as lightness of spread, ease of spreading, and no unevenness.
４）また、被覆量や熱処理条件をコントａ−ルすること
により、つやや色間を自由に調整でき、所望のつや、色
調をもった外観的に優れた着色顔料を得ることができる
。4) Furthermore, by controlling the coating amount and heat treatment conditions, gloss and color spacing can be freely adjusted, and a colored pigment with desired gloss and color tone and excellent appearance can be obtained.
次に、本発明方法により得られる着色真珠光沢顔料の使
用例を示す。例中、配合割合はそれぞれ重′！ｋｔｓで
示されている。Next, examples of using the colored pearlescent pigment obtained by the method of the present invention will be shown. In the example, the mixing ratio is heavy'! It is indicated by kts.
使用例１ アイシャドー
黒色真珠光沢顔料（製造例３ ） ６１−′
セリサイト １０
タ ル り
５色素顔料 ５
ステアリン酸アルミ ５カルボキ
シメチルセルロース ５スクワラ
ン ５シリコーン油
５使用例２ 固型ファンデー７
：ｉン
セリサイト ４８マ
イ カ
１０絃化チタン
６ケイ酸カルシウム
５赤色真珠光沢顔料（製造例２）４
黄色酸化鉄 ３黒色真珠
光沢顔料（製造例８） ０．７紺ＩＩ″酸
化鉄 α１防腐剤
α１
スクワラン ７シリコー
ン油 ５ラノリン
２
香 料
０．１メチルセルロース ２イ
オン交換水 １０使用例６
はぼ紅Usage example 1 Eyeshadow black pearlescent pigment (Production example 3) 61-'
Sericite 10
Tarri
5 Color pigment 5 Aluminum stearate 5 Carboxymethylcellulose 5 Squalane 5 Silicone oil
5 Usage example 2 Solid foundation 7
: iInseriSite 48Myka
10 stringed titanium
6 calcium silicate
5 Red pearlescent pigment (Production example 2) 4 Yellow iron oxide 3 Black pearlescent pigment (Production example 8) 0.7 Navy II" Iron oxide α1 Preservative
α1 Squalane 7 Silicone oil 5 Lanolin
2 Fragrance
0.1 Methyl cellulose 2 Ion exchange water 10 Usage example 6
Habonoku
Claims (1)
液に塩基を加えてｐＨを調整し、これと同時に酸化剤と
鉄（II）塩とを含有する水溶液を徐々に加え、二酸化チ
タン被覆雲母粒子の表面に四三酸化鉄（Ｆｅ＿３Ｏ＿４
）の沈殿を生ぜしめ被覆することを特徴とする黒色系の
着色真珠光沢顔料の製造法。 ２）二酸化チタン被覆雲母を水中に分散させ、この分散
液に塩基を加えてｐＨを調整し、これと同時に酸化剤と
鉄（II）塩とを含有する水溶液を徐々に加え、二酸化チ
タン被覆雲母粒子の表面に四三酸化鉄（Ｆｅ＿３Ｏ＿４
）の沈殿を生ぜしめ被覆した後、大気中で５００〜１０
００℃の範囲で熱処理することを特徴とする赤色系の着
色真珠光沢顔料の製造法。 ３）酸化剤が硝酸塩または塩素酸塩である特許請求の範
囲第１）項および第２）項記載の着色真珠光沢顔料の製
造法。[Claims] 1) Titanium dioxide-coated mica is dispersed in water, a base is added to this dispersion to adjust the pH, and at the same time an aqueous solution containing an oxidizing agent and iron (II) salt is gradually added to the dispersion. In addition, triiron tetroxide (Fe_3O_4
) A method for producing a black colored pearlescent pigment characterized by forming a precipitate and coating the pigment. 2) Disperse the titanium dioxide-coated mica in water, add a base to this dispersion to adjust the pH, and at the same time gradually add an aqueous solution containing an oxidizing agent and iron (II) salt to disperse the titanium dioxide-coated mica. Triiron tetroxide (Fe_3O_4
) is precipitated and coated, 500 to 10
1. A method for producing a red colored pearlescent pigment, characterized by heat treatment in the range of 00°C. 3) The method for producing a colored pearlescent pigment according to claims 1) and 2), wherein the oxidizing agent is a nitrate or a chlorate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13941584A JPS6119666A (en) | 1984-07-05 | 1984-07-05 | Production of colored pearlescent pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13941584A JPS6119666A (en) | 1984-07-05 | 1984-07-05 | Production of colored pearlescent pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6119666A true JPS6119666A (en) | 1986-01-28 |
Family
ID=15244695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13941584A Pending JPS6119666A (en) | 1984-07-05 | 1984-07-05 | Production of colored pearlescent pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119666A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62115071A (en) * | 1985-11-14 | 1987-05-26 | Pola Chem Ind Inc | Production of black pigment |
| JPS62146962A (en) * | 1985-12-20 | 1987-06-30 | Teikoku Kako Kk | Iron oxide-coated inorganic sphere |
| JPS62285956A (en) * | 1986-05-23 | 1987-12-11 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Pearl gloss pigment |
| JPH02145506A (en) * | 1988-11-26 | 1990-06-05 | Pentel Kk | Brown-colored liquid cosmetic |
| JPH05271569A (en) * | 1992-03-27 | 1993-10-19 | Dainichiseika Color & Chem Mfg Co Ltd | Black pearl pigment and its production |
| JP2003003089A (en) * | 2001-06-26 | 2003-01-08 | Kao Corp | Covered powder |
| EP0701810B1 (en) * | 1994-09-14 | 2004-11-17 | Shiseido Company Limited | Skin-colour adjusting method, and coloured titanium oxide coated mica used therefor |
| WO2005028566A1 (en) | 2003-09-22 | 2005-03-31 | Nippon Sheet Glass Company, Limited | Black bright pigment, and cosmetic, coating composition, resin composition and ink composition comprising the same |
| JP2005307155A (en) * | 2003-10-01 | 2005-11-04 | Merck Patent Gmbh | Glossy black interference pigment |
| JP2007277107A (en) * | 2006-04-03 | 2007-10-25 | Kao Corp | Makeup cosmetic |
| JP2011516688A (en) * | 2008-04-09 | 2011-05-26 | サン・ケミカル・コーポレーション | Process for improving magnetic pigments and magnetic properties |
| WO2013111771A1 (en) * | 2012-01-23 | 2013-08-01 | トピー工業株式会社 | Iron oxide-coated layered silicate pigment |
| CN103249783A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Magnetic pigments |
| CN103249782A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Brilliant black pigments |
| JP2017501241A (en) * | 2013-10-28 | 2017-01-12 | Cqv株式会社Cqv Co., Ltd. | Iron oxide black luster pigment and method for producing the same |
| WO2022013681A1 (en) * | 2020-07-14 | 2022-01-20 | 東洋アルミニウム株式会社 | Coated pigment |
-
1984
- 1984-07-05 JP JP13941584A patent/JPS6119666A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62115071A (en) * | 1985-11-14 | 1987-05-26 | Pola Chem Ind Inc | Production of black pigment |
| JPS62146962A (en) * | 1985-12-20 | 1987-06-30 | Teikoku Kako Kk | Iron oxide-coated inorganic sphere |
| JPS62285956A (en) * | 1986-05-23 | 1987-12-11 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Pearl gloss pigment |
| JPH02145506A (en) * | 1988-11-26 | 1990-06-05 | Pentel Kk | Brown-colored liquid cosmetic |
| JPH05271569A (en) * | 1992-03-27 | 1993-10-19 | Dainichiseika Color & Chem Mfg Co Ltd | Black pearl pigment and its production |
| EP0701810B1 (en) * | 1994-09-14 | 2004-11-17 | Shiseido Company Limited | Skin-colour adjusting method, and coloured titanium oxide coated mica used therefor |
| JP2003003089A (en) * | 2001-06-26 | 2003-01-08 | Kao Corp | Covered powder |
| WO2005028566A1 (en) | 2003-09-22 | 2005-03-31 | Nippon Sheet Glass Company, Limited | Black bright pigment, and cosmetic, coating composition, resin composition and ink composition comprising the same |
| JP2005307155A (en) * | 2003-10-01 | 2005-11-04 | Merck Patent Gmbh | Glossy black interference pigment |
| JP2007277107A (en) * | 2006-04-03 | 2007-10-25 | Kao Corp | Makeup cosmetic |
| JP2011516688A (en) * | 2008-04-09 | 2011-05-26 | サン・ケミカル・コーポレーション | Process for improving magnetic pigments and magnetic properties |
| CN103249783A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Magnetic pigments |
| CN103249782A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Brilliant black pigments |
| CN103249783B (en) * | 2010-12-09 | 2015-04-15 | 默克专利股份有限公司 | Magnetic pigments |
| CN103249782B (en) * | 2010-12-09 | 2015-05-20 | 默克专利股份有限公司 | Brilliant black pigments |
| WO2013111771A1 (en) * | 2012-01-23 | 2013-08-01 | トピー工業株式会社 | Iron oxide-coated layered silicate pigment |
| JPWO2013111771A1 (en) * | 2012-01-23 | 2015-05-11 | トピー工業株式会社 | Iron oxide coated layered silicate pigment |
| EP2808363A4 (en) * | 2012-01-23 | 2015-10-14 | Topy Ind | Iron oxide-coated layered silicate pigment |
| US9637638B2 (en) | 2012-01-23 | 2017-05-02 | Topy Kogyo Kabushiki Kaisha | Iron oxide-coated layered silicate pigment |
| JP2017501241A (en) * | 2013-10-28 | 2017-01-12 | Cqv株式会社Cqv Co., Ltd. | Iron oxide black luster pigment and method for producing the same |
| WO2022013681A1 (en) * | 2020-07-14 | 2022-01-20 | 東洋アルミニウム株式会社 | Coated pigment |
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