JPH0781093B2 - Mica coated with titanium compound - Google Patents

Mica coated with titanium compound

Info

Publication number
JPH0781093B2
JPH0781093B2 JP59041665A JP4166584A JPH0781093B2 JP H0781093 B2 JPH0781093 B2 JP H0781093B2 JP 59041665 A JP59041665 A JP 59041665A JP 4166584 A JP4166584 A JP 4166584A JP H0781093 B2 JPH0781093 B2 JP H0781093B2
Authority
JP
Japan
Prior art keywords
titanium
mica
color
pigment
colored
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.)
Expired - Lifetime
Application number
JP59041665A
Other languages
Japanese (ja)
Other versions
JPS60184570A (en
Inventor
朝 木村
福二 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Shiseido Co Ltd
Original Assignee
Mitsubishi Materials Corp
Shiseido Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp, Shiseido Co Ltd filed Critical Mitsubishi Materials Corp
Priority to JP59041665A priority Critical patent/JPH0781093B2/en
Publication of JPS60184570A publication Critical patent/JPS60184570A/en
Publication of JPH0781093B2 publication Critical patent/JPH0781093B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • A61K8/29—Titanium; 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

Description

【発明の詳細な説明】 本発明は塗料、インキ、プラスチック、化粧品、装飾
品、日用雑貨、繊維製品、セラミック等の顔料、有色パ
ール光沢材料として有用であり、記録紙用の導電層や記
録層、並びに正電気防止材料などの導電性材料としての
用途も期待される雲母チタン系複合材料に関する。The present invention is useful as paints, inks, plastics, cosmetics, ornaments, sundries, textiles, pigments such as ceramics, colored pearl luster materials, and conductive layers for recording paper and recording materials. The present invention relates to a mica-titanium-based composite material which is expected to be used as a layer and a conductive material such as a positive electricity prevention material.

従来から、微細な薄片状雲母の表面に二酸化チタン層を
形成させた雲母チタン系複合材料は、真珠光沢と種々の
干渉色を有するところから、化粧品、塗料、プラスチッ
ク等の顔料として広く用いられている。その製法として
は真空蒸着処理もあるがデュポンの特許（特公昭43−25
644号公報）に見られるようなチタンの無機酸塩（たと
えば硫酸チタニル）の水溶液を雲母の存在下で加水分解
し、雲母表面に含水二酸化チタンを析出させたのち加熱
する方法が一般的である。使用する雲母は、一般には白
雲母系雲母（muscovite mica）を用いるが、場合によっ
ては黒雲母などを用いることも可能である。また雲母は
あらかじめ水粉砕し、フルイを用いて粒子径をそろえた
ものを使用する。生成した雲母チタン系複合材料は、雲
母粒子表面上の二酸化チタン被覆層の厚さによって様々
な干渉色を呈する。干渉色は二酸化チタンの量が生産物
の10〜26重量％の場合、通常銀色であるが、26〜40％で
は金色、40〜50％の範囲では二酸化チタン層の増加の方
向で、赤、青、緑色へと変化し、さらに50〜60％では高
いオーダーの干渉色が得られる。Conventionally, a mica titanium-based composite material in which a titanium dioxide layer is formed on the surface of fine flaky mica has pearl luster and various interference colors, and is therefore widely used as a pigment in cosmetics, paints, plastics, etc. There is. There is also vacuum deposition as a manufacturing method, but DuPont's patent (Japanese Patent Publication No. 43-25)
No. 644), an aqueous solution of an inorganic acid salt of titanium (for example, titanyl sulfate) is hydrolyzed in the presence of mica to precipitate hydrous titanium dioxide on the surface of mica, and then heated. . The mica used is generally muscovite mica, but in some cases, biotite may be used. In addition, mica is used after being pulverized with water and made to have a uniform particle size using a sieve. The produced mica titanium-based composite material exhibits various interference colors depending on the thickness of the titanium dioxide coating layer on the surface of the mica particles. The interference color is usually silver when the amount of titanium dioxide is 10-26% by weight of the product, but is gold in 26-40%, red in the direction of increasing titanium dioxide layer in the range of 40-50%, red, It changes to blue and green, and at 50-60%, high order interference colors are obtained.

こうした雲母チタン系複合材料は真珠光沢と種々の淡い
干渉色を有するものの、外観色は常に白色に近く、干渉
色と一致した鮮やかな外観色を呈するものは得られてい
ない。Although such a mica titanium-based composite material has pearl luster and various pale interference colors, the appearance color is always close to white, and no vivid appearance color matching the interference color has been obtained.

そこで従来、様々な外観色を出すためには、生成した雲
母チタン系複合材料に酸化鉄、紺青、酸化クロム、カー
ボンブラック、カーミンなどの有色顔料を添加して対処
していた。こうした有色の雲母チタン系複合材料の安全
性、安定性、耐光性、耐酸性、耐アルカリ性、耐溶媒
性、耐熱性などは添加した有色顔料の性質に負うところ
が多く、例えば紺青を添加した青色の雲母チタン系複合
材料はアルカリ溶液中で褪色し、カーミンを添加した赤
色の雲母チタン系複合顔料は光によって褐色劣化する。
一方、カーボンブラックを添加した黒色雲母チタン系複
合材料、酸化クロムを添加した緑色の雲母チタン系複合
顔料などのように、カーボンブラックに混入する可能性
のある３、４−ベンズピレンの発ガン性、あるいは六価
クロムの経口毒性など、安全性が問われているものも少
なくない。更に、上記有色の雲母チタン系複合材料は有
色顔料を添加している為、溶媒中で色分かれを起すな
ど、従来の有色雲母チタン系複合材料は種々の欠点を有
していた。Therefore, conventionally, colored pigments such as iron oxide, dark blue, chromium oxide, carbon black, and carmine have been added to the produced mica-titanium-based composite material in order to obtain various appearance colors. The safety, stability, light resistance, acid resistance, alkali resistance, solvent resistance, heat resistance, etc. of such colored mica titanium-based composite materials are largely owed to the properties of the added colored pigment. The mica titanium-based composite material is discolored in an alkaline solution, and the carmine-added red mica titanium-based composite pigment undergoes brown deterioration by light.
On the other hand, carcinogenicity of 3,4-benzpyrene, which may be mixed in carbon black, such as a black mica titanium-based composite material added with carbon black and a green mica titanium-based composite pigment added with chromium oxide, In addition, there are many cases where safety is required, such as oral toxicity of hexavalent chromium. Further, since the colored mica titanium-based composite material has a colored pigment added, the conventional colored mica titanium-based composite material has various drawbacks such as color separation in a solvent.

本発明者らは上記従来技術の欠点を改良すべく鋭意研究
を重ねた結果、雲母表面を酸化窒化チタン又は酸化窒化
チタンを必須成分として含有するチタン化合物で被覆す
ることにより明度、彩度等の色調が著しく改善され、外
観色と干渉色の良好なる一致を見、かつ安定性、安全
性、耐光性、耐酸性、耐アルカリ性、耐溶媒性、耐熱性
等の顔料特性にも優れており、更には比抵抗値等導電特
性にも優れた複合材料が得られることを見い出し、本発
明を完成するに至った。As a result of intensive studies to improve the above-mentioned drawbacks of the prior art, the inventors of the present invention coated the surface of the mica with titanium oxynitride or a titanium compound containing titanium oxynitride as an essential component to obtain lightness, saturation, etc. The color tone is remarkably improved, the appearance color and the interference color are well matched, and the stability, safety, light resistance, acid resistance, alkali resistance, solvent resistance, heat resistance, and other pigment characteristics are excellent. Furthermore, they have found that a composite material excellent in conductivity such as specific resistance value can be obtained, and completed the present invention.

すなわち、本発明にかかる雲母は、酸化窒化チタンまた
は酸化窒化チタンを必須成分として含有する酸化窒化チ
タン層を最外層として被覆されたことを特徴とする。That is, the mica according to the present invention is characterized in that titanium oxynitride or a titanium oxynitride layer containing titanium oxynitride as an essential component is coated as the outermost layer.

次に、本発明の構成について詳述する。Next, the configuration of the present invention will be described in detail.

本発明で使用される雲母はどのようなものでもよく、一
般には市販品の白雲母系雲母（muscovite mica）を用い
るのが、場合によっては黒雲母などを用いることも可能
である。粒径はとくに制限されないが、とくに化粧品等
用の顔料として利用する場合には一般市販の雲母（粒径
１〜50μ程度）のなかでも粒径が小さく粒子形状ができ
るだけ偏平なものが美しい色調と真珠光沢が発揮されや
すいため好ましい。Any mica may be used in the present invention. Generally, commercially available muscovite mica is used, but in some cases, biotite or the like may be used. The particle size is not particularly limited, but especially when it is used as a pigment for cosmetics, among commercially available mica (particle size 1 to 50μ), a small particle size and a flat particle shape as flat as possible have a beautiful color tone. It is preferable because pearl luster is easily exhibited.

本発明で使用される酸化窒化チタンとは低次酸化チタン
である一酸化チタン（Tio）に窒素が固溶した化合物（T
ixNyOz）であり、その化合物は窒素の固溶量によって変
るが、本発明においてはｘが0.2〜0.6、ｙが0.05〜0.
6、ｚが0.1〜0.9の値をとる。The titanium oxynitride used in the present invention is a compound (Tio) which is a low order titanium oxide in which nitrogen is solid-dissolved in titanium monoxide (Tio).
ixNyOz), and the compound varies depending on the solid solution amount of nitrogen, but in the present invention, x is 0.2 to 0.6 and y is 0.05 to 0.
6, z takes a value of 0.1 to 0.9.

本発明において用いられる酸化窒化チタン又は酸化窒化
チタンを必須成分として含有するチタン化合物で被覆さ
れた雲母とは、雲母の表面が前記酸化窒化チタンで被覆
されているか又は前記酸化窒化チタンを必須成分として
含有し他に低次酸化チタン、二酸化チタン等のチタン化
合物を任意量含有するチタン化合物混合物で雲母表面が
被覆されているものを指す。The mica coated with a titanium compound containing titanium oxynitride or titanium oxynitride as an essential component used in the present invention means that the surface of the mica is coated with the titanium oxynitride or the titanium oxynitride is an essential component. In addition, the mica surface is coated with a titanium compound mixture containing an optional amount of titanium compounds such as low-order titanium oxide and titanium dioxide.

ここで言う低次酸化チタンとはチタンの酸化度合が二酸
化チタン（TiO2）よりも低いものを指し、例えばTi2O,T
iO,Ti2O3，Ti3O5，Ti4O7等があげられる。The low-order titanium oxide referred to here means that the degree of oxidation of titanium is lower than that of titanium dioxide (TiO 2 ). For example, Ti 2 O, T
Examples include iO, Ti 2 O 3 , Ti 3 O 5 , and Ti 4 O 7 .

本発明の酸化窒化チタン又は酸化窒化チタンを必須成分
として含有するチタン化合物で被覆された雲母におい
て、酸化窒化チタンの含有量は雲母100部に対して0.01
〜60重量部であることが好ましい。In the mica coated with a titanium compound containing titanium oxynitride or titanium oxynitride as an essential component of the present invention, the content of titanium oxynitride is 0.01 with respect to 100 parts of mica.
It is preferably about 60 parts by weight.

酸化窒化チタンの含有量が0.01重量部未満では得られた
雲母は干渉色は有してもこれと一致する外観色は得にく
く、60重量部を超える場合は粒子の凝集をおこし易く好
ましくない。When the content of titanium oxynitride is less than 0.01 parts by weight, the obtained mica has an interference color, but it is difficult to obtain an appearance color matching with the interference color.

また、本発明において、雲母上に被覆されるチタン化合
物の総量は厚さで200Å以上あることが好ましく、更に
黒色以外の色調の優れた外観色および干渉色を得ようと
する場合には900Å以上あることが好ましい。Further, in the present invention, the total amount of the titanium compound coated on the mica is preferably 200 Å or more in thickness, and 900 Å or more when it is desired to obtain an excellent appearance color and interference color other than black. Preferably there is.

次に本発明のチタン化合物で被覆された雲母の製造方法
について例示すると、市販の二酸化チタン被覆雲母を50
0℃〜1000℃、好ましくは700℃〜900℃の温度でアンモ
ニアガスによって、あるいはアンモニアガスとヘリウム
ガス、アルゴンガス、窒素ガスなどの不活性ガスとの混
合ガスによって加熱還元する方法、市販の二酸化チタン
被覆雲母に二酸化チタンを混合し、該混合物を上記の方
法によって加熱還元する方法等を挙げることができる。
更にはデュポンの特許（特公昭43−25644号公報）に見
られるようなチタンの無機酸塩（たとえば硫酸チタニ
ル）の水溶液を前述した雲母の存在下で加水分解し、雲
母粒子表面に含水二酸化チタンを析出させ、これを500
℃〜1000℃好ましくは700℃〜900℃の温度でアンモニア
ガスによって、あるいはアンモニアガスとヘリウムガ
ス、アルゴンガス、窒素ガスなどの不活性ガスとの混合
ガスによって加熱還元するか、あるいは雲母粒子表面に
含水二酸化チタンを析出させたのち加熱し雲母チタンを
生成させてこれを上記市販の雲母チタン系顔料と同様な
方法で還元してもよい。Next, the method for producing the mica coated with the titanium compound of the present invention will be exemplified.
A method of heating and reducing with ammonia gas at a temperature of 0 ° C. to 1000 ° C., preferably 700 ° C. to 900 ° C. or with a mixed gas of ammonia gas and an inert gas such as helium gas, argon gas or nitrogen gas, commercially available dioxide. Examples thereof include a method in which titanium dioxide is mixed with titanium-coated mica, and the mixture is heated and reduced by the above method.
Further, an aqueous solution of an inorganic acid salt of titanium (for example, titanyl sulfate) as found in the DuPont patent (Japanese Patent Publication No. 43-25644) is hydrolyzed in the presence of the above-mentioned mica, and the surface of the mica particles is hydrous titanium dioxide. To deposit 500
℃ ~ 1000 ℃ preferably at a temperature of 700 ℃ ~ 900 ℃ with ammonia gas, or by heating and reducing with a mixed gas of ammonia gas and an inert gas such as helium gas, argon gas, nitrogen gas, or mica particle surface The water-containing titanium dioxide may be precipitated and then heated to form mica titanium, which may be reduced in the same manner as the commercially available mica titanium pigment.

本発明のチタン化合物で被覆された雲母において重要な
ことは、雲母上に被覆されているチタン化合物中に酸化
窒化チタンを必須成分として含むことである。What is important in the mica coated with the titanium compound of the present invention is that titanium oxynitride is contained as an essential component in the titanium compound coated on the mica.

酸化窒化チタンが存在しなければ当初目的とした明度、
彩度等の色調に優れ、外観色と干渉色の良好なる一致性
等は達成されない。チタン化合物が全て酸化窒化チタン
である場合には外観色と干渉色が黒色のものが得られ、
チタン化合物が酸化窒化チタンの他に低次酸化チタンや
二酸化チタンをも含有する場合には雲母表面を被覆する
前記のチタン化合物の量を調節することにより銀色、金
色、赤色、青色、緑色等の種々の外観色と干渉色を有す
るものを得ることができる。If titanium oxynitride does not exist, the originally intended brightness,
The color tone such as saturation is excellent, and good matching between the appearance color and the interference color is not achieved. When the titanium compound is all titanium oxynitride, a black appearance color and interference color are obtained,
When the titanium compound contains low-order titanium oxide or titanium dioxide in addition to titanium oxynitride, silver amount, gold color, red color, blue color, green color, etc. can be adjusted by adjusting the amount of the titanium compound coating the mica surface. Those having various appearance colors and interference colors can be obtained.

本発明のチタン化合物で被覆された雲母は、明度、彩度
等の色調に優れ、外観色と干渉色の良好なる一致性を有
し、かつ安定性、安全性、耐光性、耐酸性、耐アルカリ
性、耐溶媒性、耐熱性に優れる等その効果の大なる点で
画期的で、化粧料、塗料、日用雑貨、装飾品等の顔料、
有色パール光沢材料等として又、比抵抗値が低いことか
ら記録紙用の導電層や記録層、並びに静電気防止材料な
どの導電性材料としての用途も考えられる等産業上利用
価値の大なるものがある。The mica coated with the titanium compound of the present invention is excellent in color tone such as lightness and saturation, and has good matching of appearance color and interference color, and stability, safety, light resistance, acid resistance, resistance It is epoch-making in terms of its great effects such as excellent alkalinity, solvent resistance, heat resistance, and pigments for cosmetics, paints, sundries, ornaments, etc.
As a colored pearly luster material, etc., it is also considered to have a great industrial value such as a conductive layer or recording layer for recording paper due to its low specific resistance value, and a conductive material such as an antistatic material. is there.

次に実施例をあげて本発明をさらに詳細に説明するが、
本発明はこれに限定されるものではない。Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to this.

実施例１ 雲母50gをイオン交換水500gに添加して十分に攪拌し均
一に分散させた。得られた分散液に濃度40重量％の硫酸
チタニル水溶液208.5gを加えて、攪拌しながら加熱し６
時間沸謄させた。放冷後、過水洗し900℃で焼成し
て、二酸化チタンで被覆された雲母（雲母チタン）80g
を得た。次に得られた雲母チタンを流速3l/minのアンモ
ニアガス気流下で700℃、６時間の還元処理を行ない、
冷却後、粉末70gを回収した。得られた粉末は外観色、
干渉色ともに青色の真珠光沢を呈するものであり、比抵
抗は4.8Ωcmであった。Example 1 50 g of mica was added to 500 g of ion-exchanged water, and the mixture was thoroughly stirred and uniformly dispersed. To the obtained dispersion liquid, 208.5 g of a 40% strength by weight titanyl sulfate aqueous solution was added, and the mixture was heated with stirring 6
Let it boil for hours. After standing to cool, wash with excess water and bake at 900 ° C, 80 g of titanium dioxide-coated mica (titanium mica)
Got Next, the mica titanium thus obtained was subjected to reduction treatment at 700 ° C. for 6 hours in an ammonia gas stream having a flow rate of 3 l / min,
After cooling, 70 g of powder was recovered. The obtained powder has an appearance color,
The interference color was blue pearlescent and the specific resistance was 4.8 Ωcm.

得られた粉末の粒子表面の金属組織写真（倍率30,000倍
の走査型電子顕微鏡で撮影）を第１図に示す。これによ
れば、得られた粉末の粒子一個の表面が微粒子状のもの
で充分に被覆されている状態を観察することができる。A metallographic photograph (taken with a scanning electron microscope at a magnification of 30,000) of the particle surface of the obtained powder is shown in FIG. According to this, it can be observed that the surface of each particle of the obtained powder is sufficiently covered with fine particles.

また、得られた粉末のＸ線回折図（Cu−Ｋα線）は第２
図に示すとおりであり、これによれば雲母の回折ピーク
の他に回折角（ブラッグ角２θ）25.3°付近にピークが
認められる。これはアナターゼ型二酸化チタンの最強ピ
ークの（101）に相当している。又、ブラッグ角２θが4
3°付近と37°付近にややブロードのピークが認められ
るがこのピークはASTM検索からASTM No.8−117の一酸化
チタン（TiO）とASTM No.6−0462の窒化チタン（TiN）
の回折角の中間付近である。このことを結晶学的に説明
すれば、一酸化チタンと窒化チタンは同一結晶系の立方
晶系で、格子定数が異なるために回折角が異なる。In addition, the X-ray diffraction pattern (Cu-Kα ray) of the obtained powder is the second
As shown in the figure, according to this, in addition to the diffraction peak of mica, a peak is recognized near the diffraction angle (Bragg angle 2θ) of 25.3 °. This corresponds to the strongest peak (101) of anatase titanium dioxide. Bragg angle 2θ is 4
There are some broad peaks around 3 ° and around 37 °, but these peaks are found by ASTM search to be ASTM No.8-117 titanium monoxide (TiO) and ASTM No.6-0462 titanium nitride (TiN).
It is near the middle of the diffraction angle of. This can be explained crystallographically. Titanium monoxide and titanium nitride have the same crystal system of cubic system, and have different diffraction constants because they have different lattice constants.

すなわち、得られた粉末中に含まれていてＸ線の回折角
２θが43°と37°付近に認められる化合物は、一酸化チ
タンと窒化チタンの固溶体の状態であることを意味して
いる。固溶体を一般式で示せばTixNyOzとなり酸化窒化
チタンである。Ｘ線回折線の強度比からその組成比を求
めると雲母が60重量％、二酸化チタンが22.7重量％、酸
化窒化チタンが17.3重量％の組成比であった。更に酸素
量と窒素量を定量するためLACO社製TC−136型で酸素、
窒素の同時定量分析を行った。その結果酸素が41.7重量
％、窒素が4.3重量％であった。上述の組成分析の結果
から酸化窒化チタンはTi0.30N0.19O0.51であることが分
かる。That is, the compound contained in the obtained powder and having an X-ray diffraction angle 2θ of around 43 ° and 37 ° means that it is in the state of a solid solution of titanium monoxide and titanium nitride. If the solid solution is expressed by a general formula, it becomes TixNyOz, which is titanium oxynitride. When the composition ratio was calculated from the intensity ratio of X-ray diffraction lines, the composition ratio was 60% by weight of mica, 22.7% by weight of titanium dioxide and 17.3% by weight of titanium oxynitride. Furthermore, in order to quantify the amount of oxygen and the amount of nitrogen, LACO TC-136 type oxygen,
Simultaneous quantitative analysis of nitrogen was performed. As a result, oxygen was 41.7% by weight and nitrogen was 4.3% by weight. From the above compositional analysis results, it is found that titanium oxynitride is Ti 0.30 N 0.19 O 0.51 .

以上のことから雲母粒子表面を被覆している二酸化チタ
ン及び酸化窒化チタンの量を決定することができる。From the above, the amounts of titanium dioxide and titanium oxynitride coating the surface of the mica particles can be determined.

さらに得られた粉末のESCA（Electron Spectroscopy of
Chemical Analysis）にてTi2P結合エネルギーを分析し
た結果を第３図に示す。In addition, ESCA (Electron Spectroscopy of
Fig. 3 shows the result of analysis of Ti2P binding energy by chemical analysis).

装置は島津製作所製ESCA 650Bを使用した。図中（１）
は得られた粉末の表面層を分析したもの、（２）はアル
ゴンエッチングを施し表面から400Åの深さの層を分析
したもの、（３）は同じく表面から1000Åの深さの層を
分析したものである。（１）、（２）、（３）に共通に
みられるピーク（Ａ）は二酸化チタン（Ti−O2）の結合
エネルギーピークであり、（２）にのみ見られる（Ｂ）
および（Ｃ）のピークはそれぞれ一酸化チタン（Ti−
Ｏ）と窒化チタン（Ti−Ｎ）の結合エネルギーピークで
ある。As the device, ESCA 650B manufactured by Shimadzu Corporation was used. (1) in the figure
Is an analysis of the surface layer of the obtained powder, (2) is an argon-etched layer with a depth of 400 Å from the surface, and (3) is an analysis of a layer with a depth of 1000 Å from the surface. It is a thing. The peak (A) commonly seen in (1), (2), and (3) is the binding energy peak of titanium dioxide (Ti-O 2 ), and is only seen in (2) (B).
The peaks of (C) and (C) are titanium monoxide (Ti-
It is a bond energy peak of O) and titanium nitride (Ti-N).

図から明らかなように得られた粉末は雲母の表面が二酸
化チタンと酸化窒化チタンとで被覆され、さらにその表
面の一部が酸化されて二酸化チタンに変わっていること
がわかる。As is apparent from the figure, it is understood that the surface of the mica of the obtained powder is coated with titanium dioxide and titanium oxynitride, and a part of the surface is oxidized to be titanium dioxide.

実施例２ 雲母50gをイオン交換水500gに添加して十分に攪拌し均
一に分散させた。得られた分散液に濃度40重量％の硫酸
チタニル水溶液312.5gを加えて、攪拌しながら加熱し６
時間沸謄させた。放冷後、過水洗し900°で焼成し
て、表面が二酸化チタンで被覆された雲母（雲母チタ
ン）100gを得た。Example 2 Mica (50 g) was added to ion-exchanged water (500 g) and sufficiently stirred to uniformly disperse the mixture. To the resulting dispersion was added 312.5 g of a 40% strength by weight aqueous titanyl sulfate solution, and the mixture was heated with stirring.
Let it boil for hours. After cooling, it was washed with excess water and baked at 900 ° to obtain 100 g of mica (titanium mica) having a surface coated with titanium dioxide.

次に得られた雲母チタンを流速１/minのアンモニアガ
スと流速3l/minの窒素ガスとの混合ガス気流下で800
℃、４時間の還元処理を行ない、冷却後、粉末97gを回
収した。得られた粉末は外色、干渉色ともに緑色の真珠
光沢を呈するものであり比抵抗値は0.14Ωcmであった。Then, the titanium mica obtained was subjected to 800 times in a mixed gas flow of ammonia gas at a flow rate of 1 / min and nitrogen gas at a flow rate of 3 l / min.
After reduction treatment at 4 ° C. for 4 hours and cooling, 97 g of powder was recovered. The powder obtained had a green pearlescent luster for both the external color and the interference color, and the specific resistance value was 0.14 Ωcm.

また、得られた粉末を実施例１と同様な方法で組成比を
求めると、雲母が49.5重量％、二酸化チタンが10.1重量
％、酸化窒化チタンが40.4重量％の組成比であった。ま
た、酸素量と窒素量から酸化窒化チタンはTi0.35 NO.29
00.37であった。The composition ratio of the obtained powder was determined by the same method as in Example 1. The composition ratio was 49.5% by weight of mica, 10.1% by weight of titanium dioxide and 40.4% by weight of titanium oxynitride. In addition, from the oxygen and nitrogen contents, titanium oxynitride is Ti0.35 NO.29.
It was 00.37.

実施例３ 雲母50gをイオン交換水500mlに添加して十分に攪拌し均
一に分散させた。得られた分散液に濃度40重量％の硫酸
チタニル水溶液125gを加えて攪拌しながら加熱し、６時
間沸謄させた。放冷後、過水洗し900℃で焼成して二
酸化チタンで被覆された雲母（雲母チタン）70gを得
た。次に得られた雲母チタンを流速3l/minのアンモニア
ガス気流下で800℃、２時間の還元処理を行ない粉末68g
を得た。得られた粉末は外観色、干渉色ともに銀灰色の
真珠光沢を呈するものであり、比抵抗は2.1×103Ωcmで
あった。また、この得られた粉末は雲母が71重量％、二
酸化チタンが22.7重量％、酸化窒化チタンが6.32重量％
の組成比であった。また、酸素量と窒素量から酸化窒化
チタンはTi0.55 N0.26 01.17であった。Example 3 50 g of mica was added to 500 ml of ion-exchanged water, and the mixture was thoroughly stirred and uniformly dispersed. 125 g of an aqueous titanyl sulfate solution having a concentration of 40% by weight was added to the obtained dispersion, and the mixture was heated with stirring and boiled for 6 hours. After standing to cool, it was washed with excess water and baked at 900 ° C. to obtain 70 g of mica (titanium mica) coated with titanium dioxide. Next, the obtained mica titanium was subjected to reduction treatment at 800 ° C. for 2 hours under an ammonia gas flow with a flow rate of 3 l / min to obtain 68 g of powder.
Got The obtained powder had silver gray pearl luster in both appearance color and interference color, and the specific resistance was 2.1 × 10 3 Ωcm. The powder obtained was 71% by weight of mica, 22.7% by weight of titanium dioxide and 6.32% by weight of titanium oxynitride.
Was the composition ratio. Further, titanium oxynitride was Ti0.55 N0.26 01.17 based on the amounts of oxygen and nitrogen.

実施例４〜７ 市販（米国マール社製）の干渉色を有する雲母チタン系
真珠光沢顔料４種類を各50部とり、還元ガスの種類、ガ
ス流速、還元温度、還元時間を変えて各々還元した。放
冷後、生成物50部を得た。得られた粉末の色、干渉色を
肉眼で観察した。Examples 4 to 7 50 parts each of 4 types of commercially available (manufactured by Marl, USA) interference mica titanium-based pearlescent pigments were taken and reduced by changing the type of reducing gas, the gas flow rate, the reducing temperature and the reducing time. . After cooling, 50 parts of the product was obtained. The color and interference color of the obtained powder were visually observed.

得られた粉末の組成比及び酸化窒化チタン組成を実施例
１と同様に求めた。結果を第１表に示す。The composition ratio and the titanium oxynitride composition of the obtained powder were determined in the same manner as in Example 1. The results are shown in Table 1.

以上の実施例１〜７で得られた製品である有色の雲母チ
タン系顔料の顔料特性を試験した。比較のため米国マー
ル社から市販されている有色の雲母チタン系真珠光沢顔
料（従来の雲母チタン系顔料に有色顔料を添加したも
の）の顔料特性を同様に試験した。比較した市販の有色
雲母チタン系真珠光沢顔料には、実施例１〜７の製品で
ある有色の雲母チタン系顔料の色調と対応するものを選
んでいる。結果を第２表に示す。 The pigment characteristics of the colored mica titanium-based pigments, which are the products obtained in Examples 1 to 7 above, were tested. For comparison, the pigment properties of a colored mica titanium-based pearlescent pigment (a conventional mica titanium-based pigment plus a colored pigment) marketed by Marl, USA were similarly tested. As the commercially available colored mica titanium-based pearlescent pigments for comparison, ones corresponding to the color tone of the colored mica titanium-based pigments as the products of Examples 1 to 7 are selected. The results are shown in Table 2.

市販品の組成は第３表に示す通りである。 The composition of the commercial product is as shown in Table 3.

試験項目は酸安定性、アルカリ安定性、光安定性、熱安
定性、分散安定性であり、試験方法と試験結果は次のと
おりである。 The test items are acid stability, alkali stability, light stability, heat stability, and dispersion stability. The test methods and test results are as follows.

酸安定性試験 本発明の製品である有色の雲母チタン系顔料および市販
の有色雲母チタン系真珠光沢顔料1.5gをそれぞれ共栓付
50ml入り試験管に入れ、これに2N塩酸水溶液30mlを加え
て分散後、試験管立てに立てて静置し、24時間後の色調
を肉眼で観察した。結果を第４表に示す。Acid stability test 1.5 g of colored mica titanium-based pigments, which are the products of the present invention, and commercially available colored mica titanium-based pearlescent pigments, 1.5 g each, are attached with stoppers.
The mixture was placed in a test tube containing 50 ml, 30 ml of a 2N hydrochloric acid aqueous solution was added thereto to disperse, and the test tube stand was stood still and the color tone after 24 hours was visually observed. The results are shown in Table 4.

第４表の結果から明らかなように本発明の製品である有
色の雲母チタン系顔料は酸に対して全て安定であった
が、市販の有色雲母チタン系真珠光沢顔料はいずれも不
安定で徐々に褐色し、24時間後には市販品のクロイゾネ
レッドは白色に変化し、クロイゾネゴールド、クロイゾ
ネブルー、クロイゾネグリーンは色調が薄く白っぽくな
り、真珠光沢も極端に低下した。このように本発明の製
品である有色の雲母チタン系顔料は酸安定性に優れてい
ることがわかる。As is clear from the results shown in Table 4, all of the colored mica titanium-based pigments as the products of the present invention were stable to acid, but all the commercially available colored mica titanium-based pearlescent pigments were unstable and gradually. After 24 hours, commercial Cloisone Red turned white, and Cloisone Gold, Cloisone Blue, Cloisone Green became pale and whitish, and the pearl luster was extremely reduced. Thus, it can be seen that the colored mica titanium-based pigment, which is a product of the present invention, has excellent acid stability.

アルカリ安定性試験 本発明の製品である有色の雲母チタン系顔料および市販
の有色雲母チタン系真珠光沢顔料1.5gをそれぞれ共栓付
50ml入り試験管に入れ、これに2N苛性ソーダ水溶液30ml
を加えて分散後、試験管立てに静置し24時間後の色調を
肉眼で観察した。結果を第５表に示す。 Alkali stability test 1.5 g of colored mica titanium-based pigment, which is a product of the present invention, and commercially available colored mica titanium-based pearlescent pigment, 1.5 g each, are attached with stoppers.
Put it in a test tube containing 50 ml, and add 30 ml of 2N caustic soda solution to it.
After adding and dispersing, the mixture was allowed to stand in a test tube stand and the color tone after 24 hours was visually observed. The results are shown in Table 5.

第５表の結果から明らかなように、本発明の製品である
有色の雲母チタン系顔料はアルカリに対して全く安定な
のに対して、、市販の有色雲母チタン系真珠光沢顔料は
いずれも不安定で徐々に褐色し、24時間後には市販品の
クロイゾネレッドとクロイゾネブルーは白色に変化し、
クロイゾネゴールド、クロイゾネグリーンは色調がうす
く白っぽくなり、真珠光沢も極端に低下した。このよう
に本発明の製品である有色の雲母チタン系顔料はアルカ
リ安定性に優れていることがわかる。 As is clear from the results in Table 5, the colored mica titanium-based pigment that is the product of the present invention is quite stable against alkali, while the commercially available colored mica titanium-based pearlescent pigment is unstable. It gradually turns brown, and after 24 hours, commercially available Cloisone Red and Cloisone Blue change to white,
Cloisone Gold and Cloisone Green have become slightly whitish in color, and the pearl luster is also extremely reduced. Thus, it can be seen that the colored mica titanium-based pigment, which is a product of the present invention, has excellent alkali stability.

光安定性試験 本発明の製品である有色の雲母チタン系顔料および市販
の有色雲母チタン系真珠光沢顔料をそれぞれタルク（浅
田製粉社製）と3:7の割合で混合し、該混合物2.5gをそ
れぞれ厚さ3mm、一辺20mmの正方形のアルミ製中皿に成
型し、これにキセノンランプを30時間照射した。照射後
の色調と照射前の色調をカラーアナライザー607を用い
て測色して、測色値から照射前後の色差（ΔＥ）を求め
た。結果を第６表に示す。Light Stability Test A colored mica titanium-based pigment that is a product of the present invention and a commercially available colored mica titanium-based pearlescent pigment are mixed with talc (manufactured by Asada Flour Milling Co., Ltd.) at a ratio of 3: 7, and 2.5 g of the mixture is added. Each was molded into a square aluminum inner plate having a thickness of 3 mm and a side of 20 mm, and this was irradiated with a xenon lamp for 30 hours. The color tone after irradiation and the color tone before irradiation were measured with a color analyzer 607, and the color difference (ΔE) before and after irradiation was determined from the colorimetric value. The results are shown in Table 6.

第６表の結果から明らかなように本発明の製品である有
色の雲母チタン系顔料は照射前後で色差（ΔＥ）が0.5
以下とほとんど変らず、肉眼ではほとんど色調の差が判
別できないのに対して、市販品のクロイゾネレッドやク
ロイゾネゴールドがそれぞれ35.3、18.0と極端に大き
く、肉眼でも色調の変化が明瞭であった。また、クロイ
ゾネグリーンやクロイゾネブルーもそれぞれ色差6.0、
5.2と大きく、肉眼でもはっきりと色調変化を起してい
ることが認められた。 As is clear from the results shown in Table 6, the color mica titanium pigment, which is a product of the present invention, has a color difference (ΔE) of 0.5 before and after irradiation.
The difference in color tone is almost the same as the following, and the difference in color tone is almost invisible to the naked eye, whereas commercially available Cloisone Red and Cloisone Gold are extremely large at 35.3 and 18.0, respectively, and the change in color tone was clear even with the naked eye. . In addition, Cloisone green and Cloisone blue have a color difference of 6.0,
It was as large as 5.2, and it was recognized that the color tone was clearly changed with the naked eye.

熱安定性試験 本発明の製品である有色の雲母チタン系顔料および市販
の有色雲母チタン系真珠光沢顔料を各々20ml入磁性ルツ
ボに3g秤り取り、大気中で200℃、300℃、400℃、500℃
の各温度条件下、２時間熱処理した。処理後の粉末をカ
ラーアナライザー607で測色し、処理前の顔料との色差
（ΔＥ）を求めた。また色調変化を肉眼観察した。各々
の結果を第７表に示す。Thermal stability test 3 m of each colored mica titanium-based pigment which is a product of the present invention and a commercially available colored mica titanium-based pearlescent pigment are weighed in a magnetic crucible containing 20 ml, and 200 ° C., 300 ° C. and 400 ° C. in the atmosphere. 500 ° C
Heat treatment was performed for 2 hours under each temperature condition. The color of the treated powder was measured with a color analyzer 607, and the color difference (ΔE) from the pigment before treatment was determined. Further, the change in color tone was visually observed. The results of each are shown in Table 7.

第７表の結果から明らかなように本発明の製品である有
色の雲母チタン系顔料は、400℃までは色差0.5以下で肉
眼ではほとんど色調に変化がなく安定である。500℃に
なると黄白色に変化する。これは雲母粒子表面の低次酸
化チタンが酸化され酸化チタンに変化したためである。
即ち本発明の製品である有色の雲母チタン系顔料は500
℃未満の温度まで安定であることがわかる。これに対
し、市販品のクロイゾネレッドやクロイゾネブルーは、
200℃で色差がそれぞれ3.2、3.5となり、肉眼でも色調
変化がはっきりみられる。300℃になると色調が36.4、2
6.2とさらに大きくなり色調も赤から黄赤色に、青から
赤茶色に変化する。即ちクロイゾネレッドとクロイゾネ
ブルーは200℃で色調が変化することから熱安定性に劣
ることがわかる。クロイゾネグリーンは400℃で色差が
7.8となり、彩度が低下し暗緑色に変化する。即ち400℃
未満までは安定であるが、それ以上の温度では不安定で
ある。クロイゾネゴールドに限っては500℃になっても
多少彩度が劣る程度であり、色差も1.0以下で安定性が
高い。As is clear from the results in Table 7, the colored mica titanium-based pigment, which is a product of the present invention, is stable with a color difference of 0.5 or less up to 400 ° C. and almost no change in color tone with the naked eye. It turns yellowish white at 500 ℃. This is because the low-order titanium oxide on the surface of the mica particles was oxidized and changed to titanium oxide.
That is, the colored mica titanium-based pigment that is the product of the present invention is 500
It can be seen that it is stable up to a temperature of less than ° C. On the other hand, commercially available Cloisone Red and Cloisone Blue are
At 200 ° C, the color difference is 3.2 and 3.5, respectively, and the change in color is clearly visible to the naked eye. At 300 ℃, the color tone is 36.4, 2
It becomes even larger at 6.2 and the color tone changes from red to yellow-red and from blue to reddish brown. That is, it can be seen that since the color tone of Cloisone red and Cloisone blue changes at 200 ° C, the thermal stability is poor. Cloisone green has a color difference at 400 ℃
It becomes 7.8, and the saturation decreases and it changes to dark green. That is 400 ℃
It is stable up to less than, but unstable at higher temperatures. Only with Cloisone Gold, the saturation is slightly inferior even at 500 ° C, and the color difference is 1.0 or less, and the stability is high.

分散（色分れ）安定性試験 本発明の製品である有色の雲母チタン系顔料および市販
の有色雲母チタン系真珠光沢顔料をそれぞれ1.0g、共栓
目盛付50ml試験管に入れ、これに0.2重量％のヘキサメ
タリン酸水溶液50mlを加えて、ポリトロンにて30秒間分
散させ、更にこの分散液を超音波にて分散させた。分散
後、試験管立てにて静置し、静置直後、５分間後、10分
間後、30分間後、１時間後の分散状態を肉眼で観察し
た。結果は第８表に示す通りであった。 Dispersion (color separation) stability test 1.0 g each of the colored mica titanium-based pigment and the commercially available colored mica titanium-based pearlescent pigment, which are the products of the present invention, were put into a 50 ml test tube with a stopper plug scale, and 0.2 weight % Hexametaphosphoric acid aqueous solution (50 ml) was added, and the mixture was dispersed with a polytron for 30 seconds, and this dispersion was further dispersed by ultrasonic waves. After the dispersion, the sample was allowed to stand in a test tube stand, and immediately after standing, the dispersed state after 5 minutes, 10 minutes, 30 minutes, and 1 hour was visually observed. The results are as shown in Table 8.

第８表の結果から明らかなように本発明の製品である雲
母チタン系顔料は、１時間静置後も均一に分散している
のに対して、市販品のクロイゾネブルーとクロイゾネレ
ッドは、静置後５分間で沈降がみられしかも上澄液が青
色や赤色をしていた。これは、単に混合した紺青やカー
ミンが分離したためである。クロイゾネグリーンは、静
置後30分で沈降がみられ、しかも上澄液の方が沈降した
粒子の緑色より、濃い緑色をしていた。これは単に混合
した酸化クロムが分離したためである。As is clear from the results in Table 8, the mica titanium-based pigment that is the product of the present invention is uniformly dispersed even after standing for 1 hour, whereas the commercially available products, Cloisone Blue and Cloisone Red, are After 5 minutes of standing, sedimentation was observed, and the supernatant was blue or red. This is simply due to the separation of the mixed dark blue and carmine. As for Cloisone green, sedimentation was observed after 30 minutes of standing, and the supernatant liquid was darker green than the sedimented green particles. This is simply due to the separation of the mixed chromium oxides.

【図面の簡単な説明】[Brief description of drawings]

第１図は実施例１で得られた本発明品の粒子表面の金属
組織写真（30,000倍）、第２図は実施例１で得られた本
発明品のＸ線回折図（Cu−Ｋα線）第３図は実施例１で
得られた本発明品のTi2PのESC分析図である。FIG. 1 is a metallographic photograph (30,000 times) of the particle surface of the product of the present invention obtained in Example 1, and FIG. 2 is an X-ray diffraction diagram (Cu-Kα line of the product of the present invention obtained in Example 1. ) FIG. 3 is an ESC analysis chart of Ti 2 P of the product of the present invention obtained in Example 1.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 福二 神奈川県横浜市港北区新羽町1050番地 株 式会社資生堂研究所内 (56)参考文献 特公 平５−46385（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Fukuji Suzuki 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Prefecture Shiseido Research Institute Co., Ltd. (56) References Japanese Patent Publication 5-46385 (JP, B2)

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】酸化窒化チタンまたは酸化窒化チタンを必
須成分として含有する酸化窒化チタン層を実質的に最外
層として被覆された雲母。1. A mica coated with titanium oxynitride or a titanium oxynitride layer containing titanium oxynitride as an essential component, substantially as the outermost layer.
JP59041665A 1984-03-05 1984-03-05 Mica coated with titanium compound Expired - Lifetime JPH0781093B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59041665A JPH0781093B2 (en) 1984-03-05 1984-03-05 Mica coated with titanium compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59041665A JPH0781093B2 (en) 1984-03-05 1984-03-05 Mica coated with titanium compound

Publications (2)

Publication Number Publication Date
JPS60184570A JPS60184570A (en) 1985-09-20
JPH0781093B2 true JPH0781093B2 (en) 1995-08-30

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JP59041665A Expired - Lifetime JPH0781093B2 (en) 1984-03-05 1984-03-05 Mica coated with titanium compound

Country Status (1)

Country Link
JP (1) JPH0781093B2 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2114913C (en) * 1993-02-05 2003-12-09 Takafumi Atarashi Powder having at least one layer and process for preparing the same
DE4419089A1 (en) * 1994-06-01 1995-12-07 Basf Ag Interference pigments used for security documents and packaging
DE19511696A1 (en) * 1995-03-30 1996-10-02 Basf Ag Luster pigments based on reduced titanium dioxide coated silicate flakes
DE19511697A1 (en) * 1995-03-30 1996-10-02 Basf Ag Process for the preparation of bluish gloss pigments
JP2003171232A (en) * 2001-12-10 2003-06-17 Kao Corp Lip cosmetic
CN101811677B (en) * 2010-05-06 2011-11-09 东华大学 Method for preparing hollow porous quadruped titanium nitride
AU2014283736B2 (en) * 2013-06-17 2017-07-20 Merck Patent Gmbh Transparent, optically variable interference pigments with electrical semi-conducting properties
MX2015017041A (en) * 2013-06-17 2016-04-21 Merck Patent Gmbh Transparent, electrically semiconducting interference pigments with high color strength.

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60170670A (en) * 1984-02-15 1985-09-04 Shiseido Co Ltd Mica coated with titanium compound

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Publication number Publication date
JPS60184570A (en) 1985-09-20

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