JP2872903B2 - Method for producing green pearlescent pigment - Google Patents
Method for producing green pearlescent pigmentInfo
- Publication number
- JP2872903B2 JP2872903B2 JP5340218A JP34021893A JP2872903B2 JP 2872903 B2 JP2872903 B2 JP 2872903B2 JP 5340218 A JP5340218 A JP 5340218A JP 34021893 A JP34021893 A JP 34021893A JP 2872903 B2 JP2872903 B2 JP 2872903B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- pearlescent pigment
- oxide
- green
- green pearlescent
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、真珠光沢顔料に関し、
更に詳しくは従来の光の干渉色のみの色調を有する真珠
光沢顔料と比べ、特に下地が白色の場合強い緑色を呈
し、光輝性があり且つより強く発色した色調を有する緑
色真珠光沢顔料であって、これらの色調を求める分野、
例えば、樹脂、塗料、インキ、建材等の分野の他、意匠
性を求める分野に有用な真珠光沢顔料の提供を目的とす
る。The present invention relates to a pearlescent pigment,
More specifically, as compared with a conventional pearlescent pigment having a color tone of only an interference color of light, a green pearlescent pigment which exhibits a strong green color, particularly when the base is white, has a brilliant color, and has a more strongly developed color tone. , The fields seeking these colors,
For example, an object of the present invention is to provide a pearlescent pigment that is useful in fields requiring design, in addition to fields such as resins, paints, inks, and building materials.
【0002】[0002]
【従来の技術】従来知られている着色した真珠光沢顔料
において最もポピュラーなものは、雲母フレーク上に被
覆する二酸化チタンの膜厚を変化させることにより色調
を変える、いわゆる虹彩色によるものが一般的である。
しかしながら、これらの方法によって得られる真珠光沢
顔料の色相は全般に淡く且つソフトな感じのものでり、
濃色を出すことは出来ない。この理由は全体の光の中で
干渉色として利用される光が、ごく一部に限られている
からである。2. Description of the Related Art Among the known pearlescent pigments, the most popular one is a so-called iris color in which the color tone is changed by changing the film thickness of titanium dioxide coated on mica flakes. It is.
However, the hue of the pearlescent pigment obtained by these methods is generally pale and soft,
It cannot produce dark colors. This is because the light used as the interference color in the entire light is limited to only a small part.
【0003】上記従来の真珠光沢顔料を用いた塗料を塗
布した場合、下地を黒くすることにより散乱光が取り除
かれる為、全体として色調がやや強くなるが、下地が白
い場合は錯乱光の影響で白っぽくなり、僅かに虹彩色が
現れるという状況である。又、比較的強い色調を有する
ものとしては、二酸化チタンと同様に高い隠蔽性のある
酸化鉄を雲母フレークに被覆した顔料があるが、この真
珠光沢顔料は黄色から茶色系のいわゆるゴールドからラ
ッセット系の色調であり、強い色彩のバリエーションに
欠ける面があった。[0003] When a paint using the above-mentioned conventional pearlescent pigment is applied, scattered light is removed by making the base black, so that the color tone becomes slightly stronger as a whole, but when the base is white, it is affected by confusion light. It is a situation where it becomes whitish and a slight iris color appears. Further, as a pigment having a relatively strong color tone, there is a pigment in which mica flakes are coated with iron oxide having a high concealing property like titanium dioxide, and this pearlescent pigment is a so-called gold to russet pigment of yellow to brown. Color tone and lacked strong color variations.
【0004】[0004]
【発明が解決しようとしている問題点】上述の様に雲母
フレークの被覆層として二酸化チタンをベースとした従
来の真珠光沢顔料は、虹彩色を利用するのみで色調が弱
く、被覆層として二酸化チタンをベースとしたもの以外
では、比較的色の強い酸化鉄系があるが、黄色又は茶色
系の色調で、色調のバリエーションに欠ける嫌いがあっ
た。従って本発明の目的は、上記従来技術の状況に鑑
み、二酸化チタンの有する強い光輝性を保ちつつ、より
強い色調で且つ色彩のバリエーションも多い緑色真珠光
沢顔料を提供することである。As described above, the conventional pearlescent pigment based on titanium dioxide as a coating layer of mica flakes has a weak color tone only by using the iris color, and titanium dioxide is used as the coating layer. Other than the base, there was an iron oxide type having a relatively strong color, but the color tone was yellow or brown and there was a dislike for lack of color variation. Accordingly, an object of the present invention is to provide a green pearlescent pigment having a stronger color tone and a large variety of colors while maintaining the strong brilliancy of titanium dioxide in view of the above-mentioned state of the art.
【0005】[0005]
【問題点を解決する為の手段】上記目的は以下の本発明
によって達成される。即ち、本発明は、雲母フレーク上
に二酸化チタン層を有する二酸化チタン被覆雲母フレー
クを水性媒体中に懸濁させ、その表面に、沈澱剤によっ
てコバルト塩、ニッケル塩及び亜鉛塩からこれらの金属
の複合酸化物又はその水和物を析出させ、次いで焼成し
て酸化コバルト、酸化ニッケル及び酸化亜鉛からなる複
合酸化物層の被覆を形成させる緑色真珠光沢顔料の製造
方法において、上記金属塩の沈澱剤として、加熱によっ
てアンモニアを発生する物質を使用することを特徴とす
る緑色真珠光沢顔料の製造方法である。The above object is achieved by the present invention described below. That is, the present invention provides a titanium dioxide-coated mica flake having a titanium dioxide layer on the mica flake.
The click is suspended in an aqueous medium, on the surface thereof, by the precipitant
These metal Te cobalt salts, nickel salts and zinc salts
To precipitate a composite oxide or a hydrate thereof, followed by calcination
Cobalt oxide Te, in the manufacturing method of the green pearlescent pigments Ru to form a coating of the composite oxide layer made of nickel oxide and zinc oxide, as a precipitant of the metal salts, the use of a substance that generates ammonia by heating This is a method for producing a green pearlescent pigment.
【0006】[0006]
【作用】雲母フレーク上に二酸化チタン層を、その上に
酸化コバルト、酸化ニッケル及び酸化亜鉛からなる複合
酸化物層を被覆することによって、隠蔽力が高く且つ光
輝性が出やすい二酸化チタン層の優れた光輝性を維持し
つつ、該二酸化チタン層の表面に着色成分としてより強
い緑色の発色を示すコバルト、ニッケル及び亜鉛の複合
酸化物層を被覆して熱処理し、複合酸化物層をスピネル
相を形成させることによって、緑色真珠光沢顔料として
の特性を出現させると同時に、上記複合酸化物層の有す
る諸特性も併せ有させることが出来る。[Function] By coating a titanium dioxide layer on mica flakes and a composite oxide layer composed of cobalt oxide, nickel oxide and zinc oxide on the mica flakes, the titanium dioxide layer has a high hiding power and is easy to produce a glitter. While maintaining the brilliancy, the surface of the titanium dioxide layer is coated with a composite oxide layer of cobalt, nickel, and zinc exhibiting a stronger green color as a coloring component, and heat-treated to form a spinel phase in the composite oxide layer. By forming the pigment, properties as a green pearlescent pigment can be exhibited, and at the same time, various properties of the composite oxide layer can be obtained.
【0007】[0007]
【好ましい実施態様】次に好ましい実施態様を挙げて本
発明を更に詳しく説明する。本発明の緑色真珠光沢顔料
に用いる被覆母体である雲母フレークとしては、一般に
使われている白雲母を使用することが出来る。しかしな
がら、被覆母体として使用することが出来る雲母フレー
クは、この白雲母に限定される訳ではなく、表面の平滑
性やアスペクト比が上記白雲母と類似であれば、他の雲
母フレークも同様に使用可能なことは云うまでもない。
上記白雲母の粒径は1〜100μm程度のものが使用さ
れるが、好ましくは20〜50μmの比較的粒子の揃っ
た厚さ0.1μm程度の薄いものが良好である。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. As the mica flakes which are the coating base used for the green pearlescent pigment of the present invention, commonly used muscovite can be used. However, the mica flakes that can be used as a coated mother body are not limited to muscovite, and other mica flakes can be used as long as the surface smoothness and aspect ratio are similar to the above muscovite. Needless to say, this is possible.
The muscovite having a particle size of about 1 to 100 [mu] m is used, and a thin one having a relatively uniform particle size of about 20 to 50 [mu] m and a thickness of about 0.1 [mu] m is preferable.
【0008】雲母フレークの表面にコーティングする二
酸化チタンは、チタン源としてチタン塩を用い、より具
体的には硫酸チタニル、四塩化チタン等の試薬若しくは
工業用材料を使用することが出来る。白雲母フレークに
二酸化チタンを被覆する方法としては、予め加熱してあ
る白雲母懸濁液に、予め溶解したチタン溶液を添加し、
チタン塩を加水分解することにより白雲母フレーク上に
チタンの水和物若しくは酸化物を沈着させる方法であ
り、この方法自体は公知である。For the titanium dioxide to be coated on the surface of the mica flake, a titanium salt is used as a titanium source, and more specifically, a reagent such as titanyl sulfate, titanium tetrachloride or an industrial material can be used. As a method of coating titanium dioxide on muscovite flakes, a pre-dissolved titanium solution is added to a pre-heated muscovite suspension,
This is a method of depositing a hydrate or oxide of titanium on muscovite flakes by hydrolyzing a titanium salt, and this method is known per se.
【0009】この様にして得られた二酸化チタン被覆雲
母スラリーは、水洗し、更にその表面に酸化コバルト、
酸化ニッケル及び酸化亜鉛からなる複合酸化物層を形成
する為の被覆母体に供される。又、この際、スラリーを
一旦濾過し、得られたケーキを120℃で12時間程度
乾燥し、その後この乾燥フレークを700〜900℃で
1時間程度熱処理し、前述の複合酸化物の被覆に供する
ことも可能である。[0009] The titanium dioxide-coated mica slurry thus obtained is washed with water, and further coated with cobalt oxide,
It is provided to a coating base for forming a composite oxide layer composed of nickel oxide and zinc oxide. At this time, the slurry is once filtered, and the obtained cake is dried at 120 ° C. for about 12 hours, and then the dried flakes are heat-treated at 700 to 900 ° C. for about 1 hour to be provided with the coating of the composite oxide. It is also possible.
【0010】上述の如くして得られた二酸化チタン被覆
雲母フレークは、緑色の虹彩色を発し、熱処理するしな
いに拘わらず、優れた光輝性を発揮する。雲母フレーク
上の二酸化チタン層に被覆される複合酸化物としては、
最終的に二酸化チタンとも反応して二次的複合酸化物を
形成する。その際に選ばれる複合酸化物は、その形成後
今までに無い強い発色を示し、且つ諸耐性、即ち耐候性
や耐薬品性等が優れたものとなる金属の組み合わせが選
ばれる。[0010] The titanium dioxide-coated mica flakes obtained as described above emit a green iris color and exhibit excellent glitter regardless of whether they are heat-treated. As the composite oxide coated on the titanium dioxide layer on mica flakes,
Finally, it reacts with titanium dioxide to form a secondary composite oxide. As the composite oxide selected at that time, a combination of metals is selected which exhibits an unprecedented strong color development after its formation and has excellent various resistances, that is, excellent weather resistance and chemical resistance.
【0011】より具体的には、従来技術の複合酸化物系
顔料中で強い発色を示し、スピネル系結晶構造を有する
コバルト、ニッケル、亜鉛及びチタン系の複合酸化物が
選ばれる。この系は無機顔料として、他の複合酸化物
系、例えば、ルチル型のチタン、アンチモン、ニッケル
系や、チタン、アンチモン、クロム系の黄色顔料に比べ
発色が強いばかりでなく、それらの系と同様に諸耐性が
極めて優れている。又、二酸化チタンベースである為、
光輝性も充分に確保される。More specifically, cobalt-, nickel-, zinc- and titanium-based composite oxides exhibiting strong color development in the prior art composite oxide pigments and having a spinel crystal structure are selected. This system, as an inorganic pigment, not only has a stronger color development than other complex oxide systems, for example, rutile type titanium, antimony, nickel system, titanium, antimony, chromium system yellow pigments, as well as those systems Extremely excellent resistance to Also, because it is based on titanium dioxide,
Brightness is also sufficiently ensured.
【0012】本発明では、以上の理由により着色成分と
して二酸化チタン以外に、コバルト、ニッケル及び亜鉛
の複合酸化物が選択された。これら被覆の際に利用され
る金属塩は、従来の複合酸化物顔料を製造する際に使用
される硫酸塩、硝酸塩、塩化物、酢酸塩等は総て利用可
能で、これら金属の好ましい割合は、化学量論的にはチ
タン:コバルト:ニッケル:亜鉛=2:1:2:1であ
るが、光輝性を確保しつつ、顔料粒子表面への被覆とい
う性格と、各金属の沈澱特性の違いを考慮すれば、チタ
ンに対し最高でコバルト:ニッケル:亜鉛=1:2:1
と考えられる。In the present invention, a composite oxide of cobalt, nickel and zinc is selected as a coloring component in addition to titanium dioxide for the above reasons. The metal salts used for these coatings, sulfates, nitrates, chlorides, acetates, and the like used in the production of conventional composite oxide pigments can all be used, and the preferable ratio of these metals is Although the stoichiometric ratio is titanium: cobalt: nickel: zinc = 2: 1: 2: 1, the difference between the characteristics of coating on the pigment particle surface and the precipitation characteristics of each metal while securing the brilliancy. In consideration of the maximum, cobalt: nickel: zinc = 1: 2: 1 with respect to titanium.
it is conceivable that.
【0013】つまり、二酸化チタンを雲母フレークに被
覆後、新たに被覆される複合金属酸化物は、量的に少な
い方がより効果的に雲母フレークの二酸化チタン層の表
面に付着し易いと考えられる。従って、二酸化チタンに
対する金属の量的関係は、最終的な色調の強さを考慮す
れば、0.1/1<(コバルト+ニッケル+亜鉛)/チ
タン<0.5/1が望ましい。この範囲より多い場合
は、被覆反応中に雲母フレーク同士の凝集が生じ、著し
く光輝性を損ねる。又、0.1/1より少ないと強い色
調のものは得られない。In other words, it is considered that the smaller the amount of the composite metal oxide newly coated after coating the mica flakes with titanium dioxide, the easier it is to adhere to the surface of the titanium dioxide layer of the mica flakes more effectively. . Therefore, the quantitative relation of metal to titanium dioxide is desirably 0.1 / 1 <(cobalt + nickel + zinc) / titanium <0.5 / 1 in consideration of the strength of the final color tone. If the amount is larger than this range, agglomeration of the mica flakes occurs during the coating reaction, and the glitter is significantly impaired. If the ratio is less than 0.1 / 1, a strong color tone cannot be obtained.
【0014】チタンを除く各金属の配合割合は、基本的
に化学量論的配合によるが、多少この割合よりずれても
色調への影響は少ない。しかし、大きくずれると発色が
弱かったり、くすみの原因となる為注意が必要である。
この様な金属塩は、予め二酸化チタンにより被覆された
光輝性緑色雲母フレークの水性懸濁液中に投入及び溶解
されるが、この緑色雲母フレーク懸濁液の濃度は100
g/リットル以下が望ましい。濃度が濃すぎると被覆反
応中に雲母フレーク同士の凝集が起こり、著しく光輝性
を損ねる。The mixing ratio of each metal except for titanium basically depends on the stoichiometric mixing ratio. However, even if the ratio slightly deviates from this ratio, the effect on the color tone is small. However, it should be noted that a large deviation may cause weak coloring or dullness.
Such a metal salt is introduced and dissolved in an aqueous suspension of bright green mica flakes previously coated with titanium dioxide, and the concentration of the green mica flake suspension is 100%.
g / liter or less is desirable. If the concentration is too high, the mica flakes agglomerate during the coating reaction, significantly impairing the glitter.
【0015】又、この様な金属塩を雲母フレークの二酸
化チタン層表面に折出させる沈澱剤として、本発明で
は、加熱によってアンモニアを生じる化合物、例えば、
尿素又はその誘導体を使用する。上述の雲母フレーク懸
濁液に尿素又はその誘導体を投入及び溶解することによ
り、室温付近では何の変化も生じないが、撹拌しながら
加熱すると、系全体に均一に溶解している尿素又はその
誘導体が分解を始め、全体に均一且つ微細な複合酸化物
又はその水和物粒子が雲母フレーク上に折出してくる。
この理由は、沈澱剤である尿素又はその誘導体が溶液中
で局所的な濃度匂配が無い為であり、従来から採用され
ている滴下法により沈澱剤を逐次投入する方法では決し
て得られない完全な均一性が保証される。In the present invention, as a precipitating agent for depositing such a metal salt on the surface of the titanium dioxide layer of mica flakes, a compound which produces ammonia by heating, for example,
Urea or a derivative thereof is used. By introducing and dissolving urea or its derivative in the above mica flake suspension, no change occurs around room temperature, but when heated with stirring, urea or its derivative uniformly dissolved in the entire system Starts to decompose, and uniform and fine composite oxide or hydrate particles thereof are deposited on the mica flakes.
The reason for this is that urea or a derivative thereof as a precipitant has no local concentration odor in the solution, and the complete precipitant which can never be obtained by the method of successively adding the precipitant by a dropping method conventionally used is not obtained. Uniformity is assured.
【0016】以上の様な尿素又はその誘導体は、金属塩
に対し金属1当量につき1〜5モルの使用が好適であ
る。この範囲より多いと複合金属酸化物被膜に亀裂が入
ったり、表面の荒れや、雲母同士の凝集が起きる様にな
る。この様にして光輝性緑色雲母フレークと金属塩及び
尿素又はその誘導体の混合懸濁液は、好ましくは70〜
100℃の温度範囲で0.5〜12時間加熱撹拌するこ
とにより、雲母フレーク上の二酸化チタン層に金属の酸
化物又はその水和物の折出が行われる。The urea or its derivative as described above is preferably used in an amount of 1 to 5 mol per equivalent of the metal relative to the metal salt. If the amount is more than this range, the composite metal oxide film is cracked, the surface is roughened, and mica aggregates occur. In this way, the mixed suspension of the brilliant green mica flakes and the metal salt and urea or its derivative is preferably 70 to
By heating and stirring in a temperature range of 100 ° C. for 0.5 to 12 hours, metal oxides or hydrates thereof are deposited on the titanium dioxide layer on the mica flakes.
【0017】次に酸化物又はその水和物が沈着したスラ
リーを水洗及び濾過し120℃にて12時間程度乾燥
し、この乾燥雲母フレークを酸化性の雰囲気で600〜
1,000℃にて0.5〜2時間熱処理することによ
り、二酸化チタンを含む複合酸化物からスピネル相を形
成させ、本発明の光輝性のある強い発色の緑色真珠光沢
顔料を得ることが出来る。Next, the slurry on which the oxide or its hydrate is deposited is washed with water, filtered, and dried at 120 ° C. for about 12 hours.
By performing a heat treatment at 1,000 ° C. for 0.5 to 2 hours, a spinel phase is formed from the composite oxide containing titanium dioxide, and the bright pearlescent pigment of the present invention having a strong brilliant color can be obtained. .
【0018】[0018]
【実施例】次に実施例及び比較例を挙げて本発明を具体
的に説明する。尚、文中にある部又は%は断りに無い限
り重量基準である。 実施例1 下記比較例1の光輝性緑色雲母フレーク顔料45部を
1,000部の水に懸濁させ、次いで塩化ニッケル6水
塩6.7部、硝酸亜鉛6水塩4.2部及び硝酸コバルト
6水塩4.1部を100部の水に溶解し懸濁液に投入す
る。この混合懸濁液を良く撹拌し、各成分を均一に溶解
させた後昇温を開始し、100℃になったら一定に保
ち、そのままの状態を保持する。しばらくすると、二酸
化チタン被覆雲母フレーク上に各金属の酸化物又はその
水和物の沈澱が折出してくるが、その後も加熱撹拌を続
け、3時間経過したら反応を終了させ、水洗及び濾過す
る。得られたケーキを120℃で12時間以上乾燥させ
る。Next, the present invention will be described specifically with reference to examples and comparative examples. The parts or percentages in the text are based on weight unless otherwise specified. Example 1 45 parts of the bright green mica flake pigment of Comparative Example 1 below was suspended in 1,000 parts of water, and then 6.7 parts of nickel chloride hexahydrate, 4.2 parts of zinc nitrate hexahydrate and nitric acid 4.1 parts of cobalt hexahydrate are dissolved in 100 parts of water and added to the suspension. This mixed suspension is stirred well, and after each component is uniformly dissolved, temperature rise is started. When the temperature reaches 100 ° C., the temperature is kept constant, and the state is maintained as it is. After a while, a precipitate of an oxide or a hydrate of each metal starts to precipitate on the titanium dioxide-coated mica flakes. Thereafter, heating and stirring are continued, and after 3 hours, the reaction is terminated, followed by washing with water and filtration. The cake obtained is dried at 120 ° C. for at least 12 hours.
【0019】この乾燥した雲母フレークを酸化性雰囲気
にて700℃で1時間熱処理し、本発明の光輝性緑色真
珠光沢顔料を得た。このものをアクリルクラッカーにて
塗料化し、6ミルフィルムアプリケーターにて黒帯付き
アート紙に塗布したところ、黒帯部分は比較例1と同様
の光輝性のある緑色を発色し、下地が白い部分は光輝性
を保持しつつ、強い発色の緑色の色調を示した。The dried mica flakes were heat-treated at 700 ° C. for 1 hour in an oxidizing atmosphere to obtain a bright green pearlescent pigment of the present invention. This was made into a paint with an acrylic cracker, and applied to art paper with a black band using a 6 mil film applicator. The black band developed the same brilliant green color as in Comparative Example 1, and the white base was A strong green color tone was exhibited while maintaining the brilliancy.
【0020】 比較例1 厚さ0.05〜0.2μm及び平均粒径40μmの鱗片
状白雲母20部に550部の水を加え撹拌しながら懸濁
させこれをA液とした。次に硫酸チタニル70部(二酸
化チタン32%)と水150部を混合し、チタンを溶解
させ、更に98%硫酸100部を加えB液とした。上記
A液を撹拌しながら加熱し、95℃になった時点でB液
を投入し3時間加熱熟成した後、生成した二酸化チタン
被覆雲母スラリーを水洗及び濾過し、得られたケーキを
120℃で12時間乾燥した。Comparative Example 1 550 parts of water was added to 20 parts of flaky muscovite having a thickness of 0.05 to 0.2 μm and an average particle diameter of 40 μm, and the mixture was suspended with stirring to obtain a liquid A. Next, 70 parts of titanyl sulfate (32% of titanium dioxide) and 150 parts of water were mixed to dissolve titanium, and 100 parts of 98% sulfuric acid was further added to obtain a liquid B. The solution A was heated with stirring, and when the temperature of the solution reached 95 ° C., the solution B was added and the mixture was aged by heating for 3 hours. The resulting titanium dioxide-coated mica slurry was washed with water and filtered. Dry for 12 hours.
【0021】次いでこの乾燥ケーキを酸化性雰囲気で8
00℃で1時間熱処理し、二酸化チタンで被覆された光
輝性のある緑色の虹彩色を発生する白色雲母フレーク顔
料を得た。このものをアクリルクラッカーにて塗料化
し、6ミルフィルムアプリケーターにて黒帯付アート紙
に塗布したところ、黒帯部分は光輝性のある緑色を発色
し、下地が白い部分は光輝性はあるものの、殆ど白色に
近い色調であった。Next, the dried cake is placed in an oxidizing atmosphere for 8 hours.
Heat treatment was performed at 00 ° C. for 1 hour to obtain a white mica flake pigment that generates a bright green iris color coated with titanium dioxide. This was made into a paint with an acrylic cracker and applied to art paper with a black belt using a 6 mil film applicator. The black band developed a bright green color, and the white background provided a glitter, The color was almost white.
【0022】 比較例2 比較例1によって製造した光輝性白色雲母フレーク顔料
45部を1,000部の水に懸濁させ、次いで塩化ニッ
ケル6水塩6.7部、硝酸亜鉛6水塩4.2部及び硝酸
コバルト6水塩4.1部を100部の水に溶解し、沈澱
剤溶液として苛性ソーダ4.5部を水100部に溶解さ
せる。この様にして得られた金属塩溶液と苛性ソーダ溶
液を撹拌中の上記の雲母フレーク懸濁液中にPH8にて
徐々に同時に滴下し、光輝性緑色雲母フレーク顔料上に
金属酸化物又はその水和物を折出させる。Comparative Example 2 45 parts of the glittering white mica flake pigment prepared according to Comparative Example 1 were suspended in 1,000 parts of water, then 6.7 parts of nickel chloride hexahydrate and zinc nitrate hexahydrate. 2 parts and 4.1 parts of cobalt nitrate hexahydrate are dissolved in 100 parts of water, and 4.5 parts of caustic soda as a precipitant solution are dissolved in 100 parts of water. The metal salt solution and the caustic soda solution thus obtained are gradually and simultaneously dropped into the above mica flake suspension under stirring at PH8, and the metal oxide or its hydration is placed on the bright green mica flake pigment. Let the objects come out.
【0023】滴下終了後被覆された雲母フレークを水洗
及び濾過し、得られたケーキを120℃で12時間以上
乾燥させる。金属酸化物又はその水和物で被覆された二
酸化チタン被覆雲母フレークは、この時点で既にかなり
凝集しており、金属塩滴下前に見られた光輝性は殆ど失
われていた。この乾燥した雲母フレークを酸化性雰囲気
で700℃で1時間熱処理し、比較例の光輝性緑色真珠
光沢顔料を得た。このものをアクリルクラッカーにて塗
料化し、6ミルフィルムアプリケーターにてアート紙に
て黒帯付きアート紙に塗布したところ、黒帯部分及び下
地が白い部分共に光輝性が全く見られなくなり、下地が
白色の部分では白っぽい緑色の色調を示した。After completion of the dropping, the coated mica flakes are washed with water and filtered, and the obtained cake is dried at 120 ° C. for 12 hours or more. Metal oxide or coated titanium dioxide coated mica flakes with their hydrates are already fairly aggregated at this time, it was observed before dropping metal salt glitter was almost lost. This dried mica flake was heat-treated at 700 ° C. for 1 hour in an oxidizing atmosphere to obtain a glittering green pearlescent pigment of Comparative Example. This was made into a paint with an acrylic cracker and applied to art paper with a black belt using an art paper with a 6 mil film applicator. In the part, a whitish green color tone was shown.
【0024】[0024]
【効果】以上の如き本発明によれば、雲母フレーク上に
二酸化チタン層、及び酸化コバルト、酸化ニッケル及び
酸化亜鉛からなる複合酸化物層を被覆することによっ
て、隠蔽力が高く且つ光輝性が出やすい二酸化チタン層
の優れた光輝性を維持しつつ、該二酸化チタン層の表面
に着色成分としてより強い緑色の発色を示すコバルト、
ニッケル及び亜鉛の複合酸化物層を被覆して熱処理し、
スピネル相を形成させることによって緑色真珠光沢顔料
としての特性を出現させると同時に、上記複合酸化物層
の有する諸特性も併せ有させることが出来る。According to the present invention as described above, by covering a mica flake with a titanium dioxide layer and a composite oxide layer composed of cobalt oxide, nickel oxide and zinc oxide, a high hiding power and a high brilliancy can be obtained. Cobalt showing a stronger green color development as a coloring component on the surface of the titanium dioxide layer while maintaining the excellent glitter of the titanium dioxide layer,
Coating a composite oxide layer of nickel and zinc and heat treating,
By forming a spinel phase, characteristics as a green pearlescent pigment can be exhibited, and at the same time, various characteristics of the composite oxide layer can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 待鳥 峰喜 東京都中央区日本橋馬喰町1丁目7番6 号 大日精化工業株式会社内 (56)参考文献 特開 平4−65741(JP,A) 特開 平7−157688(JP,A) (58)調査した分野(Int.Cl.6,DB名) C09C 1/00 - 3-12 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Mineki Machitori 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-4-65741 (JP, A) JP-A-7-157688 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C09C 1/00-3-12
Claims (5)
る二酸化チタン被覆雲母フレークを水性媒体中に懸濁さ
せ、その表面に、沈澱剤によってコバルト塩、ニッケル
塩及び亜鉛塩からこれらの金属の複合酸化物又はその水
和物を析出させ、次いで焼成して酸化コバルト、酸化ニ
ッケル及び酸化亜鉛からなる複合酸化物層の被覆を形成
させる緑色真珠光沢顔料の製造方法において、上記金属
塩の沈澱剤として、加熱によってアンモニアを発生する
物質を使用することを特徴とする緑色真珠光沢顔料の製
造方法。1. Titanium dioxide-coated mica flakes having a titanium dioxide layer on mica flakes are suspended in an aqueous medium and the composite oxides of these metals are precipitated from cobalt, nickel and zinc salts by means of a precipitant. Thing or its water
Precipitate and then bake to form a coating of a composite oxide layer consisting of cobalt oxide, nickel oxide and zinc oxide
The method of manufacturing a green pearlescent pigment was Ru is as precipitant of the metal salt, the manufacturing method of the green pearlescent pigment, characterized by using a substance that generates ammonia by heating.
項1に記載の緑色真珠光沢顔料の製造方法。2. The method for producing a green pearlescent pigment according to claim 1, wherein the precipitant is urea or a derivative thereof.
ー濃度が100g/リットル以下である請求項1に記載
の緑色真珠光沢顔料の製造方法。3. The method for producing a green pearlescent pigment according to claim 1, wherein the slurry concentration of the titanium dioxide-coated mica flake is 100 g / liter or less.
の金属1当量に対し1〜5モルの範囲である請求項2に
記載の緑色真珠光沢顔料の製造方法。4. The method according to claim 1, wherein the amount of urea or a derivative thereof is the above-mentioned metal salt.
3. The method for producing a green pearlescent pigment according to claim 2 , wherein the amount is 1 to 5 mol per 1 equivalent of the metal.
した前記の複合酸化物又はその水和物を600〜1,0
00℃で熱処理する請求項1に記載の緑色真珠光沢顔料
の製造方法。5. Precipitation on mica flakes coated with titanium dioxide
The composite oxide or its hydrate of the who 600~1,0
The method for producing a green pearlescent pigment according to claim 1, wherein the heat treatment is performed at 00 ° C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5340218A JP2872903B2 (en) | 1993-12-08 | 1993-12-08 | Method for producing green pearlescent pigment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5340218A JP2872903B2 (en) | 1993-12-08 | 1993-12-08 | Method for producing green pearlescent pigment |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07157689A JPH07157689A (en) | 1995-06-20 |
JP2872903B2 true JP2872903B2 (en) | 1999-03-24 |
Family
ID=18334828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5340218A Expired - Fee Related JP2872903B2 (en) | 1993-12-08 | 1993-12-08 | Method for producing green pearlescent pigment |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2872903B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100774632B1 (en) | 2006-08-11 | 2007-11-08 | 현대자동차주식회사 | Room temperature process of pearly pigments by precipitation method |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3683951B2 (en) * | 1995-08-31 | 2005-08-17 | 株式会社資生堂 | Yellow scale powder |
CN100462407C (en) * | 2005-09-28 | 2009-02-18 | 北京工商大学 | Production of cobalt-titanium series random chromo pigment |
DE102006027025A1 (en) | 2006-06-08 | 2007-12-13 | Merck Patent Gmbh | Silver-white effect pigments |
CN113518839A (en) * | 2019-03-04 | 2021-10-19 | Viavi科技有限公司 | Thin film interference pigments with nanoparticle coatings |
-
1993
- 1993-12-08 JP JP5340218A patent/JP2872903B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100774632B1 (en) | 2006-08-11 | 2007-11-08 | 현대자동차주식회사 | Room temperature process of pearly pigments by precipitation method |
Also Published As
Publication number | Publication date |
---|---|
JPH07157689A (en) | 1995-06-20 |
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