JP3212065B2 - Fine particle composite oxide black pigment and method for producing the same - Google Patents
Fine particle composite oxide black pigment and method for producing the sameInfo
- Publication number
- JP3212065B2 JP3212065B2 JP19793695A JP19793695A JP3212065B2 JP 3212065 B2 JP3212065 B2 JP 3212065B2 JP 19793695 A JP19793695 A JP 19793695A JP 19793695 A JP19793695 A JP 19793695A JP 3212065 B2 JP3212065 B2 JP 3212065B2
- Authority
- JP
- Japan
- Prior art keywords
- composite oxide
- black pigment
- oxide black
- pigment
- manganese
- 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
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、微粒子複合酸化物ブラ
ック顔料に関し、従来の同種顔料よりも一次粒子が小さ
く、且つ黒度、着色力、鮮映性及び発色性等に優れ、
又、絶縁性を示す微粒子複合酸化物ブラック顔料及びそ
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fine particle composite oxide black pigment, which has smaller primary particles than conventional pigments of the same type, and is excellent in blackness, coloring power, sharpness, color development and the like.
Further, the present invention relates to a fine particle composite oxide black pigment exhibiting insulating properties and a method for producing the same.
【０００２】更に詳しくは、顔料を一層微粒子化するこ
とにより新たに現れる特性を利用し、例えば、カラーフ
ィルター等のブラックマトリックス用ブラック顔料、ジ
ェットインキ用ブラック顔料、絶縁性の特殊塗料用ブラ
ック顔料、トーナー用ブラック顔料、ソーラーコレクタ
ー塗料用ブラック顔料、又はカーボンブラックとの調色
による青み付け及び絶縁性の付与等の他にも、自動車塗
料、薄膜、印刷インキ、セラッミックス等にも有用な微
粒子複合酸化物ブラック顔料に関する。More specifically, by utilizing the properties newly appeared by making the pigment finer, the black pigment for a black matrix such as a color filter, the black pigment for a jet ink, the black pigment for an insulating special paint, Fine particle composite oxidation that is useful for automotive paints, thin films, printing inks, ceramics, etc., in addition to bluish tinting and insulation imparting by toning with black pigment for toner, black pigment for solar collector paint, or carbon black. Black pigment.
【０００３】[0003]
【従来の技術】従来、複合酸化物ブラック顔料はスピネ
ル型の化合物であり、Ｃｕ−Ｃｒ系、Ｃｕ−Ｃｒ−Ｍｎ
系、Ｃｕ−Ｍｎ系、Ｃｕ−Ｆｅ−Ｍｎ系等があり、いず
れも耐熱性の優れた無機顔料として広く知られ、塗料、
建材、合成樹脂の着色、窯業用着色剤等として幅広く使
われている。又、これらの複合酸化物ブラック顔料は絶
縁性を示すことから、特殊塗料用ブラック顔料としても
利用されている。2. Description of the Related Art Conventionally, composite oxide black pigments are spinel type compounds, such as Cu--Cr-based and Cu--Cr--Mn.
System, Cu-Mn system, Cu-Fe-Mn system, etc., all of which are widely known as heat-resistant inorganic pigments, paints,
It is widely used as a coloring material for building materials and synthetic resins, and as a coloring agent for the ceramic industry. Further, since these composite oxide black pigments have insulating properties, they are also used as black pigments for special paints.
【０００４】[0004]
【発明が解決しようとしている課題】近年のカラーフィ
ルター等の薄膜技術の発展により、他色の顔料と共にブ
ラック顔料についても粒子の小さい微粒子顔料が切望さ
れている。しかしながら、現行品の上記複合酸化物ブラ
ック顔料は、主として構成成分の酸化物を混合焼結させ
るいわゆる乾式で合成されており、構成成分の酸化物や
炭酸化合物等をフラックスの存在下で所定温度で焼成
し、次いで焼結した粒子を強力な粉砕機により粉砕し顔
料化する為に、微粒子状の顔料は得られにくいという問
題がある。With the recent development of thin-film technology such as color filters, there has been a growing demand for fine-particle pigments having small particles for black pigments as well as pigments of other colors. However, the above-mentioned composite oxide black pigment of the current product is mainly synthesized by a so-called dry method in which the constituent oxides are mixed and sintered, and the constituent oxides and carbonate compounds are mixed at a predetermined temperature in the presence of a flux. Since the calcined and then sintered particles are pulverized into a pigment by a powerful pulverizer, there is a problem that it is difficult to obtain a finely divided pigment.
【０００５】又、一部の顔料は構成成分の塩をアルカリ
剤により共沈させる湿式法においても製造されている
が、得られる顔料のＢＥＴ比表面積が３０ｍ2／ｇ未満
であり、切望される様な黒度、着色力、鮮映性等に優れ
る微粒子複合酸化物ブラック顔料は得られていない。し
かしながら、上記複合酸化物ブラック顔料の中で、Ｃｕ
−Ｃｒ系及びＣｕ−Ｃｒ−Ｍｎ系については、本出願人
らによって微粒子化の特許（特公平４−５０１１９号公
報）が出願されている。しかしながら、この系統の複合
酸化物ブラック顔料は、赤みの黒を示す為に、更に青み
の微粒子ブラック顔料が熱望されている。Some pigments are also produced by a wet method in which a salt of a constituent component is coprecipitated with an alkali agent. However, the BET specific surface area of the obtained pigment is less than 30 m 2 / g, so that it is desired. Fine composite oxide black pigments having excellent blackness, coloring power, sharpness and the like have not been obtained. However, among the composite oxide black pigments, Cu
Regarding the -Cr system and the Cu-Cr-Mn system, the present applicant has filed an application for a fine particle patent (Japanese Patent Publication No. 4-50119). However, since this type of composite oxide black pigment shows reddish black, a bluish fine particle black pigment has been eagerly desired.
【０００６】[0006]
【課題を解決する為の手段】本発明は上述の従来技術の
要望に応えるべく鋭意研究の結果、複合酸化物ブラック
顔料の中でも青み〜緑みのブラックを示すＣｕ−Ｍｎ系
又はＣｕ−Ｆｅ−Ｍｎ系の複合酸化物ブラック顔料の製
造において、湿式沈澱法で合成する際に、水性媒体中で
アルカリ剤によって中和及び混合析出し、この析出物を
析出と同時又は析出後に液相中で酸化処理することによ
り、青み〜緑みの微粒子複合酸化物ブラック顔料が得ら
れることを見い出し本発明を完成した。The present invention has been intensively studied in order to meet the above-mentioned demands of the prior art. As a result, among composite oxide black pigments, a Cu-Mn based pigment or a Cu-Fe-based pigment exhibiting a bluish to greenish black is obtained. In the production of Mn-based composite oxide black pigments, when synthesizing by the wet precipitation method, neutralization and mixing are performed by an alkaline agent in an aqueous medium, and the precipitates are oxidized in the liquid phase simultaneously with or after the precipitation. The present inventors have found that a fine-grained composite oxide black pigment having a bluish to greenish color can be obtained by the treatment, and completed the present invention.
【０００７】即ち、本発明は、銅／マンガンのモル比が
約１／２である銅及びマンガンの酸化物からなるスピネ
ル構造を有し、且つそのＢＥＴ比表面積が３０ｍ2／ｇ
以上で、青味のブラックを示すことを特徴とする微粒子
複合酸化物ブラック顔料、及び銅塩及びマンガン塩を含
む２成分を水中に溶解して混合塩溶液とし、これを水性
媒体中でアルカリ剤によって中和して混合析出せしめ、
この析出物を析出と同時又は析出後に液相中で酸化処理
し、次いで得られた析出物を、濾過、水洗及び乾燥し、
５２０〜６５０℃で焼成することを特徴とする微粒子複
合酸化物ブラック顔料の製造方法である。That is, according to the present invention, the molar ratio of copper / manganese is
It has a spinel structure composed of an oxide of copper and manganese of about 1/2 , and has a BET specific surface area of 30 m 2 / g
As described above, a particulate composite oxide black pigment characterized by exhibiting a bluish black , and two components including a copper salt and a manganese salt are dissolved in water to form a mixed salt solution, and this is an alkaline agent in an aqueous medium. Neutralize and precipitate mixed,
This precipitate is subjected to oxidation treatment in the liquid phase at the same time as or after the precipitation, and then the obtained precipitate is filtered, washed with water and dried ,
This is a method for producing a fine particle composite oxide black pigment, which is fired at 520 to 650 ° C.
【０００８】本発明によれば、微粒子複合酸化物ブラッ
ク顔料を構成する金属の塩をアルカリ沈澱剤により、そ
れら金属の水酸化物として混合析出させ、この析出物を
析出と同時又は析出後に液相中で酸化処理することによ
り、その後の比較的低温の焼成温度でも単一スピネル構
造を有する黒度、着色力及び鮮映性に優れ、且つ絶縁性
を示す青み〜緑みの微粒子複合酸化物ブラック顔料が得
られ、更に微粒子複合酸化物ブラック顔料にも関わら
ず、ソフトな粒子で粉砕が容易である。According to the present invention, a salt of a metal constituting the fine particle composite oxide black pigment is mixed and precipitated as a hydroxide of the metal with an alkali precipitant, and the precipitate is subjected to liquid phase simultaneous with or after the precipitation. Oxidation treatment in baking, even at a relatively low baking temperature thereafter, has a single spinel structure, is excellent in blackness, coloring power and sharpness, and exhibits insulating properties from bluish to greenish fine particle composite oxide black. A pigment is obtained, and in spite of the fine particle composite oxide black pigment, it is easy to grind with soft particles.
【０００９】従って、本発明による微粒子複合酸化物ブ
ラック顔料は、カラーフィルター等のブラックマトリッ
クス用ブラック顔料、ジェットインキ用ブラック顔料、
絶縁性の特殊塗料用ブラック顔料、トーナー用ブラック
顔料、ソーラーコレクター塗料用ブラック顔料、又はカ
ーボンブラックとの調色による青み付け及び絶縁性の付
与等の他にも、自動車塗料、薄膜、印刷インキ、セラッ
ミックス等にも有用である。Accordingly, the fine particle composite oxide black pigment according to the present invention is a black pigment for a black matrix such as a color filter, a black pigment for a jet ink,
In addition to black pigments for insulating special paints, black pigments for toners, black pigments for solar collector paints, or tinting with carbon black to impart bluish and insulating properties, etc., automotive paints, thin films, printing inks, etc. It is also useful for ceramics and the like.
【００１０】[0010]
【発明の実施の形態】次に好ましい発明の実施の形態を
挙げて本発明を更に詳しく説明する。本発明で使用する
各構成元素の塩は、硫酸塩、硝酸塩、炭酸塩、塩化物、
酢酸塩等、従来複合酸化物顔料を製造するときに使用さ
れているものは全て使用することが出来る。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments of the invention. Salts of the respective constituent elements used in the present invention include sulfates, nitrates, carbonates, chlorides,
All of those conventionally used when producing composite oxide pigments, such as acetates, can be used.
【００１１】上記において、銅とマンガンの割合はモル
比でＣｕ／Ｍｎ≒１／２が適当であり、この割合におい
て更にマンガンの一部を適宜鉄で置換することが出来
る。即ち、鉄とマンガンのモル比はＦｅ／Ｍｎ＝３／７
以下が適当であり、この範囲を外れる場合は、得られる
顔料の黒度が著しく低下し、単一スピネル構造を維持す
ることが出来なくなる。又、一部に鉄を添加するに従い
得られる顔料の粒子径は更に小さくなるが、絶縁性に影
響を与える傾向にある。In the above, the ratio of copper and manganese is suitably Cu / Mn ≒ 1/2 by molar ratio, and at this ratio, a part of manganese can be further substituted with iron. That is, the molar ratio of iron to manganese is Fe / Mn = 3/7.
The following is appropriate. When the value is outside this range, the blackness of the obtained pigment is remarkably reduced, and a single spinel structure cannot be maintained. Further, the particle size of the pigment obtained as iron is partially added becomes smaller, but tends to affect the insulating properties.
【００１２】以上の如き各構成元素の金属塩を水に溶か
して混合塩水溶液を形成する。その際の濃度は上記の如
きモル比で全体として約５〜５０重量％程度の濃度とす
るのが適当である。この混合溶液は沈澱剤として苛性ソ
ーダ等のアルカリ水溶液を用いて予め用意した沈澱媒体
中に同時に滴下される。沈澱剤としてアンモニア水は金
属塩の銅がアンモニウム錯体を形成し、沈澱を生成しな
い為に使用するのは不適当である。The above-mentioned metal salts of the constituent elements are dissolved in water to form a mixed salt aqueous solution. The concentration at that time is suitably about 5 to 50% by weight as a whole in a molar ratio as described above. This mixed solution is simultaneously dropped into a previously prepared precipitation medium using an aqueous alkali solution such as caustic soda as a precipitant. Ammonia water is not suitable for use as a precipitant because the metal salt copper forms an ammonium complex and does not form a precipitate.
【００１３】この際の反応濃度は沈澱物生成に対しては
特に悪い影響は与えないが、酸化処理の際、スラリー濃
度の低い場合、即ち、沈澱量の少ない場合はスラリー濃
度の高い場合、即ち、沈澱量の多い場合に比べて酸化効
率が上がる為に得られる顔料の微細化に効果があり、銅
濃度規準で０．０５モル〜０．５モル／リットルが適当
である。反応及び酸化処理の際のｐＨは７〜１３の範囲
が適当であり、ｐＨが高く、即ちアルカリ濃度の高い
程、微粒子化に効果があるが、得られる顔料の分散性を
悪くする傾向にある。合成温度は２０℃〜４０℃範囲が
好ましく、又、熟成温度は７０℃〜１００℃の範囲が好
ましく、この温度範囲内であればその効果は充分発揮す
ることが出来る。[0013] The reaction concentration at this time does not particularly adversely affect the formation of precipitates, but during the oxidation treatment, when the slurry concentration is low, ie, when the amount of precipitation is small, when the slurry concentration is high, Since the oxidation efficiency is increased as compared with the case where the precipitation amount is large, it is effective in making the obtained pigment finer, and the copper concentration is suitably 0.05 mol to 0.5 mol / liter. The pH at the time of the reaction and the oxidation treatment is suitably in the range of 7 to 13. The higher the pH, that is, the higher the alkali concentration, the more effective the fine particles are, but tends to deteriorate the dispersibility of the obtained pigment. . The synthesis temperature is preferably in the range of 20 ° C. to 40 ° C., and the aging temperature is preferably in the range of 70 ° C. to 100 ° C. Within this temperature range, the effect can be fully exerted.
【００１４】本発明においては、この様にして得られた
スラリー中の２価の金属イオンを３価の金属イオンに酸
化することが必要である。使用する酸化剤としては、過
酸化水素、酸素、塩素酸ナトリウム等、いずれの酸化剤
でもよいが、好ましい酸化剤は、酸化によって不純物を
生じない酸化剤、例えば、過酸化水素や酸素ガスが好ま
しい。酸化剤の使用量は、２価の金属が３価の金属イオ
ンに酸化されるに必要な量であればよいが、酸化を完全
にする為にある程度過剰な割合で使用するのが好まし
い。In the present invention, it is necessary to oxidize divalent metal ions in the slurry thus obtained into trivalent metal ions. The oxidizing agent to be used may be any oxidizing agent such as hydrogen peroxide, oxygen, and sodium chlorate. Preferred oxidizing agents are oxidizing agents that do not generate impurities by oxidation, such as hydrogen peroxide and oxygen gas. . The amount of the oxidizing agent used may be an amount necessary to oxidize the divalent metal to the trivalent metal ion, but it is preferable to use the oxidizing agent in a somewhat excessive ratio in order to complete the oxidation.
【００１５】次に酸化処理後のスラリー中の各種の不要
なイオンを濾過、水洗等によって除去し、これを１００
℃〜１２０℃程度の温度で乾燥し、これを酸化性雰囲気
下で５２０℃から６５０℃の温度で３０分間〜１時間焼
成して完全なスピネル構造を有する顔料を得ることが出
来る。Next, various unnecessary ions in the slurry after the oxidation treatment are removed by filtration, washing with water or the like.
The pigment is dried at a temperature of about 120 ° C. to 120 ° C. and calcined in an oxidizing atmosphere at a temperature of 520 ° C. to 650 ° C. for 30 minutes to 1 hour to obtain a pigment having a complete spinel structure.
【００１６】以上の如くして得られた微粒子複合酸化物
ブラック顔料は、ＢＥＴ比表面積が３０ｍ2／ｇ以上で
あり、従来の湿式法で得られる複合酸化物ブラック顔料
に比べ、一次粒子が小さく且つ鮮映性にも優れ、更に黒
度及び着色力の有る青みのブラックを示す。The fine particulate composite oxide black pigment obtained as described above has a BET specific surface area of 30 m 2 / g or more, and has smaller primary particles than the composite oxide black pigment obtained by a conventional wet method. In addition, it exhibits excellent brilliance and exhibits bluish black having blackness and coloring power.
【００１７】[0017]
【実施例】次に実施例及び比較例を挙げて本発明を更に
具体的に説明する。尚、文中部又は％とあるのは特に断
わりのない限り重量規準であるNext, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, it is a weight standard in the sentence part or%.
【００１８】実施例１ 硫酸銅１２０部及び硫酸マンガン２２７部を計り、約８
００部の水に完全に溶かした水溶液とする。次に沈澱剤
として苛性ソーダ２４０部を計りとり、約８００部の水
に完全に溶解し混合塩水溶液を作る。Example 1 120 parts of copper sulfate and 227 parts of manganese sulfate were weighed, and about 8 parts were obtained.
An aqueous solution completely dissolved in 00 parts of water. Next, 240 parts of caustic soda is measured as a precipitating agent, and completely dissolved in about 800 parts of water to prepare a mixed salt aqueous solution.
【００１９】予め用意しておいた沈澱媒体である水８０
０部をガスバーナーや電熱器等で２６℃に加熱保持し、
ここに混合塩水溶液と苛性ソーダ水溶液とを同時に滴下
し、約３０分間から１時間かけて沈澱反応を完了させ
る。この際のｐＨは１２になる様に注意し、滴下が終了
したらｐＨを保持したまま、過酸化水素水（濃度３５
％）を１００部滴下して酸化処理を行う。この際の酸化
反応が完全に行われたか否かを酸化還元電位を測定しな
がら確認する。Water 80, which is a precipitating medium prepared in advance,
Heat 0 parts to 26 ° C with a gas burner or electric heater, etc.
Here, the mixed salt aqueous solution and the aqueous sodium hydroxide solution are simultaneously dropped, and the precipitation reaction is completed in about 30 minutes to 1 hour. At this time, care was taken so that the pH was 12, and when the dropping was completed, the pH was maintained and the hydrogen peroxide solution (concentration: 35) was used.
%) Is dropped and oxidation treatment is performed. Whether or not the oxidation reaction at this time has been completed is confirmed while measuring the oxidation-reduction potential.
【００２０】次に酸化処理終了後、液温を７０℃にアッ
プさせ１時間程度熟成を行う。こうして得られた生成物
を十分に水洗し残塩を洗い流して濾過を行う。次いで１
００℃〜１２０℃の温度にて８時間以上乾燥させる。こ
の乾燥物を５２０℃で１時間酸化雰囲気にて焼成する。Next, after the completion of the oxidation treatment, the liquid temperature is raised to 70 ° C., and aging is performed for about one hour. The product thus obtained is thoroughly washed with water to remove residual salts and filtered. Then 1
Dry at a temperature of 00C to 120C for 8 hours or more. The dried product is fired at 520 ° C. for one hour in an oxidizing atmosphere.
【００２１】この様にして得られた顔料は一次粒子が小
さく、ＢＥＴ比表面積が４２ｍ2／ｇであり、且つ鮮映
性にも優れて、更に着色力があり、分散性も良好な青み
のブラックを示す微粒子複合酸化物ブラック顔料であっ
た。The pigment obtained in this way has a small primary particle, a BET specific surface area of 42 m 2 / g, is excellent in sharpness, has coloring power, and has good bluish dispersibility. It was a fine particle composite oxide black pigment showing black.
【００２２】この微粒子複合酸化物ブラック顔料をペイ
ントコンディショナー（レッドデビル社製）でメラミン
／アルキッド樹脂（ＰＨＲ３０）にて十分分散させ、ア
ート紙を展色基材として、クリアランス０．１５ｍｍの
フィルムアプリケーターにて展色したものについては色
調を、又、酸化チタンで薄めたものについて着色力を観
察した。又、同様にペイントコンディショナーでメラミ
ン／アルキッド樹脂（ＰＨＲ５）にて分散させ、石英ガ
ラスを基材として膜厚３０μｍにて塗布したものについ
て遮光性及び黒度について比較した。This fine-particle composite oxide black pigment is sufficiently dispersed in a melamine / alkyd resin (PHR30) with a paint conditioner (manufactured by Red Devil Co., Ltd.), and is applied to a film applicator having a clearance of 0.15 mm using art paper as a developing base material. The color tone was observed for the color-developed product, and the coloring power was observed for the product diluted with titanium oxide. Similarly, a melamine / alkyd resin (PHR5) was dispersed with a paint conditioner, and a light-shielding property and a blackness were compared for those coated with quartz glass as a substrate at a thickness of 30 μm.
【００２３】実施例２ 硫酸銅１２０部及び硫酸マンガン１７０部及び硫酸鉄７
水塩１０４部を計り、約８００部の水に完全に溶かした
水溶液とする。次に沈澱剤として苛性ソーダ２４０部を
計りとり、約８００部の水に完全に溶解する。Example 2 120 parts of copper sulfate, 170 parts of manganese sulfate and iron sulfate 7
The water salt (104 parts) is weighed to obtain an aqueous solution completely dissolved in about 800 parts of water. Next, 240 parts of caustic soda is measured as a precipitant, and completely dissolved in about 800 parts of water.
【００２４】予め用意しておいた沈澱媒体である水８０
０部をガスバーナーや電熱器等で２６℃に加熱保持し、
ここに混合塩水溶液と苛性ソーダ水溶液とを同時に滴下
し、約３０分間から１時間かけて沈澱反応を完了させ
る。以下実施例１と同様の方法にて得られた顔料も、一
次粒子が小さくＢＥＴ比表面積が大きな顔料であり、鮮
映性にも優れて、更に着色力があり、分散性も良好な青
みのブラックを示す微粒子複合酸化物ブラック顔料であ
った。Water 80, a precipitating medium prepared in advance,
Heat 0 parts to 26 ° C with a gas burner or electric heater, etc.
Here, the mixed salt aqueous solution and the aqueous sodium hydroxide solution are simultaneously dropped, and the precipitation reaction is completed in about 30 minutes to 1 hour. Hereinafter, the pigment obtained by the same method as in Example 1 is also a pigment having a small primary particle and a large BET specific surface area, excellent in sharpness, further having coloring power, and having a good bluish dispersibility. It was a fine particle composite oxide black pigment showing black.
【００２５】実施例３ 硫酸銅１２０部、硫酸マンガン１７０部及び硫酸鉄７水
塩１０４部を計り、約８００部の水に完全に溶かした水
溶液とする。次に沈澱剤として苛性ソーダ２４０部を計
りとり、約８００部の水に完全に溶解する。Example 3 120 parts of copper sulfate, 170 parts of manganese sulfate and 104 parts of iron sulfate heptahydrate were weighed to obtain an aqueous solution completely dissolved in about 800 parts of water. Next, 240 parts of caustic soda is measured as a precipitant, and completely dissolved in about 800 parts of water.
【００２６】以下実施例１と同様に沈澱反応終了後、撹
拌しながらエアーを５０リットル／ｍｉｎの流量で反応
槽の底面よりバブリングし酸化処理を行う。この際の酸
化反応も酸化還元電位を測定しながら完全に酸化反応が
行われたか否かを確認する。以下実施例１と同様の方法
で熟成工程を経て得られた顔料も、一次粒子が小さくＢ
ＥＴ比表面積が大きく、着色力が有り且つ鮮映性にも優
れ、分散性の良好な青みのブラックを示す微粒子複合酸
化物ブラック顔料であった。After completion of the precipitation reaction in the same manner as in Example 1, air is bubbled from the bottom of the reaction tank at a flow rate of 50 l / min with stirring to perform an oxidation treatment. At this time, it is checked whether the oxidation reaction has been completed while measuring the oxidation-reduction potential. Hereinafter, the pigment obtained through the aging step in the same manner as in Example 1 also has a small primary particle and B
It was a fine particle composite oxide black pigment having a large ET specific surface area, having coloring power, excellent image clarity, and exhibiting a bluish black with good dispersibility.
【００２７】比較例１ 硫酸銅１２０部及び硫酸マンガン２２７部を計り、約８
００部の水に完全に溶かした水溶液とする。次に沈澱剤
として苛性ソーダ２４０部を計りとり約８００部の水に
完全に溶解する。予め用意しておいた沈澱媒体である水
８００部をガスバーナーや電熱器等で２６℃に加熱保持
し、ここに混合塩水溶液と苛性ソーダ水溶液とを同時に
滴下し、約３０分間から１時間かけて沈澱反応を完了さ
せる。以下熟成終了後の酸化処理を行うことを除き、実
施例１と同様に得られた微粒子複合酸化物ブラック顔料
は粒子が大きく、ＢＥＴ比表面積が１９ｍ2／ｇ程度で
鮮映性に欠ける顔料であった。Comparative Example 1 120 parts of copper sulfate and 227 parts of manganese sulfate were weighed,
An aqueous solution completely dissolved in 00 parts of water. Next, 240 parts of caustic soda is measured as a precipitant and completely dissolved in about 800 parts of water. 800 parts of water as a precipitating medium prepared in advance is heated and maintained at 26 ° C. by a gas burner, an electric heater or the like, and a mixed salt aqueous solution and a caustic soda aqueous solution are simultaneously dropped therein, and it takes about 30 minutes to 1 hour. Complete the precipitation reaction. The fine particle composite oxide black pigment obtained in the same manner as in Example 1 except that an oxidation treatment is performed after the completion of aging is a pigment having large particles, a BET specific surface area of about 19 m 2 / g, and lacking sharpness. there were.
【００２８】比較例２ 硫酸銅１２０部、硫酸マンガン１７０部及び硫酸鉄７水
塩１０４部を計り、約８００部の水に完全に溶かした水
溶液とする。次に沈澱剤として苛性ソーダ２４０部を計
りとり、約８００部の水に完全に溶解する。予め用意し
ておいた沈澱媒体である水８００部をガスバーナーや電
熱器等で２６℃に加熱保持し、ここに混合塩水溶液と苛
性ソーダ水溶液とを同時に滴下し、約３０分間から１時
間かけて沈澱反応を完了させる。Comparative Example 2 120 parts of copper sulfate, 170 parts of manganese sulfate and 104 parts of iron sulfate heptahydrate were weighed to obtain an aqueous solution completely dissolved in about 800 parts of water. Next, 240 parts of caustic soda is measured as a precipitant, and completely dissolved in about 800 parts of water. 800 parts of water as a precipitating medium prepared in advance is heated and maintained at 26 ° C. by a gas burner, an electric heater or the like, and a mixed salt aqueous solution and a caustic soda aqueous solution are simultaneously dropped therein, and it takes about 30 minutes to 1 hour. Complete the precipitation reaction.
【００２９】以下熟成終了後の酸化処理を行うことを除
き、実施例１と同様に得られた微粒子複合酸化物ブラッ
ク顔料は粒子が大きく、ＢＥＴ比表面積が２５ｍ2／ｇ
程度で鮮映性に欠ける顔料であった。The fine particulate composite oxide black pigment obtained in the same manner as in Example 1 except that an oxidizing treatment after completion of aging is performed has large particles and a BET specific surface area of 25 m 2 / g.
It was a pigment lacking in sharpness to a degree.
【００３０】比較例３ 試薬１級の一酸化コバルト５６．３部、二酸化マンガン
８９．０部及び二酸化鉄３０．０部を計り、適当量の水
に入れて湿式混合する。これを６５０℃で焼成する。次
にこの焼成品を粉砕して試料を得た。この様にして得ら
れた従来例の顔料は、実施例１、２及び３で得られた顔
料と比較して一次粒子が大きく、発色が充分ではなく、
黒度、着色力及び鮮映性の点で劣るものであった。Comparative Example 3 56.3 parts of reagent grade 1 cobalt monoxide, 89.0 parts of manganese dioxide and 30.0 parts of iron dioxide were weighed, put in an appropriate amount of water, and wet-mixed. This is fired at 650 ° C. Next, the fired product was pulverized to obtain a sample. The pigment of the conventional example obtained in this way has larger primary particles than the pigments obtained in Examples 1, 2 and 3, and has insufficient color development.
It was inferior in blackness, coloring power and sharpness.
【００３１】以上の結果をまとめて表１に示す。 表１ The above results are summarized in Table 1. Table 1
【００３２】[0032]
【効果】以上の通り、本発明によれば、従来の同種顔料
よりも粒子径が小さく、且つ黒度、着色力、鮮映性等に
優れ、又、絶縁性を示す微粒子複合酸化物ブラック顔料
が得られ、該顔料は従来の顔料として塗料用、建材用着
色剤として使用される以外に、顔料を微粒子化すること
により新たに現れる特性を利用し、例えば、カラーフィ
ルター等のブラックマトリックス用ブラック顔料、ジェ
ットインキ用ブラック顔料、絶縁性の特殊塗料用ブラッ
ク顔料、トーナー用ブラック顔料、ソーラーコレクター
塗料用ブラック顔料、又はカーボンブラックとの調色に
よる青み付け及び絶縁性の付与等の他にも、自動車塗
料、薄膜、印刷インキ、セラッミックス等への応用が期
待される。As described above, according to the present invention, a fine particle composite oxide black pigment having a smaller particle size, excellent blackness, coloring power, sharpness, and the like than conventional pigments of the same type, and exhibiting insulating properties. The pigment is used as a conventional pigment for paints and as a colorant for building materials.In addition, it utilizes the characteristics that newly appear when the pigment is finely divided, for example, black for a black matrix such as a color filter. Other than pigment, black pigment for jet ink, black pigment for insulating special paint, black pigment for toner, black pigment for solar collector paint, or tinting with carbon black and imparting insulation, etc. It is expected to be applied to automotive paints, thin films, printing inks, ceramics, etc.
フロントページの続き (72)発明者 寺田 裕美 東京都中央区日本橋馬喰町一丁目７番６ 号 大日精化工業株式会社内 (72)発明者 西尾 章 東京都中央区日本橋馬喰町一丁目７番６ 号 大日精化工業株式会社内 (72)発明者 太田 隆敬 東京都中央区日本橋馬喰町一丁目７番６ 号 大日精化工業株式会社内 (56)参考文献 特開 平４−89873（ＪＰ，Ａ) 特開 昭63−315557（ＪＰ，Ａ) 特開 平４−50119（ＪＰ，Ａ) 特開 昭59−21504（ＪＰ，Ａ) 特開 平４−275922（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 45/00 C01G 49/00 ＣＡ（ＳＴＮ)Continued on the front page (72) Inventor Hiromi Terada 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (72) Inventor Akira Nishio 1-76 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large Inside Nissei Chemical Industry Co., Ltd. (72) Inventor Takataka Ota 1-7-6, Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Daishin Seika Kogyo Co., Ltd. (56) References JP 4-89873 (JP, A) JP JP-A-63-315557 (JP, A) JP-A-4-50119 (JP, A) JP-A-59-21504 (JP, A) JP-A-4-275922 (JP, A) (58) Fields investigated (Int) .Cl. 7 , DB name) C01G 45/00 C01G 49/00 CA (STN)
Claims (4)
銅及びマンガンの酸化物からなるスピネル構造を有し、
且つそのＢＥＴ比表面積が３０ｍ2／ｇ以上で、青味の
ブラックを示すことを特徴とする微粒子複合酸化物ブラ
ック顔料。1. A spinel structure comprising an oxide of copper and manganese having a molar ratio of copper / manganese of about 1/2 ,
And in that the BET specific surface area of 30 m 2 / g or more, bluish
A fine-particle composite oxide black pigment exhibiting black.
求項１に記載の微粒子複合酸化物ブラック顔料。2. The particulate composite oxide black pigment according to claim 1, wherein a part of manganese is substituted by iron.
に溶解して混合塩溶液とし、これを水性媒体中でアルカ
リ剤によって中和して混合析出せしめ、この析出物を析
出と同時又は析出後に液相中で酸化処理し、次いで得ら
れた析出物を、濾過、水洗及び乾燥し、５２０〜６５０
℃で焼成することを特徴とする微粒子複合酸化物ブラッ
ク顔料の製造方法。3. A mixed salt solution obtained by dissolving two components including a copper salt and a manganese salt in water, neutralizing the mixed salt solution with an alkaline agent in an aqueous medium, and depositing the mixed salt solution. After the precipitation, the precipitate is subjected to an oxidation treatment in a liquid phase, and the obtained precipitate is filtered, washed with water, and dried .
A method for producing a fine-particle composite oxide black pigment, which is fired at a temperature of ° C.
求項３に記載の微粒子複合酸化物ブラック顔料の製造方
法。4. The method for producing a fine particle composite oxide black pigment according to claim 3, wherein a part of manganese is substituted by iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19793695A JP3212065B2 (en) | 1995-07-12 | 1995-07-12 | Fine particle composite oxide black pigment and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19793695A JP3212065B2 (en) | 1995-07-12 | 1995-07-12 | Fine particle composite oxide black pigment and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0925126A JPH0925126A (en) | 1997-01-28 |
| JP3212065B2 true JP3212065B2 (en) | 2001-09-25 |
Family
ID=16382764
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19793695A Expired - Lifetime JP3212065B2 (en) | 1995-07-12 | 1995-07-12 | Fine particle composite oxide black pigment and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3212065B2 (en) |
Cited By (2)
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|---|---|---|---|---|
| WO2013099690A1 (en) | 2011-12-26 | 2013-07-04 | 大日精化工業株式会社 | Composite oxide black pigment and method for producing same |
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| US9732230B2 (en) | 2012-04-02 | 2017-08-15 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Composite oxide black pigment and method for producing same |
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| Publication number | Publication date |
|---|---|
| JPH0925126A (en) | 1997-01-28 |
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