JPS63319216A - Production of cobalt blue pigment - Google Patents
Production of cobalt blue pigmentInfo
- Publication number
- JPS63319216A JPS63319216A JP15133287A JP15133287A JPS63319216A JP S63319216 A JPS63319216 A JP S63319216A JP 15133287 A JP15133287 A JP 15133287A JP 15133287 A JP15133287 A JP 15133287A JP S63319216 A JPS63319216 A JP S63319216A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- blue pigment
- cobalt blue
- cobalt
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001055 blue pigment Substances 0.000 title claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 24
- 239000010941 cobalt Substances 0.000 title claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract 4
- 238000010304 firing Methods 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- -1 etc. Chemical compound 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000049 pigment Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical class [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- C09C1/40—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はコバルトブルー系顔料の製造方法に関し、更に
詳しくは赤味の冴えた色調を有し、分散性の良好なコバ
ルトブルー系顔料の製造方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a cobalt blue pigment, and more specifically, to a method for producing a cobalt blue pigment that has a bright reddish tone and has good dispersibility. Regarding the method.
（従来の技術）
コバルトブルー系顔料は耐熱性に優れた無機顔料として
広く知られ、例えば、塗料や合成樹脂の着色剤、蛍光体
更には窯業用着色剤等として幅広く使用されている。(Prior Art) Cobalt blue pigments are widely known as inorganic pigments with excellent heat resistance, and are widely used, for example, as colorants for paints and synthetic resins, phosphors, and colorants for ceramics.
上記コバルトブルー系顔料はアルミニウムの酸化物とコ
バルトの酸化物を主体とするスピネル型化合物であり、
必要に応じてクロムやマグネシウム等の他の金属の酸化
物も含み得るものである。The above cobalt blue pigment is a spinel type compound mainly composed of aluminum oxide and cobalt oxide,
If necessary, oxides of other metals such as chromium and magnesium may also be included.
上記コバルトブルー系顔料の製造は主として乾武力法及
び湿式方法により製造されている。The above-mentioned cobalt blue pigment is mainly produced by a dry force method and a wet method.
（発明が解決しようとしている問題点）乾式方法は酸化
コバルトと酸化アルミニウムとを混合し、フラックスを
併存させて高温で焼成し、次いで、焼結した粒子を強力
な粉砕機によって粉砕し顔料化する方法であるが、粉砕
に大きなエネルギーを要するという欠点と、得られる顔
料に色のくすみが現われ、鮮明な色調が得られないとい
う問題がある。(Problem to be solved by the invention) The dry method involves mixing cobalt oxide and aluminum oxide, sintering the mixture at high temperature in the presence of flux, and then pulverizing the sintered particles using a powerful pulverizer to form pigments. However, this method has the drawback that it requires a large amount of energy for grinding, and the resulting pigment has a dull color, making it difficult to obtain a clear color tone.
一方、湿式方法は、アルミニウム塩とコバルト塩の混合
溶液をアルカリで中和して両者を水酸化物として共沈さ
せ、これを焼成して発色させる方法であるが、沈澱する
水酸化物の粒子径は著しく小さいこと、及びアルミニウ
ムの水酸化物がゲル状沈澱となるために、共沈物の含水
率が高く、その乾燥に大きなエネルギーを要するという
問題があり、更に含水物を乾燥するときに粒子が凝集し
て固い魂りとなり、焼成すると更に固い粒子となるため
、その粉砕が困難であるという問題がある。On the other hand, in the wet method, a mixed solution of aluminum salt and cobalt salt is neutralized with an alkali to co-precipitate the two as hydroxide, and this is fired to develop color, but the precipitated hydroxide particles Because the diameter is extremely small and the aluminum hydroxide forms a gel-like precipitate, the moisture content of the coprecipitate is high and requires a large amount of energy to dry. There is a problem in that the particles agglomerate into hard particles and become even harder particles when fired, making it difficult to crush them.
更に、いずれの方法によっても得られる顔料は緑味の色
調を有し、赤味の色調が要求される用途には使用できな
いという問題がある。Furthermore, there is a problem in that the pigments obtained by either method have a greenish color tone and cannot be used in applications requiring a reddish color tone.
従って、焼成、乾燥及び粉砕等の消費エネルギーか少な
くて済み、且つ鮮明で赤味の冴えた色調を有するコバル
トブルー系顔料が要望されている。Therefore, there is a need for a cobalt blue pigment that requires less energy for firing, drying, grinding, etc., and has a clear, reddish color tone.
（問題点を解決するための手段）
本発明者は」−述の要望に応えるべく鋭意研究の結果、
アルミニウムの水酸化物とコバルトの水酸化物との共沈
に、特定の沈澱剤を用いることにより、上記の要望に応
えることができることを見い出し本発明を完成した。(Means for Solving the Problems) As a result of intensive research in response to the above-mentioned demands, the present inventors have
The inventors have discovered that the above needs can be met by using a specific precipitating agent for coprecipitation of aluminum hydroxide and cobalt hydroxide, and have completed the present invention.
すなわち、本発明は、アルミニウム塩、コバルト塩及び
尿素を水中に溶解して混合液とし、これを加熱すること
によってアルミニウムの水酸化物とコバルトの水酸化物
とを共沈させ、共沈物を濾過及び水洗後焼成することを
特徴とするコバルトブルー系顔料の製造方法である。That is, the present invention dissolves an aluminum salt, a cobalt salt, and urea in water to form a mixed solution, and heats the mixture to co-precipitate aluminum hydroxide and cobalt hydroxide, thereby producing a coprecipitate. This is a method for producing a cobalt blue pigment, which is characterized by filtration, washing with water, and then firing.
（作 用）
水酸化物の沈澱剤として尿素を用いることによって、ア
ルミニウムの水酸化物とコバルトの水酸化物との共沈が
均一に行われ、共沈物の脱水が容易であり、且つ比較的
低温の焼成でも赤味で鮮明なコバルトブルー系顔料が得
られ、該コバルトブルー系顔料はソフトな粒子であるの
で粉砕が容易である。(Function) By using urea as a precipitant for hydroxide, co-precipitation of aluminum hydroxide and cobalt hydroxide is carried out uniformly, and dehydration of the coprecipitate is easy, and compared to A reddish and clear cobalt blue pigment can be obtained even by firing at a relatively low temperature, and since the cobalt blue pigment is soft particles, it is easy to crush.
（好ましい実施態様）
次に本発明を本発明の好ましい実施態様を挙げて更に詳
しく説明する。(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments of the present invention.
本発明で使用するアルミニウム塩及びコバルトの塩とは
アルミニウム又はコバルトの硫酸塩、硝酸塩、塩化物、
酢酸塩等従来のコバルトブルー系顔料の製造に使用され
ている塩はいずれも使用することができる。又、上記の
必須成分に加えてクロムやマグネシウム等の如き他の金
属塩も少量併用可能であり、特にアルミニウム１モルに
対し、０．３モル以下の少量のクロム塩を併用すること
によって、得られる顔料の色調を緑味に優れたものとす
ることができる。The aluminum salts and cobalt salts used in the present invention are aluminum or cobalt sulfates, nitrates, chlorides,
Any salt used in the production of conventional cobalt blue pigments, such as acetate, can be used. In addition to the above essential components, small amounts of other metal salts such as chromium and magnesium can also be used together, and in particular, by using a small amount of chromium salt of 0.3 mol or less per 1 mol of aluminum, the results can be improved. The color tone of the pigment can be made to have an excellent green tinge.
上記においてアルミニウム塩とコバルト塩の使用量はモ
ル比でＣｏ／ＡＩＬ＝］／２乃至１７５程度の範囲が適
当である。In the above, the amounts of aluminum salt and cobalt salt to be used are suitably in the range of about Co/AIL=]/2 to 175 in terms of molar ratio.
以−Ｌの如きアルミニウム塩、コバルト塩又は他の金属
塩を水に溶解して混合塩水溶液を形成するが、その濃度
は上記の如き範囲のモル比で全体として約２０重量％（
硝酸アルミニウム基準）以下程度の濃度とするのがよい
。Aluminum salts, cobalt salts or other metal salts such as those listed below are dissolved in water to form a mixed salt aqueous solution, the concentration of which is approximately 20% by weight (by weight) in the molar ratio range as described above.
It is best to keep the concentration below (aluminum nitrate standard).
上記混合塩溶液から混合水酸化物を析出させるために使
用する沈澱剤として尿素を使用する。Urea is used as the precipitant used to precipitate the mixed hydroxide from the mixed salt solution.
本発明者の詳細な研究によれば、前記混合塩水溶液に尿
素を溶解することによって、常温付近の温度では特別の
変化を生じないが、これを撹拌しながら昇温すると、例
えば、６０℃以上、好ましくは７０℃以−トの温度に加
熱すると、アルミニウムの水酸化物とコバルトの水酸化
物は均一に沈澱し、且つ沈澱物の粒子は従来のアルカリ
沈澱法によるものと異なり、ある程度の大きさを有し、
濾過等による脱水が非常に容易となり、又、脱水物は乾
燥時に固く凝集することがなく、その後に焼酸処理を施
しても殆ど粉砕を必要としない程度のソフトなコバルト
ブルー系顔料が容易に得られることを見い出したもので
ある。According to detailed research by the present inventor, dissolving urea in the mixed salt aqueous solution does not cause any particular change at a temperature around room temperature, but when the temperature is raised while stirring, for example, 60°C or higher. When heated to a temperature of preferably 70°C or higher, aluminum hydroxide and cobalt hydroxide precipitate uniformly, and the precipitate particles have a certain size, unlike those obtained by conventional alkaline precipitation methods. It has a
Dehydration by filtration etc. becomes very easy, and the dehydrated product does not aggregate hard when drying, making it easy to produce a soft cobalt blue pigment that hardly requires pulverization even if it is subsequently subjected to baking acid treatment. This is what I found out.
又、水酸化物の析出時には、全成分が均一に溶解した状
態から水酸化物の析出が始まるので、析出物は十分に均
一な混合物であり、焼成時に何らのフラックスを用いる
必要もないものであった。Furthermore, when hydroxide is precipitated, the hydroxide begins to precipitate from a state in which all components are uniformly dissolved, so the precipitate is a sufficiently uniform mixture, and there is no need to use any flux during firing. there were.
以上の如き沈澱剤である尿素は上記金属塩全体に対し、
金属塩１当量につき約１．０乃至２．０モルの使用割合
が好適であり、使用モル比が上記範囲未満であると金属
水酸化物の沈澱が不十分となり、一方、上記範囲を越え
る使用割合では不要な尿素を用いることになり不経済で
ある。Urea, which is a precipitant as mentioned above, has a
A ratio of about 1.0 to 2.0 moles per equivalent of metal salt is suitable; if the molar ratio is less than the above range, precipitation of the metal hydroxide will be insufficient; on the other hand, if the molar ratio is less than the above range, This ratio is uneconomical as unnecessary urea is used.
更に本発明によれば、上記の水酸化物の共沈工程におい
て、系中に硫酸イオンを共存させることにより、共沈す
る水酸化物の粒子径のコントロールができ、共沈物の粒
子径を大きくして脱水、乾燥が容易となり、更に焼成時
にも粒子が凝集しないので、焼成後殆ど粉砕を要しない
程ソフトな製品が得られることを見い出した。Furthermore, according to the present invention, in the above hydroxide coprecipitation step, by coexisting sulfate ions in the system, the particle size of the coprecipitated hydroxide can be controlled, and the particle size of the coprecipitate can be controlled. It has been found that by increasing the size, dehydration and drying become easier, and since the particles do not aggregate during firing, a soft product can be obtained that hardly requires pulverization after firing.
硫酸イオンの使用量を増す程大きな粒子径の共沈物が得
られるが、好ましい使用割合は水溶液濃度として０．０
５Ｍ／１乃至０．２Ｍ／Ｉｔ程度である。As the amount of sulfate ion used increases, a coprecipitate with a larger particle size can be obtained, but the preferred ratio is 0.0 as the aqueous solution concentration.
It is about 5M/1 to 0.2M/It.
以上の如き本発明の方法は各成分を水中に溶解し、溶解
が完了したら全体を撹拌しながら６０℃以上、好ましく
は７０乃至１００℃の温度で約３乃至１０時間程度撹拌
することによって水酸化物の共沈が完了する。水酸化物
の共沈の完了は反応液の１部を濾過し、その濾液にアル
カリを加えて、濾液が着色しないことを確認することに
よって行うことができる。In the method of the present invention as described above, each component is dissolved in water, and after the dissolution is completed, the whole is stirred at a temperature of 60° C. or higher, preferably 70 to 100° C., for about 3 to 10 hours to oxidize the hydroxide. Co-precipitation of the substance is completed. Completion of coprecipitation of hydroxide can be accomplished by filtering a portion of the reaction solution, adding an alkali to the filtrate, and confirming that the filtrate is not colored.
次に析出した共沈物を濾過することによって含水率が約
４０乃至６０部程度となり、これを約１００乃至１２０
℃程度の温度で乾燥し、これを酸化性雰囲気下で約９０
０乃至１，２００℃の温度で約３０乃至９０分間焼成す
ることにより発色し、本発明のコバルトブルー系顔料が
得られる。Next, by filtering the precipitated coprecipitate, the water content becomes about 40 to 60 parts, which is reduced to about 100 to 120 parts.
It is dried at a temperature of approximately 90°C and heated under an oxidizing atmosphere
Color is developed by firing at a temperature of 0 to 1,200° C. for about 30 to 90 minutes, and the cobalt blue pigment of the present invention is obtained.
従来方法における焼成温度は一般的に１．０００乃至１
，２００℃程度が要求されるが、本発明方法ではそれ以
下の温度、例えば９００℃乃至１．２００℃の温度でも
十分な焼成を行うことができる。The firing temperature in conventional methods is generally 1.000 to 1.
, 200°C, but the method of the present invention can perform sufficient firing even at lower temperatures, for example, from 900°C to 1.200°C.
又、得られたコバルトブルー系顔料は、従来のコバルト
ブルー系顔料がくすんだ色調の緑味の青色であるのに対
し、くすみのない鮮明な赤味の青色の製品となり、粒子
が非常にソフトであるので、塗料や合成樹脂、その他の
被着色材中で非常に優れた分散性を示すものである。In addition, the obtained cobalt blue pigment is a product with a clear reddish blue color without dullness, and the particles are extremely soft, whereas conventional cobalt blue pigments have a dull greenish blue color. Therefore, it exhibits excellent dispersibility in paints, synthetic resins, and other colored materials.
（効 果）
以上の如き本発明によれば水酸化物の沈澱剤として尿素
を用いることによって、アルミニウムの水酸化物とコバ
ルトの水酸化物との共沈が均一に行なわれ、共沈物の脱
水が容易であり、且つ比較的低温の焼成でも赤味で鮮明
なコバルトブルー系顔料が得られ、該コバルトブルー系
顔料はソフトな粒子であるので粉砕が容易である。(Effects) According to the present invention as described above, by using urea as a precipitant for hydroxide, co-precipitation of aluminum hydroxide and cobalt hydroxide is carried out uniformly, and the coprecipitate is It is easy to dehydrate, and a bright reddish cobalt blue pigment can be obtained even when fired at a relatively low temperature, and since the cobalt blue pigment is soft particles, it is easy to crush.
実施例１
硝酸アルミニウム９水塩４１．４部と硝酸コバルト６水
塩１６部に尿素を６０部加え、更に硫酸ソーダ５．５部
を加え、溶解水を加え全体で６００部とする。よく撹拌
し各成分を完全に溶解させた後、水が飛ばないように時
計皿をかぶせ、マグネチックスターラーで撹拌しながら
温度をあげる。温度が８０℃になったら一定に保ち、そ
のまま放置する。しばらくすると沈澱が析出してくる。Example 1 60 parts of urea is added to 41.4 parts of aluminum nitrate nonahydrate and 16 parts of cobalt nitrate hexahydrate, 5.5 parts of sodium sulfate are added, and dissolved water is added to make a total of 600 parts. After stirring well to completely dissolve each ingredient, cover with a watch glass to prevent water from splattering, and raise the temperature while stirring with a magnetic stirrer. Once the temperature reaches 80°C, keep it constant and leave it as is. After a while, a precipitate will start to separate out.
反応が終了間際になったならば、析出が完全に終了して
いるかを確認するため、スラリーの１部を取り、濾紙に
てこして濾液を取り、うすい苛性ソーダ液に落す。液が
透明ならば終了しているので取り出し、充分に水洗をし
、残塩を洗い流す。When the reaction is almost complete, take a portion of the slurry, strain it through a filter paper, collect the filtrate, and pour it into dilute caustic soda solution to confirm that the precipitation has completely completed. If the liquid is clear, it has finished, so take it out and rinse thoroughly with water to remove any remaining salt.
このものを１２０℃の温度にて１２時間以上乾燥させる
。This material is dried at a temperature of 120° C. for 12 hours or more.
次にこの乾燥した共沈物を９００℃で１時間酸化雰囲気
中にて焼成させる。Next, this dried coprecipitate is calcined at 900° C. for 1 hour in an oxidizing atmosphere.
このようにして得られた顔料は、全くくすみがなくしか
も冴えた色調の鮮明な青色であり、乾式法のものに比べ
て赤味であった。また分散性も優れたものであった。The pigment thus obtained had a clear blue color with no dullness at all and a clear tone, and had a reddish tinge compared to that obtained by the dry method. Moreover, the dispersibility was also excellent.
実施例２
硝酸アルミニウム９水塩４１．４部、塩化コバルト６水
塩９．１部、尿素６０部、硫酸ソーダ５．５部を加え、
更に溶解水を加え全体で６００部とする。Example 2 41.4 parts of aluminum nitrate nonahydrate, 9.1 parts of cobalt chloride hexahydrate, 60 parts of urea, and 5.5 parts of sodium sulfate were added,
Further, add dissolved water to make a total of 600 parts.
以下実施例１と同様の方法により合成を行う。Synthesis is then carried out in the same manner as in Example 1.
このようにして得られた顔料は実施例１と同様に冴えた
赤味の青色で、くすみも全くみられずソフトで分散性に
優れたものであった。The pigment thus obtained had a bright reddish blue color similar to that of Example 1, had no dullness, was soft, and had excellent dispersibility.
比較例１
硝酸アルミニウム９水塩４１．４部と硝酸コバルト６水
塩１６部とを溶解水２００部にとかし、別に苛性ソーダ
１７．６部をはかり、同様に溶解水２００部に溶かず。Comparative Example 1 41.4 parts of aluminum nitrate nonahydrate and 16 parts of cobalt nitrate hexahydrate were dissolved in 200 parts of dissolved water, and 17.6 parts of caustic soda was separately weighed, and the same solution was not dissolved in 200 parts of water.
ＩＪＺビーカーに沈澱水２００部をとり、室温にてモー
ターで撹拌しながら、用意した塩の溶液と苛性ソーダの
溶液を同時に沈澱水の中に滴下する。この時ｐＨは約９
乃至１０になるように適宜調整をする。Take 200 parts of precipitated water in an IJZ beaker, and simultaneously drop the prepared salt solution and caustic soda solution into the precipitated water while stirring with a motor at room temperature. At this time the pH is about 9
Adjust as appropriate so that the number is between 10 and 10.
滴下が終了したならば、スラリーは１時間室温にて熟成
し、その後濾過水洗を行い、１２０℃にて１２時間以上
乾燥させる。乾燥」一つの共沈物はこの時点で収縮して
カチカチの状態となる。When the dropping is completed, the slurry is aged at room temperature for 1 hour, then filtered and washed with water, and dried at 120° C. for 12 hours or more. Drying: At this point, one coprecipitate shrinks and becomes sticky.
次にこのものを１，２００℃で１時間酸化雰囲気にて焼
成させる。Next, this product is fired in an oxidizing atmosphere at 1,200° C. for 1 hour.
この様にして得られた顔料は、赤味のブルーであるが、
粒子が大変固く、粉砕機により粉砕してもザラザラであ
り分散性の大変悪いものであった。The pigment obtained in this way is reddish blue, but
The particles were very hard and even when crushed using a crusher, they were rough and had very poor dispersibility.
比較例２
酸化アルミニウム１１．３部と酸化コバルト４．１部を
乳バチにてよくすりつぶして混合し、これを１，２００
℃にて１時間酸化雰囲気下にて焼成させる。Comparative Example 2 11.3 parts of aluminum oxide and 4.1 parts of cobalt oxide were thoroughly ground and mixed with a pestle, and this was mixed into 1,200 parts of
C. for 1 hour under an oxidizing atmosphere.
この様にして得られた顔料は乳バチにて軽くつぶせばほ
ぐれるくらいのソフトなものてあったが、色調はややく
すみがあり、緑味で、冴えに乏しい色であった。The pigment thus obtained was soft enough to be loosened by crushing it lightly with a pestle, but the color tone was somewhat dull, greenish, and lacked brightness.
（以下余白） 一゛−−色 調(Margin below) One color tone
Claims (5)
解して混合液とし、これを加熱することによってアルミ
ニウムの水酸化物とコバルトの水酸化物とを共沈させ、
共沈物を濾過及び水洗後焼成することを特徴とするコバ
ルトブルー系顔料の製造方法。(1) Aluminum salt, cobalt salt, and urea are dissolved in water to form a mixed solution, and by heating this, aluminum hydroxide and cobalt hydroxide are coprecipitated,
A method for producing a cobalt blue pigment, which comprises filtering the coprecipitate, washing it with water, and then firing it.
（１）項に記載のコバルトブルー系顔料の製造方法。(2) The method for producing a cobalt blue pigment according to claim (1), wherein the heating is performed at a temperature of 70° C. or higher.
囲第（１）項に記載のコバルトブルー系顔料の製造方法
。(3) The method for producing a cobalt blue pigment according to claim (1), in which sulfate ions are coexisted in the mixed solution.
（１）項に記載のコバルトブルー系顔料の製造方法。(4) The method for producing a cobalt blue pigment according to claim (1), wherein the firing temperature is 900°C or higher.
ロムの塩を共存させる特許請求の範囲第（１）項に記載
のコバルトブルー系顔料の製造方法。(5) The method for producing a cobalt blue pigment according to claim (1), in which 0.3 mole or less of a chromium salt is coexisting per mole of aluminum salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15133287A JPH0696454B2 (en) | 1987-06-19 | 1987-06-19 | Method for producing cobalt bull-based pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15133287A JPH0696454B2 (en) | 1987-06-19 | 1987-06-19 | Method for producing cobalt bull-based pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63319216A true JPS63319216A (en) | 1988-12-27 |
| JPH0696454B2 JPH0696454B2 (en) | 1994-11-30 |
Family
ID=15516272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15133287A Expired - Fee Related JPH0696454B2 (en) | 1987-06-19 | 1987-06-19 | Method for producing cobalt bull-based pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696454B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02283771A (en) * | 1989-04-25 | 1990-11-21 | Dainichiseika Color & Chem Mfg Co Ltd | Particulate cobalt blue pigment and preparation thereof |
| JPH0455322A (en) * | 1990-06-22 | 1992-02-24 | Dainichiseika Color & Chem Mfg Co Ltd | Blue-green pigment of multiple oxide fine particle and its production |
| CN1078182C (en) * | 1998-03-13 | 2002-01-23 | 咸阳多晶材料厂 | Cobalt aluminate for colour kinescope and preparation technology thereof |
| JP2009215385A (en) * | 2008-03-07 | 2009-09-24 | Toda Kogyo Corp | Blue pigment with infrared reflectivity, coating material using the same, and resin composition |
| CN107057408A (en) * | 2017-06-22 | 2017-08-18 | 中国科学院兰州化学物理研究所 | Regulate and control the method for cobalt blue/tectosilicate hybrid pigment color using metal ion mixing |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2009012564A (en) * | 2007-05-23 | 2009-12-09 | Dsm Ip Assets Bv | Colored suture. |
| CN111218131B (en) * | 2019-12-12 | 2021-08-03 | 西北永新涂料有限公司 | Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method |
-
1987
- 1987-06-19 JP JP15133287A patent/JPH0696454B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02283771A (en) * | 1989-04-25 | 1990-11-21 | Dainichiseika Color & Chem Mfg Co Ltd | Particulate cobalt blue pigment and preparation thereof |
| JPH0455322A (en) * | 1990-06-22 | 1992-02-24 | Dainichiseika Color & Chem Mfg Co Ltd | Blue-green pigment of multiple oxide fine particle and its production |
| CN1078182C (en) * | 1998-03-13 | 2002-01-23 | 咸阳多晶材料厂 | Cobalt aluminate for colour kinescope and preparation technology thereof |
| JP2009215385A (en) * | 2008-03-07 | 2009-09-24 | Toda Kogyo Corp | Blue pigment with infrared reflectivity, coating material using the same, and resin composition |
| CN107057408A (en) * | 2017-06-22 | 2017-08-18 | 中国科学院兰州化学物理研究所 | Regulate and control the method for cobalt blue/tectosilicate hybrid pigment color using metal ion mixing |
| CN107057408B (en) * | 2017-06-22 | 2019-02-01 | 中国科学院兰州化学物理研究所 | Regulate and control cobalt blue/tectosilicate hybrid pigment color method using metal ion mixing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0696454B2 (en) | 1994-11-30 |
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