JPH05124820A - Bismuth vanadate composition for pigment and its production - Google Patents
Bismuth vanadate composition for pigment and its productionInfo
- Publication number
- JPH05124820A JPH05124820A JP10024892A JP10024892A JPH05124820A JP H05124820 A JPH05124820 A JP H05124820A JP 10024892 A JP10024892 A JP 10024892A JP 10024892 A JP10024892 A JP 10024892A JP H05124820 A JPH05124820 A JP H05124820A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- pigment
- zirconium
- yellow
- bismuth vanadate
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01P2006/62—L* (lightness axis)
-
- 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
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
-
- 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
- C01P2006/65—Chroma (C*)
-
- 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
- C01P2006/66—Hue (H*)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、顔料用バナジン酸ビス
マス組成物及びその製造方法に関し、更に詳しくは、そ
の高い純度（インテンシチー）、着色力、隠蔽力によ
り、従来の黄色系顔料が使用されている分野、例えば、
一般樹脂及びエンジニヤリングプラスチック樹脂の着
色、塗料、インキ、セラミックス、建材等の分野におい
て有用な黄色系バナジン酸ビスマス顔料組成物の提供を
目的とする。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bismuth vanadate composition for pigments and a method for producing the same. More specifically, a conventional yellow pigment is used because of its high purity (intenseness), coloring power and hiding power. Fields, for example,
An object of the present invention is to provide a yellow bismuth vanadate pigment composition useful in the fields of coloring general resins and engineering plastic resins, paints, inks, ceramics, building materials and the like.
【０００２】[0002]
【従来の技術】現在広く用いられている黄色系顔料に
は、無機顔料としては硫化カドミウム、クロム酸鉛、チ
タンイエロー、酸化鉄イエロー等があり、又、有機顔料
としては、アゾ顔料及びキナクリドン等の高級顔料があ
る。しかしながら、硫化カドミウム及びクロム酸鉛は、
着色濃度及び隠蔽力の点で優れているが、毒性に関して
問題があり、使用が限定されている。又、今後において
もこの傾向は続くものと考えられている。チタンイエロ
ーは、高い諸耐性と隠蔽性を有するものの、色の純度や
着色力においては前二者よりも劣っており、使用される
分野も同様に限定されている。又、酸化鉄イエローは、
純度、着色力及び耐熱性の点で劣っている。アゾ顔料等
の有機顔料は一般に無機顔料に比べて更に高い純度と着
色力を有しているが、隠蔽力や諸耐性において劣ってい
る。又、耐ブリード性においても劣っている場合が多
い。2. Description of the Related Art Yellow pigments widely used at present include inorganic pigments such as cadmium sulfide, lead chromate, titanium yellow, and iron oxide yellow, and organic pigments such as azo pigments and quinacridone. There are high quality pigments. However, cadmium sulfide and lead chromate
It is excellent in terms of color density and hiding power, but has problems regarding toxicity and its use is limited. It is considered that this tendency will continue in the future. Although titanium yellow has high resistance and hiding power, it is inferior to the former two in terms of color purity and tinting strength, and its field of use is also limited. Iron oxide yellow is
Poor in terms of purity, coloring power and heat resistance. Organic pigments such as azo pigments generally have higher purity and coloring power than inorganic pigments, but are inferior in hiding power and various resistances. In addition, the bleeding resistance is often poor.
【０００３】[0003]
【発明が解決しようとしている問題】本発明は上述の如
き問題を念頭に置き為されたものである。即ち、黄色系
顔料では、チタンイエローや酸化鉄イエローは、色調の
点で有機顔料並の高い純度と着色力を有しておらず、そ
れらを要求される無機顔料として、今現在カドミ顔料や
クロム酸鉛系顔料があるが、毒性の点でその使用が限定
される為、市場の要望としてそれに代わる顔料が望まれ
ている。又、有機顔料では望めない高耐性下での使用を
求める分野や有機溶剤に対する安定性を求める分野にお
ける要望として、同様に黄色系の顔料が求められてい
る。SUMMARY OF THE INVENTION The present invention has been made with the above problems in mind. That is, among the yellow pigments, titanium yellow and iron oxide yellow do not have high purity and coloring power comparable to those of organic pigments in terms of color tone. Although there are lead acid-based pigments, their use is limited in terms of toxicity, so that a substitute pigment is desired as a market demand. In addition, as a demand in the field of using under high resistance which is not desired with an organic pigment and in the field of seeking stability against an organic solvent, a yellow pigment is also required.
【０００４】更に本発明の顔料の母体となるバナジン酸
ビスマス単独品については多くの研究がなされ、例え
ば、特開昭５２−１５６８００号公報、特開昭５３−３
６５２７号公報、特開昭５５−７８０６３号公報及び特
開昭６３−１６２７６５号公報等があり、色調及び諸耐
性の改良の試みがなされているが、実用になるものはな
かなか見い出せないのが現状である。従って、本発明の
目的は、高い純度（インテンシチー）、着色力、隠蔽力
を有し、従来の黄色系顔料で使用されている分野、例え
ば、一般樹脂及びエンジニヤリングプラスチック樹脂の
着色、塗料、インキ、セラミックス、建材等の分野にお
いて有用な黄色系バナジン酸ビスマス顔料組成物を提供
することである。Further, a lot of researches have been conducted on bismuth vanadate alone as a base material of the pigment of the present invention, for example, JP-A-52-156800 and JP-A-53-3.
There are Japanese Patent No. 6527, Japanese Patent Application Laid-Open No. 55-78063, Japanese Patent Application Laid-Open No. 63-162765, etc., and attempts have been made to improve the color tone and various resistances, but it is difficult to find a practical one. Is. Therefore, an object of the present invention is to have high purity (intenseness), coloring power, hiding power, and fields used in conventional yellow pigments, for example, coloring of general resins and engineering plastic resins, paints, A yellow bismuth vanadate pigment composition useful in the fields of inks, ceramics, building materials and the like.
【０００５】[0005]
【問題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、ジルコニウム、バ
ナジウム及びビスマスよりなることを特徴とする黄色系
顔料用バナジン酸ビスマス組成物、及びその製造方法で
ある。The above object can be achieved by the present invention described below. That is, the present invention is a bismuth vanadate vanadate composition for yellow pigments, which comprises zirconium, vanadium and bismuth, and a method for producing the same.
【０００６】[0006]
【作用】本発明は前述の要望に応えるべく鋭意研究の結
果、湿式法にてバナジウムのアルカリ水溶液と、ビスマ
ス及びジルコニウムの塩とを適当な割合で混合し、加熱
・熟成を行うことにより、バナジン酸ビスマス単独品で
は出す事の出来ない、冴えた色調、大きな着色力及び高
い堅牢度を備え、又、カドミ顔料やクロム酸鉛系顔料と
同等の性質を具備した顔料組成物が得られることを見い
出した。本発明によるジルコニウム共存バナジン酸ビス
マス系顔料組成物は、単独品に無い色調における高い純
度と、着色力、隠蔽力により、前述の要望に十分に応え
られるものであり、高耐性下や有機溶剤下での使用にも
有用である。As a result of extensive research to meet the above-mentioned demands, the present invention shows that vanadium can be prepared by mixing an alkaline aqueous solution of vanadium and a salt of bismuth and zirconium at an appropriate ratio by a wet method and then heating and aging the mixture. It is possible to obtain a pigment composition that has a clear color tone, large coloring power and high fastness that cannot be obtained with bismuth acid alone, and has properties equivalent to those of cadmium pigments and lead chromate pigments. I found it. The zirconium-containing bismuth vanadate-based pigment composition according to the present invention is capable of sufficiently satisfying the above-mentioned demands due to high purity in color tone, coloring power and hiding power which are not present in individual products. Also useful for use in.
【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。本発明のバナジン酸ビスマ
ス系顔料組成物は、湿式法において、ジルコニウム及び
ビスマスの塩の各々の水溶液と、バナジウムのアルカリ
水溶液とを、沈澱水中に個別ないし同時に混合し、各元
素を目的の割合に沈澱させ、濾過、水洗及び乾燥するこ
とにより得られる。本発明の本質は、基本的に顔料とし
ての諸適性を具備していない、バナジン酸ビスマスに、
ジルコニウムを湿式にて目的とする割合まで混合し、目
的とする顔料組成物を構成させるもので、その際、加熱
・熟成することにより、その特性をより確かなものとす
ることが出来る。本発明によりジルコニウムを混在させ
ることにより、バナジン酸ビスマス単独品に対して実使
用に耐え得る、より確実な顔料適性を付与するものであ
り、具体的にはより高い純度と着色力及び諸耐性を与え
ることが出来る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The bismuth vanadate-based pigment composition of the present invention is a wet method in which each aqueous solution of zirconium and bismuth salts and an aqueous alkaline solution of vanadium are mixed individually or simultaneously in the precipitation water, and each element is mixed in a desired ratio. It is obtained by precipitation, filtration, washing with water and drying. The essence of the present invention is basically bismuth vanadate, which has no aptitude as a pigment.
Zirconium is mixed in a wet ratio up to a desired ratio to form a desired pigment composition. At that time, its characteristics can be made more reliable by heating and aging. By mixing zirconium according to the present invention, it is possible to endure actual use to a bismuth vanadate alone, and to impart more reliable pigment aptitude, and specifically, to provide higher purity and coloring power and various resistances. Can be given.
【０００８】本発明で使用する構成元素の原材料として
は、各元素の塩を使用することが出来る。ビスマス及び
ジルコニウムの塩を用いた場合、苛性ソーダやソーダ灰
等のアルカリ沈澱剤を用いて、又、バナジウムのアルカ
リ溶液を用いて湿式により各構成成分の元素を沈澱さ
せ、均一に混合し目的物を得ることが出来る。原材料と
してのバナジウムは、Ｎａ3 ＶＯ4 等のバナジン酸のア
ルカリ塩を用いることが出来る他、Ｖ2 Ｏ5 を苛性ソー
ダ等のアルカリに溶解してアルカリ水溶液として用いる
ことも出来る。上記において各元素の比は、モル比でジ
ルコニウム：ビスマス：バナジウムが０．１〜１．５：
１：１、好ましくは０．２５〜１．０：１：１が適当で
あり、混合するジルコニウムの割合が０．１モル以上で
あれば有効な効果を発揮することが出来る。又、１．５
モルを越えると着色濃度が落ち込み、満足することが出
来る色調のものが得られない。As raw materials for the constituent elements used in the present invention, salts of each element can be used. When salts of bismuth and zirconium are used, an alkaline precipitating agent such as caustic soda or soda ash is used, or an alkaline solution of vanadium is used to wet-precipitate the elements of the respective constituents and uniformly mix to obtain the desired product. You can get it. As vanadium as a raw material, an alkali salt of vanadic acid such as Na 3 VO 4 can be used, or V 2 O 5 can be dissolved in an alkali such as caustic soda to be used as an alkaline aqueous solution. In the above, the molar ratio of each element is 0.1 to 1.5 for zirconium: bismuth: vanadium.
1: 1, preferably 0.25 to 1.0: 1: 1 is suitable, and if the ratio of zirconium to be mixed is 0.1 mol or more, an effective effect can be exhibited. Also, 1.5
When it exceeds the molar amount, the coloring density is lowered, and a satisfactory color tone cannot be obtained.
【０００９】上記のビスマス塩の溶液濃度は、０．５モ
ル／リットル〜１．０モル／リットル程度が好ましい。
それより濃度が低い場合は作業性が悪くなるばかりか、
ビスマス塩の場合は加水分解しやすい為、一般に使用さ
れる硝酸、硫酸、塩酸等の無機酸を用いて酸性度を上げ
る必要があり、この酸の割合はビスマスに対し加える水
の量に依存し、濃度の低い場合はより多くの酸が必要で
ある。ジルコニウムの塩は、場合によってはビスマスの
塩に混合して使用する方が合理的であるが、その場合の
混合溶液の濃度も各塩が析出しない範囲であれば問題無
い。バナジウムの場合は、アルカリ溶液の濃度が極端に
低くない限り特に問題は無いが、作業性を考えると０．
１モル／リットル〜０．５モル／リットルの範囲が適当
である。The solution concentration of the above bismuth salt is preferably about 0.5 mol / liter to 1.0 mol / liter.
If the concentration is lower than that, not only the workability deteriorates,
Since bismuth salts are easily hydrolyzed, it is necessary to increase the acidity by using commonly used inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, etc.The ratio of this acid depends on the amount of water added to bismuth. However, if the concentration is low, more acid is needed. It is rational to use the zirconium salt mixed with the bismuth salt in some cases, but in that case, there is no problem as long as the concentration of the mixed solution is within a range in which each salt does not precipitate. In the case of vanadium, there is no particular problem unless the concentration of the alkaline solution is extremely low, but in consideration of workability, it is 0.
A range of 1 mol / l to 0.5 mol / l is suitable.
【００１０】以上の様な塩の溶液は、先ず、所定量のジ
ルコニウム塩の溶液と苛性ソーダの溶液が、予め用意さ
れた沈澱水中に同時に滴下され、ジルコニウムの沈澱が
形成される。この際のｐＨはジルコニウムが沈澱するｐ
Ｈ領域であれば特に問題ないが、形成される塩基性塩の
悪影響を考慮すれば、好ましくはｐＨ＝７付近で行うの
が良い。In the salt solution as described above, first, a predetermined amount of a zirconium salt solution and a caustic soda solution are simultaneously dropped into precipitating water prepared in advance to form a zirconium precipitate. The pH at this time is such that zirconium precipitates.
There is no particular problem in the H region, but considering the adverse effect of the basic salt formed, it is preferably carried out at around pH = 7.
【００１１】次いでビスマス：バナジウム＝１：１にて
配合された、ビスマス塩の溶液とバナジウムのアルカリ
溶液が同時に沈澱水中に滴下される。このときのｐＨも
ジルコニウムの場合と同様にｐＨ＝７付近で行う方が効
果的である。この様にして３０分間から１時間かけて撹
拌しながら沈澱を生成させた後、色調及び諸特性を完全
なものとする為、９０℃〜１００℃にて３〜６時間加熱
熟成を行い、反応を完了させることが出来る。この際の
熟成温度は低すぎるとバナジン酸ビスマスの結晶化が遅
くなり、時間の無駄であると共に目的とする特性が十分
に発揮されない。滴下の順序は上述の様にジルコニウム
を先に落としてもよいが、ビスマス、バナジウムを先に
落として、その後ジルコニウムを滴下しても、又、ビス
マス、バナジウム及びジルコニウムを３点同時に滴下し
ても、上述の如き所定の時間内に沈澱を行えば特に問題
はない。しかし、高乱流下にて一気に沈澱を生成せしめ
る方法においては、ミクロ的な混合の均一性は保証する
ことが出来ず、従って熟成中での結晶成長は遅くなり、
これを達成する為に熱処理を必要とし、こうした方法に
おける顔料組成物のミクロ的な原子配列の乱れは、溶媒
中や樹脂中における諸耐性の劣化の大きな原因となる。Then, a solution of bismuth salt and an alkali solution of vanadium, which are mixed with bismuth: vanadium = 1: 1, are simultaneously dropped into the precipitation water. At this time, it is more effective to carry out the pH at around pH = 7 as in the case of zirconium. After forming a precipitate with stirring for 30 minutes to 1 hour, heat aging at 90 ° C to 100 ° C for 3 to 6 hours to complete the color tone and various characteristics, and the reaction Can be completed. If the aging temperature at this time is too low, the crystallization of bismuth vanadate will be slowed down, which is a waste of time and the desired properties cannot be sufficiently exhibited. The order of dropping may be such that zirconium is dropped first as described above, but bismuth and vanadium may be dropped first and then zirconium may be dropped, or bismuth, vanadium and zirconium may be dropped simultaneously at three points. If the precipitation is carried out within the predetermined time as described above, there is no particular problem. However, in the method of forming precipitates at a stretch under high turbulence, it is not possible to guarantee the uniformity of microscopic mixing, and therefore the crystal growth during aging becomes slow,
In order to achieve this, heat treatment is required, and the disorder of the microscopic atomic arrangement of the pigment composition in such a method is a major cause of deterioration of various resistances in the solvent or the resin.
【００１２】次に析出した共沈物は残塩を除去する為、
電導度にて３００マイクロムオー程度まで十分に水洗し
且つ濾過することによって、含水率が４０重量％〜８０
重量％程度となり、これを１００℃〜１２０℃程度の温
度にて乾燥することにより、本発明の目的とするバナジ
ン酸ビスマス系顔料組成物を得ることが出来る。この様
にして得られたジルコニウム共存バナジン酸ビスマス系
顔料組成物は、バナジン酸ビスマス単独品と比べて色調
及び諸耐性において優れたものである。このものは、こ
の状態においても通常の使用下においては何等問題は無
いが、引き続き熱処理を施すことにより、ジルコニウム
がバナジン酸ビスマスの母体に固溶し、諸耐性が一層確
かなものとなる。熱処理は３００℃〜６００℃にて、１
時間程度行うのが良好で、それより低温の場合は、特性
の向上が見られず、高い場合は焼結気味になり、着色濃
度や分散性の低下を招く。この様にして得られたジルコ
ニウム固溶バナジン酸ビスマス系顔料組成物は、未熱処
理品と比べて色調及び諸耐性において一層優れたもので
あった。The coprecipitate deposited next removes residual salts.
The water content is 40% by weight to 80% by sufficiently washing with water to a conductivity of about 300 μm and filtering.
The bismuth vanadate-based pigment composition aimed at by the present invention can be obtained by drying it at a temperature of about 100 ° C to 120 ° C. The zirconium-containing bismuth vanadate-based pigment composition thus obtained is superior in color tone and various resistances to the bismuth vanadate alone. In this state, there is no problem even under normal use even in this state, however, when heat treatment is continued, zirconium is solid-dissolved in the base body of bismuth vanadate, and the various resistances become more certain. Heat treatment at 300 ℃ ~ 600 ℃ 1
It is preferable to carry out the treatment for about a time, and if the temperature is lower than that, no improvement in properties is observed, and if it is higher than that, sintering tends to occur, leading to a decrease in coloring density and dispersibility. The zirconium-dissolved bismuth vanadate-based pigment composition thus obtained was more excellent in color tone and various resistances than the unheated product.
【００１３】[0013]
【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
りのない限り重量基準である。 実施例１ オキシ塩化ジルコニル６水塩１６．１１部と溶解水１０
０部とを混合し、ジルコニウム塩の溶液を調製する。次
にこの沈澱剤として苛性ソーダ４．５部及び水１００部
をはかりとり、アルカリ溶液を調製する。これらを予め
用意した沈澱水８００部中に３０分程度でｐＨ＝７にて
同時添加し、ジルコニウムの沈澱を析出させる。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on weight. Example 1 16.11 parts of zirconyl oxychloride hexahydrate and 10 parts of dissolved water
0 parts are mixed to prepare a solution of zirconium salt. Next, 4.5 parts of caustic soda and 100 parts of water are weighed as the precipitant to prepare an alkaline solution. These are simultaneously added to 800 parts of precipitation water prepared in advance in about 30 minutes at pH = 7 to precipitate a zirconium precipitate.
【００１４】このものは引続き、硝酸ビスマス５水塩９
７．０２部、濃硝酸４２部及び水２００部を混合した硝
酸ビスマス酸性水溶液と五酸化バナジウム１８．２部、
苛性ソーダ４２．５部及び水２８０部を混合したバナジ
ウムのアルカリ溶液との同時添加に供される。この沈澱
反応はｐＨ＝７で添加を行い約３０分間かけて行う。こ
の際に沈澱の色は透明に近い白色からやや赤味の黄色へ
と変化して行く。このものは続いて９０℃にて３時間撹
拌しながら熟成を行い、反応をより完全なものとする。
この時沈澱物は徐々に単斜晶系の結晶が成長して行き、
色調において冴えが増して行く。生成した沈澱物は十分
に水洗の後濾過し、１００℃〜１２０℃の範囲で乾燥す
る。この様にして得られた本発明の顔料は、後述の方法
による展色試験、耐候性及び耐熱試験に供し、後記表１
及び表２の結果を得た。This is followed by bismuth nitrate pentahydrate 9
Bismuth nitrate acidic aqueous solution prepared by mixing 7.02 parts, concentrated nitric acid 42 parts and water 200 parts and vanadium pentoxide 18.2 parts,
It is subjected to simultaneous addition with an alkaline solution of vanadium mixed with 42.5 parts of caustic soda and 280 parts of water. This precipitation reaction is carried out for about 30 minutes by adding at pH = 7. At this time, the color of the precipitate changes from a nearly transparent white to a slightly reddish yellow. This is then aged at 90 ° C. for 3 hours with stirring to make the reaction more complete.
At this time, the precipitate gradually grows into monoclinic crystals,
The color tone becomes sharper. The formed precipitate is thoroughly washed with water, filtered, and dried in the range of 100 ° C to 120 ° C. The thus-obtained pigment of the present invention was subjected to a color development test, a weather resistance and a heat resistance test according to the methods described below, and Table 1 below.
And the results of Table 2 were obtained.
【００１５】実施例２ オキシ塩化ジルコニル６水塩３２．２２部と溶解水１０
０部とを混合し、ジルコニウム塩の溶液を調製する。次
にこの沈澱剤として苛性ソーダ９．０部及び水１００部
をはかりとり、アルカリ溶液を調製する。これらを予め
用意した沈澱水８００部中に２０分間程度でｐＨ＝７に
て同時添加し、ジルコニウムの沈澱を析出させる。この
様にして得られた沈澱は、以下実施例１と同様の方法に
て顔料合成を行い、得られた顔料について後記表１及び
表２の結果を得た。Example 2 32.22 parts of zirconyl oxychloride hexahydrate and 10 parts of dissolved water
0 parts are mixed to prepare a solution of zirconium salt. Next, 9.0 parts of caustic soda and 100 parts of water are weighed as the precipitant to prepare an alkaline solution. These are simultaneously added to 800 parts of precipitation water prepared in advance at pH = 7 for about 20 minutes to precipitate a zirconium precipitate. The precipitate thus obtained was subjected to pigment synthesis in the same manner as in Example 1 below, and the results of Table 1 and Table 2 below were obtained for the obtained pigment.
【００１６】実施例３ オキシ塩化ジルコニル６水塩６４．４４部と溶解水２０
０部とを混合し、ジルコニウム塩の溶液を調製する。次
にこの沈澱剤として苛性ソーダ１８．０部及び水２００
部をはかりとり、アルカリ溶液を調製する。これらを予
め用意した沈澱水８００部中に２０分間程度でｐＨ＝７
にて同時添加し、ジルコニウムの沈澱を析出させる。こ
の様にして得られた沈澱は、以下実施例１と同様の方法
にて顔料合成を行い、得られた顔料について後記表１及
び表２の結果を得た。Example 3 Zirconyl oxychloride hexahydrate 64.44 parts and dissolved water 20
0 parts are mixed to prepare a solution of zirconium salt. Next, 18.0 parts of caustic soda and 200 parts of water were used as the precipitant.
Weigh out parts to prepare an alkaline solution. PH = 7 in 800 parts of precipitation water prepared in advance for about 20 minutes
At the same time to precipitate a precipitate of zirconium. The precipitate thus obtained was subjected to pigment synthesis in the same manner as in Example 1 below, and the results of Table 1 and Table 2 below were obtained for the obtained pigment.
【００１７】比較例１ 硝酸ビスマス５水塩９７．０２部、濃硝酸４２部及び水
２００部を混合した硝酸ビスマス酸性水溶液と、五酸化
バナジウム１８．２部、苛性ソーダ４２．５部及び水２
８０部を混合したバナジウムのアルカリ溶液を調製し、
予め用意した沈澱水８００部中に同時添加される。この
沈澱反応はＰＨ＝７で添加を行い約３０分間かけて行
う。この際に沈澱の色は透明に近い白色からやや赤色へ
と変化して行く。このものは続いて９０℃にて３時間撹
拌しながら熟成を行い、反応をより完全なものとする。
この時沈澱物は徐々に単斜晶系の結晶が成長して行き、
色調において冴えが増して行く。生成した沈澱物は十分
に水洗の後濾過し１００℃〜１２０℃の範囲で乾燥す
る。この様にして得られた比較例の顔料は、後述の方法
による展色試験及び耐候性試験に供し後記表１及び表２
の結果を得た。Comparative Example 1 Bismuth nitrate pentahydrate 97.02 parts, concentrated nitric acid 42 parts and water 200 parts mixed bismuth nitrate acidic aqueous solution, vanadium pentoxide 18.2 parts, caustic soda 42.5 parts and water 2
Prepare an alkaline solution of vanadium mixed with 80 parts,
Simultaneously added to 800 parts of previously prepared precipitation water. This precipitation reaction is carried out by adding PH = 7 for about 30 minutes. At this time, the color of the precipitate changes from nearly transparent white to red. This is then aged at 90 ° C. for 3 hours with stirring to make the reaction more complete.
At this time, the precipitate gradually grows into monoclinic crystals,
The color tone becomes sharper. The formed precipitate is thoroughly washed with water, filtered, and dried in the range of 100 ° C to 120 ° C. The pigments of Comparative Examples thus obtained were subjected to a color development test and a weather resistance test by the methods described below, and shown in Tables 1 and 2 below.
Got the result.
【００１８】展色試験 得られた顔料組成物を、ペイントシェイカーにてメラミ
ン・アルキッド樹脂中に４０ＰＨＲで分散して塗料を作
成し、黒帯付きアート紙に６ミルのアプリケーターにて
塗布し色調を観察した。又、測色機にて色の純度を測定
し、比較例との違いを調べた。着色力は市販の酸化チタ
ンを用いてＰｉｇ／ＴｉＯ2 ＝１／９にて展色し、濃色
の場合と同様に色調、純度及び着色濃度を観察した。耐候性試験 得られた顔料組成物を、ペイントシェイカーにてメラミ
ン・アルキッド樹脂中に４０ＰＨＲで分散して塗料を作
成し、アルミ塗板に塗布し、スーパーＵＶ耐候性促進機
にかけ８０時間の暴露を行い、測色により促進前と促進
後の△Ｅ* 値を測定し、その違いを観測した。 Color development test The pigment composition obtained was dispersed in a melamine alkyd resin at 40 PHR with a paint shaker to prepare a paint, which was applied to a black strip art paper with an applicator of 6 mils to obtain a color tone. I observed. Further, the color purity was measured with a colorimeter to examine the difference from the comparative example. The tinting strength was developed using Pigment / TiO 2 = 1/9 using commercially available titanium oxide, and the color tone, purity and coloring density were observed in the same manner as in the dark color. Weather resistance test The pigment composition obtained was dispersed in melamine alkyd resin at 40 PHR with a paint shaker to prepare a paint, which was applied to an aluminum coated plate and exposed to a super UV weather resistance accelerator for 80 hours of exposure. Then, the ΔE * value before and after acceleration was measured by color measurement, and the difference was observed.
【００１９】[0019]
【表１】 展色試験結果 [Table 1] Color development test results
【００２０】[0020]
【表２】耐候性試験結果 [Table 2] Results of weather resistance test
【００２１】実施例４ 実施例１で得られた乾燥顔料を、空気中で通常の電気炉
にて５００℃にて１時間熱処理を行う。この様にして得
られた顔料は、更に一段と冴えた色調となり、後述の方
法による展色試験、耐候性及び耐熱試験に供し、後記表
３〜５の様な結果を得た。 比較例２ 実施例１において得られた乾燥顔料を後述の方法による
展色試験、耐候性及び耐熱試験に供し、後記表３〜５の
様な結果を得た。展色試験 ：得られた顔料組物をペイントシェイカーにて
メラミン・アルキッド樹脂中に４０ＰＨＲで分散し、塗
料を作成し黒帯付きアート紙に６ミルのアプリケーター
にて塗布し色調を観察した。又、測色機にて色の純度を
測定し、比較例との違いを調べた。Example 4 The dry pigment obtained in Example 1 is heat-treated in air in an ordinary electric furnace at 500 ° C. for 1 hour. The thus-obtained pigment had a more vivid color tone, and was subjected to a color development test, a weather resistance and a heat resistance test by the methods described below, and the results shown in Tables 3 to 5 below were obtained. Comparative Example 2 The dry pigment obtained in Example 1 was subjected to a color development test, a weather resistance and a heat resistance test by the methods described below, and the results shown in Tables 3 to 5 below were obtained. Color development test : The pigment composition thus obtained was dispersed in a melamine alkyd resin at 40 PHR using a paint shaker to prepare a paint, which was applied to art paper with a black belt by a 6 mil applicator, and the color tone was observed. Further, the color purity was measured with a colorimeter to examine the difference from the comparative example.
【００２２】耐候性試験：得られた顔料組成物をペイン
トシェイカーにてメラミン・アルキッド樹脂中に４０Ｐ
ＨＲで分散し、塗料を作成しアルミ塗板に塗布し、スー
パーＵＶ耐候性促進機にかけ８０時間暴露を行い、測色
により促進前と促進後の△Ｅ ＊値を測定し違いを観測し
た。耐熱試験 ：得られた顔料組成物を、顔料組成物：ステア
リン酸亜鉛＝４：１にて充分混合したものを高密度ポリ
エチレン樹脂に０．５ＰＨＲで添加し、射出成型機にて
２１０℃、２４０℃、２８０℃にて１０分間保持した
後、射出成型し、成形物の変色具合を測色し△Ｅ＊値に
て評価した。[0022]Weather resistance test: Pain the obtained pigment composition
40P in melamine alkyd resin with Toshaker
Disperse with HR, create paint, apply to aluminum coated plate, and
Per-UV weather resistance accelerator, exposed for 80 hours, and measured color
Due to △ E before and after promotion *Measure the values and observe the differences
It wasHeat resistance test : Pigment composition: steer
A mixture of zinc phosphate = 4: 1 and high density poly
Add 0.5 PHR to ethylene resin and use injection molding machine
Hold at 210 ° C, 240 ° C, 280 ° C for 10 minutes
After that, injection molding is performed, and the color change of the molded product is measured.*To value
Evaluated.
【００２３】[0023]
【表３】 [Table 3]
【表４】 [Table 4]
【００２４】[0024]
【表５】 [Table 5]
【００２５】[0025]
【効果】以上の如き本発明によれば、高い純度（インテ
ンシチー）、着色力、隠蔽力を有し、従来の黄色系顔料
で使用されている分野、例えば、一般樹脂及びエンジニ
ヤリングプラスチック樹脂の着色、塗料、インキ、セラ
ミックス、建材等の分野において有用な黄色系バナジン
酸ビスマス顔料組成物を提供することが出来る。[Effect] According to the present invention as described above, it has high purity (intenseness), coloring power, and hiding power, and is used in the fields used in conventional yellow pigments, for example, general resins and engineering plastic resins. A yellow bismuth vanadate pigment composition useful in the fields of coloring, paints, inks, ceramics, building materials, etc. can be provided.
フロントページの続き (72)発明者 西尾 章 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 (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Front page continuation (72) Inventor Akira Nishio 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Within Dainichi Seika Kogyo Co., Ltd. Dainichi Seika Kogyo Co., Ltd.
Claims (6)
よりなることを特徴とする黄色系顔料用バナジン酸ビス
マス組成物。1. A bismuth vanadate composition for a yellow pigment, which comprises zirconium, vanadium and bismuth.
のモル比が０．１〜１．５：１：１の範囲である請求項
１に記載の顔料用黄色系バナジン酸ビスマス組成物。2. The yellow bismuth vanadate composition for pigments according to claim 1, wherein the molar ratio of zirconium, vanadium and bismuth is in the range of 0.1 to 1.5: 1: 1.
の混合に際し、各塩の水溶液を３点同時又は２点同時に
添加し、全ての塩の沈澱を生ぜしめる請求項１に記載の
顔料用黄色系バナジン酸ビスマス組成物の製造方法。3. The yellow bismuth vanadate vanadate for pigments according to claim 1, wherein when zirconium, vanadium and bismuth are mixed, an aqueous solution of each salt is added simultaneously at 3 points or 2 points simultaneously to cause precipitation of all salts. A method for producing a composition.
拌しながら熟成を行う請求項３に記載の顔料用黄色系バ
ナジン酸ビスマス組成物の製造方法。4. The method for producing a yellow bismuth vanadate composition for pigments according to claim 3, wherein after the precipitation is formed, aging is carried out while heating and stirring at 90 to 100 ° C.
ある請求項４に記載の顔料用黄色系バナジン酸ビスマス
組成物の製造方法。5. The process for producing a yellow bismuth vanadate vanadate composition for pigments according to claim 4, wherein the aging time after the precipitation is 3 to 6 hours.
する請求項３に記載の顔料用黄色系バナジン酸ビスマス
組成物の製造方法。6. The method for producing a yellow bismuth vanadate vanadate composition for pigments according to claim 3, wherein the precipitate is heat-treated at a temperature of 300 to 600 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4100248A JP2743298B2 (en) | 1991-09-06 | 1992-03-27 | Method for producing bismuth vanadate composition for pigments |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25417491 | 1991-09-06 | ||
| JP3-254174 | 1991-09-06 | ||
| JP4100248A JP2743298B2 (en) | 1991-09-06 | 1992-03-27 | Method for producing bismuth vanadate composition for pigments |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05124820A true JPH05124820A (en) | 1993-05-21 |
| JP2743298B2 JP2743298B2 (en) | 1998-04-22 |
Family
ID=26441307
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4100248A Expired - Fee Related JP2743298B2 (en) | 1991-09-06 | 1992-03-27 | Method for producing bismuth vanadate composition for pigments |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2743298B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2655052A1 (en) * | 1989-11-30 | 1991-05-31 | Ciba Geigy Ag | PROCESS FOR STABILIZING BISMUTH VANADATE PIGMENTS AGAINST ATTACK BY HYDROCHLORIC ACID, AND MACROMOLECULAR ORGANIC MATERIALS THAT HAVE BEEN COLORED BY PIGMENTS SO STABILIZED |
| JPH04321520A (en) * | 1990-12-20 | 1992-11-11 | Bayer Ag | Bismuth vanadate pigment and manufacturing and use of same |
-
1992
- 1992-03-27 JP JP4100248A patent/JP2743298B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2655052A1 (en) * | 1989-11-30 | 1991-05-31 | Ciba Geigy Ag | PROCESS FOR STABILIZING BISMUTH VANADATE PIGMENTS AGAINST ATTACK BY HYDROCHLORIC ACID, AND MACROMOLECULAR ORGANIC MATERIALS THAT HAVE BEEN COLORED BY PIGMENTS SO STABILIZED |
| GB2238549A (en) * | 1989-11-30 | 1991-06-05 | Ciba Geigy Ag | Process for stabilising bismuth vanadate pigments against attack by hydrochloric acid |
| DE4037878A1 (en) * | 1989-11-30 | 1991-06-06 | Ciba Geigy Ag | METHOD FOR STABILIZING WISMUTHVANADAT PIGMENTS AGAINST THE ATTACK OF SALT ACID |
| JPH03227373A (en) * | 1989-11-30 | 1991-10-08 | Ciba Geigy Ag | Method for stabilizing bismuth vanadate pigment against hydrochloric acid attack |
| JPH04321520A (en) * | 1990-12-20 | 1992-11-11 | Bayer Ag | Bismuth vanadate pigment and manufacturing and use of same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2743298B2 (en) | 1998-04-22 |
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