JP2720578B2 - Method for producing fine black powder - Google Patents
Method for producing fine black powderInfo
- Publication number
- JP2720578B2 JP2720578B2 JP14770690A JP14770690A JP2720578B2 JP 2720578 B2 JP2720578 B2 JP 2720578B2 JP 14770690 A JP14770690 A JP 14770690A JP 14770690 A JP14770690 A JP 14770690A JP 2720578 B2 JP2720578 B2 JP 2720578B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- titanium hydroxide
- hydroxide sol
- black powder
- water
- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、黒色度、着色力に優れたプラスチック用黒
色材の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a black material for plastics having excellent blackness and coloring power.
（従来の技術と問題点） 黒色顔料はカーボン粉末（Ｃ）、マグネタイト（Fe3O
4）、焼成顔料（Cu−Cr−Mn−（−Fe）複合酸化物）が
一般に知られている。カーボン粉末は表面に活性官能基
が存在するためにプラスチック中での分散の困難とプラ
スチックの劣化の問題がある。マグネタイトは熱安定正
と磁性に由来する分散性の劣悪の問題があり、焼成顔料
は粒子の粗大化による着色力の低下があり、また生理的
安全性にも問題がある。(Prior art and problems) Black pigment is carbon powder (C), magnetite (Fe 3 O
4 ), calcined pigments (Cu-Cr-Mn-(-Fe) composite oxide) are generally known. Carbon powder has a problem of dispersion in plastic and deterioration of plastic due to the presence of active functional groups on the surface. Magnetite has a problem of poor thermal stability and poor dispersibility due to magnetism, and calcined pigment has a problem of a decrease in coloring power due to coarsening of particles and a problem of physiological safety.
以上の欠点を解決した黒色顔料としてTinO2n-1（ｎ＝
２〜６）で表されるチタンの低原子価の酸化物及びTiOx
Ny（0.3＜Ｘ＋Ｙ＜1.7）の酸窒化チタンの粉末がある。
黒色の低次酸化チタン系粉末は二酸化チタンをチタン金
属粉またはアンモニアガスなどと、加熱反応させること
によって得られ、微細化するに伴って、顔料特性（黒色
度、着色力等）は向上する。このため出発物質となる二
酸化チタン粉末を微細化する必要があり、通常、水酸化
チタン粉末、好ましくは水酸化チタンゾルが利用される
（特開昭60−200827、62−56324）。As a black pigment that has solved the above disadvantages, Ti n O 2n-1 (n =
2-6) low-valent oxide of titanium and TiO x
There is a powder of titanium oxynitride of N y (0.3 <X + Y <1.7).
The black low-order titanium oxide-based powder is obtained by heating titanium dioxide with titanium metal powder or ammonia gas or the like, and the pigment properties (blackness, coloring power, etc.) are improved as the fineness is reduced. For this reason, it is necessary to make the titanium dioxide powder as a starting material finer, and usually a titanium hydroxide powder, preferably a titanium hydroxide sol is used (JP-A-60-200827, 62-56324).
なお、二酸化チタンとアンモニアの反応には、バナジ
ウムの共存が有利なことが知られており（特開昭61−20
2620、特願平１−192726）、今日では、この方法によっ
て造られることが多い。It is known that the coexistence of vanadium is advantageous for the reaction between titanium dioxide and ammonia (Japanese Patent Laid-Open No. 61-20 / 1986).
2620, Japanese Patent Application No. 1-192726). Today, it is often made by this method.
上記の方法においては、微細な水酸化チタンゾルはメ
タチタン酸（TiO（OH）２）、オルトチタン酸（Ti（O
H）４）、チタン酸アルカリを塩酸、硝酸、酢酸等の鉱
酸、有機酸で解膠することによって得られるが、極めて
粒子が細かい（200Å以下）ために洗浄、固液分離が困
難であった。In the above method, the fine titanium hydroxide sol is composed of metatitanic acid (TiO (OH) 2 ) and orthotitanic acid (Ti (O (O)).
H) 4 ) It is obtained by peptizing alkali titanate with mineral acids such as hydrochloric acid, nitric acid and acetic acid, and organic acids. However, since the particles are extremely fine (200 mm or less), washing and solid-liquid separation are difficult. Was.
（問題解決に係わる知見） 本発明者らは、この問題を解決すべく研究を進め、こ
の水酸化チタンゾルに水可溶性のポリアクリルアミド高
分子化合物を添加すると凝集体を形成し、洗浄、固液分
離が容易になり、しかも、その後の処理が容易になるこ
とを見出した。(Knowledge related to problem solving) The present inventors proceeded with research to solve this problem, and when a water-soluble polyacrylamide polymer compound was added to this titanium hydroxide sol, an aggregate was formed, and washing and solid-liquid separation were performed. Was found to be easy, and further, the subsequent processing was easy.
（発明の構成） 本発明は水酸化チタンゾル液に水可溶性のポリアクリ
ルアミド高分子化合物を添加し、固液分離、乾燥した
後、アンモニアガスを含む還元性雰囲気中、600〜1000
℃で加熱処理することからなる微細な黒色粉末の製造方
法を提供する。(Constitution of the Invention) In the present invention, a water-soluble polyacrylamide polymer compound is added to a titanium hydroxide sol solution, solid-liquid separated, dried, and then reduced to 600 to 1000 in a reducing atmosphere containing ammonia gas.
Provided is a method for producing a fine black powder, which comprises heat-treating at a temperature of ° C.
前述のように、二酸化チタンとアンモニアの反応にお
いてバナジウムを共存させることは当技術分野の確立さ
れた技法であり、本発明の技術範囲に含まれる。バナジ
ウムはバナジウム塩の形でバナジウムとしてTiO2換算量
に対して重量で0.1〜7.0％の割合で水酸化チタンゾルに
添加される。As mentioned above, the coexistence of vanadium in the reaction of titanium dioxide and ammonia is an established technique in the art and is within the scope of the present invention. Vanadium is added to the hydroxide sol at a rate of 0.1 to 7.0% by weight with respect to TiO 2 equivalent amount as vanadium in the form of vanadium salt.
本発明の製法において用いるポリアクリルアミド高分
子は分子量1000万以上のノニオン系の高分子で −［CH2−CHCONH2］− の繰り返し単位を有する。このものは凝集剤として作用
し、水酸化チタンのフロックを造り、沈降速度を速める
働きをするので作業時間を短縮できる。The polyacrylamide polymer used in the production method of the present invention is a nonionic polymer having a molecular weight of 10,000,000 or more and has a repeating unit of-[CH 2 -CHCONH 2 ]-. This acts as a flocculant, produces a floc of titanium hydroxide and acts to increase the sedimentation speed, so that the working time can be shortened.
本発明の製法において、ポリアクリルアミド高分子化
合物は、その添加量が水酸化チタンゾルのTiO2換算量に
対し重量比で0.001〜0.05の範囲にある場合にその効果
が著しく現れる。In the production method of the present invention, the effect of the polyacrylamide polymer compound is remarkably exhibited when the amount of the polyacrylamide polymer is in the range of 0.001 to 0.05 in terms of the weight ratio with respect to the TiO 2 equivalent of the titanium hydroxide sol.
本発明の製法において、二酸化チタンのアンモニアに
よる還元を進行させるためには600〜1000℃に加熱する
ことを要する。これは1000℃を越える温度では焼結によ
り黒色粉末が粗大になり600℃より低い温度では十分に
黒色化が進まないからである。In the production method of the present invention, it is necessary to heat the titanium dioxide to 600 to 1000 ° C. in order to promote the reduction of titanium dioxide with ammonia. This is because at a temperature exceeding 1000 ° C., the black powder becomes coarse due to sintering, and at a temperature lower than 600 ° C., the blackening does not proceed sufficiently.
本発明の製法において、水酸化チタンゾル液に水可溶
性のポリアクリルアミド高分子化合物を添加し、固液分
離して得られる固体を350〜450℃の範囲の温度で乾燥す
ると、粉砕工程なしに自然に5mm角程度の小塊となり、
これをアンモニアガスによる還元性雰囲気で加熱処理す
ると、黒色化が促進され、通常の粉砕工程を経て微細な
（比表面積25m2/g以上の）黒色粉末が得られる利点を有
する。その理由は明らかではないが、生成複合体がアン
モニアガスの浸透しやすい構造を有しているためと推察
される。In the production method of the present invention, a water-soluble polyacrylamide polymer compound is added to the titanium hydroxide sol solution, and the solid obtained by solid-liquid separation is dried at a temperature in the range of 350 to 450 ° C .; It becomes a small lump of about 5 mm square,
When this is heat-treated in a reducing atmosphere with ammonia gas, blackening is promoted, and there is an advantage that a fine black powder (having a specific surface area of 25 m 2 / g or more) can be obtained through a usual pulverizing step. Although the reason is not clear, it is presumed that the formed complex has a structure that allows the ammonia gas to easily penetrate.
（発明の具体的記載） 実施例１ メタチタン酸スラリー60kg（TiO2換算20kgに相当）を
リパルプしたものに、25％アンモニア水３を撹拌しな
がら注入し、撹拌した後に静置して自然沈降させた。上
澄液を除去したものを36％塩酸4.0kgで解膠させた。こ
れを25％アンモニア水３でpH値を7.0前後に調整し十
分な水で洗浄した。このようにして得られた水酸化チタ
ンゾルにノニオン系ポリアクリルアミド高分子（分子量
1300万）60g（酸化チタン分に対して重量比0.003）を投
入して静止し自然沈殿させた後上澄液を除去し、フィル
タープレスで脱水して400℃で12時間乾燥することによ
り5mm角程度の酸化チタン小塊が得られた。この方法で
得られた酸化チタンは造粒工程を経ずにそのまま還元炉
に入れることができ、アンモニアガスを含む還元性雰囲
気中600〜1000℃で加熱処理した後にボールミルによっ
て粒子の凝集を解きほぐすことにより微細な黒色粉末が
得られた。(Specific description of the invention) Example 1 A 25% aqueous ammonia 3 was poured into a repulp of 60 kg of metatitanic acid slurry (corresponding to 20 kg in terms of TiO 2 ) while stirring, and the mixture was allowed to stand and then allowed to settle naturally. Was. The supernatant was removed and peptized with 4.0 kg of 36% hydrochloric acid. This was adjusted to a pH value of about 7.0 with 25% ammonia water 3 and washed with sufficient water. A nonionic polyacrylamide polymer (molecular weight) is added to the titanium hydroxide sol thus obtained.
13 million) 60 g (0.003 weight ratio based on the titanium oxide content) was added, the mixture was allowed to stand still and allowed to settle naturally, then the supernatant was removed, dewatered with a filter press, and dried at 400 ° C for 12 hours to form a 5 mm square. A small amount of titanium oxide lumps was obtained. The titanium oxide obtained by this method can be put into a reduction furnace as it is without going through a granulation step, and after heat treatment at 600 to 1000 ° C in a reducing atmosphere containing ammonia gas, disintegrate the particles by a ball mill. As a result, a fine black powder was obtained.
第１表に高分子凝集剤を添加した場合としない場合の
収率とアンモニアの原単位を示す。Table 1 shows the yields with and without the addition of the polymer flocculant and the basic unit of ammonia.
実施例２ 実施例１と同様にして得られた水酸化チタンにノニオ
ン系ポリアクリルアミド高分子化合物（分子量1000万）
600g（酸化チタン分に対して重量比で0.03）を加え、以
下実施例１と同様に処理することにより微細な黒色粉末
を得た。 Example 2 Nonionic polyacrylamide polymer (molecular weight: 10,000,000) was added to titanium hydroxide obtained in the same manner as in Example 1.
600 g (0.03 by weight ratio with respect to titanium oxide) was added, and the same treatment as in Example 1 was performed to obtain a fine black powder.
第２表に高分子凝集剤を添加した場合としない場合の
収率とアンモニアの原単位を示す。Table 2 shows the yield and the basic unit of ammonia with and without the addition of the polymer flocculant.
実施例３ 実施例１と同様にして得られた水酸化チタンゾルに、
バナジウム400g（メタバナジン酸アンモニウムとして91
8.5g）を添加し、リパルプして２％バナジウム添加水酸
化チタンゾルを得た。 Example 3 To a titanium hydroxide sol obtained in the same manner as in Example 1,
Vanadium 400 g (91% as ammonium metavanadate
8.5 g) and repulped to obtain a 2% vanadium-added titanium hydroxide sol.
これにノイオン系ポリアクリルアミド高分子（分子量
1400万）120g（酸化チタン分に対して重量比で0.006）
を加え、以下実施例１と同様に処理した後、ハンマーミ
ルによって粒子の凝集を解きほぐすことにより微細な黒
色粉末を得た。In addition to this, a nonionic polyacrylamide polymer (molecular weight
14 million) 120 g (0.006 by weight relative to titanium oxide)
Was added thereto, and the mixture was treated in the same manner as in Example 1. Thereafter, aggregation of the particles was broken by a hammer mill to obtain a fine black powder.
第３表に高分子凝集剤を添加した場合としない場合の
収率とアンモニアの原単位を示す。Table 3 shows the yields with and without the addition of the polymer flocculant and the basic unit of ammonia.
（発明の効果） このようにポリアクリルアミド高分子を加えることに
より水酸化チタンゾルの沈降速度が速くなり、ろ過作業
性は著しく向上した。また350〜450℃の温度で乾燥を行
なったこの水酸化チタンゾルの乾燥物は5mm角程度に割
れており、粉砕工程を経ずに造粒することができ、その
まま還元炉に投入することも可能である（この酸化チタ
ンの大きさは小さすぎるとキャリーオーバーされ、大き
すぎると還元が十分におこなれない）。また原単位にお
いて従来の３分の２、作業時間において従来の３分の２
の時間で同じ特性を持つ黒色粉末を得ることができる。 (Effect of the Invention) By adding the polyacrylamide polymer as described above, the sedimentation speed of the titanium hydroxide sol was increased, and the filtration workability was significantly improved. The dried product of this titanium hydroxide sol dried at a temperature of 350 to 450 ° C is broken into about 5 mm square, and can be granulated without going through the pulverization process, and can be put into the reduction furnace as it is (If the size of the titanium oxide is too small, it is carried over, and if it is too large, the reduction is not sufficiently performed). In addition, two-thirds of the conventional unit and two-thirds of the conventional work time
A black powder having the same properties can be obtained in a time period as shown in FIG.
Claims (5)
アミド高分子化合物を混合し、固液分離、乾燥した後、
アモニアガスを含む還元性雰囲気中、600〜1000℃で加
熱することからなる微細な黒色粉末の製造方法。1. A water-soluble polyacrylamide polymer compound is mixed with titanium hydroxide sol, solid-liquid separated and dried.
A method for producing a fine black powder, comprising heating at a temperature of 600 to 1000 ° C. in a reducing atmosphere containing ammonia gas.
以上のノニオン系の高分子で−［CH2−CHCONH2］−の繰
り返し単位を有するものである請求項１に記載の方法。2. The method according to claim 1, wherein the polyacrylamide compound is a nonionic polymer having a molecular weight of 10,000,000 or more and having a repeating unit of-[CH 2 -CHCONH 2 ]-.
が水酸化チタンゾル中のTiO2換算量に対し重量比0.001
〜0.05である請求項１に記載の方法。3. A weight ratio of the polyacrylamide polymer compound to the titanium oxide sol in terms of TiO 2 in a weight ratio of 0.001 to 0.001.
2. The method of claim 1, wherein the value is -0.05.
をバナジウムとしてTiO2換算量に対して重量で0.1〜7.0
％の割合で添加する請求項１に記載の方法。4. A titanium hydroxide sol containing 0.1 to 7.0 parts by weight of a water-soluble vanadium salt in terms of TiO 2 in terms of vanadium.
The method according to claim 1, wherein the compound is added in a ratio of%.
アミド高分子化合物を混合し、固液分離して得られる固
体の乾燥を350〜450℃の範囲の温度で行なう請求項１に
記載の方法。5. The method according to claim 1, wherein a water-soluble polyacrylamide polymer compound is mixed with the titanium hydroxide sol, and the solid obtained by solid-liquid separation is dried at a temperature in the range of 350 to 450 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14770690A JP2720578B2 (en) | 1990-06-06 | 1990-06-06 | Method for producing fine black powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14770690A JP2720578B2 (en) | 1990-06-06 | 1990-06-06 | Method for producing fine black powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0442811A JPH0442811A (en) | 1992-02-13 |
| JP2720578B2 true JP2720578B2 (en) | 1998-03-04 |
Family
ID=15436392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14770690A Expired - Lifetime JP2720578B2 (en) | 1990-06-06 | 1990-06-06 | Method for producing fine black powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2720578B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100475687B1 (en) * | 2002-10-26 | 2005-03-10 | 한국과학기술원 | Preparation method of titania particles |
-
1990
- 1990-06-06 JP JP14770690A patent/JP2720578B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0442811A (en) | 1992-02-13 |
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