JPH07292276A - Titanium dioxide pigment - Google Patents
Titanium dioxide pigmentInfo
- Publication number
- JPH07292276A JPH07292276A JP12669694A JP12669694A JPH07292276A JP H07292276 A JPH07292276 A JP H07292276A JP 12669694 A JP12669694 A JP 12669694A JP 12669694 A JP12669694 A JP 12669694A JP H07292276 A JPH07292276 A JP H07292276A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- substrate
- terms
- antimony
- titanium dioxide
- 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.)
- Pending
Links
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐光性が改善された二酸
化チタン顔料の製造方法に関し、特に高度の耐光性が要
求されるプラスチックスや合成樹脂化粧板に好適な二酸
化チタン顔料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a titanium dioxide pigment having improved light resistance, and more particularly to a titanium dioxide pigment suitable for plastics and synthetic resin decorative boards which require a high degree of light resistance.
【０００２】[0002]
【従来からの技術】二酸化チタン顔料は、高い屈折率を
有するところから白色顔料として使われているが他方光
化学的活性が強く、このため使用媒体系の耐候性あるい
は耐光性を著しく損なうことが多い。従って、古くから
この点を改善するために多くの研究がなされて来てい
る。二酸化チタンに弗素イオンを被覆しその後、アルミ
ニウムの水和酸化物を被覆する方法（特願 昭５９−６
５２９５）、二酸化チタンにアンチモンの水和酸化物を
被覆し、その後アルミナ−シリカの共沈殿物を被覆し、
４００〜８００℃で再熔焼する方法（特願 昭５８−５
２６９３）、二酸化チタンにアンチモン及びアルミニウ
ムの一つ、もしくは複数の水和酸化物を被覆する方法
（特願 昭５４−１５３７２８）等が知られている。し
かし二酸化チタン顔料の使用が拡大されるにともなっ
て、幅広い用途で耐光性を満足することが難しくなっ
た。2. Description of the Related Art Titanium dioxide pigments are used as white pigments because they have a high refractive index, but on the other hand, they have strong photochemical activity, and therefore the weather resistance or light resistance of the medium used is often significantly impaired. . Therefore, much research has been conducted since ancient times to improve this point. A method of coating titanium dioxide with fluorine ions and then coating aluminum hydrated oxide (Japanese Patent Application No. 59-6).
5295), coating titanium dioxide with a hydrated oxide of antimony, followed by a co-precipitate of alumina-silica,
Method of re-melting at 400-800 ° C (Japanese Patent Application No. 58-5
2693), a method of coating titanium dioxide with one or more hydrated oxides of antimony and aluminum (Japanese Patent Application No. 54-153728). However, as the use of titanium dioxide pigments has expanded, it has become difficult to satisfy the light resistance in a wide range of applications.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、前記
光化学的問題点を解決せんとするものであって広い分野
の媒体中での耐光性に優れた性能をもつ二酸化チタン顔
料を得ることにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned photochemical problems, and to obtain a titanium dioxide pigment having excellent light resistance in a wide range of media. It is in.
【０００４】[0004]
【課題を解決するための手段】本発明はジルコニウムの
酸化物をＺｒＯ２として０．１〜５重量％含有するルチ
ル型酸化チタン（以下基体という）の表面にアンチモン
の水和酸化物がＳｂ２Ｏ５として０．１〜３重量％、ア
ルミニウムの水和酸化物がＡｌ２Ｏ３として１〜５重量
％、弗素イオンがＦとして０．１〜２重量％存在するこ
とを特徴とする二酸化チタン顔料（基体 ９０〜９８．
８重量％）である。SUMMARY OF THE INVENTION The present invention is an oxide hydrated oxide of antimony on the surface of rutile type titanium oxide containing 0.1 to 5 wt% as Z r O 2 (hereinafter referred to as substrate) of zirconium 0.1 to 3% by weight of Sb 2 O 5, 1 to 5 % by weight of aluminum hydrate oxide as Al 2 O 3 and 0.1 to 2 % by weight of fluorine ion as F. Titanium dioxide pigment (Substrate 90-98.
8% by weight).
【０００５】ここで基体とはチタニル硫酸溶液あるいは
四塩化チタンを加水分解して得られる水酸化チタン（メ
タチタン酸等）に所定量のジルコニウム化合物を混合
し、９００℃〜１，０００℃で焼成したものである。使
用するジルコニウム化合物としては硫酸ジルコニウム、
炭酸ジルコニウム等が挙げられる。Here, the substrate is a titanyl sulfuric acid solution or titanium hydroxide (meta-titanic acid, etc.) obtained by hydrolyzing titanium tetrachloride, mixed with a predetermined amount of zirconium compound, and baked at 900 ° C to 1,000 ° C. It is a thing. The zirconium compound used is zirconium sulfate,
Examples thereof include zirconium carbonate.
【０００６】ジルコニウム酸化物の存在量はＺｒＯ２と
して０．１〜５重量％である。０．１％以下では耐光性
が十分でなく、５％以上ではそれ以上の改善効果が認め
られないだけでなく酸化チタンの顔料としての性質であ
る隠蔽力、分散性等を低下させる。[0006] The presence of zirconium oxide is 0.1 to 5 wt% as Z r O 2. If it is 0.1% or less, the light resistance is not sufficient, and if it is 5% or more, no further improvement effect is observed, and the hiding power, dispersibility, etc., which are properties of titanium oxide as a pigment, are reduced.
【０００７】該基体にアンチモンの水和酸化物、アルミ
ニウムの水和酸化物、弗素イオンを存在させるには基体
２００〜５００ｇ／ｌの水性スラリーに所定量のアンチ
モン水和酸化物、アルミニウム水和酸化物、弗素イオン
が基体上に存在するに必要な原料化合物水溶液を一度に
あるいは順番に添加し、特に限定はされないが常温〜１
００℃に保ち、中和反応を行って沈殿生成後、普通１０
〜３０分間熟成する。熟成後、水洗・濾過し乾燥後粉砕
処理を施して二酸化チタン顔料製品とする。In order to allow the hydrated oxide of antimony, the hydrated oxide of aluminum and the fluorine ion to exist in the substrate, a predetermined amount of the hydrated oxide of antimony and aluminum hydrated oxide is added to an aqueous slurry of 200 to 500 g / l of the substrate. Substances and fluorine ions are added at once or sequentially to the raw material compound solution necessary for existing on the substrate, but not limited to room temperature to 1
After keeping the temperature at 00 ° C and conducting a neutralization reaction to form a precipitate, usually 10
Aging for ~ 30 minutes. After aging, it is washed with water, filtered, dried and then pulverized to obtain a titanium dioxide pigment product.
【０００８】弗素イオン（Ｆ−）は実際は一部が基体上
に吸着したり、アルミ化合物と何らかの結合をしたりし
た状態で存在すると堆測される。[0008] fluorine ion (F -) is actually or adsorbed partly on the substrate, when present in a state or have some binding the aluminum compound Uzutakahaka.
【０００９】使用する原料としては、アンチモンの可溶
性化合物は五塩化アンチモン等が、弗素の可溶性化合物
は弗化アンモニウム、弗化カリウム、弗化ナトリウム、
弗化リチウム等が、アルミニウムの可溶性化合物は硫酸
アルミニウム、アルミン酸ナトリウム等が挙げれられ
る。中和処理に用いられる酸性溶液には、例えば塩酸、
硝酸、硫酸が、また塩基性溶液としては、水酸化ナトリ
ウム、水酸化アンモニウム、水酸化カリウム等が挙げら
れる。中和処理には、酸性の可溶性化合物には塩基性溶
液を、塩基性の可溶性化合物には酸性溶液を用いること
ができる。アンチモン、弗素、アルミニウムの添加量の
下限以下では耐光性が十分ではなく、又上限以上ではそ
れ以上の改善効果が認められないだけでなく、酸化チタ
ンの顔料としての性質である隠蔽力、分散性等を低下さ
せる。As the raw material to be used, antimony soluble compounds include antimony pentachloride and the like, and fluorine soluble compounds include ammonium fluoride, potassium fluoride, sodium fluoride,
Examples of the soluble compound of aluminum include lithium fluoride, and aluminum sulfate and sodium aluminate. The acidic solution used for the neutralization treatment is, for example, hydrochloric acid,
Nitric acid and sulfuric acid may be used, and examples of the basic solution include sodium hydroxide, ammonium hydroxide, potassium hydroxide and the like. For the neutralization treatment, a basic solution can be used for the acidic soluble compound and an acidic solution can be used for the basic soluble compound. If the addition amount of antimony, fluorine, or aluminum is less than the lower limit, the light resistance is not sufficient, and if it is more than the upper limit, further improvement effect is not observed, and the hiding power and dispersibility that are properties of titanium oxide as a pigment are not observed. Etc.
【００１０】[0010]
【実施例】以下に実施例により具体的に説明する。[Examples] Specific examples will be described below.
【実施例１】チタニル硫酸溶液を加水分解し、水洗・濾
過することによって得られたメタチタン酸に重量基準で
ＺｒＯ２として１．０％の炭酸ジルコニウム水溶液を添
加し、充分に混練した後、９００℃で熔焼して得られた
二酸化チタン基体の水性スラリー（ＴｉＯ２濃度４００
ｇ／ｌ）を６０℃に加熱後、五塩化アンチモン溶液を該
基体の重量基準でＳｂ２Ｏ５として１．０％添加しアン
チモンの水和酸化物を沈殿させ２０分間熟成させた。次
いで弗化アンモニウム水溶液を該基体の重量基準でＦと
して１．０％添加して、２０分間熟成させた。引続きア
ルミン酸ナトリウム溶液を該基体の重量基準でＡｌ２Ｏ
３として２．０％添加した後、稀硫酸で中和しアルミニ
ウムの水和酸化物を沈殿させ、その後２０分間熟成させ
た。次いで水洗・濾過し、１３０℃で５時間乾燥し、粉
砕してアンチモン・アルミニウムの水酸化物及び弗化物
を存在させた本発明の二酸化チタン顔料を得た。（顔料
Ａ）EXAMPLE 1 A titanyl sulfate solution was hydrolyzed by adding 1.0% of zirconium carbonate solution as Z r O 2 by weight to metatitanic acid obtained by washing and filtration, was thoroughly kneaded , 900熔焼to an aqueous slurry of the resulting titanium dioxide base body at ℃ (T i O 2 concentration 400
g / l) was heated to 60 ° C., and then 1.0% of Sb 2 O 5 was added to the antimony pentachloride solution based on the weight of the substrate to precipitate a hydrated oxide of antimony and aged for 20 minutes. Next, an ammonium fluoride aqueous solution was added as 1.0% as F based on the weight of the substrate and aged for 20 minutes. Subsequently, a sodium aluminate solution is added to the substrate based on the weight of Al 2 O.
After adding 2.0% as No. 3, it was neutralized with dilute sulfuric acid to precipitate a hydrated oxide of aluminum, and then aged for 20 minutes. Then, it was washed with water, filtered, dried at 130 ° C. for 5 hours, and pulverized to obtain a titanium dioxide pigment of the present invention in which antimony aluminum hydroxide and fluoride were present. (Pigment A)
【００１１】[0011]
【比較例１】実施例１の本発明顔料と比較するため、次
の様にして顔料Ｂ〜Ｅを製造した。 顔料Ｂ：ジルコニウムを含有しない二酸化チタンを使用
すること以外は実施例と同様に処理した。 顔料Ｃ：アンチモンの水和酸化物を存在させないこと以
外は実施例と同様に処理した。 顔料Ｄ：ジルコニウムを含有しない二酸化チタンを使用
することと表面にアンチモンの水和酸化物を存在させな
いこと以外は実施例と同様に処理した。 顔料Ｅ：ジルコニウムを含有しない二酸化チタンを使用
することと表面にアンチモンの水和酸化物を存在させな
いことと弗化物イオンを存在させないこと以外は実施例
と同様に処理した。Comparative Example 1 In order to compare with the pigment of the present invention of Example 1, pigments B to E were produced as follows. Pigment B: Processed as in Example except that titanium dioxide containing no zirconium was used. Pigment C: Treated as in Example except that the hydrated oxide of antimony was not present. Pigment D: The same treatment as in Example was performed except that titanium dioxide containing no zirconium was used and no hydrated oxide of antimony was present on the surface. Pigment E: The same treatment as in Example was carried out except that titanium dioxide containing no zirconium was used, no hydrated oxide of antimony was present on the surface, and no fluoride ion was present.
【００１２】[0012]
【試験例】前記実施例及び比較例の二酸化チタン顔料Ａ
〜Ｅについて、その性能を試験し表１の結果を得た。[Test Example] Titanium dioxide pigment A of the above Examples and Comparative Examples
About -E, the performance was tested and the result of Table 1 was obtained.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表１の性能評価は次の様にして行った。 耐光性（１） Ａ〜Ｅの二酸化チタン０．３ｇを塩化ビ
ニル樹脂１００ｇ／鉛系安定剤３．０ｇ中へ混合し６イ
ンチ２本ロールで混練した後、１６０℃に調整した１０
０ｋｇ／ｃｍ２の圧搾機で加熱圧縮して硬質の塩化ビニ
ルシートを作成した。この硬質塩ビの試験片をカーボン
アーク型サンシャインウエザーメーター装置（スガ試験
機ＫＫ製、ＷＥ−ＳＵＮ−ＤＣ型）内で２４時間促進暴
露した後、色差計（スガ試験機ＫＫ製、ＳＭ−５型）で
ＣＩＥ１９８１標準着色系のＸ，Ｙ，Ｚを測定し、その
値に基づいてΔＹ（明度変化）を計算した。この数値が
小さいものほど変色が少なく耐光性の良好なることを示
す。 ΔＹ＝暴露後Ｙ値−初期Ｙ値The performance evaluation in Table 1 was performed as follows. Light resistance (1) 0.3 g of titanium dioxides A to E was mixed into 100 g of vinyl chloride resin / 3.0 g of lead-based stabilizer and kneaded with a 6-inch two-roll mill, and then adjusted to 160 ° C. 10
A hard vinyl chloride sheet was prepared by heating and compressing with a 0 kg / cm 2 press. This hard PVC test piece was subjected to accelerated exposure for 24 hours in a carbon arc type sunshine weather meter device (Suga Tester KK, WE-SUN-DC type), and then a color difference meter (Suga Tester KK, SM-5 type). ) Was used to measure X, Y, and Z of the CIE1981 standard coloring system, and ΔY (change in lightness) was calculated based on the measured values. The smaller this value is, the less the discoloration is and the better the light resistance is. ΔY = Y value after exposure−Initial Y value
【００１５】耐光性（２） Ａ〜Ｅの二酸化チタン１．
０ｇポリエチレン樹脂１００ｇ／酸化防止剤（ＢＨＴ）
０．１ｇ中へ混合し、６インチ２本ロールで混練した
後、１３０℃に調整した１００ｋｇ／ｃｍ２の圧搾機で
加熱圧縮してポリエチレンシートを作成した。このポリ
エチレンシートをＮＨ３雰囲気の中で市販の３波長計蛍
光灯（２７Ｗ型）を４８時間連続照射した後、色差計
（スガ試験機ＫＫ製、ＳＭ−５型）でＨｕｎｔｅｒ着色
系のＬ，ａ，ｂを測定し、その値に基づいてΔｂ（黄変
度）を計算した。この数値が小さいものほど黄変が少な
く耐光性の良好なることを示す。 Δｂ＝暴露後ｂ値−初期ｂ値Light resistance (2) Titanium dioxide of A to E 1.
0g polyethylene resin 100g / antioxidant (BHT)
After mixing into 0.1 g and kneading with a 6-inch two-roll mill, a polyethylene sheet was prepared by heating and compressing with a 100 kg / cm 2 squeezing machine adjusted to 130 ° C. This polyethylene sheet was continuously irradiated with a commercially available three-wavelength meter fluorescent lamp (27 W type) in an NH 3 atmosphere for 48 hours, and then a Hunter coloring system L, A and b were measured, and Δb (yellowing degree) was calculated based on the measured values. The smaller this value is, the less yellowing is and the better the light resistance is. Δb = b value after exposure−initial b value
【００１６】耐光性（３） Ａ〜Ｅの二酸化チタン１５
ｇを水溶性メラミン樹脂（重量比１／１）１５ｇ中へ混
合し、ペイントシェーカー（レッドデビル社製、＃５１
１０）で分散して塗料化した後、画用紙に１０ミルの厚
さに塗布し、８０℃で６０分間乾燥させ、試験片とし
た。この試験片をフェードメーター（スガ試験機ＫＫ
製、ＦＡＬ−５型）内で４８時間暴露した後、色差計
（スガ試験機ＫＫ製、ＳＭ−５型）でＨｕｎｔｅｒ系の
Ｌ，ａ，ｂを測定し、その値に基づいてΔＥを計算し
た。ΔＥは初期と暴露後の色差を示し、この数値が小さ
いものほど耐光性の良好なることを示す。 ΔＥ＝｛（Ｌ１−Ｌ２）２＋（ａ１−ａ２）２＋（ｂ１
−ｂ２）２｝１／２ Light resistance (3) Titanium dioxide 15 of A to E
15 g of a water-soluble melamine resin (weight ratio 1/1) was mixed, and a paint shaker (# 51 manufactured by Red Devil Co., Ltd.) was mixed.
After being dispersed in 10) to form a paint, it was applied to a drawing paper in a thickness of 10 mil and dried at 80 ° C. for 60 minutes to obtain a test piece. This test piece is a fade meter (Suga Tester KK
Manufactured by FAL-5 type) for 48 hours, and then measured the Hunter system L, a, b with a color difference meter (Suga Tester KK, SM-5 type), and calculate ΔE based on the value. did. ΔE indicates the color difference between the initial stage and the post-exposure stage, and the smaller this value is, the better the light resistance is. ΔE = {(L 1 −L 2 ) 2 + (a 1 −a 2 ) 2 + (b 1
-B 2 ) 2 } 1/2
【００１７】[0017]
【発明の効果】本発明により、幅広い用途で光化学的に
安定な二酸化チタン顔料を得ることができ、初期性能を
長期に渡って維持することができるようになった。Industrial Applicability According to the present invention, a photochemically stable titanium dioxide pigment can be obtained in a wide range of applications, and the initial performance can be maintained for a long period of time.
Claims (1)
０．１〜５重量％含有するルチル型酸化チタン（以下基
体という）の表面にアンチモンの水和酸化物がＳｂ２Ｏ
５として０．１〜３重量％、アルミニウムの水和酸化物
がＡｌ２Ｏ３として１〜５重量％、弗素イオン（Ｆ−）
がＦとして０．１〜２重量％存在することを特徴とする
二酸化チタン顔料（基体 ９０〜９８．８重量％）。1. A hydrated oxide of antimony is Sb 2 O on the surface of rutile titanium oxide (hereinafter referred to as a substrate) containing 0.1 to 5% by weight of zirconium oxide as Z r O 2.
5 , 0.1 to 3% by weight, hydrated oxide of aluminum is 1 to 5% by weight as Al 2 O 3 , and fluorine ion (F − ).
Is present in the amount of 0.1 to 2% by weight as F (titanium dioxide pigment (base: 90 to 98.8% by weight)).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12669694A JPH07292276A (en) | 1994-04-28 | 1994-04-28 | Titanium dioxide pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12669694A JPH07292276A (en) | 1994-04-28 | 1994-04-28 | Titanium dioxide pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07292276A true JPH07292276A (en) | 1995-11-07 |
Family
ID=14941592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12669694A Pending JPH07292276A (en) | 1994-04-28 | 1994-04-28 | Titanium dioxide pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07292276A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2202278A1 (en) | 2008-12-25 | 2010-06-30 | Sakai Chemical Industry Co., Ltd. | Titanium dioxide pigment and method for producing the same |
| EP2267088A2 (en) | 2009-06-26 | 2010-12-29 | Sakai Chemical Industry Co., Ltd. | Surface-modified titanium dioxide particle and method for producing the same |
| WO2018123928A1 (en) | 2016-12-28 | 2018-07-05 | 中国塗料株式会社 | Anti-fouling paint composition, anti-fouling paint film, base material having anti-fouling paint film attached thereto and method for producing same, and fouling prevention method |
-
1994
- 1994-04-28 JP JP12669694A patent/JPH07292276A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2202278A1 (en) | 2008-12-25 | 2010-06-30 | Sakai Chemical Industry Co., Ltd. | Titanium dioxide pigment and method for producing the same |
| JP2010150087A (en) * | 2008-12-25 | 2010-07-08 | Sakai Chem Ind Co Ltd | Titanium dioxide pigment and production method thereof |
| EP2267088A2 (en) | 2009-06-26 | 2010-12-29 | Sakai Chemical Industry Co., Ltd. | Surface-modified titanium dioxide particle and method for producing the same |
| JP2011006292A (en) * | 2009-06-26 | 2011-01-13 | Sakai Chem Ind Co Ltd | Titanium dioxide particles and method for producing the same |
| US8070874B2 (en) | 2009-06-26 | 2011-12-06 | Sakai Chemical Industry, Co., Ltd. | Surface-modified titanium dioxide particle and method for producing the same |
| WO2018123928A1 (en) | 2016-12-28 | 2018-07-05 | 中国塗料株式会社 | Anti-fouling paint composition, anti-fouling paint film, base material having anti-fouling paint film attached thereto and method for producing same, and fouling prevention method |
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