JP3379191B2 - Method for producing low chlorinated copper phthalocyanine pigment - Google Patents

Method for producing low chlorinated copper phthalocyanine pigment

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Publication number
JP3379191B2
JP3379191B2 JP01281294A JP1281294A JP3379191B2 JP 3379191 B2 JP3379191 B2 JP 3379191B2 JP 01281294 A JP01281294 A JP 01281294A JP 1281294 A JP1281294 A JP 1281294A JP 3379191 B2 JP3379191 B2 JP 3379191B2
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JP
Japan
Prior art keywords
copper phthalocyanine
pigment
weight
parts
sulfuric acid
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
Application number
JP01281294A
Other languages
Japanese (ja)
Other versions
JPH07216252A (en
Inventor
哲朗 大泉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Ink SC Holdings Co Ltd
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Toyo Ink SC Holdings Co Ltd
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Priority to JP01281294A priority Critical patent/JP3379191B2/en
Publication of JPH07216252A publication Critical patent/JPH07216252A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • C09B67/0035—Mixtures of phthalocyanines

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Description

【発明の詳細な説明】 【０００１】 【産業上の利用分野】本発明は塗料化し、塗布された塗
膜の耐候性に優れた塩素含有量１〜６重量％の低塩素化
銅フタロシアニン顔料の製造法に関する。 【０００２】 【従来の技術】銅フタロシアニン顔料は安価で色調が美
しいこと、着色力が大きいこと、耐候性、耐熱性、耐溶
剤性等の諸機能が良好であることなどから、色材工業の
分野において多量に、しかも広範の用途に使用されてい
る。通常、粗製銅フタロシアニン、及び粗製低塩素化銅
フタロシアニンは、無水フタル酸もしくはその誘導体、
尿素および銅源を、またはフタロジニトリルもしくはそ
の誘導体および銅源を、モリブデン酸アンモニウムある
いは四塩化チタンなどの触媒の存在下もしくは不存在
下、アルキルベンゼン、トリクロロベンゼンあるいはニ
トロベンゼンなどの有機溶媒中で常圧または加圧下で反
応させることにより製造される。しかしながら、合成さ
れたフタロシアニン分子はその合成溶媒中で結晶成長を
起こし、その長径が１０〜２００μｍ程度の粗大に針状
化した結晶形でしか得られず、インキ、塗料、プラスチ
ック等の色材としてはその適性は非常に低いか、全くな
い。したがって粗製銅フタロシアニンは色彩上利用価値
の高い粒子、即ち０．０１〜０．５μｍ程度まで微細化
すること（以下その操作を顔料化と称す）が必要とな
る。 【０００３】α型銅フタロシアニン顔料の工業的製法と
しては、粗製銅フタロシアニンを９５重量％以上の硫酸
に溶解し、これを多量の水に注加して微細な粒子を再沈
殿させるアシッドペースティング法と、６５〜８０重量
％の硫酸中で得られる硫酸塩を加水分解して微細な粒子
を得るアシッドスラリー法が一般的に行われている。こ
れらの顔料化は着色力を重視するため、硫酸量は銅フタ
ロシアニンに対し、２０重量倍程度と多量であり、また
処理温度は高くても５０℃程度である。上記の方法を用
いて得られる低塩素化銅フタロシアニンは、極めて微細
な粒子で、そのため着色力は高いが耐候性は著しく劣る
欠点を有している。特開平４−１１３号公報には、粗製
銅フタロシアニンを濃度７０〜９０重量％の硫酸に溶解
させ、次いで５０〜８０℃の温度で加熱処理を行った後
加水分解（６０〜１０重量％に硫酸濃度を調整）し、５
０〜６０℃で１時間攪拌してクロロフリーのα型銅フタ
ロシアニン顔料を得る方法が記載されている。しかし、
この方法は塩素を含まない銅フタロシアニンに限定され
るため耐候性の低い顔料しか得られない。 【０００４】 【発明が解決しようとする課題】本発明は上記欠点を改
良し、耐光性を有する低塩素化銅フタロシアニン顔料の
製法を提供するものである。 【課題を解決するための手段】すなわち、本発明は、塩
素含有量１〜６重量％の粗製銅フタロシアニン（但し、
乾式粉砕物を除く）１００重量部と一般式（１）で示さ
れる顔料誘導体１〜２５重量部を濃度７０〜９０重量％
の硫酸中６０〜１２０℃で浸漬処理し、次いで硫酸の濃
度が３５重量％以下になるように水で希釈することから
なる低塩素化銅フタロシアニン顔料の製造方法に関す
る。 【化２】 （式中のｎは、１〜８の整数、Ｐｃはフタロシアニン骨
格、ＭはＣｕ，Ｆｅ，ＮｉまたはＣｏ、Ｒ1 ，Ｒ2 ，Ｒ
3 ，Ｒ4 はそれぞれ独立に水素原子，ハロゲン原子また
はニトロ基を表す。）。 【０００５】次に本発明についてさらに詳しく説明す
る。本発明に原料として使用される粗製低塩素化銅フタ
ロシアニンは一般的な合成法で得られたものを用いるこ
とができる。例えば無水フタル酸、モノクロル無水フタ
ル酸、尿素及び銅源、あるいはフタロジニトリル及び塩
化銅を加熱し、得られたものを通常用いる。本発明に適
用される硫酸濃度は、７０〜９０重量％である。また、
硫酸の使用量としては、銅フタロシアニンに対し１〜１
５重量倍である。硫酸の使用量が多くなる程粒子の成長
速度が大きくなり、粒子の調整が困難になるばかりか、
廃酸処理の点で不利になる。また、硫酸の使用量が少な
くなる程粘度が上昇し、攪拌効率が悪くなったり、目的
とする粒径の顔料を得るために操作が煩雑になる。工業
的製造方法としては、銅フタロシアニンに対して４〜１
２重量倍使用することが有利である。 【０００６】本発明においては、粗製銅フタロシアニン
を所定の濃度および量の硫酸中に加え、ついで加熱処理
を行う。このときの結晶の成長は処理温度および時間に
依存し、温度は高いほど成長速度が大きくなる。成長速
度は大きすぎると粒子径の調整が困難になる。時間が長
い程、均一に揃った粒子が得られる。耐候性の良い粒子
を得るには、６０℃以上１００℃以下の温度で３〜８時
間の加熱処理が好ましい。本発明で、顔料の硫酸ペース
トに添加する式（１）で示される顔料誘導体は高温で浸
漬処理を行う場合、均一な粒子を得るために必要であ
る。高温で浸漬処理を行うとスラリー中の粒子は成長す
る方向に向かい、そのため粒子の大きさの分布は広くな
る。分布が広いと微細な粒子も顔料中に含まれ、微細な
粒子は耐候性が不良であることから、全体として耐候性
が劣る。式（１）で示される顔料誘導体の添加量は均一
な粒子を得るためには、粗製銅フタロシアニン１００重
量部に対して１〜２５重量部、更に好ましくは５〜１５
重量部である。このようにして加熱処理を行ったのち加
水分解を行う。加水分解は６０〜９５℃で行われる。硫
酸の使用量が少ないときはスラリーが粘稠であり、多量
の水を滴下する方法が、さらに硫酸の使用量が多いとき
は、多量の水中に投入する方法が好ましい。加水分解後
常法によりろ別し、低塩素化銅フタロシアニン顔料が得
られる。 【０００７】 【実施例】以下、実施例により本発明を説明する。例
中、部とは重量部を、％とは重量％をそれぞれ表す。 実施例１ ８２％硫酸２４００部中に式（２）で示される顔料誘導
体２０重量部投入し、完全に溶解したことを確認の上、
塩素含有量３．０％の粗製銅フタロシアニン１８０部を
投入し、温度を１００℃に保ちながら４時間浸漬処理を
する。９０℃の水１００００部に注加したのち、ろ過、
水洗によって洗液が中性であることを確認し取り出し乾
燥する。以上の操作によって低塩素化銅フタロシアニン
顔料を得た。この顔料の耐候性をウェザーメーターで測
定したところ、表１に示すように実施例１のものは比較
例１、２より良好であった。式（２） 【化３】 【０００８】実施例２ 実施例１で使用した硫酸スラリーを、温度を７０℃に保
ちながら４時間浸漬処理をする。７０℃の水１００００
部に注加したのち、ろ過、水洗によって洗液が中性であ
ることを確認し取り出し乾燥する。以上の操作によって
低塩素化銅フタロシアニン顔料を得た。この顔料の耐候
性をウェザーメーターで測定したところ、表１に示すよ
うに実施例２のものは比較例１、２より良好であった。 実施例３ 実施例１で使用した硫酸スラリーを、温度を８０℃に保
ちながら４時間浸漬処理をする。８０℃の水１００００
部に注加したのち、ろ過、水洗によって洗液が中性であ
ることを確認し取り出し乾燥する。以上の操作によって
低塩素化銅フタロシアニン顔料を得た。この顔料の耐候
性をウェザーメーターで測定したところ、表１に示すよ
うに実施例３のものは比較例１、２より良好であった。 実施例４ 実施例１で使用した硫酸スラリーを、温度を９０℃に保
ちながら４時間浸漬処理をする。９０℃の水１００００
部に注加したのち、ろ過、水洗によって洗液が中性であ
ることを確認し取り出し乾燥する。以上の操作によって
低塩素化銅フタロシアニン顔料を得た。この顔料の耐候
性をウェザーメーターで測定したところ、表１に示すよ
うに実施例４のものは比較例１、２より良好であった。 【０００９】実施例５ ８４％硫酸３０００部中に式（２）で示される顔料誘導
体４０重量部投入し、完全に溶解したことを確認の上、
塩素含有量３．０％の粗製銅フタロシアニン１６０部を
投入し、温度を１１０℃に保ちながら４時間浸漬処理を
する。９０℃の水１００００部に注加したのち、ろ過、
水洗によって洗液が中性であることを確認し取り出し乾
燥する。以上の操作によって低塩素化銅フタロシアニン
顔料を得た。この顔料の耐候性をウェザーメーターで測
定したところ、表１に示すように実施例５のものは比較
例１、２より良好であった。 実施例６ ７８％硫酸２０００部中に式（２）で示される顔料誘導
体１０重量部を投入し、完全に溶解したことを確認の
上、塩素含有量３．０％の粗製銅フタロシアニン１９０
部を投入し、温度を７０℃に保ちながら４時間浸漬処理
をする。７０℃の水１００００部に注加したのち、ろ
過、水洗によって洗液が中性であることを確認し取り出
し乾燥する。以上の操作によって低塩素化銅フタロシア
ニン顔料を得た。この顔料の耐候性をウェザーメーター
で測定したところ、表１に示すように実施例６のものは
比較例１、２より良好であった。 実施例７ ８２％硫酸２４００部中に式（２）で示される顔料誘導
体２０重量部投入し、完全に溶解したことを確認の上、
塩素含有量５．０％の粗製銅フタロシアニン１８０部を
投入し、温度を１００℃に保ちながら４時間浸漬処理を
する。９０℃の水１００００部に注加したのち、ろ過、
水洗によって洗液が中性であることを確認し取り出し乾
燥する。以上の操作によって低塩素化銅フタロシアニン
顔料を得た。この顔料の耐候性をウェザーメーターで測
定したところ、表１に示すように実施例７のものは比較
例１、２より良好であった。 実施例８ ８２％硫酸２４００部中に式（２）で示される顔料誘導
体２０重量部投入し、完全に溶解したことを確認の上、
塩素含有量１．０％の粗製銅フタロシアニン１８０部を
投入し、温度を１００℃に保ちながら４時間浸漬処理を
する。９０℃の水１００００部に注加したのち、ろ過、
水洗によって洗液が中性であることを確認し取り出し乾
燥する。以上の操作によって低塩素化銅フタロシアニン
顔料を得た。この顔料の耐候性をウェザーメーターで測
定したところ、表１に示すように実施例８のものは比較
例１、２より良好であった。 【００１０】比較例１ ８２％硫酸２４００部中に式（２）で示される顔料誘導
体２０重量部を投入し、完全に溶解したことを確認の
上、塩素含有量３．０％の粗製銅フタロシアニン１８０
部を投入し、温度を１０℃に保ちながら４時間浸漬処理
をする。１０℃の水１００００部に注加したのち、ろ
過、水洗によって洗液が中性であることを確認し取り出
し乾燥する。以上の操作によって低塩素化銅フタロシア
ニン顔料を得た。 比較例２ ８２％硫酸２４００部に塩素含有量３．０％の粗製銅フ
タロシアニン２００部を投入し、７０℃に保ち４．５時
間浸漬処理する。７０℃の水に注加し、６０分攪拌した
のちろ過、水洗によって洗液が中性であることを確認し
取り出し乾燥する。以上の操作によって低塩素化銅フタ
ロシアニン顔料を得た。 【００１１】 【表１】 【００１２】 【発明の効果】本発明によって得られる低塩素化銅フタ
ロシアニン顔料は従来のアシッドスラリー法で得られる
顔料と比較すると、これらの顔料を用いた塗料による塗
膜の耐候性ははるかに優れている。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low chlorinated copper phthalocyanine pigment having a chlorine content of 1 to 6% by weight which is excellent in weatherability of a coated film formed by coating. Related to manufacturing method. BACKGROUND OF THE INVENTION Copper phthalocyanine pigments are inexpensive and beautiful in color tone, have high coloring power, and have good functions such as weather resistance, heat resistance and solvent resistance. It is used in large quantities and in a wide range of applications in the field. Usually, crude copper phthalocyanine and crude low chlorinated copper phthalocyanine are phthalic anhydride or a derivative thereof,
Urea and copper source, or phthalodinitrile or its derivative and copper source, in the presence or absence of a catalyst such as ammonium molybdate or titanium tetrachloride in an organic solvent such as alkylbenzene, trichlorobenzene or nitrobenzene under normal pressure Alternatively, it is produced by reacting under pressure. However, the synthesized phthalocyanine molecule undergoes crystal growth in the synthesis solvent, and its major axis is obtained only in a coarsely acicular crystal form of about 10 to 200 μm, and is used as a coloring material for inks, paints, plastics, and the like. Has very low or no suitability. Therefore, the crude copper phthalocyanine needs to be refined to particles having high color value, that is, to about 0.01 to 0.5 μm (this operation is hereinafter referred to as pigmentation). [0003] As an industrial method for producing an α-type copper phthalocyanine pigment, an acid pasting method in which crude copper phthalocyanine is dissolved in 95% by weight or more of sulfuric acid and poured into a large amount of water to reprecipitate fine particles is performed. And an acid slurry method of hydrolyzing a sulfate obtained in 65 to 80% by weight of sulfuric acid to obtain fine particles is generally performed. Since the pigmentation emphasizes the coloring power, the amount of sulfuric acid is as large as about 20 times the weight of copper phthalocyanine, and the processing temperature is about 50 ° C. at the highest. The low-chlorinated copper phthalocyanine obtained by the above method is a very fine particle, and therefore has a drawback that the coloring power is high but the weather resistance is extremely poor. Japanese Patent Application Laid-Open No. 4-113 discloses that crude copper phthalocyanine is dissolved in sulfuric acid having a concentration of 70 to 90% by weight, then heated at a temperature of 50 to 80 ° C., and then subjected to hydrolysis (to 60 to 10% by weight of sulfuric acid). Adjust the concentration)
A method for obtaining a chlorofree α-type copper phthalocyanine pigment by stirring at 0 to 60 ° C. for 1 hour is described. But,
Since this method is limited to copper phthalocyanine containing no chlorine, only a pigment having low weather resistance can be obtained. An object of the present invention is to provide a method for producing a light-fast, low-chlorinated copper phthalocyanine pigment which improves the above-mentioned drawbacks. That is, the present invention provides a crude copper phthalocyanine having a chlorine content of 1 to 6% by weight (however,
100 parts by weight and 1 to 25 parts by weight of the pigment derivative represented by the general formula (1) in a concentration of 70 to 90% by weight.
The immersed treated at 60 to 120 ° C. in sulfuric acid and then about the low chlorinated copper production method of the phthalocyanine pigments which comprises diluting with water so that the concentration of sulfuric acid is 35 wt% or less
You. Embedded image (In the formula, n is an integer of 1 to 8, Pc is a phthalocyanine skeleton, M is Cu, Fe, Ni or Co, R 1 , R 2 , R
3 and R 4 each independently represent a hydrogen atom, a halogen atom or a nitro group. ). Next, the present invention will be described in more detail. As the crude low-chlorinated copper phthalocyanine used as a raw material in the present invention, those obtained by a general synthesis method can be used. For example, phthalic anhydride, monochlorophthalic anhydride, urea and a copper source, or phthalodinitrile and copper chloride are heated and obtained. The sulfuric acid concentration applied to the present invention is 70-90% by weight. Also,
The amount of sulfuric acid used is 1 to 1 with respect to copper phthalocyanine.
5 times the weight. As the amount of sulfuric acid used increases, the growth rate of the particles increases, making it difficult to adjust the particles,
It is disadvantageous in terms of waste acid treatment. In addition, as the amount of sulfuric acid used decreases, the viscosity increases, the stirring efficiency decreases, and the operation becomes complicated to obtain a pigment having a target particle size. As an industrial production method, 4-1 to copper phthalocyanine is used.
It is advantageous to use twice the weight. In the present invention, crude copper phthalocyanine is added to sulfuric acid at a predetermined concentration and amount, and then heat treatment is performed. The crystal growth at this time depends on the processing temperature and time, and the higher the temperature, the higher the growth rate. If the growth rate is too high, it becomes difficult to adjust the particle size. The longer the time, the more uniform the particles are obtained. In order to obtain particles having good weather resistance, a heat treatment at a temperature of 60 ° C. or more and 100 ° C. or less for 3 to 8 hours is preferable. In the present invention, the pigment derivative represented by the formula (1) to be added to the pigment sulfuric acid paste is necessary for obtaining uniform particles when immersion treatment is performed at a high temperature. When the immersion treatment is performed at a high temperature, the particles in the slurry are directed toward the growth direction, so that the particle size distribution is widened. If the distribution is wide, fine particles are also included in the pigment, and the fine particles have poor weather resistance, and therefore have poor weather resistance as a whole. The amount of the pigment derivative represented by the formula (1) is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight, per 100 parts by weight of the crude copper phthalocyanine in order to obtain uniform particles.
Parts by weight. After performing the heat treatment in this manner, hydrolysis is performed. The hydrolysis is performed at 60-95C. When the amount of sulfuric acid used is small, the slurry is viscous and a large amount of water is dropped, and when the amount of sulfuric acid is large used, a method of pouring into a large amount of water is preferred. After the hydrolysis, the resultant is filtered by a conventional method to obtain a low chlorinated copper phthalocyanine pigment. Hereinafter, the present invention will be described by way of examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”. Example 1 20 parts by weight of a pigment derivative represented by the formula (2) was added to 2400 parts of 82% sulfuric acid, and after confirming that the pigment derivative was completely dissolved,
180 parts of crude copper phthalocyanine having a chlorine content of 3.0% is charged, and immersion treatment is performed for 4 hours while maintaining the temperature at 100 ° C. After pouring into 10000 parts of water at 90 ° C., filtration,
After confirming that the washing liquid is neutral by washing with water, take out and dry. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of this pigment was measured with a weather meter. As shown in Table 1, the pigment of Example 1 was better than Comparative Examples 1 and 2. Formula (2) Example 2 The sulfuric acid slurry used in Example 1 is immersed for 4 hours while maintaining the temperature at 70 ° C. 10000 water at 70 ° C
After pouring into the part, the washing liquid is confirmed to be neutral by filtration and washing with water, taken out and dried. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of the pigment was measured by weatherometer, was better than Comparative Examples 1 and 2 that in Example 2 as shown in Table 1. Example 3 The sulfuric acid slurry used in Example 1 is immersed for 4 hours while keeping the temperature at 80 ° C. 10000 water at 80 ° C
After pouring into the part, the washing liquid is confirmed to be neutral by filtration and washing with water, taken out and dried. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of this pigment was measured with a weather meter. As shown in Table 1, the pigment of Example 3 was better than Comparative Examples 1 and 2. Example 4 The sulfuric acid slurry used in Example 1 is immersed for 4 hours while maintaining the temperature at 90 ° C. 10000 water at 90 ° C
After pouring into the part, the washing liquid is confirmed to be neutral by filtration and washing with water, taken out and dried. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of this pigment was measured with a weather meter. As shown in Table 1, the pigment of Example 4 was better than Comparative Examples 1 and 2. Example 5 Into 3000 parts of 84% sulfuric acid, 40 parts by weight of a pigment derivative represented by the formula (2) were added, and after confirming that the pigment derivative was completely dissolved,
160 parts of crude copper phthalocyanine having a chlorine content of 3.0% is charged, and immersion treatment is performed for 4 hours while maintaining the temperature at 110 ° C. After pouring into 10000 parts of water at 90 ° C., filtration,
After confirming that the washing liquid is neutral by washing with water, take out and dry. Thus, a low chlorinated copper phthalocyanine pigment was obtained. When the weather resistance of this pigment was measured with a weather meter, the pigment of Example 5 was better than Comparative Examples 1 and 2, as shown in Table 1. Example 6 10 parts by weight of the pigment derivative represented by the formula (2) was added to 2,000 parts of 78% sulfuric acid, and after confirming complete dissolution, crude copper phthalocyanine 190 having a chlorine content of 3.0% was added.
Then, the immersion treatment is performed for 4 hours while maintaining the temperature at 70 ° C. After pouring into 10,000 parts of water at 70 ° C., filtration and washing with water are carried out to confirm that the washing liquid is neutral. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of this pigment was measured with a weather meter. As shown in Table 1, the pigment of Example 6 was better than Comparative Examples 1 and 2. Example 7 20 parts by weight of a pigment derivative represented by the formula (2) was added to 2400 parts of 82% sulfuric acid, and after confirming that the pigment derivative was completely dissolved,
180 parts of crude copper phthalocyanine having a chlorine content of 5.0% is charged, and immersion treatment is performed for 4 hours while maintaining the temperature at 100 ° C. After pouring into 10000 parts of water at 90 ° C., filtration,
After confirming that the washing liquid is neutral by washing with water, take out and dry. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of this pigment was measured with a weather meter. As shown in Table 1, the pigment of Example 7 was better than Comparative Examples 1 and 2. Example 8 20 parts by weight of a pigment derivative represented by the formula (2) was added to 2400 parts of 82% sulfuric acid, and after confirming that the pigment derivative was completely dissolved,
180 parts of crude copper phthalocyanine having a chlorine content of 1.0% is charged, and immersion treatment is performed for 4 hours while maintaining the temperature at 100 ° C. After pouring into 10000 parts of water at 90 ° C., filtration,
After confirming that the washing liquid is neutral by washing with water, take out and dry. Thus, a low chlorinated copper phthalocyanine pigment was obtained. The weather resistance of this pigment was measured with a weather meter. As shown in Table 1, the pigment of Example 8 was better than Comparative Examples 1 and 2. Comparative Example 1 20 parts by weight of a pigment derivative represented by the formula (2) was added to 2400 parts of 82% sulfuric acid, and after confirming that the pigment derivative was completely dissolved, crude copper phthalocyanine having a chlorine content of 3.0% was used. 180
Then, the immersion treatment is performed for 4 hours while maintaining the temperature at 10 ° C. After pouring into 10,000 parts of water at 10 ° C., filtration and washing with water are carried out to confirm that the washing liquid is neutral. Thus, a low chlorinated copper phthalocyanine pigment was obtained. Comparative Example 2 200 parts of crude copper phthalocyanine having a chlorine content of 3.0% was added to 2400 parts of 82% sulfuric acid, and the mixture was immersed at 70 ° C. for 4.5 hours. The mixture is poured into water at 70 ° C., stirred for 60 minutes, filtered, washed with water to confirm that the washing liquid is neutral, and taken out and dried. Thus, a low chlorinated copper phthalocyanine pigment was obtained. [Table 1] The low chlorinated copper phthalocyanine pigment obtained according to the present invention is much more excellent in the weather resistance of a coating film formed by a paint using these pigments than the pigment obtained by the conventional acid slurry method. ing.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C09B 67/14 C09B 67/20 C09B 67/22 C09B 67/16 C09B 67/50 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C09B 67/14 C09B 67/20 C09B 67/22 C09B 67/16 C09B 67/50

Claims (1)

(57)【特許請求の範囲】 【請求項１】塩素含有量１〜６重量％の粗製銅フタロシ
アニン（但し、乾式粉砕物を除く）１００重量部と一般
式（１）で示される顔料誘導体１〜２５重量部を濃度７
０〜９０重量％の硫酸中６０〜１２０℃で浸漬処理し、
次いで硫酸の濃度が３５重量％以下になるように水で希
釈することからなる低塩素化銅フタロシアニン顔料の製
造方法 【化１】 （式中のｎは、１〜８の整数、Ｐｃはフタロシアニン骨
格、ＭはＣｕ，Ｆｅ，ＮｉまたはＣｏ、Ｒ1 ，Ｒ2 ，Ｒ
3 ，Ｒ4 はそれぞれ独立に水素原子，ハロゲン原子また
はニトロ基を表す。）。(57) [Claim 1] 100 parts by weight of crude copper phthalocyanine having a chlorine content of 1 to 6% by weight (excluding dry pulverized products ) and a pigment derivative 1 represented by the general formula (1) Concentration of 25 parts by weight
Immersion treatment in sulfuric acid of 0 to 90% by weight at 60 to 120 ° C.,
Then, a method for producing a low-chlorinated copper phthalocyanine pigment comprising diluting with water so that the concentration of sulfuric acid is 35% by weight or less. (In the formula, n is an integer of 1 to 8, Pc is a phthalocyanine skeleton, M is Cu, Fe, Ni or Co, R 1 , R 2 , R
3 and R 4 each independently represent a hydrogen atom, a halogen atom or a nitro group. ).
JP01281294A 1994-02-04 1994-02-04 Method for producing low chlorinated copper phthalocyanine pigment Expired - Lifetime JP3379191B2 (en)

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JP3379191B2 true JP3379191B2 (en) 2003-02-17

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