JP3030880B2 - Method for producing ε-type copper phthalocyanine pigment - Google Patents
Method for producing ε-type copper phthalocyanine pigmentInfo
- Publication number
- JP3030880B2 JP3030880B2 JP3008485A JP848591A JP3030880B2 JP 3030880 B2 JP3030880 B2 JP 3030880B2 JP 3008485 A JP3008485 A JP 3008485A JP 848591 A JP848591 A JP 848591A JP 3030880 B2 JP3030880 B2 JP 3030880B2
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- Prior art keywords
- copper phthalocyanine
- type copper
- pigment
- type
- parts
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は色材、電子材料等に利用
価値の高いε型銅フタロシアニン顔料を工業的に有利に
製造する方法に関するもである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for industrially and advantageously producing an .epsilon.-type copper phthalocyanine pigment having a high value for coloring materials, electronic materials and the like.
【０００２】[0002]
【従来の技術】従来、ε型銅フタロシアニン顔料の製造
としては、α型、γ型、δ型あるいはそれらの混合物の
銅フタロシアニンをボールミルで長時間乾式摩砕し一旦
α型とε型の混合物とした後、これを溶剤処理しε型へ
結晶変換させる方法（英国特許弟１４１１８８０号公
報）、例えばα型銅フタロシアニンをボールミル中で鋼
球と１６時間摩砕してα型とε型の銅フタロシアニンの
重量比が１：１の混合物とし、これを２０倍量のエタノ
ールで８時間還流することでα型をε型に転換させε型
銅フタロシアニンを得る方法が提案されている。2. Description of the Related Art Conventionally, as a method for producing an ε-type copper phthalocyanine pigment, copper phthalocyanine of α-type, γ-type, δ-type or a mixture thereof is dry-milled for a long time by a ball mill, and once mixed with a mixture of α-type and ε-type. After that, this is subjected to a solvent treatment to convert the crystal into ε-type (GB Patent No. 141,880). For example, α-type copper phthalocyanine is milled with steel balls in a ball mill for 16 hours to form α-type and ε-type copper phthalocyanine. A method has been proposed in which a mixture having a weight ratio of 1: 1 is refluxed with a 20-fold amount of ethanol for 8 hours to convert α-form into ε-form to obtain ε-type copper phthalocyanine.
【０００３】[0003]
【発明が解決しようとする課題】しかし、この方法で使
用できる原料の銅フタロシアニンの結晶形は、α型、γ
型あるいはδ型で、β型が含まれていてはならない。ま
たその製造条件ではα型、γ型あるいはδ型からε型に
結晶変換するのに１６時間以上の長時間の摩砕を必要と
し、更にその後の溶剤処理では多量の溶剤と長時間を要
し、生産性が著しく低い。しかもその溶剤処理時には溶
剤の種類に応じて処理温度に制約があり、その処理温度
より高い温度で処理するとβ型銅フタロシアニンが発生
する欠点がある。特に結晶変換能力の高い芳香族系溶
剤、例えばトルエンを用いた場合は３０℃以上ではβ型
銅フタロシアニンが多量に発生し、純粋なε型銅フタロ
シアニンが得られない等の欠点がある。その他、顔料粒
子サイズのコントロールがしにくく、任意の粒径の顔料
を得るのが難しいという欠点もある。However, the raw material copper phthalocyanine which can be used in this method has a crystal form of α-form, γ-form.
It must be of type or δ and must not contain β. Further, under the manufacturing conditions, a long grinding time of 16 hours or more is required to convert the α-form, γ-form or δ-form into ε-form, and further solvent treatment requires a large amount of solvent and a long time. , The productivity is extremely low. In addition, during the solvent treatment, there is a restriction on the treatment temperature depending on the type of the solvent, and when the treatment is performed at a temperature higher than the treatment temperature, there is a disadvantage that β-type copper phthalocyanine is generated. Particularly, when an aromatic solvent having a high crystal conversion capacity, for example, toluene, is used, a large amount of β-type copper phthalocyanine is generated at 30 ° C. or higher, and pure ε-type copper phthalocyanine cannot be obtained. In addition, there is a disadvantage that it is difficult to control the pigment particle size and it is difficult to obtain a pigment having an arbitrary particle size.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、かかる課
題を解決するためにε型銅フタロシアニン顔料の製造法
について鋭意研究した結果、粗製ε型銅フタロシアニン
を乾式摩砕してε型銅フタロシアニンとα型銅フタロシ
アニンの混合物とした後、有機溶剤中で加熱処理する方
法が、摩砕が短時間でよく、芳香族溶剤中で３０℃以上
の加熱処理してもβ型銅フタロシアニンの発生等の問題
がなく、顔料粒子サイズのコントロールも容易であるこ
とを見い出し、本発明を完成するに至った。Means for Solving the Problems The present inventors have intensively studied a method for producing an ε-type copper phthalocyanine pigment in order to solve the above-mentioned problems. As a result, the crude ε-type copper phthalocyanine was dry-milled to obtain ε-type copper phthalocyanine. A method in which a mixture of phthalocyanine and α-type copper phthalocyanine is subjected to heat treatment in an organic solvent requires only a short grinding time, and β-type copper phthalocyanine is generated even when heat-treated at 30 ° C. or more in an aromatic solvent. It has been found that there is no problem in that the control of the pigment particle size is easy, and the present invention has been completed.
【０００５】即ち、本発明は、ε型銅フタロシアニンを
主成分として含む粗製ε型銅フタロシアニンを乾式摩砕
してε型銅フタロシアニンとα型銅フタロシアニンの混
合物とした後、有機溶剤中で加熱処理することを特徴と
するε型銅フタロシアニン顔料の製造法を提供するもの
である。That is, according to the present invention, a crude ε-type copper phthalocyanine containing ε-type copper phthalocyanine as a main component is dry-milled into a mixture of ε-type copper phthalocyanine and α-type copper phthalocyanine, and then heat-treated in an organic solvent. And a method for producing an ε-type copper phthalocyanine pigment.
【０００６】本発明の方法によりε型銅フタロシアニン
顔料を製造するには、例えば粗製ε型銅フタロシアニン
を、摩砕助剤の存在下あるいは不存在下に、通常５０〜
２００分間乾式摩砕してε型銅フタロシアニンとα型銅
フタロシアニンの重量比（ε／α）を、例えば５／９５
〜６０／４０に調整した後、常圧あるいは加圧下、有機
溶剤中で２〜６時間加熱処理すればよく、これにより純
粋なε型銅フタロシアニン顔料が容易に得られる。しか
も、重量比（ε／α）を調整することにより、得られる
顔料の粒子サイズをコントロールすることが出来る。な
かでも色相、鮮明性、着色力等に優れるε型銅フタロシ
アニン顔料が効率良く製造できる点で、重量比（ε／
α）を１５／８５〜３５／６５に調整した後、溶剤処理
することが好ましい。[0006] In order to produce an ε-type copper phthalocyanine pigment by the method of the present invention, for example, a crude ε-type copper phthalocyanine is prepared by adding a crude ε-type copper phthalocyanine, usually in the presence or absence of a milling aid, to 50 to 50%.
After dry milling for 200 minutes, the weight ratio (ε / α) of ε-type copper phthalocyanine to α-type copper phthalocyanine is, for example, 5/95.
After adjusting to ６０60/40, heat treatment may be performed in an organic solvent under normal pressure or under pressure for 2 to 6 hours, whereby a pure ε-type copper phthalocyanine pigment can be easily obtained. In addition, the particle size of the obtained pigment can be controlled by adjusting the weight ratio (ε / α). Above all, an ε-type copper phthalocyanine pigment excellent in hue, sharpness, coloring power, etc. can be efficiently produced, and the weight ratio (ε /
After adjusting α) to 15/85 to 35/65, it is preferable to carry out solvent treatment.
【０００７】本発明に使用される粗製ε型銅フタロシア
ニンとしては、ε型銅フタロシアニンを主成分として含
むものであれば良く、いずれも使用できるが、なかでも
ε型銅フタロシアニンを９０重量％以上含有するものが
好ましい。その例としては、無水マレイン酸と銅フタロ
シアニンスルホンアミド誘導体とをニトロベンゼン等の
有機溶剤中で反応させてなる粗製ε型銅フタロシアニン
や、特公平１−６２３４号公報、特公平１−７１０８号
公報等に記載された如く無水マレイン酸と銅フタロシア
ニンスルホンアミド誘導体とをε型銅フタロシアニンの
存在下にアルキルベンゼン等の有機溶剤中で反応させて
なる粗製ε型銅フタロシアニン等が挙げられるが、α
型、γ型、δ型以外にβ型等の異種結晶形の銅フタロシ
アニンが含まれていてもよい。そのなかでβ型の含有率
が高い場合、例えば５０重量％程度の場合であっても、
乾式摩砕を十分行い、β型をほぼ完全にα型に変えれば
何等問題はないが、摩砕時間を長くする必要がある。そ
の場合には乾式摩砕を行う際に、フタルイミドメチル銅
フタロシアニン等の銅フタロシアニンの誘導体を添加す
ることにより、摩砕時間を短縮できる。銅フタロシアニ
ンの誘導体としては銅フタロシアニンの結晶成長を抑制
するものなら何でもよく、他に銅フタロシアニンスルホ
ンアミド類、アミノメチル銅フタロシアニン類等が挙げ
られる。The crude ε-type copper phthalocyanine used in the present invention may be any one containing ε-type copper phthalocyanine as a main component, and any of them can be used. Are preferred. Examples thereof include crude ε-type copper phthalocyanine obtained by reacting maleic anhydride and a copper phthalocyanine sulfonamide derivative in an organic solvent such as nitrobenzene, and Japanese Patent Publication Nos. 1-6234 and 1-7108. The crude ε-type copper phthalocyanine obtained by reacting maleic anhydride and a copper phthalocyanine sulfonamide derivative in an organic solvent such as alkylbenzene in the presence of ε-type copper phthalocyanine as described in
Heterocrystalline copper phthalocyanine such as β-type in addition to type γ-type and δ-type may be contained. Among them, when the content of β type is high, for example, even when it is about 50% by weight,
There is no problem if dry milling is performed sufficiently and β-form is almost completely changed to α-form, but it is necessary to lengthen the milling time. In that case, when performing dry milling, the milling time can be reduced by adding a derivative of copper phthalocyanine such as phthalimidomethyl copper phthalocyanine. Any derivative of copper phthalocyanine may be used as long as it suppresses the crystal growth of copper phthalocyanine, and other examples include copper phthalocyanine sulfonamides and aminomethyl copper phthalocyanine.
【０００８】乾式摩砕に使用できる装置の例としては、
例えばアトライター、ボールミル、ビーズミル、振動ミ
ル、ハンマーミル等を挙げることができる。有機溶剤と
しては、銅フタロシアニンに対して結晶変換能力を有し
ていれば任意のものが使用できる。その例としては、ベ
ンゼン、トルエン、キシレン、ミネラルスピリッツ等の
炭化水素類、トリクロロエタン、トリクロロエチレン、
クロロベンゼン等のハロゲン化炭化水素類、プロパノー
ル、ｎ−ブタノール、イソブタノール、メチルセロソル
ブ、エチルセロソルブ、ブチルセロソルブ、シクロヘキ
サノール等のアルコール類、メチルエチルケトン、メチ
ルブチルケトン、メチルイソブチルケトン、シクロヘキ
サノン等のケトン類、テトラヒドロフラン、ジオキサ
ン、ジグライム、アニソール等のエーテル類、酢酸エチ
ル、酢酸プロピル、酢酸ブチル、セロソルブアセテー
ト、ブチルセロソルブアセテート、安息香酸メチル等の
エステル類、ジメチルホルムアミド、Ｎ−メチルピロリ
ドン等のアミド類等が挙げられ、これらは２種以上の混
合して用いることもできる。なかでもα型からε型への
結晶変換能力、溶剤の回収の容易さ、得られる顔料の品
質、特に分散性に優れるε型銅フタロシアニン顔料が得
られる点で、トルエンとｎ−ブタノールと水の３種の混
合溶剤を用いることが好ましい。Examples of devices that can be used for dry milling include:
For example, an attritor, a ball mill, a bead mill, a vibration mill, a hammer mill and the like can be mentioned. As the organic solvent, any one can be used as long as it has a crystal conversion ability for copper phthalocyanine. Examples include benzene, toluene, xylene, hydrocarbons such as mineral spirits, trichloroethane, trichloroethylene,
Halogenated hydrocarbons such as chlorobenzene, alcohols such as propanol, n-butanol, isobutanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and cyclohexanol; ketones such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone; and tetrahydrofuran Dioxane, diglyme, ethers such as anisole, ethyl acetate, propyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, esters such as methyl benzoate, dimethylformamide, amides such as N-methylpyrrolidone, and the like. These can be used in combination of two or more. Among them, the ability to convert crystals from α-type to ε-type, the ease of solvent recovery, and the quality of the obtained pigment, especially in that ε-type copper phthalocyanine pigment excellent in dispersibility is obtained, toluene, n-butanol and water It is preferable to use three types of mixed solvents.
【０００９】処理温度は、処理溶剤系の結晶成長能力に
応じて室温から当該溶剤系の沸点あるいは混合溶剤では
その共沸点の範囲で適宜選択することができる。また必
要に応じて、加圧状態で処理することもできる。The processing temperature can be appropriately selected from room temperature to the boiling point of the solvent system or the azeotropic point of the mixed solvent in accordance with the crystal growth capacity of the processing solvent system. Further, if necessary, the treatment can be performed in a pressurized state.
【００１０】以下に製造例、実施例および比較例を示し
て本発明を具体的に説明する。なお、例中「部」、
「％」とあるのはそれぞれ重量部、重量％を示す。 製造例１（粗製ε型銅フタロシアニンの製造） グラスライニング製耐圧反応装置に、無水フタル酸１２
７０部、尿素１６１５部、塩化第一銅２１０部、モリブ
デン酸アンモニウム５部、Ｎ−フェニル銅フタロシアニ
ンスルホンアミド（平均置換基数１．７）１１５部、ε
型銅フタロシアニン１００部およびｔｅｒｔ−アミルベ
ンゼン３０００部を仕込み、攪拌しながら加熱し、５時
間で２００℃まで昇温させ、さらに２時間、２００℃に
保持した。内部圧は反応釜内ガスを放出することにより
３Ｋｇ／ｃｍ2 に保った。放冷後、減圧蒸留にて溶媒を
留去した。残査を１％塩酸１７０００部に加え、約８０
℃で２時間攪拌した後、濾過、水洗した。次いで、得ら
れた顔料の水性ケーキを１％水酸化ナトリウム１７００
０部に加え、約８０℃で攪拌した後、濾過し、濾液が中
性になるまで水洗して、乾燥し、純度９７．８％で結晶
形が完全にε型の粗製銅フタロシアニン１３５２部を得
た。Hereinafter, the present invention will be described in detail with reference to Production Examples, Examples and Comparative Examples. In the example, "part",
“%” Indicates parts by weight and% by weight, respectively. Production Example 1 (Production of crude ε-type copper phthalocyanine) Phthalic anhydride 12 was added to a glass-lined pressure-resistant reactor.
70 parts, urea 1615 parts, cuprous chloride 210 parts, ammonium molybdate 5 parts, N-phenyl copper phthalocyanine sulfonamide (average number of substituents 1.7) 115 parts, ε
100 parts of type copper phthalocyanine and 3000 parts of tert-amylbenzene were charged, heated with stirring, heated to 200 ° C. in 5 hours, and kept at 200 ° C. for 2 hours. The internal pressure was maintained at 3 kg / cm 2 by discharging gas in the reactor. After cooling, the solvent was distilled off under reduced pressure. Add the residue to 17000 parts of 1% hydrochloric acid and add about 80
After stirring at 2 ° C. for 2 hours, the mixture was filtered and washed with water. Next, the obtained aqueous cake of pigment was washed with 1% sodium hydroxide (1700).
After stirring at about 80 ° C., the mixture was filtered, washed with water until the filtrate became neutral, and dried, and 1352 parts of crude copper phthalocyanine having a purity of 97.8% and a crystal form completely of ε type was added. Obtained.
【００１１】実施例１ 製造例１で得た粗製ε型銅フタロシアニン５００部を５
ｌアトライター（直径３／８インチのスチールボール１
３Ｋｇを含む。以下同様。）で９０分間乾式摩砕した。
このときの摩砕物のε型銅フタロシアニンとα型銅フタ
ロシアニンの重量比（ε／α）は、図１に示すＸ線回折
図から求めることができ、２６／７４であった。次い
で、得られた摩砕物６０部をトルエン１８０部、ｎ−ブ
タノール９０部および水４００部からなる混合溶剤に投
入し、共沸温度で４時間加熱した後、溶剤を蒸留回収
し、濾過、乾燥してε型銅フタロシアニン顔料４９６ｇ
を得た。この顔料は、図２に示すＸ線回折図から明らか
様に完全にε型の顔料であった。また、この顔料の比表
面積は７０ｍ2 ／ｇであった。Example 1 500 parts of the crude ε-type copper phthalocyanine obtained in Production Example 1 was
l Attritor (3/8 inch diameter steel ball 1
Contains 3 kg. The same applies hereinafter. ) For 90 minutes.
At this time, the weight ratio (ε / α) of the ε-type copper phthalocyanine and the α-type copper phthalocyanine of the milled material was determined from the X-ray diffraction diagram shown in FIG. 1, and was 26/74. Next, 60 parts of the obtained milled material was put into a mixed solvent consisting of 180 parts of toluene, 90 parts of n-butanol and 400 parts of water, and heated at an azeotropic temperature for 4 hours. 496 g of ε-type copper phthalocyanine pigment
I got This pigment was completely an ε-type pigment, as apparent from the X-ray diffraction diagram shown in FIG. The specific surface area of this pigment was 70 m 2 / g.
【００１２】なお、ε型銅フタロシアニンとα型銅フタ
ロシアニンの重量比（ε／α）は、図１に示すＸ線解析
図中のε型結晶形を表すピーク高さＳεとα型結晶形を
表すのピーク高さＳαの比（Ｓε／Ｓα）から求める。
さらに詳しく説明すると、Ｓεは回折角度（２θ）＝
９．２゜でのピーク高さであり、Ｓαは回折角度（２
θ）＝６．８゜でのピーク高さである。この時のＸ線回
折条件は、ターゲット：Ｃｕ、フィルター：Ｎｉ、電
圧：３６ＫＶ、電流：３２ｍＡである。The weight ratio (ε / α) between ε-type copper phthalocyanine and α-type copper phthalocyanine is determined by comparing the peak height Sε and α-type crystal form in the X-ray analysis diagram shown in FIG. It is determined from the ratio of peak height Sα (Sε / Sα).
More specifically, Sε is the diffraction angle (2θ) =
9.2 ° is the peak height, and Sα is the diffraction angle (2
θ) = 6.8 ° peak height. The X-ray diffraction conditions at this time are: target: Cu, filter: Ni, voltage: 36 KV, current: 32 mA.
【００１３】実施例２ 製造例１で得た粗製ε型銅フタロシアニン５００部を５
ｌアトライターで１８０分間摩砕してε型銅フタロシア
ニンとα型銅フタロシアニンの重量比（ε／α）が１６
／８４の摩砕物を得、この摩砕物を用いた以外は実施例
１と同様にしてε型銅フタロシアニン顔料４９４ｇを得
た。この顔料の比表面積は７５ｍ2 ／ｇであった。Example 2 500 parts of the crude ε-type copper phthalocyanine obtained in Production Example 1 was added to 5 parts
The mixture was ground for 180 minutes with an attritor and the weight ratio (ε / α) of ε-type copper phthalocyanine to α-type copper phthalocyanine was 16
/ 84 was obtained, and 494 g of ε-type copper phthalocyanine pigment was obtained in the same manner as in Example 1 except that this milled material was used. The specific surface area of this pigment was 75 m 2 / g.
【００１４】実施例３ 製造例１で得た粗製ε型銅フタロシアニン５００部を５
ｌアトライターで６０分間摩砕してε型銅フタロシアニ
ンとα型銅フタロシアニンの重量比（ε／α）が３３／
６７の摩砕物を得た。得られた摩砕物を６０部をｎ−ブ
タノール１８０部および水４００部からなる混合溶剤に
投入し、加圧下１４０℃で４時間加熱した後、溶剤を蒸
留回収し、濾過、乾燥してε型銅フタロシアニン顔料４
９４ｇを得た。この顔料はＸ線回折図から完全にε型の
顔料であった。この顔料の比表面積は６２ｍ2 ／ｇであ
った。Example 3 500 parts of the crude ε-type copper phthalocyanine obtained in Production Example 1 was added to 5 parts
1 triturated with an attritor for 60 minutes and the weight ratio (ε / α) of ε-type copper phthalocyanine to α-type copper phthalocyanine was 33 /
67 grinds were obtained. 60 parts of the resulting milled material was put into a mixed solvent consisting of 180 parts of n-butanol and 400 parts of water, and heated under pressure at 140 ° C. for 4 hours. Copper phthalocyanine pigment 4
94 g were obtained. This pigment was completely ε-type pigment from the X-ray diffraction pattern. The specific surface area of this pigment was 62 m 2 / g.
【００１５】実施例４ 製造例１で得た粗製ε型銅フタロシアニン５００部を５
ｌアトライターで６０分間摩砕してε型銅フタロシアニ
ンとα型銅フタロシアニンの重量比（ε／α）が３３／
６７の摩砕物を得た。得られた摩砕物を６０部をメチル
イソブチルケトン１８０部および水４００部からなる混
合溶剤に投入し、１２０℃で４時間加熱した後、溶剤を
蒸留回収し、濾過、乾燥してε型銅フタロシアニン顔料
４９５ｇを得た。この顔料はＸ線解析図から完全にε型
の顔料であった。この顔料の比表面積は６４ｍ2 ／ｇで
あった。Example 4 500 parts of the crude ε-type copper phthalocyanine obtained in Production Example 1 was added to 5 parts
1 triturated with an attritor for 60 minutes and the weight ratio (ε / α) of ε-type copper phthalocyanine to α-type copper phthalocyanine was 33 /
67 grinds were obtained. 60 parts of the obtained milled material was put into a mixed solvent consisting of 180 parts of methyl isobutyl ketone and 400 parts of water, and heated at 120 ° C. for 4 hours. Then, the solvent was distilled and recovered, filtered and dried to obtain ε-type copper phthalocyanine. 495 g of a pigment were obtained. This pigment was completely ε-type pigment from the X-ray analysis diagram. The specific surface area of this pigment was 64 m 2 / g.
【００１６】実施例５ 実施例１で得た摩砕物〔重量比（ε／α）＝２６／７
４〕６０部をキシレン１８０部に投入し、沸点で２時間
加熱した後、メタノール５００部を加えた後、濾過、乾
燥してε型銅フタロシアニン顔料４９３ｇを得た。この
顔料はＸ線回折図から完全にε型の顔料であった。この
顔料の比表面積は５５ｍ2 ／ｇであった。Example 5 The milled material obtained in Example 1 [weight ratio (ε / α) = 26/7]
4] 60 parts of xylene was added to 180 parts of xylene, heated at the boiling point for 2 hours, 500 parts of methanol was added, followed by filtration and drying to obtain 493 g of ε-type copper phthalocyanine pigment. This pigment was completely ε-type pigment from the X-ray diffraction pattern. The specific surface area of this pigment was 55 m 2 / g.
【００１７】実施例６ 実施例１で得た摩砕物〔重量比（ε／α）＝２６／７
４〕６０部をジメチルホルムアミド１８０部に投入し、
沸点で２時間加熱した後、メタノール８００部を加えた
後、濾過、乾燥してε型銅フタロシアニン顔料４９２ｇ
を得た。この顔料はＸ線回折図から完全にε型の顔料で
あった。この顔料の比表面積は５０ｍ2 ／ｇであった。Example 6 Milled product obtained in Example 1 [weight ratio (ε / α) = 26/7]
4] Charge 60 parts to 180 parts of dimethylformamide,
After heating at the boiling point for 2 hours, 800 parts of methanol was added, followed by filtration and drying, and 492 g of ε-type copper phthalocyanine pigment.
I got This pigment was completely ε-type pigment from the X-ray diffraction pattern. The specific surface area of this pigment was 50 m 2 / g.
【００１８】実施例７ 実施例１で得た摩砕物〔重量比（ε／α）＝２６／７
４〕６０部をアニソール１８０部に投入し、沸点で２時
間加熱した後、メタノール８００部を加えた後、濾過、
乾燥してε型銅フタロシアニン顔料４９３ｇを得た。こ
の顔料はＸ線回折図から完全にε型の顔料であった。こ
の顔料の比表面積は５２ｍ2 ／ｇであった。Example 7 The milled material obtained in Example 1 [weight ratio (ε / α) = 26/7]
4] 60 parts were charged into 180 parts of anisole, heated at the boiling point for 2 hours, 800 parts of methanol was added, followed by filtration.
After drying, 493 g of ε-type copper phthalocyanine pigment was obtained. This pigment was completely ε-type pigment from the X-ray diffraction pattern. The specific surface area of this pigment was 52 m 2 / g.
【００１９】実施例８ 実施例１で得た摩砕物〔重量比（ε／α）＝２６／７
４〕６０部を安息香酸メチル１８０部に投入し、沸点で
２時間加熱した後、メタノール８００部を加えた後、濾
過、乾燥してε型銅フタロシアニン顔料４９４ｇを得
た。この顔料はＸ線回折図から完全にε型の顔料であっ
た。この顔料の比表面積は５３ｍ2 ／ｇであった。Example 8 The milled product obtained in Example 1 [weight ratio (ε / α) = 26/7]
4] 60 parts were charged into 180 parts of methyl benzoate, heated at the boiling point for 2 hours, 800 parts of methanol was added, followed by filtration and drying to obtain 494 g of ε-type copper phthalocyanine pigment. This pigment was completely ε-type pigment from the X-ray diffraction pattern. The specific surface area of this pigment was 53 m 2 / g.
【００２０】実施例９ 実施例１で得た摩砕物〔重量比（ε／α）＝２６／７
４〕６０部をトリクレン１８０部に投入し、沸点で２時
間加熱した後、メタノール５００部を加えた後、濾過、
乾燥してε型銅フタロシアニン顔料４９５ｇを得た。こ
の顔料はＸ線回折図から完全にε型の顔料であった。こ
の顔料の比表面積は６１ｍ2 ／ｇであった。Example 9 The milled material obtained in Example 1 [weight ratio (ε / α) = 26/7]
4] 60 parts were charged into 180 parts of trichlene, heated at the boiling point for 2 hours, added with 500 parts of methanol, filtered,
After drying, 495 g of ε-type copper phthalocyanine pigment was obtained. This pigment was completely ε-type pigment from the X-ray diffraction pattern. The specific surface area of this pigment was 61 m 2 / g.
【００２１】実施例１０ 製造例１で得た粗製ε型銅フタロシアニン４５０部と、
粗製β型銅フタロシアニン５０部とを５ｌアトライター
で１２０分間摩砕してε型銅フタロシアニンとα型銅フ
タロシアニンの重量比（ε／α）が２３／７７で、β型
の全てがα型に変換している摩砕物を得た。得られた摩
砕物を６０部をトルエン１８０部、ｎ−ブタノール９０
部および水４００部からなる混合溶剤に投入し、共沸温
度で４時間加熱した後、溶剤を蒸留回収し、濾過、乾燥
してε型銅フタロシアニン顔料４９６ｇを得た。この顔
料はＸ線解析図から完全にε型の顔料であった。この顔
料の比表面積は７３ｍ2 ／ｇであった。Example 10 450 parts of the crude ε-type copper phthalocyanine obtained in Production Example 1
50 parts of crude β-type copper phthalocyanine was ground for 120 minutes with a 5-liter attritor to obtain a weight ratio of ε-type copper phthalocyanine to α-type copper phthalocyanine (ε / α) of 23/77, and all β-type became α-type. A converted trituration was obtained. 60 parts of the obtained milled material were mixed with 180 parts of toluene and 90 parts of n-butanol.
And 440 g of water, and the mixture was heated at an azeotropic temperature for 4 hours. The solvent was distilled and recovered, filtered and dried to obtain 496 g of ε-type copper phthalocyanine pigment. This pigment was completely ε-type pigment from the X-ray analysis diagram. The specific surface area of this pigment was 73 m 2 / g.
【００２２】実施例１１ 製造例１で得た粗製ε型銅フタロシアニン２５０部と、
粗製β型銅フタロシアニン２５０部と、フタルイミドメ
チル銅フタロシアニン１５部とを５ｌアトライターで４
００分間摩砕して、ε型銅フタロシアニンとα型銅フタ
ロシアニンの重量比（ε／α）が１５／８５で、β型の
全てがα型に変換している摩砕物を得た。得られた摩砕
物を６０部をトルエン１８０部、ｎ−ブタノール９０部
および水４００部からなる混合溶剤に投入し、共沸温度
で４時間加熱した後、溶剤を蒸留回収し、濾過、乾燥し
てε型銅フタロシアニン顔料５１０ｇを得た。この顔料
はＸ線解析図から完全にε型の顔料であった。この顔料
の比表面積は７７ｍ2 ／ｇであった。Example 11 250 parts of crude ε-type copper phthalocyanine obtained in Production Example 1
250 parts of crude β-type copper phthalocyanine and 15 parts of phthalimidomethyl copper phthalocyanine
Milling was performed for 00 minutes to obtain a milled material in which the weight ratio (ε / α) of ε-type copper phthalocyanine to α-type copper phthalocyanine was 15/85, and all β-types were converted to α-type. 60 parts of the resulting milled material was put into a mixed solvent consisting of 180 parts of toluene, 90 parts of n-butanol and 400 parts of water, and heated at an azeotropic temperature for 4 hours. Then, the solvent was distilled and recovered, filtered and dried. Thus, 510 g of an ε-type copper phthalocyanine pigment was obtained. This pigment was completely ε-type pigment from the X-ray analysis diagram. The specific surface area of this pigment was 77 m 2 / g.
【００２３】[0023]
【発明の効果】本発明の製造法は、摩砕時間および溶剤
処理時間の大幅な短縮と生産性の大幅な向上が可能で、
しかもβ型銅フタロシアニンの発生等の問題がなく、顔
料粒子サイズのコントロールも容易であり、工業的に優
れた製造法である。According to the production method of the present invention, the grinding time and the solvent treatment time can be greatly reduced and the productivity can be greatly improved.
In addition, there is no problem such as generation of β-type copper phthalocyanine, the control of the pigment particle size is easy, and this is an industrially excellent production method.
【図１】図１は実施例１で得た摩砕物のＸ線解析図であ
る。FIG. 1 is an X-ray analysis diagram of the milled material obtained in Example 1.
【図２】図２は実施例１で得たε型銅フタロシアニン顔
料のＸ線解析図である。FIG. 2 is an X-ray analysis diagram of the ε-type copper phthalocyanine pigment obtained in Example 1.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C09B 67/50 C09B 67/20 C09B 67/54 C09B 67/04 C09B 67/12 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C09B 67/50 C09B 67/20 C09B 67/54 C09B 67/04 C09B 67/12
Claims (3)
む粗製ε型銅フタロシアニンを乾式摩砕してε型銅フタ
ロシアニンとα型銅フタロシアニンの混合物とした後、
有機溶剤中で加熱処理することを特徴とするε型銅フタ
ロシアニン顔料の製造法。Claims 1. A crude ε-type copper phthalocyanine containing ε-type copper phthalocyanine as a main component is dry-milled to obtain a mixture of ε-type copper phthalocyanine and α-type copper phthalocyanine.
A method for producing an ε-type copper phthalocyanine pigment, which is heat-treated in an organic solvent.
タロシアニンの含有率が９０重量％以上である請求項１
記載の製造法。2. The crude ε-type copper phthalocyanine contains 90% by weight or more of ε-type copper phthalocyanine.
Production method as described.
型銅フタロシアニンの混合物中のε型銅フタロシアニン
とα型銅フタロシアニンの重量比（ε／α）が１５／８
５〜３５／６５である請求項１又は２記載の製造法。3. The ε-type copper phthalocyanine and α after dry milling.
Weight ratio (ε / α) of ε-type copper phthalocyanine to α-type copper phthalocyanine in the mixture of type copper phthalocyanine is 15/8
The method according to claim 1 or 2, wherein the ratio is from 5 to 35/65.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3008485A JP3030880B2 (en) | 1991-01-28 | 1991-01-28 | Method for producing ε-type copper phthalocyanine pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3008485A JP3030880B2 (en) | 1991-01-28 | 1991-01-28 | Method for producing ε-type copper phthalocyanine pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04252273A JPH04252273A (en) | 1992-09-08 |
| JP3030880B2 true JP3030880B2 (en) | 2000-04-10 |
Family
ID=11694418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3008485A Expired - Lifetime JP3030880B2 (en) | 1991-01-28 | 1991-01-28 | Method for producing ε-type copper phthalocyanine pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3030880B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI418597B (en) * | 2006-06-16 | 2013-12-11 | Toyo Ink Mfg Co | Ε-type copper phthalocyanine pigment, its manufacturing method and coloring composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100215919B1 (en) * | 1996-11-25 | 1999-08-16 | 박경재 | Preparation of epsilon phthalocyanine pigment using new copper phthalocyanine derivative |
| JP2002121420A (en) * | 2000-08-07 | 2002-04-23 | Dainippon Ink & Chem Inc | Copper phthalocyanine pigment and method for producing the same |
| JP2007002114A (en) * | 2005-06-24 | 2007-01-11 | Toyo Ink Mfg Co Ltd | MANUFACTURING METHOD OF epsilon-TYPE PHTHALOCYANINE PIGMENT |
| JP2007100008A (en) * | 2005-10-07 | 2007-04-19 | Toyo Ink Mfg Co Ltd | METHOD FOR PREPARING epsilon-PHTHALOCYANINE PIGMENT |
| JP2009013300A (en) * | 2007-07-05 | 2009-01-22 | Dic Corp | Epsilon-type copper phthalocyanine pigment and its manufacturing method |
| EP2039727A1 (en) * | 2007-09-18 | 2009-03-25 | SOLVAY (Société Anonyme) | Preparation of epsilon copper phthalocyanine of small primary particle size and narrow particle size distribution |
| EP2060608A1 (en) * | 2007-11-15 | 2009-05-20 | SOLVAY (Société Anonyme) | Preparation of epsilon copper phthalocyanine of small primary particle size and narrow particle size distribution by kneading |
| CN102352128A (en) * | 2011-08-08 | 2012-02-15 | 江苏双乐化工颜料有限公司 | Method for preparing epsilon type phthalocyanine blue |
| JP2013060487A (en) * | 2011-09-12 | 2013-04-04 | Dic Corp | ε-TYPE COPPER PHTHALOCYANINE PIGMENT AND PIGMENT COMPOSITION FOR COLOR FILTER USING THE SAME |
-
1991
- 1991-01-28 JP JP3008485A patent/JP3030880B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI418597B (en) * | 2006-06-16 | 2013-12-11 | Toyo Ink Mfg Co | Ε-type copper phthalocyanine pigment, its manufacturing method and coloring composition |
| KR101404497B1 (en) * | 2006-06-16 | 2014-06-09 | 토요잉크Sc홀딩스주식회사 | ε-TYPE COPPER PHTHALOCYANINE PIGMENT, METHOD OF PREPARING THE SAME AND COLORED COMPOSITION |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04252273A (en) | 1992-09-08 |
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