（微細化顔料（ＰＢ−６））
式（５３）で表されるアルミニウムフタロシアニン顔料を１００部に、ピリジン２００部、キシレン８００部、およびフェニルホスホン酸５４．６部を加え、８時間加熱還流を続けた。ろ過して、メタノールで洗浄後、乾燥して、１１０部の下記式（５７）で表わされるアルミニウムフタロシアニン顔料を得た。
式（５７）
続けて、青色着色剤（ＰＢ−２）と同様の方法でソルトミリング処理を行い、微細化顔料（ＰＢ−６）を製造した。得られた着色剤の体積平均一次粒子径は３７ｎｍであった。
（微細化顔料（ＰＢ−７））
三つ口フラスコに、９８％硫酸５００部、下記式（５８）で表されるフタロシアニン顔料５０部、１,２−ジブロモ−５,５−ジメチルヒダントイン（ＤＢＤＭＨ）１０４．４部を加え撹拌し、２０℃、４時間、反応させた。その後、３℃の氷水５０００部に上記反応混合物を注入し、析出した固体をろ取し、水洗した。ビーカーに２．５％水酸化ナトリウム水溶液５００部、ろ取した残渣を加え、８０℃、１時間撹拌した。その後、この混合物をろ取、水洗、乾燥して、フタロシアニン環に臭素原子が平均で８．０個置換された顔料を得た。
次に、３口フラスコに、Ｎ−メチルピロリドンを５００部、得られたフタロシアニン環に臭素原子が平均で８．０個置換された顔料を５０部およびリン酸ジフェニル１８．２部を加え、９０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、下記式（５９）で表されるフタロシアニン顔料（ＰＢ−７）を得た。得られた着色剤の体積平均一次粒子径は２７ｎｍであった。
式（５８）
式（５９）
（微細化顔料（ＰＢ−８））
次に、３口フラスコに、Ｎ−メチルピロリドンを５００部、（ＰＢ−７）で作製したフタロシアニン環に臭素原子が平均で８．１個置換された顔料を５０部およびジフェニルホスフィン酸１３．８部を加え、９０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、下記式（６０）で表されるフタロシアニン顔料（ＰＢ−８）を得た。得られた着色剤の体積平均一次粒子径は３１ｎｍであった。
式（６０）
（微細化顔料（ＰＢ−９））
次に、３口フラスコに、Ｎ−メチルピロリドンを５００部、（ＰＢ−７）で作製したフタロシアニン環に臭素原子が平均で８．０個置換された顔料を５０部およびリン酸ビス（４−ニトロフェニル）２１．５部を加え、９０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、下記式（６１）で表されるフタロシアニン顔料（ＰＢ−９）を得た。得られた着色剤の体積平均一次粒子径は３２ｎｍであった。
式（６１）
（微細化顔料（ＰＢ−１０））
三つ口フラスコに、９８％硫酸５００部、式（５８）で表されるフタロシアニン顔料５０部、１,２−ジブロモ−５,５−ジメチルヒダントイン（ＤＢＤＭＨ）１２９．３部を加え撹拌し、２０℃、６時間、反応させた。その後、３℃の氷水５０００部に上記反応混合物を注入し、析出した固体をろ取し、水洗した。ビーカーに２．５％水酸化ナトリウム水溶液５００部、ろ取した残渣を加え、８０℃、１時間撹拌した。その後、この混合物をろ取、水洗、乾燥して、フタロシアニン環に臭素原子が平均で１０．１個置換された顔料を得た。
次に、３口フラスコに、Ｎ−メチルピロリドンを５００部、得られたフタロシアニン環に臭素原子が平均で１０．１個置換された顔料を５０部およびリン酸ジフェニル１３．９部を加え、９０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、下記式（６２）で表されるフタロシアニン顔料（ＰＢ−１０）を得た。得られた着色剤の体積平均一次粒子径は２７ｎｍであった。
式（６２）
（微細化顔料（ＰＢ−１１））
臭化アルミニウム２０３部、臭化ナトリウム４７部および臭化第二鉄５部を加温して溶融し、１４０℃で式（５８）で表されるフタロシアニン顔料５０部を加えた。１６０℃に昇温して臭素２１５．４部を吹き込みながら、１６０℃にて７時間反応させた。３℃の氷水２５００部に上記反応混合物を注入し、析出した固体をろ取し、水洗した。残渣を１％塩酸水溶液、温水、１％水酸化ナトリウム水溶液洗、温水の順で洗浄し、その後、乾燥して臭素化アルミニウムフタロシアニン９８部を得た。得られた粗製臭素化アルミニウムフタロシアニンを濃硫酸９８０部に溶解し、５０℃で３時間撹拌した。その後、３℃の氷水９８００部に上記硫酸溶液を注入し、析出した固体をろ取、水洗し、乾燥させた。次いでビーカーに２．５％水酸化ナトリウム水溶液５００部、ろ取した残渣を加え、８０℃、１時間撹拌した。その後、この混合物をろ取、水洗、乾燥して、フタロシアニン環に臭素原子が平均で１５．０個置換された顔料を得た。
次に、３口フラスコに、Ｎ−メチルピロリドンを５００部、得られたフタロシアニン環に臭素原子が平均で１５．０個置換された顔料を５０部およびリン酸ジフェニル１０．８部を加え、９０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、下記式（６３）で表されるフタロシアニン顔料（ＰＢ−１１）を得た。得られた着色剤の体積平均一次粒子径は３１ｎｍであった。
式（６３）
（微細化顔料（ＰＢ−１２））
三つ口フラスコに、塩化アルミニウム２５０部、塩化ナトリウム６０部、ヨウ素２．２５部加え１５０℃、３０分間撹拌した。そこへ、式（５３）で表されるアルミニウムフタロシアニン顔料５０部加え、１５５℃、３０分間撹拌し、溶解させた。さらにトリクロロイソシアヌル酸５８．５部加え、１９０℃、５時間撹拌した。その後、３℃の氷水５０００部に上記反応混合物を注入し、析出した固体をろ取し、水洗した。ビーカーに２．５％水酸化ナトリウム水溶液５００部、ろ取した残渣を加え、８０℃、１時間撹拌した。その後、この混合物をろ取、水洗、乾燥して、フタロシアニン環に塩素原子が平均で８．１個置換された顔料を得た。
次に、３口フラスコに、Ｎ−メチルピロリドンを５００部、得られたフタロシアニン環に臭素原子が平均で１１．９個置換された顔料を５０部およびリン酸ジフェニル２２．６部を加え、９０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、下記式（６４）で表されるフタロシアニン顔料（ＰＢ−１２）を得た。得られた着色剤の体積平均一次粒子径は２９ｎｍであった。
式（６４）
（微細化顔料（ＰＲ−１））
Ｃ．Ｉ．ピグメントレッド２５４（ＢＡＳＦ社製「Ｂ−ＣＦ」）２００部、塩化ナトリウム１４００部、およびジエチレングリコール３６０部をステンレス製１ガロンニーダー（井上製作所製）に仕込み、８０℃で６時間混練した。次にこの混練物を８０００部の温水に投入し、８０℃に加熱しながら２時間攪拌してスラリー状とし、濾過、水洗を繰り返して塩化ナトリウムおよびジエチレングリコールを除いた後、８５℃で一昼夜乾燥し、１９０部の微細化顔料（ＰＲ−１）を得た。平均一次粒子径は２７．６ｎｍであった。
(Fine refined pigment (PB-6))
To 100 parts of the aluminum phthalocyanine pigment represented by the formula (53), 200 parts of pyridine, 800 parts of xylene and 54.6 parts of phenylphosphonic acid were added, and heating and refluxing were continued for 8 hours. After filtration, washing with methanol, and drying, 110 parts of an aluminum phthalocyanine pigment represented by the following formula (57) was obtained.
Formula (57)
Subsequently, a salt milling treatment was performed in the same manner as for the blue colorant (PB-2) to produce a finer pigment (PB-6). The obtained colorant had a volume average primary particle size of 37 nm.
(Fine refined pigment (PB-7))
In a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (58), 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 4 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 8.0 average bromine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.0 bromine atoms substituted on the resulting phthalocyanine ring, and 18.2 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PB-7) represented by the following formula (59). The obtained colorant had a volume average primary particle size of 27 nm.
Formula (58)
Formula (59)
(Fine refined pigment (PB-8))
Next, in a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.1 bromine atoms substituted on the phthalocyanine ring prepared in (PB-7), and 13.8 of diphenylphosphinic acid Part was added, heated to 90 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PB-8) represented by the following formula (60). The obtained colorant had a volume average primary particle size of 31 nm.
Formula (60)
(Fine refined pigment (PB-9))
Next, in a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring prepared in (PB-7), and bis (4- 21.5 parts of nitrophenyl) was added, heated to 90 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PB-9) represented by the following formula (61). The obtained colorant had a volume average primary particle size of 32 nm.
Formula (61)
(Fine refined pigment (PB-10))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the formula (58), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 0 ° C. for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain a phthalocyanine pigment (PB-10) represented by the following formula (62). The obtained colorant had a volume average primary particle size of 27 nm.
Formula (62)
(Refinement pigment (PB-11))
203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and 50 parts of a phthalocyanine pigment represented by the formula (58) was added at 140 ° C. The temperature was raised to 160 ° C., and reaction was carried out at 160 ° C. for 7 hours while blowing 215.4 parts of bromine. The above reaction mixture was poured into 2500 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. The residue was washed with 1% hydrochloric acid aqueous solution, warm water, 1% sodium hydroxide aqueous solution and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Thereafter, the sulfuric acid solution was poured into 9800 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. Next, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added to the beaker, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 15.0 bromine atoms were substituted on the phthalocyanine ring on average.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having 15.0 bromine atoms substituted on the resulting phthalocyanine ring and 10.8 parts of diphenyl phosphate were added, The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PB-11) represented by the following formula (63). The obtained colorant had a volume average primary particle size of 31 nm.
Formula (63)
(Fine refined pigment (PB-12))
In a three-necked flask, 250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added and stirred at 150 ° C. for 30 minutes. Thereto was added 50 parts of an aluminum phthalocyanine pigment represented by the formula (53), and the mixture was stirred at 155 ° C. for 30 minutes to be dissolved. Further, 58.5 parts of trichloroisocyanuric acid was added and stirred at 190 ° C. for 5 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 8.1 average chlorine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 11.9 bromine atoms substituted on the resulting phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PB-12) represented by the following formula (64). The obtained colorant had a volume average primary particle size of 29 nm.
Formula (64)
(Refined pigment (PR-1))
C. I. 200 parts of Pigment Red 254 ("B-CF" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of refined pigment (PR-1) was obtained. The average primary particle size was 27.6 nm.