JP3879872B2 - Method for producing copper phthalocyanine - Google Patents

Description

【００３６】
【表２】

【００３７】
［比較例１］
イオウを添加しなかった以外は、実施例１の方法と同様に実施し、湯洗品としての銅フタロシアニン１７４グラムを得た。この湯洗品中のＤＭＦ不純物量は３．９％、遊離銅は０．７０％であった。
一方、酸洗品として１７１グラムの銅フタロシアニンが得られた。このもののＤＭＦ不純物量は１．９％、遊離銅は０．２８％であった。
これら湯洗品及び酸洗品のドライミリング法による顔料化品位の試験結果を［表１］及び［表２］に示した。
【００３８】
［実施例７］
反応溶媒として、ｔｅｒｔ−アミルベンゼンの代わりに、１，２，４−トリクロルベンゼン５００グラムを用いた以外は、実施例６と同様に行ない、湯洗品として１７１グラムの銅フタロシアニンを得た。このもののＤＭＦ不純物量は１．３％、遊離銅は０. ３７％であった。
一方、酸洗品として１７０グラムの銅フタロシアニンを得た。このもののＤＭＦ不純物量は０．７％、遊離銅は０. ０５％であった。
これら湯洗品及び酸洗品のドライミリング法による顔料化品位の試験結果を［表３］及び［表４］に示した。
【００３９】
［比較例２］
硫化銅（ＩＩ）を用いずに、塩化第一銅を３０．３グラムを用いた以外は、実施例７と同様に行ない、湯洗品としての銅フタロシアニン１７３グラムを得た。この湯洗品中のＤＭＦ不純物量は４．６％、遊離銅は０．６２％であった。
一方、酸洗品として１７１グラムの銅フタロシアニンが得られた。このもののＤＭＦ不純物量は２．３％、遊離銅は０．１３％であった。
これら湯洗品及び酸洗品のドライミリング法による顔料化品位の試験結果を［表３］及び［表４］に示した。
【００４０】
【表３】

【００４１】
【表４】

【００４２】
【発明の効果】
本発明の方法によって得られる銅フタロシアニンは、遊離銅及び顔料化等の工業的な処理において阻害となるような不純物が少ない製品が得られるという特徴を有しており、特に、（１）ドライミリング法による顔料化の溶媒処理において結晶型の転移速度が向上する。この転移速度が向上することは、顔料化処理時間の短縮となり、工業的に著しいコスト削減になる。（２）遊離銅が少ないことは、硫酸等による顔料化処理法において、排出する廃液処理の際における銅イオンの処理の負担を軽減する工業的な効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing copper phthalocyanine that has few impurities and free copper and is extremely easy to be pigmented.
[0002]
[Prior art]
Copper phthalocyanine is phthalic acid or a phthalic acid derivative (hereinafter referred to as “phthalic acid”), urea or a urea derivative (hereinafter referred to as “urea”) and a copper compound in the presence of a phthalocyanination catalyst such as a molybdenum compound. A method of heating and producing in an active organic solvent is known as an industrially established method.
[0003]
In this production method, to obtain copper phthalocyanine used for pigmentation, after completion of the heating reaction, the solvent is usually removed from the reaction product by distillation under reduced pressure, and the resulting residue is washed with hot water. The method is adopted industrially.
[0004]
[Problems to be solved by the invention]
However, these copper phthalocyanines still have a large amount of unreacted substances, free copper and other impurities, which often causes inconveniences when pigmented. As a pigmentation method, for example, there is a dry milling method (JP-A-4-320458, etc.) which is a pigmentation method for solvent treatment after dry pulverization, and when these impurities are present in the solvent treatment of this dry milling method In general, the crystal transition rate becomes slow, and a reduction in pigmentation quality such as sharpness and coloring is observed.
[0005]
In recent years, when copper phthalocyanine is subjected to a treatment such as pigmentation, it is required that the amount of copper compound is reduced as much as possible in the waste liquid discharged during the treatment.
[0006]
Although it is economically preferable to use a copper phthalocyanine product obtained by hot water washing, as described above, a large amount of free copper and other impurities causes problems in use of the product and the environment. For this reason, acid washing may be performed using diluted sulfuric acid or the like instead of hot water washing to reduce free copper and other impurities. In this case, there is a drawback that the product yield is lowered and a step of neutralizing the used acid is required.
[0007]
Thus, the present invention is a product in which impurities are reduced as compared with the conventional method for producing copper phthalocyanine, whereby crystal transition is easy in pigmentation, for example, solvent treatment of dry milling method, and free copper is low. It is in providing the method of manufacturing.
[0008]
[Means for Solving the Problems]
As a result of intensive studies on impurities in the so-called Weiler method, which is a conventional method for producing copper phthalocyanine, the present inventors have found that impurities extracted into N, N-dimethylformamide (hereinafter abbreviated as DMF) are particularly pigmented. In particular, in the solvent treatment of the dry milling method, it was found that the rate of crystal transition was significantly inhibited, and as a result of searching for an effective production method using the amount of impurities as an index, a small amount of sulfur was added to the reaction system. The present invention has been completed by finding that the above problems can be solved.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The method according to the present invention comprises an inert organic solvent using phthalic acid or a phthalic acid derivative (abbreviated as phthalic acid or the like), urea or a urea derivative (abbreviated as urea or the like), a copper compound and molybdenum or a molybdenum compound as a catalyst. In the method for producing copper phthalocyanine by heating reaction in the presence or absence of sulfur, sulfur is added to this reaction system.
[0010]
As the phthalic acid or the like used in the method according to the present invention, any phthalic acid that can be finally obtained as copper phthalocyanine or a derivative thereof in the method according to the present invention can be employed. For example, it may be a salt such as phthalic acid, phthalic anhydride, phthalimide, sodium phthalate, phthalamic acid or phthalonitrile, or a mixture thereof. The phthalic acid or the like may have a substituent that is inert in the reaction system, such as an alkyl group, a benzyl group, a phenyl group, or a chloro group.
[0011]
Examples of urea include urea, biuret, and triuret. Urea is generally used, but it may include biuret, triuret, and the like. The amount of urea used varies depending on the type of phthalic acid used normally, but is selected from 1.5 to 3.5 mol times, preferably 2.0 to 3.0 mol times relative to phthalic acid etc. It is.
[0012]
Examples of the copper compound include copper powder, copper oxide, copper hydroxide, copper sulfate, cuprous chloride, cupric chloride, copper acetate, etc., but generally copper chloride such as cuprous chloride. Is used. The usage-amount of a copper compound is normally chosen 0.2-0.3 mol times with respect to phthalic acid etc., Preferably it is chosen from 0.23-0.27 mol times.
[0013]
Examples of the molybdenum or molybdenum compound as the catalyst include metal molybdenum and molybdenum salts such as ammonium molybdate and sodium molybdate, and molybdenum compounds such as ammonium phosphomolybdate and molybdenum oxide. Is used. The amount of the catalyst used is 0.003 to 5% by weight, preferably 0.02 to 0.5% by weight, based on phthalic acid or the like.
[0014]
In the present invention, as the solvent, an inert organic solvent used for the production of copper phthalocyanine by a known urea method, so-called Weiler method, can be used as long as it meets the purpose of the present invention. For example, an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent, or a solvent substituted with such halogen or the like can be used. Specifically, inert alkylbenzene solvents such as diisopropylbenzene, monoisopropylxylene, diisopropyltoluene, tert-amylbenzene, naphthalene solvents such as isopropylnaphthalene and tert-butylnaphthalene, and halogenated aromas such as trichlorobenzene. Or nitrated aromatic solvents such as nitrobenzene. These solvents can be used singly or as a mixed solvent, but aromatic hydrocarbon solvents, particularly alkylbenzene solvents are preferred in view of environmental sanitation and price.
[0015]
The amount of the solvent used is usually 1.5 to 7 times by weight, preferably 1.7 to 3 times by weight with respect to phthalic acid or the like.
Moreover, it is also possible to implement reaction of this invention in absence of an organic solvent by using it as a solvent substantially by using urea excessively.
[0016]
The reaction conditions for producing copper phthalocyanine in the present invention are selected from 140 to 250 ° C., preferably 170 to 220 ° C. as the temperature of the heating reaction, and 0 to 20 kg / square centimeter G as the reaction pressure. Loss from the reaction system due to entrainment of the solvent with the reaction gas, decomposition of urea as a raw material and decomposition of phthalic acid, loss of intermediate products such as ammonium cyanate, In consideration of the operability of the reactor, 2 to 5 kg / square centimeter G is preferable.
[0017]
The reaction method is carried out batchwise or continuously. After completion of the reaction, the solvent is removed from the reaction product by distillation under reduced pressure or the like, and the obtained residue is washed with 3 to 10 times by weight of hot water (60 to 80 ° C.). Furthermore, when a product with high purity is desired, a purification method in which the residue obtained after removing the solvent is washed with dilute sulfuric acid (for example, 5 to 10 times by weight) can be employed.
[0018]
Sulfur used in the present invention may be any kind such as crystalline sulfur such as orthorhombic and monoclinic crystals, rubbery sulfur, and amorphous sulfur such as sulfur flower, but is usually readily available. It is economical to use stable orthorhombic sulfur.
[0019]
As a method for adding sulfur, sulfur may be added to a reaction system as it is together with raw materials such as phthalic acid or urea, or may be added in a form dissolved or dispersed in a solvent used for the reaction.
It is also possible to add sulfur to molten urea together with copper chloride and molybdenum compounds and add them to the reaction system. In this case, it is presumed that at least a part of the added sulfur reacts with the copper compound to become copper sulfide before being added to the reaction system.
[0020]
The amount of sulfur added is selected from 0.05 to 4% by weight, preferably 0.1 to 1% by weight, relative to phthalic acid or the like. When the addition amount is 0.01% by weight or less, the effect is hardly recognized, and even when the addition amount is 4% by weight or more, the effect becomes constant and is economically wasteful.
In addition to sulfur, a metal sulfide such as sodium sulfide may coexist to form a polysulfide substantially.
[0021]
Further, by using copper sulfide as a part of the copper compound instead of adding sulfur, substantially the same effect as the addition of sulfur can be obtained. Examples of the copper sulfide include cuprous sulfide (copper sulfide (I)), cupric sulfide (copper sulfide (II)), and polysulfide (polycopper sulfide). Cupric is preferred. The amount of copper sulfide used is selected from 0.05 to 4% by weight, preferably 0.1 to 1% by weight, based on phthalic acid, etc. in terms of sulfur. When the amount used is 0.01% by weight or less, almost no effect is observed. Even when the amount used is 4% by weight or more, the effect is constant and is economically wasteful.
[0022]
As described above, copper phthalocyanine obtained by adding sulfur or using copper sulfide has less free copper and less impurities extracted by DMF, so when used in the pigmentation process, particularly the dry milling process, There is a feature that can proceed advantageously.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by an Example. “%” Represents wt% unless otherwise specified, and the values used for the free copper content and impurities extracted by DMF were calculated by the following measurement method. The comparison of pigmentation quality by the dry milling method is also shown below.
[0024]
(1) Method for measuring free copper content After accurately weighing 3.0 grams of copper phthalocyanine, 30.0 grams of sulfuric acid was added and dissolved, and then added to 150 grams of cold water, followed by stirring at 90 ° C for 30 minutes. Next, the precipitate is filtered, and the filter cake is washed with ion-exchanged water. The obtained filtrate (including washing water for the filter cake) is cooled to room temperature, and the total amount is made 500 ml. The copper ion concentration in this solution is measured by atomic absorption method, and displayed by weight percentage (in terms of metallic copper) with respect to the sample used.
[0025]
(2) Measuring method of impurities extracted by DMF (referred to as DMF impurities) 10.0 g of copper phthalocyanine is precisely weighed and treated with 140 g of DMF at 140 ° C. to extract impurities. After filtering off the insoluble matter, the residue obtained by distilling off DMF under reduced pressure is used as an impurity, and is indicated by the weight percentage of the sample used.
[0026]
(3) Comparison of pigmentation quality by dry milling method In the dry milling method, first, in order to finely pulverize copper phthalocyanine, dry pulverization is performed with a ball mill or the like. Since it changes to a mold and agglomerates firmly, it cannot be used as a pigment as it is.
For this reason, it is further immersed in a solvent such as aromatics such as toluene and xylene, alcohols such as propanol and ethylene glycol, or diols to transfer α-type crystals to β-type, and in the solvent. This is a pigmentation method in which copper phthalocyanine having pigment suitability is dispersed.
Therefore, in the pigmentation by this method, there are few α-type crystals generated during dry pulverization, and it is desirable that the transition from α-type to β-type occurs rapidly during solvent treatment.
[0027]
In the present invention, the pigmentation quality by the dry milling method was compared as follows.
100 grams of copper phthalocyanine was dry pulverized in a ball mill at 20-30 ° C. for 10 hours, and then immersed in isopropanol at 35 ° C. About the sample for every elapsed time in this solvent treatment, the diffraction intensity by α-type and β-type crystals was measured by the powder X-ray diffraction method, the existence ratio of α-type crystals was obtained as a percentage, and used as an index of pigmentation quality .
[0028]
[Example 1]
180 grams of phthalimide, 30.3 grams of cuprous chloride, 170 grams of urea, 0.09 grams of ammonium molybdate, 310 grams of tert-amylbenzene (trade name, Hysol P, Nippon Oil Co., Ltd., alkylbenzene mixture) as a solvent And 0.9 gram of sulfur were charged into a 1 liter glass autoclave and reacted at a pressure of 2.5 kg / square centimeter G for 3.5 hours while gradually raising the reaction temperature from 170 ° C. to 210 ° C. . The solvent was distilled off under reduced pressure from the resulting slurry at 175 ° C. and 5 mmHg over 3 hours.
[0029]
To this residue, 1200 grams of water was added and stirred at 60 ° C for 2 hours and washed with hot water. After filtration, the cake was washed with 800 grams of hot water at 60 ° C, dried and 172 grams of water. Copper phthalocyanine (hereinafter, a product washed with hot water is referred to as a “bathwashed product”) was obtained. The amount of DMF impurities in this hot water washing product was 2.3%, and the free copper was 0.51%.
[0030]
On the other hand, the above residue was slurry-washed with 1200 grams of 1% dilute sulfuric acid at 60 ° C. for 2 hours, filtered, and washed with hot water at 60 ° C. until no acid was present in the wash water. And dried to obtain 169 grams of copper phthalocyanine (hereinafter, a product washed with dilute sulfuric acid is referred to as “pickled product”). The amount of DMF impurities in the pickled product was 0.7%, and the free copper was 0.17%. [Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[0031]
[Example 2]
The procedure was the same as in Example 1 except that the amount of sulfur added was 0.36 grams, and 173 grams of copper phthalocyanine was obtained as a hot water washing product. The amount of DMF impurities in this hot water washing product was 3.0%, and free copper was 0.59%.
On the other hand, 169 grams of copper phthalocyanine was obtained as a pickled product. This product had a DMF impurity content of 1.2% and free copper of 0.22%. [Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[Example 3]
The procedure was the same as in Example 1 except that the amount of sulfur added was 1.44 grams, and 172 grams of copper phthalocyanine was obtained as a hot water washing product. The amount of DMF impurities in this hot water washing product was 1.9%, and free copper was 0.48%.
On the other hand, 169 grams of copper phthalocyanine was obtained as a pickled product. This product had a DMF impurity content of 0.7% and a free copper content of 0.15%. [Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[0032]
[Example 4]
The procedure was the same as Example 1 except that 0.2 g of anhydrous sodium sulfide was further added in addition to sulfur, and 172 g of copper phthalocyanine was obtained as a hot water washing product. This had a DMF impurity content of 2.4% and free copper of 0.49%.
On the other hand, 168 grams of copper phthalocyanine was obtained as a pickled product. This had a DMF impurity content of 0.7% and free copper of 0.15%.
[Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[0033]
[Example 5]
Instead of adding sulfur, 2.68 grams of copper (II) sulfide was used and 27.5 grams of cuprous chloride was used, except that 170 grams of copper phthalocyanine was obtained as a hot water product. . The amount of DMF impurities in this product was 2.5%, and the free copper was 0.31%.
On the other hand, 167 grams of copper phthalocyanine was obtained as a pickled product. This had a DMF impurity content of 0.9% and free copper of 0.13%.
[Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[0034]
[Example 6]
The procedure was the same as Example 5 except that 3.35 grams of copper (II) sulfide was used and 26.8 grams of cuprous chloride was used, and 171 grams of copper phthalocyanine was obtained as a hot water washing product. This had a DMF impurity content of 2.1% and free copper of 0.28%.
On the other hand, 168 grams of copper phthalocyanine was obtained as a pickled product. The amount of DMF impurities in this product was 0.7%, and the free copper was 0.12%.
[Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[0035]
[Table 1]

[0036]
[Table 2]

[0037]
[Comparative Example 1]
Except not adding sulfur, it implemented like the method of Example 1, and obtained 174 grams of copper phthalocyanine as a hot-water washing article. The amount of DMF impurities in this hot water washing product was 3.9%, and free copper was 0.70%.
On the other hand, 171 grams of copper phthalocyanine was obtained as a pickled product. This product had a DMF impurity content of 1.9% and free copper of 0.28%.
[Table 1] and [Table 2] show the test results of the pigmentation quality by the dry milling method for these hot-washed products and pickled products.
[0038]
[Example 7]
The reaction was performed in the same manner as in Example 6 except that 500 g of 1,2,4-trichlorobenzene was used instead of tert-amylbenzene, and 171 g of copper phthalocyanine was obtained as a hot water washing product. This had a DMF impurity content of 1.3% and free copper of 0.37%.
On the other hand, 170 grams of copper phthalocyanine was obtained as a pickled product. This had a DMF impurity content of 0.7% and a free copper content of 0.05%.
[Table 3] and [Table 4] show the test results of the pigmentation quality of these hot-washed products and pickled products by the dry milling method.
[0039]
[Comparative Example 2]
Except for using 30.3 g of cuprous chloride without using copper (II) sulfide, the same procedure as in Example 7 was carried out to obtain 173 g of copper phthalocyanine as a hot water washing product. The amount of DMF impurities in this hot-washed product was 4.6%, and free copper was 0.62%.
On the other hand, 171 grams of copper phthalocyanine was obtained as a pickled product. This had a DMF impurity content of 2.3% and free copper of 0.13%.
[Table 3] and [Table 4] show the test results of the pigmentation quality of these hot-washed products and pickled products by the dry milling method.
[0040]
[Table 3]

[0041]
[Table 4]

[0042]
【The invention's effect】
The copper phthalocyanine obtained by the method of the present invention is characterized in that a product with few impurities that can be hindered in industrial treatment such as free copper and pigmentation can be obtained. The transition rate of the crystal form is improved in the solvent treatment for pigmentation by the method. This improvement in the transfer rate shortens the pigmentation processing time, resulting in a significant cost reduction industrially. (2) The fact that there is little free copper has an industrial effect of reducing the burden of copper ion treatment during waste liquid treatment in the pigmentation treatment method using sulfuric acid or the like.

Claims (5)

  Phthalic acid or phthalic acid derivatives (abbreviated as phthalic acid, etc.), urea or urea derivatives, copper compounds, and molybdenum or molybdenum compounds as catalysts, and heat-reacted in the presence or absence of an inert organic solvent to produce copper. A method for producing copper phthalocyanine, comprising adding sulfur in the method for producing phthalocyanine. The method according to claim 1 , wherein the sulfur to be added is 0.05 to 4% by weight relative to phthalic acid or the like. Phthalic acid or phthalic acid derivatives (abbreviated as phthalic acid, etc.), urea or urea derivatives, copper compounds, and molybdenum or molybdenum compounds as catalysts, and heat-reacted in the presence or absence of an inert organic solvent to produce copper. In the method for producing phthalocyanine, copper sulfide is used as a part of the copper compound, and the amount of copper sulfide used is 0.1 to 1% by weight with respect to phthalic acid or the like in terms of sulfur. A method for producing copper phthalocyanine. The method according to any one of claims 1 to 3, wherein the obtained copper phthalocyanine is a product used in the pigmentation step. The method according to claim 4, wherein the pigmentation step is a dry milling step.