JPH0116272B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an efficient method for producing ε (epsilon) type metal-free phthalocyanine. Phthalocyanine is highly valued for its properties such as high coloring power, beautiful color tone, and excellent heat resistance, chemical resistance, and light resistance, and has a wide range of applications in the color material industry, and its importance is increasing year by year. There is. Further, as an organic semiconductor, consideration is being given to its use in electronics-related applications such as photoconductor elements. Phthalocyanines include metal phthalocyanines and metal-free phthalocyanines, and phthalocyanines with different crystal forms are known within each phthalocyanine. The metal-free phthalocyanine related to the present invention includes:
It is known that there are crystals called α-type, β-type, γ-type, and X-type depending on the crystal shape. These are X
Easily distinguished by comparing line diffraction patterns. The β type is a blue pigment with a strong green tinge produced by heating aminoiminoisoindolenine in trichlorobenzene at about 200°C. The α type is a greenish blue pigment obtained by the so-called acid paste method, in which metal-free phthalocyanine is dissolved in sulfuric acid, poured into water, and reprecipitated. Among them, it is known that crystal transition occurs to the more stable β form. Other known crystal forms include the γ type, which does not exhibit clear crystallinity, and a method for producing X type metal-free phthalocyanine by milling for a sufficient period of time.
This method requires grinding for more than 100 hours, which consumes a large amount of electricity and requires complicated milling equipment, and when used as an organic semiconductor, it has a negative effect on the properties of the semiconductor. A disadvantage is that harmful impurities can be introduced into the phthalocyanine from the metal or ceramic milling equipment. Furthermore, a method is known in which α-type metal-free phthalocyanine is treated with X-type metal-free phthalocyanine and an aliphatic organic solvent, but the X-type metal-free phthalocyanine must be produced in advance, and in this case, However, it is accompanied by the above-mentioned drawbacks. For example, even if only a small amount of Type X is to be manufactured, this is not a preferable method from a process standpoint since it requires two stages of operation. Furthermore, it cannot be said that these methods necessarily yield phthalocyanine with good crystallinity. In other words, in X-ray diffraction,
No clear peak appears on the high angle side, which indicates that the crystal transition from the raw material phthalocyanine to the target metal-free phthalocyanine has not been completed. In other words, it cannot be said to be a metal-free phthalocyanine with good crystallinity. The present invention relates to a method for producing ε-type metal-free phthalocyanine that does not require milling and is extremely efficient in production. Furthermore, it is a manufacturing method that allows crystal transition to occur in a short period of time. That is, the following mixture was dimethylformamide, N-methyl 2-
60 in an aprotic polar solvent selected from pyrrolidone, acetamide, ethylene carbonate, γ-butyrolactone and dimethyl sulfoxide.
This is a method for producing ε-type metal-free phthalocyanine, which involves heat treatment at a temperature of 100°C or higher, preferably 100°C to 200°C. (A) α-type metal-free phthalocyanine 100 parts by weight (B) Benzene nucleus with amino group: nitro group: alkyl group: alkoxy group: cyano group: mercapto group:
Halogen atom: Sulfonic acid group: Carboxylic acid group:
Metal salts, ammonium salts, or salts with cationic activators of sulfonic acid groups or carboxylic acid groups: substituents via divalent bonds of methylene groups, carbonyl groups, sulfonyl groups, or imino groups,
A metal or metal-free phthalocyanine derivative introduced with a substituent selected from 0.1 to 10 parts by weight The ε-type metal-free phthalocyanine referred to in the present invention is
When the linear diffraction angle (2θ) is measured, it has diffraction angles corresponding to interplanar spacings of 7.6° and 9.1°. In the production of the present invention, there is no need for seeds of phthalocyanine having the crystal form to be obtained, for example, the ε-type crystal form. In addition, what is particularly advantageous industrially is that the manufacturing process is simple, that is, by simply heating α-type metal-free phthalocyanine and a small amount of a phthalocyanine derivative in which a substituent has been introduced into the benzene nucleus in an aprotic polar solvent. An ε-type metal-free phthalocyanine with good crystallinity can be obtained, and surprisingly, the transition occurs in a short time. Specifically, the metastasis occurs in about 10 minutes and does not change even after a long period of time (more than 1 hour). The metal-free phthalocyanine that is the raw material of the present invention is obtained by acid treatment of metal phthalocyanine containing metal phthalocyanine (for example, lithium phthalocyanine, sodium phthalocyanine, calcium phthalocyanine, magnesium phthalocyanine, etc.) that can be demetalized with a strong acid such as sulfuric acid. Also, those made directly from phthalodinitrile, aminoiminoisoindolenine, alkoxyiminoisoindolenine, etc. are used. Metal-free phthalocyanine obtained by the already known method is dissolved in sulfuric acid or made into a sulfate salt, and then poured into water or ice water, and then reprecipitated or hydrolyzed, resulting in a crystal form called α-type. The treated product can be used in a dry state or in the form of a water paste. As the metal or metal-free phthalocyanine derivative used in the present invention, conventionally known derivatives are used. The substituents of phthalocyanine having a substituent on the benzene nucleus include amino group, nitro group, alkyl group, alkoxy group, cyano group, mercapto group, and halogen atom, as well as sulfonic acid group,
Examples include carboxylic acid groups or their metal salts, ammonium salts, and salts with cationic activators. Various derivatives in which the benzene nucleus is substituted via a divalent bond, such as a methylene group, a carbonyl group, a sulfonyl group, or an imino group, are also advantageously used.
For example −CH ₂ N, −CON, −SO ₂ N, −NH
−, −CO−, −SO ₂ −, −SO ₃ , −COCH ₂ −, −
CH ₂ CH ₂ −, etc. The phthalocyanine derivative used in the present invention is conventionally added for the purpose of improving dispersibility, dispersion stability, fluidity, etc. when phthalocyanine pigments are used in paints and the like. That is, it is known to have effects such as improving fluidity, suppressing pigment crystallization, and suppressing crystal conversion when used in paints or gravure inks. The present invention differs from the prior art in that by heat-treating α-type metal-free phthalocyanine and these phthalocyanine derivatives in an aprotic polar solvent, the present invention achieves good crystallinity and clear hue without milling. This invention provides a metal-free phthalocyanine having the following properties. In the present invention, examples of the aprotic polar solvent used include dimemelformamide, N
-methyl 2-pyrrolidone, acetamide, ethylene carbonate, etc., and the amount of the solvent is
The amount used is at least enough to cover the α-type metal-free phthalocyanine and the phthalocyanine derivative, preferably at least the amount that can be stirred. Also, a mixture of 100 parts by weight of metal-free phthalocyanine and 0.5 to 20 parts by weight of a phthalocyanine derivative is used. This mixing ratio is appropriately selected depending on the object to be used so as not to impede the properties as a pigment or the electrical properties. The temperature range in the crystal transition step of the present invention is 60
℃ or higher, preferably 100℃ to 200℃. Usually carried out at a temperature of 60°C to 240°C. Further, crystal nuclei of ε-type metal-free phthalocyanine may be used as in the conventionally known crystal transition process. The metal-free phthalocyanine obtained by the present invention can also be used as a photoconductor element of an electrophotographic photosensitive plate. Reference examples and examples are shown below. Examples include "part" and "%"
and indicate parts by weight and % by weight, respectively. Reference Example 1 14.5 parts of aminoiminoisoindolenine was heated at 200°C for 2 hours in 50 parts of trichlorobenzene,
After the reaction, the solvent was removed by steam distillation, purified with a 2% aqueous hydrochloric acid solution, followed by a 2% aqueous sodium hydroxide solution, thoroughly washed with water, and dried to obtain 8.8 g of metal-free phthalocyanine (yield 70%). ) was obtained.
The metal-free phthalocyanine thus obtained has a β-type crystal form. The transition from β type to α type is produced by the following operation. Approximately 1 part of β-type metal-free phthalocyanine is gradually dissolved in 10 parts of 98% sulfuric acid at a temperature below 5°C, and the mixture is stirred for about 2 hours while maintaining the temperature below 5°C. Subsequently, the sulfuric acid solution is poured into 200 parts of ice water, and the precipitated crystals are filtered. The obtained crystals are washed with distilled water until no acid remains and are dried to obtain 0.95 parts of α-type metal-free phthalocyanine. Reference example 2 15 parts of copper phthalocyanine, trichlorobenzene
500 parts acetyl chloride (ClCH ₂ COCl)
80 to 80 parts of a mixture of 25 parts and 70 parts of aluminum chloride
The mixture was stirred at 90°C for 10 hours, then poured into ice water, and the solid content was filtered, washed with water, and dried to obtain a compound represented by the following formula. Cu-PC (-COCH ₂ Cl) _1.2 (In the formula, Cu-Pc is a copper phthalocyanine residue, and 1.2 indicates the average number of substitutions determined by analysis. The same applies hereinafter.) This compound is reacted with amines to form various phthalocyanine derivatives. Obtained. Examples of this series of copper phthalocyanine derivatives are shown in Table 1.

[Table] Example 1 N,N'-dimethylformamide (hereinafter referred to as DMF)
) 200 parts α-type metal-free phthalocyanine 20
part, the compound shown in Reference Example 1 (Cu-Pc(-
Mix 0.5 parts of COCH ₂ Cl) _1.2 ) and stir for 10 minutes at a temperature of 140°C to 150°C. After cooling, the mixture was filtered and washed with water to obtain 20.3 parts of ε-type metal-free phthalocyanine. FIG. 1 shows the results of measuring the X-ray diffraction angle of the obtained ε-type metal-free phthalocyanine with Cukd/Ni using a self-recording X-ray diffractometer (powder). The horizontal axis indicates the diffraction angle 2θ. The results of similar measurements for the α-type and β-type are shown in FIGS. 2 and 3. Example 2 Phthalocyanine derivatives shown in Table 2 were obtained by reacting chlorosulfonated copper phthalocyanine, metal-free phthalocyanine, nickel phthalocyanine, and cobalt phthalocyanine with various amines by a conventional method.

【table】

[Table] 1 part of each of the above phthalocyanine derivatives, 200 parts of N-methyl 2-pyrrolidone, and 10 parts of α-type metal-free phthalocyanine are mixed and stirred at 180 to 200°C for 10 minutes. After cooling, the mixture was filtered, washed with water, and dried to obtain 10.1 parts of ε-type metal-free phthalocyanine. Example 3 0.2 parts of the following phthalocyanine derivative obtained by condensing copper phthalocyanine, phthalimide, and formaldehyde in concentrated sulfuric acid, 100 parts of DMF, and 5 parts of α-type metal-free phthalocyanine were mixed and stirred at 100° C. for 30 minutes. After cooling, the mixture was filtered and washed with water to obtain 5 parts of ε-type metal-free phthalocyanine. Example 4 Copper phthalocyanine was chloromethylated and reacted with various amines to obtain copper phthalocyanine derivatives. Examples of what was obtained are shown in Table 3.

【table】

[Table] Similar results were obtained by treating the various phthalocyanine derivatives shown in Table 3 with DMF and α-type metal-free phthalocyanine in the same manner as in Example 1. Example 5 α-type metal-free phthalocyanine water paste 200g
(solid content 70%), γ-butyrolactone 500g, Table 3
A mixture of 2 parts of the compound shown in is stirred at 125°C for 10 minutes, cooled, filtered, and washed with water to obtain 140.0 parts of ε-type metal-free phthalocyanine. Example 6 1 part of the compound used in Example 3 and 100 parts of β-type metal-free phthalocyanine were dissolved in concentrated sulfuric acid and poured into water.
After filtering, washing with water, and drying, 96 parts of uniform and fine α-type metal-free phthalocyanine was obtained. 10 parts of the resultant, dimethyl sulfoxide
150 parts were stirred at 150°C for 1 hour. After cooling,
Filtered, washed with water, dried, ε-type metal-free phthalocyanine
Got 9.8 copies.

[Brief explanation of drawings]

Figures 1 to 3 show ε type, α type, and β type, respectively.
An X-ray diffraction diagram of type-free gold phthalocyanine is shown.

Claims (1)

[Claims] 1. The following mixture is dimethylformamide, N-
60°C or higher, preferably 100°C to 200°C in an aprotic polar solvent selected from methyl 2-pyrrolidone, acetamide, ethylene carbonate, γ-butyrolactone and dimethyl sulfoxide.
1. A method for producing an ε-type metal-free phthalocyanine, which comprises heat-treating at ℃. (A) α-type metal-free phthalocyanine 100 parts by weight (B) Benzene nucleus, amino group: nitro group: alkyl group: alkoxy group: cyano group: mercapto group: halogen atom: sulfonic acid group: carboxylic acid group: sulfonic acid group or a metal salt of a carboxylic acid group, an ammonium salt, or a salt with a cationic activator: a metal introduced with a substituent selected from a substituent via a divalent bond of a methylene group, a carbonyl group, a sulfonyl group, or an imino group. or metal-free phthalocyanine derivative 0.1 to 10 parts by weight