JP2961901B2 - Method for producing oxytitanium phthalocyanine crystal - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing oxytitanium phthalocyanine (hereinafter abbreviated as TiOPc) crystals, and more particularly, to dichlorotitanium phthalocyanine (hereinafter abbreviated as TiCl ₂ Pc) and / or. By performing a specific treatment using dibromotitanium phthalocyanine (hereinafter abbreviated as TiBr ₂ Pc) as a raw material, a powder X-ray diffraction spectrum has a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 °. The present invention relates to a method for producing a TiOPc crystal.

[0002]

2. Description of the Related Art Phthalocyanines are useful compounds for coloring paints, printing inks, resins or as electronic materials.
In recent years, it has been actively used as a material for electrophotography. In the present invention, as a result of various studies on the production method of TiOPc, the existence of three types of crystal forms was confirmed, and their production methods were proposed (JP-A-62-256865 and JP-A-6-256865).
2-25667, JP-A-63-366). The above production method is a method of synthesizing TiCl ₂ Pc by a condensation reaction of orthophthalodinitrile and titanium tetrachloride, hydrolyzing with water, and treating with N-methylpyrrolidone to obtain TiOPc.

According to JP-A-61-2117050, TiCl ₂ Pc is boiled with concentrated aqueous ammonia and hydrolyzed, and then washed with acetone using a Soxhlet extractor to obtain TiOPc. Methods for producing TiOPc of a specific crystal form using physical means include Ti
A method has been proposed in which OPc is ground with a sand grinder together with polyethylene glycol, and then treated with dilute sulfuric acid to cause crystal transformation (see JP-A-64-17066).

[0004]

However, the above-mentioned conventional method requires not only delicate control of the heating rate during the condensation reaction, the temperature during the hydrolysis or the stirring conditions during the milling, but also the purpose. There is a tendency that two types of crystal forms are mixed in the product,
The production of TiOPc crystals suitable for practical use has not been enough. The present inventor has conducted intensive studies to solve such problems, and as a result, has found that TiCl ₂ Pc and / or Ti
By subjecting Br ₂ Pc to a specific treatment, X
Angle of X-ray diffraction spectrum (2θ ± 0.2 °) 2
Crystalline form of TiOP having a major diffraction peak at 7.3 °
The inventors have found that c is formed, and have reached the present invention. That is,
An object of the present invention is to produce TiOPc useful for various uses in a factory advantageous manner. The crystal form intended in the present invention has the strongest diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 ° in the powder X-ray diffraction spectrum, and is usually 9.5 °, 24 °. .1 ° has a relatively clear peak.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
After contacting TiCl ₂ Pc or TiBr ₂ Pc with phenols, (a) water and coexisting organic solvents other than phenols and aromatic hydrocarbons, or (b) phenols and alcohols coexisting with alcohols It is easily achieved by contact with an organic solvent other than the class. Hereinafter, the present invention will be described in more detail. The phenol used in the present invention is a monohydric or polyhydric phenol, and examples thereof include phenol, catechol, resorcin, hydroquinone, and pyrogallol. Of course, phenols other than the above can also be used.

[0006] Phenols are generally solid at normal temperature, but when contacting TiCl ₂ Pc and / or TiBr ₂ Pc, it is necessary to maintain the temperature at or above the melting point of the phenols used. Further, if necessary, the operability can be improved by coexisting a solvent such as water up to about 80%, preferably 50% or less. TiCl ₂ P
The contact treatment temperature of c and / or TiBr ₂ Pc with phenols is usually 20 to 200 ° C., preferably 50 to 20 ° C.
It is in the range of 0 ° C. If the treatment temperature is too high, a part of the phthalocyanine may be decomposed, and if the treatment temperature is too low, the reaction rate decreases, which is not practical.

[0007] TiCl ₂ Pc and / or TiBr ₂ Pc
There is no particular limitation on the ratio of phenols to phenols, but a weight ratio of 1: 5 to 100 is preferable in consideration of the contact efficiency between the two. If the use ratio of the phenols is too low, the contact efficiency becomes poor and the treatment time becomes long. Processing time is Ti
Preferably, it is selected such that Cl ₂ Pc and / or TiBr ₂ Pc are sufficiently converted to an intermediate as shown in the powder X-ray diffraction spectrum of FIG. The time required for the conversion is selected mainly according to the processing temperature and the amount of phenol used,
Specifically, a suitable value may be appropriately selected according to each case. For example, the temperature is usually 1 to 3 hours at 130 ° C.
The method of treating while passing in air often gives good results.

[0008] The treatment method is not particularly limited, but in a stirring tank.
A method of mixing is preferred. TiCl _TwoPc and / or T
iBr_TwoPhenols are distributed through a column packed with Pc.
It is also possible to make the two contact efficiently
Any method may be used. Then, TiCl_TwoPc or Ti
Br_TwoIntermediate obtained by contacting Pc with phenols
And (a) water and phenols and aromatic hydrocarbons
Organic solvents other than hydrogen or (ii) alcohols
Contact with organic solvents other than phenols and alcohols
But usually before that, the intermediates and phenols are separated
Let it. Separation operation, if both are in a mixed state,
The intermediate and phenols are separated by filtration, etc.
To virtually eliminate phenols adhering to the interstitial body
Wash thoroughly with water and organic solvent used in the next step
Is preferred.

In the present invention, the organic solvent used for contacting with the intermediate is not particularly limited as long as a TiOPc crystal can be obtained. It does not matter. For example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic compounds, and a functional group introduced into these compounds, lactams, acid amides, alkyl sulfoxides, esters, nitriles, Examples include halogen compounds, ketones, alcohols, ethers, carboxylic acids, aldehydes and the like. Further, two or more of these may be mixed.

When the intermediate is brought into contact with an organic solvent in which water coexists, phenols and aromatic hydrocarbons are excluded from the organic solvent. When the intermediate is brought into contact with an organic solvent in which alcohols coexist, phenols and alcohols are excluded from the organic solvent. When an organic solvent having a high melting point is used, the operability can be improved by melting by heating or coexisting with an organic solvent having a low melting point.

The conditions for the treatment with an organic solvent in which water coexists are not particularly limited, and the weight ratio of water to the organic solvent is 1: 0.01 to 10, preferably 1: 0.05 to 5 by weight.
Range. Further, the use ratio of the organic solvent in which the intermediate and water coexist is 1: 3 to 200, preferably 1: 5 to 200 by weight.
100. The treatment temperature is 5 to 100 ° C, preferably 1
5 to 70 ° C., and the treatment time is 0.1 to 3 hours.
The treatment method is not particularly limited, and any method may be used as long as the two can be efficiently contacted. Generally, a method of mixing in a stirring tank is preferable.

In the present invention, the alcohol used when the organic solvent coexists with the alcohol may be selected from a wide range, and specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, Octanol, glycol,
Any of aliphatic monohydric to polyhydric alcohols such as glycerin, alicyclic alcohols such as cyclopentanol and cyclohexanol, and aromatic alcohols such as benzyl alcohol and cinnamyl alcohol can be used. Of course, alcohols other than these can also achieve the purpose. The conditions for the treatment with an organic solvent in which alcohols coexist are the same as the conditions for the treatment with an organic solvent in which water coexists.

[0013]

Industrial Applicability The present invention provides a novel method for producing a crystal of TiOPc. TiOPc having a specific crystal form can be obtained very easily and selectively as compared with the conventional method, so that it can be used on an industrial scale. It is also very advantageous for production at
In addition, TiOPc obtained by the method of the present invention has excellent performance as a charge generation material for an electrophotographic photoreceptor, and has an advantage that it is particularly remarkably high in sensitivity.

[0014]

The present invention will be further described below with reference to Examples and Comparative Examples.
As will be described in detail, the present invention does not depart from the gist thereof.
It is not limited by the following examples. TiC
l_TwoSynthesis example of Pc Temperature type, equipped with stirrer and reflux condenser
Orthophthalodinitrile 184 was added to a 2 l reaction flask.
g (1.436 mol) and α-chloronaphthalene 1200
of titanium tetrachloride with stirring (0.364 m
Was added to the mixture, and the mixture was heated to 200 ° C. and reacted for 5 hours. reaction
The solution was cooled to 120 ° C., filtered hot, and the resulting TiC
l _TwoThe crude cake of Pc was treated with α-chloronaphthalene at 120 ° C.
Wash with 1000 ml, then with 600 ml of methanol
After drying, refined TiCl_Two163 g of blue powder of Pc was obtained.
Was.

The elemental analysis values (dry product) were as follows. CH N Cl Theoretical% 60.88 2.55 17.75 11.23 Actual% 60.66 2.37 17.68 11.08 Example 1 14 g of TiCl ₂ Pc and 150 g of phenol obtained in the above synthesis example were charged into a 200 ml flask, heated to 90 ° C. and stirred for 5 hours. After cooling to 50 ° C., the product is filtered off, washed with 150 ml of water and dried to give a dark blue intermediate13.
3 g were obtained. Elemental analysis value (%) CHNCl 68.28 3.13 16.68 0.55 The X-ray powder diffraction spectrum is shown in FIG.

The obtained intermediate, water (300 ml) and n-heptane (30 ml) were charged into a 500 ml reaction flask, and heated at 25 ° C.
After stirring for 1 hour, the aqueous layer was separated and removed, 200 ml of methanol was added to an n-heptane tank to coagulate the product, followed by filtration and drying to obtain 10.9 g of a blue powder of TiOPc. Elemental analysis value CHN theoretical value% 66.68 2.80 19.44 actual value% 66.47 2.70 19.26 The powder X-ray diffraction spectrum is shown in FIG.

Example 2 An experiment was conducted in the same manner as in Example 1 except that phenol containing 10% of water was used instead of phenol. As a result, 10.3 g of a blue powder of TiOPc was obtained. The powder X-ray diffraction spectrum was the same as in Example 1.

Example 3 An experiment was conducted in the same manner as in Example 1 except that resorcin containing 10% of water was used instead of phenol. As a result, 9.8 g of a blue powder of TiOPc was obtained. The powder X-ray diffraction spectrum was the same as in Example 1.

Example 4 An experiment was carried out in the same manner as in Example 1 except that 150 ml of methanol and tetrahydrofuran were used instead of water and n-heptane, and that the treatment temperature was changed to 50 ° C. As a result, 10.4 g of blue powder of TiOPc was obtained. Obtained. The powder X-ray diffraction spectrum was the same as in Example 1.

Example 5 An experiment was carried out in the same manner as in Example 1 except that cyclohexane was used instead of n-heptane and the treatment time was changed to 1.5 hours. As a result, 10.8 g of a blue powder of TiOPc was obtained. The powder X-ray diffraction spectrum is shown in FIG.

Examples 6 to 14 The experiment was carried out in the same manner as in Example 5 except that another organic solvent was used instead of cyclohexane. As a result, a blue powder of TiOPc was obtained. Table 1 shows the type of the organic solvent used and the yield of the obtained TiOPc. All of the powder X-ray diffraction spectra were the same as in Example 1.

Table 1 Example Yield (g) of organic solvent TiOPc 6 Chloroform 10.97 1,2-Dichloroethane 10.68 1-Chlorooctane 10.19 n-Butanol 10.2 10 2-Ethylhexanol 10 0.111 allyl ether 9.8 12 n-butyraldehyde 10.0 13 diisopropyl ketone 10.14 quinoline 9.7 Example 15 Instead of 300 ml water and 30 ml n-heptane, 150 water was used.
As a result of conducting an experiment in the same manner as in Example 5 except for using 150 ml of tetrahydrofuran, 10.3 g of a blue powder was obtained. The powder X-ray diffraction spectrum was the same as in Example 5.

EXAMPLE 16 Instead of 300 ml of water and 30 ml of n-heptane, 150 ml of water were used.
As a result of conducting an experiment in the same manner as in Example 1 except that the treatment temperature was 50 ° C. and the treatment time was 2 hours, 10.4 g of TiOPc blue powder was used.
I got The powder X-ray diffraction spectrum was the same as in Example 5.

Example 17 An experiment was conducted in the same manner as in Example 16 except that N, N-dimethylformamide was used instead of 1,4-dioxane and the treatment time was changed to 3 hours. As a result, a blue powder of TiOPc was obtained. 6 g were obtained. The powder X-ray diffraction spectrum was the same as in Example 5.

Example 18 Instead of N, N-dimethylformamide, N-methyl-
As a result of conducting an experiment in the same manner as in Example 17 except for using 2-pyrrolidone, 9.6 g of a blue powder of TiOPc was obtained. The powder X-ray diffraction spectrum was the same as in Example 1.

Example 19 An experiment was carried out in the same manner as in Example 1 except that ethyl acetate was used instead of n-heptane and the treatment time was changed to 2 hours. As a result, 10.6 g of TiOPc blue powder was obtained. The powder X-ray diffraction spectrum was the same as in Example 1.

Example 20 An experiment was conducted in the same manner as in Example 17 except that methanol and butyl benzoate were used instead of water and N, N-dimethylformamide. As a result, 10.2 g of a blue powder of TiOPc was obtained. The powder X-ray diffraction spectrum was the same as in Example 5.

Example 21 An experiment was conducted in the same manner as in Example 17 except that 2-ethylhexanol was used instead of water. As a result, a blue powder of TiOPc was obtained.
9 g were obtained. The powder X-ray diffraction spectrum was the same as in Example 5.

Comparative Example 1 150 ml of water and 150 ml of N, N-dimethylformamide
As a result of conducting an experiment in the same manner as in Example 17 except that 300 ml of water was used instead of using, no reaction occurred.

Comparative Example 2 150 ml of water and 150 ml of N, N-dimethylformamide
As a result of conducting an experiment in the same manner as in Example 17 except that 300 ml of methanol was used instead of the above, no reaction occurred.

[Brief description of the drawings]

FIG. 1 is a powder X-ray diffraction spectrum of an intermediate obtained in Example 1.

FIG. 2 is a powder X-ray diffraction spectrum of TiOPc obtained in Example 1.

FIG. 3 is a powder X-ray diffraction spectrum of TiOPc obtained in Example 5.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09B 67/50 C09B 67/20 G03G 5/06 371

Claims (1)

(57) [Claims] Claims 1. After contacting dichlorotitanium phthalocyanine and / or dibromotitanium phthalocyanine with a phenol, an organic solvent other than phenol and an aromatic hydrocarbon, or (b) an alcohol, in the presence of (a) water, is added. 27.3 Bragg angle (2θ ± 0.2 °) in powder X-ray diffraction spectrum characterized by contact with coexisting organic solvent other than phenols and alcohols
A method for producing an oxytitanium phthalocyanine crystal having a main diffraction peak at °.