JPH04306264A - Production of crystalline oxytitanium phthalocyanine - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful for electrophotographic photoreceptor, etc., in high productivity by heat-treating an amorphous oxytitanium phthalocyanine in the presence of an organic solvent free from water. CONSTITUTION:The objective compound can be produced by heat-treating 1 pt. of an amorphous oxytitanium phthalocyanine, e.g. at 40-200 deg.C in the presence of preferably 4-30 pts. of an organic solvent (e.g. hydrocarbon) substantially free from water.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for producing oxytitanium phthalocyanine (hereinafter abbreviated as TiOPc) crystals, and more specifically relates to a method for producing oxytitanium phthalocyanine (hereinafter abbreviated as TiOPc) crystals.
The present invention relates to a method for producing crystalline TiOPc by heat-treating Pc in the presence of an organic solvent substantially free of water.

0002

[Prior Art] Phthalocyanines are compounds useful for coloring paints, printing inks, and resins, and as electronic materials.
In recent years, it has been widely used as a material for electrophotographic photoreceptors. As a result of various studies on the manufacturing method of TiOPc, the present inventors found that the Bragg angle (2θ±0.2°) was 9.3°, 10.6° in the powder X-ray diffraction spectrum.
°, 13.2°, 15.2°, 20.8°, 26.3°
TiOPc (hereinafter referred to as A-type T) has a main diffraction peak in
abbreviated as iOPc) and 7.6°, 10.2°, 22
．． TiOPc having main diffraction peaks at 3°, 25.3°, and 28.6° (hereinafter abbreviated as B-type TiOPc)
, furthermore, 7.0°, 15.6°, 23.4°, 25.
TiOPc (hereinafter referred to as C
We confirmed the existence of crystalline forms of type TiOPc (abbreviated as TiOPc) and proposed a method for their production (Japanese Patent Application Laid-Open No. 62-256865).
No., JP-A-62-256867, JP-A-63-366
(see publication). Also, Bragg angle (2θ±0.2°)9.
TiOPc (hereinafter abbreviated as D-type TiOPc) having main diffraction peaks at 7°, 21.4°, and 27.3° has also been proposed (see JP-A-64-17066).
.

[0003] In the above production method, it is necessary to carefully control the temperature increase rate during the reaction of orthophthalodinitrile and titanium tetrachloride, the filtration temperature after the reaction, etc. There was a tendency for crystal forms to be mixed. Furthermore, according to Japanese Patent Application Laid-Open No. 61-217050, TiOPc is obtained by heating dichlorotitanium phthalocyanine (hereinafter abbreviated as TiCl2Pc) with concentrated ammonia water and washing it with acetone, but the operation is complicated. The crystal form also has the disadvantage that it tends to be a mixture of type A and type B.

0004

[Problems to be Solved by the Invention] TiOPc is mechanically ground to make it substantially amorphous, and an organic solvent is added to a suspension obtained by dispersing this in water and heat-treated to obtain D-type. A method of obtaining a crystalline form has been proposed (Patent Application No. 1999-2-
No. 43705), the operation of separating TiOPc crystals from a mixture of water and an organic solvent after heat treatment was complicated, and in particular, it was difficult to remove water.

[0005]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems and to develop a method for selectively producing crystals such as A-type and B-type crystals, the present inventors have developed an amorphous TiOPc crystal.
It has been discovered that crystalline TiOPc can be easily produced by treating TiOPc under certain conditions, and the present invention has been achieved. That is, the gist of the present invention resides in a method for producing crystalline TiOPc, which is characterized by heat-treating amorphous TiOPc in the presence of an organic solvent that does not substantially contain water.

The present invention will be explained in detail below. The amorphous TiOPc used in the present invention can be produced by various methods. Examples include a method in which TiOPc is dissolved in concentrated sulfuric acid and then poured into water to dilute and reprecipitate, and a method in which TiOPc is mechanically ground using a ball mill, paint shaker, automatic mortar, etc. In the present invention, "amorphous" refers to cases in which the powder X-ray diffraction spectrum shows complete amorphism, and cases in which the intensity is low even though there are some distinguishable peaks, and it can be considered as almost amorphous as a whole. includes. The object of the present invention can be easily achieved by heat-treating the thus obtained amorphous TiOPc in the presence of an organic solvent substantially free of water.

[0007] The organic solvent used in the present invention is not particularly limited and can be appropriately selected depending on the desired crystal. For example, hydrocarbons, alcohols, esters, ethers, aldehydes, ketones, aromatic amines, aromatic nitro compounds, aromatic halides, acid amides, alkyl sulfoxides, N-alkyl lactams, nitriles, All lactones etc. are applicable.

[0008] Although the amount of organic solvent used can be selected arbitrarily,
Preferably, the amount is 4 to 30 times that of amorphous TiOPc. If the amount of organic solvent used is too small, the viscosity of the processing liquid will increase, making uniform mixing difficult, and if the amount used is too large, the amount of treatment per unit volume will be reduced, so it is desirable to avoid this. Note that in the present invention, water is substantially absent, that is, the water content in the organic solvent is 5% or less,
Particularly preferably, the heat treatment is performed at a concentration of 1% or less.

[0009] The treatment temperature is 30 to 300°C, preferably 40°C.
~200 range. Below this range, TiOPc
Since the crystallization rate of 20% decreases, the processing time tends to become longer. Furthermore, heating above 300° C. may cause TiOPc to decompose, so it is desirable to avoid this. The treatment time varies depending on the type of organic solvent, treatment temperature, etc., but is usually about 1 to 5 hours.

0010

Effects of the Invention As detailed above, the present invention provides amorphous T.
The desired crystalline form of TiOPc can be obtained by an extremely simple method of treating iOPc with an organic solvent that does not substantially contain water, and can be separated extremely easily, so it is extremely advantageous for production on an industrial scale. Further, the crystalline TiOPc obtained by the method of the present invention can also be used in electrophotographic photoreceptors and the like.

[0011]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Example of manufacturing amorphous TiOPc In a reaction flask equipped with a temperature control, stirrer, and reflux condenser,
Orthophthalodinitrile 184g (1.436mol)
and 1200 ml of α-chloronaphthalene, and while stirring, 40 ml (0.364 mol) of titanium tetrachloride was added.
The temperature was raised to 0°C and the reaction was carried out for 5 hours. The reaction solution was cooled to 120°C and filtered, and the resulting crude cake of TiCl2Pc was washed with 1000ml of α-chloronaphthalene at 120°C, and then with 600ml of methanol to remove refined Ti.
224 g of a wet cake of Cl2Pc was obtained. 2000 ml of water was added to this wet cake, the temperature was raised to 95°C, and the mixture was stirred for 2 hours, filtered (this operation was repeated twice) and dried to obtain 145 g of blue TiOPc.

The elemental analysis values were as follows. C
H N
Cl theoretical value% 66
．． 68 2.80 19.44
0 Actual value% 66.49
2.77 19.23 0.42 The above TiOPc was subjected to the following treatment to form three types of amorphous TiO.
Pc was manufactured.

Production Example 1 The above TiOPc10 was placed in a 250ml polyethylene reagent bottle.
g and 100ml of glass beads with a diameter of 1mm.
Amorphous TiOPc was obtained by grinding for 8 hours using a paint shaker (Model 488 manufactured by Toyo Seiki Seisakusho). The powder X-ray diffraction spectrum is shown in Figure 1.

Production Example 2 Amorphous TiOPc was obtained in the same manner as Production Example 1 except that the milling time was changed to 16 hours. The powder X-ray diffraction spectrum is shown in Figure 2.

Production Example 3 5 g of TiOPc was dissolved in 350 g of 98% sulfuric acid, and the solution was poured into 2500 ml of water to cause reprecipitation. The precipitate was filtered, washed with water, and dried to obtain amorphous TiOPc. The powder X-ray diffraction spectrum is shown in Figure 3.

Example 1 A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 5 g of the amorphous TiOPc of Production Example 1 and 100 ml of toluene, heated to 110°C, stirred for 2 hours, and then cooled to 50°C. , then filtered and dried to obtain blue crystals of A-type TiOPc 4
．． 8g was obtained. The powder X-ray diffraction spectrum is shown in Figure 4.

Examples 2 to 5 Other organic solvents were used in place of toluene, and the treatment temperature was 120°C.
A-type TiOPc was obtained as a result of the same experiment as in Example 1 except that the temperature was changed to .degree. Table 1 shows the types of organic solvents used.

[Table 1] Example Organic solvent 2 n-octane 3
n-butyl acetate 4
Nitrobenzene 5
O-dichlorobenzene

00
18] Example 6 A-type TiOPc was obtained as a result of the same experiment as in Example 1, except that tetrahydrofuran was used instead of toluene and the treatment temperature was changed to 60°C.

Example 7 An experiment was carried out in the same manner as in Example 1 except that 1,4-dioxane was used instead of toluene and the treatment temperature was changed to 80°C.
A type TiOPc was obtained.

Example 8 A type TiOPc was obtained as a result of the same experiment as in Example 2 except that diethylene glycol dimethyl ether was used instead of n-octane and the treatment time was changed to 3 hours.

Example 9 A-type TiOPc was obtained as a result of the same experiment as in Example 6 except that 1,2-dichloroethane was used instead of tetrahydrofuran and the treatment time was changed to 3 hours.

Example 10 A-type TiOPc was obtained as a result of the same experiment as in Example 9 except that cyclohexanone was used instead of 1,2-dichloroethane and the treatment temperature was changed to 90°C.

Examples 11 to 13 Same as Example 2 except that the amorphous TiOPc of Production Example 2 was used instead of the amorphous TiOPc of Production Example 1, and another organic solvent was used instead of n-octane. As a result of the experiment, A
A type TiOPc was obtained. Table 2 shows the types of organic solvents used.

[Table 2] Example Organic solvent 11 n-butyl benzoate 12
Aniline 13
dimethyl sulfoxide

Example 14 Same as Example 2 except that the amorphous TiOPc of Production Example 3 was used instead of the amorphous TiOPc of Production Example 1, and N-methyl-2-pyrrolidone was used instead of n-octane. As a result of experiments, A-type TiOPc was obtained.

Example 15 As a result of conducting the same experiment as in Example 9 except that chloroform was used instead of 1,2-dichloroethane, B-type TiOPc
I got it.

Example 16 As a result of conducting the same experiment as in Example 2 except that 2-ethylhexanol was used instead of n-octane, B-type TiOPc
I got it.

Example 17 Using methyl isobutyl ketone instead of n-octane,
As a result of the same experiment as in Example 2 except that the treatment temperature was changed to 110° C., type B TiOPc was obtained.

Example 18 As a result of conducting the same experiment as in Example 11 except that 4-methyl-4-methoxypentanone-2 was used instead of n-butyl benzoate, type B TiOPc was obtained.

Example 19 Amorphous TiOPc of Production Example 3 was used in place of the amorphous TiOPc of Production Example 2, and N,N-dimethylformamide was used in place of 4-methyl-4-methoxypentanone-2. As a result of conducting the same experiment as in Example 18 except for the following, B-type Ti
Obtained OPc.

Example 20 D-type TiOPc was obtained as a result of the same experiment as in Example 9 except that n-butyraldehyde was used instead of 1,2-dichloroethane and the treatment temperature was changed to 70°C.

[Brief explanation of the drawing]

FIG. 1: Amorphous TiOPc powder X obtained in Production Example 1
Line diffraction spectrum.

[Figure 2] Amorphous TiOPc powder X obtained in Production Example 2
Line diffraction spectrum.

[Figure 3] Amorphous TiOPc powder X obtained in Production Example 3
Line diffraction spectrum.

FIG. 4 is a powder X-ray diffraction spectrum of A-type TiOPc obtained in Example 1.

FIG. 5 B-type TiOPc powder X obtained in Example 15
Line diffraction spectrum.

FIG. 6: D-type TiOPc powder X obtained in Example 20
Line diffraction spectrum.

Claims (1)

[Claims] 1. A method for producing crystalline oxytitanium phthalocyanine, which comprises heat-treating amorphous oxytitanium phthalocyanine in the presence of an organic solvent substantially free of water.