JP2002285024A - Manufacturing method for oxotitanium phthalocyanine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a titanium phthalocyanine compound which does not require complicated operations such as recrystallization, reprecipitation, sublimation purification, or the like and is suitable for electronics related materials. SOLUTION: In X-ray diffraction of CuKα ray, an oxotitanium phthalocyanine compound is obtained by hydrolizing a dihalogenotitanium phthalocyanine compound having a main peak at 7.4 deg. of 2θ (±0.2 deg.) in a mixture of water and a water soluble organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an oxotitanium phthalocyanine compound which can be used as an electronic material such as a photoconductive material.

[0002]

2. Description of the Related Art In recent years, organic photoconductors having sensitivity in the oscillation wavelength region of a semiconductor laser in the near infrared region have been actively developed. Examples of the organic photoconductive material used for such an organic photoreceptor include phthalocyanine compounds, bisazo and trisazo compounds, thiapyrylium compounds, squarylium compounds, azurenium compounds, thiopyrrolopyrrole compounds, and the like. Among organic photoconductive materials, phthalocyanine-based compounds have weather resistance,
It is widely studied because of its excellent light fastness. Also,
Phthalocyanine-based compounds utilize their unique electrical characteristics, and their application to various electronic devices such as photoelectric conversion devices and switching devices has been actively studied.

[0003] As the phthalocyanine compound, metal-free and copper in the center, magnesium, indium, titanium,
Metal phthalocyanine compounds containing metals such as gallium have been widely studied, and in particular, titanium phthalocyanine compounds include various titanium phthalocyanine compounds in which an oxygen atom or an alcoholate is coordinated to a titanium atom, together with the crystal state thereof, for electrophotographic photoreceptors. It is useful as a photoelectric conversion material. For example, JP-A-3-50270 discloses that the X-ray diffraction spectrum shows a Bragg angle 2θ.
(± 0.2 °) of 9.3 °, 10.6 °, 13.2 °,
15.2 °, 20.8 °, 26.3 °, Bragg angle 2θ
(± 0.2 °) 7.6 °, 10.2 °, 22.3 °, 2
Oxo titanium phthalocyanine having main diffraction peaks at 5.3 ° and 28.6 °, Bragg angle 2θ (±
0.2 °) 7.0 °, 15.6 °, 23.4 °, 2
A method of obtaining oxotitanium phthalocyanine having a peak at 5.6 ° from dichlorotitanium phthalocyanine is disclosed, but halides and the like by-produced at the same time as the conversion of crystals have an adverse effect, and further purification operations are required. Also, JP-A-61-239248 discloses that
The crude titanium phthalocyanine compound synthesized from orthophthalodinitrile and titanium tetrachloride is dissolved in concentrated sulfuric acid, and further precipitated with a large amount of water. In the X-ray diffraction spectrum, the compound having a Bragg angle of 2θ (± 0.2 °). Although an oxotitanium phthalocyanine compound having a peak at 6 ° is disclosed, there is a problem that a large amount of purification operation is required to remove residual impurities such as sulfate ions.

[0004]

In particular, when a phthalocyanine-based compound is used for an electronics-related material whose properties and quality are greatly affected by its crystal form and residual impurities, the phthalocyanine-based compound is complicated by recrystallization, reprecipitation, sublimation, or the like. There is a problem that productivity is low and special equipment is required. An object of the present invention is to provide, recrystallization, reprecipitation, without requiring complicated operations such as sublimation purification, provides a method for producing oxotitaniumphthalocyanine compound of specific crystal forms can be used as the electronics-related material It is to.

[0005]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that in producing an oxotitanium phthalocyanine compound, the dihalogenothitanium phthalocyanine compound as a raw material is converted to a specific water-soluble The inventors have found that a specific crystal form of an oxotitanium phthalocyanine compound that can be used as an electronics-related material can be obtained by hydrolysis in the presence of a solvent, thereby completing the present invention.

Namely, the present invention provides an X-ray diffraction of the CuKα line, 2 [Theta] mixture of the dihalogeno phthalocyanine compound water and a water-soluble organic solvent having a 7.4 ° main peak of (± 0.2 °) The present invention provides a method for producing an oxotitanium phthalocyanine compound, which is hydrolyzed in water.

[0007] solve the dihalogeno phthalocyanine down compounds of the present invention to hydrolyze, as the water-soluble organic solvent used together with water, morpholine, N- methylmorpholine, pyridine, N, N- dimethylformamide,
Examples include dimethylsulfoxide, sulfolane, tetrahydrofuran, ethylene glycol, diethylene glycol and the like. The organic solvent is generally although solubility in water varies with temperature, is preferably one which dissolves in water in any ratio at room temperature, is preferably one modified hardly occurs due to decomposition by operation of hydrolysis. Further, when hydrolysis is performed using these water-soluble solvents, the oxotitanium phthalocyanine compound after decomposition can be induced into various crystal forms.In particular, when pyridine is used together with aqueous ammonia, CuKα radiation X-ray diffraction of 2θ (±
0.2%) It is preferable since an oxotitanium phthalocyanine compound having a main peak at 7.5% can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, will be described in detail a method for manufacturing the oxotitanium phthalocyanine compound of the present invention.

The oxotitanium phthalocyanine compound obtained by the production method of the present invention has a molecular structure represented by the following structural formula, and further has a part of hydrogen atoms of an aromatic ring substituted by a halogen atom, a nitro group or the like. including the case where you are.

[0010]

(Equation 1)

However, if the oxotitanium phthalocyanine compound having a substituent is present in a large amount, it is difficult to sufficiently control the crystallinity, and the stability as an electronic material is lost. Oxotitaniumphthalocyanine compounds, for commonly used pigments state, it is difficult to grasp the individual molecular structure, of the hydrogen atoms of the aromatic ring, 1 to 2 are substituted with chlorine atoms, etc. It is desirable that unsubstituted oxotitanium phthalocyanine be the main component. In particular, in X-ray diffraction of CuKα ray, 2θ
An oxotitanium phthalocyanine compound having a main peak at 7.5 ° of (± 0.2 °) is preferable.

In general industrial phthalocyanine compound synthesizing reactions, a solvent as a solvent may not always be used. However, in order to obtain a high-performance oxotitanium phthalocyanine compound used in an electronic material as in the present invention, It is desirable to use a sufficient amount of solvent.

[0013] The solvent used in the synthesis reaction is inert to the phthalocyanine compound to be formed such as aromatic hydrocarbons, aromatic halogenated hydrocarbons, and N-methylpyrrolidone, has a high boiling point, contains little water, and has a low water content. Are preferred because they have relatively high solubility in phthalodinitrile. The orthophthalodinitrile derivative is reacted with the titanium compound in these solvents to obtain a titanium phthalocyanine compound, but other solvents, catalysts, and additives can be used as necessary. In particular, when using orthophthalodinitrile and titanium halide, a dihalogenothitanium phthalocyanine compound is obtained, and further hydrolyzed by the production method of the present invention to obtain an oxotitanium phthalocyanine compound having a crystal form. Obtainable.

The dihalogenotitanium phthalocyanine compound has a molecular structure represented by the following structural formula 2, and includes a case where a part of hydrogen atoms of an aromatic ring is substituted with a halogen atom, a nitro group or the like. In the formula, X represents a halogen atom.

[0015]

(Equation 2)

These dihalogenothitanium phthalocyanine compounds have various crystal forms, and these crystal forms affect the crystal form of the oxotitanium phthalocyanine compound according to the production method of the present invention.
Careful selection is necessary, and particularly in X-ray diffraction of CuKα radiation, by using a dihalogenotitanium phthalocyanine compound having a main peak at 7.4 of 2θ (± 0.2 °), oxotitanium having a preferable crystalline form can be obtained. A phthalocyanine compound can be obtained. Here, the dihalogeno titanium phthalocyanine compound is preferably a dichloro titanium phthalocyanine compound.

The amount of water and the water-soluble organic solvent used during the hydrolysis of the dihalogenotitanium phthalocyanine compound in the production method of the present invention may be appropriately selected so that the dihalogenotitanium phthalocyanine compound can be suspended. From the viewpoints of reactivity, workability and post-treatment, 1 part by weight of the dihalogenotitanium phthalocyanine compound is added to water 5 parts by weight.
It is preferably used in an amount of not less than 10 parts by weight, preferably not less than 10 parts by weight and not more than 100 parts by weight. The water-soluble solvent is used in an amount of 1 part by weight or more, preferably 10 parts by weight or more, based on 1 part by weight of the dihalogenotitanium phthalocyanine compound.
It is desirable to use 0 parts by weight or less. The reaction temperature and time can be appropriately selected, but when a pressure-resistant device such as an autoclave is not used, the reaction is desirably performed within a range from room temperature to the boiling point of water, from an industrial point of view for 10 minutes or more and 5 hours or less. Since the crude oxotitanium phthalocyanine compound after hydrolysis contains inorganic impurities, it is necessary to sufficiently wash with water, but the water-soluble solvent of the present invention has low solubility in phthalocyanines in the presence of water, It is excellent in that it selectively removes only impurities and does not adversely affect the crystal form of the oxotitanium phthalocyanine compound.

Further, the production method of the present invention, in addition to water and a water-soluble organic solvents may be used in combination both of them to miscible aqueous ammonia, alkali metal hydroxide and the aqueous solution or the like, if necessary .

[0019] Generally, oxotitanium phthalocyanine compound used in the electronics field, a solid or a state of being supported to the carrier by adsorption or the like, a thin film, is used in a state of being dispersed into the polymer compound. The oxotitanium phthalocyanine compound desirably contains as little impurities as possible which adversely affect the properties during use, and it is necessary to remove residual solvents by washing, vacuum drying and the like. Oxotitaniumphthalocyanine compounds according to the manufacturing method of the present invention, upon hydrolysis by the use of water-soluble organic solvent, dissolving the organic impurities dihalogeno phthalocyanine compound as a raw material, it was removed, and further, water-soluble organic In order to minimize contamination of the produced oxotitanium phthalocyanine compound by the solvent itself, it is possible to wash with water which has almost no influence on crystallinity. As a result, the oxotitanium phthalocyanine compound according to the production method of the present invention contains a trace amount of a water-soluble organic solvent, but is usually in a range that does not adversely affect properties by suspension washing in water and vacuum drying. be able to. That is, it is not necessary to carry out Soxhlet extraction or sublimation purification of easily decomposable organic substances and ions that adversely affect properties, and also to obtain an industrially excellent oxotitanium phthalocyanine compound without increasing impurities by acid washing or acid paste. be able to.

[0020] Specifically, when using pyridine as water-soluble organic solvent, after hydrolysis treatment, the cleaning and vacuum drying with pure water or ion-exchanged water, 0 residual pyridine content of oxotitaniumphthalocyanine compound. It can be 5% or less, preferably 0.2% or less.

In general, the amount of the residual solvent of the oxotitanium phthalocyanine compound can be set to a specific value by appropriately controlling the separation conditions such as the solvent used in the treatment or by adding a solvent. The amount of pyridine as the residual solvent in the present invention means a normal vacuum drying operation in which the phthalocyanine compound itself is not decomposed or volatilized, more specifically, a pressure reduction degree of 5 to 30 hPa, a temperature of 50 to 150 ° C., and 3 times.
After drying for about 12 hours, the value is a value in a state in which a dry atmosphere of a desiccator or the like is kept at normal temperature and normal pressure, and a change is hardly recognized by weight measurement. More specifically, it can be quantified by thermal analysis or chromatographic analysis of the extract.

However, the production method of the present invention does not exclude the addition of an operation such as acid paste or sublimation purification, and if necessary, obtains a titanium phthalocyanine compound having a different crystal form. crystal transformation method and purification method can be combined for.

[0023] Specifically, oxotitanium phthalocyanine compound according to the production method of the present invention, a physical treatment by grinding and temperature due to further mechanical pressure or chemical treatment by contact with other compounds, such as solvents applied Thus, a material having characteristics required as an electronic material can be obtained.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Example 1 In a 1-liter reaction flask equipped with a thermometer, a stirrer, and a reflux condenser, 50 g of orthophthalodinitrile (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 750 g of 1-chloronaphthalene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and quinoline charged (Tokyo Kasei reagent) 3 g, it was purged with dry nitrogen under stirring reaction flask. After heating and confirming that the content became a homogeneous solution at 50 ° C., 19 g of titanium tetrachloride (a reagent manufactured by Kanto Chemical Co., Ltd.) was added dropwise. Two hours after the addition, the temperature was raised to 220 ° C., and the reaction was continued for another 3 hours. During this time, the reaction solution changed color from dark brown to green. After cooling to around room temperature, the contents were immediately filtered and washed with a small amount of 1-chloronaphthalene to obtain 46 g of a titanium phthalocyanine compound in a dark black solid state.
This was sealed and stored in a glass container, and the powder X-ray diffraction with respect to Cu-Kα radiation was measured with an X-ray diffraction analyzer RAD-B system manufactured by Rigaku Corporation.
(0.2 °) was a titanium phthalocyanine compound having a main diffraction peak at 7.4 °. In the analysis by FD-mass spectrum, m / z = 631, 665.
The main components were dichlorotitanium phthalocyanine and monochlorodichlorotitanium phthalocyanine having a peak at. m / z is the strongest ion peak due to the isotope abundance ratio.

The dichlorotitanium phthalocyanine compound was suspended and washed with 700 g of acetone, and then a thermometer was used.
20 g was charged into a 1 liter reaction flask equipped with a stirrer and a dry distillation cooler, and 700 g of ion-exchanged water and 700 g of pyridine were added.
g, and the mixture was stirred for 3 hours under reflux. After standing to cool, the precipitate was separated by filtration, washed sufficiently with ion-exchanged water, separated by filtration, washed with acetone, filtered, and vacuum-dried at 120 ° C. for 8 hours to obtain 17 g of a blue powder solid. It was obtained. According to the analysis by FD-mass spectrum,
A partially chlorinated oxotitanium phthalocyanine compound having m / z = 576, 610 as a main component.
It is the strongest ion peak based on the respective isotope element ratios, and the ratio of partially substituted oxotitanium phthalocyanine to unsubstituted oxotitanium phthalocyanine was 11%: 88% from the intensity ratio. According to powder X-ray diffraction for Cu-K [alpha line of this powder was α-type oxotitanium phthalocyanine compound having a main diffraction peak at 7.5 ° of Bragg angle 2θ (± 0.2 °). A portion was sampled, and the contained organic solvents were measured by gas chromatography. As a result, 0.009% of chloronaphthalene and 0.19% of pyridine were detected.

Comparative Example 1 Dichlorotitanium phthalocyanine compound 2 of Example 1
A hydrolysis reaction of 0 g was performed using 700 g of aqueous ammonia without using pyridine. After the same post-treatment as in Example 1, the obtained blue solid was analyzed by gas chromatography. As a result, pyridine was not detected, but 0.1% of chloronaphthalene was detected. To remove chloronaphthalene from this oxotitanium phthalocyanine compound, a Soxhlet extraction operation with acetone was required.

[0028]

As described above, according to the present invention, an oxotitanium phthalocyanine compound which can be used as an electronics-related material without requiring complicated operations such as recrystallization, reprecipitation, Soxhlet extraction, and sublimation purification. Obtainable.

[Brief description of the drawings]

FIG. 1 is a powder X-ray diffraction diagram of a dichlorotitanium phthalocyanine compound in Example 1.

FIG. 2 is a powder X-ray diffraction diagram of the oxotitanium phthalocyanine compound in Example 1.

Claims (3)

[Claims] In the X-ray diffraction of CuKα ray, 2θ (±
0.2)). A process for producing an oxotitanium phthalocyanine compound, comprising hydrolyzing a dihalogenothitanium phthalocyanine compound having a main peak at 7.4 ° in a mixture of water and a water-soluble organic solvent. 2. The dihalogeno titanium phthalocyanine compound is a dichloro titanium phthalocyanine compound,
The method for producing an oxotitanium phthalocyanine compound according to claim 1, wherein the water-soluble organic solvent is pyridine. 3. An oxotitanium phthalocyanine compound is obtained by X-ray diffraction of CuKα ray at 2θ (± 0.2
3. The method for producing an oxotitanium phthalocyanine compound according to claim 1 or 2, wherein the method has a main peak at 7.5} of (iii).