KR100901879B1 - Charge Generation Materials and The manufacturing Method thereof - Google Patents

Abstract

The present invention relates to a charge generating material and a method for producing the charge generating material, and in particular, further comprising a salt treatment step of stirring the oxytitanium phthalocyanine crude in the basic solution before stirring the oxytitanium phthalocyanine crude in sulfuric acid. When forming an electrophotographic photosensitive member by adding an oxytitanium phthalocyanine charge generating material, which is smaller than conventional particles, and adding an oxytitanium phthalocyanine charge generating material, which is smaller than conventional particles, together with a binder resin, a binder resin The present invention relates to a charge generating material and a method for producing the charge generating material to allow the oxytitanium phthalocyanine charge generating material to be more dispersed and exhibit high sensitivity.

Charge generating material, oxytitanium phthalocyanine, salt treatment step

Description

Charge generation materials and the manufacturing method

The present invention relates to a charge generating material and a method for producing the charge generating material, and in particular, further comprising a salt treatment step of stirring the oxytitanium phthalocyanine crude in the basic solution before stirring the oxytitanium phthalocyanine crude in sulfuric acid. When forming an electrophotographic photosensitive member by adding an oxytitanium phthalocyanine charge generating material, which is smaller than conventional particles, and adding an oxytitanium phthalocyanine charge generating material, which is smaller than conventional particles, together with a binder resin, a binder resin The present invention relates to a charge generating material and a method for producing the charge generating material to allow the oxytitanium phthalocyanine charge generating material to be more dispersed and exhibit high sensitivity.

An electrophotographic photosensitive member is used in an electrophotographic image forming apparatus, and the electrophotographic photosensitive member includes a photosensitive layer containing a charge generating material, a charge transporting material, and the like on a conductive substrate. Separated by. The first type is a stack type, and has a two-layer structure of a charge generating layer including a binder resin and a charge generating material (CGM) and a charge transport layer including a binder resin and a hole transporting material (HTM). It is generally used for the manufacture of the (-) type organophotoreceptor. The second type is a single layer structure, which includes a binder resin, a charge generating material, a hole transporting material, and an electron transporting material (ETM) in one layer, and is generally used for the manufacture of a (+) type photosensitive member. Is used.

The electrophotographic photosensitive member was manufactured by mixing an inorganic charge generating material having high photosensitivity, selenium, zinc oxide, cadmium sulfide, and the like on a conductive substrate by mixing it with a polymer of charge transporting material. There is an unsatisfactory problem in many physical properties such as photosensitivity, thermal stability, water resistance, durability, handleability required by a copier or laser light printer.

In order to solve these problems, various organic charge generating materials have been researched and developed. As the organic charge generating material having the physical properties required for laser light, azo compounds, azulenium salt compounds, pyryllium salt compounds, naphthoquinone compounds and the like are known. However, naphthoquinone-based compounds are not suitable for use in photoreceptors in terms of sensitivity, and azo-based compounds have a disadvantage in that synthesis of stable materials is difficult. In particular, these compounds still have problems in that they are not stable to strong light.

On the other hand, the phthalocyanide-based organic charge generating material has abundant π-electron field and thus has excellent properties as photoconductivity and organic semiconductor, and is excellent in properties such as high photosensitivity, excellent durability and high thermal stability. It is used. Specific examples of such phthalocyanine-based compounds include metal-phthalocyanine-based compounds such as crawlo-aluminum phthalocyanine, chloro-indium phthalocyanine, oxyvanadium phthalocyanine, chloro-gallium phthalocyanine, magnesium phthalocyanine and oxy Phthalophthalocyanates, nonmetal-phthalocyanine compounds and the like have attracted attention.

On the other hand, oxytitanium phthalocyanine crude is phthalonitrile, phthalimide, phthalic anhydride, diimnoisoindoline, 1,2cyanobenzamide (1,2) -Cyanobenzamide or o-phthalicacid derivatives as the main raw materials, and titanium butoxide or tetraalkoxy titanium as the titanium source, 1-octanol, quinoline, N-methyl pyrrolidone, 1,2-dichlorobenzene, diethylene glycol, tetramethylene sulfone or 1chloronaphthalene Reaction is carried out for 10 minutes to 120 minutes at 200 ℃ to 250 ℃ under a high boiling solvent such as to form a composite. Japanese Patent No. 62-256865 describes a method of using 1,2-dicyanobenzene and titanium tetrachloride, and US Patent 4,971,877 describes a method of using 1,3-diiminoisoindolin and tetraalkoxytitanium. Paper Bull. Chem. Soc. Jpn., 68, 1001-1005, 1995, describes a method using 1,2-dicyanobenzene and tetrabutoxytitanium. The thus obtained oxytitanium phthalocyanine crude can be used as a charge generating material having high photosensitivity through a post-treatment process. Structural formula of the oxytitanium phthalocyanine is represented by the following formula (1).

Since the conventional oxytitanium phthalocyanine charge generating material is manufactured in an aggregate crystal state of tens of microns or more in which primary particles are aggregated, it is prepared by dispersing it in an organic solvent together with a hole transporting material, an electron transporting material, and a binder resin for use in an electrophotographic photosensitive member. The photosensitive layer forming composition is coated and dried on a conductive substrate to form a single layer photosensitive layer.

However, the conventional oxytitanium phthalocyanine has a particle size of about 100 nm or more, so that the dispersion is not well formed in the binder resin in the process of forming the photosensitive layer forming composition, causing agglomeration or gelation, thereby deteriorating stability and characteristics of the composition itself. There is still a problem that causes deterioration and black spots, image defects or deterioration of resolution occur on the image.

The present invention has been made to solve the above problems, an object of the present invention, the salt treatment step of stirring the oxytitanium phthalocyanine crude in the basic solution before the acid treatment step of simply dissolving the oxytitanium phthalocyanine crude in sulfuric acid It is further included to produce an oxytitanium phthalocyanine charge generating material, which is a smaller particle than the existing particles, so that the oxytitanium phthalocyanine charge generating material is better dispersed in a binder added during coating to form an electrophotographic photosensitive member. In addition, to provide a charge generating material having a high sensitivity characteristics and a method for producing the charge generating material.

Another object of the present invention, by further comprising a salt treatment step of stirring the oxytitanium phthalocyanine crude in the basic solution to neutralize a lot of sulfuric acid wastewater with salt to reduce the generation of wastewater to prevent environmental pollution It is to provide a charge generating material and a method for producing the charge generating material.

The charge generating material and the method of manufacturing the charge generating material for achieving the above object of the present invention includes the following configuration.

According to a first embodiment of the present invention, the method for preparing a charge generating material according to the present invention is a crude synthesis step of synthesizing oxytitanium phthalocyanine crude, and the oxytitanium phthalocyanine crude produced in the crude synthesis step is basic A salt treatment step of stirring the solution, an acid treatment step of stirring the oxycytium phthalocyanine crude salted in the salt treatment step with an acid to form an amorphous oxytitanium phthalocyanine, and an amorphous oxytitanium phthalocyanine after the acid treatment step A phase conversion step of converting to crystalline oxytitanium phthalocyanine,
The phase conversion step is to perform the phase conversion of the amorphous oxytitanium phthalocyanine formed in the acid treatment step by using a mixed solvent mixed with a solvent and distilled water,
The solvent used in the mixed solvent is characterized in that any one of benzaldehyde, nitrobenzene or dimethylaniline, methylaniline.

According to a second embodiment of the present invention, in the method for preparing a charge generating material according to the first embodiment of the present invention, the basic solution of the salt treatment step is sodium hydroxide or potassium hydroxide having a concentration of 0.1 to 95% by weight. Characterized in that consists of.

According to a third embodiment of the present invention, in the method for preparing a charge generating material according to the first embodiment of the present invention, in the salt treatment step, the stirring is performed at a temperature of −10 ° C. to 50 ° C. .

According to a fourth embodiment of the present invention, in the method for preparing a charge generating material according to the third embodiment of the present invention, the agitation in the salt treatment step is characterized in that for 0.1 hours to 24 hours.

According to a fifth embodiment of the present invention, in the method for preparing a charge generating material according to the second embodiment of the present invention, in the acid treatment step, the acid is formed of sulfuric acid, and the sulfuric acid and the salt treated oxytitanium Phthalocyanine crude is mixed in a ratio of 100: 1 to 0.5: 1, and the sulfuric acid is characterized by having a concentration of 20% by weight to 100% by weight.

According to a sixth embodiment of the present invention, in the method of manufacturing a charge generating material according to the fifth embodiment of the present invention, the phase conversion step is characterized in that the stirring is carried out at a temperature of -10 ℃ ~ 10 ℃. .
According to the seventh embodiment of the present invention, in the method for preparing a charge generating material according to the sixth embodiment of the present invention, the solvent and the distilled water of the mixed solvent are mixed in a volume ratio of 1: 1.

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According to a ninth embodiment of the present invention, in the method for preparing a charge generating material according to the seventh embodiment of the present invention, the method for preparing an oxytitanium phthalocyanine charge generating material is a crystalline form after stirring is completed in the phase conversion step. Separation of oxytitanium phthalocyanine and washed with a washing solvent, characterized in that it further comprises a drying step of drying for 1 hour to 24 hours at 50 ℃ ~ 70 ℃.

According to a tenth embodiment of the present invention, in the method for preparing a charge generating material according to the ninth embodiment of the present invention, the washing solvent in the drying step may be selected from aliphatic alcohols and aromatic organic solvents, or a mixture thereof. The aliphatic alcohols are one selected from the group consisting of methanol and ethanol, and the aromatic organic solvents are one selected from the group consisting of benzaldehyde, nitrobenzene, dimethylaniline, and methylaniline.

According to an eleventh embodiment of the invention, the charge generating material according to the invention is produced by the method of the sixth embodiment of the invention, with peaks appearing between Bragg angle 8.4 ± 0.2 ° and 10.2 ± 0.2 °, in particular 9.4 ± Peaks at 0.2 and have X-ray diffraction peaks at 11.6 ± 0.2 °, 13.2 ± 0.2 °, 14.2 ± 0.2 °, 14.8 ± 0.2 °, 17.9 ± 0.2 °, 24.0 ± 0.2 ° and 27.2 ± 0.2 ° It features.

The present invention can achieve the following effects by the configuration and combination described above with the present embodiment.

The present invention further includes a salt treatment step of stirring the oxytitanium phthalocyanine crude in the basic solution before the acid treatment step of simply dissolving the oxytitanium phthalocyanine crude in sulfuric acid, which is smaller than the existing particles. This results in better dispersion of the oxytitanium phthalocyanine charge generating material in the binder added during the coating to form the electrophotographic photoconductor, and since the particles are smaller, the sensitivity is higher than that of the conventional charge generating material. A more elevated photosensitive member can be obtained.

The present invention further includes a salt treatment step of agitating an oxytitanium phthalocyanine crude in a basic solution to neutralize a large amount of sulfuric acid wastewater with salts, thereby reducing the generation of wastewater, thereby preventing environmental pollution. can do.

Hereinafter, the present invention will be described in more detail.

7 is a block diagram illustrating a method of manufacturing a charge generating material according to the present invention.

Referring to Figure 7, the method for producing a charge generating material according to an embodiment of the present invention, the crude synthesis step (S1), salt treatment step (S2), acid treatment step (S3), phase conversion step (S4), It comprises a drying step (S5).

The crude synthesis step (S1) is a step of synthesizing oxytitanium phthalocyanine crude, 옥 oxytitanium phthalocyanine crude used in the present invention is not particularly limited, but phthalonitrile (phthalonitrile), phthalamide (phthalimide), as a main raw material One or more selected from the group consisting of phthalic anhydride, diimnoisoindoline, 1,2-cyanobenzamide, and derivatives of o-phthalicacid It is preferable to use a titanium source, it is preferable to use titanium butoxide (titanium butoxide) or tetraalkoxy titanium, and as a solvent 1 octanol (1-Octanol), quinoline (Quinoline), en-methyl pyrroli N-methyl pyrrolidone, 1,2-dichlorobenzene, diethylene glycol, tetramethylene sulfone or 1 group A naphthalene (1-chloronaphthalene) preferably at 200 ~ 250 ℃ at least one selected from the group consisting of high boiling point solvent to be synthesized by reacting for 10-120 minutes and the like.

In the salt treatment step (S2), the oxytitanium phthalocyanine charge generating material is more dispersed in a binder added during the coating to form an electrophotographic photosensitive member by producing smaller particles of oxytitanium phthalocyanine than the particles of conventional oxytitanium phthalocyanine. The step of stirring the oxytitanium phthalocyanine crude produced in the crude synthesis step (S2) for a long time in the basic solution so as to have a high sensitivity and to reduce the generation of waste water to prevent environmental pollution.

In the present invention, the basic solution is not particularly limited, but is preferably a basic solution having a concentration of 0.1 to 95% by weight of sodium hydroxide (NaOH) or potassium hydroxide (KOH) in distilled water. Moreover, the temperature at the time of stirring a basic solution and an oxytitanium phthalocyanine crude is suitable at fixed temperature, Preferably it is -10-50 degreeC. If the temperature is less than -10 ℃ or more than 50 ℃ during stirring may cause problems that the oxytitanium phthalocyanine crude is not well stirred or lumped. In addition, the temperature at the time of stirring is preferably carried out at a temperature of 25 ~ 50 ℃ in order to reduce the production cost and increase the yield.

On the other hand, the stirring time in the salt treatment step (S2) is suitable for a predetermined time, preferably 0.1 to 24 hours of stirring so that the basic solution and oxytitanium phthalocyanine crude can be sufficiently homogeneously stirred, shortening the production time In order to reduce the cost and increase the yield, stirring is preferably performed for 2 to 5 hours.

The acid treatment step (S3) is a step of forming an amorphous oxytitanium phthalocyanine by filtering and stirring the dried oxytitanium phthalocyanine crude with acid after the stirring is completed in the salt treatment step (S2), and the acid is particularly limited. Sulfuric acid, phosphoric acid or halogenated carboxylic acid are suitable, in particular sulfuric acid, and it is suitable to mix a certain volume ratio, preferably salted oxytitanium phthalocyanine crude with sulfuric acid in a volume ratio of 1: 0.5 to 1: 100. Do. At this time, it is preferable to use sulfuric acid having a concentration of 20 to 100% by weight. If the concentration of sulfuric acid is less than 20% by weight or if the ratio of sulfuric acid is less than 1: 0.5 compared to the salted oxytitanium phthalocyanine crude, the salted oxytitanium phthalocyanine crude does not stir well in sulfuric acid. This can happen.

On the other hand, the temperature at the time of stirring sulfuric acid and oxytitanium phthalocyanine crude is preferably 30 to 10 ° C, and the stirring time is preferably 0.1 to 24 hours. The oxytitanium phthalocyanine crude is sufficiently stirred in sulfuric acid only after stirring for this range of time. Preferably it is suitable to stir for 2 to 5 hours to reduce the cost and increase the working efficiency. After stirring, washing with distilled water until the pH (acidity) is neutral and drying gives an amorphous oxytitanium phthalocyanine, but the present invention is recrystallized, extracted, thermally suspended or Various methods such as sublimation can be used to remove unreacted or reaction by-products to obtain amorphous oxytitanium phthalocyanine.

On the other hand, the present invention does not exclude a method of directly adding sulfuric acid in the salt treatment step (S2) even if the acid treatment step (S3) after the salt treatment step (S2).

The phase conversion step (S4) is a step of converting amorphous oxytitanium phthalocyanine to crystalline oxytitanium phthalocyanine, but does not particularly limit the mixed solvent of the present invention, preferably the amorphous obtained in the acid treatment step (S3) It is preferable to convert oxytitanium phthalocyanine into crystalline oxytitanium phthalocyanine using a 1: 1 mixed solvent of a solvent and distilled water. The solvent used in the mixed solvent is preferably made of one or two or more selected from benzaldehyde, nitrobenzene or dimethylaniline, methylaniline.

If the temperature at the time of stirring in the phase conversion step (S4) is less than -10 ° C, there is a problem that the amorphous oxytitanium phthalocyanine obtained in the acid treatment step is not well stirred in the mixed solvent, and the temperature at the time of stirring is 10 ° C. If it exceeds, the particle size may increase after amorphous oxytitanium phthalocyanine is converted to crystalline oxytitanium phthalocyanine. Therefore, the temperature at the time of stirring is preferably set to a constant temperature, preferably -10 to 10 ° C. On the other hand, the stirring time is preferably 0.1 to 24 hours, but in order to lower the production cost and increase the yield, the stirring time is preferably stirred for 10 to 12 hours, and the temperature at the time of stirring is performed at a temperature of 0 to 5 ° C. Is suitable.

The drying step (S5) is a step of separating the crystalline oxytitanium phthalocyanine after the agitation is completed in the phase conversion step (S4) and washing with a washing solvent to dry, washing with a washing solvent and then 50 to 70 It is preferable to dry at 1 ° C. for 1 to 24 hours to obtain crystalline oxytitanium phthalocyanine, and the washing solvent is an aromatic organic solvent consisting of aliphatic alcohols consisting of methanol and ethanol, benzaldehyde, nitrobenzene or dimethylaniline and methylaniline. It is preferable to select from the group, or a mixture thereof. On the other hand, the present invention is a crystalline oxytitanium phthalocyanine by a grinding or milling device in addition to chemical methods such as acid-pasting method or acid slurry method as long as the object of the present invention is not impaired. It is not excluded to the method of obtaining.

As described above, the crystalline oxytitanium phthalocyanine charge generating material prepared by the method of the present invention exhibits a broad peak between Bragg angles of 8.4 ± 0.2 ° and 10.2 ± 0.2 °, and peaks at 9.4 ± 0.2, in addition to 11.6 ± 0.2 °, It has X-ray diffraction characteristic peaks at 13.2 ± 0.2 °, 14.2 ± 0.2 °, 14.8 ± 0.2 °, 17.9 ± 0.2 °, 24.0 ± 0.2 ° and 27.2 ± 0.2 °. In particular, the crystalline oxytitanium phthalocyanine charge generating material has the strongest X-ray diffraction peak at a Bragg angle of 27.2 ± 0.2 °. The crystalline oxytitanium phthalocyanine charge generating material may be usefully used to prepare photoconductors, especially organic photoconductors.

Applicants conducted the following experiment to compare the size of the crystalline oxytitanium phthalocyanine obtained by the method for producing a charge generating material according to the present invention and the size of the oxytitanium phthalocyanine without a salt treatment step, but the present invention It is not limited by these examples.

(1) Preparation of Psalms

1) Example 1

10 g of oxytitanium phthalocyanine crude was salted in a 2 wt% sodium hydroxide solution at 30 ° C. for 5 hours, filtered, and then salted in a 250 ml round flask, 10 g of oxytitanium phthalocyanine crude and 40 wt% sulfuric acid were stirred for 10 hours. After washing, dry until the pH is neutral. 10 g of dried oxytitanium phthalocyanine is mixed with 100 ml of distilled water and 100 ml of benzaldehyde and stirred in a round flask. At this time, the stirring temperature is 8 ℃, and stirred for 10 hours. After stirring is complete, benzaldehyde is washed off using methanol as a washing solvent. The filter was dried for 24 hours in a dryer at 60 ° C. to obtain an oxytitanium phthalocyanine charge generating material. On the other hand, the X-ray diffraction pattern of the oxytitanium phthalocyanine crude used in Example 1 is as shown in FIG.

2) Example 2

In Example 1, a specimen was prepared under the same conditions as in Example 1 except that 10 g of oxytitanium phthalocyanine was mixed with 100 ml of distilled water and 100 ml of benzaldehyde, and the stirring temperature when stirring was 15 ° C.

3) Comparative Example 1

10 g of oxytitanium phthalocyanine crude and 40 wt% sulfuric acid were added to a 250 ml round flask, and the mixture was stirred for 10 hours, washed and dried until the pH was neutral. 10 g of dried oxytitanium phthalocyanine is mixed with 100 ml of distilled water and 100 ml of benzaldehyde and stirred in a round flask. At this time, the stirring temperature is 8 ℃, and stirred for 10 hours. After stirring is complete, benzaldehyde is washed off using methanol as a washing solvent. The filter was dried for 24 hours in a dryer at 60 ° C. to obtain an oxytitanium phthalocyanine charge generating material.

(2) experiment

Experiment 1: X-ray Diffraction Analysis

In order to analyze the peak characteristics of the crystalline oxytitanium phthalocyanine prepared in Example 1 and Comparative Example 1, a diffraction pattern was obtained using an X-ray diffractometer and shown in FIGS. 2 and 3, respectively. 2 is an X-ray diffraction pattern of oxytitanium phthalocyanine according to Example 1, and FIG. 3 is an X-ray diffraction pattern of oxytitanium phthalocyanine according to Comparative Example 1.

The X-ray diffraction pattern of the oxytitanium phthalocyanine is X-ray light bulb: Cu, Cu K-alpha wavelength (Å): 1.54056, voltage (kV): 40.0, current (mA): 40.0, starting angle (° 2 Theta): 5.00, stopping angle (° 2 Theta): 45.00, stepping angle (° 2 Theta): 0.020 was measured under the same conditions.

Experiment 2: TEM Photo Analysis

In order to analyze the particle size of the oxytitanium phthalocyanine prepared in Examples 1 and 2 and Comparative Example 1, TEM (Transmission Electron Microscope) pictures were taken. 4 is a TEM photograph of Example 1 after phase conversion of oxytitanium phthalocyanine crude through a salt treatment step, FIG. 5 is a TEM photograph after phase conversion in Example 2, and FIG. 6 after phase conversion in Comparative Example 1 TEM picture.

Experiment 3: Particle Size Measurement

Particle size analysis (PSA) was used to measure the particle size of the oxytitanium phthalocyanine prepared in Examples 1 and 2 and Comparative Example 1. The results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Stirring temperature 8 ℃ 15 ℃ 8 ℃ Particle size 54.3 nm 107.2 nm 121.7 nm

(3) Consideration

1) In Experiment 1, Example 1 is an oxytitanium phthalocyanine obtained after undergoing a phase change after the salt treatment step, Comparative Example 1 is an oxytitanium phthalocyanine that undergoes a phase change without a conventional salt treatment step, As shown in FIG. 2, the X-ray diffraction characteristics of Example 1 showed a wide peak between Bragg angles of 8.1 ± 0.2 ° and 10.3 ± 0.2 °, particularly peaking at 9.4 ± 0.2, and in addition to 11.7 ± 0.2 °, While peaks appear at 13.3 ± 0.2 °, 14.1 ± 0.2 °, 14.8 ± 0.2 °, 17.9 ± 0.2 °, 23.6 ± 0.2 ° and 27.2 ± 0.2 °, the X-ray diffraction of Comparative Example 1 as shown in FIG. Characteristics are Bragg angle 9.2 ± 0.2 °, 10.5 ± 0.2 °, 12.3 ± 0.2 °, 13.1 ± 0.2 °, 15.0 ± 0.2 °, 15.8 ± 0.2 °, 16.0 ± 0.2 °, 20.7 ± 0.2 °, 23.2 ± 0.2 °, 26.2 It can be seen that peaks appear at ± 0.2 °, 27.1 ± 0.2 ° and 28.3 ± 0.2 °. Therefore, it was confirmed that the Bragg angle of Example 1 is different from the Bragg angle of Comparative Example 1.

2) In Experiment 2, TEM photographs were taken to analyze particle sizes of oxytitanium phthalocyanine after phase transformation in Examples 1, 2, and Comparative Example 1, and in Experiment 3, Examples 1 and 2 and Comparative Example 1 The particle size of oxytitanium phthalocyanine prepared at was measured.

4 to 6 and Table 1, the size of the particles of the oxytitanium phthalocyanine obtained by the phase conversion after the salt treatment as in Example 1 or Example 2 without the salt treatment as in Comparative Example 1 It was confirmed that the particle size of the oxytitanium phthalocyanine obtained by the phase conversion is smaller than, on the other hand, Example 1 in which the stirring temperature in the phase conversion step is 8 ℃ Example 15 in the phase conversion step is 15 ℃ It was confirmed that the particle size is smaller than 2.

Therefore, it was found that the oxytitanium phthalocyanine obtained by the phase conversion after the salt treatment step was smaller in size than the oxytitanium phthalocyanine obtained by the phase conversion without the salt treatment step. Even in the case of phase conversion, when the stirring temperature is 8 ° C, the size of oxytitanium phthalocyanine becomes 54.3 nm, which is about 2 times smaller than the size of oxycitanium phthalocyanine obtained by phase conversion without undergoing a salt treatment step. there was.

On the other hand, when the stirring temperature is 15 ℃, the size of the oxytitanium phthalocyanine is 107.2nm, which is smaller than the size of the oxytitanium phthalocyanine obtained by the phase conversion without undergoing the salt treatment step, but the stirring temperature during the phase conversion is about 10 It is considered that the size of oxytitanium phthalocyanine at or below C is smaller than that of oxytitanium phthalocyanine at a stirring temperature of 15 C, so that the charge generating material may be more uniformly dispersed in the binder resin at the time of coating, thereby having high photosensitivity. . However, if the stirring temperature during the phase conversion is less than -10 ℃ oxytitanium phthalocyanine dissolved in sulfuric acid is not agitated well, it is judged that the stirring temperature during the phase conversion is composed of -10 ℃ ~ 10 ℃.

The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various, substitutions, modifications, and alterations can be made within the scope without departing from the technical spirit of the present invention. It will be evident to those who have knowledge of.

1 is an X-ray diffraction pattern of an oxytitanium phthalocyanine crude used in Example 1

2 is an X-ray diffraction pattern of oxytitanium phthalocyanine according to Example 1

3 is an X-ray diffraction pattern of oxytitanium phthalocyanine according to Comparative Example 1

4 is a TEM photograph after phase conversion of an oxytitanium phthalocyanine crude through a salt treatment step

5 is a TEM photograph after phase transformation in Example 2

6 is a TEM photograph after phase transformation in Comparative Example 1

Figure 7 is a block diagram of a method for producing a charge generating material of the present invention

Claims (11)

A crude synthesis step of synthesizing oxytitanium phthalocyanine crude, a salt treatment step of stirring the oxytitanium phthalocyanine crude produced in the crude synthesis step in a basic solution, and the salt treated oxytitanium phthalocyanine crew in the salt treatment step An acid treatment step of stirring the acid with an acid to form amorphous oxytitanium phthalocyanine, and after the acid treatment step, a phase conversion step of converting amorphous oxytitanium phthalocyanine to crystalline oxytitanium phthalocyanine, The phase conversion step is to perform the phase conversion of the amorphous oxytitanium phthalocyanine formed in the acid treatment step by using a mixed solvent mixed with a solvent and distilled water, The solvent used in the mixed solvent is benzaldehyde, nitrobenzene or dimethylaniline, methylaniline any one of the manufacturing method of the charge generating material, characterized in that. According to claim 1, wherein the basic solution of the salt treatment step, Method for producing a charge generating material, characterized in that consisting of sodium hydroxide or potassium hydroxide having a concentration of 0.1 to 95% by weight. The method of claim 1, wherein the stirring in the salt treatment step, Method for producing a charge generating material, characterized in that at a temperature of -10 ℃ ~ 50 ℃. The method of claim 3, wherein the stirring in the salt treatment step, Method for producing a charge generating material, characterized in that made for 0.1 hours to 24 hours. The method of claim 2, wherein in the acid treatment step, The acid is formed of sulfuric acid, the sulfuric acid and the salted oxytitanium phthalocyanine crude is mixed in a volume ratio of 100: 1 to 0.5: 1, wherein the sulfuric acid has a concentration of 20% to 100% by weight Method of producing a charge generating material. The method of claim 5, wherein the phase conversion step, Method for producing a charge generating material characterized in that the stirring is carried out at a temperature of -10 ℃ ~ 10 ℃. The method of claim 6, wherein the solvent and distilled water of the mixed solvent Method for producing a charge generating material, characterized in that mixed in a volume ratio of 1: 1. delete The method of claim 7, wherein the method for producing an oxytitanium phthalocyanine charge generating material, After the stirring is completed in the phase conversion step, the crystalline oxytitanium phthalocyanine is separated and washed using a washing solvent, and further comprising a drying step of drying for 1 hour to 24 hours at 50 ℃ ~ 70 ℃ Method for producing a charge generating material. 10. The method of claim 9, wherein the washing solvent of the drying step is composed of an alternative to a mixture of aliphatic alcohols and aromatic organic solvents, the aliphatic alcohol is one selected from the group consisting of methanol and ethanol, the aromatic organic The solvent is a method for producing a charge generating material, characterized in that one selected from the group consisting of benzaldehyde, nitrobenzene, dimethyl aniline and methyl aniline. Prepared by the method of claim 6, peaks appear between Bragg angles of 8.4 ± 0.2 ° and 10.2 ± 0.2 °, peaking at 9.4 ± 0.2, in addition to 11.6 ± 0.2 °, 13.2 ± 0.2 °, 14.2 ± 0.2 °, 14.8 A charge generating material having an X-ray diffraction characteristic peak at ± 0.2 °, 17.9 ± 0.2 °, 24.0 ± 0.2 ° and 27.2 ± 0.2 °.

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