KR100389765B1 - Phthalocyanine composition and electrophotographic photosensitive member comprising the same - Google Patents

Abstract

An object of the present invention is to provide a phthalocyanine crystal composition of a mixed pigment of oxo titanyl phthalocyanine and a halogenated metal phthalocyanine and an electrophotographic organophotoreceptor having a charge generating layer comprising the same.

The phthalocyanine composition of the present invention has a major angle of 9.2 ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , 26.1 ⁰ , 27.0 ⁰ at the Brac angle (2θ ± 0.2 ⁰ ) in X-ray diffraction analysis (Cu kα). Characterized by having a diffraction peak, the composition of the present invention and the electrophotographic photosensitive member is applied to photosensitive members such as electrophotographic laser printing, facsimile and digital copier, excellent sensitivity characteristics, excellent light stability even in repeated use And stability to the environment of use.

Description

Phthalocyanine composition and electrophotographic photosensitive member comprising the same

The present invention relates to a crystal composition of phthalocyanine consisting of a mixed pigment of Oxotitanyl phthalocyanine and halogenated metal phthalocyanine and an electrophotographic photosensitive member using the crystal composition as a charge generating material.

Conventional electrophotographic photoreceptors include selenium (Se, about 50 μm), cadmium sulfide (Cd-S), and oxides formed on a substrate such as aluminum, which is a conductive material, by vacuum deposition. Inorganic photoconductors such as zinc (ZnO) were used. On the other hand, these inorganic photoconductors are excellent in durability and excellent in sensitivity characteristics, but are currently rarely used as electrophotographic photoconductors because they have many disadvantages such as complicated manufacturing process, high manufacturing cost and deterioration of environmental stability.

On the other hand, as an organic photoreceptor to improve the disadvantages of the inorganic photoreceptor, as a charge generating material Chlorocyan Blue or squaraine (Squaraine) is formed on the aluminum substrate with a thickness of about 1㎛, on top of the polyvinylcar There is an example in which a polyvinylcarbazole or pyrazoline derivative compound is used as a charge transport material. However, these photoreceptors have the disadvantage that they do not have an intensity at a wavelength of 700 nm or more.

Recently, phthalocyanine pigments absorbing light around the wavelength range of 800 nm, which is a laser diode, have been applied as charge generators. Absorption spectrum and photoconductivity of the phthalocyanine compound have different properties depending on the center metal, but also show different physical properties for the change in crystal form. Accordingly, electrophotographic photosensitive members characterized by various crystalline structures of these phthalocyanine compounds, particularly oxo titanyl phthalocyanine, have been used. For example, α-crystalline form (or Form B) is disclosed in Japanese Patent Application Laid-Open No. 61-217050, US Patent No. 4,728,592; β-crystalline form (or Form A) is described in US Pat. No. 4,664,997; C-crystal forms are disclosed in Japanese Patent Laid-Open No. 62-256865; D-crystal forms are disclosed in Japanese Patent Laid-Open No. 62-67094, US Pat. Y-crystal form is disclosed in Japanese Patent Laid-Open No. 64-17066; γ-crystal form is disclosed in Japanese Patent Laid-Open No. Hei 1-299874; ω-crystal forms are disclosed in Japanese Patent Laid-Open No. 2-99969, respectively, and D-, Y- and γ-crystal forms show strong peaks at Bragg angles around 27.2 ⁰ in X-ray diffraction analysis. Have

On the other hand, laser printers, fax mills, and copiers using electrophotographic photosensitive members must have electrostatic characteristics such as sensitivity, dark attenuation, and residual potential appropriate to the device due to the inherent characteristics of the device, and the charge applied to the photosensitive member in order to display an optimal image. The harmonization of the generating material and the charge transport material is important, and depends in particular on the nature of the charge generating material. Therefore, recently, in addition to using the above oxo titanyl phthalocyanine alone, metal-free phthalocyanine (US Pat. No. 5,595,846), a phthalocyanine having a substituent (US Pat. No. 5,283,146), and a halogenated metal phthalocyanine (US Pat. No. 5,292,604; The form which mixed 5,449,581; 5,494,767) with oxo titanyl phthalocyanine attracts attention.

However, the above-mentioned phthalocyanine and phthalocyanine mixtures have high sensitivity and good electrostatic properties depending on the conversion of crystalline forms, but the optical fatigue phenomenon that reduces storage stability due to simple mixing of two or more kinds of phthalocyanines or deteriorates the image characteristics in long-term light exposure. Has the disadvantage that occurs.

An object of the present invention is a crystal composition of phthalocyanine and a charge generating material having a specific crystal structure containing oxo titanyl phthalocyanine suitable for producing an electrophotographic photosensitive member having excellent electrostatic stability and excellent environmental stability even after repeated use. It is to provide an electrophotographic photosensitive member using the composition.

The present inventors have made a number of efforts to develop the composition and product for the purpose of the above, as a result of studying the crystalline forms of various phthalocyanine compounds, finally to develop a photosensitive member having excellent photosensitive properties and durability of the electrophotographic method. In other words, good electrostatic homogeneity was found in the crystalline form between halogenated indium phthalocyanine or gallium phthalocyanide and hasotananyl phthalocyanine, and through numerous repeated experiments, it has excellent crystal structure stability, excellent dispersibility, and excellent strength properties. The optimum mixing ratio of the metal halide phthalocyanine and oxo titanyl phthalocyanine suitable as the photoreceptor was derived.

1 is a cross-sectional view of an electrophotographic photosensitive member having a stacked structure.

2 is a cross-sectional view of an electrophotographic photosensitive member having a single layer structure.

3 is an X-ray diffraction spectrum of oxo titanyl phthalocyanine of Form A crystal structure.

4 is an X-ray diffraction spectrum of oxo titanyl phthalocyanine of Form B crystal structure.

5 is an X-ray diffraction spectrum of indium phthalocyanine chloride.

6 is an X-ray diffraction spectrum of the phthalocyanine composition prepared in Example 1 (amorphous phthalocyanine crystal).

7 is an X-ray diffraction spectrum of the phthalocyanine composition prepared in Example 3 (Type A TiOPc + InClPc).

8 is an X-ray diffraction spectrum of a phthalocyanine composition prepared in Comparative Example 2 (A / B type mixed TiOPc + InClPc).

9 is an X-ray diffraction spectrum of a phthalocyanine composition prepared in Comparative Example 3 (A / D type mixed TiOPc + InClPc).

10 is an X-ray diffraction spectrum (Type A TiOPc + InClPc) of the phthalocyanine composition prepared in Example 9. FIG.

1 ---- conductive support 2 ---- charge generating layer

3 ---- charge transport layer 4 ---- undercoat

5 ---- protective layer 6 ---- photosensitive layer

The present invention relates to a phthalocyanine crystal composition consisting of a mixed pigment of oxo titanyl phthalocyanine having a maximum Brac angle (2θ ± 0.2 ⁰ ) peak of 26.1 ⁰ and a halogenated metal phthalocyanine having a trivalent metal as the charge generating material. It is to provide.

In addition, the present invention is to provide an electrophotographic photosensitive member having a charge generating layer containing the phthalocyanine crystal composition.

More specifically, oxo titanyl phthalocyanine and halide gallium phthalocyanine or oxo titanyl having a Brack angle of 9.2 ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , 26.1 ⁰ , 27.0 ⁰ as the main diffraction peaks A phthalocyanine crystal composition comprising a mixed pigment of phthalocyanine and halogenated indium phthalocyanine and an electrophotographic photosensitive member having a charge generating layer comprising the same.

Oxotitanyl phthalocyanine used in the present invention was prepared according to a known method, and a method of reacting 1,2-dicyanated benzene (1,2-Dicyanobenzene) and titanium tetrachloride (TiCl ₄ ) in a suitable solvent condition and di It can be prepared by reacting iminoisoindolin (Tiiminoisoindoline) with titanium tetraalkoxide [Ti (OR) ₄ ] in a suitable organic solvent.

Gallium halide phthalocyanine or indium phthalocyanide halide can be prepared by reacting gallium trichloride (GaCl ₃ ) or indium trichloride (InCl ₃ ) with 1,2-dicyanated benzene or diiminoisoindolin under appropriate solvent conditions.

In the phthalocyanine crystal composition comprising oxo titanyl phthalocyanine and a halogenated metal phthalocyanine having a trivalent central metal in the present invention, the content of oxo titanyl phthalocyanine is 20 to 99% by weight, preferably 50 to 99% by weight, most preferably. The range of 75 to 95% by weight has excellent characteristics in sensitivity and optical fatigue.

The general method of preparing the phthalocyanine mixture is a simple mixing of two or more phthalocyanine crystals by a physical method, which has the disadvantage of showing irregular X-ray diffraction patterns and easily losing stability to dispersibility and environmental changes.

In the present invention, the phthalocyanine mixed pigment is converted into an amorphous state by an acid-paste method, and then the amorphous phthalocyanine in the dried state is milled under conditions of an organic solvent. This results in a mixture of two phthalocyanine crystals at the molecular structural level, which has a single crystal structure, i.e. a very good regular X-ray diffraction pattern and dispersion stability, i.e., 9.2 in X-ray diffraction analysis (Cu Kα). Phthalocyanine crystal structures having a Bragg angle of ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , 26.1 ⁰ , 27.0 ⁰ as the main diffraction peaks can be prepared.

The acid-paste method for preparing the phthalocyanine crystal composition will be described in more detail.Oxitanyl phthalocyanine and a metal halide phthalocyanine are mixed in an appropriate ratio, dissolved in an inorganic acid such as concentrated sulfuric acid, and then distilled water or distilled water / methanol at 0 to 5 ° C. Re-precipitate slowly while dropping. If the pH of the washing water is maintained below 6 or above 7, deterioration of characteristics such as sensitivity, chargeability, and residual potential, which are electrostatic characteristics, occurs. The resulting phthalocyanine mixed pigment is dried at about 110 ° C. At this time, the phthalocyanine does not have any characteristic peak in X-ray diffraction analysis.

In the X-ray diffraction analysis, the amorphous phthalocyanine mixed pigment was prepared in a phthalocyanine crystal composition having a maximum peak at a Bragg angle of 26.1 ^{0 by} a bowl-mill, sand-mill and paint shaker under organic solvent conditions. It is treated and formulated. The organic solvent used at this time may be an alcohol such as methanol, ethanol, isopropanol, butanol, 2-ethoxyethanol, 1-methoxy-2-propanol; Aliphatic hydrocarbons such as hexane octane; Ethers such as diethyl ether, dioxane, tetrahydrofuran (THF), n-butyl ether, isobutyl ether; Organic polar solvents include, for example, pyridine, N-methyl-2-pyrrolidone, quinoline and the like, and are not limited to any particular organic solvent.

Among the organic solvents, the most suitable solvent for preparing the phthalocyanine crystal composition of the present invention is ethers such as diethyl ether, dioxane, tetrahydrofuran, n-butyl ether, isobutyl ether and the like.

In another aspect, the present invention provides an electrophotographic photosensitive member, which is formed on the surface of a conductive material by X-ray diffraction analysis (Cu Kα), which is 9.2 ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , An organic photoconductor having a photoconductive layer containing a phthalocyanine composition having a Bragg angle of 26.1 ⁰ and 27.0 ⁰ as the main diffraction peak as an organophotoreceptor.

The phthalocyanine composition of the present invention is usefully used as a charge generating material in an electrophotographic photosensitive member and provides excellent stability and excellent strength characteristics even in repeated use.

The photoconductor structure using the phthalocyanine crystal formed in the present invention can be described with reference to Figures 1 and 2 of the accompanying drawings, Figure 1 shows a laminated structure of the organic photosensitive layer, Figure 2 shows a single layer structure.

That is, in the photoconductor shown in FIG. 1A, the charge generating layer 2 and the charge transport layer 3 are sequentially stacked on the conductive support 1. 1 (b) and 1 (c) further comprise an undercoat 4 between the conductive support 1 and the charge generating layer 2, in particular FIG. 1 (c) to protect the photoconductor. The protective layer 5 is provided.

In FIG. 2 (a), the photosensitive layer 6 having the charge generating layer and the charge transporting layer together exist on the conductive support 1. 2 (b) and 2 (c) both have a lower layer 4 between the photosensitive layer 6 and the conductive support 1, and in particular, FIG. 2 (c) is for protecting the photoreceptor at the outermost layer. The protective layer 5 is provided.

In the laminated photoconductor shown in Fig. 1, the conductive support 1 includes aluminum, an aluminum alloy, copper, stainless, nickel, and the like, which are conductive materials; Aluminum, aluminum alloy, indium oxide or the like formed on the plastic surface; Deposition of a conductive polymer or conductive particles on plastic or paper may be used.

In the photoconductor of the present invention, a primer layer or an undercoat layer 4 serving as a barrier for enhancing adhesion and charge transfer between the conductive support 1 and the charge generating layer 2 or between the conductive support 1 and the photosensitive layer 6. Leave. The undercoat layer 4 is made of a material such as casein, polyvinyl alcohol, polyvinyl butyral, polyamide, polyurethane, etc., the thickness of the undercoat layer 4 is preferably 0.1 to 10㎛, more preferably 0.1-3 micrometers.

A conductive layer may be formed between the conductive support 1 and the undercoat 4 to prevent interference caused by scattering when image input is caused by defects on the surface of the support 1 or by laser light. The conductive layer is mainly composed of carbon black, metal powder, metal oxide and a suitable resin, and preferably 5 to 40 mu m in thickness, and more preferably 10 to 30 mu m in thickness.

In addition, in order to protect the electrophotographic photosensitive member, the protective layer 5 can be formed in the outermost layer, Preferably the thickness is 0.1-5 micrometers, More preferably, the thickness of 0.2-3 micrometers is preferable.

The charge generating layer 2 is composed of the phthalocyanine crystal composition and the bonding resin in the present invention. As the binding resin, polyvinyl butyral, polyarylate, polycarbonate, polyester, polyvinylacetate, polyamide, epoxy resin, urethane resin, casein, polyvinyl alcohol, etc. can be selected from various polymer resins. Can be used. When binding resins are used, additives such as plasticizers, antioxidants, flow enhancers and pin-hole removal agents may be additionally used if necessary.

The charge generating layer 2 is obtained by coating the photosensitive medicine formed by uniformly dispersing the phthalocyanine composition of the present invention on the conductive support 1 in a solution of a bonding resin dissolved in an organic solvent. At this time, the binding resin is preferably in the range of 0 to 200% by weight, preferably 10 to 100% by weight, based on the crystal composition of phthalocyanine. If the ratio of the phthalocyanine composition is too high, the dispersion stability of the photosensitive drug for the charge generation layer is greatly reduced, on the contrary, if it is too low, the strength characteristics of the charge generation layer are greatly deteriorated, and thus, it is impossible to function as a photosensitive member. As the above-mentioned additive, it is suitable to add 0.1 to 5% by weight, and more preferably 0.1 to 2% by weight, based on the crystal composition of phthalocyanine.

The solvent used for the photosensitive medicine for the charge generating layer 2 is preferably low in the property of melting the undercoat when the charge generating layer 2 is formed. Suitable organic solvents include alcohols, that is, methanol, ethanol, isopropanol, n-butanol, 2-ethoxyethanol, 1-methoxy-2-propanol and the like; Ketones such as acetone, methyl ethyl ketone, cyclolexanone, and the like; Amides such as N, N-dimethylacetamide, N, N-dimethylformamide and the like; Ethers, ie, tetrahydrofuran, dioxane and the like; Esters such as methyl acetate, ethyl acetate, butyl acetate and the like; Hydrocarbons, ie, benzene, toluene, xylene, cyclohexane and the like.

The photosensitive agent for the charge generating layer 2 is coated to form a charge generating layer. As a coating method, a dip coating (Sip-Coat), a spray coating (Spray-Coat), a spin coating (Spin-Coat), Wire-Bar Coat is possible. Drying conditions after coating is preferably carried out at a high temperature if possible, high temperature drying conditions are preferably carried out within 5 minutes to 2 hours at 50 to 200 ℃. In addition, the charge generation layer 2 is preferably 0.05 to 5 mu m, preferably 0.05 to 2 mu m in thickness. If the thickness of the charge generating layer 2 is less than 0.05 µm, it is impossible to form a uniform layer and cannot play a role as the charge generating layer 2. On the contrary, when it exceeds 5 micrometers, electrostatic characteristic, ie, charging property will fall largely.

In the photosensitive member of the stacked structure, the charge transport layer 3 is composed of a charge transport material and a bonding resin. Examples of charge transport materials include polymers such as poly-N-vinylcarbazole, polyvinylylene, polyvinyl benzothiophene, and polyvinyl anthracene, oxadiazoles, triphenylamines, hydrazones, butadienes, stilbenes, and benzidines. Monomolecular compounds are applied. Next, structural formulas of mainly used charge transport materials are illustrated.

The bonding resin used in the charge transport layer 3 may be applied in the same manner as the resin used in the charge generating layer 2.

The charge transport layer (2) is a charge generation comprising a photosensitive chemical for charge transport layer on the conductive support (1) comprising the above-mentioned charge transport material, the bonding resin and a solvent that does not dissolve the already coated charge generating layer (2) It can form on the layer 2 by a coating method. The solvent and the coating method are the same as the composition method of the previous charge generating layer 2.

In the charge transport layer 3 to which the charge transport material is applied, the bonding resin is suitably in the range of 30 to 500% by weight with respect to the charge transport material, and more preferably in the range of 50 to 500% by weight. In addition, when the charge transport material is used as a monomolecular compound, the binding resin is preferably in the range of 50 to 500% by weight of the aforementioned material, and more preferably in the range of 50 to 300% by weight. As for the thickness of the telephone carrying layer 3, 5-50 micrometers is suitable, More preferably, 10-40 micrometers is preferable. If the thickness is less than 5㎛ the initial chargeability is lowered, if it exceeds 50㎛ there is a disadvantage that the sensitivity characteristic is sharply lowered.

Paraffin halide, diethylnaphthalene and dibutyl phthalate are used as the above-mentioned plasticizers, and Alkanox 240 (trade name), ADK STAB AO-50 (trade name) and Anox IC-14 (trade name) are used as antioxidants. , Miwon Co., Ltd. may be used, Modaflow (trade name, Monsanto Chemical Co.) and Akulonal 4F (trade name, BASF Co.), and benzoin and dimethylphthalate may be applied as a pinhole remover.

In the photoconductor having a single layer structure as shown in FIG. 2, the photoconductive layer including the phthalocyanine crystal composition and the charge transport material in the present invention and the bonding resin is used as the photosensitive layer 6. The mixing ratio of the charge transport material to the binding resin is most effective in the range of 30 to 200% by weight, and the ratio of phthalocyanine to the charge transport material is 1 to 100% by weight with the best physical properties.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Production Example

Preparation of Type A oxo titanyl phthalocyanine (Type A TiOPc)

In a nitrogen atmosphere, 335 ml of α-naphthalene was added to a four-necked flask containing 48.75 g of 1,2-dicyanide benzene, and 11 ml of titanium tetrachloride was diluted in about 40 ml of α-naphthalene and added to the dropping funnel. Drop the flask while heating it. At this time, the heating temperature of the reactor is raised to 200 to 220 ℃ within about 30 to 40 minutes at room temperature, and the diluted solution of titanium tetrachloride is added within the same time and then mixed for about 4 to 5 hours. After the reaction, the reaction solution is cooled to about 100 to 130 ° C. and then purified. At this time, it is washed with about 100 ml of α-naphthalene and then with about 400 ml of hot methanol. After that, the product was added to about 400 ml of distilled water, stirred for 1 hour while heating, and washed until the pH of the washing water was 6 to 7. Subsequently, oxo titanyl phthalocyanine as a product was added to 400 ml of N-methyl-2-pyrrolidone at about 140 ° C., stirred for about 30 minutes, washed, and then washed with about 400 ml of methanol. Finally, the resultant was dried under reduced pressure at room temperature to obtain 43 g of oxo titanyl phthalocyanine (FIG. 3: X-ray diffraction spectrum of Form A TiOPc).

Preparation of type B oxo titanyl phthalocyanine (type B TiOPc)

Synthesis of type B oxo titanyl phthalocyanine is carried out by the method disclosed in US Patent No. 4,728,592, the preparation method is as follows. 40 g of 1,2-dicyanide benzene and 18 g of titanium tetrachloride were added to 500 ml of α-naphthalene and reacted at a temperature of about 240 to 250 ° C. and a nitrogen atmosphere. After about 3 hours of reaction, the temperature is gradually cooled and purified to obtain a solid product. TiCl ₂ Pc, the recovered product, was added to 300 ml of concentrated ammonia water and 300 ml of pyridine and stirred under reflux for about 1 hour. The oxo titanyl phthalocyanine obtained at this time is washed with N, N-dimethylformaldehyde, and subsequently washed with acetone and dried under reduced pressure at room temperature (Fig. 4. X-ray diffraction spectrum of Form B TiOPc).

Preparation of Monohalogenated Metal Phthalocyanine

In the present invention, the halogenated metal phthalocyanine having a central metal of trivalent means indium (In) or gallium (Ga), and the halogen includes Cl or Br in a monosubstituted form to the central metal. A method for synthesizing monohalogenated metal phthalocyanines has already been published in Inorganic Chemistry, 19, 3131 (1980).

Briefly, the synthesis of indium phthalocyanine chloride (InClPc) is as follows.

Secondary purified quinoline (100 ml) was added to 1,2-dicyanated benzene (78.2 mmoles) and trivalent indium trichloride (15.8 mmoles), followed by stirring at reflux for about 0.5 to 3 hours. After the reaction, the temperature is gradually lowered to about 0 ° C. and purification is performed. The crystals produced at this time are washed successively with methanol, toluene and acetone. And the product, indium phthalocyanine chloride, is dried at about 110 ℃ (Fig. 5: X-ray diffraction spectrum of InClPc).

Example 1

A phthalocyanine mixed pigment containing 0.9 g of type A oxo titanyl phthalocyanine and 0.1 g of indium phthalocyanine chloride prepared in the present invention was placed in 30 ml of sulfuric acid and completely dissolved. It was then reprecipitated dropping slowly into 500 ml of distilled water maintained at 0-5 ° C. The precipitate was washed several times with distilled water and washed until the washing water had a pH of 6-7. After washing with a mixed solution of methanol / distilled water, the mixture was dried at about 100 to 110 ° C. to obtain 0.95 g of an amorphous phthalocyanine mixed pigment in a powder state (FIG. 6: XRD spectrum).

Example 2

Except for using the type B oxo titanyl phthalocyanine instead of type A oxo titanyl phthalocyanine in Example 1, 0.95 g of an amorphous phthalocyanine mixed pigment was obtained (similar to the XRD spectrum of FIG. 6). .

Comparative Example 1

In the same manner as in Example 1, except that 1 g of type A oxo titanyl phthalocyanine was used instead of the phthalocyanine mixed pigment, 0.95 g of an amorphous phthalocyanine mixed pigment was obtained (similar to the XRD spectrum of FIG. 6).

Example 3

0.95 g of the amorphous phthalocyanine mixed pigment obtained in Example 1 was placed in 20 ml of tetrahydrofuran (THF), and 50 g of 1 mm glass beads were added. Then, milling was performed for 20 hours using a bowl-mill at room temperature. Thereafter, the phthalocyanine mixed pigment as a solid was recovered from the dispersed liquid mixture, and dried under reduced pressure at room temperature to obtain 0.8 g of phthalocyanine crystal composition (FIG. 7; XRD spectrum).

The results are shown in Table 1 below.

Examples 4-8 and Comparative Examples 2-4

As shown in Table 1 below, except that the mixed pigment, the treatment solvent conditions and the treatment time of the phthalocyanine as the starting material in Example 3 were changed in the same manner as in Example 3 to obtain a phthalocyanine crystal composition. The results are shown in Table 1 below.

division Phthalocyanine Blend Pigment Solvent Processing time (hours) X-ray diffraction diffraction peak shape Example 3 Example 1 Tetrahydrofuran 20 7 Example 4 Example 1 Dioxane 20 Same as FIG. Example 5 Example 1 n-butyl ether 20 Same as FIG. Example 6 Example 2 Tetrahydrofuran 15 Same as FIG. Example 7 Example 2 Dioxane 15 Same as FIG. Example 8 Example 2 n-butyl ether 15 Same as FIG. Comparative Example 2 Example 1 N-methyl-2-pyrrolidone 20 8 Comparative Example 3 Example 1 ethanol 20 9 Comparative Example 4 Comparative Example 1 Tetrahydrofuran 20 Similar to Figure 3

Comparative Example 5

In Example 1, an amorphous phthalocyanine mixed pigment dried in the absence of sufficient washing process with distilled water after treatment under the conditions of Example 3 was obtained, thereby obtaining 0.8 g of phthalocyanine crystal composition having an X-ray diffraction spectrum similar to that of FIG. .

Comparative Example 6

0.95 g of the amorphous phthalocyanine mixed pigment produced in Example 2 was added to 10 ml of N-methyl-2-pyrrolidone and stirred with heating at 150 ° C. for 1 hour. After that, the mixture was slowly cooled down, purified, and washed with methanol. The resulting crystals were dried under reduced pressure at room temperature to obtain 0.75 g of phthalocyanine crystal composition (X-ray diffraction pattern similar to that of FIG. 4).

Example 9

A mixed phthalocyanine pigment containing 0.8 g of type A oxo titanyl phthalocyanine and 0.2 g of indium phthalocyanine chloride prepared in Example 3 was completely dissolved in 30 ml of sulfuric acid. It was then reprecipitated dropping slowly into 500 ml of distilled water / methanol (4/1, weight ratio) maintained at 0-5 ° C. The precipitate was washed several times with distilled water and washed until the washing water had a pH of 6-7. Then, the mixture was washed with distilled water / methanol mixed solution and dried at about 100 to 110 ° C. to obtain 0.95 g of amorphous phthalocyanine mixed pigment in powder form.

0.95 g of the above-mentioned amorphous phthalocyanine mixed pigment was added to 20 ml of tetrahydrofuran (THF), and 50 g of 1 mm glass beads were further added. Then, milling was performed for 20 hours using a bowl-mill at room temperature. Thereafter, the phthalocyanine mixed pigment as a solid was recovered from the dispersed liquid mixture, and dried under reduced pressure at room temperature to obtain 0.8 g of phthalocyanine crystal composition (FIG. 10; XRD spectrum).

Example 10

In the electrophotographic photosensitive member used in this example, cylindrical aluminum (30 mm in diameter and 24.3 mm in length) was used as the conductive support. The coating solution for the undercoat layer was prepared by dissolving 50 g of polyamide resin Amilan CM-8000 (trade name, Toray Nippon Co., Ltd.) in a mixed solvent of 700 g of methanol and 250 g of 1-butanol. The above composition was then dried at 120 ° C. for about 30 minutes. 0.5 micrometer of the thickness of the undercoat layer which was formed at this time was obtained.

Phthalocyanine crystal composition obtained in Example 3, that is, 15 g of crystal composition of oxo titanyl phthalocyanine and indium phthalocyanine chloride, 10 g of polyvinyl butyral Denka butyral # 6,000-C (trade name, Denki Kagaku Kogyo Co., Ltd.), and 1 g of 975 g -Methoxy-2-propanol was mixed and dispersed by milling for 10 hours with a bowl-mill by adding 2,000 g of 1 mm glass beads. Using the charge-generating layer photosensitive chemicals prepared, the aluminum cylinder having the undercoat layer was settled and coated, and dried at 120 ° C. for 30 minutes. At this time, the thickness of the formed charge generating layer was obtained to be 0.5㎛.

100 g of the above-mentioned charge transport material of Structural Formula (I) and polycarbonate resin Panlite TS-2050 (trade name, Japan Chemical Industries, Ltd.) were placed in 800 g of tetrahydrofuran (THF), sufficiently stirred, and dissolved to form a charge transport layer. The drug was prepared. In the coating method, a charge transport layer was formed on an aluminum cylinder having a charge generating layer formed by the sedimentation coating method described above, and dried at 120 ° C. for 30 minutes. At this time, the thickness of the formed charge transport layer was 20㎛.

Dispersion stability of the charge generating layer prepared above was observed for 90 days in a thermostat repeating the temperature of 35 ℃ and -10 ℃ every 24 hours, and then observed the phenomenon that the phthalocyanine crystal sinks to the bottom of the mixed solution. Dispersion of the photosensitive drug up to this time prepared in the example showed a stable state without sinking (Table 2).

In addition, the physical properties of the photosensitive layer of the electrophotographic photosensitive drum manufactured in this example were measured by attaching the photosensitive drum prepared above to a laser beam printer (DocuPrint 4508, trade name of Xerox). When the photosensitive drum was charged with a -1.4 kV charging roller under dark conditions, the initial potential of the photosensitive drum was initially -800 V, and the surface potential immediately after output of 1,000 continuous images was -780 V. The resistance to development was excellent. In addition, the sensitivity and residual potential were measured by Cynthia 91KSE (trade name, Gentec), an electrostatic measuring device. The sensitivity (E ₁₀₀ ) was 1.25 μJ / cm 2 as light energy required for the initial potential to fall to the potential level of -100 V. The residual potential means the potential value of the drum surface that appears after 4 seconds when exposed to 1.0 μJ / cm 2 light energy. The results are shown in Table 2 below.

Examples 11-14 and Comparative Examples 7-10

As shown in Table 2, instead of the composition of phthalocyanine in Example 10 to the phthalocyanine composition shown in Examples 11 to 14 and Comparative Examples 7 to 10 in the same manner as in Example 10 to prepare an electrophotographic photosensitive drum The results are shown in Table 2 below.

Comparative Example 11

Instead of 15 g of the crystal composition of the charge generating material, oxo titanyl phthalocyanine and indium phthalocyanine chloride pigment, which was used in Example 10, 13.5 g of type A oxo titanyl phthalocyanine and 1.5 g of indium phthalocyanine chloride were used as in Example 10, respectively. After preparing the charge-generating layer photosensitive chemicals, a photosensitive drum was prepared and its overall characteristics were measured. The results are shown in Table 2 below.

division Phthalocyanine Dispersion stability Initial potential potential (-V) 1kP continuous potential potential (-V) Sensitivity (E ₁₀₀ , μJ / ㎠) Residual potential (-V) Example 10 Example 3 stability 800 785 1.25 6 Example 11 Example 4 stability 805 790 1.23 7 Example 12 Example 5 stability 795 780 1.25 6 Example 13 Example 6 stability 800 780 1.24 6 Example 14 Example 9 stability 780 765 1.27 10 Comparative Example 7 Comparative Example 2 stability 765 730 1.45 20 Comparative Example 8 Comparative Example 4 stability 800 750 1.40 15 Comparative Example 9 Comparative Example 5 Instability 750 675 1.50 35 Comparative Example 10 Comparative Example 6 Instability 785 745 1.30 15 Comparative Example 11 Comparative Example 11 Instability 795 750 1.35 20

Example 15

Instead of the charge transport material of formula (I) used in Example 10, a charge transport material of formula (II) was used, and polycarbonate resin Upilon S-3000 [trade name, Mitsubishi Gas instead of polycarbonate Panlite TS-2050 as a bonding resin. Chemistry Co., Ltd.] was used to prepare a charge transport layer photosensitive drug, and a photosensitive drum was prepared according to Example 10, and various characteristics were measured. The results are shown in Table 3 below.

Examples 16-17 and Comparative Examples 12-15

Next, as shown in Table 3, instead of the composition of phthalocyanine applied in Example 15 to the phthalocyanine composition shown in Examples 16 to 17 and Comparative Examples 12 to 15 to prepare an electrophotographic photosensitive drum in the same manner as in Example 15 The results are shown in Table 3 below.

division Phthalocyanine Dispersion stability Initial potential potential (-V) 1kP continuous potential potential (-V) Sensitivity (E ₁₀₀ , μJ / ㎠) Residual potential (-V) Example 15 Example 3 stability 805 785 1.27 9 Example 16 Example 6 stability 805 785 1.25 10 Example 17 Example 9 stability 790 765 1.30 15 Comparative Example 12 Example 4 stability 800 745 1.45 25 Comparative Example 13 Example 5 Instability 755 660 1.53 50 Comparative Example 14 Example 6 Instability 790 735 1.35 20 Comparative Example 15 Example 11 Instability 795 740 1.45 35

Exemplary Tables 1 to 3 are only a part of the present invention, and only representative compositions and results are illustrated. Compositions not illustrated may show results consistent with the present invention.

According to the present invention, the main diffraction peaks of 9.2 ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , 26.1 ⁰ , 27.0 ⁰ at the Brac angle (2θ ± 0.2 ⁰ ) in X-ray diffraction analysis (Cu Kα) Phosphorus is a phthalocyanine crystal composition of a mixed pigment of oxo titanyl phthalocyanine and a halogenated metal phthalocyanine and an electrophotographic photosensitive member to which the same is applied. In addition, the photoreceptor including the same has an advantage of having high durability by providing excellent sensitivity characteristics when used in an electrophotographic laser printer, a fax mill and a digital copier, excellent light stability even in repeated use, and a stable environment.

Claims (11)

In the X-ray diffraction analysis (Cu Kα), with the Bragg angle (2θ ± 0.2 ⁰ ), the major diffraction peaks of 9.2 ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , 26.1 ⁰ , 27.0 ⁰ Phthalocyanine crystal composition of a mixed pigment of tanyl phthalocyanine and a trivalent halogenated metal phthalocyanine The method of claim 1, wherein the composition is converted to an amorphous form by the acid-paste method of the mixed pigment of oxo titanyl phthalocyanine and a trivalent metal halide phthalocyanine and washed with water until the wash water is pH 6-7 and Phthalocyanine crystal composition prepared by treating the phthalocyanine mixed pigment with an organic solvent after drying. The phthalocyanine crystal composition according to claim 1, wherein in the metal halide phthalocyanine, the central metal is indium (In) or gallium (Ga) and the halogen is chlorine (Cl) or bromine (Br). The phthalocyanine crystal composition according to claim 1, wherein the content of oxo titanyl phthalocyanine in the mixed pigment is in the range of 20 to 99% by weight. In the X-ray diffraction analysis (Cu Kα), with the Bragg angle (2θ ± 0.2 ⁰ ), the major diffraction peaks of 9.2 ⁰ , 10.5 ⁰ , 13.1 ⁰ , 15.0 ⁰ , 15.9 ⁰ , 20.6 ⁰ , 26.1 ⁰ , 27.0 ⁰ An electrophotographic photosensitive member having a photosensitive layer containing a crystal composition of a mixed pigment of tanyl phthalocyanine and a trivalent metal halide phthalocyanine having a trivalent metal as a charge generating material. The composition according to claim 5, wherein the composition is prepared by converting a mixed pigment of oxo titanyl phthalocyanine and a trivalent halogenated metal phthalocyanine into an amorphous form by an acid-paste method, and washing with water until the washing water reaches a pH of 6 to 7. An electrophotographic photosensitive member that is prepared by drying a phthalocyanine mixed pigment with an organic solvent. 6. An electrophotographic photosensitive member according to claim 5, wherein in the metal halide phthalocyanine, the central metal is indium (In) or gallium (Ga) and the halogen is chlorine (Cl) or brom (Br). The electrophotographic photosensitive member according to claim 5, wherein the content of oxo titanyl phthalocyanine in the mixed pigment is in the range of 20 to 99% by weight. The electrophotographic photosensitive member according to claim 5, further comprising a photosensitive layer formed by dispersing a crystal composition of a phthalocyanine mixed pigment in a bonding resin. The electrophotographic photosensitive member according to claim 5 or 9, further comprising a photosensitive layer containing a charge transport material. The electrophotographic photosensitive member according to claim 5, wherein a charge generating layer is formed by applying a phthalocyanine mixed pigment, and a charge transport layer is formed by applying a charge transport material.