JPH08176456A - Production of titanyl phthalocyanine crystal - Google Patents

Abstract

PURPOSE: To facilitate the production of a highly phososensitive titanyl phthalocyanine crystal having a maximum diffraction peak at a Bragg angle of 27.3 deg. to Cu-Kα rays. CONSTITUTION: Organic compounds which form a phthalocyanine ring are reacted with a titanium compound in a dialkylaminoalcohol to obtain titanyl phthalocyanine having a maximum diffraction peak at a Bragg angle of 27.3 deg. to Cu-Kα rays in the X-ray spectrum.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a titanyl phthalocyanine crystal useful as a photoconductive material.

[0002]

2. Description of the Related Art Conventionally, an inorganic photoconductive substance such as selenium has been used for an electrophotographic photosensitive member. However, since it has problems in terms of thermal stability and toxicity, it has no toxicity and is easy to process. Organic photoconductive materials having characteristics have become mainstream.

In recent years, organic photoconductors having sensitivity in the oscillation wavelength region of semiconductor lasers have been actively developed. For example, phthalocyanine compounds, bisazo and trisazo compounds, thiapyrylium compounds, squarylium compounds, azurenium compounds, Thiopyrrolopyrrole compounds have been studied. Among them, phthalocyanine compounds have been widely studied because they are easy to synthesize and have excellent weather resistance and light resistance. In particular, many titanyl phthalocyanines have been studied.

Titanyl phthalocyanine is disclosed, for example, in JP-A-59-49544 and JP-A-59-166959.
Japanese Patent Laid-Open No. 61-239248, Japanese Patent Laid-Open No. 62-239248
-67094, JP 63-366, JP 63-116158, JP 63-19806.
No. 7, JP-A 1-170666, JP-A 2-8
As disclosed in Japanese Patent Publication No. 256-256, various crystal types can be obtained depending on the manufacturing conditions.

Among these, in the X-ray diffraction spectrum disclosed in JP-A-2-8256, C
Bragg angle (2θ ± 0.2 °) for u-Kα ray 2
It is known that titanyl phthalocyanine, which has a maximum diffraction peak at 7.3 °, has high photosensitivity.

[0006]

However, the titanyl phthalocyanine described in JP-A-2-8256 is obtained by treating the acid-treated amorphous titanyl phthalocyanine with an organic solvent, or by working with an organic solvent. It was manufactured by mechanical grinding and was extremely complicated.

The problem to be solved by the present invention is Cu-
Bragg angle (2θ ± 0.2 °) 27.3 for Kα line
An object of the present invention is to provide a method for easily producing a titanyl phthalocyanine crystal having a maximum diffraction peak at a high degree and high photosensitivity.

[0008]

In order to solve this problem, the inventors of the present invention have conducted extensive studies and found that by reacting an organic compound capable of forming a phthalocyanine ring with a titanium alkoxide in a dialkylamino alcohol. , C
Bragg angle (2θ ± 0.2 °) for u-Kα line is 2
A crystal of titanyl phthalocyanine having a maximum diffraction peak at 7.3 ° can be directly produced, does not require a crystal conversion operation, and has excellent performance as a photoconductive material. The use of the titanyl phthalocyanine provides high sensitivity. It was found that the electrophotographic photosensitive member of 1) was obtained, and the present invention was completed.

That is, in order to solve the above problems, the present invention is characterized in that an organic compound capable of forming a phthalocyanine ring is reacted with a titanium compound in a dialkylaminoalcohol, and Cu-K in an X-ray diffraction spectrum is used.
Provided is a method for producing titanyl phthalocyanine having a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 ° with respect to α rays.

Hereinafter, the present invention will be described in detail.

Examples of the organic compound capable of forming a phthalocyanine ring used in the production method of the present invention include phthalonitrile, 1,3-diiminoisoindoline, an alkyl group, an alkoxy group, a halogen atom, a nitro group,
Substituted derivatives with a sulfamoyl group and the like can be mentioned.

As the titanium compound used in the production method of the present invention, for example, titanium alkoxide can be mentioned, in particular titanium tetraethoxide and titanium tetra-n.
A titanium alkoxide composed of an alkoxyl group having 2 to 4 carbon atoms such as -propoxide, titanium tetra-isopropoxide, titanium tetra-n-butoxide, titanium tetra-isobutoxide and the like is preferable.

Examples of the dialkylamino alcohol used in the production method of the present invention include dialkylaminoethanol and dialkylaminopropanol. Particularly, when the alkyl group is a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, a carbon atom is used. The dialkylaminoethanols or dialkylaminopropanols of the numbers 1 to 3 are preferred.

In the reaction, urea or ammonia may be used together.

The titanyl phthalocyanine crystal obtained by the production method of the present invention may be milled within a range in which the crystal form does not change. As the mechanical grinding method, for example, a paint shaker, a sand grinder, a ball mill, a roll mill, an attritor, a kneader, a vibration mill, a colloid mill or the like can be used. Grinding may be done dry,
It may be carried out wet using a liquid substance. A grinding aid such as salt or sodium sulfate may also be used.

The titanyl phthalocyanine crystal obtained by the production method of the present invention is used as a photoconductive material of an electrophotographic photoreceptor.

The electrophotographic photosensitive member may be of a laminated type or a single layer type. The laminated-type photoreceptor may have a structure in which the charge transport layer is stacked on the charge generation layer or the reverse structure. An insulating undercoat layer may be provided on the conductive support, and a surface protective layer may be provided on the top.

The charge generation layer may be composed of a single substance of the titanyl phthalocyanine crystal obtained by the production method of the present invention,
Alternatively, as the photoconductive substance or the charge generating substance (photoconductive substance or the like), other various known charge generating substances or the like can be used in combination with the low crystalline titanyl phthalocyanine of the present invention. Examples of the photoconductive substance that can be used in combination include, for example, α-type, β-type, γ-type, and Y-type titanyl phthalocyanine, titanyl phthalocyanine described in JP-A-1-17066, and titanyl phthalocyanine described in JP-A-2-267563. , Japanese Patent Application Laid-Open No. 3-269064, Japanese Patent Application Laid-Open No. 5-257307, Japanese Patent Application Laid-Open No. 5-273.
775, the titanyl phthalocyanine, α type, β
-Type, γ-type, τ-type, τ'-type, π-type, η-type, η'-type, K-type metal-free phthalocyanine, X-type metal-free phthalocyanine described in US Pat. No. 3,357,989, JP-A-60-2.
No. 43089, a metal-free phthalocyanine, a metal-free phthalocyanine described in JP-A-2-233769, a phthalocyanine compound having a central metal such as copper, indium, manganese, aluminum, magnesium, tin, and silicon, a metal-free or Central metal-containing naphthalocyanine compounds, bisazo and trisazo compounds, anthraquinone compounds, perylene compounds, perinone compounds, polycyclic quinone compounds, dioxazine compounds, quinacridone compounds, azulenium compounds, squarylium salt compounds , Pyrylium salt-based compounds, pyrrolopyrrole-based compounds, and the like.

Examples of the conductive support include a metal drum made of aluminum, stainless steel, copper or the like, a sheet, a laminate of these metal foils, or a vapor deposition product.
Further, a plastic film, a plastic drum, a plastic belt, etc., which are made conductive by applying a conductive substance such as metal powder, carbon Bragg, and polymer electrolyte together with a binder, may be mentioned.

The photosensitive layer of the electrophotographic photosensitive member can be obtained by applying a coating solution containing at least the titanyl phthalocyanine crystal of the present invention on the conductive support and then drying it.

Examples of the binder include polyvinyl butyral resin, polyester resin, polycarbonate resin, polyvinyl carbazole resin, polystyrene resin, polyvinyl acetate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, acrylic resin, acrylic resin. -Styrene resin, methacrylic resin, silicone resin, alkyd resin, melamine-alkyd resin, melamine resin, phenol resin, polyamide resin, polyurethane resin, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, vinyl chloride-
Examples thereof include vinyl acetate copolymers and vinyl chloride-vinyl acetate-maleic anhydride copolymers.

The weight ratio of titanyl phthalocyanine crystals to the binder is preferably in the range of 20: 1 to 1:10,
Particularly, the range of 10: 1 to 1: 5 is preferable. If the ratio of titanyl phthalocyanine crystals is more than 10: 1,
The dispersion stability of the coating liquid tends to decrease, and if the ratio of titanyl phthalocyanine crystals is less than 10: 1, the sensitivity tends to decrease, which is not preferable.

Examples of the organic solvent that can be used to prepare the coating liquid include alcohols such as methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, cyclohexanol, and isopropyl alcohol; acetone, methyl ethyl ketone, methyl. Ketones such as butyl ketone, methyl isobutyl ketone, cyclohexanone; N, N-dimethylformamide, N, N-dimethylacetamide, N
-Amides such as methylpyrrolidone; ethers such as tetrahydrofuran, dioxane, monoglyme, diglyme, and anisole; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate; chloroform, methylene chloride, dichloroethane , Carbon tetrachloride, halogenated hydrocarbons such as trichloroethylene, monochlorobenzene and dichlorobenzene, hydrocarbons such as benzene, toluene, xylene and ligroin, and a mixture of two or more of these solvents may be used. it can.

The coating solution comprises a ball mill, a bead mill, a titanyl phthalocyanine of the present invention, a binder and a solvent.
It can be prepared by dispersing with a dispersing means such as a paint shaker, a sand grinder, an attritor, a disperser, and a homomixer.

For coating the coating liquid, for example, a dipping coating method, a spray coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, a curtain coating method and the like can be used. The coating film is in the range of 20 to 200 ° C, preferably 60 to 120 ° C.
Heat dry in the range of. The film thickness after drying is preferably in the range of 0.1 to 3.0 μm for the charge generation layer in the case of a laminated type photoreceptor and in the range of 10 to 20 μm for a single layer type photoreceptor.

Examples of the charge transport material used for the function-separated type photoreceptor include hydrazone compounds, oxazole compounds, oxadiazole compounds, oxathiazole compounds, thiazole compounds, thiadiazole compounds, triazole compounds, Styryl / stilbene compounds, pyrazoline compounds, triarylamine compounds, dibenzylamine compounds, triarylmethane compounds, triphenylmethane compounds, azine compounds, imidazole compounds, imidazolidine compounds, dicyanomethylene compounds Examples thereof include compounds and benzidine compounds. Among these compounds, those having an aromatic ring may have a fused polycyclic structure such as a benzo analog in the relevant portion. The charge transport layer in the case of a laminated type photoreceptor can be formed by dispersing the charge transport substance and the binder in an organic solvent, and then coating and drying.
The weight ratio of the charge transport material to the binder is 5: 1 to 1: 1.
A range of 5 is preferred. The thickness of the charge transport layer after drying is 5
The range of ˜50 μm is preferable.

Further, an undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer is effective for preventing unnecessary injection of charges from the conductive support, and can enhance the chargeability of the photosensitive layer. Further, it also has the function of enhancing the adhesion between the photosensitive layer and the conductive support. Examples of the material for forming the undercoat layer include polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpolyzine,
Cellulose ethers, polyamides, polyurethanes and the like can be mentioned. The thickness of the undercoat layer is preferably in the range of 0.05 to 1 μm.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. In the following examples and comparative examples,
“Part” represents “part by weight”.

(Example 1) 192 parts of phthalonitrile and 127.6 of titanium tetra-n-butoxide were placed in a reactor.
Parts, urea 90 parts and 2-dimethylaminoethanol 50
0 part was added, and the temperature was raised with stirring under a nitrogen atmosphere.
The reaction was carried out at 0 ° C for 4 hours. Cooled to room temperature and filtered.
The obtained crude product was added to 630 parts of methanol, stirred at room temperature for 1 hour, and then filtered. After repeating this operation 3 times, it was dried to obtain the titanyl phthalocyanine crystal 14
I got 0 copies. (Yield 65%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

Example 2 150 parts of titanyl phthalocyanine crystals were obtained in the same manner as in Example 1 except that ammonia was introduced into the liquid at 150 ml / min instead of urea. (Yield 69.5%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

Example 3 In the same manner as in Example 1 except that urea was not added, 97 parts of titanyl phthalocyanine was obtained. (Yield 45%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

Example 4 A titanyl phthalocyanine crystal was prepared in the same manner as in Example 1 except that 217.7 parts of 1,3-diiminoisoindoline was used instead of 192 parts of phthalonitrile. Obtained 65 parts. (Yield 30%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

Example 5 The same as Example 1 except that 106.6 parts of titanium tetra-n-propoxide was used in place of 127.6 parts of titanium tetra-n-butoxide. Thus, 135 parts of titanyl phthalocyanine crystal was obtained. (Yield 62.6%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

Example 6 In the same manner as in Example 1 except that 500 parts of 3-dimethylaminopropanol was used instead of 500 parts of 2-dimethylaminoethanol, 130 parts of titanyl phthalocyanine crystal was prepared. Got (60% yield)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

(Embodiment 7) SUS3 having a diameter of 6 mm is placed in a pot.
240 parts of 04-made balls and 4 parts of titanyl phthaloanine obtained in Example 1 were charged and ground at room temperature for 24 hours.

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

(Comparative Example 1) In the same manner as in Example 1 except that 500 parts of n-octanol was used instead of 500 parts of 2-dimethylaminoethanol, 164 parts of titanyl phthalocyanine crystal was obtained. It was (Yield 76%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

(Comparative Example 2) In the same manner as in Example 1 except that 500 parts of n-butanol was used instead of 500 parts of 2-dimethylaminoethanol.
138 parts of titanyl phthalocyanine crystals were obtained. (Yield 6
4%)

The X-ray diffraction pattern of the titanyl phthalocyanine thus obtained is shown in FIG.

<Application Example 1> An electrophotographic photosensitive member having the layer structure shown in FIG. 10 was manufactured by the following method. FIG.
In 0, 1 is an aluminum substrate, 2 is a charge generation layer formed on the aluminum substrate 1, and 3 is a charge transfer layer formed on the charge generation layer 2.

Polyvinyl butyral resin (Sekisui Chemical Co., Ltd.
0.18 parts of "S-REC BH-3" manufactured by Co., Ltd.) was dissolved in 14.82 parts of a mixed solvent of methylene chloride and 1,1,2-trichloroethane of 4: 6, and titanyl obtained in Example 1 was dissolved. The dispersion obtained by thoroughly mixing with 0.18 part of the phthalocyanine crystal was applied on an aluminum substrate using a bar coater and then dried at 100 ° C. to form a charge generation layer having a thickness of 1 μm.

Next, a solution prepared by dissolving 1 part of a polycarbonate resin ("Upilon Z-200" manufactured by Mitsubishi Gas Chemical Co., Inc.) in 5.25 parts of a mixed solvent of methylene chloride and chlorobenzene of 8: 2, and the following structure: Formula [1]

[0050]

Embedded image

A charge-transporting layer-forming coating material obtained by thoroughly stirring and mixing with 1 part of the charge-transporting substance represented by the formula (Et represents an ethyl group) is applied onto the charge-generating layer.
Then, it was dried at 110 ° C. to form a charge transport layer having a thickness of 20 μm.

(Application Examples 2 to 7) In Application Example 1, instead of the titanyl phthalocyanine obtained in Example 1, Example 2 is used.
An electrophotographic photoreceptor was prepared in the same manner as in Application Example 1 except that the titanyl phthalocyanine crystals obtained in Examples 1 to 7 were each used.

(Comparative Application Examples 1-2) In Application Example 1,
An electrophotographic photoreceptor was prepared in the same manner as in Application Example 1, except that the titanyl phthalocyanine crystals obtained in Comparative Examples 1 and 2 were used instead of the titanyl phthalocyanine obtained in Example 1.

(Application Example 8) In Application Example 1, as the charge transport material, the following structural formula [2] is used.

[0055]

Embedded image

An electrophotographic photosensitive member was prepared in the same manner as in Application Example 1 except that the substance represented by

(Application Examples 9 to 14) Application Example 8 is the same as Application Example 8 except that the titanyl phthalocyanine crystals obtained in Examples 2 to 7 are used instead of the titanyl phthalocyanine obtained in Example 1. Then, an electrophotographic photoreceptor was prepared.

(Comparative Application Examples 3 to 4) In Application Example 8,
An electrophotographic photosensitive member was prepared in the same manner as in Application Example 8 except that the titanyl phthalocyanine crystals obtained in Comparative Examples 1 and 2 were used instead of the titanyl phthalocyanine obtained in Example 1.

<Evaluation> Application Examples 1 to 14 and Comparative Application Example 1
About each electrophotographic photosensitive member obtained in ~ 4, EP manufactured by Kawaguchi Electric
A negatively charged surface potential (V ₀ ) was measured by performing a corona discharge of −6.0 KV in a dark place using an A-8100 type electrostatic paper analyzer, and then measuring 10
Surface potential retention rate (V ₁₀ / V 10 seconds after leaving in the dark for 10 seconds)
₀ ) was measured. Furthermore, the light of a mercury-xenon lamp was irradiated through monochromatic light of 780 nm obtained through a monochromator, the time when the surface potential decreased to 1/2 and 1/5 was measured, and the photosensitivity was determined by the light energy irradiated at each time. E _1/2 and E _1/5 are collectively shown in Tables 1 and 2.

Similarly, the surface potential (V _r15 ) 15 seconds after the light irradiation was measured, and the results are summarized in Tables 1 and 2.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

According to the manufacturing method of the present invention, Cu-Kα
A titanyl phthalocyanine crystal having a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 ° with respect to a line and high photosensitivity can be easily produced.

[Brief description of drawings]

1 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 1. FIG.

2 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 2. FIG.

3 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 3. FIG.

FIG. 4 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 4.

5 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 5. FIG.

6 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 6. FIG.

7 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Example 7. FIG.

8 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Comparative Example 1. FIG.

9 is an X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in Comparative Example 2. FIG.

FIG. 10 is a schematic cross-sectional view of a laminated electrophotographic photosensitive member manufactured in an application example.

[Explanation of symbols]

 1 Aluminum substrate 2 Charge generation layer 3 Charge transfer layer

Claims (6)

[Claims] 1. A Bragg angle (2θ ± 0.2 °) with respect to Cu—Kα line in an X-ray diffraction spectrum, characterized by reacting an organic compound capable of forming a phthalocyanine ring with a titanium compound in a dialkylamino alcohol.
A method for producing titanyl phthalocyanine having a maximum diffraction peak at 27.3 °. 2. The method according to claim 1, wherein urea or ammonia is added to the reaction system. 3. The method according to claim 1 or 2, wherein phthalonitrile or 1,3-diiminoisoindoline is used as the organic compound capable of forming a phthalocyanine ring. 4. The production method according to claim 1, wherein a titanium alkoxide is used as the titanium compound. 5. A titanium compound having 2 to 4 carbon atoms
The production method according to claim 4, wherein the titanium alkoxide comprising the alkoxyl group is used. 6. A compound selected from the group consisting of dialkylaminoethanol having an alkyl group having 1 to 3 carbon atoms and dialkylaminopropanol is used as the dialkylamino alcohol.
Or the manufacturing method according to 5.