JP2775832B2 - X-type metal-free phthalocyanine composition, method for producing the same, and electrophotographic photoreceptor using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a stable X-type metal-free phthalocyanine-containing composition, a method for producing the same, and a high-sensitivity electrophotographic photoreceptor using the same.

[Prior Art and Problems Thereof] Phthalocyanines and metal phthalocyanines have been known to exhibit excellent photoconductivity, and some of them have been used in electrophotographic photoreceptors. In recent years, with the development of non-impact printer technology, laser printers and electrophotographic optical printers using LEDs as a light source, which are capable of high image quality and high speed, are becoming widespread. It is thriving.

In particular, when a laser is used as a light source, semiconductor lasers are often used because of their small size, low cost, simplicity, and the like. However, the oscillation wavelength of the semiconductor lasers currently used in these lasers is relatively long in the near infrared region. Limited. Therefore, it is inappropriate to use a photoreceptor that has sensitivity in the visible region, which has been used in conventional electrophotographic copiers, for semiconductor lasers. It has become to.

As organic type materials satisfying this requirement, conventionally, methine squarate dyes, indoline dyes, cyanine dyes, pyrylium dyes, polyazo dyes, phthalocyanine dyes, naphthoquinone dyes, and the like are known. Of these, methine squaric acid dyes, indoline dyes, cyanine dyes, and pyrylium dyes can be made longer in wavelength, but lack practical stability (repeating characteristics), and polyazo dyes are difficult to make longer in wavelength. In addition, it is disadvantageous in terms of production and naphthoquinone dyes have difficulty in sensitivity at present.

In contrast, phthalocyanine dyes have a spectral sensitivity peak in the long wavelength region of 600 nm or more, and also have high sensitivity,
Since the spectral sensitivity varies depending on the type of the central metal and the crystal form, it is considered to be suitable as a dye for a semiconductor laser, and research and development are being vigorously conducted.

Among the phthalocyanine compounds studied so far,
Examples of the compound exhibiting high sensitivity in a long wavelength region of 780 nm or more include X-type metal-free phthalocyanine, ε-type copper phthalocyanine, and vanadyl phthalocyanine.

On the other hand, in order to increase the sensitivity, a stacked photoreceptor using a phthalocyanine deposited film as a charge generation layer has been studied.
Some phthalocyanines having a group I and group IV metal as central metals having relatively high sensitivity have been obtained. References relating to such metal phthalocyanines include, for example, JP-A-57-211149, JP-A-57-148745, JP-A-59-36254, JP-A-59-44054, and JP-A-59-44054.
Nos. 30541, 59-31965 and 59-166959. However, the production of a vapor-deposited film requires a high-vacuum vapor-deposition apparatus, and equipment costs are high. Therefore, the above-mentioned organic photoreceptor must be expensive.

On the other hand, using phthalocyanine not as a vapor deposition film but as a resin dispersion layer and using this as a charge generation layer,
A composite photoreceptor having a charge transfer layer applied thereon has also been studied. Examples of such composite photoreceptors include metal-free phthalocyanine (Japanese Patent Application Laid-Open No. 58-182639) and indium phthalocyanine (Japanese Patent Application Laid-Open No. No. 155551), which are relatively high-sensitivity photoconductors.
In the long wavelength region of 800 nm or longer, there is a drawback such as a sharp decrease in sensitivity, and the latter has a drawback such as insufficient sensitivity in practical use when the charge generation layer is made of a resin dispersion system. doing.

In addition, phthalocyanines generally have a polymorphic form, but are transformed into the most stable crystalline form in an aromatic solvent, generally called a β-form.

Therefore, crystals in an unstable state such as α-form, X-form and ε-form are prepared by adding a phthalocyanine derivative as disclosed in JP-A-57-141453, JP-A-52-6300, and the like. For practical use.

However, these derivatives not only have little photoconductivity, but also cause deterioration of any performance such as photosensitivity, chargeability, and dark decay rate which are important in electrophotographic characteristics.
This is presumed to be due to the fact that by providing a side chain to the outer benzene ring of phthalocyanine, the intermolecular distance is shortened, the conductivity in the molecular plane direction is increased, and the crystallinity is poor.

In particular, US Pat. No. 3,357,989 (1961) having good photoconductive properties
The X-type metal-free phthalocyanine shown in 7) is not practically used because the above-mentioned instability of the crystal, the accompanying difficulty in control during manufacture, and the photoconductive spectrum starts to decrease around 800 nm. However, when applied to a photoconductor for an optical printer using a semiconductor laser whose emission center is 780 nm, whose oscillation wavelength generally fluctuates by about ± 10 nm depending on temperature, a change in sensitivity appears, which is inconvenient. Because there was.

The present invention has been made in view of the conventional circumstances as described above, and has a good photoconductive property and produces a stable X-type metal-free phthalocyanine composition, and thereby has a photosensitivity suitable for a semiconductor laser. An object of the present invention is to provide an electrophotographic photoreceptor which has and can control characteristics.

Means for Solving the Problems The present inventors have intensively studied an X-type metal-free phthalocyanine which can improve the above-mentioned drawbacks and can be practically used as a charge generating agent for a semiconductor laser with high sensitivity and a method for producing the same. An X-type metal-free phthalocyanine composition having stable and good photoelectric properties was successfully developed, and the present invention was achieved.

That is, the present invention relates to a non-metallic phthalocyanine, after adding the same amount or less of titanyl phthalocyanine to the non-metallic phthalocyanine, performing a sulfuric acid treatment to obtain an amorphous metal-free phthalocyanine, and then performing stirring to form an X-type metal-free phthalocyanine. A method for producing an X-type metal-free phthalocyanine composition characterized by being phthalocyanine, and an X-type metal-free phthalocyanine composition produced by the method.

Further, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor containing a charge generating agent and a charge transfer agent, wherein titanyl phthalocyanine obtained by the method described above and X
An X-type metal-free phthalocyanine composition comprising a non-type metal-free phthalocyanine, or a composition comprising the composition and titanyl phthalocyanine as main components. Here, titanyl phthalocyanine contained in the electrophotographic photoreceptor is CuK
It is a titanyl phthalocyanine compound crystal having a maximum diffraction peak at 27.2 of the Bragg angle (2θ + 0.2 degrees) and a characteristic diffraction peak at 9.7, 24.1. It is preferred.

 Hereinafter, the present invention will be described in detail.

The metal-free phthalocyanine used in the present invention has a general formula [I]; (Wherein, X ¹ , X ² , X ³ , and X ⁴ each independently represent various halogen atoms, and n, m, l, and k each independently represent a number from 0 to 4). Compound.

Among the metal-free phthalocyanines used in the present invention, particularly preferred are metal-free phthalocyanines, metal-free chlorophthalocyanines, and mixtures thereof.

These metal-free phthalocyanines can be obtained by any known method. For example, the production of α- and β-metal-free phthalocyanines, titanyl phthalocyanines, described by F. Moser and A. Thomas in "Phthalocyanine Compounds" (1963) published by Reinhold. And a method of synthesizing O-phthalodinatrile in an alcoholic solvent in the presence of a strong base catalyst as disclosed in JP-A-58-23854.

The metal-free phthalocyanine thus obtained is
Washing with acids and alkalis, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, 2-ethoxyethanol, diglyme, N, N-dimethylformamide, Washing with an electron-donating solvent such as N-methylpyrrolidone, pyridine, morpholine and quinoline is preferred.

X-based metal-free phthalocyanine is disclosed in
It can be obtained by crystallization by the method described in JP-A-14106 / 46-42512 and the like.

In the present invention, an X-type metal-free phthalocyanine obtained by any of the methods can be used. However, when used as a charge generating agent for an electrophotographic photoreceptor, milling which can be obtained with a small particle size to obtain good dispersing power is required. Those obtained by the method are preferred. In addition, the milling raw materials at that time include:
In order to obtain good photoelectric characteristics, it is preferable to use the α-form obtained by the acid pasting method or the mechanical pulverization method and well washed.

The acid pasting method, which is well known as a chemical treatment method for obtaining an α-form metal-free phthalocyanine, is known as 95%.
% Of sulfuric acid dissolved in sulfuric acid or sulphate is poured into water or ice water and reprecipitated. However, sulfuric acid and water are desirably kept at 5% or less, and sulfuric acid is added to water stirred at high speed. By slowly injecting, fine particles can be obtained with better conditions.

In addition, there are a method in which the crystalline particles are directly ground by a mechanical processing device for a very long time, a method in which the particles obtained by the acid pasting method are treated with the solvent or the like, and then ground.

Stabilization of X-type metal-free phthalocyanine by addition of titanyl phthalocyanine is possible in various steps during production of X-form.

That is, each of the following cases can be considered: addition in the normal β form (partially mixed with the α form) after the crude synthesis purification, addition at the stage of the α form, addition during the transition to the X form, and addition to the X form; Either case is good, but in order to obtain a good X-type crystal,
Or is practically preferable.

In particular, in the X-type manufacturing method by the milling method, stirring and purification with a solvent is performed in the final step, but in the conventional method, only an aliphatic solvent can be used in consideration of β-formation of the crystal, and there remains a problem in terms of cleaning effect. .

At this time, if titanyl phthalocyanine is added, even if an ester solvent or an aromatic solvent with high purification efficiency is used, β
Since it is stable in the X form without being transformed into the form, it is preferably present at least in this step in order to obtain the stable X form with good purity.

Accordingly, the solvent used at this time can be freely selected from solvents having good dispersibility, solvents having excellent purification effects, etc., for example, ethers and esters such as tetrahydrofuran and dimethylformamide, ketones such as methyl ethyl ketone and acetone, and toluene. And the like, aromatics such as methylene chloride, and electron-donating solvents such as N-methylpyrrolidone.

Further, the addition amount of titanyl phthalocyanine is 100 parts by weight or less based on 100 parts by weight of metal-free phthalocyanine,
In particular, it is preferably at most 50 parts by weight. This is because, in the X-ray diffraction measurement for confirming the crystal form, if a large amount of titanyl phthalocyanine is present, the resolution is deteriorated, and it becomes difficult to identify the crystal form.

The X-type metal-free phthalocyanine composition thus obtained shows a strong diffraction peak at 7.5, 9.16.7, and 17.3 in the X-ray diffraction spectrum at Bragg angles (2θ ± 0.2 degrees), which is characteristic of X-type. Have.

On the other hand, in the infrared absorption spectrum, 971 ± 2 cm ^-1 ,
Characteristic absorption at 965 ± 2 cm ^-1 , 955 ± 2 cm ^-1 , 980 ± 2
It is desirable that cm ^-1 does not show characteristic absorption. In contrast, the additive-free X-type metal-free phthalocyanine shows a characteristic absorption at 955 ± 2 cm ⁻¹ .

The titanyl phthalocyanine used in the present invention has a general formula: (Wherein, X ¹ , X ² , X ³ , and X ⁴ each independently represent various halogen atoms, and n, m, l, and k each independently represent a number from 0 to 4). Compound.

Among the titanyl phthalocyanines used in the present invention,
Particularly preferred are titanyl phthalocyanines (TiOP
c), titanyl chlorophthalocyanine (TiOPcCl) and mixtures thereof.

These titanyl phthalocyanine compounds, for example,
It can be easily synthesized from 1,2-dicyanobenzene (o-phthalodinitrile) or a derivative thereof and a metal or metal compound according to a known method.

Purification and washing of the synthesized product can be performed in the same manner as in the case of the metal-free phthalocyanine described above.

Further, in the preparation of a paint necessary for producing an electrophotographic photosensitive member by a coating method, stability and dispersibility of the paint are important, and for this purpose, it is preferable that dispersed particles are minute. These titanyl phthalocyanines can be micronized by a single chemical method or mechanical method, but more preferably by a combination of various methods.

For example, extremely fine particles can be obtained by weakening agglomeration between particles by a method such as an acid pasting method or an acid slurry method and then grinding by a mechanical treatment method. The equipment used for grinding is kneader, Banbury mixer, attritor, edge runner mill, roll mill, ball mill, sand mill, SPEX
Examples include, but are not limited to, mills, homomixers, dispersers, agitators, jaw crushers, stamp mills, cutter mills, micronizers, and the like. The acid pasting method, which is well known as a chemical treatment method, is a method in which a pigment is dissolved or sulfated in 95% or more sulfuric acid and poured into water or ice water to reprecipitate. Is maintained at preferably 5 ° C. or lower, and sulfuric acid is slowly injected into water stirred at a high speed, whereby fine particles can be obtained with better conditions.

In addition, there are a method in which the crystalline particles are directly ground by a mechanical processing device for a very long time, a method in which the particles obtained by the acid pasting method are treated with the solvent or the like, and then ground.

The fine titanyl phthalocyanine particles obtained as described above are further purified and washed with various solvents. The same washing solvent as that used for washing the crude synthetic product is appropriately used as the washing solvent. In particular, those purified with tetrahydrofuran have good electrophotographic properties and good dispersibility, and are suitable for use in the present invention. This means that when the X-ray diffraction spectrum is CuK as the source, the Bragg angle (2θ ± 0.2 degrees) is 9.7 ゜, 24.
It has strong peaks characteristic of 1 ゜ and 27.2 ゜ (maximum). Any other known X-ray diffraction patterns can be used for stabilizing the crystal of the X-type metal-free phthalocyanine of the present invention, and there is no difference in the stabilizing function.

An electrophotographic photoreceptor is prepared using the stabilized X-type metal-free phthalocyanine composition obtained as described above.
The photoreceptor is preferably one in which an undercoat layer, a charge generation layer, and a charge transfer layer are laminated on a conductive substrate in this order. A coating material in which a charge generating agent and a charge transfer agent are dispersed and coated in an appropriate resin may be used on the coat layer. Also,
These undercoat layers can be omitted as necessary.

The X-type metal-free phthalocyanine composition according to the present invention or the composition is coated on a substrate with a titanyl phthalocyanine compound together with a suitable binder as a charge generating agent, whereby a uniform, highly sensitive charge generating layer can be obtained. The mixing ratio between the X-type metal-free phthalocyanine composition and titanyl phthalocyanine can be appropriately changed as necessary.

When only X type is used, the peak of the spectral wavelength is 770n.
In the vicinity of m, the optical sensitivity is reduced at 780 nm, which is the oscillation wavelength of the semiconductor laser.

On the other hand, titanyl phthalocyanine has a spectral sensitivity peak near 820 nm, and 780 nm is not always the highest sensitivity.

FIG. 11 is a correlation diagram between the amount of titanyl phthalocyanine and the peak wavelength of spectral sensitivity with respect to the X-type metal-free phthalocyanine composition. As can be seen from FIG. 11, by appropriately mixing the above two types of charge generating agents, For example, a photoreceptor having a spectral sensitivity peak at 780 nm can be manufactured.
Further, since the physical properties such as the specific resistance and the work function are different depending on the two types of blending, the carrier injection from the substrate and the injection efficiency into the charge generation layer can be adjusted. It is possible to finely adjust the characteristics of the photoreceptor required every time, and to provide a photoreceptor having extremely wide practical suitability.

When the composition according to the present invention is used as a charge generating agent, the method for coating the charge generating layer is as follows: spin coater, applicator, spray coater, bar coater, immersion coater,
The drying is carried out using a doctor blade, a roller coater, a curtain coater or a bead coater, and drying is preferably carried out by heating and drying at 40 to 200 ° C. for 10 minutes to 6 hours under static or blowing conditions. The film thickness after drying is 0.01 to 5 μm,
Desirably, it is coated so as to have a thickness of 0.1 to 1 μm.

The binder that can be used when forming the charge generation layer by coating can be selected from a wide range of insulating resins. Further, it can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. Preferably, polyvinyl butyral, polyarylate (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinyl pyridine, cellulose resin, urethane resin , Epoxy resin, silicone resin,
Examples include insulating resins such as polystyrene, polyketone, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, polyacrylonitrile, phenolic resin, melamine resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. 100% by weight or less, preferably 40% by weight of resin contained in the charge generation layer
The following are suitable: These resins may be used alone or in combination.
It may be used in combination of more than one kind.

The solvent for dissolving these resins differs depending on the type of the resin, and it is preferable to select a charge generation layer or an undercoat layer described later from those that do not affect the coating. Specifically, aromatic hydrocarbons such as benzene, xylene, ligroin, monochlorobenzene and dichlorobenzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropanol, and ethyl acetate and methyl cellosolve. Esters, carbon tetrachloride, chloroform, dichloromethane,
Aliphatic halogenated hydrocarbons such as dichloroethane and trichloroethylene, ethers such as tetrahydrofuran and dioxane ethylene glycol monomethyl ether, N,
Amides such as N-dimethylformamide and N, N-dimethylacetamide, and sulfoxides such as dimethyl sulfoxide are used.

The charge transfer layer is formed by dissolving and dispersing in a charge transfer agent alone or a binder resin. Any known charge transfer material can be used. As charge transfer materials,
There are electron transfer materials and hole transfer materials. Examples of electron transfer materials are chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-
9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,7-trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8- There are electron withdrawing substances such as trinitrothioxanthone, and those obtained by polymerizing these electron withdrawing substances.

Examples of the hole transfer material include pyrene, N-ethylcarbazole, N-isopropylcarbazole, N-methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene- 9
-Ethylcarbazole, N, N-diphenylhydrazino-3
-Methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α-naphthyl-N -Phenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone, 2-methyl-4-dibenzylaminobenzaldehyde-1′-ethyl-1′-benzothiazolylhydrazone, 2
-Methyl-4-dibenzylaminobenzaldehyde-
1'-propyl-1'-benzothiazolylhydrazone, 2
-Methyl-4-dibenzylaminobenzaldehyde-
1 ', 1'-diphenylhydrazone, 9-ethylcarbazole-3-carboxaldehyde-1'-methyl-1'-
Phenylhydrazone, 1-benzyl-1,2,3,4-tetrahydroquinoline-6-carboxaldehyde-1 ′, 1′-
Hydrazones such as diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2,5-bis (P
-Diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- (p-diethylaminostyryl)
-5- (p-diethylaminophenyl) pyrazolin, 1-
[Quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylamino Phenyl) pyrazolin, 1- [6-methoxy-pyridyl (2)]-3-
(P-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (3)]-
3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl)-
4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (α-methyl-p
-Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p-diethylaminostyryl) -4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α
-Benzyl-p-diethylaminostyryl) -5- (p
Pyrazolines such as -diethylaminophenyl) -6-pyrazolin and spiropyrazolin, 2- (p-diethylaminostyryl) -6-diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-diethylaminophenyl) -5- (2-chlorophenyl)
An oxazole compound such as oxazole, a thiazole compound such as 2- (p-diethylaminostyryl) -6-diethylaminobenzothiazole, a triarylmethane compound such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1 , 1-bis (4-N, N-diethylamino-2-methylphenyl) heptane, 1,1,2,2-
Polyarylalkanes such as tetrakis (4-N, N-dimethylamino-2-methylphenyl) ethane; stilbene compounds such as 1,1-diphenyl and p-diphenylaminoethylene; and 4,4'-3-methylphenyl Triarylamine compounds such as phenylaminobiphenyl, poly-N
Polysilylene resins such as vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazoleformaldehyde resin, and polymethylphenylsilylene.

In addition to these organic charge transfer materials, selenium, selenium
Inorganic materials such as tellurium amorphous silicon and cadmium sulfide can also be used.

These charge transfer materials can be used alone or in combination of two or more. Resins used for the charge transfer layer include silicone resin, ketone resin, polymethyl methacrylate, polyvinyl chloride, acrylic resin polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, Insulating resins such as polysulfone, polyacrylamide, polyamide and chlorinated rubber, poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene and the like are used.

The coating method of the charge transfer layer is performed using a spin coater, an applicator, a spray coater, a bar coater, an immersion coater, a doctor blade, a roller coater, a curtain coater, a bead coater, and the film thickness after drying is 5 to 50 μm. Desirably, the material is coated so as to have a thickness of 10 to 20 μm.

In addition to these layers, an undercoat layer can be provided on the conductive substrate for the purpose of preventing a decrease in chargeability and improving adhesiveness. Nylon for the undercoat layer
Alcohol-soluble polyamides such as 6, nylon 66, nylon 11, nylon 610, copolymerized nylon, alkoxymethylated nylon, casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, gelatin, polyurethane, polyvinyl butyral, and aluminum oxide Metal oxide is used. It is also effective to include conductive particles such as metal oxides and carbon black in the resin.

The material of the present invention has an absorption peak at a wavelength near 800 nm, and is suitable not only as an electrophotographic photosensitive member for copying machines and printers but also as an absorbing material for solar cells, photoelectric conversion elements and optical disks.

Example Next, an example of the present invention will be described. In the example,
The term “parts” means “parts by weight” unless otherwise specified.

Raw Material Production Example 1 100 parts of o-phthalodinitrile (manufactured by BASF) and 10 parts of piperidine were stirred and reacted in 300 parts of chlorotoluene at 200 ° C. for 10 hours to obtain a purple-red crystal. Further, after washing with acid and alkali, washing and purifying with methanol, N, N-dimethylformamide, N-methylpyrrolidone, and drying,
A pigment powder was obtained. As a result of IR spectrum and mass spectrometry,
It was confirmed to be metal-free phthalocyanine.

Raw Material Production Example 2 1 part of the metal-free phthalocyanine obtained in Raw Material Production Example 1
Cooled to 5 ° C. It is sufficiently dissolved in 20 parts of sulfuric acid (95% concentration) and dropped into 200 parts of water for reprecipitation. This was filtered, washed and purified with alkali, methanol, N, N-dimethylformamide and N-methylpyrrolidone, and dried to obtain a pigment flake. According to X-ray diffraction, it was α-form metal-free phthalocyanine.

Raw material production example 3 After heating and reacting 20.4 parts of o-phthalodinitrile and 7.6 parts of titanium tetrachloride in 50 parts of quinoline at 200 ° C. for 2 hours, the solvent was removed by steam distillation, and a 2% aqueous hydrochloric acid solution and then a 2% water solution were used. Purified with aqueous sodium oxide solution, washed with acetone and N-methylpyrrolidone, dried, and titanyl phthalocyanine (TiOP
c) 21.3 parts were obtained. The X-ray diffraction pattern after washing with water is shown in FIG. 3, and the X-ray diffraction pattern after washing with solvent is shown in FIG.

Raw Material Production Example 4 2 parts of titanyl phthalocyanine obtained in Raw Material Production Example 3
The mixture is dissolved little by little in 40 parts of 98% sulfuric acid at 80 ° C. and the mixture is stirred for about 1 hour, keeping the temperature below 5 ° C. Subsequently, the sulfuric acid solution is slowly poured into 400 parts of ice water with high-speed stirring, and the precipitated crystals are filtered. The crystals were washed with distilled water until no acid remained, to obtain 1.8 parts of amorphous titanyl phthalocyanine. The X-ray diffraction pattern of the product is shown in FIG.

Raw Material Production Example 5 2 parts of the amorphous titanyl phthalocyanine obtained in Raw Material Production Example 4 is stirred in 100 parts of tetrahydrofuran for about 5 hours. Next, filtration and washing with tetrahydrofuran were performed, and after drying, 1.7 parts of titanyl phthalocyanine were obtained.
The X-ray diffraction pattern of the product thus obtained was in a crystal form as shown in FIG.

Example 1 10 parts of the α-type metal-free phthalocyanine and 1 part of the X-type metal-free phthalocyanine obtained in Raw Material Production Example 2 were stirred for 4 days by a porcelain ball mill. After confirming that it was almost converted to X form by X-ray diffraction, 1 part of titanyl phthalocyanine obtained in Raw Material Production Example 4 and 200 parts of tetrahydrofuran were added, and after further stirring for 5 hours, X-ray analysis was performed. 10.5 parts of an X-type metal-free phthalocyanine composition having good crystallinity were obtained. The X-ray diffraction pattern is shown in FIG. 1 and the infrared absorption spectrum is shown in FIG.

Thereafter, the mixture was filtered and dried, and 1 part of this composition, 1 part of butyral resin (manufactured by Sekisui Chemical Co., Ltd .; Bx-1) and 35 g of tetrohydrafuran were kneaded in a ball mill for 10 hours to obtain a paint.

This is 0.5μ of polyamide resin (Toray; CM-8000).
m, applied to an aluminum plate to a thickness of 0.3 μm, and further added 1 part of diethylaminobenzdiphenylhydrazone to polycarbonate (Mitsubishi Gas Chemical; P-z200).
The coating material dissolved in one part was applied to a thickness of 15 μm to obtain a photoconductor sample. This was measured with an electrostatic recording paper measuring device (Kawaguchi Electric; EPA-8100) with a charging voltage of -5 kV, an exposure of 5 lux,
It was measured with white light. Table 1 shows the results.

Example 2 An X-type metal-free phthalocyanine composition was prepared in a ball mill in the same manner as in Example 1, and without removing the pigment,
Furthermore, butyral resin (Sekisui Chemical Co .; B;
L-1) Add 12 parts and stir for 10 hours to adjust the pigment.
Then, a measurement sample was prepared and measured in the same manner as in Example 1 below. Table 1 shows the results.

Example 3 One part of the X-type metal-free phthalocyanine composition obtained in Example 1 and 0.5 part of titanyl phthalocyanine obtained in Raw Material Production Example 5 were mixed with 1.5 parts of a formal resin (D200; # 200) and 50 parts of tetrahydrofuran. At the same time, the mixture was kneaded with a ball mill for 10 hours to prepare a paint.

The same paint was applied to an aluminum substrate coated with a polyamide resin to a thickness of 0.2 μm in the same manner as in Example 1, and a 15 μm film of hydrazone / polycarbonate used in Example 1 was further applied to prepare a sample. did. Table 1 shows the results.

Example 4 A coating was prepared in the same manner as in Example 1, using 0.7 parts of the X-type metal-free phthalocyanine composition prepared in the same manner as in Example 1 and 0.3 parts of titanyl phthalocyanine obtained in Raw Material Production Example 3. An electrophotographic photosensitive member was prepared and measured. Table 1 shows the results.

Example 5 10 parts of the metal-free phthalocyanine obtained in Raw Material Production Example 2, 0.5 part of the X-type metal-free phthalocyanine, and 2 parts of titanyl phthalocyanine obtained in Raw Material Production Example 5 were stirred with a ball mill for 5 days and taken out. And purified. The X-ray diffraction pattern of the product is shown in FIG.

Next, an electrophotographic photosensitive member was prepared by the method described in Example 1, and the characteristics were evaluated. Table 1 shows the results.

Example 6 10 parts of the metal-free phthalocyanine obtained in Raw Material Production Example 1 and 0.5 part of titanyl phthalocyanine obtained in Raw Material Production Example 3 were subjected to sulfuric acid treatment in the same manner as in Raw Material Production Example 2, and then a ball mill was used for 7 days. Stirring was performed, and finally, solvent treatment was performed with toluene to obtain an X-type metal-free phthalocyanine composition. The X-ray diffraction pattern of the product is shown in FIG.

Further, an electrophotographic photosensitive member was prepared and measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 10 parts of the metal-free phthalocyanine obtained in Raw Material Production Example 2 and 1 part of X-type metal-free phthalocyanine were stirred in a porcelain ball mill for 4 days. After it was confirmed by X-ray diffraction that the crystal had almost been transformed into the X form, 100 parts of methyl ethyl ketone was added, and the mixture was stirred for 3 hours to obtain an X form metal-free phthalocyanine. The X-ray diffraction pattern and infrared absorption spectrum are shown in FIG. 9 and FIG.
Shown in the figure.

Further, an electrophotographic photosensitive member was prepared and measured in the same manner as in Example 1. Table 1 shows the results.

In addition, X according to the present invention obtained in Examples 1, 5 and 6
The form-free metal-free phthalocyanine composition is prepared in various organic solvents by 10
Even after heating at 0 ° C for 5 hours, no crystal transition was observed and the crystal was extremely stable.

[Effects of the Invention] As described above, according to the present invention, crystal stability was originally poor against solvents, heat, etc., and it was difficult to obtain stable crystals.
The form-free metal phthalocyanine is stably provided.

Further, according to the method of the present invention, the paint required for producing a photoreceptor can be simultaneously prepared in a series of steps for producing a pigment composition, which saves steps and simplifies, and is industrially extremely effective. is there.

Further, since titanyl phthalocyanine used as a stabilizer also has good electric properties, extremely excellent stable X
The resulting non-metallic phthalocyanine composition provides an electrophotographic photosensitive member that is effective for laser printers and the like.

Further, by changing the composition ratio of stable X-free metal phthalocyanine and titanyl phthalocyanine having different characteristics, the characteristics of the photoreceptor can be adjusted, and a desired photoreceptor for the apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of the X-type metal-free phthalocyanine composition according to Example 1, FIG. 2 is an infrared absorption spectrum diagram of the X-type metal-free phthalocyanine composition according to Example 1, and FIG. X-ray diffraction pattern of titanyl phthalocyanine after washing with water according to Example 3, FIG. 4 is an X-ray diffraction pattern after washing of titanyl phthalocyanine with solvent according to Production Example 3, and FIG. 5 is an X-ray diffraction pattern of titanyl phthalocyanine according to Production Example 4. FIG. 6 shows the X of titanyl phthalocyanine according to Raw Material Production Example 5.
7 is an X-ray diffraction pattern of the X-type metal-free phthalocyanine composition according to Example 5, and FIG. 8 is an X-ray diffraction pattern according to Example 6.
X-ray diffraction pattern of the metal-free phthalocyanine composition, FIG. 9 is an X-ray diffraction pattern of the metal-free phthalocyanine according to Comparative Example 1, FIG.
FIG. 10 is an infrared absorption spectrum diagram of the metal-free phthalocyanine according to Comparative Example 1, and FIG. 11 is a correlation diagram between the mixing ratio of titanyl phthalocyanine to the X-type metal-free phthalocyanine and the peak wavelength of spectral sensitivity.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-163749 (JP, A) JP-A-60-20970 (JP, A) JP-A-58-183758 (JP, A) JP-A-59-183758 49107 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 67/50 C09B 47/30 G03G 5/06 G03C 1/73 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) To a non-metallic phthalocyanine, after adding the same amount or less of titanyl phthalocyanine to the non-metallic phthalocyanine, performing a sulfuric acid treatment to obtain an amorphous metal-free phthalocyanine, and then stirring to form an X-type metal-free phthalocyanine. A method for producing an X-type metal-free phthalocyanine composition, which is phthalocyanine. 2. An amorphous metal-free phthalocyanine is added to the metal-free phthalocyanine by adding an equal amount or less of titanyl phthalocyanine to the metal-free phthalocyanine, and then subjected to sulfuric acid treatment. An X-type metal-free phthalocyanine composition obtained by forming phthalocyanine. 3. An electrophotographic photoreceptor containing a charge generator and a charge transfer agent, wherein the charge generator comprises titanyl phthalocyanine obtained by the method of claim 1 and an X-form metal-free phthalocyanine. An electrophotographic photoreceptor comprising: as a main component. 4. An electrophotographic photoreceptor containing a charge generator and a charge transfer agent, wherein the charge generator comprises titanyl phthalocyanine obtained by the method of claim 1 and an X-form metal-free phthalocyanine. And an electrophotographic photoreceptor comprising titanyl phthalocyanine as a main component. 5. An X-ray diffraction spectrum using Cuk as a source, wherein titanyl phthalocyanine has a Bragg angle (2).
θ + 0.2 degrees) at 27.2 with the largest diffraction peak, and 9.7
5. The electrophotographic photoreceptor according to claim 3, wherein the photoreceptor is a titanyl phthalocyanine compound crystal having a characteristic diffraction peak at 24.1.