JPH05257308A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide a photosensitive body having high sensitivity and no dependence of the sensitivity on humidity, and especially to provide a titanyl phthalocyanine crystal which gives such a dispersion liquid that is stable against an org. solvent and hardly causes dislocation of crystal. CONSTITUTION:A specified titanyl phthalocyanine crystal, namely, an additional compd. of titanyl phthalocyanine and 1,2-butane diol is used for the photosensitive body. It is preferable that the crystal is a N-type crystal showing the max. peak at 26.6 deg. Bragg angle (2theta+ or -0.2) in the X-ray diffraction spectrum for CuKalpha. More preferably, the crystal is a N1-type crystal of the additional compd. having peaks at 12.6 deg., 16.2 deg., and 26.2 deg., or a N2-type crystal having peaks at 9.0 deg., 13.9 deg., 16.3 deg., and 26.2 deg..

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor. In particular, the present invention relates to a photoconductor that is used in a printer or the like and is effective for LED light and semiconductor laser light.

[0002]

2. Description of the Related Art In recent years, the development of electronic equipment has been remarkable, and the demand for printers and digital copying machines used for computer output is increasing. These devices require a photoconductor that is sensitive to red to near infrared light because a semiconductor laser or LED is used as a light source. A conventional inorganic photoreceptor such as a selenium type is not sufficient for this purpose, and many organic photoreceptors (OPC) in which phthalocyanines are dispersed have been studied.

Among them, titanyl phthalocyanine, especially
Y-type titanyl phthalocyanine, which is characterized by having peaks at 27.2 and 9.6 degrees, is an excellent material with a high photon efficiency of 0.94 (Japan Hardcopy 89, Proceedings 103, (19
89)).

However, this product has a drawback that its sensitivity is somewhat changed depending on humidity. Even if it can be used for a printer having only binary values of ON-OFF, this is not preferable for an attempt to obtain a higher-level image and to produce gradation according to the exposure amount. Further, as a defect of the Y-type, this substance is a metastable crystal and is easily transformed into a stable crystal. The crystal transition due to heat is about 250 ° C, so there is no practical problem if it is used as a photoreceptor. However, depending on the type of solvent used in the dispersion during the production of the photoreceptor, crystal transition occurs even at a low temperature, resulting in a problem that the life of the coating solution is shortened.

The fact that the service life of the coating dispersion is shortened means that in dipping coating, the pigment is discarded before it is completely consumed as a photoreceptor. In other words, the cost is high.

[0006]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a photoreceptor having high sensitivity and humidity sensitivity independent of humidity. A second object of the present invention is to provide a titanyl phthalocyanine crystal which is stable to an organic solvent and gives a dispersion liquid which hardly causes crystal transition.

[0007]

SUMMARY OF THE INVENTION The present invention was accomplished by a photoreceptor containing certain titanyl phthalocyanine crystals.

The specific titanyl phthalocyanine crystal is an adduct of titanyl phthalocyanine and 1,2-butanediol. Of these, preferred is an adduct of titanyl phthalocyanine with 1,2-butanediol and a Bragg angle (2θ ± 2) in an X-ray diffraction spectrum with respect to CuKα.
0.2) which has a maximum peak at 26.2 degrees (named N type crystal). More preferably, a crystal (N1 type crystal) having a diffraction peak at at least 12.6, 16.2 degrees in addition to 26.2 degrees, or at least 9.0, 13.9, 1 in addition to 26.2 degrees
Crystals with diffraction peaks at 6.3 and 26.2 degrees (N2 type crystals)
That is.

[0009] The adduct is composed of titanyl phthalocyanines and 1,2-butanediol as shown in the synthesis example described later, and it is proved that it releases 1,2-butanediol when heated. In addition, as a proof that it is an adduct, there is a feature that when a thermal analysis (TG) is measured at a temperature rising rate of 10 ° C / min, a weight loss is observed at a temperature higher than the boiling point of 198 ° C of 1,2-butanediol of 198 ° C by 50 ° C. , Distinguished from mere mixing. Among the titanyl phthalocyanine-1,2-butanediol adducts of the present invention, a particularly preferred one is a 1,2-butanediol / titanyl phthalocyanine = 1/2 adduct. Although various means can be considered for the synthesis of the adduct of the present invention, the amorphous titanyl phthalocyanines are 1,2-
Preference is given to working in the presence of butanediol. As the treatment method, titanyl phthalocyanine may be mixed as it is with 1,2-butanediol alone, or it may be diluted with another solvent. As the solvent, for example, ethers such as tetrahydrofuran, aromatic compounds such as orthodichlorobenzene,
Examples thereof include ketones such as methyl ethyl ketone and cyclopentanone, and esters such as butyl methacrylate. The temperature can be treated in a wide range in which 1,2-butanediol is present as a liquid, but a range of room temperature to 150 ° C is preferable. Crystal conversion operations include general synthetic chemistry experiments and mere stirring in solvents as seen in industrialized products, as well as operations involving mechanical shearing such as milling as often seen in phthalocyanines. Included in the present invention. Amorphous titanyl phthalocyanines, which are intermediates, can be formed by a known method such as dissolving in sulfuric acid and pouring it into water (acid paste treatment), mechanical pulverization, or milling.

The titanyl phthalocyanines are represented by the following general formula.

[0011]

[Chemical 1]

In the formula, X ¹ to ⁴ are hydrogen atoms, halogen atoms,
Represents an alkyl group or an alkoxy group, n, m,
l and k represent integers of 0 to 4.

The above X-ray diffraction spectrum was measured under the following conditions.

X-ray tube Cu voltage 40.0 kv current 100 mA start angle 6.00 deg. Stop angle 35.00 deg. Step angle 0.020 deg. Measurement time 0.50 sec. Specific titanyl phthalocyanine crystal or 1,2- of titanyl phthalocyanine of the present invention. A photoconductor containing a butanediol adduct is excellent in sensitivity and humidity dependency. The cause of this excellent property is unknown. The crystal structure itself, which appears in the X-ray diffraction spectrum,
Or the added 1,2-butanediol, either of these may be the cause. Based on the theory that the added 1,2-butanediol is the main cause, the following explanation can be made.

Fujimaki found that the sensitivity of the Y-type crystal of the highly sensitive material titanyl phthalocyanine decreases when it is dehydrated by heating or in a dry nitrogen atmosphere.

Since the sensitivity is restored again when water is reabsorbed at room temperature and normal humidity, the Y-type particles are crystals adsorbing water, and holes from the titanyl phthalocyanine excitons generated by the water molecules being exposed to light. It assists the dissociation of photoelectrons and speculates that this may be one of the causes of the high sensitivity of Y-type titanyl phthalocyanine (Y.Fujimaki: IS &T's 7thInt
ernational Congress on Advance in Nonimpact Printi
ng Technologies, Paper Summaries, 269, (1991)). Based on this idea, it can be said that the crystals of the present invention have 1,2-butanediol added in place of water. Unlike water, it is difficult to separate from water because it has a high boiling point, but in the case of 1,2-butanediol, since there are two OH groups in the same molecule, the probability of separating from two adsorption points at the same time is only one adsorption point. It can be guessed that it is much lower than that.

Next, the method for producing the titanyl phthalocyanine of the present invention will be specifically illustrated.

(Synthesis Example 1) (Synthesis of titanyl phthalocyanine-amorphous product) 1,
2-Diiminoisoindoline (29.2 g) was dispersed in ortho-dichlorobenzene (200 ml), titanium tetra-n-butoxide (20.4 g) was added, and the mixture was heated at 150 to 160 ° C. for 5 hours under a nitrogen atmosphere. After cooling, the precipitated crystals were filtered, washed with chloroform, washed with 2% aqueous hydrochloric acid solution, washed with water and methanol, and dried to obtain 26.2 g (91.0%) of crude titanyl phthalocyanine. The crystal form of this product is shown in FIG. Then, 20.0 g of this crude titanyl phthalocyanine was added to concentrated sulfuric acid at 5 ° C or lower.
Dissolve by stirring in 200 ml for 1 hour, and add 4 l of water at 20 ° C.
Pour into. The precipitated crystals were filtered and sufficiently washed with water to obtain 180 g of a wet paste product. Dry this one,
The crystal form of the powder is in an amorphous state as shown in FIG.

(Preparation of Titanyl Phthalocyanine Crystals of the Present Invention) 150 ml of 1,2-butanediol was placed in a flask, and 8 g of the above titanyl phthalocyanine-amorphous dry powder was added thereto. The mixture was then stirred at room temperature for 10 hours. After leaving for half a day, this was poured into 800 ml of methanol to precipitate crystals. The crystals were filtered, washed with methanol, and dried to obtain 8.4 g of desired titanyl phthalocyanine crystals. As shown in FIG. It is a crystal (N1 type crystal) having a maximum peak at a Bragg angle 2θ of 26.2 degrees but also having peaks at 12.6 and 16.2 degrees.

(Synthesis Example 2) 100 ml of ortho-dichlorobenzene and 50 ml of 1,2-butanediol were placed in a flask, and 8 g of titanyl phthalocyanine-amorphous dry powder of Synthesis Example 1 was added thereto. The mixture was then stirred at room temperature for 10 hours. After leaving for half a day, this was poured into 800 ml of methanol to precipitate crystals. The crystals were filtered, washed with methanol, and dried to obtain 8.4 g of desired titanyl phthalocyanine crystals. As shown in FIG. It is a crystal (N1 type crystal) having a maximum peak at a Bragg angle 2θ of 26.6 degrees but having peaks at 12.6 and 16.2 degrees.

(Synthesis Example 3) 100 ml of ortho-dichlorobenzene and 50 ml of 1,2-butanediol were placed in a flask, and 8 g of titanyl phthalocyanine-amorphous dry powder obtained by the method of Synthesis Example 1 was added thereto. The mixture was then heated to 70 ° C. for 7 hours. After cooling down, this is methanol
It was poured into 800 ml to precipitate crystals. The crystals were filtered, washed with methanol, and dried to obtain 8.4 g of desired titanyl phthalocyanine crystals. As shown in FIG. Similar to Synthetic Example 1, Bragg angle 2θ; maximum peak at 26.2 degrees, but otherwise 9.
Crystals with peaks at 0, 13.9, 16.3 degrees (N2 type crystals)
Is.

For comparison, an existing titanyl phthalocyanine crystal was prepared, and an example is shown below.

Comparative Synthesis Example (1) (Preparation of Y-type titanyl phthalocyanine crystal) 60 ml of methyl ethyl ketone and 20 ml of water and 40 g of the titanyl phthalocyanine-wet paste product described in Synthesis Example 1 (solid content: 11%) were added to a beaker, and the mixture was heated to room temperature. For 8 hours and left for half a day.
To this viscous mixture was added 500 ml of methanol to precipitate crystals. The crystals were filtered, washed with methanol, and dried to obtain 4.2 g of desired titanyl phthalocyanine crystals. The crystal form of this product is shown in FIG. Bragg angle 2θ; 9.5 degrees and 2
The feature is that there is a significantly developed peak at 7.2 degrees.
(Y-type crystal) Comparative synthesis example (2) (Synthesis of B-type titanyl phthalocyanine) 5 g of the above titanyl phthalocyanine-amorphous dry powder was added to 300 m of acetic acid.
It was suspended in 1 and heated to reflux for 8 hours. After standing for half a day, it was filtered to obtain B-type titanyl phthalocyanine. The X-ray diffraction spectrum of this product is shown in FIG. 7. This is JP 61217050
It has the same crystal form as that described in No.

Comparative Synthesis Example (3) (Synthesis of A-Type Titanyl Phthalocyanine) 5 g of the above-mentioned titanyl phthalocyanine-amorphous dry powder was recrystallized from 150 ml of chloronaphthalene to obtain A-type titanyl phthalocyanine. The X-ray diffraction spectrum of this product is shown in FIG. It has the same crystal form as that described in JP-A-62-67094.

Next, TG and DSC were measured in order to investigate the basic properties of the titanyl phthalocyanine crystal of the present invention. TG (temperature rising rate 10 ° C./min) is shown in FIG.

The weight loss of the Y-type titanyl phthalocyanine of Comparative Synthesis Example (1) is observed at around 100 ° C. On the other hand, the weight loss of the N-type titanyl phthalocyanine of the present invention described in Synthesis Examples 1, 2, and 3 is recognized at around 350 ° C., which greatly exceeds the boiling point of 1,2-butanediol of 192 ° C. .. It means that 1,2-butanediol does not only exist on the side of the titanyl phthalocyanine particle but also forms some kind of bond (adsorption) with some force. 35
The weight change amounts near 0 ° C. were 7.4, 7.5 and 7.5% in Examples 1, 2 and 3, respectively, and the calculated value was 7.2 assuming that 1,2-butanediol was added in 1/2 mol to titanyl phthalocyanine. Close to%. The A and B types of the comparative example do not have the same weight change as the Y type and the present invention.

FIG. 10 shows the DSC (heating rate 30 ° C./min).

In the Y-type titanyl phthalocyanine of Comparative Synthesis Example (1), an endothermic peak, which seems to be desorption of water, is seen at around 105 ° C. On the other hand, the N-type titanyl phthalocyanine of the present invention of Synthesis Examples 1, 2 and 3 has an endothermic peak at around 410 ° C. and greatly exceeds the boiling point like TG.

Next, the constitution of the photoreceptor of the present invention will be described.

In addition to the above-mentioned titanyl phthalocyanine compound, the photoreceptor of the present invention may further contain other carrier generating substances. Specifically, a titanyl phthalocyanine crystal having a crystal form different from that of the present invention, for example, A, B, Y
You can name the mold.

In addition, various phthalocyanines such as vanadyl phthalocyanine, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine and ε-type copper phthalocyanine, as well as condensed polycyclic pigments such as azo pigments, anthraquinone pigments and perylene pigments can be used. it can.

[0032]

[Chemical 2]

[0033]

[Chemical 3]

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

In order to form the photosensitive layer of the photosensitive member of the present invention, a layer in which the above-mentioned carrier generating substance is dispersed in a binder may be provided on the conductive support. Alternatively, the carrier generating substance and the carrier transporting substance may be combined to provide a laminated type so-called function separation type photosensitive layer. In these layer structures, an intermediate layer is provided between the photosensitive layer of each of the single layer and the laminated layer and the support, or an intermediate layer is provided for the purpose of preventing injection of free electrons from the conductive support, and further a protective layer is provided on the surface. May be.

As the solvent or dispersion medium used for forming the carrier generating layer and the carrier transporting layer, acetone, methyl ethyl ketone, cyclohexanone, toluene, dichlorobenzene, dichloromethane, dichloroethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, Ethyl acetate, butyl acetate, etc. can be raised.

When a binder is used for forming the carrier generating layer or the carrier transporting layer, any binder can be used, but a high molecular polymer forming a hydrophobic electrically insulating film is particularly preferable. Examples thereof will be described below, but the present invention is not limited to these.

1) Polycarbonate 2) Polyester 3) Methacrylic resin 4) Acrylic resin 5) Polyvinyl chloride 6) Polyvinylidene chloride 7) Polystyrene 8) Polyvinyl acetate 9) Styrene-butadiene copolymer 10) Vinylidene chloride-acrylonitrile copolymer Combined 11) Vinyl chloride-vinyl acetate copolymer 12) Vinyl chloride-vinyl acetate-maleic anhydride copolymer 13) Silicone resin 14) Silicone-alkyd resin 15) Phenol-formaldehyde resin 16) Styrene-acrylic copolymer resin 17 ) Styrene-alkyd resin 18) Poly-N-vinylcarbazole 19) Polyvinyl butyral 20) Polycarbonate Z resin These binders can be used alone or as a mixture of two or more kinds.

The ratio of the carrier generating substance to the binder 100 is 10 to 600 wt / wt, preferably 20 to 400 wt / wt, and the carrier transporting substance is 10 to 400 wt / wt.

The thickness of the carrier generating layer thus formed is preferably 0.05 to 30 μm, and particularly preferably 0.5 to 5 μm in the case of lamination. The thickness of the carrier transport layer is 2
˜100 μm, preferably 5˜30 μm.

Further, the photosensitive layer may contain one or more electron accepting substances for the purpose of improving sensitivity, reducing residual potential and reducing fatigue during repeated use.
Examples of the electron acceptor that can be used here include maleic anhydride, tetrachlorophthalic anhydride, tetracyanoethylene, tetracyanoquinone dimethane, dinitrobenzene, nitrobenzonitrile, chloranil, anthraquinone, nitrobenzoic acid, and nitrofluorenone. A compound having a high electron affinity can be given.

Further, the photosensitive layer may contain a deterioration inhibitor such as an antioxidant or a light stabilizer for the purpose of improving storability, durability and environmental dependency. Examples of compounds used for such purpose include chromanol derivatives such as tocophenol and etherified or esterified compounds thereof, polyarylalkane compounds, hydroquinone derivatives, benzotriazole derivatives, phosphite esters, hindered phenol compounds, hindered amine compounds. And so on.

Specifically, "IRGANOX1010" and "IRGANOX56
5 "(made by Ciba Geigy)," Sumilyzer BHT ",
Examples include hindered phenol compounds such as "Sumilizer MDP" (manufactured by Sumitomo Chemical Co., Ltd.) and hindered amine compounds such as "Sanol LS-2626" and "Sanol LS-622LD".

As the binder used for the intermediate layer and the protective layer, those mentioned above for the carrier generation layer and the carrier transport layer can be used. Further, polyamide resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol, cellulose derivative and the like are effective. The support on which the photosensitive layer is provided is a metal plate, a metal drum, a conductive polymer, a conductive thin film made of a conductive compound such as indium oxide or a metal such as aluminum, palladium or gold, and a paper plastic film. It is possible to use those provided by means of coating, vapor deposition, lamination, etc. on a substrate such as.

The intermediate layer functioning as an adhesive layer or a barrier layer is made of a polymer such as the above-described binder resin, an organic polymer such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide or titanium oxide. Can be used.

[0049]

EXAMPLES As described above, the present invention provides an electrophotographic photosensitive member useful for LED light and semiconductor laser light by using a specific titanyl phthalocyanine crystal. The photoconductor of the present invention has high sensitivity, and the environment (humidity)
It is a good thing without any dependence. The features of the present invention will be described below with reference to examples.

Example 1 3 parts of the titanyl phthalocyanine N1 type crystal of the present invention (FIG. 3) obtained in Synthesis Example 1 and a silicone resin (“KR-524”
0,15% xylene butanol solution "manufactured by Shin-Etsu Chemical Co., Ltd.) 20
Parts and 100 parts (wt) of methyl ethyl ketone were pulverized and dispersed by a sand grinder to obtain a dispersion liquid. The obtained dispersion was applied to an aluminum vapor-deposited polyester base to form a carrier generation layer having a thickness of 0.2 μm. On the other hand, carrier transport material (2) 1
Parts and polycarbonate resin (“UPILON Z200” manufactured by Mitsubishi Gas Chemical Co., Ltd.) 2 parts (wt) and 0.01 parts of silicone oil (“KF-54” manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 15 parts (wt) of 1,2-dichloroethane. This was blade-coated on the carrier generating layer to form a carrier transporting layer having a dry film thickness of 22 μm to prepare a photoreceptor. Sample 1 is used.

Example 2 A photoconductor was prepared in the same manner as in Example 1, except that the titanyl phthalocyanine pigment in Example 1 was replaced with the N1-type crystal obtained in Synthesis Example 2. This is sample 2.

Example 3 A photoconductor was prepared in the same manner as in Example 1 except that the titanyl phthalocyanine pigment in Example 1 was replaced with the N2 type crystal obtained in Synthesis Example 3. This is sample 3.

Comparative Example (1) A photoconductor was prepared in the same manner except that the titanyl phthalocyanine N1 type crystal in Example 1 was replaced with the Y type crystal obtained in Comparative Synthesis Example (1). This is a comparative sample (1).

Comparative Example (2) A photoconductor was prepared in the same manner as in Example 1, except that the titanyl phthalocyanine N1 type crystal was replaced with the B type crystal obtained in Comparative Synthesis Example 2. This is Comparative Sample 2. Comparative Example (3) A photoconductor was prepared in the same manner except that the titanyl phthalocyanine N1 type crystal in Example 1 was replaced with the A type crystal obtained in Comparative Synthesis Example 3. This is Comparative Sample 3.

(Evaluation 1) Each of the samples obtained above is used as a paper analyzer EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.).
It evaluated using. -Electrically charged for 5 seconds under a discharge condition of -80 μA, exposed so that the surface potential immediately after charging [Va], the surface potential after standing for 5 seconds in the dark [Vi], and the surface illuminance become 2 (lux), and the surface potential is 1 Exposure amount until it becomes / 2Vi [E1
/ 2 (lux.sec)] was calculated. Further, the attenuation rate [D (%)] of the potential in a dark place was obtained by the formula: D = (Va-Vi) / Va × 100. The results are shown in Table 1.

[0056]

[Table 1]

The type A given for comparison has poor sensitivity, and the type B has D
Is large, that is, the surface potential cannot be maintained in the dark. On the other hand, the N-type crystals (N1-type crystal and N2-type crystal) of the present invention are excellent in both sensitivity and dark decay. In the evaluation of this method, the Y type given in the comparison is at room temperature and humidity (humidity).
45-55%), which is superior to that of the present invention.

(Evaluation 2) Samples 1, 2, 3 and comparative samples (1), (2), on the drum of a color printer 9028 (manufactured by Konica) modified machine using a semiconductor laser as a light source.
(3) was attached, and the charging electrode was adjusted so that the surface potential of the unexposed portion of Sample 1 was about 800v. Then, the amount of laser light was varied and the surface potential at each amount of light was measured. Furthermore, we brought this in an atmosphere with a humidity of 20% and saw a decrease in the surface potential with the same laser power. It shows in Table 2.

[0059]

[Table 2]

In the comparative sample (2), the B type is less likely to carry a potential, and the A type is poor in sensitivity. On the contrary, the N type of the present invention is sensitive and has a potential. The Y type given in Comparative sample (1) has good sensitivity, but its change with humidity is large. Considering that the light intensity of laser light is normally distributed in reality (Fig. 11), the drawback is that the reproduction of higher-level images that require gradation changes depending on the humidity at that time. Means there is. In that respect, it can be seen that the N-type crystal of the present invention shows no change in sensitivity due to humidity and is resistant to change in environment.

(Evaluation 3) The dispersions of Examples 1, 2 and 3 using the N-type crystal of the present invention and the dispersion of Comparative Example (1) using Y-type titanyl phthalocyanine were stored at room temperature for 50 days. Then, a photoreceptor sample was prepared with this. Then, the electrophotographic characteristics were measured by the same method as (Evaluation 1). The results are shown in Table 3.

[0062]

[Table 3]

The performance of Samples 1, 2, and 3 using the N-type crystal, which is the compound of the present invention, was not changed, but the sensitivity of the comparative sample using the Y-type was significantly lowered. The Y-type is an excellent crystal and belongs to a category of good performance even after deterioration, but considering the stability in production, the change itself with time rather than the absolute value of sensitivity becomes a problem. That is, the coating liquid with reduced sensitivity is inevitably discarded. In that respect, the present invention is suitable for stable production without any change.

[0064]

INDUSTRIAL APPLICABILITY The N-type titanyl phthalocyanine of the present invention has good sensitivity, good potential application, little dark decay, and good humidity stability. Moreover, the paint stability is good.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum diagram of crude titanyl phthalocyanine in Synthesis Example 1.

FIG. 2 is an X-ray diffraction spectrum diagram of the wet paste titanyl phthalocyanine obtained in Synthesis Example 1.

FIG. 3 is an X-ray diffraction spectrum diagram of N1-type crystalline titanyl phthalocyanine.

FIG. 4 is an X-ray diffraction spectrum diagram of N1-type crystalline titanyl phthalocyanine.

FIG. 5: X-ray diffraction spectrum diagram of N2-type crystal titanyl phthalocyanine obtained in Synthesis Example 3

FIG. 6 is an X-ray diffraction spectrum diagram of Y-type crystal titanyl phthalocyanine.

FIG. 7: X-ray diffraction spectrum of B-type crystalline titanyl phthalocyanine

FIG. 8: X-ray diffraction spectrum diagram of A-type crystalline titanyl phthalocyanine

FIG. 9 is a TG diagram of N1 and N2 type crystals and Y type titanyl phthalocyanine obtained in Synthesis Examples 1, 2 and 3.

FIG. 10: DS of Y, N type crystalline titanyl phthalocyanine
Figure C

FIG. 11 is a luminance distribution diagram of a laser beam

Claims (4)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer containing a titanyl phthalocyanine crystal on a conductive support, and the titanyl phthalocyanine crystal is an adduct of titanyl phthalocyanine and 1,2-butanediol. .. 2. The titanyl phthalocyanine 1,2-butanediol adduct is a crystal having a maximum peak at 26.2 degrees of Bragg angle (2θ ± 0.2) in an X-ray diffraction spectrum for CuKα. The electrophotographic photoconductor according to item 1. 3. The 1,2-butanediol adduct of titanyl phthalocyanine has an Bragg angle (2θ ± 0.2) of at least 12.6, 16. in the X-ray diffraction spectrum for CuKα.
2, a crystal with a peak at 26.2 degrees or at least 9.0,
The electrophotographic photoreceptor according to claim 1 or 2, which is selected from crystals having peaks at 13.9, 16.3, and 26.2 degrees. 4. An electrophotographic photoconductor comprising a 1,2-butanediol adduct of titanyl phthalocyanine produced by treating an amorphous form of titanyl phthalocyanine in the presence of 1,2-butanediol.