JP3470451B2 - Modified chlorogallium phthalocyanine crystal, method for producing the same, and electrophotographic photoreceptor using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a modified chlorogallium fluoride.
TarocyanineCrystalManufacturing methodTo the lawIt is about. [0002] 2. Description of the Related Art Conventionally, a photoconductive material of an electrophotographic photosensitive member has been used.
Various inorganic and organic photoconductive materials are known.
ing. Organic photoconductive materials are used for electrophotography.
If the film has transparency, good film forming property, flexibility, cost
Is relatively low, etc.
Various things have been proposed. In recent years, conventional organic light
Conductive wavelength range of conductive material
Laser wavelength by extending it to the wavelength range of
Requirements for use as a photoconductor for digital recording such as linters
Are increasing, and from this point of view,
Lithium compounds (JP-A-49-105536 and
JP-A-58-21416), triphenylamine
Trisazo compounds (JP-A-61-151659)
Report), phthalocyanine compounds (Japanese Patent Application Laid-Open No. 48-34189)
And Japanese Patent Application Laid-Open No. 57-148745).
It has been proposed as an organic photoconductive material for conductor lasers.
Organic photoconductive materials are used as photosensitive materials for semiconductor lasers.
First, the photosensitive wavelength range extends to longer wavelengths.
Then the sensitivity and durability of the photoreceptor formed
It is required to have excellent properties. In order to meet the above requirements, an organic photoconductive
Vigorous R & D has been attempted on substances.
In the case of phthalocyanine compounds, their crystal forms and
Many reports have been made on the characteristics of child photographs. General
In addition, the phthalocyanine compound is produced or treated
Separation into several crystal forms due to differences in methods, and
Of phthalocyanine compounds with different crystal forms
It is known to have a significant effect on sex. Phthalasi
For the crystal form of the anine compound, for example, copper phthalocyanine
Looking at Anin, in addition to the stable β-form, α, ε,
Crystal types such as π, x, ρ, γ, and δ are known.
These crystal forms impart mechanical strain, or
By sulfuric acid treatment, organic solvent treatment, heat treatment, etc.
It is also known that mutual transfer is possible (eg,
For example, U.S. Pat. Nos. 2,770,629 and 3,
Nos. 160,635 and 3,708,292
JP-A No. 3,357,989). Also no money
For the genus phthalocyanine, α, β, γ and x type etc.
Is known. Furthermore, chlorogariu
Regarding muphthalocyanine, see Journal of the Society of Electrophotography, 26
(3), 240 (1987), to a specific Bragg angle
Bonding of chlorogallium phthalocyanine with diffraction peak
The crystal form is described, but the crystal form is
The crystal type is different from that of the present invention, and
There is no report on its application to electrophotography. On the other hand,
JP-A-59-44053 and Religious Technical Report CPM81-
69, 39 (1981), etc.
And Japanese Patent Application Laid-open No. Hei 1-222159.
The report shows that there is a diffraction peak at a specific Bragg angle.
Rogalium phthalocyanine and electrophotographic feeling using it
Light bodies are described. [0004] SUMMARY OF THE INVENTION However, the conventional
Chlorogallium phthalocyanine is dispersible in binder resin
And inferior stability of the dispersion, such as fog and black spots
There is a problem that image quality defects are likely to occur.
Good was desired. By the way, the dispersibility of general pigments
Improvement methods include silane coupling agents and titanium
Modification of pigment surface with additives such as salt coupling agent
And pigment surface treatment by plasma CVD
However, the former causes a decrease in sensitivity and an increase in residual potential
In the latter case, the process becomes complicated and cost
There is a problem that the impact on
And from these methods chlorogallium phthalocyanine
Applying to was not practical. [0005] The present invention relates to the above-described prior art.
This was done in order to solve the various problems. Sand
That is, an object of the present invention is to exhibit high sensitivity and good electrophotographic characteristics.
As well as a modified resin with excellent dispersibility in the binder resin.
Lologallium phthalocyanineCrystalProvide manufacturing method
In thatYou. [0006] Means for Solving the Problems The present inventorIsRologari
Hydroxygallium on the crystal surface of um phthalocyanine crystal
Changed to muphthalocyanineResults
FruitThe present invention has been completed. SandChi, bookInvention
The method for producing the crystalline chlorogallium phthalocyanine is
Lologallium phthalocyanine crystals in alkaline aqueous solution
By processingThe saidChlorogallium phthalocyanine
The chlorogallium phthalocyanine is bonded to the crystal surface of the crystal.
In the range where the chlorine reduction rate from the crystal becomes 5 to 20% by weight,
Roxygallium phthalocyanineToFeatures
TossYou. Hereinafter, the present invention will be described in detail. Book
inventionbyThe modified chlorogallium phthalocyanine crystal is
On the crystal surfaceFrom chlorogallium phthalocyanine crystals
In the range where the chlorine reduction rate of
Gallium phthalocyanineCoating formed
Chlorogallium phthalocyanine crystal
In particular, the Bragg angle (2
θ ± 0.2 °) at least 7.4 °, 16.6 °, 2
Strong diffraction peaks at 5.5 ° and 28.3 °
Is preferred. [0008] The present inventionbyThe above modified chlorogallium lid
Russiannin crystals can be produced as follows
You. First, to synthesize phthalocyanine, use phthalonite
Addition of ril or diiminoisoindoline and metal chloride
Phthalonitrile heated in the presence of heat melting or organic solvent
Phthalic anhydride, heat melting of urea and metal chlorides
Or the Wiler method of heating in the presence of an organic solvent, cyano
Method of reacting benzamide and metal salt at high temperature,
Such as a method of reacting a metal salt with a titanium phthalocyanine.
Bragg for CuKα characteristic X-rays by a known method
At least 11.0 ° of angle (2θ ± 0.2 °), 1
Quarters with strong diffraction peaks at 3.5 ° and 27.1 °
A lologallium phthalocyanine crystal (a) is synthesized. Up
Examples of the organic solvent used include α-chlorona
Phthalene, β-chloronaphthalene, methoxynaphthale
, Diphenylethane, ethylene glycol, dialky
Ruether, quinoline, sulfolane, dimethyl sulfoxy
Reaction of sid, dichlorobenzene, dichlorotoluene, etc.
Active high-boiling solvents are mentioned. Next, the chlorogallium obtained by the above method is used.
A vitreous mill, an automatic mortar,
Sand mill, sueco mill, attritor, ball mill, etc.
After dry pulverization using a pulverizer,
Benzyl alcohol, isopropyl alcohol, cyclo
Hexanone, toluene, dimethylsulfoxide, acetate acetate
CuK by wet grinding using a solvent such as chill
α-characteristic X-ray Bragg angle (2θ ± 0.2 °)
At least 7.4 °, 16.6 °, 25.5 ° and 2
Chlorogallium lid with a strong diffraction peak at 8.3 °
Russiannin crystals (b) are obtained. [0010] The present inventionAtModified chlorogallium lid
Russinine crystal is chlorogallium phthalocyanine
(B) is added to an alkaline aqueous solution, and room temperature to 100 ° C.
Can be produced by treating with This place
The method of operation includes propeller and magnetic stirrer.
Stirring, ultrasonic cleaner, ball mill, attritor
-Dispersion processing and mixer by vibration mill, sand mill, etc.
-Shaking with a shaker, shaker, etc.
Is preferred. MaCrazyChlorogallium phthalocyanine
Nin crystals are treated with alkaline aqueous solution after dry grinding
And then wet grinding.
Can be used, and after dry grinding, use an alkaline aqueous solution
It can also be obtained by wet pulverization. this
As an aqueous alkaline solution, dissolve the alkaline compound in water.
The dissolved solution is used. The alkali used at that time
Sodium hydroxide, potassium hydroxide
, Magnesium hydroxide, calcium hydroxide, sodium carbonate
Lium, potassium carbonate, ammonia, sodium bicarbonate
Inorganic compounds such as ethylamine, diethylamine,
Organic compounds such as triethylamine, aniline and pyridine
Is raised. The concentration of this alkaline aqueous solution is
Can be appropriately selected in consideration of the solubility of the hydrophilic compound. The chlorogallium phthalocyanine crystal is
Hydrolyzed in hydroxygallium phthalocyanine
And hydrogen chloride, but alkaline aqueous solution
Hydrogen chloride generated in the medium quickly by the alkali
Hydrolysis is promoted because
The crystal surface in contact with the aqueous solution easily hydrolyzes
Changes to roxygallium phthalocyanine. But that
The crystal inside does not come into contact with the alkaline aqueous solution,
Lologallium phthalocyanine is maintained,
A reaction occurs only on the crystal surface and hydroxygallium phthalo
CyanineChange toBecause In the present invention,
Hydroxygallium in lologallium phthalocyanine crystal
The presence of muphthalocyanine indicates that
Salt calculated from elemental analysis of lithium phthalocyanine crystal
It can be obtained from the elementary reduction rate. The modified black of the present invention
The chlorine reduction rate of the loggallium phthalocyanine crystal is 5-2.
The range is 0%. If this chlorine reduction rate is too large,
Insensitive crystals in modified chlorogallium phthalocyanine crystals
Of hydroxygallium phthalocyanine in crystalline form
If the sensitivity is reduced because it increases, and if it is too small
The effect of improving dispersibility cannot be obtained. [0012] In the present invention, chlorogallium phthalocyanine is used.
By treating nin crystals with an aqueous alkaline solutionWhat,
On the crystal surface of chlorogallium phthalocyanine crystal,chlorine
In the range where the reduction rate is 5 to 20% by weightHydroxygaliu
MuphthalocyanineChanged toTo form a film
More sensitive properties of chlorogallium phthalocyanine
Can be maintained and its dispersibility can be improved
You. Chlorogallium phthalocyanine has an electrostatic polarity
Is significantly negatively biased, causing affinity with binder resin and solvent.
Lacking dispersibility, thus making it easier to aggregate and dispersing
It is thought that it is getting worse. So, chlorogallium
Phthalocyanine crystals, some of which are hydroxygallium
Polarity is weakened by changing to phthalocyanine
To achieve electrostatic harmony with the binder resin and solvent.
Therefore, the aggregation of the pigment is less likely to occur, and the dispersibility is reduced.
It will be improved. Also, with an alkaline aqueous solution
The treatment removes ionic impurities in the pigment, which deteriorate dispersibility.
It is possible to further improve dispersibility because it can be removed
it can. Next, the present inventionObtained byModified chloro
Gallium phthalocyanine crystal in electrophotographic photoreceptor
The case where it is used as a photoconductive material will be described.the above
StrangeCrystalline chlorogallium phthalocyanine crystal
The photosensitive layer of the photoreceptor has a single layer structure, or the charge generation layer
Whether it is a layered structure separated in function from the charge transport layer
It can also be applied to As a conductive support
Whatever is used conventionally
A thing may be used. The surface of the conductive support must be
Perform various types of processing as necessary without affecting the image quality
be able to. For example, anodizing the surface,
Surface treatment, chemical treatment, coloring treatment, etc.
It can be carried out. In the case of a stacked photoconductor, the conductive support
At least the charge generation layer and the charge transport layer are laminated on the support
Are provided, but the order of lamination is
It may be on the substrate side. The charge generation layer is a modified chlorogallium phthalo
Consists of cyanine crystals and a suitable binder resin solution
However, it is not always necessary to use a binder resin. Also charge
Generated material is modified chlorogallium phthalocyanine
In addition to the crystals, other known charge generating materials may be used in combination.
No. Further, any known binder resin may be used.
Can be used. Distribution of charge generation material and binder resin
The mixing ratio is 40: 1 to 1: 4, preferably 20: 1 to 1:
2. If the charge generation material ratio is too high,
If the stability of the fabric solution is too low,
Therefore, it is preferable to set the above range. Electric
Solvents used to disperse load-generating materials include methanol
, Ethanol, n-butanol, benzyl alcohol
, Methyl cellosolve, ethyl cellosolve, acetone,
Methyl ethyl ketone, cyclohexanone, methyl acetate,
Ethyl acetate, n-butyl acetate, dioxane, tetrahydride
Lofran, methylene chloride, chloroform, benzene,
Ruene, xylene, chlorobenzene, dimethylforma
Organic solvents such as amide and dimethylacetamide
A mixed solvent is mentioned. As a dispersing means, Sun
Domill, colloid mill, attritor, ball mill, da
Uses methods such as INNO mill, Koball mill, and roll mill
it can. The coating method is blade coating.
Method, wire bar coating method, spray coating
Coating, dip coating, bead coating,
A method such as a curtain coating method can be used.
You. The thickness of the charge generation layer is preferably in the range of 0.01 to 5 μm.
More preferably, it is in the range of 0.03 to 2 μm. The charge transport layer comprises a charge transport material and a film-forming resin.
And known ones can be used. this
As the material used for the film-forming resin, for example, polycarbonate
Nate, polyarylate, polystyrene, polyester
Styrene-acrylonitrile copolymer, polysulfo
, Polymethacrylate, styrene-methacryl
Acid ester copolymers, polyolefins, and the like.
Of these, polycarbonate with excellent durability is preferred
It is. Mixing ratio of charge transport material and film-forming resin (weight)
Is 5: 1 to 1: 5, preferably 3: 1 to 1: 3
You. If the charge transport material ratio is too high,
If the mechanical strength of the layer is too low,
Therefore, it is preferable to set the above range. Ma
When the charge transport material has a film forming property,
The conductive resin can be omitted. The charge transport layer is the charge transport layer described above.
Dissolve the material and film-forming resin in a suitable solvent and apply
It is formed by
Use the same method as described for the charge generation layer.
Can be. The thickness of the charge transport layer is in the range of 5 to 50 μm.
Enclosed, preferably formed in the range of 10 to 40 μm
Is preferred. [0016]the aboveElectrophotographic photoreceptor, the photosensitive layer
In the case of a single-layer structure, the photosensitive layer is modified chlorogallium.
Phthalocyanine crystal and charge transport material are separated into film-forming resin.
It is formed from the scattered photoconductive layer. In this case, charge transport
Any known materials can be used,
As the film-forming resin, the same as those described above
Since the photosensitive layer can be used, any of the photosensitive layers described above can be used.
It can be formed by such a method. At that time, electric charge
The mixing ratio (weight) of the transport material and the film-forming resin is 1:20.
５5: 1, preferably modified chloroform
Compounding ratio of lithium phthalocyanine crystal to charge transport material
(Weight) is preferably set to 1:10 to 10: 1
No. Also,the aboveThe electrophotographic photoreceptor can be
An undercoat layer may be provided between the optical layer and the substrate. Undercoat layer
Is used to prevent unnecessary charge injection from the substrate.
And has the effect of improving the chargeability of the photoreceptor.
are doing. Furthermore, the adhesion between the photosensitive layer and the substrate has been improved.
Has the effect of causing Further, the electrophotographic photosensitive of the present invention
The body has a protective layer on top of the photosensitive layer to improve durability
May be provided. [0017] The present invention will be described in more detail with reference to the following examples.
I will tell. In addition, "part" means "part by weight". (Synthesis of chlorogallium phthalocyanine) Production Example 1 (Comparative Example) 1,3-diiminoisoindoline 30 parts, gallium trichloride
9.1 parts into 230 parts of quinoline,
After reacting for 4 hours, the product was filtered off.
After washing with N-dimethylformamide and methanol,
After drying the wet cake, chlorogallium phthalocyanine
28 parts of crystals were obtained. The obtained chlorogallium phthalos
FIG. 1 shows a powder X-ray diffraction pattern of the anine crystal. In that crystal
The chlorine value by elemental analysis was 5.74 times the same as the theoretical value.
%, And the chlorine reduction rate was 0%. Production Example 2 (Comparative Example) Chlorogallium phthalocyanine crystal obtained in Preparation Example 1
3 parts were shaken with a vibrating mill (MB-1 type, manufactured by Chuo Kakoki Co., Ltd.).
Milled for 8 hours. The obtained chlorogallium phthalocyanine
FIG. 2 shows a powder X-ray diffraction pattern of the crystal. Production Example 3 (Comparative Example) Chlorogallium phthalocyanine crystal obtained in Preparation Example 2
0.5 parts together with 60 parts of 1 mmΦ glass beads
48 hours at room temperature in 20 parts of Zyl alcohol
After the milling, the mixture was filtered off, and this was
Part to obtain chlorogallium phthalocyanine crystals
Was. Powder of the obtained chlorogallium phthalocyanine crystal
The X-ray diffraction diagram is shown in FIG. Production Example 4 (Example) Dissolve 0.5 g of sodium hydroxide in 100 g of distilled water
An aqueous sodium hydroxide solution was prepared. Next, a production example
5 parts of the chlorogallium phthalocyanine crystal obtained in
In addition to the aqueous sodium hydroxide solution, add
For 24 hours. Then, wash it with water,
Separately, the crystal surface becomes hydroxygallium phthalocyanine
Obtained modified chlorogallium phthalocyanine crystals
Was. Of the resulting modified chlorogallium phthalocyanine crystal
The powder X-ray diffraction pattern is shown in FIG. In addition, the source of the obtained crystal
The chlorine value by elementary analysis was 4.84% by weight.
Was 15.7%. Production Example 5 (Example) A mixture of 50 g of diethylamine and 50 g of distilled water
100 g of a ruamine aqueous solution was prepared and obtained in Preparation Example 3.
5 parts of chlorogallium phthalocyanine crystal was
To the aqueous solution of ruamine
The mixture was stirred for 1 hour with a light stirrer. Then add this to water
Washed, filtered, and modified chlorogallium phthalocyanine crystals
I got Obtained modified chlorogallium phthalocyanine
The powder X-ray diffraction pattern of the crystal is shown in FIG. Element of the obtained crystal
The chlorine value by analysis was 5.15% by weight.
The chlorine reduction rate was 10.3%. Manufacturing Example 6 (Example) 5 parts of chlorogallium phthalocyanine crystal obtained in Preparation Example 3
To 100 parts of 1N ammonia water and use an ultrasonic cleaner
And dispersed at room temperature for 1 hour. Then, the dispersion is added to water
By washing and filtering, modified chlorogallium phthalos
Anine crystals were obtained. Obtained modified chlorogallium lid
FIG. 6 shows a powder X-ray diffraction pattern of the Russiannin crystal. Obtained
The chlorine value of the crystal obtained by elemental analysis was 5.37% by weight.
The chlorine reduction rate was 6.4%. [0021]applicationExample 1 First, wet honing of aluminum pipes as follows
Processing (described in JP-A-2-87154)
Was. Use 40φ × 319mm mirror surface aluminum pipe
Using a liquid honing device, an abrasive (trade name:
Green Dessic GC # 400, manufactured by Showa Denko) 10k
g in 40 liters of water and pump 6 liters
At a flow rate of 60 mm / min.
Min, air pressure 0.85kgf / cm^TwoAnd aluminum
The shaft is moved in the axial direction while rotating at 120 rpm.
And a wet honing treatment was performed. The center line flat at this time
The average roughness Ra was 0.16 μm. Next, polyvinyl
Butyral (trade name: Eslec BM-1, Sekisui Chemical Co., Ltd.)
8 parts) was added to 152 parts of n-butyl alcohol.
This was dissolved by stirring, and polyvinyl butyral of 5% by weight was dissolved.
A solution was prepared. Next, tributoxy zirconium a
Cetyl acetonate 50% toluene solution (trade name: Z
C540, manufactured by Matsumoto Koshosha) 100 parts, γ-aminopropyl
Lutriethoxysilane (trade name: A1100, Nihon Uni
10 parts and n-butyl alcohol 130 parts
Into the polyvinyl butyral solution
Then, the mixture is stirred with a stirrer to form a coating for forming an undercoat layer.
A cloth solution was prepared. Apply this coating solution on an aluminum pipe
Dip coating, then heat drying at 165 ° C for 15 minutes,
An undercoat layer having a thickness of 0.15 μm was formed. On the other hand, a vinyl chloride-vinyl acetate copolymer
Fat (brand name: VMCH, manufactured by Union Carbide) 3 parts
Was previously dissolved in 100 parts of n-butyl alcohol
The modified chlorogallium phthalocyanine obtained in Preparation Example 4
One part of the crystal was added, and the mixture was dispersed in a sand mill for 24 hours.
Diluted with chilled alcohol and charged with a solid content of 3.0% by weight.
A coating liquid for forming a load generating layer was prepared. Apply the obtained coating solution
Apply on the undercoat layer described above with a ring coater,
Heat and dry at 00 ° C for 10 minutes.
A charge generation layer was formed. In addition, the modified chloro
The crystal form of the gallium phthalocyanine crystal was determined by X-ray diffraction.
As a result, the crystal form was the same as that before dispersion,
It was confirmed that it did not become. Next, the resulting charge generation
A charge transport layer was formed on the layer. That is, N, N'-bi
S- (p-tolyl) -N, N'-bis- (p-ethyl
Phenyl) -3,3'-dimethylbenzidine (4 parts)
As a material to be sent, together with 6 parts of polycarbonate Z resin,
Dissolve in 40 parts of chlorobenzene and immerse the resulting solution
Using a coating device, apply on the charge generation layer,
Heat drying at 115 ° C for 60 minutes and charge transport of 23 μm thickness
Forming an electrophotographic photoreceptor by forming a layer
Was. [0023]applicationExample 2 As a charge generation material,applicationExample of fabrication used in Example 1
In place of the modified chlorogallium phthalocyanine crystal obtained in Step 4.
And the modified chlorogallium phthalocyanine obtained in Preparation Example 5
Other than using crystals,applicationIn the same manner as in Example 1,
A photoconductor was prepared.application Example 3 As a charge generation material,applicationExample of fabrication used in Example 1
In place of the modified chlorogallium phthalocyanine crystal obtained in Step 4.
And the modified chlorogallium phthalocyanine obtained in Production Example 6
Other than using crystals,applicationIn the same manner as in Example 1,
A photoconductor was prepared. Comparative Example 1 As a charge generation material,applicationExample of fabrication used in Example 1
In place of the modified chlorogallium phthalocyanine crystal obtained in Step 4.
And the chlorogallium phthalocyanine crystal obtained in Preparation Example 1
Other than usingapplicationElectronic photography was performed in the same manner as in Example 1.
A true photoreceptor was prepared. Comparative Example 2 As a charge generation material,applicationExample of fabrication used in Example 1
In place of the modified chlorogallium phthalocyanine crystal obtained in Step 4.
Chlorogallium phthalocyanine crystal obtained in Preparation Example 2
Other than usingapplicationElectronic photography was performed in the same manner as in Example 1.
A true photoreceptor was prepared. Comparative Example 3 As a charge generation material,applicationExample of fabrication used in Example 1
In place of the modified chlorogallium phthalocyanine crystal obtained in Step 4.
And the chlorogallium phthalocyanine crystal obtained in Preparation Example 3
Other than usingapplicationElectronic photography was performed in the same manner as in Example 1.
A true photoreceptor was prepared. Each of the aboveapplicationElectrons obtained in Examples and Comparative Examples
A laser printer (X
P-11 modified machine, manufactured by Fuji Xerox Co., Ltd.)
Was measured. This operation is performed at 20 ° C and 50% RH.
Scorotron band with grid applied voltage -600V under the border
(A), using a 780 nm semiconductor laser
And 10.0 ergs / cm after 1 second^TwoIrradiate the light
(B), and after 3 seconds, 50 ergs / c
m^TwoIrradiates the red LED light to remove electricity (C)
The potential of each part was measured by the process. in this case,
The higher the potential VH of (A), the higher the potential of the photosensitive member.
To increase the contrast,
The lower the potential VL of (B) is, the higher the sensitivity is.
The lower the potential is, the smaller the residual potential is, and the image memory and fog
Can be evaluated as a photoreceptor having a small number of particles. Also,
Measurement of the potential of each part after 5,000 repetitions of charging and exposure
I also decided. Furthermore, these electrophotographic photoreceptors
Is a laser printer (XP-11, Fuji Xerox
Copy under the environment of 30 ° C. and 85% RH
Thereby, the image quality was evaluated. Table 1 shows these results.
Shown in [0026] [Table 1] [0027] The present inventionbyModified chlorogallium phthalo
The cyanine crystal is chlorogallium phthalocyanine as described above.
By treating anine crystals with an alkaline aqueous solution,
The surface of the crystal is hydrated with a chlorine reduction rate of 5 to 20% by weight.
Roxygallium phthalocyanine
To expose this modified chlorogallium phthalocyanine crystal
Layer for high sensitivity and good electrophotographic properties.
Excellent image quality with excellent dispersibility and no fog or black spots
An electrophotographic photoreceptor having quality characteristics can be obtained. Ma
The modified chlorogallium phthalocyanine crystal of the present invention
The manufacturing method is simple and requires complicated equipment.
Are not economical and have good characteristics.
Stable production of crystalline chlorogallium phthalocyanine crystals
Can be

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal obtained in Production Example 1. FIG. 2 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal obtained in Production Example 2. FIG. 3 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal obtained in Production Example 3. FIG. 4 is a powder X-ray diffraction diagram of a modified chlorogallium phthalocyanine crystal obtained in Production Example 4 (Example). FIG. 5 is a powder X-ray diffraction diagram of a modified chlorogallium phthalocyanine crystal obtained in Production Example 5 (Example). FIG. 6 is a powder X-ray diffraction diagram of the modified chlorogallium phthalocyanine crystal obtained in Production Example 6 (Example).

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09B 67/08-67/12 C09B 67/50

Claims (1)

(57) [Claims] [Claim 1] A chlorogallium phthalocyanine crystal is
The chlorogallium is treated by a lukari aqueous solution.
The crystal surface of the muphthalocyanine crystal is
Chlorine reduction rate from phthalocyanine crystal is 5 to 20% by weight
Changes to hydroxygallium phthalocyanine within the range
Modified chlorogallium phthalocyanine
A method for producing nin crystals.