JP3476488B2 - Titanium phthalocyanine and method for preparing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates generally to titanyl phthalocyanines and methods for their preparation. More specifically, the present invention relates to known type I, type II, type III
And type IV (eg, US Pat. No. 4,898,79).
No. 9, the entire disclosure of said U.S. patent is hereby incorporated by reference), as well as methods for obtaining titanyl phthalocyanine polymorphs or crystals such as their novel crystal variants such as X-titanyl phthalocyanine, It further relates to a multi-layer photoconductive member containing these titanyl phthalocyanine polymorphs. In one embodiment, the present invention employs a titanyl phthalocyanine, either by first using the titanyl phthalocyanine or by reacting the titanium tetra (alkoxide) with a diiminoisoindrene in a solvent such as chloronaphthalene. Preparation is carried out; the resulting pigment is dissolved in a solvent mixture of trifluoroacetic acid and methylene chloride; then the desired titanyl phthalocyanine polymorph is precipitated, for example by adding the above mixture to water with stirring; The product is isolated, for example by filtration; and a method for the preparation of titanyl phthalocyanines by washing the product obtained. Titanyl phthalocyanines, especially,
The known polymorphs IV and forms X above can be used as organic photogenerator pigments in photosensitive imaging members containing charge transport layers, especially hole transport layers such as arylamine hole transport molecules. These photosensitive imaging members can be negatively charged when the photogenerating layer is placed between the hole transport layer and the substrate,
Alternatively, the hole transport layer may be positively charged when placed between the photogenerating layer and the supporting substrate. These multi-layered photoconductive imaging members can be used, for example, in electrophotographic imaging methods, and more particularly in xerographic imaging methods in which a negatively or positively charged image is visualized with a toner composition of suitable charge and It can be used in many different known imaging and printing methods, such as printing methods. Generally, these imaging members are photosensitive in the wavelength region of about 700 to about 850 nn, and therefore diode lasers can be used as the light source. Further, titanyl phthalocyanines can be used as a strong blue light stable colorant used in coatings such as paints and inks, and as a near infrared absorbing pigment suitable for use as an IR laser optical recording material.

In the present invention, for example, in one embodiment, TiOPc (titanyl phthalocyanine),
In particular, polymorphs of types I, II, III and IV, and economical methods for preparing at least three novel crystalline forms not previously disclosed are disclosed. This method goes beyond the prior art in that it is, for example, uncomplicated, rapid, and does not require the use of harsh reactants such as sulfuric acid or the use of energy-intensive methods such as sand milling. It is an improved method.

[0003]

One object of the present invention is to provide a process for the preparation of titanyl phthalocyanine which has many advantages as described herein. Another feature of the present invention is the high degree of flexibility of the process of the present invention which allows the preparation of at least 7 TiOPc polymorphs with minor modification of the process. Another feature of the invention is that the method of the invention comprises, in one embodiment, XRPD.
The purpose is to enable the preparation of a new crystalline form of TiOPc, designated X-form, which differs from the shape conventionally described on the basis of patterns (see eg FIG. 7). Furthermore, another feature of the present invention is that the method of the present invention has the XR shown in FIG.
Novel TiOPc crystal form with PD pattern, ie
To allow the preparation of type Z-1. Yet another feature of the present invention is the novel TiOPc crystal form having the XRPD pattern shown in FIG. 6, namely type Z-2.
To provide a method for preparing titanyl phthalocyanine which gives Yet another feature of the present invention is to provide a process for preparing TiOPc polymorphs having small particle size of about 0.1 micron which is advantageous in making electrophotographic devices, for example because it can be easily dispersed in coating compositions. It is to be.

The above and other objects of the invention, in each embodiment of the present invention, are directed to certain titanyl phthalocyanines, processes for preparing the titanyl phthalocyanines, and photosensitizers containing these titanyl phthalocyanines. This is accomplished by providing an imaging member.
More specifically, in one embodiment of the invention,
Dissolving the titanyl phthalocyanine in a mixture of trifluoroacetic acid and methylene chloride, precipitating the desired titanyl phthalocyanine such as type IV, separating, for example by filtration, and optionally washing the resulting product. Titanyl phthalocyanine (TiOP
c) A method for preparing the polymorph is provided. The resulting product can be identified by various known means, such as X-ray powder diffraction (XRPD). One embodiment of the present invention comprises reacting titanium tetrapropoxide with diiminoisoindolene in a N-methylpyrrolidone solvent to provide Type I
Or β-type titanyl phthalocyanine (as determined by X-ray powder diffraction) is prepared; the resulting titanyl phthalocyanine is dissolved in a mixture of trifluoroacetic acid and methylene chloride; the resulting mixture is stirred with methanol. Such an organic solvent or water;
For example, it relates to a process for the preparation of titanyl phthalocyanine, characterized in that it is separated by vacuum filtration through glass fiber paper in a Buchner funnel; and the resulting titanyl phthalocyanine product is washed.

Of trifluoroacetic acid solvent mixtures, for example:
Examples of titanyl phthalocyanine reactants which can be used in effective amounts of from about 1 to about 40% by weight are known and available titanyl phthalocyanines; titanium halides such as titanium trichloride, titanium tetrachloride or titanium tetrabromide. , Titanium tetra-methoxide, -ethoxide, -propoxide,-
Titanium tetraalkoxides such as butoxide, -isopropoxide, or other titanium salts can be prepared by combining compounds such as phthalonitrile and diiminoisoindole with 1-chloronaphthalene, quinoline, N-methylpyrrolidone, and xylene. Titanyl phthalocyanines synthesized by reacting in a solvent such as alkylbenzene at a temperature of about 120 to about 300 ° C .;
Specific polymorphs of titanyl phthalocyanines such as types I, II, III and IV (their preparations are described, for example, in the literature), or any other suitable TiO 2.
Pc polymorphs; substituted titanyl phthalocyanine pigments having 1 to 16 substituents attached to the outer ring of the compound, which substituents are, for example, halogens such as chloro-, bromo-, iodo- and fluoro-. An alkyl having 1 to about 6 carbon atoms such as methyl-, ethyl-, propyl-, isopropyl-, butyl-, pentyl- and hexyl-; nitro, amino; like methoxy-, ethoxy- and propylthio- Are alkoxy and alkylthio groups); and mixtures thereof.

Solvent mixtures include strong organic acids such as trihaloacetic acid such as trifluoroacetic acid or trichloroacetic acid, alkylene halides such as methylene chloride, chloroform, trichloroethylene, bromoform, and chlorofluorocarbons and hydrochlorofluorocarbons. Other short-chain halogenated alkanes and alkenes containing from about 6 carbon atoms to 1 to about 6 halogen atoms; halos such as chlorobenzene, dichlorobenzene, chloronaphthalene, fluorobenzene, bromobenzene, and benzene. Aromatic compounds; alkylbenzenes such as toluene and xylene; and miscible with strong organic acids and, for example, from about 1 to about 50 parts acid to about 50 parts cosolvent (such as methylene chloride). Titanyl in effective amount of proportion There are co-solvents such as other organic solvents to effectively dissolve Taroshianin. In one embodiment of the present invention, a preferred solvent mixture comprises trifluoroacetic acid and methylene chloride in a ratio of about 5 parts acid to about 95 parts methylene chloride to 25 parts acid to 75 parts methylene chloride.

After solubilization by stirring with a solvent mixture as described above and stirring for an effective time of, for example, about 5 minutes to several days, the resulting mixture allows the precipitation of the desired titanyl phthalocyanine polymorph, such as type IV. Add to solvent. This solvent is
Alcohols such as alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, n-butanol, pentanol; ethers such as diethyl ether and tetrahydrofuran; pentane, hexane and the like, for example, about 4 to about 10 Hydrocarbons containing carbon atoms; aromatic solvents such as halobenzenes such as benzene, toluene, xylene, chlorobenzene; carbonyl compounds such as acetone, methyl ethyl ketone and butyraldehyde; glycols such as ethylene glycol and propylene glycol; glycerin; Includes polar aprotic solvents such as dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone; water; and / or a mixture of solvents. The resulting titanyl phthalocyanine polymorph is then filtered and then acts to remove residual solvent and impurities that may have been released during the dissolution and reprecipitation steps of the pigment, such as deionized water, methanol. Wash with various solvents such as various alcohols. The solid obtained is then dried, for example by heating, to give the desired dark blue pigment of titanyl phthalocyanine, the shape of which is determined by the composition of the precipitant solvent. The polymorphic form and purity of the product is X
It was measured by RPD analysis.

In one embodiment of the invention, 1)
The precursor pigment, which may be in any TiOPc crystalline form, is added into a mixture of trifluoroacetic acid and methylene chloride containing about 5 to about 25 parts acid and about 95 to about 75 parts methylene chloride, and the resulting mixture is added to the mixture. For example, about 5 minutes to several days (in one embodiment, 2 weeks), about 0 to about 50.
The precursor pigment is dissolved in the acid mixture by stirring at a temperature of ℃, the amount of the precursor pigment,
For example, 5 to about 25 parts of precursor pigment to about 100 parts of acid solution; 2) add the resulting solution to the precipitant solution under rapid agitation, about 1 part of the pigment solution to 2 parts of the precipitant. solution~
A ratio of about 1 part of the pigment solution to about 50 parts of the precipitant solution is added at a temperature of about 0 to about 100 ° C. for 1 minute to about 60 minutes to effect rapid effective mixing, and the precipitant solution is allowed to react. Stir at a speed sufficient to form a deep vortex in the vessel, the pigment is poured into the side of the vortex in a slow stream; 3) After pouring, the resulting dispersion of the desired TiOPc polymorph is 0 to about 0. Stir for about 5 minutes to about 24 hours at a temperature of 100 ° C .; 4) then separate the titanyl phthalocyanine from the mother liquor, for example by filtering through a glass fiber filter in a porcelain filter funnel to give the product titanyl phthalocyanine pigment. To remove most of the acid mother liquor in the funnel with an effective amount of wash solvent (such as methanol), eg about 20 parts wash solvent to about 1 part starting pigment; 5).
The wet cake obtained is placed in a solvent such as methanol, acetone, or water, for example, about 20 to about 100 parts of solvent to 1 part.
In an effective amount, such as some pigments, at a temperature of from 0 to about 100 ° C.
Redispersed for about 24 hours, the main purpose of such washing is residual acid or the specific TiOP produced in the precipitation step.
c) to further remove other impurities from the polymorph; 6) isolate the desired titanyl phthalocyanine polymorph by, for example, filtering with a glass fiber filter as in step 4), and then optionally. Thus, there is provided a method for preparing a titanyl phthalocyanine polymorph, which comprises washing the obtained solid product with a solvent such as water, methanol or acetone to complete the purification.
The final product can be obtained by drying the solid product at a temperature of about 25 to about 150 ° C. for 1 to about 24 hours, for example in air or under vacuum. About 9 starting materials
A yield equivalent to 5-75% by weight can be obtained. The polymorphic form of the final product was determined by XRPD analysis (Table 1
reference).

A typical small scale conversion reaction, in one embodiment of the invention, was carried out as follows: 2
g of titanyl phthalocyanine synthesized by the method of Example 1 described below is stirred in 20 ml of trifluoroacetic acid / methylene chloride 1: 4 mixture (V / V) in a 25 ml Erlenmeyer flask at room temperature for 5 minutes. Dissolved by. The resulting dark green solution, which did not contain any insoluble material, was then poured into 200 ml of methanol in a 250 ml Erlenmeyer flask at room temperature with vigorous stirring. The resulting dark blue suspension,
Allow to stir for an additional 30 minutes at room temperature, then 4.25 cm
Filtered through a glass fiber filter (Whatman GF / A grade), and the solid obtained was washed with about 20 ml of methanol in a funnel. The wet filter cake obtained was transferred to a 125 ml flask and redispersed in 50 ml of methanol. The resulting dispersion was stirred for 30 minutes, then re-filtered as above and the solid obtained in a funnel with methanol (20 ml) then water (2 × 20 ml) and finally again. Methanol (20 ml)
Washed with. The solid obtained was dried at 70 ° C. for 2 hours to obtain about 1.8 g of a dark blue pigment. This was determined to be a novel TiOPc polymorph, referred to herein as type Z-1 (see XRPD pattern in Figure 5).

[0009]

TABLE 1 precipitating agents acting standard test of the solvent with respect polymorphs: the 20 ml 1: poured TiOPc of _{4 CF 3 CO 2 H / CH} 2 2g in Cl ₂ to 200 ml of precipitant solvent . Precipitant XRPD analysis Water type IV Methanol type Z-1 1: 1 Methanol / water type X 95: 5 Methanol / water type III (main amount) Isopropanol type II Diethyl ether type I 1: 1 Toluene / water type IV 1: 1 Chlorobenzene / water Type IV 1: 1 acetone / water Type III (main amount) 1: 1 ethanol / water Type X 1: 1 isopropanol / water Type IV 1: 1 ethylene glycol / water Type Z-2 1: 1 dimethylformamide / Water Type III + Type IV 1: Dimethyl sulfoxide / Water Type III + Type IV ^* Crystal form not previously reported.

When the above procedure was repeated with a series of different precipitants as shown in Table 1, the resulting polymorphic form was found to depend on the nature of the precipitant solvent. That is, all known types (type I, II, III or IV) were obtained as shown in Table 1. These polymorphs have their respective XRP
D was identified by comparison with the known form of XRPD shown in FIGS. Precipitation in ethylene glycol / water (1: 1) also gave a previously undescribed TiOPc polymorph called Type Z-2. The XRPD is shown in FIG. A third novel type of titanyl phthalocyanine, found from a 50:50 mixture of methanol or ethanol and water and found to have very high sensitivity to 780 nm light, identified herein as Form X, is shown in FIG. It had an XRPD pattern shown in. This new type X polymorph is a Bragg
gg) Similar to type IV TiOPc in that it exhibits its strongest peak at an angle 2θ = 27.3 °, but is very clear in the XRPD of the type IV titanyl phthalocyanine pigment, about 2θ = 9.5 and 9.7. It is substantially different from Type IV in that the peak in degrees does not exist for Type X material. Moreover, the type X form peak at 2θ = about 7.4 degrees is relatively much more pronounced than the same peak of type IV XRPD shown in FIG. 4 (compared to the other peaks in the diffractogram). ). These are the most major differences between the Type IV and Type X polymorphs, but other more subtle differences that are apparent to those familiar with the interpretation of X-ray diffraction may be observed. In addition, the X form has 2θ of 14.1 and 17.8 degrees.
The value shows a broad diffraction peak. Each 2θ value reported is Cu
It is related to the diffraction of alpha radiation (wavelength = 0.1542 nm). In another embodiment of the invention, TiOPc in a 1: 4 mixture of trifluoroacetic acid and methylene chloride.
The solution was precipitated into a mixture of methanol and water varying from 100% methanol to 100% water. After isolation as described above, each sample was analyzed by XRPD. The results are shown in Table 2 below.

[0011]

TABLE 2 precipitant solvent ratio (MeOH / H ₂ O) XRPD Analysis 100: 1 Type Z-1 95: 5 Type III (major amount) 90:10 Type III (major amount) 85:15 Type III ( Main amount) 80:20 Type III (main amount) 75:25 Type III (main amount) 70:30 Type III (main amount) 65:35 Type III (small amount) + Type X 60:40 Type X 55:45 type X 50:50 Type X 45:55 Type X 40:60 Type X 35:65 Type X 30:70 Type IV 25:75 Type IV 20:80 Type IV 0: 100 Type IV

The data in Table 2 show that at relatively high methanol concentrations, the predominant amount of polymorphs prepared was the Type III form. However, at a composition of about 65% methanol and about 35% water, Type X prevails. Polymorphically pure type X has an acid solution of 60 to 3
Obtained when precipitated in a methanol / water composition in the range of 5% methanol. Compositions containing less than about 35% methanol and pure water have XRPD at 2θ = 9.8 degrees.
Generates type IV with peaks. Another embodiment of the present invention comprises 3-5 molar equivalents of diiminoisoindolene and 1 molar equivalent of titanium tetrapropoxide.
It relates to a process for the preparation of titanyl phthalocyanine, which comprises reacting in a chloronaphthalene or N-methylpyrrolidone solvent at a solvent ratio of about 1 part diiminoisoindolene to about 5 to about 10 parts. The ingredients are stirred and warmed to a temperature of about 160-240 ° C. for about 30 minutes to about 8 hours. After this time, the reaction mixture is charged with about 100-160.
Cool to a temperature of ° C and filter through a sintered glass funnel (M porosity). A sufficient amount of boiling dimethylformamide was added to the resulting pigment in this funnel to remove all of the deeply colored impurities from the solid (as evidenced by the initial black to pale blue-green color change of the filtrate). Wash with (DMF) solvent. After this time, the pigment is placed in the funnel described above with a sufficient amount of boiling DMF.
To prepare a loose suspension and re-filter the suspension. Finally, the solid obtained is washed with DMF at room temperature followed by a small amount of methanol and dried at about 70 ° C. for about 2 to about 24 hours. Generally, an amount of DMF equal to the amount of solvent (chloronaphthalene or N-methylpyrrolidone) used in the synthesis step is required in the washing step. The yield from this synthesis is 60 to about 80%. X-ray powder diffraction, i.e. XRPD analysis, of the product thus obtained showed that the pigment was a type I polymorph, i.e. a beta type of titanyl phthalocyanine.

In a particular embodiment of the invention, the following may be done: 5 g of Type I TiOPc, 10
It can be dissolved in 0 ml of trifluoroacetic acid (TFA) / methylene chloride (CH ₂ Cl ₂ ) 1: 4 mixture (V / V) to prepare a dark green solution containing no undissolved material. Then, the obtained solution was divided into 5 × 20 ml. A 20 ml aliquot of the solution prepared above is taken for about 2 minutes to
A good stirring solution of methanol in 00 ml of water (1: 1, V /
V) poured into. The resulting dark blue precipitate was vacuum filtered with a 4.25 cm glass fiber filter in a Buchner funnel. The solid obtained was washed in this funnel with the following washes: a) 20 ml 1: 1 (V / V) water / methanol b) 3 x 10 ml methanol c) 3 x 5 ml deionized water d ) 2 x 5 ml of methanol The resulting solid was dried at 70 ° C for 16 hours to give 0.9
5 g of dark blue pigment was obtained. XRPD analysis of this material
This material was shown to be the Type X polymorph of TiOPc.

A second 20 ml aliquot of the TFA / CH ₂ Cl ₂ solution prepared above was poured into 100 ml of isopropyl alcohol. The resulting precipitated blue powder was isolated and dried as described above, but the first wash used 20 ml of isopropanol. The product, 0.93 g of a blue powder, was analyzed by XRPD to give Type II T
Identified as iOPc. A third 20 ml aliquot of the solution prepared above was poured into 100 ml diethyl ether and the precipitated product was isolated as described above, but the first wash was with 20 ml diethyl ether. . The obtained 0.82 g of blue powder is XRPD.
Was identified as type I TiOPc by. A fourth 20 ml aliquot of the TFA / CH ₂ Cl ₂ solution prepared above was added to 100 ml chlorobenzene. A dark green solution was obtained. This solution was treated with 20 ml of water with vigorous stirring and the resulting suspension was further treated as described above, but omitting the initial washing step a),
93 g of blue powder was obtained. The product was identified by XRPD as type IV TiOPc. 20 ml of a fifth aliquot of the above TFA / CH ₂ Cl ₂ solution
Was poured into a vigorously stirring suspension of toluene in water (1: 1, V / V) for 1 minute. The precipitated solid was isolated exactly as described above. The product is 0.93 g of a blue solid, which by XRPD is of type IV TiOPc
Identified as. Type when identified by XRPD
II TiOPc was synthesized by acid pasting a sample of Type I pigment in concentrated sulfuric acid. A 1.05 g sample of the material obtained was dissolved in 20 ml of a trifluoroacetic acid / methylene chloride 1: 4 mixture. The resulting solution was poured into 200 ml of a 1: 1 mixture of methanol / water. The precipitated solids are treated with Type X TiOP
isolated exactly as described above for c
1.02 identified as type X TiOPc by D
g of blue pigment was obtained.

Many different multilayer light sensitive imaging members can be made containing the titanyl phthalocyanine pigments obtained by the method of the present invention. In one embodiment, these multilayer photosensitive imaging members include a support substrate, a charge transport layer,
In particular, it includes an arylamine hole transport layer and a photogenerator layer comprising a Type X, Type Z-1, Type Z-2 or Type IV titanyl phthalocyanine sandwiched therebetween. Another embodiment of the invention comprises a support substrate, a charge transport layer, in particular an arylamine hole transport layer, and a positively containing titanyl phthalocyanine type X or type IV obtained by the method of the invention as a topover coating. The present invention relates to a chargeable multilayer type photosensitive image forming member. Furthermore, according to the invention, a supporting substrate, a thin adhesive layer, a photogenerator layer of titanyl phthalocyanine obtained by the method of the invention dispersed in a polymeric resin binder, and a polymeric resin binder as a top layer. An improved negatively charged photosensitive imaging member is provided that includes an arylamine hole transport molecule dispersed therein. Imaging members containing the titanyl phthalocyanine pigments of this invention are useful in a variety of electrostatographic imaging and printing systems, especially those commonly known as xerographic processes. In particular, the imaging members of this invention are useful in xerographic imaging methods in which titanyl phthalocyanine absorbs light at wavelengths of about 600 to about 900 nm. In these known methods, an electrostatic latent image is first formed on the imaging member, then developed and then the image is transferred to a suitable substrate. Furthermore, the imaging members of this invention can also be used in electronic printing processes with gallium arsenide light emitting diodes that typically function at wavelengths of 660 to about 830 nm.

In FIG. 8, the support substrate 1; polyester 4 available from Goodyear Chemical Company, for example.
Solution coating adhesive layer 2 containing 9,000; a titanyl phthalocyanine such as type IV, Z-1, Z-2 or X obtained by the method of the present invention, optionally dispersed in an inert resin binder. A photogenerator layer 3 (eg,
Example 4); and N, N ^, -diphenyl-N, N ^, -dispersed in a polycarbonate resin binder 7.
Bis (3-methylphenyl) -1,1 ^, -biphenyl-
The negative charging type photosensitive image forming member of the present invention including the hole transport layer 5 containing 4,4 ^, -diamine will be exemplified. In FIG. 9, the substrate 10; N, N ^, -diphenyl-N, N ^, -bis (3-methylphenyl) -1,1 ^, -biphenyl-4, dispersed in a polycarbonate resin binder 14,
4 ^{, a} diamine-containing charge transport layer 12; and a positively charged photosensitive imaging of the present invention comprising a photogenerator layer 16 obtained by the method of the present invention optionally dispersed in an inert resin binder. A member is illustrated.

The substrate layer used in the imaging member of this invention can be opaque or substantially transparent and can include any suitable material having the desired mechanical properties. That is, the substrate is a layer of insulating material such as commercially available Mylar, titanium containing Mylar; a layer of organic or inorganic material having a semi-conductive surface layer such as indium tin oxide or aluminum; or It may include conductive materials such as aluminum, chrome, nickel, brass and the like. The substrate may be flexible, seamless or rigid, eg
It can have many different shapes such as plates, cylindrical drums, scrolls, endless flexible belts and the like. In one embodiment, the substrate is in the form of a seamless flexible belt. In some cases, especially when the substrate is a flexible organic polymeric material, the backside of the substrate is coated with an anti-curl layer, such as polycarbonate commercially available as Makrolon. Is desirable. The thickness of the substrate layer depends on many factors such as economics, and thus this layer is
It can have a substantial thickness of 3,000 microns or more, or a minimum thickness without adversely affecting the imaging system. In one embodiment, this layer has a thickness of about 7
5 to about 300 microns.

Further, in the imaging member of this invention, the photogenerator layer preferably comprises the titanyl phthalocyanine pigment obtained by the method of this invention dispersed in a resin binder. In general, the thickness of the photogenerator layer depends on many factors, such as the thickness of each of the other layers and the amount of photogenerator material included in the photogenerator layer. Thus, this layer comprises about 0.05 to about 1 when the titanyl phthalocyanine photogenerator compound is present in an amount of about 5 to about 100% by volume.
It can have a thickness of 0 micron. In one embodiment, this layer comprises from 30 to 30% of the photogenerator compound in this layer.
When present in an amount of 75% by volume, it has a thickness of about 0.25 to about 1 micron. Specific examples of polymeric resin materials that can be used for the photogenerator pigment include US Pat.
There are polymers such as those disclosed in US Pat. No. 1,006,
The entire description of the US patents is incorporated herein by reference. As the adhesive, various known substances such as polyester, polyamide, poly (vinyl butyral), poly (vinyl alcohol), polyurethane and polyacrylonitrile can be used. This layer has a thickness of about 0.05 to 1 micron. Optionally, this layer contains conductive and non-conductive particles such as zinc oxide, titanium dioxide, silicon nitride, carbon black, etc., for example, in the embodiments of the present invention, the desired electrical conductivity is achieved. Optical and optical properties can be imparted. Arylamines generally used for hole transport layers having a thickness of about 5 to about 75 microns, preferably about 10 to about 40 microns include the following formulas dispersed in a highly insulating, transparent organic resin binder. There is a molecule:

[0019]

[Chemical 1] [Wherein, X is an alkyl group or halogen, particularly a substituent selected from the group consisting of (ortho) CH ₃ , (para) CH ₃ , (ortho) Cl, (meth) Cl, and (para) Cl. Is. ]

Examples of specific arylamines include N, N ^,
-Diphenyl-N, N ^, -bis (alkylphenyl)-
1,1 ^, -biphenyl-4,4 ^, -diamine ^, wherein alkyl is from the group consisting of methyl such as 2-methyl, 3-methyl and 4-methyl, ethyl, propyl, butyl, hexyl and the like. To be elected. In chloro substitution, the amine is N, N ^, -diphenyl-N, N ^, -
Bis (halophenyl) -1,1 ^, -biphenyl-4,4
^, -Diamine, wherein halo is 2-chloro, 3-
It is chloro or 4-chloro. Other known hole transport compounds may also be used. Examples of the highly insulating and transparent resin material for the transport layer, that is, the inert binder resin material include the materials described in US Pat. No. 3,121,006, all of which are incorporated by reference. Referenced herein. Specific examples of organic resin materials include polycarbonate,
Acrylate polymer, vinyl polymer, cellulose polymer, polyester, polysiloxane, polyamide,
There are polyurethanes and epoxies and their block, random or alternating copolymers. Preferred electrically inactive binders are from about 20,000 to about 10
50,000 molecular weight (about 50,000 to about 100,000)
Polycarbonate resins having a molecular weight of 0 are particularly preferred). Generally, the resin binder is about 10
It contains about 75% by weight, preferably about 35 to about 50% by weight, of the active substance corresponding to the above formula. Further, the scope of the present invention also includes an image forming method and a printing method using the above-mentioned photosensitive device of the present invention. These methods generally form an electrostatic latent image on the imaging member and then transfer the image to a toner composition (US Pat. No. 4,560,635).
No. 4,298,697 and 4,338,39
No. 0, all descriptions of said U.S. patents are incorporated herein by reference), followed by transfer to a suitable substrate and permanent fixing. When the image forming apparatus of the present invention is used in a printing method, the image forming method includes the same steps as described above except that the exposure step is performed by a laser device or an image forming bar.

[0021]

【Example】

Example 1 Synthesis of type I titanyl phthalocyanine : 32.7 g in a 300 ml three-necked flask equipped with mechanical stirrer, condenser and thermometer and maintained under argon atmosphere.
(0.225 mol) of 1,3-diiminoisoindolene, 170 ml of N-methylpyrrolidone, and 15.
99 g (0.056 mol) of titanium tetrapropoxide (all these reactants are available from Aldrich Chemical Company) were added. The resulting mixture was stirred, warmed and refluxed for 2 hours (about 198 ° C). The resulting black suspension was cooled to about 160 ° C. and then 350 ml preheated with boiling dimethylformamide (DMF).
Suction filtered through a M porosity sintered glass funnel. The solid obtained was washed with 150 ml of boiling DMF.
The filtrate, which was initially black, had a pale blue-green color. The solid was slurried in the above funnel with 150 ml boiling DMF and the resulting suspension was filtered. The obtained solid is
In the funnel, 150 ml of DMF at 25 ° C. and then 50
Wash with ml of methanol. The resulting shiny dark blue solid was dried at 70 ° C. overnight to 17.4 g (54
%) Of the pigment, which was identified as Type I TiOPc on the basis of its XRPD. Elemental analysis of the product was as follows: C 66.44; H 2.
62; N 20.00; ash (TiO ₂ ) 12.3
5. TiOPc requires the following components: C 66.6.
7; H 2.80; N 19.44; ash 13.8
6.

[0022]

Example 2 Synthesis of Type I titanyl phthalocyanine : In a 1 liter three neck flask equipped with mechanical stirrer, condenser and thermometer and maintained under an argon atmosphere, diiminoisoindolene (94.3 g, 0 .65 mol), titanium tetrabutoxide (55.3 g, 0.1625 mol);
Aldrich), and 650 ml of 1-chloronaphthalene. The resulting mixture was stirred and warmed.
At about 140 ° C., the mixture turned dark green and began to reflux.
At this point, the condenser was removed and the vapor (which was identified by gas chromatography as n-butanol) was allowed to dissipate until the reflux temperature reached 230 ° C. The reaction was maintained at approximately this temperature for 1.5 hours and then cooled to 15 ° C. By filtering with a 1 liter sintered glass funnel and washing with boiling DMF followed by methanol as in Example 1,
69.7 g (74% yield) of a blue pigment was obtained, which was identified by XRPD as type I TiOPc. The elemental analysis of this product was as follows: C
67.38; H 2.78; N 19.10; ash
13.61. TiOPc requires the following components: C6
6.67; H 2.80; N 19.44; Ash 1
3.61.

[0023]

Example 3 Preparation of Type X Titanyl Phthalocyanine : Trifluoroacetic acid (1) in methylene chloride (400 ml) magnetically stirred in a 1 liter Erlenmeyer flask.
To a solution of 00 ml) was added 50 g of Type I TiOPc synthesized as in Example 1 over 2 minutes. No heat was generated and the resulting dark green solution was stirred for 15 minutes at room temperature. Methanol containing this solution in a 12 liter glass cylinder for 2 minutes and stirring with a 100 mm long magnetic stir bar (which extends almost to the bottom of the flask) at a speed sufficient to generate swirl. Poured into a solution of (2.5 liters) and water (2.5 liters). After this pouring, the blue suspension obtained was stirred at room temperature for 4 hours.
Stir for 5 minutes and then leave for 25 minutes without stirring. The tan supernatant was almost completely separated from the precipitated solids by careful decantation of the reaction vessel. The remaining blue residue was redispersed in 2 liters of methanol for 1 hour at room temperature with magnetic stirring. The resulting suspension is placed in a porcelain filter funnel with 18
After filtering through a cm fiberglass filter, the filter cake was washed successively with 2 x 100 ml methanol, 2 x 100 ml water, 500 ml water, then 2 x 100 ml methanol. The product obtained was dried overnight at 75 ° C. to give 47.6 g (95% yield) of a dark blue pigment which was analyzed by XRPD to produce a Type X TiOP.
identified as c.

[0024]

Example 4 Preparation of Type IV TiOPc : 10 in 100 ml trifluoroacetic acid / methylene chloride (1: 4, V / V) mixture.
g Type I TiOPc (N-as described in Example 1).
A 20 ml aliquot of the solution (prepared in methylpyrrolidone solvent) was added to methanol (45 ml) and water (135 m).
l) was added to the rapidly stirred solution. The resulting crude suspension was stirred at room temperature for 35 minutes then allowed to stand. The supernatant
It was filtered using a 7 cm diameter glass fiber filter in a porcelain funnel. The solid obtained was placed in this funnel at 2 x 10
ml methanol, 4 x 20 ml deionized water, 2 x
Washed with 10 × 20 ml water and 2 × 10 ml methanol. The solid obtained is dried at 75 ° C. and subjected to XR
1.8 identified as Type IV TiOPc by PD
5 g of blue pigment was obtained.

[0025]

Example 5 Preparation of Type Z-1 TiOPc : TiOP of Example 4
A 20 ml aliquot of the acid solution of c was stirred rapidly at room temperature in a 125 ml Erlenmeyer flask.
Poured into 0 ml of methanol. The resulting dispersion was stirred for 45 minutes and then filtered using a 7 cm glass fiber filter. The solid obtained was washed in the above funnel with 2 × 10 ml methanol, 4 × 20 ml water and 2 × 10 ml methanol. The product obtained is dried at 75 ° C. and subjected to type Z by XRPD.
2.09 g of blue pigment identified as TiOPc of -1 was obtained.

[0026]

Example 6 Preparation of Type Z-2 TiOPc : The solution was prepared as 6 g of type I synthesized as in Example 1.
Was prepared by dissolving 60 ml of TiOPc in 60 ml of trifluoroacetic acid / methylene chloride 1: 4 mixture (V / V). A 10 ml portion of this solution was precipitated into 100 ml water / ethylene glycol 1: 1 mixture. Phase separation occurred and the pigment and methylene chloride formed a sticky mass at the bottom of the flask. The mixture was stirred for 30 minutes, then the supernatant was decanted and the pigment phase was redispersed in 50 ml of methanol. Filter, wash with water and methanol as in the three examples above,
0.90 g of an almost black solid was obtained, the product of which was characterized from its XRPD as type Z-2 TiO 2.
It was identified as a new crystalline form of Pc. Each of the resulting titanyl phthalocyanines was evaluated as a photogenerator of a xerographic image forming device prepared by the following procedure. An aluminized Mylar substrate with a nylon 8 solution prepared by dissolving 5 g nylon 8 (Dyne Nippon Ink & Chemicals) in 24 g n-butanol and 4 g water with a 1 mil (25.4 micron) gap applicator. Was used for coating. This layer at 135 ° C
And dried for 20 minutes to give a final thickness of 0.6 microns. A dispersion of TiOPc was charged with 0.35 g of Ti in a 30 ml jar containing 70 g of 1/8 inch (3.175 mm) stainless steel balls.
OPc and poly (vinyl butyral) were prepared by ball milling in 13.4 g of butyl acetate.
The dispersion was milled for 20 hours and then coated onto the nylon 8 layer above using a 1 mil (3.175 mm) applicator. The photogenerating layer thus formed was dried at 100 ° C. for 10 minutes and measured for a final thickness of about 0.40 micron.

The hole transport layer solution was added with 5.4 g of N, N ^, -
Diphenyl-N, N ^, -bis (3-methylphenyl)-
1,1 ^, -biphenyl-4,4 ^, -diamine, 8.1 g
Of polycarbonate was dissolved in 52 g of chlorobenzene. The resulting solution was coated on the above TiOPc generator layer using an 8 mil (203.2 micron) film applicator. The charge transport layer thus obtained was dried at 115 ° C. for 60 minutes to give a final thickness of about 23 microns. The surface potential of the xerographic electrical characteristics of the photosensitive image forming member prepared as described above was -8 when measured by a corona discharge power source and a capacitive coupling probe connected to a voltmeter.
It was measured by electrostatic charging until an initial darkness value V ₀ of 00 volts was obtained. After resting for 0.5 second in the dark, the charging member reached the surface potential V _ddp , the development potential in the dark. The member was then exposed to filtered light from a xenon lamp. A decrease in the surface potential from V _ddp to the background potential V _{bg due} to the _{photodischarge} effect was observed. The dark decay in volts / second is (V ₀ −V _{dd p} ) /
It was calculated as 0.5. The percentage of photodischarge is 100
It was calculated as × (V _ddp −V _bg ) / V _ddp . The half-exposure energy E _1/2 , ie the exposure energy required to reduce V _ddp to half its initial value, was measured. The wavelength of the light used for these measurements was 800 nm.

[0028]

Example 7 The photogenerating pigment is the type X described in Example 3.
Of the TiOPc, and made and evaluated as described in Example 6, had the following properties: V _ddp 805 volts; dark decay 27 volts / sec; E _{1 / 2} 1.3 ergs / cm ² .

[0029]

Example 8 A xerographic apparatus made and evaluated from the Type IV TiOPc described in Example 4 had the following properties: V _ddp 803 volts; dark decay 56 volts / second; E _{1 / 2} 1.5 ergs / cm ² .

[Brief description of drawings]

FIG. 1 is an XRPD diffractogram of a known polymorph, type I, titanyl phthalocyanine.

FIG. 2 is an XRPD diffractogram of a known polymorph, type II titanyl phthalocyanine.

FIG. 3 is an XRPD diffractogram of a known polymorph, type III titanyl phthalocyanine.

FIG. 4 is an XRPD diffractogram of a known polymorph, type IV titanyl phthalocyanine.

FIG. 5 is a novel Z-1 of titanyl phthalocyanines obtained from, for example, precipitation in 100% methanol.
FIG. 7 is a diffraction pattern of XRPD in crystalline form.

FIG. 6 is an XRPD diffractogram of the novel Z-2 crystalline form of titanyl phthalocyanine obtained from, for example, precipitation in water / ethylene glycol.

FIG. 7 is an XRPD diffractogram of the novel type X polymorph titanyl phthalocyanine.

FIG. 8 is a partial cross-sectional view of the negative charging type photosensitive image forming member of the present invention.

FIG. 9 is a partial cross-sectional view of the positive charging type photosensitive image forming member of the present invention.

[Explanation of symbols]

1 base 2 Adhesive layer 3 Photogenerator layer 5 Hole transport layer 7 Polycarbonate resin binder 10 Base 12 Charge transport layer 14 Polycarbonate resin binder 16 Photogenerator layer 18 Inert resin binder

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chen Kuo Xiao Canada L5L4Wai3Ontario Mississauga Garthwood Road 3106 (72) Inventor Army Ho Canada L5L5B1onta Rio Mississauga Malcaster Lord 3407 (72) Inventor Terry El Bloom Canada El 6 Cay 1 Wy 2 Onta Rio Oakville Stevens Crescent 583 (72) Inventor Gordon Kay Hammer Canada El 5 L 2 P 4 Onta Rio Mississauga South Milway 1-2280 ( 72) Inventor Peter M Kazmeyer Canada L5L1E5Entario Mississauga Council Ring Road 2421 (56) Reference JP-A-5-940 2 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09B 67/10 C09B 67/50

Claims (4)

(57) [Claims] 1. Titanyl phthalocyanine is dissolved in a solution of trifluoroacetic acid and methylene chloride at room temperature, and the resulting solution contains 100: 1 by volume of methanol and water.
A method for the preparation of titanyl phthalocyanine of type Z-1 wherein the product titanyl phthalocyanine is separated from the above solution and then washed, if necessary, by adding it to a solvent which allows precipitation at room temperature. 2. Titanyl phthalocyanine is dissolved in a solution of trifluoroacetic acid and methylene chloride at room temperature, and the resulting solution is mixed with ethylene glycol and water at a volume ratio of 1: 1.
A process for the preparation of titanyl phthalocyanine of type Z-2, which comprises adding to the solvent allowing precipitation at room temperature, separating the product titanyl phthalocyanine from the above solution and then washing if necessary. 3. 2θ = 6.6, 8.8, 12.0, 1
Z-1 type titanyl phthalocyanine having XRPD peaks at 6.0, 17.3, 21.0, 21.5 and 26.2. 4. 2θ = 7.4, 8.8, 11.0, 1
Z-2 type titanyl phthalocyanine having XRPD peaks at 7.3, 17.9, 20.1, 26.5, 27.5 and 29.0.