JPH0742419B2 - Method for producing titanyl phthalocyanine - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is generally directed to titanyl phthalocyanines and processes for making the same, and more specifically, the present invention relates to known type I and type IV (see, for example, U.S. Pat. No. 4,898,799). The disclosure is incorporated herein by reference in its entirety), a polymorph or crystalline form of titanyl phthalocyanine, including Type X and the aforementioned titanyl phthalocyanine polymorph, especially Type IV.
And a method for obtaining a laminated photoconductive member containing type X.

In one embodiment of the invention, the invention provides crude titanyl phthalocyanine by reaction of titanium tetra (alkoxide), especially butoxide with diiminoisoindole in a solvent such as halonaphthalene; , Directed to a process for the production of titanyl phthalocyanine, where the product is purified by washing with a solvent such as dimethylformamide. The purified titanyl phthalocyanine, in particular the type I product obtained, can then be dissolved in a mixed solvent of trifluoroacetic acid and methylene chloride. Subsequently, the aforementioned mixture is added to the alcohol solution. Titanyl phthalocyanine type IV is
The titanyl type X to type X can be obtained, for example, by treating it with chlorobenzene. Laminated imaging members having Type IV as described above as a photogenerator, a charge transport agent, particularly the arylamines described herein, and a supporting substrate have excellent photosensitivity. These titanyl phthalocyanines, especially the polymorphs IV and X known in the art, are used as organic photogenerating pigments in photoresponsive imaging members containing charge transport layers, especially hole transport layers such as the well known arylamine hole transport molecules. Can be chosen. The photoresponsive imaging member described above can be negatively charged when the photogenerating layer is located intermediate the hole transport layer and the substrate, and when the hole transport layer is located intermediate the photogenerating layer and the supporting substrate. Can be positively charged.
The laminated photoconductive imaging member may be processed, for example, by an electrophotographic imaging method, particularly a xerographic imaging and printing method in which a negatively charged or positively charged image is visible with a suitably charged toner composition. Many different known imaging and printing methods can be selected, including. Generally, the imaging member is sensitive in the wavelength range of about 700 to 850 nm, so a diode laser may be chosen as the light source. Titanyl phthalocyanine may also be selected for use in coatings such as paints, inks as a dark blue light stable colorant, and as a near infrared absorbing pigment suitable for use as an IR laser optical recording material. Good.

[0003]

BACKGROUND OF THE INVENTION Japanese Patent Application No. 63-20365 / 86 to Sanyo Shixo refers to known crystals, alpha and beta TiOPc (probably Type II and I, respectively), the specification of which is also incorporated herein by reference. , A method for the production of a new type of titanyl phthalocyanine, which has not been explicitly named, is described. U.S. Pat.No. 4,728,592, for example, from 500
The use of alpha-type TiOPc (Type II) in electrophotographic devices sensitive over a wide wavelength range of 900 nm has been described. This form was prepared by treatment of dichlorotitanium phthalocyanine with concentrated aqueous ammonia and pyridine at reflux for 1 hour. Konica's Japanese Patent Application Sho 64
-17066/89 includes, for example, alpha type pigments (Type I
I) describes the use of a new crystal refinement of TiOPc produced by grinding it with salt and polyethylene glycol in a sand mill. This pigment is 2
It had a strong XRPD peak at a 2-theta value of 7.3 degrees. Mitsubishi's Japanese Patent Publication No. 90-269776 (Published November 5, 1990)
(The disclosure of which is hereby incorporated by reference in its entirety), for example, phthalocyanines, such as metal-free, metal phthalocyanines, or their derivatives, in a solvent or trifluoroacetic acid-containing solvent or trifluoroacetic acid. It describes the production of titanyl phthalocyanine by treatment with a mixed solvent of fluoroacetic acid and a halogenated hydrocarbon such as methylene chloride. Example 1 of this Japanese patent publication describes the production of C type of TiOPc.
The other molds obtained are described in Examples 2 and 3.

[0004]

A feature of the present invention is to provide the preparation of titanyl phthalocyanine which has many of the advantages illustrated herein.

[0005]

These and other features of the present invention are accomplished in its embodiments by providing a method of making titanyl phthalocyanine and its photoresponsive imaging members. More specifically, one embodiment of the present invention provides a method for producing a polymorph of titanyl phthalocyanine (TiOPc), which method comprises dissolving titanyl phthalocyanine type I in a mixture of trifluoroacetic acid and methylene chloride. The resulting mixture is added slowly, eg, dropwise, to an aliphatic alcohol having 1 to about 12 carbon atoms, such as methanol, ethanol, propanol, butanol, etc .; eg the desired titanyl such as type X. Precipitation of the phthalocyanine, for example separation by filtration, and optionally washing the product, and subsequent treatment of the resulting type X titanyl phthalocyanine with a halobenzene such as chlorobenzene to give a type IV titanyl phthalocyanine . The product is identified by various known means including X-ray powder diffraction (XRPD).

In one embodiment, the present invention provides a titanium tetraalkoxide, especially tetrabutoxide and D
I ³ (1,3-diiminoisoindolene) and halonaphthalene, especially directed to the production of type I titanyl phthalocyanine by reaction with 1-chloronaphthalene, the type I titanyl phthalocyanine obtained is used in an effective ratio of : 4
In a volume ratio of haloacetic acid, especially trifluoroacetic acid, and an alkylene halide, especially methylene chloride, and the resulting mixture is slowly added, for example over a useful period of about 10 minutes to about 30 minutes, preferably about 20 minutes. For example, by dropwise addition to an alcohol, especially cold methanolic aqueous solution in an effective ratio of, for example, 1: 1 and, for example, after separation by filtration, for example about 0.05 to about 0.1, preferably about 0.05
To obtain a Type X titanyl phthalocyanine having a particle size of about 0.5 micron. The aforementioned type X is converted to type IV by treating it with, for example, chlorobenzene as described herein. The aforementioned mixture solution is cooled with, for example, an ice bath, and in an embodiment, the temperature is about 0.
It can be lower than ℃, preferably lower than about -5 ℃, more preferably -10 ℃.

One embodiment of the present invention is directed to a process for preparing titanyl phthalocyanine type I, which comprises reacting a titanium tetraalkoxide, particularly its tetrabutoxide with diiminoisoindrene in a chloronaphthalene solvent. To provide crude type I titanyl phthalocyanine, which is then washed with a compound such as dimethylformamide to provide the pure form of type I as determined by X-ray powder diffraction; the resulting titanyl phthalocyanine with trifluoroacetic acid and chloride. Dissolved in a mixture of methylene; the resulting mixture is added to a stirred organic solvent such as methanol, and / or water; the resulting precipitate is isolated by vacuum filtration, for example through glass fiber filter paper in a Buchner funnel; And the resulting titanyl phthalocyanine product Comprising washing. When a Type X product is obtained, it can be converted to Type IV by treatment with chlorobenzene. In an embodiment, a ratio of about 60:40 to about 35:65, preferably 50:
Type X titanyl phthalocyanines are obtained when a mixture of alcohols, especially methanol and water, in a ratio of 50 is chosen. Type IV titanyl phthalocyanine is usually
The ratio of alcohol, especially methanol to water, is about 30:70.
To 0: 100, preferably 25:75. Also, the Type IV titanyl phthalocyanines described above can be treated or washed with chlorobenzene which provides Type IV superior photosensitivity of imaging members. In the above treatment, a ratio of chlorobenzene to phthalocyanine type IV of about 1: 1, 10: 1, and preferably 3: 1 is selected.

In the manufacture of Type I titanyl phthalocyanine, the process in an embodiment comprises the reaction of DI ³ (1,3-diiminoisoindolene) with tetrabutoxide in the presence of a 1-chloronaphthalene solvent, This gives crude titanyl phthalocyanine type I, which is then purified to a purity of about 99.5% and washed, for example with dimethylformamide.

Type I titanyl phthalocyanine is also
1) about 1 part to about 10 parts of titanium tetrabutoxide
Part, preferably about 4 parts, of a stirred solution of 1,3-diiminoisoindolene; 2) about 1 to about 10 degrees per minute using a suitably sized heating mantle. Relatively slow heat input until reflux occurs at a temperature of about 130 to about 180 degrees, preferably at a rate of about 5 degrees per minute; 3) Claisen Hea
d) Obtaining the temperature of the reactants using a suitable device such as a condenser from 190 to about 230 degrees (all temperatures are degrees Celsius unless otherwise noted), preferably up to about 200 degrees. Dropwise removal and collection of distillate (although it is shown by NMR spectroscopy to be butyl alcohol); 4) from about 1/2 hour to about 8 hours, preferably about 2 hours. Continued stirring at reflux temperature; 5) cooling the reactants to about 130 to about 180 degrees, preferably about 160 degrees by removing the heat source; 6) contents of the flask, e.g. M-porosity (10.
-15 μm) through a sintered glass funnel, and a solvent capable of raising the temperature of the funnel, for example, to about 150 ° C., such as boiling N, N-dimethylformamide, is used to prevent clogging of the funnel. Filter in an amount sufficient to completely cover the bottom; 7) add the resulting purple solid to about 1 to about 10 volumes of the solid to be washed in a funnel or in a separate container. Wash the hot filtrate to a pale blue color by slurrying with a double ratio, preferably about 3 volumes of boiling DMF; 8) cooling the impure solids, and further cooling the solids to room temperature, about Wash by slurrying with N, N-dimethylformamide in an amount approximately equal to about 3 volumes of solids to be washed at 25 ° C; 9) the impure solids at room temperature, about 25 ° C. About 3 times the capacity Wash the filtrate several times with an organic solvent such as methanol and acetone, water, etc. until the filtrate becomes pale blue; 10) about 25
About 2 to about 200 degrees, preferably about 70 degrees,
Oven drying the purple solid under vacuum or in air for about 48 hours to about 24 hours, preferably about 24 hours, thus producing a lustrous purple solid identified by X-ray powder diffraction traces as Type I titanyl phthalocyanine. It can be produced by isolating the product.

The type I titanyl phthalocyanine obtained is then of the type by dissolving it in trifluoroacetic acid and methylene chloride and then reprecipitating the dissolved pigment product obtained, for example in a solvent mixture of methanol and water. It can be converted to X titanyl phthalocyanine (see US Patent Application No. 533,261 (D / 90198), the disclosure of which is hereby incorporated by reference in its entirety).

In one specific embodiment, the method of the present invention, from the resulting Type I titanyl phthalocyanine, 1) 1 part by weight of Type I pigment, 1 part by volume of haloacetic acid, in this embodiment trifluoro About 1 to about 100 parts by volume of acetic acid and about 1 to about 100 parts by volume of a halogenated hydrocarbon such as methylene chloride, preferably about 1 to 10 parts by volume, in this embodiment 4 parts by volume of a cosolvent. In an amount of 10 parts by volume of solvent in this embodiment, and the pigment described above in air at an effective time of about 30 seconds to about 24 hours, in this embodiment for about 5 minutes at room temperature and about 25 degrees. Dissolved by stirring in the solvent mixture in or in an inert atmosphere such as argon or nitrogen; 2) about 0.5 ml to about 10 parts per minute of the type I pigment dissolved solution.
ml at a rate of about 1 ml per minute in this embodiment, alcohols such as, but not limited to, methanol, ethanol, isopropanol, butanol, acetone,
Methyl ethyl ketone, ketones such as isobutyl ketone, water, N, N-dimethylformamide, tetrahydrofuran or a non-solvent containing a mixture thereof, is added dropwise.
In this embodiment, it is added dropwise to a mixture containing 1 part by volume of methanol and 1 part by volume of water, the solvent mixture being cooled to a temperature of about -25 ° to about 10 °, in this embodiment about 2 °, At the same time re-precipitate the dissolved Type I titanyl phthalocyanine pigment while stirring at a rate sufficient to create an expanding vortex at the bottom of the flask containing the solvent mixture; Filter through a glass fiber filter attached to a porcelain funnel; 4) Approximately 1 part of the isolated solid in an organic solvent such as methanol or acetone.
Minutes to about 24 hours, about 1 hour in this embodiment, about 10 to about 100 parts by volume, in this embodiment about 5 parts by volume, based on the original weight of the solid Type I pigment used.
Redispersion by stirring in 0 volume followed by washing by filtration as described herein; 5)
Further, the solid type I used, heated to a temperature of about 75 to about 100 degrees, in this embodiment about 95 degrees.
Redispersed in about 10 to about 100 parts by volume, and in this embodiment about 50 parts by volume of deionized water, based on the original weight of the pigment, followed by washing by filtration as described herein. 6) repeating step 5); 7) adding the obtained blue pigment in air or under vacuum to a temperature of about 25 to about 200;
At a temperature of about 5 degrees, in this embodiment about 70 degrees in air, about 5
Drying for between about minutes and about 48 hours, in this embodiment for about 1 hour, yields the XR at a desired yield of about 75% to about 99%, and in this embodiment about 97%.
A dark blue powder is obtained which is identified as Type X titanyl phthalocyanine based on the PD spectrum and is converted to Type IV.

[0012] The foregoing types X Chitanirufuta b cyanine multilayer photoconductive device or chosen it can as photogenerating agent used in an image forming member, and is, for example the proportions as described herein, It is utilized as an intermediate in the conversion to type IV titanyl phthalocyanine by treatment with chlorobenzene in the presence of an alcohol-water mixture. Other co-solvents may be chosen in place of methylene chloride, such as chloroform, carbon tetrachloride, etc., alcohols such as methanol, ethanol, isopropanol, butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, N. , N-dimethylformamide and the like are considered to be selected.

[0013] Subsequently, the type X Chitanirufuta b cyanine thus obtained is, for example, be treated with a halogenated aromatic solvent such as chlorobenzene, the stacked photoconductive imaging member having a supporting substrate and a charge transport layer Provided is a Type IV titanyl phthalocyanine having excellent xerographic properties when selected as a photogenerator. Other solvents may be selected in place of chlorobenzene, such as tetrahydrofuran, bromobenzane, 1,2,4
-Trichlorobenzene, 1,1,2-trichloromethane, fluorobenzene, xylene, etc. could be chosen. In one embodiment, Chitanirufuta b cyanine type IV light generating agent, xerographic characteristics of aryl diamine charge transport layer, and the aforementioned image forming member having an aluminum substrate in contact with the light generation layer as the top layer, E
_1/2 is 0.8 ergs / cm ² and dark decay is 5
-15 volts / sec, 5 ergs / cm ² and 10
87% and 90% discharge at ergs / cm ² respectively
Met. Utilizing type X as an intermediate to type IV offers a number of advantages over, for example, obtaining type IV directly from type I. Furthermore, the treatment with chlorobenzene type X intermediates, as compared to when the Type IV intermediate is treated in a similar manner, the type IV Chitanirufuta furnace was <br/> cyanine having higher xerographic photosensitivity It has been measured to provide.

The type determined by X-ray powder diffraction traces, for example by dissolution of a Type I pigment obtained by the method described herein, followed by reprecipitation in a 1: 1 methanol / water mixture. X Chitanirufuta Russia <br/> Nin is obtained, for example, type IV pigment is produced.
Treatment of the Type X intermediates described above with chlorobenzene as described herein, in embodiments of imaging members, when the Type IV thus obtained was selected as the photogenerator for the laminated imaging member. E _1/2 is 0.8er
A gs / cm ^2, a dark decay 5-15 volts / sec, discharge at 5ergs / cm ² and 10ergs / cm ² has provided Type IV Chitanirufuta b cyanine 87% and 90%, respectively.

[0015] When the type I Chitanirufuta b cyanine <br/> emissions pigment dissolved is reprecipitated in a mixture of 25/75 methanol / water, the type IV Chitanirufuta The product as determined by X-ray powder diffraction trace Russia was cyanine. Treatment of the Type IV intermediate with chlorobenzene as described herein results in an imaging member having an E _1/2 of 1.3 ergs / cm ² and a dark decay of 31 volts / second. Yes, 5 ergs / cm ² and 1
81% and 87% discharge at 0 ergs / cm ² , respectively.
It provided the type IV Chitanirufuta b <br/> cyanine having electrical characteristics that%. Type X or Type IV is obtained, for example, as described herein, depending on the selected proportion of alcohol, especially methanol and water. The imaging member can include the specific compounds described herein and in Table 3, and devices 1 and 2 in Table
Are substantially equivalent in each of the measured properties illustrated.

[0016] In Type X is a specific embodiment, immediately follows the second hot water wash (Step 6), 1) wet filter cake comprising the solid type X Chitanirufuta B cyanine 1 part which is thus obtained To about 10 parts to about 100 parts, in this embodiment about 50 parts of chlorobenzene, based on the weight of the solid type X pigment used, for an effective time of about 5 minutes to about 2 hours, in this embodiment about 1 hour. Redispersion by stirring followed by filtration as described above; 2) the resulting blue pigment in air or under vacuum at a temperature of about 25 to about 200 degrees, in this embodiment air. Treated with chlorobenzene by drying at about 70 ° C. for about 5 minutes to about 48 hours, and in this embodiment for about 1 hour, at a desired yield of about 75% to about 99%. In about 97% yield, its XRPD
Obtaining a dark blue powder that is identified is a type IV Chitanirufuta b cyanine <br/> emissions based on spectrum.

As one solvent mixture for the conversion of type I, strong organic acids such as trihaloacetic acid, including trifluoroacetic acid or trichloroacetic acid, and methylene chloride,
Like loroform, trichlorethylene, bromoform
Alkylene halides and chlorofluorocarbons and
1 to about 6 carbon sources including hydrochlorofluorocarbons
And other single-chain halogens having 1 to about 6 halogen atoms
Alkanes and alkenes ; haloaromatic compounds such as chlorobenzene, dichlorobenzene, chloronaphthalene, fluorobenzene, bromobenzene, and benzene; alkylbenzenes such as toluene and xylene; and miscible with strong organic acids to effectively enable titanyl phthalocyanine Dissolution
Auxiliary solvent such as other organic solvent
The amount is, for example, about 1 to 50 parts of acid and methylene chloride.
Such co-solvent is about 50 parts . In one embodiment of the invention, the preferred solvent mixture comprises trifluoroacetic acid and methylene chloride in a ratio of about 5 parts acid and about 95 parts methylene chloride to about 25 parts acid and about 75 parts methylene chloride. Including.

In the method of the present invention, the range of small average particle sizes illustrated herein, such as from about 0.02 to about 0.
Type X titanyl lid with an average particle size of 5 microns
To obtain B cyanine, e.g. Chitanirufuta b cyanine such as the type I following the dissolution in a solvent mixture of an alcohol solution, especially the slow addition to an aqueous solution of methanol and water, and alcohol solution of above additives it is important, which is cooled from the previous example, about 0 ℃ valid temperature of about -10 ° C., thus, to precipitate type X Chitanirufuta b cyanine, isolated by a number of known means such as filtration sell.

[0019] 2g of Chitanirufuta b cyanine synthesized by the method of Example 1 below, in methylene chloride trifluoroacetic acid 1: 20 ml of 4 mixture (V / V)
It was dissolved by stirring in a 25 ml Erlenmeyer flask for 5 minutes at room temperature. The resulting dark green solution contained no undissolved material, then 250 m
It was poured into 200 ml of methanol in a 1 L Erlenmeyer flask at room temperature with vigorous stirring. The resulting dark blue suspension was stirred for an additional 30 minutes at room temperature, after which a 4.25 cm glass fiber filter paper (Whatman (W
hatman) GF / A grade),
The solid was washed on the funnel with about 20 ml of methanol. 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 and then re-filtered as above and the solid obtained was filtered on a funnel with methanol (2
0 ml) followed by water (2 × 20 ml) and finally again with methanol (20 ml). The solid for 2 hours,
Drying at 70 ° C. yielded about 1.8 g of dark blue pigment.

[0020]

[Table 1]

When the above procedure was repeated with the various precipitant series illustrated in Table 1, it was found that the resulting polymorphs depended on the nature of the precipitating solvent.
Thus, any of the known phases (Type I, II, III or IV) are obtained as shown in Table 1.
These were identified by comparing their XRPDs with known phase XRPDs shown in FIGS. 1, 2, 3, 4 and 5. Precipitation in 1: 1 ethylene glycol / water (1: 1) also provided a polymorph of TiOPc designated Type Z-2. The third new type of Chitanirufuta b cyanine obtained from a mixture of about 50:50 methanol or ethanol and water, seen to provide a xerographic devices having very high sensitivity to 780nm light Issued, identified herein as Form X, and had the XRPD pattern shown in FIG. This type X
Is that polymorphs showing the strongest peak at Bragg angle 2 [Theta] = 27.3 degrees, is the same as the TiOPc type IV, about 2 [Theta] = 9.5 degrees and 9.7 degrees peak at the type IV Chitanirufuta b It differs substantially from type IV in that it is clearly present in the XRPD of cyanine and not in the type X material. In addition, the peak of type X at 2θ = about 7.4 degrees is relatively much more distinct (compared to other peaks in the diffraction graph) than the same peak of type IV XRPD. . These are the most prominent differences between the Type IV and Type X polymorphs, but other more subtle differences apparent to those familiar with X-ray diffraction are also noted. In addition, the X type is 14.
It shows broad diffraction peaks with 2θ values of 1 ° and 17.8 °. The 2θ value reported is related to the diffraction of copper alpha radiation (wavelength = 0.1542 nm).

Also, a solution of TIPc type I of a 1: 4 mixture of trifluoroacetic acid and methylene chloride is reprecipitated in various methanol and water mixtures ranging from 100% methanol to 100% water. Following the isolation above, the sample was XRPD
The results are shown in Table 2 below.

[0023]

Table 2 Methanol / water ratio of precipitation solvent XRPD analysis 100: 0 Type Z-1 95: 5 Type III (mainly) 90:10 Type III (mainly) 85:15 Type III (mainly) 80: 20 Type III (mainly) 75:25 Type III (mainly) 70:30 Type III (mainly) 65:35 Type III + 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 polymorphic form is Type III. However, 65% methanol and 35%
Type X dominates from this water composition. Polymorphically pure Type X is obtained when the acid solution is precipitated into a methanol / water composition ranging from 60% to about 35% methanol. Compositions containing less than about 35% methanol and pure water have a Type I having an XRPD peak at 2θ = 9.8 degrees.
Results in the formation of a V-shape.

The titanyl phthalocyanine may also be used in a ratio of about 5 to about 10 parts solvent to about 1 part diiminoisoindolene, in a chloronaphthalene solvent, with 3 to 5 molar equivalents of diiminoisoindrene. Titanium tetrabutoxide is produced by reaction in a ratio of 1 molar equivalent.
These ingredients are stirred and warmed to a temperature of about 160 to about 240 ° C. for about 30 minutes to about 8 hours. After this time, the reaction mixture is cooled to a temperature of about 100 to about 160 ° C. and the mixture is filtered through a sintered glass funnel (M porosity). The resulting titanyl phthalocyanine type I pigment was washed in a funnel with a sufficient amount of boiling dimethylformamide (DMF) solvent to remove all dark colored impurities from the solid, which was removed from the initial black color. Evidenced by a change in the color of the filtrate to a pale blue-green color. Following this, the pigment is stirred in a funnel with boiling DMF in an amount sufficient to form a loose suspension, which is filtered. The solid is finally washed with room temperature DMF, followed by a small amount of methanol, and finally about 2 hours to about 2
Dry for 4 hours at about 70 ° C. Generally, an amount of DMF equal to the amount of solvent (chloronaphthalene) used in the synthesis reaction is required for this washing step. The yield from this synthesis is 60% to 80%. The X-ray powder diffraction and XRPD analysis of the product thus obtained
It was shown to be a Type I polymorph, titanyl phthalocyanine.

A number of different layered photoresponsive imaging members, especially Type IV, obtained by the method of the present invention can be prepared. In one embodiment, the photoresponsive imaging member comprises a support substrate, a charge transport layer, particularly an arylamine hole transport layer, and a type IV, type I, or type X, preferably between the substrate and the transport layer. Includes a photogenerating layer containing type IV titanyl phthalocyanine. Another embodiment of the invention is a positively charged laminate containing a supporting substrate, a charge transport layer, in particular an arylamine hole transport layer, and a titanyl phthalocyanine pigment type IV obtained by the method of the invention as an overcoat. It is directed to photoresponsive imaging members. Further according to the present invention, a support substrate, a thin adhesive layer, a titanyl phthalocyanine type IV photogenerator obtained according to the present invention dispersed in a polymeric resin binder, and an aryl dispersed in a polymeric resin binder as the top layer. Provided are improved negatively charged, photoresponsive imaging members containing amine hole transporting molecules.

The photoresponsive imaging members of this invention are made by a number of known methods, layer coating sequences which depend on the process parameters and the desired member. Imaging members suitable for positive charging can be prepared by reversing the deposition order of the photogenerator and the hole transport layer. The photogenerating layer and charge transport layer of the imaging member are a spray coater,
Coated as a solution or dispersion on selected substrates by the use of dip coaters, extrusion coaters, roller coaters, wire-bar coaters, slot coaters, doctor blade coaters, gravure coaters, etc., at about 40 to about 200 ° C. Dried for about 10 minutes to about several hours under static conditions or in an air stream. The coating is carried out so that the final coating thickness is 0.01 to about 30 microns after drying. The assembly conditions suitable for a given layer are tailored to achieve optimal performance and cost in the final device.

The titanyl phthalocyanine pigments of the present invention, especially the Type IV imaging members, are useful in a variety of electrostatic imaging and printing systems, especially those known as the zero fraphy system. In particular, the imaging member of this invention contains a titanyl phthalocyanine pigment from about 600 nm to about 9 nm.
It is useful for a zero-fraffy image forming system that absorbs light with a wavelength of 00 nm. In these known methods, an electrostatic latent image is first formed on the imaging member, followed by development, after which the image is transferred to a suitable support. In addition, the imaging members of this invention have an about 660 nm to about 830 nm
It can be selected for electronic printing with a light emitting diode (LED) array that typically operates at a wavelength of nm.

Shown in FIG. 6 is a support substrate 1, eg a solution coated adhesive layer 2 containing 49,000 polyesters available from Goodyear Chemical, obtained by the method of the present invention and optionally inert. Resin binder 4
Photogenerating layer 3 containing titanyl phthalocyanine type IV dispersed therein, and polycarbonate resin binder 7
The invention comprising a hole transport layer 5 comprising N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine dispersed therein. Is a negatively charged photoresponsive image forming member. Shown in FIG. 7 is a support substrate 10,
N dispersed in the polycarbonate resin binder 14,
N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-
Hole transport layer 12 containing biphenyl-4,4'-diamine, obtained by the method of the invention and optionally an inert resin binder 18.
A positively charged, photoresponsive imaging member of the present invention comprising a titanyl phthalocyanine Type IV or Type X photogenerating layer 16 dispersed therein.

[0030]

【Example】

Example 1 Synthesis of type I titanyl phthalocyanine : 250 ml three necked flask equipped with mechanical stirrer under argon atmosphere, 1,3-diiminoisoindolene (14.5 g, 0.1 mol) in condenser and thermometer. , Titanium tetrabutoxide (8.5 g, 0.025 mol; Aldrich) and 75
1 ml of 1-chloronaphthalene was charged. The mixture was stirred and warmed. At 140 ° C the mixture turns dark green and begins to reflux. At this time, the vapor, which was identified by gas chromatography as n-butanol, was allowed to escape into the atmosphere until the reflux temperature reached 200 ° C. The reaction was held at this temperature for 2 hours and then cooled to 150 ° C by removing the heat source. The product was filtered through 150 ml of M-porosity sintered glass funnel preheated to about 150 ° C with boiling DMF, followed by thorough washing with 100 ml of boiling DMF and then three times with 100 ml of room temperature DMF. Then 5
Wash 3 times with 0 ml of methanol and then use Type IT by XRPD.
10.3 g (7% yield) of a lustrous purple pigment identified as iOPc
2%).

Example 2 Preparation of Type IV TiOPc : 2 g of type I TiOPc prepared as described in Example 1 was dissolved in 20 ml of a mixture of trifluoroacetic acid and methylene chloride (1: 4, V / V). A rapidly stirred solution of methanol (100 ml) and water (100 ml) was added over 2 minutes. 45 to the resulting coarse suspension
It was stirred for one minute at room temperature and then left standing. The supernatant was decanted and the blue residue was redispersed in 100 ml of methanol by stirring for 30 minutes. The suspension was filtered in a porcelain funnel using 7 cm diameter glass fiber filter paper. The solid was redispersed twice in 100 ml of hot (about 90 ° C.) deionized water and filtered by vacuum filtration through a 7 cm diameter porcelain funnel fitted with Whatman 934-AH grade filter paper fibers. Finally, the solid was identified as type X titanyl phthalocyanine on the basis of its XRPD spectrum, redispersed in 100 ml of monochlorobenzene, filtered, oven dried at a temperature of 70 ° C. for 1 hour and by XRPD. Identified as type IV titanyl phthalocyanine
1.6 g of powdery blue pigment was obtained.

The titanyl phthalocyanine was selected as the photogenerating layer for the laminated imaging member prepared by the following procedure. Aluminum coated mylar (MYLA) with a thickness of about 4 mils
R; substrate, 5 g of nylon 8 (Dainippon Ink and Chemical Company) and 1
Nylon 8 solution prepared by dissolving 6 g n-butanol in 24 g methanol and 4 g water was coated using a 1 mil gap applicator. The layer was dried for 20 minutes at 135 ° C; final thickness was measured at 0.6 microns. Add TiOPc Type IV dispersion to 0.
35 g of TiOPc and poly (vinyl butyral) were prepared by ball milling in 13.4 g of butyl acetate in a 30 ml jar containing 70 g of 1/8 inch stainless steel balls. Mill the dispersion for 20 hours and then use the 1 mil applicator described above for nylon 8
Applied on top of the layer. The photogenerating layer thus formed was dried at 100 ° C. for 10 minutes to a final thickness of about 0.40 micron.

The hole transport layer solution was mixed with 57.6 g of chlorobenze.
5.4 g of N, N'-diphenyl-N, N'-bis (3-methylphene)
Nyl) -1,1'-biphenyl-4,4'-diamine and 8.1 g of poly
It was prepared by dissolving the carbonate. That melt
TIPc the liquid using an 8 mil film applicator.
It was coated on the type IV generator layer. The charge thus obtained
Dry the transport layer at 115 ° C for 60 minutes to a final thickness of approximately 23 m.
It became Kron. Photoresponsive image produced as described above
The xerographic electrical properties of the forming member adhere to the electrometer
Measured by a capacitively coupled probe
The surface potential is -800 V, the initial dark value, V₀Reach
Until its surface is electrostatically charged with a corona discharge power source
It is measured by After leaving it in the dark for 0.5 seconds,
The charged member is the surface potential, V_ddp, Or to the dark development potential
Reached Then fill this part with a xenon lamp.
Exposed to light through the tar. V due to photodischarge effect _ddp
To background potential, V_bgThe decrease of the surface potential of
Was perceived. The dark decay voltage per second is (V₀-
V_ddp) /0.5 was calculated. Photodischarge percentage
Is 100 × (V_ddp-V_bg) / V_ddpIs calculated as
It was Half exposure energy, E_1/2, V_ddpOf its initial value
Exposure energy required to cause a reduction in half
Was measured. The wavelength of light selected for our measurements
Is 800 nm. This imaging member is 15-20 volts / sec
Dark decay and E_1/2= 0.8ergs / cm²Had. 5ergs / cm
²And 10 ergs / cm²The discharges at 87% and 90% respectively.
It was Table 3 below shows image formation for devices 1 and 2.
Shows information and data for parts, which are
It contains the components described in the examples. Devices 1 and 2 are shown
In the data presented, titani obtained from the examples given
Ruphthalocyanine-same as except type IV
Including ingredients such as. NMP is N-methylpyrrolidine, Cl
Np is chloronaphthalene, the listed salts are reactive
Chosen as one of the bodies.

Example 3 Synthesis of type I titanyl phthalocyanine : Titanyl phthalocyanine type I pigment was prepared by adding 1,3-diiminoisoindolene (14.5 g, 0.1 mol) and titanium tetrapropoxide (7.1).
g, 0.025 mol; Aldrich) and 75 ml of 1-chloronaphthalene prepared by repeating the procedure of Example 1. 11.3 g (78% yield) of a lustrous purple solid identified as type I titanyl phthalocyanine by XRPD was obtained. Preparation of Type IV TIOPc : Titanyl phthalocyanine Type IV pigment was prepared by repeating the method of Example 2 to obtain 1.7 g (85% yield) of a powdery blue solid identified by XRPD as Type IV titanyl phthalocyanine. It was The Type IV pigment produced was selected for use as a photogenerating layer in the laminated imaging member of Example 2,
The results are reported in Table 3. The dark decay of one imaging member is about 15 to 20 volts / sec and E _1/2 is
It was 0.9 ergs / cm ² . Discharges at 5 ergs / cm ² and 10 ergs / cm ² were 88% and 91%, respectively.

Example 4 Synthesis of Type I Titanyl Phthalocyanine : A titanyl phthalocyanine pigment was prepared using 1,3-diiminoisoindolene (14.5
g, 0.1 mol), titanium tetrabutoxide (8.5 g, 0.025
Mol; Aldrich) and 75 ml of N-methylpyrrolidone prepared by repeating the method of Example 1.
9.6 g (67% yield) of a lustrous purple solid identified as type I titanyl phthalocyanine by XRPD was obtained. Preparation of Type IV TiOPc : Titanyl phthalocyanine Type IV pigment was prepared by repeating the method of Example 2. There was obtained 1.5 g (75% yield) of a powdery blue solid identified by XRPD as type IV titanyl phthalocyanine.

Example 5 Synthesis of Type I Titanyl Phthalocyanine : A titanyl phthalocyanine pigment was prepared using 1,3-diiminoisoindrene (14.5
g, 0.1 mol), titanium tetrapropoxide (7.1 g, 0.0
25 mol; Aldrich) and 75 ml of N-methylpyrrolidone were prepared by repeating the procedure of Example 1. XR
9.1 g (63% yield) of a lustrous purple solid identified by PD as type I titanyl phthalocyanine was obtained. Preparation of Type IV TiOPc : Titanyl phthalocyanine Type IV pigment was prepared by repeating the method of Example 2. There was obtained 1.5 g (75% yield) of a powdery blue solid identified by XRPD as type IV titanyl phthalocyanine.

Example 6 Preparation of Type IV Titanyl Phthalocyanine: 2 g of Type I TIOPc was dissolved in 20 ml of a mixture of trifluoroacetic acid and methylene chloride (1: 4, V / V) and rapidly stirred with methanol (100 ml). A solution of water (100 ml) was added over 2 minutes. The crude suspension obtained was stirred for 45 minutes at room temperature and then left to stand. Decant the supernatant,
The blue residue was redispersed by stirring in 100 ml of methanol for 30 minutes. The suspension was filtered in a porcelain funnel using 7 cm diameter glass fiber filter paper. The solid was redispersed twice in 100 ml of hot (about 90 ° C) deionized water,
Filtered by vacuum filtration through a 7 cm diameter porcelain funnel fitted with Whatman 934-AH grade filtration fiber. Finally, the solid was identified as type IV titanyl phthalocyanine on the basis of its XRPD spectrum, redispersed in 100 ml monochlorobenzene, filtered and kept at 70% for 1 hour.
Oven drying at a temperature of ° C gave 1.6 g of a powdery blue pigment identified by XRPD as type IV titanyl phthalocyanine. The Type IV pigment described above was selected for use as the photogenerating layer in the laminated imaging member of Example 2, which member had a dark decay of 31 volts / sec and E _1/2 = 1.3 ergs / cm ² . Discharge at 5 ergs / cm ² and 10 ergs / cm ² respectively
81% and 87%.

Example 7 Synthesis of Type I Titanyl Phthalocyanine : A 1 liter three necked flask equipped with a mechanical stirrer kept under an argon atmosphere, a Claisen Head condenser and a thermometer, diiminoisoindo. Len
(94.3 g, 0.65 mol), titanium tetrabutoxide (55.3 g,
0.1625 mol; Aldrich) and 650 ml of 1-chloronaphthalene were charged. The mixture was stirred and warmed. 140 ° C
At that the mixture turns dark green and begins to reflux. At this time, the stopcock of the Kraisenhead was opened and the vapor (which was identified by gas chromatography as n-butanol) was allowed to escape dropwise until the reflux temperature reached 200 ° C. The reaction was held at this temperature for 2 hours and then cooled to 150 ° C by removing the heat source. 1
Filter using a 1 liter sintered glass funnel, then 3 times with 1 liter boiling DMF at room temperature, approximately 25 ° C DMF 1
Washed 3 times with 1 liter and then 3 times with 1 liter of methanol, identified by XRPD as type ITiOPc 69.7
g (74% yield) of a blue pigment was obtained. Elemental analysis of the Type I product obtained as described above: C, 67.38; H, 2.78; N,
19.10; Ash, 13.61. TiOPc is C, 66.67; H, 2.80;
N, 19.44; Ash, 13.61 required.

Example 8 Preparation of Type X Titanyl Phthalocyanine : To a solution of trifluoroacetic acid (100 ml) in magnetically stirred methylene chloride (400 ml) in a 1 liter Erlenmeyer flask.
Type ITOP synthesized in Example 1 over 2 minutes
50 g of c was added. No heat was released and the resulting dark green solution was stirred for 15 minutes at room temperature. The solution was stirred for 2 minutes in a 12 liter glass cylinder containing methanol.
Pour into a solution of (2.5 liters) and water (2.5 liters), 100m
A magnetic stir bar of m 2 was used to stir at a speed sufficient to create a vortex that broadly spreads to the bottom of the flask. Following the addition, the resulting blue suspension was stirred for 45 minutes at room temperature,
Then, it was allowed to stand for 25 minutes. The yellowish brown supernatant liquid,
Almost completely separated from the precipitated solids by careful decantation of the reaction vessel. The remaining blue residue is taken up in 2 l of methanol at room temperature for 1 hour,
Redispersion was carried out by stirring with a magnet. The resulting suspension is filtered through a 18 cm glass fiber filter in a porcelain filter funnel and the filter cake is continued to 2 x 100 m.
l methanol, 2 x 100ml water, 500ml water, then
Wash with 2 x 100 ml of methanol. This product at 75 ° C
After drying overnight at 47.6 g (95% yield) of a dark blue pigment identified by XRPD as type XTiOPc.

Example 9 Preparation of Type IV Titanyl Phthalocyanine: 2 g of Type I TIOPc prepared as described in Example 1 was mixed with a mixture of trifluoroacetic acid and methylene chloride (1: 4, V / V).
Dissolve in 20 ml for 5 minutes and rapidly stir methanol (100
ml) and water (100 ml) over 20 minutes, dip the solution in an ice-water bath and wait for 5 minutes until the addition is complete.
A temperature below ℃ was maintained. After the addition is complete,
The ice bath was removed and the resulting crude suspension was stirred for 45 minutes at room temperature before standing. The supernatant was decanted by carefully pouring it into a flask and the blue residue was identified as type X based on its XRPD spectrum.
Identified as titanyl phthalocyanine, its type X is TE
It had a particle size of about 0.05 to about 0.1 micron as measured by M and the residue was redispersed by stirring in 100 ml of methanol for 30 minutes. The suspension was filtered in a porcelain funnel using a 7 cm diameter glass fiber filter (Whatman Grade 934-AH). 100 ml of the solid
(About 90 ° C.), redispersed twice with deionized water and filtered as above. Finally, the solid was identified as type X titanyl phthalocyanine on the basis of its XRPD spectrum, redispersed by stirring in 100 ml of monochlorobenzene at room temperature for 30 minutes, filtered and kept at 70% for 1 hour.
Oven drying at a temperature of ° C gave 1.6 g of a powdery blue pigment identified by XRPD as type IV titanyl phthalocyanine.

[0041]

[Table 3] Conducted device Titanium reaction Dark decay% discharge E _1/2 Vddp Example Chair Salt Solvent (v / s) 5ergs / cm ₂ 10ergs / cm ₂ (ergs / cm ₂ per volt ) 1 17-19 84.0 87.5 1.0 -804 ~ -819 5 Ti (OPr) ₄ NMP 16-20 84.0 88.0 1.1 -719 ~ -802 15-17 82.0 86.0 1.1 -812 ~ -823 2 13-15 82.5 87.0 1.2 -812 ~ -818 1 13-16 86.0 89.5 1.0 -800 to -829 4 Ti (OBu) ₄ NMP 13-15 87.0 90.0 0.9 -817 to -823 11-16 85.5 89.0 1.0 -822 to -839 2 11-13 85.0 89.0 0.9 -812 to -821 1 20-22 88.0 90.0 0.9 -799 ~ -802 3 Ti (OPr) ₄ ClNp 18-21 88.0 91.0 0.9 -800 ~ -818 12-18 87.5 90.5 0.7 -806 ~ -837 2 11-14 87.0 90.0 0.8 -808 ~ -823 1 18-21 87.0 90.0 0.8 -796 ~ -810 1 Ti (OBu) ₄ ClNp 18-19 87.5 90.0 0.8 -800 ~ -806 12-14 87.0 89.5 0.9 -808 ~ -821 2 12-16 87.0 90.0 0.8 -806 to -841

TiOPc obtained by the method of Example 1
2 g of (Type I) was dissolved in 20 ml of a mixture of trifluoroacetic acid and methylene chloride (1: 4) over about 5 minutes. The resulting dark green solution was then added dropwise over about 10 to about 15 minutes to a 1: 1 mixture of methanol and water (200 ml) that was vigorously stirred and maintained at a temperature of 0 ° C in an ice bath. After the addition of the dissolved solution, stirring was continued for 1 hour at room temperature.
The resulting solution is filtered through a Buchner funnel fitted with glass fiber filter paper, followed by methanol, warm water (> 90
C.) and monochlorobenzene, then washed by filtration. The washed pigment was then oven dried at a temperature of 70 ° C. for 2 hours to give 1.6 g of a powdery blue pigment which was identified by X-ray powder diffraction as type IV titanyl phthalocyanine. Particle size is TEM
The average particle size was found to be about 0.05 to about 0.1 micron, with few particles having an average particle size greater than 0.1 micron being present.

The particle size of the titanyl phthalocyanine produced as described above was measured by TEM. About 1 mg of sample
2 ml of dry type IV titanyl phthalocyanine pigment
Was dispersed in methanol and sonicated for 2 minutes. A small drop, approximately 0.05 ml, was removed from the dispersion by a micropipette and deposited on a carbon-form var coated copper grid. The sample was tested by transmission on a Philip CM20 STEM machine with an accelerating voltage of 160 Kv. Particle size was measured using calipers from the resulting electron micrographs. Also, in the method of the present invention, the present and co-pending U.S. patent application (not yet granted-D / 91151), the disclosure of which is hereby incorporated by reference in its entirety, By treatment or dispersion of a Type X as described in, for example, halobenzenes such as chlorobenzene, for example about 0.
A Type IV titanyl phthalocyanine having a small particle size of 02 to about 0.05, 0.05 to about 0.3, and preferably about 0.05 to about 0.1 micron is obtained.

[0044]

[Brief description of drawings]

1 is a schematic diffraction pattern of a known polymorphic form of titanyl phthalocyanine, type I XRPD.

FIG. 2 is a schematic diffraction pattern of a known polymorphic form of titanyl phthalocyanine, type II XRPD.

FIG. 3 is a schematic diffraction pattern of a known polymorphic form of titanyl phthalocyanine, type III XRPD.

FIG. 4 is a schematic diffraction pattern of a known polymorphic form of titanyl phthalocyanine, type IV XRPD.

FIG. 5 is a schematic diffraction pattern of a known polymorphic form of titanyl phthalocyanine, type X XRPD.

FIG. 6 is a partial schematic cross-sectional view of a negatively charged, photoresponsive imaging member of the present invention.

FIG. 7 is a partial schematic cross-sectional view of a positively charged, photoresponsive imaging member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Supporting substrate 2 Solution coating adhesive layer 3 Photogenerating layer 4 Inert resin binder 5 Hole transporting layer 7 Polycarbonate resin binder 10 Supporting substrate 12 Hole transporting layer 14 Polycarbonate resin binder 16 Photogenerating layer 18 Inert resin binder

Claims (1)

[Claims] 1. A titanium tetraalkoxide is reacted with diiminoisoindolene in the presence of a halonaphthalene solvent; the resulting type I titanyl phthalocyanine is dissolved in haloacetic acid and an alkylene halide in which the alkylene contains 1 to 6 carbon atoms. The resulting mixture is slowly added to a cold aqueous solution of an aliphatic alcohol containing 1 to 12 carbon atoms to precipitate Type X titanyl phthalocyanine having a volume average particle size diameter of 0.02 to 0.5 microns; And a method for producing type X titanyl phthalocyanine, characterized in that the type X titanyl phthalocyanine is isolated.