# Patent

## Title
Organophotoreceptors with a charge transport material having multiple vinyl-containing hydrazone groups

## Abstract

Improved organophotoreceptor comprises an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:

    
    
        (a) a charge transport material having the formula
    
    






    
    
        where Y comprises an aromatic group;
        V1 and V2 comprise, each independently, a vinyl containing group; and
        R1, R2, R3, and R4 comprise, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group; and
        (b) a charge generating compound.
    
    


Corresponding electrophotographic apparatuses, electrophotographic imaging methods, and charge transport materials are also described.

## Background
FIELD OF THE INVENTION
This invention relates to organophotoreceptors suitable for use in electrophotography and, more specifically, to organophotoreceptors including a charge transport material having multiple vinyl-containing hydrazone groups bonded to an aromatic group.
BACKGROUND OF THE INVENTION
In electrophotography, an organophotoreceptor in the form of a plate, disk, sheet, belt, drum or the like having an electrically insulating photoconductive element on an electrically conductive substrate is imaged by first uniformly electrostatically charging the surface of the photoconductive layer, and then exposing the charged surface to a pattern of light. The light exposure selectively dissipates the charge in the illuminated areas where light strikes the surface, thereby forming a pattern of charged and uncharged areas, referred to as a latent image. A liquid or solid toner is then provided in the vicinity of the latent image, and toner droplets or particles deposit in the vicinity of either the charged or uncharged areas to create a toned image on the surface of the photoconductive layer. The resulting toned image can be transferred to a suitable ultimate or intermediate receiving surface, such as paper, or the photoconductive layer can operate as an ultimate receptor for the image. The imaging process can be repeated many times to complete a single image, for example, by overlaying images of distinct color components or effect shadow images, such as overlaying images of distinct colors to form a full color final image, and/or to reproduce additional images.
Both single layer and multilayer photoconductive elements have been used. In single layer embodiments, a charge transport material and charge generating material are combined with a polymeric binder and then deposited on the electrically conductive substrate. In multilayer embodiments, the charge transport material and charge generating material are present in the element in separate layers, each of which can optionally be combined with a polymeric binder, deposited on the electrically conductive substrate. Two arrangements are possible for a two-layer photoconductive element. In one two-layer arrangement (the “dual layer” arrangement), the charge-generating layer is deposited on the electrically conductive substrate and the charge transport layer is deposited on top of the charge generating layer. In an alternate two-layer arrangement (the “inverted dual layer” arrangement), the order of the charge transport layer and charge generating layer is reversed.
In both the single and multilayer photoconductive elements, the purpose of the charge generating material is to generate charge carriers (i.e., holes and/or electrons) upon exposure to light. The purpose of the charge transport material is to accept at least one type of these charge carriers and transport them through the charge transport layer in order to facilitate discharge of a surface charge on the photoconductive element. The charge transport material can be a charge transport compound, an electron transport compound, or a combination of both. When a charge transport compound is used, the charge transport compound accepts the hole carriers and transports them through the layer with the charge transport compound. When an electron transport compound is used, the electron transport compound accepts the electron carriers and transports them through the layer with the electron transport compound.
SUMMARY OF THE INVENTION
This invention provides organophotoreceptors having good electrostatic properties such as high Vacc and low Vdis.
In a first aspect, an organophotoreceptor comprises an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:
(a) a charge transport material having the formula:




where Y comprises an aromatic group, such as an aryl group, an aromatic heterocyclic group, and combinations thereof;
V1 and V2, each independently, comprise a vinyl containing group, such as an alkyl vinyl ether group and a CH2═CH—O—X— group where X comprises a bond or a —(CH2)m-group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, an aromatic group, an NRa group, a CRb group, a CRcRd group, a SiReRf group, a BRg group, or a P(═O)Rh group, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are, each independently, a bond, H, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a halogen, an acyl group, an alkoxy group, an alkylsulfanyl group, an alkenyl group, such as a vinyl group, an allyl group, and a 2-phenylethenyl group, an alkynyl group, a heterocyclic group, an aromatic group, a part of a ring group, such as cycloalkyl groups, heterocyclic groups, and a benzo group, or an alkyl group where one or more of the hydrogens of the alkyl group is optionally replaced by an aromatic group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, or a halogen; and
R1, R2, R3, and R4 comprise, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group such as cycloalkyl groups, heterocyclic groups, and a benzo group; and
(b) a charge generating compound.
The organophotoreceptor may be provided, for example, in the form of a plate, a flexible belt, a flexible disk, a sheet, a rigid drum, or a sheet around a rigid or compliant drum. In one embodiment, the organophotoreceptor includes: (a) a photoconductive element comprising the charge transport material, the charge generating compound, a second charge transport material, and a polymeric binder; and (b) the electrically conductive substrate.
In a second aspect, the invention features an electrophotographic imaging apparatus that comprises (a) a light imaging component; and (b) the above-described organophotoreceptor oriented to receive light from the light imaging component. The apparatus can further comprise a toner dispenser, such as a liquid toner dispenser. The method of electrophotographic imaging with photoreceptors containing the above noted charge transport materials is also described.
In a third aspect, the invention features an electrophotographic imaging process that includes (a) applying an electrical charge to a surface of the above-described organophotoreceptor; (b) imagewise exposing the surface of the organophotoreceptor to radiation to dissipate charge in selected areas and thereby form a pattern of at least relatively charged and uncharged areas on the surface; (c) contacting the surface with a toner, such as a liquid toner that includes a dispersion of colorant particles in an organic liquid, to create a toned image; and (d) transferring the toned image to a substrate.
In a fourth aspect, the invention features a charge transport material having Formula (I) above.
The invention provides suitable charge transport materials for organophotoreceptors featuring a combination of good mechanical and electrostatic properties. These photoreceptors can be used successfully with toners, such as liquid toners, to produce high quality images. The high quality of the imaging system can be maintained after repeated cycling.
Other features and advantages of the invention will be apparent from the following description of the particular embodiments thereof, and from the claims.


DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
An organophotoreceptor as described herein has an electrically conductive substrate and a photoconductive element including a charge generating compound and a charge transport material having multiple vinyl-containing hydrazone groups, each bonded to an aromatic group. These charge transport materials have desirable properties as evidenced by their performance in organophotoreceptors for electrophotography. In particular, the charge transport materials of this invention have high charge carrier mobilities and good compatibility with various binder materials, and possess excellent electrophotographic properties. The organophotoreceptors according to this invention generally have a high photosensitivity, a low residual potential, and a high stability with respect to cycle testing, crystallization, and organophotoreceptor bending and stretching. The organophotoreceptors are particularly useful in laser printers and the like as well as fax machines, photocopiers, scanners and other electronic devices based on electrophotography. The use of these charge transport materials is described in more detail below in the context of laser printer use, although their application in other devices operating by electrophotography can be generalized from the discussion below.
To produce high quality images, particularly after multiple cycles, it is desirable for the charge transport materials to form a homogeneous solution with the polymeric binder and remain approximately homogeneously distributed through the organophotoreceptor material during the cycling of the material. In addition, it is desirable to increase the amount of charge that the charge transport material can accept (indicated by a parameter known as the acceptance voltage or “Vacc”), and to reduce retention of that charge upon discharge (indicated by a parameter known as the discharge voltage or “Vdis”).
The charge transport materials may comprise monomeric molecules (e.g., 9-ethyl-carbazole-3-carbaldehyde N,N-diphenylhydrazone), dimeric molecules (e.g., those disclosed in U.S. Pat. Nos. 6,140,004, 6,670,085, and 6,749,978), or polymeric compositions (e.g., poly(vinylcarbazole)). The charge transport materials can also be classified as a charge transport compound or an electron transport compound. There are many charge transport compounds and electron transport compounds known in the art for electrophotography. Non-limiting examples of charge transport compounds include, for example, pyrazoline derivatives, fluorene derivatives, oxadiazole derivatives, stilbene derivatives, enamine derivatives, enamine stilbene derivatives, hydrazone derivatives, carbazole hydrazone derivatives, (N,N-disubstituted)arylamines such as triaryl amines, polyvinyl carbazole, polyvinyl pyrene, polyacenaphthylene, and the charge transport compounds described in U.S. Pat. Nos. 6,670,085, 6,689,523, 6,696,209, and 6,749,978, and U.S. patent application Ser. Nos. 10/431,135, 10/431,138, 10/699,364, 10/663,278, 10/699,581, 10/449,554, 10/748,496, 10/789,094, 10/644,547, 10/749,174, 10/749,171, 10/749,418, 10/699,039, 10/695,581, 10/692,389, 10/634,164, 10/663,970, 10/749,164, 10/772,068, 10/749,178, 10/758,869, 10/695,044, 10/772,069, 10/789,184, 10/789,077, 10/775,429, 10/775,429, 10/670,483, 10/671,255, 10/663,971, 10/760,039. All the above patents and patent applications are incorporated herein by reference.
Non-limiting examples of electron transport compounds include, for example, bromoaniline, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-indeno[1,2-b]thiophene-4-one, and 1,3,7-trinitrodibenzo thiophene-5,5-dioxide, (2,3-diphenyl-1-indenylidene)malononitrile, 4H-thiopyran-1,1-dioxide and its derivatives such as 4-dicyanomethylene-2,6-diphenyl-4H-thiopyran-1,1-dioxide, 4-dicyanomethylene-2,6-di-m-tolyl-4H-thiopyran-1,1-dioxide, and unsymmetrically substituted 2,6-diaryl-4H-thiopyran-1,1-dioxide such as 4H-1,1-dioxo-2-(p-isopropylphenyl)-6-phenyl-4-(dicyanomethylidene)thiopyran and 4H-1,1-dioxo-2-(p-isopropylphenyl)-6-(2-thienyl)-4-(dicyanomethylidene)thiopyran, derivatives of phospha-2,5-cyclohexadiene, alkoxycarbonyl-9-fluorenylidene)malononitrile derivatives such as (4-n-butoxycarbonyl-9-fluorenylidene)malononitrile, (4-phenethoxycarbonyl-9-fluorenylidene)malononitrile, (4-carbitoxy-9-fluorenylidene)malononitrile, and diethyl(4-n-butoxycarbonyl-2,7-dinitro-9-fluorenylidene)malonate, anthraquinodimethane derivatives such as 11,11,12,12-tetracyano-2-alkylanthraquinodimethane and 11,11-dicyano-12,12-bis(ethoxycarbonyl)anthraquinodimethane, anthrone derivatives such as 1-chloro-10-[bis(ethoxycarbonyl)methylene]anthrone, 1,8-dichloro-10-[bis(ethoxycarbonyl)methylene]anthrone, 1,8-dihydroxy-10-[bis(ethoxycarbonyl)methylene]anthrone, and 1-cyano-10-[bis(ethoxycarbonyl)methylene)anthrone, 7-nitro-2-aza-9-fluroenylidene-malononitrile, diphenoquinone derivatives, benzoquinone derivatives, naphtoquinone derivatives, quinine derivatives, tetracyanoethylenecyanoethylene, 2,4,8-trinitro thioxantone, dinitrobenzene derivatives, dinitroanthracene derivatives, dinitroacridine derivatives, nitroanthraquinone derivatives, dinitroanthraquinone derivatives, succinic anhydride, maleic anhydride, dibromo maleic anhydride, pyrene derivatives, carbazole derivatives, hydrazone derivatives, N,N-dialkylaniline derivatives, diphenylamine derivatives, triphenylamine derivatives, triphenylmethane derivatives, tetracyano quinodimethane, 2,4,5,7-tetranitro-9-fluorenone, 2,4,7-trinitro-9-dicyanomethylene fluorenone, 2,4,5,7-tetranitroxanthone derivatives, 2,4,8-trinitrothioxanthone derivatives, 1,4,5,8-naphthalene bis-dicarboximide derivatives as described in U.S. Pat. Nos. 5,232,800, 4,468,444, and 4,442,193 and phenylazoquinolide derivatives as described in U.S. Pat. No. 6,472,514. In some embodiments of interest, the electron transport compound comprises an (alkoxycarbonyl-9-fluorenylidene)malononitrile derivative, such as (4-n-butoxycarbonyl-9-fluorenylidene)malononitrile, and 1,4,5,8-naphthalene bis-dicarboximide derivatives.
Although there are many charge transport materials available, there is a need for other charge transport materials to meet the various requirements of particular electrophotography applications.
In electrophotography applications, a charge-generating compound within an organophotoreceptor absorbs light to form electron-hole pairs. These electrons and holes can be transported over an appropriate time frame under a large electric field to discharge locally a surface charge that is generating the field. The discharge of the field at a particular location results in a surface charge pattern that essentially matches the pattern drawn with the light. This charge pattern then can be used to guide toner deposition. The charge transport materials described herein are especially effective at transporting charge, and in particular holes from the electron-hole pairs formed by the charge generating compound. In some embodiments, a specific electron transport compound or charge transport compound can also be used along with the charge transport material of this invention.
The layer or layers of materials containing the charge generating compound and the charge transport materials are within an organophotoreceptor. To print a two dimensional image using the organophotoreceptor, the organophotoreceptor has a two dimensional surface for forming at least a portion of the image. The imaging process then continues by cycling the organophotoreceptor to complete the formation of the entire image and/or for the processing of subsequent images.
The organophotoreceptor may be provided in the form of a plate, a flexible belt, a disk, a rigid drum, a sheet around a rigid or compliant drum, or the like. The charge transport material can be in the same layer as the charge generating compound and/or in a different layer from the charge generating compound. Additional layers can be used also, as described further below.
In some embodiments, the organophotoreceptor material comprises, for example: (a) a charge transport layer comprising the charge transport material and a polymeric binder; (b) a charge generating layer comprising the charge generating compound and a polymeric binder; and (c) the electrically conductive substrate. The charge transport layer may be intermediate between the charge generating layer and the electrically conductive substrate. Alternatively, the charge generating layer may be intermediate between the charge transport layer and the electrically conductive substrate. In further embodiments, the organophotoreceptor material has a single layer with both a charge transport material and a charge generating compound within a polymeric binder.
The organophotoreceptors can be incorporated into an electrophotographic imaging apparatus, such as laser printers. In these devices, an image is formed from physical embodiments and converted to a light image that is scanned onto the organophotoreceptor to form a surface latent image. The surface latent image can be used to attract toner onto the surface of the organophotoreceptor, in which the toner image is the same or the negative of the light image projected onto the organophotoreceptor. The toner can be a liquid toner or a dry toner. The toner is subsequently transferred, from the surface of the organophotoreceptor, to a receiving surface, such as a sheet of paper. After the transfer of the toner, the surface is discharged, and the material is ready to cycle again. The imaging apparatus can further comprise, for example, a plurality of support rollers for transporting a paper receiving medium and/or for movement of the photoreceptor, a light imaging component with suitable optics to form the light image, a light source, such as a laser, a toner source and delivery system and an appropriate control system.
An electrophotographic imaging process generally can comprise (a) applying an electrical charge to a surface of the above-described organophotoreceptor; (b) imagewise exposing the surface of the organophotoreceptor to radiation to dissipate charge in selected areas and thereby form a pattern of charged and uncharged areas on the surface; (c) exposing the surface with a toner, such as a liquid toner that includes a dispersion of colorant particles in an organic liquid to create a toner image, to attract toner to the charged or discharged regions of the organophotoreceptor; and (d) transferring the toner image to a substrate.
As described herein, an organophotoreceptor comprises a charge transport material having the formula:




where Y comprises an aromatic group, such as an aryl group, an aromatic heterocyclic group, and combinations thereof;
V1 and V2 comprise, each independently, a vinyl containing group, such as an alkyl vinyl ether group and a CH2═CH—O—X— group where X comprises a bond or a —(CH2)m-group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, an aromatic group, an NRa group, a CRb group, a CRcRd group, a SiReRf group, a BRg group, or a P(═O)Rh group, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are, each independently, a bond, H, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a halogen, an acyl group, an alkoxy group, an alkylsulfanyl group, an alkenyl group, such as a vinyl group, an allyl group, and a 2-phenylethenyl group, an alkynyl group, a heterocyclic group, an aromatic group, a part of a ring group, such as cycloalkyl groups, heterocyclic groups, and a benzo group, or an alkyl group where one or more of the hydrogens of the alkyl group is optionally replaced by an aromatic group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, or a halogen; and
R1, R2, R3, and R4 comprise, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group such as cycloalkyl groups, heterocyclic groups, and a benzo group.
A heterocyclic group includes any monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.) ring compound having at least a heteroatom (e.g., O, S, N, P, B, Si, etc.) in the ring.
An aromatic group can be any conjugated ring system containing 4n+2 pi-electrons. There are many criteria available for determining aromaticity. A widely employed criterion for the quantitative assessment of aromaticity is the resonance energy. Specifically, an aromatic group has a resonance energy. In some embodiments, the resonance energy of the aromatic group is at least 10 KJ/mol. In further embodiments, the resonance energy of the aromatic group is greater than 0.1 KJ/mol. Aromatic groups may be classified as an aromatic heterocyclic group which contains at least a heteroatom in the 4n+2 pi-electron ring, or as an aryl group which does not contain a heteroatom in the 4n+2 pi-electron ring. The aromatic group may comprise a combination of aromatic heterocyclic group and aryl group bonded together either by a bond (as in N-phenylpyrrole) or by a linking group (as in N-benzylpyrrole). The linking group may include an alkyl group, an alkenyl group, an alkyne group, O, S, O═S═O, an amino group, an aromatic group, a heterocyclic group, and combinations thereof. Nonetheless, either the aromatic heterocyclic or the aryl group may have at least one heteroatom in a substituent attached to the 4n+2 pi-electron ring. Furthermore, either the aromatic heterocyclic or the aryl group may comprise a monocyclic or polycyclic (such as bicyclic, tricyclic, etc.) ring.
Non-limiting examples of the aromatic heterocyclic group are furanyl, thiophenyl, pyrrolyl, indolyl, carbazolyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, petazinyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, phenanthridinyl, phenanthrolinyl, anthyridinyl, purinyl, pteridinyl, alloxazinyl, phenazinyl, 5,10-dihydrophenazinyl, phenothiazinyl, phenoxazinyl, phenoxathiinyl, dibenzo(1,4)dioxinyl, thianthrenyl, and a combination thereof. The aromatic heterocyclic group may also include any combination of the above aromatic heterocyclic groups bonded together either by a bond (as in bicarbazolyl) or by a linking group (as in 1,6 di(10H-10-phenothiazinyl)hexane). The linking group may include an alkyl group, an alkenyl group, an alkyne group, O, S, O═S═O, an amino group, an aromatic group, a heterocyclic group, and combinations thereof. Furthermore, the linking group may comprise at least one heteroatom such as O, S, Si, and N.
Non-limiting examples of the aryl group are phenyl, naphthyl, benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl. The aryl group may also include any combination of the above aryl groups bonded together either by a bond (as in biphenyl group) or by a linking group (as in stilbenyl, diphenyl sulfone, an arylamino group such as (N,N-disubstituted)arylamino group). The linking group may include an alkyl group, an alkenyl group, an alkyne group, O, S, O═S═O, an amino group, an aromatic group, a heterocyclic group, and combinations thereof. Furthermore, the linking group may comprise at least one heteroatom such as O, S, Si, and N.
Substitution is liberally allowed on the chemical groups to affect various physical effects on the properties of the compounds, such as mobility, sensitivity, solubility, stability, and the like, as is known generally in the art. In the description of chemical substituents, there are certain practices common to the art that are reflected in the use of language. The term group indicates that the generically recited chemical entity (e.g., alkyl group, alkenyl group, aryl group, phenyl group, aromatic heterocyclic group, etc.) may have any substituent thereon which is consistent with the bond structure of that group. For example, where the term ‘alkyl group’ or ‘alkenyl group’ is used, that term would not only include unsubstituted linear, branched and cyclic alkyl group or alkenyl group, such as methyl, ethyl, ethenyl or vinyl, isopropyl, tert-butyl, cyclohexyl, cyclohexenyl, dodecyl and the like, but also substituents having heteroatom(s), such as 3-ethoxylpropyl, 4-(N,N-diethylamino)butyl, 3-hydroxypentyl, 2-thiolhexyl, 1,2,3-tribromoopropyl, and the like, and aromatic group, such as phenyl, naphthyl, carbazolyl, pyrrole, and the like. However, as is consistent with such nomenclature, no substitution would be included within the term that would alter the fundamental bond structure of the underlying group. For example, where a phenyl group is recited, substitution such as 2- or 4-aminophenyl, 2- or 4-(N,N-disubstituted)aminophenyl, 2,4-dihydroxyphenyl, 2,4,6-trithiophenyl, 2,4,6-trimethoxyphenyl and the like would be acceptable within the terminology, while substitution of 1,1,2,2,3,3-hexamethylphenyl would not be acceptable as that substitution would require the ring bond structure of the phenyl group to be altered to a non-aromatic form. Where the term moiety is used, such as alkyl moiety or phenyl moiety, that terminology indicates that the chemical material is not substituted. Where the term alkyl moiety is used, that term represents only an unsubstituted alkyl hydrocarbon group, whether branched, straight chain, or cyclic.
Organophotoreceptors
The organophotoreceptor may be, for example, in the form of a plate, a sheet, a flexible belt, a disk, a rigid drum, or a sheet around a rigid or compliant drum, with flexible belts and rigid drums generally being used in commercial embodiments. The organophotoreceptor may comprise, for example, an electrically conductive substrate and on the electrically conductive substrate a photoconductive element in the form of one or more layers. The photoconductive element can comprise both a charge transport material and a charge generating compound in a polymeric binder, which may or may not be in the same layer, as well as a second charge transport material such as a charge transport compound or an electron transport compound in some embodiments. For example, the charge transport material and the charge generating compound can be in a single layer. In other embodiments, however, the photoconductive element comprises a bilayer construction featuring a charge generating layer and a separate charge transport layer. The charge generating layer may be located intermediate between the electrically conductive substrate and the charge transport layer. Alternatively, the photoconductive element may have a structure in which the charge transport layer is intermediate between the electrically conductive substrate and the charge generating layer.
The electrically conductive substrate may be flexible, for example in the form of a flexible web or a belt, or inflexible, for example in the form of a drum. A drum can have a hollow cylindrical structure that provides for attachment of the drum to a drive that rotates the drum during the imaging process. Typically, a flexible electrically conductive substrate comprises an electrically insulating substrate and a thin layer of electrically conductive material onto which the photoconductive material is applied.
The electrically insulating substrate may be paper or a film forming polymer such as polyester (e.g., polyethylene terephthalate or polyethylene naphthalate), polyimide, polysulfone, polypropylene, nylon, polyester, polycarbonate, polyvinyl resin, polyvinyl fluoride, polystyrene and the like. Specific examples of polymers for supporting substrates included, for example, polyethersulfone (STABARTM S-100, available from ICI), polyvinyl fluoride (Tedlar®, available from E.I. DuPont de Nemours & Company), polybisphenol-A polycarbonate (MAKROFOLTM, available from Mobay Chemical Company) and amorphous polyethylene terephthalate (MELINARTM, available from ICI Americas, Inc.). The electrically conductive materials may be graphite, dispersed carbon black, iodine, conductive polymers such as polypyrroles and Calgon® conductive polymer 261 (commercially available from Calgon Corporation, Inc., Pittsburgh, Pa.), metals such as aluminum, titanium, chromium, brass, gold, copper, palladium, nickel, or stainless steel, or metal oxide such as tin oxide or indium oxide. In embodiments of particular interest, the electrically conductive material is aluminum. Generally, the photoconductor substrate has a thickness adequate to provide the required mechanical stability. For example, flexible web substrates generally have a thickness from about 0.01 to about 1 mm, while drum substrates generally have a thickness from about 0.5 mm to about 2 mm.
The charge generating compound is a material that is capable of absorbing light to generate charge carriers (such as a dye or pigment). Non-limiting examples of suitable charge generating compounds include, for example, metal-free phthalocyanines (e.g., ELA 8034 metal-free phthalocyanine available from H.W. Sands, Inc. or Sanyo Color Works, Ltd., CGM-X01), metal phthalocyanines such as titanium phthalocyanine, copper phthalocyanine, oxytitanium phthalocyanine (also referred to as titanyl oxyphthalocyanine, and including any crystalline phase or mixtures of crystalline phases that can act as a charge generating compound), hydroxygallium phthalocyanine, squarylium dyes and pigments, hydroxy-substituted squarylium pigments, perylimides, polynuclear quinones available from Allied Chemical Corporation under the trade name INDOFASTTM Double Scarlet, INDOFASTTM Violet Lake B, INDOFASTTM Brilliant Scarlet and INDOFASTTM Orange, quinacridones available from DuPont under the trade name MONASTRALTM Red, MONASTRALTM Violet and MONASTRALTM Red Y, naphthalene 1,4,5,8-tetracarboxylic acid derived pigments including the perinones, tetrabenzoporphyrins and tetranaphthaloporphyrins, indigo- and thioindigo dyes, benzothioxanthene-derivatives, perylene 3,4,9,10-tetracarboxylic acid derived pigments, polyazo-pigments including bisazo-, trisazo- and tetrakisazo-pigments, polymethine dyes, dyes containing quinazoline groups, tertiary amines, amorphous selenium, selenium alloys such as selenium-tellurium, selenium-tellurium-arsenic and selenium-arsenic, cadmium sulphoselenide, cadmium selenide, cadmium sulphide, and mixtures thereof. For some embodiments, the charge generating compound comprises oxytitanium phthalocyanine (e.g., any phase thereof), hydroxygallium phthalocyanine or a combination thereof.
The photoconductive layer of this invention may optionally contain a second charge transport material which may be a charge transport compound, an electron transport compound, or a combination of both. Generally, any charge transport compound or electron transport compound known in the art can be used as the second charge transport material.
An electron transport compound and a UV light stabilizer can have a synergistic relationship for providing desired electron flow within the photoconductor. The presence of the UV light stabilizers alters the electron transport properties of the electron transport compounds to improve the electron transporting properties of the composite. UV light stabilizers can be ultraviolet light absorbers or ultraviolet light inhibitors that trap free radicals.
UV light absorbers can absorb ultraviolet radiation and dissipate it as heat. UV light inhibitors are thought to trap free radicals generated by the ultraviolet light and after trapping of the free radicals, subsequently to regenerate active stabilizer moieties with energy dissipation. In view of the synergistic relationship of the UV stabilizers with electron transport compounds, the particular advantages of the UV stabilizers may not be their UV stabilizing abilities, although the UV stabilizing ability may be further advantageous in reducing degradation of the organophotoreceptor over time. The improved synergistic performance of organophotoreceptors with layers comprising both an electron transport compound and a UV stabilizer are described further in copending U.S. patent application Ser. No. 10/425,333 filed on Apr. 28, 2003 to Zhu, entitled “Organophotoreceptor With A Light Stabilizer,” incorporated herein by reference.
Non-limiting examples of suitable light stabilizer include, for example, hindered trialkylamines such as Tinuvin 144 and Tinuvin 292 (from Ciba Specialty Chemicals, Terrytown, N.Y.), hindered alkoxydialkylamines such as Tinuvin 123 (from Ciba Specialty Chemicals), benzotriazoles such as Tinuvan 328, Tinuvin 900 and Tinuvin 928 (from Ciba Specialty Chemicals), benzophenones such as Sanduvor 3041 (from Clariant Corp., Charlotte, N.C.), nickel compounds such as Arbestab (from Robinson Brothers Ltd, West Midlands, Great Britain), salicylates, cyanocinnamates, benzylidene malonates, benzoates, oxanilides such as Sanduvor VSU (from Clariant Corp., Charlotte, N.C.), triazines such as Cyagard UV-1164 (from Cytec Industries Inc., N.J.), polymeric sterically hindered amines such as Luchem (from Atochem North America, Buffalo, N.Y.). In some embodiments, the light stabilizer is selected from the group consisting of hindered trialkylamines having the following formula:




where R1, R2, R3, R4, R6, R7, R8, R10, R11, R12, R13, R14, R15 are, each independently, hydrogen, alkyl group, or ester, or ether group; and R5, R9, and R14 are, each independently, alkyl group; and X is a linking group selected from the group consisting of —O—CO—(CH2)m—CO—O— where m is between 2 to 20.

The binder generally is capable of dispersing or dissolving the charge transport material (in the case of the charge transport layer or a single layer construction), the charge generating compound (in the case of the charge generating layer or a single layer construction) and/or an electron transport compound for appropriate embodiments. Examples of suitable binders for both the charge generating layer and charge transport layer generally include, for example, poly(styrene-co-butadiene), poly(styrene-co-acrylonitrile), modified acrylic polymers, poly(vinyl acetate), styrene-alkyd resins, soya-alkyl resins, poly(vinyl chloride), poly(vinylidene chloride), polyacrylonitrile, polycarbonates, poly(acrylic acid), polyacrylates, polymethacrylates, styrene polymers, poly(vinyl butyral), alkyd resins, polyamides, polyurethanes, polyesters, polysulfones, polyethers, polyketones, phenoxy resins, epoxy resins, silicone resins, polysiloxanes, poly(hydroxyether) resins, poly(hydroxystyrene) resins, novolak, poly(phenylglycidyl ether-co-dicyclopentadiene), copolymers of monomers used in the above-mentioned polymers, and combinations thereof. Specific suitable binders include, for example, poly(vinyl butyral), polycarbonate, and polyester. Non-limiting examples of poly(vinyl butyral) include BX-1 and BX-5 from Sekisui Chemical Co. Ltd., Japan. Non-limiting examples of suitable polycarbonate include polycarbonate A which is derived from bisphenol-A (e.g. lupilon-A from Mitsubishi Engineering Plastics, or Lexan 145 from General Electric); polycarbonate Z which is derived from cyclohexylidene bisphenol (e.g. Iupilon-Z from Mitsubishi Engineering Plastics Corp, White Plain, N.Y.); and polycarbonate C which is derived from methylbisphenol A (from Mitsubishi Chemical Corporation). Non-limiting examples of suitable polyester binders include ortho-poly(ethylene terephthalate) (e.g. OPET TR-4 from Kanebo Ltd., Yamaguchi, Japan).
Suitable optional additives for any one or more of the layers include, for example, antioxidants, coupling agents, dispersing agents, curing agents, surfactants, and combinations thereof.
The photoconductive element overall typically has a thickness from about 10 microns to about 45 microns. In the dual layer embodiments having a separate charge generating layer and a separate charge transport layer, charge generation layer generally has a thickness from about 0.5 microns to about 2 microns, and the charge transport layer has a thickness from about 5 microns to about 35 microns. In embodiments in which the charge transport material and the charge generating compound are in the same layer, the layer with the charge generating compound and the charge transport composition generally has a thickness from about 7 microns to about 30 microns. In embodiments with a distinct electron transport layer, the electron transport layer has an average thickness from about 0.5 microns to about 10 microns and in further embodiments from about 1 micron to about 3 microns. In general, an electron transport overcoat layer can increase mechanical abrasion resistance, increases resistance to carrier liquid and atmospheric moisture, and decreases degradation of the photoreceptor by corona gases. A person of ordinary skill in the art will recognize that additional ranges of thickness within the explicit ranges above are contemplated and are within the present disclosure.
Generally, for the organophotoreceptors described herein, the charge generation compound is in an amount from about 0.5 to about 25 weight percent, in further embodiments in an amount from about 1 to about 15 weight percent, and in other embodiments in an amount from about 2 to about 10 weight percent, based on the weight of the photoconductive layer. The charge transport material is in an amount from about 10 to about 80 weight percent, based on the weight of the photoconductive layer, in further embodiments in an amount from about 35 to about 60 weight percent, and in other embodiments from about 45 to about 55 weight percent, based on the weight of the photoconductive layer. The optional second charge transport material, when present, can be in an amount of at least about 2 weight percent, in other embodiments from about 2.5 to about 25 weight percent, based on the weight of the photoconductive layer, and in further embodiments in an amount from about 4 to about 20 weight percent, based on the weight of the photoconductive layer. The binder is in an amount from about 15 to about 80 weight percent, based on the weight of the photoconductive layer, and in further embodiments in an amount from about 20 to about 75 weight percent, based on the weight of the photoconductive layer. A person of ordinary skill in the art will recognize that additional ranges within the explicit ranges of compositions are contemplated and are within the present disclosure.
For the dual layer embodiments with a separate charge generating layer and a charge transport layer, the charge generation layer generally comprises a binder in an amount from about 10 to about 90 weight percent, in further embodiments from about 15 to about 80 weight percent and in some embodiments in an amount from about 20 to about 75 weight percent, based on the weight of the charge generation layer. The optional charge transport material in the charge generating layer, if present, generally can be in an amount of at least about 2.5 weight percent, in further embodiments from about 4 to about 30 weight percent and in other embodiments in an amount from about 10 to about 25 weight percent, based on the weight of the charge generating layer. The charge transport layer generally comprises a binder in an amount from about 20 weight percent to about 70 weight percent and in further embodiments in an amount from about 30 weight percent to about 50 weight percent. A person of ordinary skill in the art will recognize that additional ranges of binder concentrations for the dual layer embodiments within the explicit ranges above are contemplated and are within the present disclosure.
For the embodiments with a single layer having a charge generating compound and a charge transport material, the photoconductive layer generally comprises a binder, a charge transport material, and a charge generation compound. The charge generation compound can be in an amount from about 0.05 to about 25 weight percent and in further embodiment in an amount from about 2 to about 15 weight percent, based on the weight of the photoconductive layer. The charge transport material can be in an amount from about 10 to about 80 weight percent, in other embodiments from about 25 to about 65 weight percent, in additional embodiments from about 30 to about 60 weight percent and in further embodiments in an amount from about 35 to about 55 weight percent, based on the weight of the photoconductive layer, with the remainder of the photoconductive layer comprising the binder, and optionally additives, such as any conventional additives. A single layer with a charge transport composition and a charge generating compound generally comprises a binder in an amount from about 10 weight percent to about 75 weight percent, in other embodiments from about 20 weight percent to about 60 weight percent, and in further embodiments from about 25 weight percent to about 50 weight percent. Optionally, the layer with the charge generating compound and the charge transport material may comprise a second charge transport material. The optional second charge transport material, if present, generally can be in an amount of at least about 2.5 weight percent, in further embodiments from about 4 to about 30 weight percent and in other embodiments in an amount from about 10 to about 25 weight percent, based on the weight of the photoconductive layer. A person of ordinary skill in the art will recognize that additional composition ranges within the explicit compositions ranges for the layers above are contemplated and are within the present disclosure.
In general, any layer with an electron transport layer can advantageously further include a UV light stabilizer. In particular, the electron transport layer generally can comprise an electron transport compound, a binder, and an optional UV light stabilizer. An overcoat layer comprising an electron transport compound is described further in copending U.S. patent application Ser. No. 10/396,536 to Zhu et al. entitled, “Organophotoreceptor With An Electron Transport Layer,” incorporated herein by reference. For example, an electron transport compound as described above may be used in the release layer of the photoconductors described herein. The electron transport compound in an electron transport layer can be in an amount from about 10 to about 50 weight percent, and in other embodiments in an amount from about 20 to about 40 weight percent, based on the weight of the electron transport layer. A person of ordinary skill in the art will recognize that additional ranges of compositions within the explicit ranges are contemplated and are within the present disclosure.
The UV light stabilizer, if present, in any one or more appropriate layers of the photoconductor generally is in an amount from about 0.5 to about 25 weight percent and in some embodiments in an amount from about 1 to about 10 weight percent, based on the weight of the particular layer. A person of ordinary skill in the art will recognize that additional ranges of compositions within the explicit ranges are contemplated and are within the present disclosure.
For example, the photoconductive layer may be formed by dispersing or dissolving the components, such as one or more of a charge generating compound, the charge transport material of this invention, a second charge transport material such as a charge transport compound or an electron transport compound, a UV light stabilizer, and a polymeric binder in organic solvent, coating the dispersion and/or solution on the respective underlying layer and drying the coating. In particular, the components can be dispersed by high shear homogenization, ball-milling, attritor milling, high energy bead (sand) milling or other size reduction processes or mixing means known in the art for effecting particle size reduction in forming a dispersion.
The photoreceptor may optionally have one or more additional layers as well. An additional layer can be, for example, a sub-layer or an overcoat layer, such as a barrier layer, a release layer, a protective layer, or an adhesive layer. A release layer or a protective layer may form the uppermost layer of the photoconductor element. A barrier layer may be sandwiched between the release layer and the photoconductive element or used to overcoat the photoconductive element. The barrier layer provides protection from abrasion to the underlayers. An adhesive layer locates and improves the adhesion between a photoconductive element, a barrier layer and a release layer, or any combination thereof. A sub-layer is a charge blocking layer and locates between the electrically conductive substrate and the photoconductive element. The sub-layer may also improve the adhesion between the electrically conductive substrate and the photoconductive element.
Suitable barrier layers include, for example, coatings such as crosslinkable siloxanol-colloidal silica coating and hydroxylated silsesquioxane-colloidal silica coating, and organic binders such as poly(vinyl alcohol), methyl vinyl ether/maleic anhydride copolymer, casein, poly(vinyl pyrrolidone), poly(acrylic acid), gelatin, starch, polyurethanes, polyimides, polyesters, polyamides, poly(vinyl acetate), poly(vinyl chloride), poly(vinylidene chloride), polycarbonates, poly(vinyl butyral), poly(vinyl acetoacetal), poly(vinyl formal), polyacrylonitrile, poly(methyl methacrylate), polyacrylates, poly(vinyl carbazoles), copolymers of monomers used in the above-mentioned polymers, vinyl chloride/vinyl acetate/vinyl alcohol terpolymers, vinyl chloride/vinyl acetate/maleic acid terpolymers, ethylene/vinyl acetate copolymers, vinyl chloride/vinylidene chloride copolymers, cellulose polymers, and mixtures thereof. The above barrier layer polymers optionally may contain small inorganic particles such as fumed silica, silica, titania, alumina, zirconia, or a combination thereof. Barrier layers are described further in U.S. Pat. No. 6,001,522 to Woo et al., entitled “Barrier Layer For Photoconductor Elements Comprising An Organic Polymer And Silica,” incorporated herein by reference. The release layer topcoat may comprise any release layer composition known in the art. In some embodiments, the release layer is a fluorinated polymer, siloxane polymer, fluorosilicone polymer, silane, polyethylene, polypropylene, polyacrylate, or a combination thereof. The release layers can comprise crosslinked polymers.
The release layer may comprise, for example, any release layer composition known in the art. In some embodiments, the release layer comprises a fluorinated polymer, siloxane polymer, fluorosilicone polymer, polysilane, polyethylene, polypropylene, polyacrylate, poly(methyl methacrylate-co-methacrylic acid), urethane resins, urethane-epoxy resins, acrylated-urethane resins, urethane-acrylic resins, or a combination thereof. In further embodiments, the release layers comprise crosslinked polymers.
The protective layer can protect the organophotoreceptor from chemical and mechanical degradation. The protective layer may comprise any protective layer composition known in the art. In some embodiments, the protective layer is a fluorinated polymer, siloxane polymer, fluorosilicone polymer, polysilane, polyethylene, polypropylene, polyacrylate, poly(methyl methacrylate-co-methacrylic acid), urethane resins, urethane-epoxy resins, acrylated-urethane resins, urethane-acrylic resins, or a combination thereof. In some embodiments of particular interest, the protective layers are crosslinked polymers.
An overcoat layer may comprise an electron transport compound as described further in copending U.S. patent application Ser. No. 10/396,536, filed on Mar. 25, 2003 to Zhu et al. entitled, “Organoreceptor With An Electron Transport Layer,” incorporated herein by reference. For example, an electron transport compound, as described above, may be used in the release layer of this invention. The electron transport compound in the overcoat layer can be in an amount from about 2 to about 50 weight percent, and in other embodiments in an amount from about 10 to about 40 weight percent, based on the weight of the release layer. A person of ordinary skill in the art will recognize that additional ranges of composition within the explicit ranges are contemplated and are within the present disclosure.
Generally, adhesive layers comprise a film forming polymer, such as polyester, poly(vinyl butyral), poly(vinyl pyrrolidone), polyurethane, poly(methyl methacrylate), poly(hydroxy amino ether) and the like. Barrier and adhesive layers are described further in U.S. Pat. No. 6,180,305 to Ackley et al., entitled “Organic Photoreceptors for Liquid Electrophotography,” incorporated herein by reference.
Sub-layers can comprise, for example, poly(vinyl butyral), organosilanes, hydrolyzable silanes, epoxy resins, polyesters, polyamides, polyurethanes, cellulosics, and the like. In some embodiments, the sub-layer has a dry thickness between about 20 Angstroms and about 20,000 Angstroms. Sublayers containing metal oxide conductive particles can be between about 1 and about 25 microns thick. A person of ordinary skill in the art will recognize that additional ranges of compositions and thickness within the explicit ranges are contemplated and are within the present disclosure.
The charge transport materials as described herein, and photoreceptors including these compounds, are suitable for use in an imaging process with either dry or liquid toner development. For example, any dry toners and liquid toners known in the art may be used in the process and the apparatus of this invention. Liquid toner development can be desirable because it offers the advantages of providing higher resolution images and requiring lower energy for image fixing compared to dry toners. Examples of suitable liquid toners are known in the art. Liquid toners generally comprise toner particles dispersed in a carrier liquid. The toner particles can comprise a colorant/pigment, a resin binder, and/or a charge director. In some embodiments of liquid toner, a resin to pigment ratio can be from 1:1 to 10:1, and in other embodiments, from 4:1 to 8:1. Liquid toners are described further in Published U.S. Patent Applications 2002/0128349, entitled “Liquid Inks Comprising A Stable Organosol,” and 2002/0086916, entitled “Liquid Inks Comprising Treated Colorant Particles,” and U.S. Pat. No. 6,649,316, entitled “Phase Change Developer For Liquid Electrophotography,” all three of which are incorporated herein by reference.
Charge Transport Material
As described herein, an organophotoreceptor comprises a charge transport material having the formula




where Y comprises an aromatic group, such as an aryl group, an aromatic heterocyclic group, and combinations thereof;
V1 and V2 comprise, each independently, a vinyl containing group, such as an alkyl vinyl ether group and a CH2═CH—O—X— group where X comprises a bond or a —(CH2)m-group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, an aromatic group, an NRa group, a CRb group, a CRcRd group, a SiReRf group, a BRg group, or a P(═O)Rh group, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are, each independently, a bond, H, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a halogen, an acyl group, an alkoxy group, an alkylsulfanyl group, an alkenyl group, such as a vinyl group, an allyl group, and a 2-phenylethenyl group, an alkynyl group, a heterocyclic group, an aromatic group, a part of a ring group, such as cycloalkyl groups, heterocyclic groups, and a benzo group, or an alkyl group where one or more of the hydrogens of the alkyl group is optionally replaced by an aromatic group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, or a halogen; and
R1, R2, R3, and R4 comprise, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group such as cycloalkyl groups, heterocyclic groups, and a benzo group.
In some embodiments, the V1 and V2 of the charge transport material of Formula (I) comprise, each independently, a CH2═CH—O—X— group where the X group is an ethylene group. In other embodiments, the Y group of the charge transport material of Formula (I) comprises a phenothiazine group, a phenoxazine group, a phenoxathiin group, a dibenzo(1,4)dioxin group, a thianthrene group, a phenazine group, an (N,N-disubstituted)arylamine group, a carbazolyl group, a bicarbazolyl group, an indolyl group, a pyrrolyl group, a furanyl group, a thiophenyl group, an alkylenedioxythiophene group, or a combination thereof. In further embodiments, the Y group is selected from the following formulae:







where R5, R6, and R7 are, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, or an aromatic group; Ar comprises a conjugation group, an aromatic group, or a combination thereof; n and p are, each independently, an integer between 1 and 20 and one or more of the methylene groups in the (CH2)n or (CH2)p groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, or an aromatic group. Non-limiting examples of suitable conjugation group include an alkenyl group, an alkynyl group, and combinations thereof. Non-limiting examples of suitable aromatic group include an aryl group, an aromatic heterocyclic group, and combinations thereof.

Substitution is liberally allowed on the Y, V1, V2, X, R1, R2, R3, R4 groups and the formulae in the previous paragraph above to affect various physical effects on the properties of the compounds, such as mobility, sensitivity, solubility, stability, and the like, as is known generally in the art. Non-limiting examples of suitable substituent include an alkyl group, an acyl group, an ester group, an ether group, a hydrazone group, an azine group, an enamine group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, and a combination thereof, such as a CH2═CH—O—CH2—CH2— group and a CH2═CH—O—C(═O)—CH2— group.
Specific, non-limiting examples of suitable charge transport materials within Formula (I) of the present invention have the following structures:










Synthesis Of Charge Transport Materials

The charge transport materials of this invention may be prepared by one of the following multi-step synthetic procedures, although other suitable procedures can be used by a person of ordinary skill in the art based on the disclosure herein.
General Synthetic Procedures for Charge Transport Materials of Formula (I)




The charge transport material of Formula (I) may be prepared by reacting corresponding dihydrazone of Formula (II) with V1-L1 and V2-L2, either simultaneously or sequentially. Furthermore, the Y group may comprise at least a reactive N—H or OH group which may react with V3-L3 to form N—V3 or O—V3 group respectively so that charge transport materials of Formula (I) comprising three or more vinyl containing groups may be obtained. sThe L1, L2, and L3 comprise, each independently, a leaving group, such as mesylate, tosylate, iodide, bromide, and chloride; and V1, V2, and V3 comprise, each independently, a vinyl containing group, such as an alkyl vinyl ether group and a CH2═CH—O—X— group where X comprises a bond or a —(CH2)m-group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, an aromatic group, an NRa group, a CRb group, a CRcRd group, a SiReRf group, a BRg group, or a P(═O)Rh group, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are, each independently, a bond, H, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a halogen, an acyl group, an alkoxy group, an alkylsulfanyl group, an alkenyl group, such as a vinyl group, an allyl group, and a 2-phenylethenyl group, an alkynyl group, a heterocyclic group, an aromatic group, a part of a ring group, such as cycloalkyl groups, heterocyclic groups, and a benzo group, or an alkyl group where one or more of the hydrogens of the alkyl group is optionally replaced by an aromatic group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, or a halogen. In some embodiments, the X group of the CH2═CH—O—X— group comprises an alkylene group, such as methylene and ethylene.
Non-limiting examples of V1-L1 and V2-L2 include 2-chloroethyl vinyl ether, 6-(vinyloxy)-1-hexyl mesylate, 4-(vinyloxy)-1-butyl mesylate, 2-(vinyloxy)ethyl mesylate, 6-(vinyloxy)-1-hexyl tosylate, 4-(vinyloxy)-1-butyl tosylate, and 2-(vinyloxy)ethyl tosylate. The mesylates and tosylates can be prepared by the reaction between 6-(vinyloxy)-1-hexanol, 1,4-butanediol vinyl ether, and 2-(vinyloxy)ethanol with mesyl chloride and tosyl chloride respectively. Other vinyl compounds, such as vinyl chloroformate, isopropenyl chloroformate, and vinyl chloroacetate, may be used to prepare charge transport materials of Formula (I) where one of the methylene groups in the CH2═CH—O—X— group is replaced with a C═O group. The above-mentioned chemicals may be obtained commercially from a supplier such as Aldrich, Milwaukee, Wis.
V1 may be the same as or different than V4, and L1 may be the same as or different than L2. When V1 is the same as V4 and L1 is the same as L2, the dihydrazone of Formula (II) may react with V1-L1 and V2-L2 in one step. When V1 is different than V4 or L1 is different than L2, the dihydrazone of Formula (II) may react with V1-L1 and V2-L2 sequentially.
The reaction may take place in a solvent, such as ethyl methyl ketone and tetrahydrofuran. The reaction may be catalyzed by a base, such as potassium hydroxide, potassium carbonate, and a combination thereof. The reaction mixture may be heated at an elevated temperature for a period of time, such as 2 to 48 hours. When the reaction is completed, the charge transport material of Formula (I) may be isolated and purified by conventional purification techniques, such as chromatography and recrystallization.
The dihydrazone of Formula (II) may be prepared by reacting the corresponding diacyl aromatic compound of Formula (III) with (N-substituted)hydrazines, R1NHNH2 and R4NHNH2, either simultaneously or sequentially. R1 and R4 comprise, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group such as cycloalkyl groups, heterocyclic groups, and a benzo group. R1 may be the same as or different than R4. When R1 is the same as R4, the diacyl aromatic compound of Formula (III) may react with the (N-substituted)hydrazines in one step. When R1 is different than R4, the diacyl aromatic compound of Formula (III) may react with the (N-substituted)hydrazines sequentially.
The hydrazone formation reaction may take place in a solvent, such as tetrahydrofuran and methanol. The hydrazone formation reaction may be catalyzed by an appropriate amount of concentrated acid, such as sulfuric acid and hydrochloric acid. The reaction mixture may be heated at an elevated temperature for a period of time, such as 2 to 14 hours. The dihydrazone of Formula (II) may be isolated and purified by conventional purification techniques, such as chromatography and recrystallization.
The diacyl aromatic compound of Formula (III) may be prepared by reacting the corresponding aromatic compound (H—Y—H) with acylating agents 1 and 2 to replace the two hydrogens in H—Y—H with two acyl groups (R2CO and R3CO), either simultaneously or sequentially. R2 may be the same as or different than R3. When R2 is the same as R3, the aromatic compound may react with the acylating agents in one step. When R2 is different than R3, the aromatic compound may react with the acylating agents sequentially.
The acylation of the aromatic compound (H—Y—H) may be done under Vilsmeier-Haack condition with a mixture of phosphorus oxychloride (POCl3) and an N,N-dialkylamide, such as N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylbenzamide. The C-acylations of thiophenes, furans, and pyrroles under Vilsmeier-Haack condition are described in Alan Katritzky, “Handbook of heterocyclic chemistry,” Pergamon Press, New York, p. 254-255 (1985), which is incorporated herein by reference. Furthermore, the Vilsmeier-Haack acylation and related reactions are described in Carey et al., “Advanced Organic Chemistry, Part B: Reactions and Synthesis,” New York, 1983, pp. 380-393, which is incorporated herein by reference. Alternatively, the acylation of the aromatic compound (H—Y—H) may be acylated by a mixture of a strong base, such as butyl lithium, and an N,N-dialkylamide, or by a mixture of Lewis acid, such as stannic chloride, and an acid anhydride, such as acetic anhydride at an elevated temperature
Specifically, the diformylation of the aromatic compound (H—Y—H) may be prepared according to the following procedure. Phosphorus oxychloride (POCl3) is added dropwise to dry dimethylformamide (DMF) in a round-bottomed flask at 0° C. under a nitrogen atmosphere to form a reaction mixture. After the reaction mixture is warmed up slowly to room temperature, a solution of a selected aromatic compound in dry DMF is added dropwise to the reaction mixture. The reaction mixture is heated at 80° C. for 24 hours and then poured into ice water. The reaction mixture is neutralized with 10% potassium hydroxide solution until the pH value reaches 6-8. The product can be extracted with a solvent such as chloroform. The product is a diformyl derivative of the aromatic compound, which may be isolated and purified by conventional purification techniques such as chromatography and recrystallization. Other diacyl aromatic compounds may be prepared accordingly by replacing the dimethylformamide with other amides.
The invention will now be described further by way of the following examples.
EXAMPLES
Example 1
Synthesis of Charge Transport Materials
This example describes the synthesis and characterization of Compounds (1)-(15) in which the numbers refer to formula numbers above. The characterization involves chemical characterization of the compositions. The electrostatic characterization, such as mobility and ionization potential, of the materials formed with the compositions is presented in a subsequent example.
Compound (1)
The preparation of bis(N-phenyl)hydrazone of 4-(4-formyldiphenylamino)benzaldehyde is disclosed in U.S. patent application Ser. No. 10/634,164, which is incorporated herein by reference.
4-(4-Formyldiphenylamino)benzaldehyde. Dimethylformamide (DMF, 271 ml, 3.5 mol, obtained from Aldrich, Milwaukee, Wis.) was added to a 1-liter 3-neck round-bottomed flask equipped with a mechanical stirrer, a thermometer, and a dropping funnel. The DMF in the flask was cooled on an ice bath with salt. When the temperature inside the flask reached 0° C., phosphorous oxychloride (POCl3, 326 ml, 3.5 mol, obtained from Aldrich, Milwaukee, Wis.) was added slowly to the flask through a dropping funnel. During the addition of POCl3, the temperature inside the flask was not allowed to rise above 5° C. After the addition of POCl3 was completed, the reaction mixture was allowed to warm to room temperature. Triphenylamine (127 g, 0.5 mole, obtained from Aldrich, Milwaukee, Wis.) was added, and then the flask was heated to 90° C. for 24 hours using a heating mantle. After the reaction mixture was cooled to room temperature, it was added slowly to a 4.5 liter beaker containing a solution of 820 g of sodium acetate dissolved in 2 liters of water. The beaker was stirred and cooled on an ice bath for 3 hours. The resulting brownish solid was filtered and washed repeatedly with water and finally with a small amount of ethanol (50 ml). The resulting product, 4-(4-formyldiphenylamino)benzaldehyde, was recrystallized once from a mixture of toluene and isopropanol using activated charcoal and dried under vacuum in an oven heated at 50° C. for 6 hours. The yield was 86 g (55%).
Bis(N-phenyl)hydrazone of 4-(4-formyldiphenylamino)benzaldehyde. 4-(4-Formyldiphenylamino)benzaldehyde (60 g, 0.2 mol, prepared in previous step) and 250 ml of tetrahydrofuran were added to a 500 ml 2-neck round-bottomed flask equipped with a reflux condenser and a mechanical stirrer. The mixture was heated until the solids were dissolved. Next, a solution of 47 ml of N-phenylhydrazine (0.5 mol, obtained from Aldrich, Milwaukee, Wis.) in 50 ml of tetrahydrofuran was added slowly using a dropping funnel. The flask was refluxed until 4-(4-formyldiphenylamino) benzaldehyde disappeared ( ̃10 min). At the end of the reaction, the mixture was cooled slowly to room temperature, and the solid was filtered off, washed with isopropanol, and dried at 300° C. under vacuum for 6 hours. The product was bis(N-phenyl)hydrazone of 4-(4-formyldiphenylamino)benzaldehyde. The yield was 80 g (84%).
N-Alkylation Step: To a mixture of bis(N-phenyl)hydrazone of 4-(4-formyldiphenylamino) benzaldehyde (3.0 g, 0.0062 mol) and 35 ml of ethyl methyl ketone in a 100 ml round-bottomed flask was added 2-chloroethyl vinyl ether (2.54 ml, 0.025 mol). A mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) was added into the heterogeneous reaction mixture. Another mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) was added after 12 hours. After refluxed for 18 hours, the reaction mixture was cooled to room temperature and the inorganic components were filtered off. The solvent was removed from the filtrate by rotary evaporation. The product was purified by column chromatography using an eluent mixture of hexane and acetone in a volume ratio of 7:1. The eluent was removed by rotary evaporation. The product was precipitated by fractional solvent evaporation from methanol, filtered and dried. The yield was 18.1% (0.7 g of yellow grains). The infrared absorption spectrum of the product was characterized by the following absorption wavelengths (KBr windows, in cm−1): ν(C—H) 2931, 2880; ν(arene C—H) 3060, 3036; ν(C═C, in Ar) 1618, 1593, 1494; ν(C—N) 1316, 1282; γ(Ar) 748, 693. The mass spectrum of the product was characterized by the following ions (in m/z): 622.18 (90%, M+1), 180.24, 120.00, and 112.96. The 1H-NMR spectrum (100 MHz) of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 3.68 (t, J=6.2, 4H, —CH2-), 4.19-4.37 (m, 8H, —CH2-, CH2=), 6.51 (q, 2H, O—CH═), 6.97 (s, 2H, CH═N), 7.1-7.62 (m, 23H, Ar).
Compound (2)
The preparation of bis(N-phenyl)hydrazone of N-ethyl-3,6-diformylcarbazole is disclosed in U.S. patent application Ser. No. 10/634,164, which is incorporated herein by reference.
N-Ethyl-3,6-diformylcarbazole. Dimethylformamide (DMF, 271 ml, 3.5 mol, obtained from Aldrich, Milwaukee, Wis.) was added to a 1-liter 3-neck round-bottomed flask equipped with a mechanical stirrer, a thermometer, and a dropping funnel. The contents were cooled in a salt/ice bath. When the temperature inside the flask reached 0° C., 326 ml of POCl3 (3.5 mol) was slowly added. During the addition of POCl3, the temperature inside the flask was not allowed to rise above 5° C. After the addition of POCl3 was completed, the reaction mixture was allowed to warm to room temperature. After the flask warmed to room temperature, N-ethylcarbazole (93 g, obtained from Aldrich) in 70 ml of DMF was added, and then the flask was heated to 90° C. for 24 hours using a heating mantle. Next, the reaction mixture was cooled to room temperature and the reaction mixture was added slowly to a cooled 4.5 liter beaker containing a solution comprising 820 g of sodium acetate dissolved in 2 liters of water. The beaker was cooled in an ice bath and stirred for 3 hours. The brownish solid obtained was filtered and washed repeatedly with water, followed by a small amount of ethanol (50 ml). After washing, the resulting product was recrystallized once from toluene using activated charcoal and dried under vacuum in an oven heated at 70° C. for 6 hours to obtain 55 g (46% yield) of N-ethyl-3,6-diformylcarbazole. The 1H-NMR spectrum (250 MHz) of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 10.12 (s, 2H); 8.63 (s, 2H); 8.07 (d, 2H); 7.53 (d, 2H); 4.45 (m, 2H); 1.53 (t, 3H).
Bis(N-phenylhydrazone) of N-ethyl-3,6-diformylcarbazole. Phenylhydrazine (0.2 mole, obtained from Aldrich, Milwaukee, Wis.) and N-ethyl-3,6-diformylcarbazole (0.1 mole) were dissolved in 100 ml of a 1:1 v/v mixture of toluene and THF in 250 ml 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The solution was refluxed for 2 hours. Thin layer chromatography indicated the disappearance of the starting materials. At the end of the reaction, the mixture was cooled to room temperature. The bis(N-phenylhydrazone) of N-ethyl-3,6-diformylcarbazole crystals formed upon standing were filtered off, washed with isopropanol and dried in a vacuum oven at 50° C. for 6 hours.
Compound (2) may be prepared from bis(N-phenylhydrazone) of N-ethyl-3,6-diformylcarbazole by the following procedure. To a mixture of bis(N-phenyl)hydrazone of N-ethyl-3,6-diformylcarbazole (0.0062 mol) and 35 ml of ethyl methyl ketone in a 100 ml round-bottomed flask is added 2-chloroethyl vinyl ether (2.54 ml, 0.025 mol). A mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) is added into the heterogeneous reaction mixture. Another mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) is added after 12 hours. After refluxing for 18 hours, the reaction mixture is cooled to room temperature and the inorganic components are filtered off. The solvent is removed from the filtrate by rotary evaporation. The product may be purified by column chromatography or other conventional purification techniques.
Compound (3)
N-Phenylcarbazole. N-phenylcarbazole may be prepared by the following procedure. A mixture of 9H-carbazole (5.51 g, 33 mmol, available from Aldrich, Milwaukee, Wis.), iodobenzene (10 g, 43 mmol, available from Aldrich), powdered potassium carbonate (36.43 g, 264 mmol), copper powder (8.38 g, 132 mmol) and 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane, 0.56 g, 2.1 mmol, available from Aldrich) is refluxed in o-dichlorobenzene (30 ml, available from Aldrich) under nitrogen for 24 hours. The copper and inorganic salts are filtered. The solvent is removed by distillation. The product, N-phenylcarbazole, may be isolated and purified by conventional purification techniques such as chromatography or recrystallization.
Compound (3) may be prepared similarly by the procedure for Compound (2) except that N-ethylcarbazole is replaced with N-phenylcarbazole.
Compound (4)
Compound (3) may be prepared similarly by the procedure for Compound (2) except that N-ethylcarbazole is replaced with 10-ethyl-10H-phenoxazine (available form Aldrich, Milwaukee, Wis.).
Compound (5)
Bis(N-phenylhydrazone) of 2,5-diacetylfuran. Bis(N-phenylhydrazone) of 2,5-diacetylfuran may be prepared similarly by the procedure for bis(N-phenylhydrazone) of N-ethyl-3,6-diformylcarbazole except that N-ethyl-3,6-diformylcarbazole is replaced with 2,5-diacetylfuran (available form Aldrich, Milwaukee, Wis.).
Compound (5) may be prepared from bis(N-phenylhydrazone) of 2,5-diacetylfuran by the following procedure. To a mixture of bis(N-phenyl)hydrazone of 2,5-diacetylfuran (0.0062 mol) and 35 ml of ethyl methyl ketone in a 100 ml round-bottomed flask is added 2-chloroethyl vinyl ether (2.54 ml, 0.025 mol). A mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) is added into the heterogeneous reaction mixture. Another mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) is added after 12 hours. After refluxing for 18 hours, the reaction mixture is cooled to room temperature and the inorganic components are filtered off. The solvent is removed from the filtrate by rotary evaporation. The product may be purified by column chromatography or other conventional purification techniques.
Compound (6)
Compound (6) may be prepared similarly by the procedure for Compound (5) except that 2,5-diacetylfuran is replaced with 3,4-dimethyl-1H-pyrrole-2,5-dicarbaldehyde (available form Aldrich, Milwaukee, Wis.).
Compound (7)
Compound (7) may be prepared similarly by the procedure for Compound (5) except that 2,5-diacetylfuran is replaced with 2,5-thiophenedicarbaldehyde (available form Aldrich, Milwaukee, Wis.).
Compound (8)
Compound (8) may be prepared similarly by the procedure for Compound (5) except that 2,5-diacetylfuran is replaced with 4-acetylbenzaldehyde (available form Aldrich, Milwaukee, Wis.).
Compound (9)
Compound (9) may be prepared similarly by the procedure for Compound (5) except that 2,5-diacetylfuran is replaced with 5,10-diacetyl-5,10-dihydrophenazine (available form Aldrich, Milwaukee, Wis.).
Compound (10)
Compound (10) may be prepared similarly by the procedure for Compound (5) except that 2,5-diacetylfuran is replaced with 3,6-diacetyl-9-ethylcarbazole (available form Aldrich, Milwaukee, Wis.).
Compound (11)
The preparation of 10-[6-(3-formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazine carbaldehyde is disclosed in U.S. patent application Ser. No. 10/789,094, which is incorporated herein by reference.
1,6-Di(10H-10-phenothiazinyl)hexane. A mixture of phenothiazine (0.15 mol), 0.1 mol of 1,6-dibromohexane, 0.15 mol of potassium hydroxide and 1% w/w of tetra-n-butyl ammonium hydrogen sulfate in 300 ml of dry toluene was stirred and refluxed for 48 hours. The reaction mixture was cooled to room temperature, filtered, and washed thoroughly with water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by evaporation. The crude product was purified by column chromatography using a mixture of ethyl acetate and hexane in a volume ratio of 1:6 as eluent. The yield of 1,6-di(10H-10-phenothiazinyl)hexane was 85%. The 1H-NMR spectrum of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 1.35-1.50(m, 4H), 1.55-1.90(m, 4H), 3.82(t, 4H), and 6.73-7.19(m, 16H).
10-[6-(3-Formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazine carbaldehyde. Phosphorus oxychloride was added dropwise to dry dimethylformamide (1:1.2 molar ratio) at 0° C. under nitrogen. A solution of 1,6-di(10H-10-phenothiazinyl)hexane (obtained in the previous step) in dry DMF was added stepwise to the reaction flask. The reaction mixture was stirred at 70° C. until the starting compound reacted completely as indicated by TLC. The reaction mixture was cooled to room temperature, poured into ice water, and neutralized with a dilute KOH solution until the pH reached 7-8. The aqueous solution was extracted several times with chloroform. The combined chloroform solutions were washed with water, dried with anhydrous sodium sulfate, and filtered. The solvent was removed by distillation. The crude product was purified by column chromatography using a mixture of ethyl acetate and hexane in a volume ratio of 1:8 as the eluent. The yield of 10-[6-(3-formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazine carbaldehyde was 56%. The 1H-NMR spectrum of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 1.35-1.50 (m, 4H), 1.55-1.90 (m, 4H), 3.82 (t, 4H), 6.73-7.19 (m, 14H), and 9.80 (s, 2H).
Compound (11) may be prepared by the following procedure. A solution of N-phenylhydrazine (4 moles) in a solvent, such as tetrahydrofuran and methanol, is added dropwise to a solution of 10-[6-(3-formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazinecarbaldehyde (1 mole, obtained in the previous step) in the solvent with stirring. The reaction mixture is refluxed until 10-[6-(3-formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazinecarbaldehyde disappears as indicated by thin layer chromatography. The reaction mixture is cooled to room temperature. The precipitated product, 10-[6-(3-formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazinecarbaldehyde bis(N-phenylhydrazone), may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography. The 10-[6-(3-formyl-10H-10-phenothiazinyl)hexyl]-10H-3-phenothiazinecarbaldehyde bis(N-phenylhydrazone) is alkylated with 2-chloroethyl vinyl ether by an alkylation procedure similar to the N-alkylation step for Compound (2). The product is Compound (11) which may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography.
Compound (12)
1,10-Bis(3-formyl-9-carbazolyl)decane may be prepared according to the procedure described in U.S. Pat. No. 6,066,426, column 22, lines 19-44. U.S. Pat. No. 6,066,426 is incorporated herein by reference.
Compound (12) may be prepared by the following procedure. A solution of N-phenylhydrazine (4 moles) in a solvent, such as tetrahydrofuran and methanol, is added dropwise to a solution of 1,10-bis(3-formyl-9-carbazolyl)decane (1 mole) in the solvent with stirring. The reaction mixture is refluxed until 1,10-bis(3-formyl-9-carbazolyl)decane disappears as indicated by thin layer chromatography. The reaction mixture is cooled to room temperature. The precipitated product, 1,10-bis(3-formyl-9-carbazolyl)decane bis(N-phenylhydrazone), may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography. The 1,10-bis(3-formyl-9-carbazolyl)decane bis(N-phenylhydrazone) is alkylated with 2-chloroethyl vinyl ether by an alkylation procedure similar to the N-alkylation step for Compound (2). The product is Compound (12) which may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography.
Compound (13)
2,2′-(3,4-Ethylenedioxy)dithienyl-ω,ω′-1,4-divinylbenzene. 2,2′-(3,4-Ethylenedioxy)dithienyl-ω, ω′-1,4-divinylbenzene may be prepared according to the procedure described in Mohanakrishnan et al., “Functionalization of 3,4-ethylenedioxythiophene,” Tetrahedron, 55, 11745-11754 (1999), which is incorporated herein by reference.
2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene. 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene may be prepared by the following procedure. A mixture of dimethylformamide and 2,2′-(3,4-ethylenedioxy)dithienyl-ω,ω′-1,4-divinylbenzene is added to a 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The reaction mixture is cooled in an ice bath. When the temperature of the solution inside the flask is 0° C., excess phosphorous oxychloride is added dropwise using a dropping funnel. The temperature inside the flask is not allowed to rise above 5° C. during the addition of phosphorous oxychloride. After the addition of phosphorous oxychloride is completed, the flask is heated at 90° C. for 24 hours. The reaction mixture is cooled to room temperature and then poured into ice water to precipitate the product, 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene. The product may be purified by conventional recrystallization and/or chromatography methods.
Compound (13) may be prepared by the following procedure. A solution of N-phenylhydrazine (4 moles) in a solvent, such as tetrahydrofuran and methanol, is added dropwise to a solution of 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene (1 mole) in the solvent with stirring. The reaction mixture is refluxed until 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene disappears as indicated by thin layer chromatography. The reaction mixture is cooled to room temperature. The precipitated product, 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene bis(N-phenylhydrazone) may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography. The 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylbenzene bis(N-phenylhydrazone) is alkylated with 2-chloroethyl vinyl ether by an alkylation procedure similar to the N-alkylation step for Compound (2). The product is Compound (13) which may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography.
Compound (14)
2,2′-(3,4-Ethylenedioxy)dithienyl-ω,ω′-1,4-divinylthiophene. 2,2′-(3,4-Ethylenedioxy)dithienyl-ω,ω′-1,4-divinylthiophene may be prepared according to the procedure described in A. K. Mohanakrishnan et al “Fictionalization of 3,4-ethylenedioxythiophene”, Tetrahedron, 55, 11745-11754 (1999), which is incorporated herein by reference.
2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophen. 2,2′-(3,4-Ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophene may be prepared by the following procedure. A mixture of dimethylformamide and 2,2′-(3,4-ethylenedioxy)dithienyl-ω,ω′-1,4-divinylthiophene is added to a 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The reaction mixture is cooled in an ice bath. When the temperature inside the flask is 0° C., excess phosphorous oxychloride is added dropwise using a dropping funnel. The temperature inside the flask is not allowed to rise above 5° C. during the addition of phosphorous oxychloride. After the addition of phosphorous oxychloride is completed, the flask is heated at 90° C. for 24 hours. The reaction mixture is cooled to room temperature and then poured into ice water to precipitate the product, 2,2′-(3,4-ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophene. The product may be purified by conventional recrystallization and/or chromatography methods.
Compound (14) may be prepared by the following procedure. A solution of N-phenylhydrazine (4 moles) in a solvent, such as tetrahydrofuran and methanol, is added dropwise to a solution of 2,2′-(3,4-ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophene (1 mole) in the solvent with stirring. The reaction mixture is refluxed until 2,2′-(3,4-ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophene disappears as indicated by thin layer chromatography. The reaction mixture is cooled to room temperature. The precipitated product, 2,2′-(3,4-ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophene bis(N-phenylhydrazone), may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography. The 2,2′-(3,4-ethylenedioxy-5-formyl)dithienyl-ω,ω′-1,4-divinylthiophene bis(N-phenylhydrazone) is alkylated with 2-chloroethyl vinyl ether by an alkylation procedure similar to the N-alkylation step for Compound (2). The product is Compound (13) which may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography
Compound (15)
Compound (15) may be prepared by the following procedure. To a mixture of bis(N-phenyl)hydrazone of 4-(4-formyldiphenylamino)benzaldehyde (3 g, 0.0062 mol, prepared previously for Compound (1)), vinyl chloroacetate (0.002 mole, available form Aldrich), and 40 ml of a solvent, such as ethyl methyl ketone and tetrahydrofuran, in a 100 ml round-bottomed flask is added a mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol). Another mixture of potassium hydroxide (1.39 g, 0.025 mol) and potassium carbonate (1.72 g, 0.0125 mol) is added after 12 hours. After refluxing for 18 hours, the reaction mixture is cooled to room temperature and the inorganic components are filtered off. The product may be isolated and purified by conventional purification techniques such as recrystallization and column chromatography.
Example 2
Charge Mobility Measurements
This example describes the measurement of charge mobility and ionization potential for charge transport materials, specifically Compound (1).
Sample 1
A mixture of 0.1 g of Compound (1) and 0.1 g of polycarbonate Z was dissolved in 2 ml of tetrahydrofuran (THF). The solution was coated on a polyester film with a conductive aluminum layer using a trough coater. After the coating was dried for 1 hour at 80° C., a clear 10 μm thick layer was formed. The hole mobility of the sample was measured and the results are presented in Table 1.
Mobility Measurements
Each sample was corona charged positively up to a surface potential U and illuminated with 2 ns long nitrogen laser light pulse. The hole mobility μ was determined as described in Kalade et al., “Investigation of charge carrier transfer in electrophotographic layers of chalkogenide glasses,” Proceeding IPCS 1994: The Physics and Chemistry of Imaging Systems, Rochester, N.Y., pp. 747-752, incorporated herein by reference. The hole mobility measurement was repeated with appropriate changes to the charging regime to charge the sample to different U values, which corresponded to different electric field strength inside the layer E. This dependence on electric field strength was approximated by the formula

μ=μ0eα√{square root over (E)}.

Here E is electric field strength, μ0 is the zero field mobility and α is Pool-Frenkel parameter. Table 1 lists the mobility characterizing parameters μ0 and α values and the mobility value at the 6.4×105 V/cm field strength as determined by these measurements for the four samples.












TABLE 1







μ (cm2/V · s)

Ionization



μ0 (cm2/
at 6.4 · 105 

Potential


Example
V · s)
V/cm
α (cm/V)0.5
(eV)







Compound
/
/
/
5.34


(1)


Sample 1
7.0 × 10−8
1.05 × 10−5
0.0064
/









Example 3
Ionization Potential Measurements
This example describes the measurement of the ionization potential for the charge transport materials described in Example 1.
To perform the ionization potential measurements, a thin layer of a charge transport material about 0.5 μm thickness was coated from a solution of 2 mg of the charge transport material in 0.2 ml of tetrahydrofuran on a 20 cm2 substrate surface. The substrate was an aluminized polyester film coated with a 0.4 μm thick methylcellulose sub-layer.
Ionization potential was measured as described in Grigalevicius et al., “3,6-Di(N-diphenylamino)-9-phenylcarbazole and its methyl-substituted derivative as novel hole-transporting amorphous molecular materials,” Synthetic Metals 128 (2002), p. 127-131, incorporated herein by reference. In particular, each sample was illuminated with monochromatic light from the quartz monochromator with a deuterium lamp source. The power of the incident light beam was 2-5·10−8 W. A negative voltage of −300 V was supplied to the sample substrate. A counter-electrode with the 4.5×15 mm2 slit for illumination was placed at 8 mm distance from the sample surface. The counter-electrode was connected to the input of a BK2-16 type electrometer, working in the open input regime, for the photocurrent measurement. A 10−15-10−12 amp photocurrent was flowing in the circuit under illumination. The photocurrent, I, was strongly dependent on the incident light photon energy hν. The I0.5=f(hν) dependence was plotted. Usually, the dependence of the square root of photocurrent on incident light quanta energy is well described by linear relationship near the threshold (see references “Ionization Potential of Organic Pigment Film by Atmospheric Photoelectron Emission Analysis,” Electrophotography, 28, Nr. 4, p. 364 (1989) by E. Miyamoto, Y. Yamaguchi, and M. Yokoyama; and “Photoemission in Solids,” Topics in Applied Physics, 26, 1-103 (1978) by M. Cordona and L. Ley, both of which are incorporated herein by reference). The linear part of this dependence was extrapolated to the hν axis, and the Ip value was determined as the photon energy at the interception point. The ionization potential measurement has an error of ±0.03 eV. The ionization potential values are given in Table 1 above.
As understood by those skilled in the art, additional substitution, variation among substituents, and alternative methods of synthesis and use may be practiced within the scope and intent of the present disclosure of the invention. The embodiments above are intended to be illustrative and not limiting. Additional embodiments are within the claims. Although the present invention has been described with reference to particular embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.

## Claims

1. An organophotoreceptor comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:
(a) a charge transport material having the formula




where Y comprises an aromatic group;
V1 and V2 comprise, each independently, a vinyl containing group; and
R1, R2, R3, and R4 comprise, each independently, H, an alkyl group, an acyl group, an ether group, an ester group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group; and
(b) a charge generating compound.

2. An organophotoreceptor according to claim 1 wherein V1 and V2, each independently, comprise an alkyl vinyl ether group or a CH2═CH—O—X— group where X comprises a bond or a —(CH2)m— group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, an aromatic group, an NRa group, a CRb group, a CRcRd group, a SiReRf group, a BRg group, or a P(═O)Rh group, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are, each independently, a bond, H, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a halogen, an acyl group, an alkoxy group, an alkylsulfanyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, a part of a ring group, or an alkyl group where one or more of the hydrogens of the alkyl group is optionally replaced by an aromatic group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, or a halogen.

3. An organophotoreceptor according to claim 2 wherein X is an ethylene group.

4. An organophotoreceptor according to claim 2 wherein V1 and V2, each independently, further comprise at least a substituent selected from the group consisting of an alkyl group, an acyl group, an ester group, an ether group, a hydrazone group, an azine group, an enamine group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, and a combination thereof.

5. An organophotoreceptor according to claim 1 wherein Y comprises an aryl group, an aromatic heterocyclic group, or a combination thereof.

6. An organophotoreceptor according to claim 5 wherein Y comprises a phenothiazine group, a phenoxazine group, a phenoxathiin group, a dibenzo(1,4)dioxin group, a thianthrene group, a phenazine group, an (N,N-disubstituted)arylamine group, a carbazolyl group, a bicarbazolyl group, an indolyl group, a pyrrolyl group, a furanyl group, a thiophenyl group, an alkylenedioxythiophene group, or a combination thereof.

7. An organophotoreceptor according to claim 6 wherein Y further comprises at least a substituent selected from the group consisting of an alkyl group, an acyl group, an ester group, an ether group, a hydrazone group, an azine group, an enamine group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, and a combination thereof.

8. An organophotoreceptor according to claim 7 wherein the charge transport material is selected from the group consisting of the following formulae:

9. An organophotoreceptor according to claim 1 wherein the photoconductive element further comprises a second charge transport material.

10. An organophotoreceptor according to claim 9 wherein the second charge transport material comprises an electron transport compound.

11. An organophotoreceptor according to claim 1 wherein the photoconductive element further comprises a binder.

12. An electrophotographic imaging apparatus comprising:
(a) a light imaging component; and
(b) an organophotoreceptor oriented to receive light from the light imaging component, the organophotoreceptor comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:
(i) a charge transport material having the formula





where Y comprises an aromatic group;
V1 and V2 comprise, each independently, a vinyl containing group; and
R1, R2, R3, and R4 comprise, each independently, H, an alkyl group, an acyl group, an ester group, an ether group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, or a part of a ring group; and
(ii) a charge generating compound.

13. An electrophotographic imaging apparatus according to claim 12 wherein V1 and V2, each independently, comprise an alkyl vinyl ether group or a CH2═CH—O—X— group where X comprises a bond or a —(CH2)m— group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, N, C, B, Si, P, C═O, O═S═O, a heterocyclic group, an aromatic group, an NRa group, a CRb group, a CRcRd group, a SiReRf group, a BRg group, or a P(═)Rh group, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are, each independently, a bond, H, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a halogen, an acyl group, an alkoxy group, an alkylsulfanyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, a part of a ring group, or an alkyl group where one or more of the hydrogens of the alkyl group is optionally replaced by an aromatic group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, or a halogen.

14. An electrophotographic imaging apparatus according to claim 13 wherein X is an ethylene group.

15. An electrophotographic imaging apparatus according to claim 13 wherein V1 and V2, each independently, further comprise at least a substituent selected from the group consisting of an alkyl group, an acyl group, an ether group, an ester group, a hydrazone group, an azine group, an enamine group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, and a combination thereof.

16. An electrophotographic imaging apparatus according to claim 12 wherein Y comprises an aryl group, an aromatic heterocyclic group, or a combination thereof.

17. An electrophotographic imaging apparatus according to claim 16 wherein Y comprises a phenothiazine group, a phenoxazine group, a phenoxathiin group, a dibenzo(1,4)dioxin group, a thianthrene group, a phenazine group, an (N,N-disubstituted)arylamine group, a carbazolyl group, a bicarbazolyl group, an indolyl group, a pyrrolyl group, a furanyl group, a thiophenyl group, an alkylenedioxythiophene group, or a combination thereof.

18. An electrophotographic imaging apparatus according to claim 17 wherein Y further comprises at least a substituent selected from the group consisting of an alkyl group, an acyl group, an ether group, an ester group, a hydrazone group, an azine group, an enamine group, an alkenyl group, an alkynyl group, a heterocyclic group, an aromatic group, and a combination thereof.

19. An electrophotographic imaging apparatus according to claim 18 wherein the charge transport material is selected from the group consisting of the following formulae:

20. An electrophotographic imaging apparatus according to claim 12 wherein the photoconductive element further comprises a second charge transport material.

21. An electrophotographic imaging apparatus according to claim 20 wherein the second charge transport material comprises an electron transport compound.

22. An electrophotographic imaging apparatus according to claim 12 further comprising a toner dispenser.