# Patent

## Title
Endless flexible members containing phosphorus for imaging devices

## Abstract

Flexible members for use in imaging devices comprise a polyamideimide comprising phosphorus.

## Background
FIELD
A novel flexible member composition, such as, an intermediate transfer belt (ITB), such as, an endless belt having an annular main body, for use in an electrophotographic imaging device is provided. The imaging device produces a fixed toner image on a recording medium.
BACKGROUND
In the electrophotographic imaging arts, an image forming apparatus forms a static latent image by exposure of a surface of a charged photosensitive member to patterns of light, develops that static latent image to form a toner image, and finally transfers the toner image to a recording or receiving medium, such as, a paper, at a predetermined transfer position, thereby forming an image thereon.
One such image forming apparatus employs, in the process of image formation and development, a flexible member, such as, an endless belt that is stretched around support rolls, and which circulates and moves as a unit, carrying the formed toner image to a transfer position. Alternatively, the endless belt can operate as a unit that transfers the recording medium to a transfer position
In an image forming apparatus that forms a color image, because toner images of individual different colors are superimposed on one another, an endless belt can be used as a unit that carries the toner images of different color which are sequentially applied or received in building the final composite color image. An endless belt also can be used as a unit for transferring a recording medium that sequentially receives toner images of different color. See, for example, U.S. Pat. No. 7,677,848 and U.S. Publ. No. 20100279217, herein incorporated by reference in entirety.
Image forming apparatus with high endurance that are capable of withstanding, for example, temperature variation and high volume output, are desirable. Hence, materials to enhance flexible member performance and preparation are desirable.
Endless flexible belts can be made by producing a film on or attached to a mold, mandrel or form. A film-forming solution or composition is applied to a form by, for example, dipping, spraying, flow coating or other known method, and the solution or composition can be dispersed or distributed to form a thin film, for example, by centrifugation over the inner wall of a hollow form, for example, a cylindrical form.
When using such forming or molding methods, the dried or cured film must be separated from the molding form, and preferably with minimal stress, deformation, damage and the like to the film. Moreover, it is desirable that the film be easily removed from the molding form.
In the electrophotographic arts, it is beneficial, if not necessary, for a flexible member surface that carries a charge and a latent image to be regular with minimal imperfections, such as, pits, valleys, indentations, waves, wrinkles, dimples and the like, an erose surface is not beneficial if maximal image fidelity is desired.
SUMMARY
According to aspects disclosed herein, there is provided a film-forming composition for making flexible members for use in electrophotography, such as, a flexible image transfer member, such as, an intermediate transfer belt (ITB), comprising a polyamideimide containing phosphorus that facilitates removal of the formed film from a mold, mandrel, form and the like.
Another disclosed embodiment comprises an imaging or printing device comprising a flexible member comprising a polyamideimide containing phosphorus.


DETAILED DESCRIPTION
As used herein, the term, “electrophotographic,” or grammatical versions thereof, is used interchangeably with the term, “xerographic.” In some embodiments, such as, in the case of forming a color image, often, individual colors of an image are applied sequentially. Thus, a, “partial image,” is one which is composed of one or more colors prior to application of the last of the colors to yield the final or composite color image. “Flexible,” is meant to indicate ready deformability, such as, observed in a belt, web, film and the like, that, for example, is adaptable to operate and for use with, for example, rollers.
For the purposes of the instant application, “about,” is meant to indicate a deviation of no more than 20% of a stated value or a mean value. Other equivalent terms include, “substantial,” and, “essential,” or grammatical forms thereof.
In electrophotographic (xerographic) reproducing or imaging devices, including, for example, a digital copier, an image-on-image copier, a contact electrostatic printing device, a bookmarking device, a facsimile device, a printer, a multifunction device, a scanning device and any other such device, a printed output is provided, whether black and white or color, or a light image of an original is recorded in the form of an electrostatic latent image on an imaging device component, for example, which may be present as an integral component of an imaging device or as a replaceable component or module of an imaging device, and that latent image is rendered visible using electroscopic, finely divided, colored or pigmented particles, or toner. The imaging device component can be a flexible member.
A flexible member can comprise an intermediate transfer member, such as, an intermediate transfer belt (ITB), a fuser belt, a pressure belt, a transfuse belt, a transport belt, a developer belt and the like. Such members can comprise a single layer or plural layers, such as, a support layer and one or more layers of particular function.
Hence, such transfer members can be present in an electrophotographic image forming device or printing device. In the case of an ITB, a photoreceptor is electrostatically charged and then is exposed to a pattern of activating electromagnetic radiation, such as, light, which alters the charge on the surface of an imaging device component leaving behind an electrostatic latent image thereon. The electrostatic latent image then is developed at one or more developing stations to form a visible image or a partial image, by depositing finely divided electroscopic colored, dyed or pigmented particles, or toner, for example, from a developer composition, on the surface of the imaging component. The resulting visible image on the photoreceptor is transferred to an ITB for transfer to a receiving member or for further developing of the image, such as, building additional colors on successive partial images. The final image then is transferred to a receiving member, such as, a paper, a cloth, a polymer, a plastic, a metal and so on, which can be presented in any of a variety of forms, such as, a flat surface, a sheet or a curved surface. The transferred particles are fixed or fused to the receiving member by any of a variety of means, such as, by exposure to elevated temperature and/or elevated pressure.
An intermediate transfer member also finds use in color systems and other multi-imaging systems. In a multi-imaging system, more than one image is developed, that is, a series of partial images. Each image is formed on the photoreceptor, is developed at individual stations and is transferred to an intermediate transfer member. Each of the images may be formed on the photoreceptor, developed sequentially and then transferred to the intermediate transfer member or each image may be formed on the photoreceptor developed and transferred in register to the intermediate transfer member. See for example, U.S. Pat. Nos. 5,409,557; 5,119,140; and 5,099,286, the contents of which are incorporated herein by reference in entirety.
It can be desirable to minimize transferring extraneous developer or developer carrier to the receiving member, that is, for example, a paper. Therefore, it can be advantageous to transfer the developed image on a photoreceptor to an intermediate transfer web, belt, roll or member, and subsequently to transfer the developed image from the intermediate transfer member to a permanent or ultimate substrate.
To obtain quality image transfer, that is, to minimize image shear, the displacement of a transfer member due to disturbance during transfer member driving can be reduced by limiting the thickness of the support or substrate, for example to about 50 μm. Thus, the thickness of the substrate or support can be from about 50 μm to about 150 μm or from 70 μm to about 100 μm.
In the instant disclosure, a substrate, film or layer of interest comprises a polyamideimide comprising phosphorus that is suitable for use as a flexible member in an imaging device. When made using a mold, mandrel, form and the like, the formed film releases readily from the device used to make same, and the presence of phosphorus also provides a fire retardant property to the formed members.
A reagent containing one or more phosphorus atoms and plural amine groups that can be used to make a polyamideimide can be obtained commercially or can be synthesized. For example, an amine, an amine carrying a carbonyl group, such as, an amine phenone or an amino acid, and a phosphorus-containing compound, such as, a phosphate, are combined in the presence of a strong organic acid to form a phosphorus-containing amine that can be used as a reagent in a polyamideimide polymerization reaction. The particular amine, amine carrying a carbonyl group and phosphorus-containing compound selected for reaction is a design choice as the other portions of each of the reagents, the R groups, will contribute to the structure of the formed polyamideimide.
The amine can be a primary amine, but also can be a secondary or tertiary amine as a design choice. The amino groups are selected to ensure the polymerization reaction is not unduly hindered. The R groups can comprise, for example, an aliphatic group, an aromatic group or a combination thereof, and carry heteroatoms. An example is aniline, which will contribute a benzene ring to the final polyamideimide.
The amine carrying a carbonyl group again can be a primary amine, but also a secondary or tertiary amine can be used as a design choice. The amino groups are selected to ensure the polymerization reaction is not unduly hindered. Also, the positions of the amine group(s) and carbonyl group(s) are selected so as not to unduly hinder the subsequent polymerization reaction. An example is an amino acid or, an example of an amine phenone is 4-aminoacetophenone. The latter will contribute an ethyl benzene group to the final polyamideimide.
The phosphorus-containing compound can be any compound that carries one or more phosphorus atoms that is suitable for the intended use. Because phosphorus is multivalent, a suitable reagent is one which carries a functional group, such as, a halogen or an oxygen, for example. An example is the commercially available, 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO), where the polycyclic phenanthrene rings contribute to the final polyamideimide.
The three reagents are combined in the presence of a strong organic acid, such as, a sulfonic acid, such as, p-toluenesulfonic acid anhydride, and are incubated at a suitable reaction temperature for a suitable time to allow the three reagents to combine into an amine carrying one or more phosphorus atoms, which can be used as a reagent in a polymerization reaction to form a polyamideimide, such as, a reaction using an acid chloride or using a diisocyanate. The resulting reagent is isolated, can be washed and/or reprecipitated, and then dried.
To form the polyamideimide containing phosphorus, the reagent of interest is included in a polymerization reaction. Thus, for example, an instant reagent containing plural amine groups and at least one phosphorus atom can be mixed with an acid chloride, such as one carrying plural carbonyl groups, such as, trimellitic acid chloride, often forming an intermediate amic acid. The reaction generally is conducted in a dipolar, aprotic solvent, such as, dimethylformamide or dimethylsulfoxide to yield the polymer of interest.
Alternatively, a diisocyanate is reacted with an anhydride, and included in the reaction is a phosphorus-containing compound of interest comprising plural amine groups. The reactants generally are mixed in a dipolar, aprotic solvent, such as DMF or DMSO. Following polymerization, the product is isolated.
A transfer member or device generally is one where the surface destined to carry an image has a low surface energy, i.e., material comprising an electrically conducting agent dispersed thereon having a contact angle of not less than about 70° or at least about 70° with respect to a water droplet as represented by wettability by water. The term, “wettability by water” as used herein is meant to indicate the angle of contact of a material constituting the surface layer as a specimen with respect to a water droplet.
Electrical property regulating materials can be added to the substrate or to a layer superficial thereto to regulate electrical properties, such as, surface and bulk resistivity, dielectric constant and charge dissipation. In general, electrical property regulating materials can be selected based on the desired resistivity of the film. High volume fractions or loadings of the electrical property regulating materials can be used so that the number of conductive pathways is always well above the percolation threshold, thereby avoiding extreme variations in resistivity. The percolation threshold of a composition is a volume concentration of dispersed phase below which there is so little particle to particle contact that the connected regions are small. At higher concentrations than the percolation threshold, the connected regions are large enough to traverse the volume of the film, see, for example, Scher et al., J Chem Phys, 53(9)3759-3761, 1970, who discuss the effects of density in percolation processes.
Particle shape of the electrical property regulating material can influence volume loading. Volume loading can depend on whether the particles are, for example, spherical, round, irregular, spheroidal, spongy, angular or in the form of flakes or leaves. Particles having a high aspect ratio do not require as high a loading as particles having a relatively lower aspect ratio. Particles which have relatively high aspect ratios include flakes and leaves. Particles which have a relatively lower aspect ratio are spherical and round particles.
The percolation threshold is practically within a range of a few volume % depending on the aspect ratio of the loadent. For any particular particle resistivity, the resistivity of the coated film can be varied over about one order of magnitude by changing the volume fraction of the resistive particles in the layer. The variation in volume loading enables fine tuning of resistivity.
The resistivity varies approximately linearly to the bulk resistivity of the individual particles and the volume fraction of the particles in the support or layer. The two parameters can be selected independently. For any particular particle resistivity, the resistivity of the reinforcing member can be varied over roughly an order of magnitude by changing the volume fraction of the particles. The bulk resistivity of the particles is preferably chosen to be up to three orders of magnitude lower than the bulk resistivity desired in the member. When the particles are mixed with the support or layer in an amount above the percolation threshold, the resistivity of the resulting reinforcing member can decrease in a manner proportional to the increased loading. Fine tuning of the final resistivity may be controlled on the basis of that proportional increase in resistivity.
The bulk resistivity of a material is an intrinsic property of the material and can be determined from a sample of uniform cross section. The bulk resistivity is the resistance of such a sample multiplied by the cross sectional area divided by the length of the sample. The bulk resistivity can vary somewhat with the applied voltage.
The surface or sheet resistivity (expressed as ohms/square, Ω/□) is not an intrinsic property of a material because that metric depends on material thickness and contamination of the material surface, for example, with condensed moisture. When surface effects are negligible and bulk resistivity is isotropic, the surface resistivity is the bulk resistivity divided by the reinforcing member thickness. The surface resistivity of a film can be measured without knowing the film thickness by measuring the resistance between two parallel contacts placed on the film surface. When measuring surface resistivity using parallel contacts, one uses contact lengths several times longer than the contact gap so that end effects do not cause significant error. The surface resistivity is the measured resistance multiplied by the contact length to gap ratio.
Particles can be chosen which have a bulk resistivity slightly lower than the desired bulk resistivity of the resulting member. The electrical property regulating materials include, but are not limited to pigments, quaternary ammonium salts, carbons, dyes, conductive polymers and the like.
A carbon black particle of interest is one with a particle diameter of from about 10 nm to about 30 nm, from about 12 nm to about 25 nm or from about 15 nm to about 20 nm. A carbon black of interest is one with a BET surface area of from about 100 m2/g to about 600 m2/g, from about 200 m2/g to about 500 m2/g or from about 300 m2/g to about 400 m2/g. A carbon black of interest is one with a DBA absorption value of about 1 ml/g to about 7 ml/g, from about 1.5 ml/g to about 6 ml/g or from about 2 ml/g to about 5 ml/g. An example of a commercially available carbon black is Special Black 4, Special Black 5, Color Black FW1, Color Black FW2 or Color Black FW200 (Evonik Industries).
Electrical property regulating materials, such as, a carbon black, may be added in amounts ranging from about 1% by weight to about 25% by weight of the total weight of the support or layer, from about 7% by weight to about 20% by weight, or from about 10% to about 15% by weight of the total weight of the support or layer.
Also, carbon black systems can be used to make a layer or layers conductive. That can be accomplished by using more than one variety of carbon black, that is, carbon blacks with different, for example, particle geometry, resistivity, chemistry, surface area and/or size. Also, one variety of carbon black or more than one variety of carbon black can be used along with other non-carbon black conductive fillers.
An example of using more than one variety of carbon black, each having at least one different characteristic from the other carbon black, includes mixing a structured black, such as, VULCAN® XC72, having a steep resistivity slope, with a low structure carbon black, such as, REGAL 250R®, having lower resistivity at increased filler loadings. The desired state is a combination of the two varieties of carbon black which yields a balanced controlled conductivity at relatively low levels of filler loading, which can improve mechanical properties.
Another example of mixing carbon blacks comprises a carbon black or graphite having a particle shape of a sphere, flake, platelet, fiber, whisker or rectangle used in combination with a carbon black or graphite with a different particle shape, to obtain good filler packing and thus, good conductivity. For example, a carbon black or graphite having a spherical shape can be used with a carbon black or graphite having a platelet shape. The ratio of carbon black or graphite fibers to spheres can be about 3:1.
Similarly, by use of relatively small particle size carbon blacks or graphites with relatively large particle size carbon blacks or graphite, the smaller particles can orient in the packing void areas of the polymer substrate to improve particle contact. As an example, a carbon black having a relatively large particle size of from about 1 μm to about 100 μm or from about 5 μm to about 10 μm can be used with a carbon black having a particle size of from about 0.1 μm to about 1 μm or from about 0.05 μm to about 0.1 μm.
In another embodiment, a mixture of carbon black can comprise a first carbon black having a BET surface area of from about 30 m2/g to about 700 m2/g and a second carbon black having a BET surface area of from about 150 m2/g to about 650 m2/g.
Also, combinations of resistivity can be used to yield a shallow resistivity change with filler loading. For example, a carbon black or other filler having a resistivity of about 10−1 to about 103 ohms-cm, or about 10−1 to about 102 ohms-cm used in combination with a carbon black or other filler having a resistivity of from about 103 to about 107 ohms-cm can be used.
Other fillers, in addition to carbon blacks, can be added to the polymer, resin or film-forming composition and dispersed therein. Suitable fillers include metal oxides, such as, magnesium oxide, tin oxide, zinc oxide, aluminum oxide, zirconium oxide, barium oxide, barium titanate, beryllium oxide, thorium oxide, silicon oxide, titanium dioxide and the like; nitrides such as silicon nitride, boron nitride, and the like; carbides such as titanium carbide, tungsten carbide, boron carbide, silicon carbide, and the like; and composite metal oxides such as zircon (ZrO2.Al2O3), spinel (MgO.Al2O3), mullite (3Al2O3.2SiO2), sillimanite (Al2O3.SiO2), and the like; mica; and combinations thereof. Optional fillers can present in the polymer/mixed carbon black coating in an amount of from about 20% to about 75% by weight of total solids, or from about 40% to about 60% by weight of total solids.
The resistivity of the coating layer can be from about 107 to about 1013Ω/□, from about 108 to about 1012Ω/□ or from about 109 to about 1011Ω/□.
In another embodiment, the layer has a dielectric thickness of from about 1 μm to about 10 μm or from about 4 μm to about 7 μm.
The hardness of the coating can be less than about 85 Shore A, from about 45 Shore A to about 65 Shore A, or from about 50 Shore A to about 60 Shore A.
In another embodiment, the surface can have a water contact angle of at least about 60°, at least about 75°, at least about 90° or at least about 95°.
Transfer members can be prepared using methods known in the art. The phosphorus-containing polyamideimide composition is prepared by mixing and dispersing the components in a dispersing machine or a mixing vessel and then is applied to the form, mandrel or mold, such as, one made from a resin, a glass, a ceramic, stainless steel and so on, for example, using methods such as those described in U.S. Pat. Nos. 4,747,992, 7,593,676 and 4,952,293, which are hereby incorporated herein by reference. Other techniques for applying materials include liquid and dry powder spray coating, dip coating, flow coating, wire wound rod coating, fluidized bed coating, powder coating, electrostatic spraying, sonic spraying, blade coating and the like. If a coating is applied by spraying, spraying can be assisted mechanically and/or electrically, such as, by electrostatic spraying.
The film is allowed to dry and/or to cure at a suitable temperature; and then is removed therefrom. As the film of interest is self-releasing, it is not necessary to add a releasing agent, such as, a silicone-based or a fluorine-based composition, to the mold, mandrel or form before applying the film-forming composition thereto or thereon. By, “self-release,” is meant that a cured or formed film releases from a mold or form without or with minimal intervention.
In such cases where a film-forming solution or composition is applied to a form, a mandrel, a mold and the like, removal of the formed film intact and with minimal damage, with little difficulty or intervention or both are desirable. The phosphorus-containing polyamideimide reagent in the solution added directly to the form, mandrel, mold and the like facilitates or enhances such subsequent facile removal of the dried and/or cured film therefrom. Moreover, phosphorus compounds are fire retardant and will render the polymer less hygroscopic, and thus easier to handle and to manipulate.
The film can be seamless or can be used to make a seamed member, as known in the art.
Various aspects of the embodiments of interest now will be exemplified in the following non-limiting examples.
EXAMPLES
Example 1
Nine,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO, 108.1 g, about 0.5 mole), 4-aminoacetophenone (67.6 g, about 0.5 mole), p-toluenesulfonic acid monohydrate (2.56 g, about 0.135 mole) and aniline (232.8 g, about 2.5 moles) were mixed by magnetic stirring and heated to 120° C. for 18 hours under nitrogen gas. After the reaction mixture was cooled to room temperature, 150 ml of methanol were added. The slight yellowish precipitate was collected by filtration and washed by 3×250 ml of methanol and dried.
Example 2
The dried powder of Example 1 was added to a mixture of 1,2,4-benzenetricarboxylic anhydride (19.2 g, about 0.01 mole) and hexamethylene diisocyanate (8.7 g, about 0.05 mole) in solvent DMF (70 g). After being stirring at room temperature for about 4 hours, the brownish clear solution was heated to 90° C. for 2.5 hours. After cooling down to room temperature, a viscous brownish liquid was obtained comprising the disclosed phosphorus-containing polyamideimide.
Example 3
An ITB coating dispersion was prepared comprising the polyamideimide containing phosphorus of Example 2, a conventional polyamideimide, VYLOMAX® HR-11N (Toyobo) and color black FW-1 (Evonik) in NMP/DMF at a weight ratio of 30/60/10. After ball milling, the solution was coated on a stainless steel substrate, and dried and cured at 200° C. for 60 minutes.
The film released readily from the stainless steel mold. The film had a thickness of about 100 μm.
Comparative Example 1
A control ITB dispersion comprising VYLOMAX® HR-11N and color black FW-1 (Evonik) in NMP at a weight ratio of 90/10 was ball milled, the solution was coated on a stainless steel substrate, and dried and cured at 200° C. for 60 minutes.
The film did not release from the stainless steel mold. The mold with attached film was immersed in water for 48 hours before the film could be separated from the mold.
Example 4
The ITB's of Example 3 and Comparative Example 1 were tested for various properties using materials and methods known in the art. The results are provided in the table below.














Surface
Young's




resistivity
modulus
ITB release from



(ohm/□)
(MPa)
metal substrate







The ITB of Example 3
8.7 × 109
3,500
Self-releasing


ITB of Comparative 
3.5 × 109
3,600
Required 2 day


Example 1


incubation in water









Thus, presence of phosphorus in the polyamideimide does not detract from the desired physical properties of an ITB made from polyamideimide. However, the self-release from the mold, the advantage of being fire retardant and the added hydrophobicity to the polymer making the polymer less hygroscopic provide advantages over a flexible belt made from polyamideimide alone.
All references cited herein are herein incorporated by reference in entirety.
It will be appreciated that variants of the above-disclosed and other features and functions, or alternatives thereof, may be combined with other and different systems or applications. Various presently unforeseen or unanticipated alternatives, changes, modifications, variations or improvements subsequently may be made by those skilled in the art to and based on the teachings herein without departing from the spirit and scope of the embodiments, and which are intended to be encompassed by the following claims.

## Claims

1. A self-releasing flexible intermediate transfer member comprising a polyamideimide comprising phosphorus and an electrical property regulating material present in an amount by weight of from about 5 wt % to about 25 wt %.

2. The self-releasing flexible intermediate transfer member of claim 1, wherein said electrical property regulating material comprises a carbon black.

3. An imaging device comprising the intermediate transfer member of claim 1.

4. The member of claim 1, comprising an intermediate transfer belt, a fuser belt, a pressure belt, a transfuse belt, a transport belt or a developer belt.

5. The member of claim 1, comprising a support layer.

6. The device of claim 3, comprising a receiving member comprising a paper or a plastic.

7. The member of claim 1, wherein said regulating material is selected from the group consisting of a pigment, a quaternary ammonium salt, a carbon or a dye.

8. The member of claim 2, wherein said carbon black comprises particles of from about 10 nm to about 30 nm.

9. The member of claim 2, wherein said carbon black comprises particles with a BET surface area of about 100 m2/g to about 600 m2/g.

10. The member of claim 2, comprising a first carbon black and a second carbon black.

11. The member of claim 1, further comprising a filler.

12. The member of claim 11, wherein said filler comprises a metal oxide, a nitride, a carbide or a composite metal oxide.