Image forming method, process cartridge and image forming apparatus

[0001] 1. Field of the Invention

[0002] The present invention relates to an image forming method utilizing electrophotography and electrostatic recording, to a process cartridge and to an image forming apparatus. In particular, the present invention relates to an image forming method, a process cartridge and an image forming apparatus using a compound having an acid-adsorbing ability.

[0003] 2. Description of the Related Art

[0004] The Karlson method has been generally used when an image is formed in copier or a laser beam printer. In conventional image forming methods, an image is formed by developing an electrostatic latent image formed on a photoreceptor by optical means, transferring the electrostatic latent image to an image receiving member such as recording paper, and next fixing to the image receiving member using heat and pressure. Because the photoreceptor is used repeatedly, a cleaning device is disposed to remove residual toner left on the photoreceptor after the transfer.

[0005] A structure referred to as a function-separating type, in which a charge generation layer is isolated from a charge transfer layer, has been devised and put to practical use in recent years as an electrophotographic photoreceptor in view of sensitivity and stability. Electrophotographic photoreceptors having such a structure comprise two layers consisting of a charge generation layer, which is produced by binding a charge generation material using a suitable resin as a binding material (binder resin), and a charge transfer layer, which is produced by dispersing or dissolving a charge transfer material in a binder resin. The layer containing a charge transfer material contains a positive hole transfer material in many cases. As the binder resin, thermoplastic resins such as polycarbonate resins, polyester resins, acryl resins and polystyrene resins, and heat-curable resins such as polyurethane resins and epoxy resins are under study.

[0006] In this case, the surface of the charge transfer layer must be negatively charged by corona charging or roller charging. This gives rise to problems in that the characteristics of the photoreceptor are adversely affected due to various causes, such as resin deterioration caused by ozone generated when the charge surface layer is negatively charged, wear, reduced sensitivity and reduced charging ability caused by the electrical impact of discharging at the photoreceptor surface, and mechanical breakdown resulting from friction during subsequent toner development, transfer to paper, and cleaning.

[0007] Various studies such as those listed below have been made in relation to the foregoing problems. Attempts have made to blend a polysiloxane resin with a copolymer component or other resins, and studies have been made with respect to improve the quality, life and cleaning characteristics of photoreceptors using the characteristics of polysiloxane, as can be seen in Japanese Patent Application Laid-open (JP-A) No. 61-238062, which discloses a photoreceptor that uses a heat-curable resin containing a polysiloxane resin for a charge transfer layer; in JS-A No. 62-108260, which discloses a photoreceptor including a protective layer containing a polysiloxane resin; in JP-A No. 4-346356, which discloses a photoreceptor disposed with a protective layer formed by dispersing silica gel, a urethane resin or a fluororesin in a heat-curable polysiloxane resin; and in JP-A No. 4-273252, which discloses a photoreceptor in which a resin obtained by dispersing a heat-curable polysiloxane resin in a thermoplastic resin is used for a protective layer or as a charge transfer binder resin.

[0008] Although polysiloxane has excellent thermal and mechanical strength, it is quite incompatible with organic compounds that function as electronic devices. For this reason, studies have been with respect to photoreceptors in which a charge transfer material having an unsaturated bond is bound directly with polysiloxane such as poly(hydrogen methylsiloxane) to make a resin, which is used as a binder resin for a protective layer or charge transfer material (JP-A No. 8-319353); photoreceptors in which a thin film produced using a sol gel method is used as a protective layer (Proceedings of IS & T's Eleventh International Congress on Advances in Non-Impact Printing Technologies, pp. 57-59); and photoreceptors in which an organic silicon modified positive positive hole transfer compound obtained by directly introducing silicon having a hydrolyzable group into a charge transfer material is used for an electrophotographic photoreceptor (JP-A No. 9-190004). In the photoreceptors described in Proceedings of IS & T's Eleventh International Congress on Advances in Non-Impact Printing Technologies, pp. 57-59, and in JP Nos. 2575536 and 9-190004, a firm film is formed because siloxane forms a three-dimensional network. As a result, these photoreceptors have attracted considerable attention because mechanical strength is largely improved.

[0009] As disclosed in JP-A Nos. 11-38656, 11-184106 and 11-316468, we developed novel materials previously and demonstrated that these materials have superior characteristics. We found that when a series of these materials is used as the surface layer of an electrophotographic photoreceptor, the surface layer had overwhelmingly superior thermal and mechanical strength with respect to conventional surface layers, whereby deterioration of the surface layer caused by wear can be significantly reduced and longevity can be improved.

[0010] However, it was found that when the surface layer is used for a long period of time, especially in a humid environment, image defects including image flow are caused.

[0011] As a result of investigating the cause of this problem, the following is surmised. It is known that, when a photoreceptor is charged by charging means such as corona charging or a conductive roller, discharge products (active products) such as ozone and NOx are produced in the process. Ozone and NOx produced in the above step not only pose a problem in terms of environmental sanitation, but they also act on the surface of the photoreceptor to increase potential fluctuation and residual potential, and impact photographic characteristics and images (e.g., image flow), thus reducing the durability of the photoreceptor. Therefore, the surface of the photoreceptor is occasionally denatured by the action of the ozone and NOx. Moreover, when the surface of the photoreceptor is hydrophilic, ozone and NOx adhere to the surface, whereby moisture in the atmosphere also tends to adhere to the surface, with the result being that electrical resistance of the surface is microscopically reduced and it is difficult to maintain the charge generated by the charging.

[0012] The surface of the photoreceptor comprising the aforementioned series of materials has overwhelmingly superior mechanical strength and significantly small abrasion loss. On the other hand, a conventional surface layer is abraded to some extent. Taking this phenomenon into account, it is surmised that a certain degree of abrasion of the surface layer can suppress the renewal of a deteriorated surface and the progress of the adhesion of products created by discharge. Accordingly, it is believed that it is difficult for the aforementioned phenomenon (suppression the adhesion of products created by discharging) to occur and easy for image defects such as image flow to be generated on a surface layer that has superior mechanical strength and small abrasion loss.

[0013] Various studies have been made to suppress these image defects. For instance, a method in which fine particles (abrasives) having an abrasive function are incorporated into a developing agent for the purpose of properly abrading the surface of a photoreceptor (JP-A No. 5-188630) and a method in which a thin film of a fatty acid metal salt is formed on the surface of a photoreceptor to protect the surface layer from adverse effects of discharge products (JP-A No. 2001-5207) have been proposed. Also, for example, a method in which a hydrotalcite compound that adsorbs anions is incorporated into a developing agent to remove discharge products (JP-A No. 2-166461) has been proposed.

[0014] However, if the particle diameter of an abrasive is small in the method in which the abrasive is used, abrasive loss is reduced because of small abrasive effects and image defects cannot be sufficiently suppressed. When the particle diameter is large, scratches are caused on the surface of the photoreceptor in the direction of rotation and lines resulting from these scratches appear on the image. Moreover, adhesion (contamination) of toner components resulting from these scratches progresses, and black points, white points and black lines resulting from the adhesion appear on the image.

[0015] In the method in which a thin film of a fatty acid metal salt is formed on the surface of a photoreceptor, the coefficient of friction decreases and cleanability is improved when the surface of the photoreceptor is cleaned in a cleaning step with a rubber blade such as a urethane blade. However, because the coefficient of friction with the photoreceptor having the surface layer resistant to abrasion rises, leading to a rise in the rotational torque of the photoreceptor, the blade end pressed to the photoreceptor is abraded or chipped, with the result being that black lines caused by cleaning inferiors appear on an image.

[0016] Moreover, in the method in which a hydrotalcite compound is incorporated into a developing agent to remove discharge products, adhesion (contamination) of the hydrotalcite compound resulting from irregularities and scratches caused by partial wear on the surface of the photoreceptor is easily caused, even though this method has initial effects. Therefore, black points, white points and black lines resulting from the adhesion appear on the image in the case of a conventional photoreceptor.

[0017] Methods of developing this electrostatic latent image include a one-component developing method, which uses only a toner, and a two-component developing method, which uses a toner and a carrier. In the case of a two-component developing agent in the two-component developing method, the toner and the carrier are stirred to frictionally charge the toner. Therefore, the amount of frictional charge of the toner can be controlled to a considerable extent by selecting carrier characteristics and stirring conditions. Thus, image quality is highly reliable and excellent.

[0018] The toner used in the electrophotographic process is usually produced by adding various resins (e.g., polyester resin, styrene-acryl resin, and epoxy resin), colorants, charge control agents, releasing agents and the like, and then melting, kneading, and uniformly dispersing the same, following by crushed the mixture into a predetermined grain size and removing excessively coarse powders and micropowders using a classifier. However, it has become necessary to further reduce toner grain size along with the demand for higher image quality in recent years. It has also, in view of the demand to reduce energy, become necessary to lower the transition temperature and softening point of resins in order to achieve fusing at lower temperatures.

[0019] With respect to color toners used in full-color copiers and printers, different color toners must be mixed sufficiently in a fusing step, and color reproducibility and the transparency of overhead projector (OHP) images are essential. Generally, these color toners are preferably formed using a sharp-melt low molecular resin in order to raise color-miscibility in comparison with black toner.

[0020] Conventionally, waxes such as polyethylene and polypropylene, which have high crystallinity and a relatively high melting point, are used,in black toner to obtain offset resistance for fusing. However, these waxes compromise the transparency of overhead projector images in full-color toner. For this reasons ordinary full-color toner contains no wax, and a method has been adopted in which silicon rubber or a fluororesin, which is highly releasable with respect to toner, is used to form,the surface of a heat-fusing roller, and a releasable liquid such as silicon oil is supplied to the surface to prevent offset. This method is very effective in terms of preventing the offset phenomenon of toner, but there is a problem in that it requires a device for supplying the offset-preventing liquid. This runs counter to the need to reduce the size and weight of copiers and printers. Moreover, the offset-preventing liquid exudes an unpleasant odor due to being vaporized by heat, and can sometimes contaminate the machine.

[0021] Therefore, studies are being made as to toners that are produced by a kneading and crushing method, comprise a sharp-melt resin, a colorant and a low-melting point wax, and have a small grain diameter. In this kneading and crushing method, a thermoplastic resin and the like are melted and kneaded together with a pigment, a charge control agent, a releasing agent such as wax; and then the melted and kneaded mixture is micronized and classified after being cooled to produce a desired toner.

[0022] However, in the case of a toner produced by the kneading and crushing method, generally its shape is undefined and its surface composition is not uniform. Although, in this method, the shape and surface composition of the toner are changed subtly corresponding to the crushing characteristics of materials to be used and conditions in a crushing step, it is difficult to control these characteristics in desired ranges intentionally. When the shape of the toner particles is undefined, only insufficient fluidity is obtained even if a fluidity adjuvant is added and fine particles of the fluidity adjuvant are moved to recesses in the toner particles and embedded in the recesses by mechanical force such as shearing force, giving rise to the problem that fluidity is lowered with time and developability, transferability and cleaning ability are impaired.

[0023] In light of this, studies being are made with respect to a suspension polymerization method and an emulsion polymerization coagulation method as methods for producing spherical toners that cannot be easily obtained by the above kneading and crushing method.

[0024] In the suspension polymerization method, a polymerizable monomer is dispersed in an aqueous medium together with a colorant and a releasing agent, and then the polymerizable monomer is polymerized to obtain a toner.

[0025] In the emulsion polymerization coagulation method, a resin dispersion is prepared by emulsion polymerization, and a colorant dispersion in which a colorant is dispersed in a solvent, and a dispersion in which a releasing agent is dispersed, are separately prepared. These dispersions are mixed to form coagulated particles having a particle diameter corresponding to that of a toner, and then fused by being heated to thereby obtain a toner. According to this emulsion polymerization coagulation method, the shape of toner particles can be arbitrarily controlled, from an undefined shape to a spherical shape, by selecting heating temperature conditions

[0026] Studies are also being made with respect to a carrier having a small particle diameter in order to stably charge toner particles having a small particle diameter. These proceed from the fact that the surface area of the carrier must be increased, because the surface area of the toner particles increases when the toner particles have a small particle diameter. Additionally, a ferrite core having a smaller specific gravity than iron powder, a magnet-dispersion carrier containing a resin as a constitutional component, and a polymerized carrier are being studied. This is because the running torque of a developing machine can be made small by decreasing the mass of a developing agent.

[0027] It is an object of the present invention to provide an image forming method, a process cartridge and an image forming apparatus with which an electrophotographic image having superior image quality and fixing ability over a long period of time is obtainable.

[0028] It is also an object of the invention to provide an image forming method, a process cartridge and an image forming apparatus with which good cleaning characteristics are secured and an electrophotographic image that remains good even in a hot and humid environment is obtainable.

[0029] The above objects of the invention are attained by the invention shown below.

[0030] According to a first aspect of the invention, there is provided an image forming method comprising:

[0031] developing, with a developing agent, an electrostatic latent image formed on a surface of a photoreceptor to form a toner image;

[0032] transferring the toner image onto an image receiving member to form a transferred image; and

[0033] fixing the transferred image onto the image receiving member to form an image,

[0034] wherein the photoreceptor includes a layer that contains a siloxane compound having charge-transferability and a crosslinking structure, with a compound having acid-adsorbing ability being supplied to the surface of the photoreceptor.

[0035] According to a second aspect of the invention, there is provided an image forming method, wherein shape factors SF-1 and SF-2 of the toner respectively satisfy expressions (1) and (2), and the average particle diameter of the toner is 3 m or more and 11 m or less:

[0036] provided that SP-1 (maximum length of diameter)100/4 and SF-2 (peripheral length of projected image)²100/4).

[0037] According to a third aspect of the invention, there is provided a process cartridge used in the image forming method, the process cartridge comprising at least:

[0038] a photoreceptor including a layer that contains a siloxane compound having charge-transferability and a crosslinking structure; and

[0039] supply means for supplying a compound having acid-adsorbing ability to a surface of the photoreceptor.

[0040] According to a fourth aspect of the invention, there is provided an image forming apparatus comprising a photoreceptorr latent image forming apparatus for forming an electrostatic latent image formed on a surface of the photoreceptor, a developing device for developing the latent image using a toner, and a transfer device for transferring the toner image to an image receiving member, wherein the photoreceptor includes at least

[0041] a layer that contains a siloxane compound having charge-transferability and a crosslinking structure, and

[0042] supply means for supplying a compound having acid-adsorbing ability to the surface of the photoreceptor.

[0043] According to a fifth aspect of the invention, there is provided an image forming apparatus, wherein shape factors SF-1 and SF-2 of the toner respectively satisfy expressions (1) and (2), and the average particle diameter of the toner is 3 m or more and 11 m or less:

[0044] provided that SF-1 (maximum length of diameter)²100/4 and SF-2 (peripheral length of projected image)²100/4).

[0045] FIG. 1 is an explanatory view for explaining an embodiment in which a compound having acid-adsorbing ability is supplied to the surface of a photoreceptor.

[0046] FIG. 2 is a sectional view showing one example of the layer structure of a photoreceptor.

[0047] FIG. 3 is a sectional view showing another example of the layer structure of a photoreceptor.

[0048] FIG. 4 is a sectional view showing still another example of the layer structure of a photoreceptor.

[0049] FIG. 5 is a sectional view showing a further example of the layer structure of a photoreceptor.

[0050] FIG. 6 is a sectional view showing a still further example of the layer structure of a photoreceptor.

[0051] FIG. 7 is a schematic structural view showing one example of an embodiment of an image forming apparatus when an image forming method according to the present invention is applied.

[0052] An image forming method, a process cartridge and an image forming apparatus according to the present invention will be explained in detail hereinbelow by way of embodiments.

[0053] The image forming method of the invention comprises developing an electrostatic latent image, formed on the surface of a photoreceptor, by using a developing agent to form a toner image, transferring the toner image to an image receiving member to form a transferred image and fixing the transferred image to the image receiving member to form an image, wherein the photoreceptor is provided with a layer that contains a siloxane compound having charge-transferability and a crosslinking structure and a compound having acid-adsorbing ability is supplied to the surface of the photoreceptor to form an image.

[0054] It is to be noted that the surface of the photoreceptor provided with a layer that contains a siloxane compound having charge-transferability and a crosslinking structure means the whole or a part of a light-sensitive layer of the photoreceptor or a protective layer when the protective layer is formed on the surface of the light-sensitive layer.

[0055] The supplied compound having acid-adsorbing ability is preferably compounds having anion-exchangeability. Specifically, hydrotalcite compounds which are aluminum hydroxide/magnesium, magnesium silicate, aluminum silicate, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum hydroxide/sodium bicarbonate coprecipitates and aluminum hydroxide/magnesium carbonate/calcium carbonate coprecipitates may be used. Among these compounds, hydrotalcite compounds are preferable and, particularly, hydrotalcite compounds having a layer structure are preferably used.

[0056] It is to be noted that the aforementioned compound having acid-adsorbing ability indicates a compound having the ability to adsorb an acid.

[0057] The hydrotalcite compound having a layer structure is a layer compound consisting of a positively charged Mg_2(1-x)Al_2x(OH)₄ layer and a negatively charged CO₃²_x.mH₂O layer and CO₃²_x in the structure is ion-exchangeable and is known to be easily substituted for other anions to thereby adsorb an acid. The hydrotalcite compound may be represented by the following general formula.

[0058] Specific examples (structural general formulae) of the hydrotalcite compound represented by the above general formula may include Mg_0.7Al_0.3(OH)₂(CO₃)_0.15.0.57H₂O; Mg_0.8Al_0.2(OH)₂(CO₃)_0.10.0.61H₂O; Mg_0.75Al_0.25(OH)₂(CO₃)_0.125.0.5OH₂O; Mg_0.8Al_0.2(OH)₂(CO₃)_0.10.0.61H₂O; and Mg_0.83A_0.17(OH)₂(CO₃)_0.085.0.47H₂O.

[0059] As these materials, commercially available materials may be used. With regard to a method of producing a MgAl hydrotalcite compound, the compound may be produced by a known production method as described in each of Japanese Patent Application Publication (JP-B) Nos. 47-32918, 50-30039, 51-29129 and 4-73457. For example, Mg; a chloride or nitrate or nitrate solution or hydroxide of a divalent metal (one type among Zn, Cu and Ni) as required; a chloride or nitrate or nitrate solution of Al or a sodium aluminate solution; and an alkali solution are used to run a reaction, thereby synthesizing a MgAl hydrotalcite compound slurry retaining, for example, a sulfuric acid ion, carbonic acid ion, chlorine ion or nitric acid ion between layers.

[0060] Next, the synthesized MgAl hydrotalcite compound slurry is subjected to a hydrothermal process performed in an aqueous medium under the condition of a temperature of about 120 C. to 250 C. for about 1 to about 40 hours to prepare a MgAl hydrotalcite compound slurry of which the average secondary particle diameter and BET specific surface area are adjusted.

[0061] The obtained MgAl hydrotalcite compound slurry (excluding a carbonic acid ion type) is mixed with a solution containing a silicon type, phosphorous type and boron type oxyacid ion to make an exchange of ions during synthesis between the anion and the silicon type, phosphorous type and boron type oxyacid ion, whereby a hydrotalcite compound which retains, for example, the anion and at least one anion among a sulfuric acid ion, carbonic acid ion, chlorine ion and nitric acid ion and of which the average secondary particle diameter and BET specific surface area are adjusted can be produced.

[0062] In the case of supplying the compound having acid-adsorbing ability such as a hydrotalcite compound to the surface of the photoreceptor, it is preferable to apply a method (1) or a method (2) explained below.

[0063] In the method (1), the compound having acid-adsorbing ability is supplied before the surface of the photoreceptor is uniformly electrified again after the toner image is transferred to the surface of the image receiving member from the surface of the photoreceptor. As to a specific supply means, it is preferable to dispose a cleaning auxiliary member to thereby supply the compound having acid-adsorbing ability through the cleaning auxiliary member.

[0064] In the case of the method (1), various structures are considered as the cleaning auxiliary member. For example, there is a method in which a solid member containing the compound having acid-adsorbing ability is used as a flicker of a brush roller. The content of the compound having acid-adsorbing ability at this time is preferably designed to be 10 mass % or more. When the content is less than 10 mass %, the ability to remove discharge products stuck to the surface layer of the photoreceptor is so low that only insufficient effect is occasionally obtained. Particularly, it is preferable to constitute the flicker only by the compound having acid-adsorbing ability.

[0065] When components other than the compound having acid-adsorbing ability are added, any of inorganic compounds and organic compounds may be used. Examples of these compounds include resins such as PMMA, cerium oxide, strontium titanate and others including known compounds as toner additives.

[0066] FIG. 1 shows an explanatory view for explaining an example in which a solid member of the compound having acid-adsorbing ability is used as a flicker of a brush roller and supplied to the surface of the photoreceptor.

[0067] In the example shown in FIG. 1, a cleaning blade 6 aligned at a fixed position by a cleaning blade-aligning member 7 and a brush roller 4 are brought into contact with a photoreceptor 1. The brush roller 4 is disposed in front of the cleaning blade 6 (the upstream side in the direction A of the rotation of the photoreceptor 1) and is also brought into contact with a flicker 3 which is aligned at a fixed position by a brush aligning roller 5 disposed at a position facing the photoreceptor 1.

[0068] It is most preferable that the cleaning blade 6 be made of urethane rubber and, particularly, polyurethane rubber having an impact resistance of 20 to 60 (under the condition of 20 C. and 505% RH). When the impact resistance is 20 or less, only insufficient cleaning ability is obtained whereas when the impact resistance exceeds 60, the blade tends to be torn off (the material properties of urethane rubber accord to JIS-K6301:1995).

[0069] The shape of the flicker 3 used as the supply means for supplying the compound having acid-adsorbing ability to the surface of the photoreceptor may be selected arbitrarily according to working conditions and any one of a bar-like form, plate-like form and the like may be used.

[0070] Also, as to the size of the flicker 3, it is desirable that the thickness be 3 to 20 mm, the longitudinal length be 5 to 20 mm and the lateral length be shorter than the longitudinal length by 0 to 50 mm in the case of the plate form. Also, it is preferable that the diameter be 3 to 20 mm and the length be shorter than the length of the photoreceptor by 0 to 50 mm in the case of the bar form.

[0071] Moreover, no particular limitation is imposed on a method of molding a supply means such as the flicker 3 as far as a desired shape is obtained and the supply means may be molded by compression molding or the like.

[0072] When the photoreceptor 1 is rotated in the direction of the arrow A on the figure, the brush roller 4 is rotated in a direction opposite or forward to the photoreceptor 1 by the rotary driving force of the photoreceptor 1. By the rotation of the brush roller 4, the flicker 3 is abraded and a powder of the abraded flicker 3 adheres to the brush of the brush roller 4. The attached powder of the flicker 3 is fed to the photoreceptor 1 by the rotation and adheres to the photoreceptor 1. Because the powder of the flicker 3 stuck to the photoreceptor 1 has acid-adsorbing ability, it serves to stick ozone, NOx and the like generated by discharging and the like to the surface of the photoreceptor 1. As a result, the products caused by discharging on the surface of the photoreceptor 1 can be removed efficiently. Also, such an effect ensures that a high quality electrophotographic image can be obtained over a long period of time even if the photoreceptor 1 is used under a high temperature and highly wet environment.

[0073] Also, as a method other than the above methods, a solution in which the compound having acid-adsorbing ability is dissolved or dispersed is made to sink into meshes of woven fabric and the resulting woven fabric may be brought into contact with the surface of the photoreceptor as a web roller instead of the brush roller 4 of FIG. 1. In such a method, tho same effect is obtained.

[0074] In the method (2), the compound having acid-adsorbing ability is added to a developing agent containing a toner which will be explained later and the compound having acid-adsorbing ability is supplied together with the toner with dispersing it on the surface of the photoreceptor when the toner image is formed.

[0075] Such a structure makes it possible to remove products caused by discharging in an efficient manner due to the foregoing acid-adsorbing ability because the compound having acid-adsorbing ability is also fed to the surface of the photoreceptor 1 when the electrostatic latent image formed on the surface of the photoreceptor 1 is developed by the toner. Accordingly, even if the photoreceptor 1 is used under a high temperature and highly wet environment, a high quality electrophotographic image can be obtained over a long period of time. Also, since it is only required to add the compound having acid-adsorbing ability in a developing agent, it is unnecessary to incorporate a newly complicated system and this method may be therefore applied easily to currently used apparatuses.

[0076] The mixing ratio by mass of the toner to the compound having acid-adsorbing ability (toner/compound having acid-adsorbing ability) is preferably 100/0.05 to 100/3 and more preferably 100/0.1 to 100/0.5.

[0077] When the ratio is less than 100/0.05, there is the case where the ability to remove the products caused by discharging which products adhere to the surface layer of the photoreceptor is so weak that only insufficient effect is obtained whereas when the ratio is greater than 100/3, the chargeability of the toner is fluctuated because of the chargeability of the compound. For example, negatively chargeable toners are largely decreased in the amount of charge, affording opportunity for causing defects such as contamination inside of the system and the generation of fogging on a print or copy image.

[0078] The shape of the compound having acid-adsorbing ability is preferably a powder form and the volumetric average particle diameter of this powder is preferably 0.05 to 3 m and more preferably 0.1 to 0.7 m. When this particle diameter is greater than 3 m, the compound itself is freed of the toner to cause contamination inside of the system whereas when the particle diameter is smaller than 0.05 m, the coagulability of the compound is strong, so that the compound cannot be dispersed uniformly on the surface of the toner and there is therefore the case where a desired effect cannot be obtained

[0079] As the developing agent to be used in the image forming method of the invention, known developing agents such as one-component type developing agents constituted only of a toner and tow-component type developing agents constituted of a toner and a carrier may be used. Explanations of the developing agent will be furnished hereinbelow.

[0080] First, the toner is explained.

[0081] In full-color copying machines and printers which have been spread in recent years, there is, for example, the problem that it is required to install a system for supplying an offset-preventive liquid to a heat fixing roll or a fixing belt with the intention of preventing contamination and offset of the toner component in the fusing step. This is contrary to the needs for small-sizing and light-weighting. Also, there is the problem that the offset-preventive liquid is vaporized by heating to exude an offensive odor and also there is the case where it causes contamination in the system. Therefore, the toner preferably contains wax to obtain good fixing ability in the condition that substantially no offset-preventive liquid is present.

[0082] The wax is preferably melted at 70 to 140 C. and has a melt viscosity of preferably 1 to 200 cp and more preferably 1 to 100 cp.

[0083] When the melt temperature is less than 70 C., the transformation temperature of the wax is too low and there is therefore the case where the blocking resistance is deteriorated and the developing ability is impaired when the temperature of a copying machine is raised. When the melt temperature exceeds 140 C., the transformation temperature of the wax becomes too high and fixing,treatment must be therefore carried out, which is undesirable from the viewpoint of energy saving.

[0084] Also, the melt viscosity higher than 200 cp sometimes causes reduced elution from the toner and insufficient fixing releasability.

[0085] The amount of the wax to be added to the toner is 1 to 15 mass % and more preferably 3 to 10 mass % based on the toner particles (a binder resin and a colorant).

[0086] When the amount of the wax is less than 1 mass %, sufficient fixing latitude (the temperature range of a fixing roll or a fixing belt at which temperatures an image can be fixed without the offset of the toner) is not obtained. On the other hand, when the amount of the wax is greater than 15 mass %, the amount of the wax which is desorbed from the toner and freed is increased and contamination to the photoreceptor tends to be caused. Also, the powder fluidity of the toner is impaired and there is the case where the free wax adheres to the surface of the photoreceptor forming an electrostatic latent image and therefore the electrostatic latent image is not always formed exactly. Also, because wax is inferior in transparency to a binder resin and the transparency of an image such as an OHP image is reduced, resulting in the formation of a dark projected image.

[0087] As the wax, paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fisher-Tropsch wax and its derivatives and polyolefin wax and its derivatives may be used.

[0088] Here, the derivatives include oxides, polymers with a vinyl monomer and graft modified products.

[0089] Besides the above compounds, alcohols, fatty acids, vegetable waxes, animal waxes, mineral waxes, ester waxes and acid amides may be utilized.

[0090] As toner particles constituting the toner to be used in the image forming apparatus of the invention, a known one consisting of at least a colorant (coloring agent) and a binder resin is used.

[0091] When the toner is produced by a kneading and crushing method, examples of the binder resin may include homopolymers or copolymers of styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene and isoprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl acetate; -methylene aliphatic monocarboxylic acid esters such as methylacrylate, ethylacrylate, butylacrylate, dodecylacrylate, octylacrylate, phenylacrylate, methylmethacrylate, ethylmethacrylate, butylmethacrylate and dodecylmethacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone.

[0092] Particularly typical examples of the binder resin may include polystyrene, styrene/alkylacrylate copolymers, styrene/alkylmethacrylate copolymers, styrene/acrylonitrile copolymers, styrene/butadiene copolymers, styrene/maleic acid anhydride copolymers, polyethylene and polypropylene. Further, polyester, polyurethane, epoxyresins, siliconresins, polyamide, denatured rosin, paraffin and waxes may be exemplified.

[0093] Particularly, the case of using polyester among these compounds as the binder resin is effective. For example, a linear polyester resin comprising a polymerization condensation product containing bisphenol A and polyvalent aromatic carboxylic acid as major monomer components is desirably used.

[0094] The above polyester resin is synthesized by polymerization condensation from a polyol component and a polycarboxylic acid component.

[0095] Examples of the polyol component to be used include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane dimethanol, hydrogenated bisphenol A, bisphenol-A ethylene oxide adducts and bisphenol-A propylene oxide adducts.

[0096] Examples of the polycarboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic:acid, dodecenylsuccinic acid, trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexatricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropanetetramethylenecarboxylic acid and their anhydrides.

[0097] Among the above compounds, resins having a softening point of 90 to 150 C., a glass transition temperature of 55 to 75 C., a number average molecular weight of 2000 to 6000, a mass average molecular weight of 8000 to 150000, an acid value of 5 to 30 and a hydroxyl value of 5 to 40 may be used particularly preferably.

[0098] Also, as the colorant of the toner particle, carbon black, nigrosine, Aniline Blue, Chalcoil Blue, Chrome Yellow, Ultramarine Blue, Du Pond Oil Red, Quinoline Yellow, Methylene Blue chloride, Phthalocyanine Blue, Malachite GreenOxalate, Lump Slack, Rose Bengale, C.I. PigmentRed 48:1, C.I. PigmentRed 122, C.I. PigmentRed 57:1, C.I. PigmentRed 238, C.I. PigmentYellow 97, C.I. PigmentYellow 12, C.I. PigmentYellow 180, C.I. PigmentBlue 15:1 and C.I. PigmentBlue 15:3 may be given as typical examples.

[0099] The toner may be constituted by compounding one or more additives such as a charge control agent used for charge control besides the toner particles (the binder resin and the colorants such as carbon black) and the foregoing wax. Also, a petroleum type resin may be contained to satisfy the crushing ability and thermal preserving ability of the toner.

[0100] The petroleum resin is those synthesized using, as starting material, diolefins and monoolefins contained in cracked oil fractions by-produced in an ethylene plant producing ethylene, propylene and the like by steam cracking of petroleums.

[0101] As a method for adding the above additives to the toner particles, a kneading treating method is preferably applied. The kneading treatment may be carried out using various heat kneading machines. As the heat kneading machine, a three-roll type, one-shaft screw type, two-shaft screw type and Banbury mixer type are known. However, the heat kneading machine is not limited to these types but known machines may be used.

[0102] Also, a method of producing the toner is optional.

[0103] The kneaded product is crushed using, for example, a micronizer, Ulmax, Jet-o-mizer, KTM(cryptone) and turbo mill. Further, an I-type Jet-Mill may be used. For classification, an elbow jet using a Coanda effect and air-separation type Acucut may be used. However,, the classifier is not limited these types but known classifiers may be used.

[0104] The toner maybe produced by a polymerization method. The polymerization method primarily includes a suspension polymerization method and an,emulsion polymerization coagulation method. Particularly, the emulsion polymerization coagulation method is advantageous to control the shape of the toner particle because the shape of the toner can be arbitrarily controlled in a range from an undefined form to a spherical form by selecting the condition of heating temperature.

[0105] In the emulsion polymerization coagulation method, a resin dispersion is prepared by emulsion polymerization, a colorant dispersion in which a colorant is dispersed in a solvent and a releasing agent dispersion in which a releasing agent is dispersed in a solvent are prepared separately from the above resin dispersion and these dispersions are mixed to form coagulated particles having a particle diameter corresponding to that of the toner particle (coagulating step), followed by heating to unite (uniting step) to obtain toner particles.

[0106] It is to be noted that the resin dispersion is produced by dispersing resin particles made of at least resins used as the binder of the toner particles.

[0107] Given as examples of the resin in the above resin particles are thermoplastic resins. Specific examples of these thermoplastic resins include homopolymers or copolymers of styrenes such as styrene, parachlorostyrene and -methylstyrene (styrene type resins); homopolymers and copolymers of esters having a vinyl group such as methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, laurylacrylate, 2-ethylhexylacrylate, methylmethacrylate, ethylmethacrylate, n-propylmethacrylate, laurylmethacrylate and 2-ethylhexylmethacrylate (vinyl type resins); homopolymers and copolymers of vinylnitriles such as acrylonitrile and methacrylonitrile (vinyl type resins); homopolymers and copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl type resins); homopolymers and copolymers of ketones such as vinyl methyl ketons, vinyl ethyl ketone and vinyl isopropenyl ketone (vinyl type resins); homopolymers and copolymers of olefins such as ethylene, propylene, butadiene and isoprene (olefin type resins); non-vinyl condensed type resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins and polyether resins and graft polymers of these non-vinyl condensed type resins and vinyl type monomers.

[0108] These resins may be used either singly or in combinations of two or more. The volumetric average particle diameter of the above resin particles is generally 1 m or less and preferably 0.01 to 1 m.

[0109] The above colorant dispersion is produced by dispersing at least a colorant.

[0110] Examples of the colorant include various pigments such as carbon black, Chrome Yellow, Hansa Yellow, Benzidine Yellow, Indanthrene Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Watchung Red, Permanent Red, Brilliant Carmine 3B, Brilliant Carmine 6B, Du Pont K.K. Oil Red, Pyrazolone Red, Lithol Red, Rhodamine B Lake, Lake Red C, Rose Bengale, Aniline Blue, ultramarine Blue, Chalcoil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green and malachite Green Oxalate; and various dyes such as an acridine type, xanthene type, azo type, benzoquinone type, azine type, anthraquinone type, dioxazine type, thiazine type, azomethine type, indigo type, thioindigo type, phthalocyanine type, aniline black type, polymethine type, triphenylmethane type, diphenylmethane type, thiazole type and xanthene type. These colorants may be used either singly or in combinations of two or more. The volumetric average particle diameter (hereinafter simply called average particle diameter) of the colorant is generally 1 m or less, preferably 0.5 m or less and particularly preferably 0.01 to 0.5 m.

[0111] The above releasing agent dispersion is produced by dispersing at least a releasing agent. The releasing agent to be used is preferably releasing agents having poor compatibility with the binder resin of the toner particle. Specific examples of the releasing agent include paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fisher-Tropsch wax and its derivatives and polyolefin wax and its derivatives.

[0112] Here, the foregoing derivatives include oxides, polymers with vinyl monomers and graft denatured products.

[0113] Besides the above compounds, alcohols, fatty acids, vegetable waxes, animal waxes, mineral waxes, ester waxes, acid amides and the like may be utilized. In the invention, these releasing agents may be used either singly or in combinations of two or more. The average particle diameter of the releasing agent particles is preferably 1 m or less and more preferably 0.01 to 1 m.

[0114] No particular limitation is imposed on the combination of the resin of the resin particles, the colorant and the releasing agent. A preferable combination may be freely selected optionally according to the object and used.

[0115] Also, other components (particles) such as internal additives, charge control agents, inorganic particles, organic particles, lubricants and abrasives maybe dispersed in at least one of the resin particle dispersion, the colorant dispersion and the releasing agent dispersion according to the purpose. In this case, other components (particles) may be dispersed in any one of the resin particle dispersion, the colorant dispersion and the releasing agent dispersion or a dispersion prepared by dispersing other components (particles) may be compounded in a mixed solution prepared by mixing the resin particle dispersion, the colorant dispersion and the releasing agent dispersion.

[0116] Given as examples of the dispersion media used for the resin particle dispersion, the colorant dispersion, the releasing agent dispersion and the other components are water-type media Examples of the water-type media include water such as distilled water and ion exchange water and alcohols. These media may be, used either singly or in combinations of two or more. Preferable examples of the combination include a combination of distilled water and ion exchange water. The addition of a surfactant is advantageous not only from the viewpoint of the stability of each dispersed particle of the resin particle dispersion, the colorant dispersion and the releasing agent dispersion in a water-type medium and therefore from the viewpoint of the preserving ability of these dispersions but also from the viewpoint of the stability of the coagulated particles in the coagulation step.

[0117] Also, rosin, rosin derivatives, coupling agents, high molecular dispersants and the like may be added as dispersants to be added to more stabilize the dispersion stability of the colorant in a water-type medium and to decrease the energy of the colorant in the toner.

[0118] The inorganic metal salt having di- or more-valent charge and used as the coagulant in the coagulation step is obtained by dissolving a usual inorganic metal compound or its polymer in a resin fine particle dispersion.

[0119] Here, the metal elements constituting the inorganic metal salt are those which have di- or more-valent charge, belong to 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B and 3B groups in the periodic table (long periodic table) and dissolve in an ion state in the coagulated system of resin fine particles.

[0120] Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and aluminum sulfate; and inorganic metal salt polymers such as aluminum polychloride, aluminum polyhydroxide and calcium polysulfide. Among these compounds, aluminum salts and polymers of these salts are preferable.

[0121] In the invention, it is preferable to add and mix a surfactant in a water-type medium in advance to improve the dispersion stability of coagulated particles.

[0122] There has been an increased demand for higher image quality in recent yeas and particularly in the formation of a color image, there is a significant tendency to develop smaller-sized toner particles having a more uniform particle diameter with the intention of attain a highly accurate image. However, when a toner particle is small-sized, force other than electrostatic force, for example, van der Waals force is made relatively high and there is the case where the transferability (transfer efficiency) is impaired. It is therefore necessary to prevent the transferability from being impaired. Therefore, the toner particle is preferably spherical to improve the transferability. Further, in the case of a spherical form, concave portions are reduced on the surface of the toner particle and the compound having acid-adsorbing ability and dispersed on its surface tends to exist in the concave portions. The probability that the compound having acid-adsorbing ability on the surface of the toner particles is in contact with the surface of the photoreceptor in a developing section is improved and the effect of removing products caused by discharging is therefore more improved. So the spherical form is desirable.

[0123] When a preferable shape of the toner particle is expressed by the shape factors SF-1 and SF-2, the following equations (1) and (2) are preferably fulfilled. It is to be noted that the following equations (1) and (2) are preferably fulfilled when the foregoing method (2) is applied.

[0124] When SF-1 is larger than 140 or SF-2 is larger than 120, there is the case where the transferability is impaired. A more preferable range is the following (3) and (4).

[0125] Also, the average particle diameter of the toner particle is preferably 3 to 11 m to improve image quality. When the particle diameter is less than 3 m, there is the case where the fluidity and transferability of the toner are impaired. When the particle diameter is larger than 11 m, only insufficient image quality is obtained.

[0126] As the core material of the carrier in the case of using a two-component type developing agent, known iron powder, ferrite, magnetite and polymerized cores may be properly used. Among these materials, ferrite and polymer cores having a low specific gravity are preferable.

[0127] Examples of the resin used when a resin coating layer is formed on the core material include polyolefin type resins such as polyethylene and polypropylene; polyvinyl type resins and polyvinylidene type resins such as polystyrene, acryl resins, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinylbutyral, polyvinyl chloride, polyvinylcarbazole, polyvinyl ether and polyvinyl ketone; vinyl chloride/vinyl acetate copolymers; styrene/acrylic acid copolymers; straight silicon resins comprising organosiloxane bonds and denatured products of these resins; fluororesins such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride and polychlorotrifluoroethylene; polyesters; polyurethanes; polycarbonates; amino resins such as urea-formaldehyde resins; and epoxy resins. These resins maybe used either singly or by mixing plural resins. Fluororesins which are polymerized while including a fluorine type monomer containing a fluorine atom and have a small surface energy are preferable. The amount of resin coating on the surface of the core is 0.8 to 5 mass % and preferably 1.5 to 3.5 mass %.

[0128] The resistance of the whole of the magnetic carrier formed in the above manner when it is in the state of a magnetic brush is preferably 10⁸ to 10¹³ cm under an electric field of 10⁴ V/cm. When the resistance of the magnetic carrier is less than 10⁶ cm, the carrier adheres to the image portion on the surface of the photoreceptor, and also, a brush mark tends to appear. On the other hand, the resistance of the magnetic carrier exceeds 110¹³ cm, an edge effect becomes seen, causing reduced image qualities.

[0129] In order to make the resistance of the resin coating layer fall in the above range, a conductive powder may be added to the resin coating layer. As the conductive powder to be added to the resin coating layer, those having a resistance of 110⁶ cm or less are preferably used. Specific examples of these powders include carbon black,, zinc oxide, titanium oxide, tin oxide, iron oxide and titanium black. The content of the conductive powder is generally 3 to 40 mass % and preferably 5 to 20 mass % based on all coating amount.

[0130] Here, the volumetric specific resistance (resistance of the resin coating layer) is preferably measured in the following manner.

[0131] First, the samples are placed in such a manner as to form a flat layer about 1 mm to 3 mm in thickness on the under pole plate of a measuring jig which is a pair of circular pole plates (made of copper) having an area of 20 cm² which plates are connected to an electrometer (trademark: KEITHLEY 610C, manufactured by Keithley Instruments, Inc.) and a high tension power source (trademark: FLUKE 415B, manufactured by Fluke Corp.). Then, the upper pole plate is placed on the samples and thereafter a 4 kg weight is put on the upper pole plate to eliminate clearances between each sample. In this condition, the thickness of the sample layer is measured. Then, the value of current is measured by applying voltage to both pole plates to calculate the volumetric specific resistance based on the following general formula. $\mathrm{Volumetric}\mathrm{specific}\mathrm{resistance}=\mathrm{Applied}\mathrm{voltage}20\left(\mathrm{Current}-\mathrm{Initial}\mathrm{current}\right)\mathrm{Thickness}\mathrm{of}\mathrm{Sample}$

[0132] where the Initial current indicates the value of current when the applied voltage is 0 and the Current indicates the value of current measured.

[0133] Examples of a method for forming the resin coating layer on the surface of the core material include a dipping method in which the core material is dipped in a resin coating layer-forming solution prepared by dispersing a conductive powder in a solvent in which a resin is dissolved, a spray method in which a resin coating layer-forming solution is sprayed on the surface of the core material, a fluidized bed method in which a resin coating layer-forming solution is sprayed on the surface of the core material which is put in a floated state by flowing air and a kneader coater method in which the core material and a resin coating layer-forming solution are mixed in a kneader coater, followed by removing solvents. No particular limitation is imposed on the solvent used for the resin coating layer-forming solution as far as it dissolves the resin. For example, aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; and ethers such as tetrahydrofuran and dioxane may be used. A sand mill, a homomixer or the like may be used for the dispersion of the conductive powder.

[0134] An inorganic powder and a resin powder may be used either respectively or in combination to more improve the long term preserving ability, fluidity, developing ability and transferability of the toner.

[0135] Examples of the inorganic powder include carbon black, silica, alumina, titania and zinc oxide.

[0136] Examples of the resin powder include spherical particles of PMMA, nylon, melamine, benzoguanamine, fluorine types and the like and amorphous powders of vinylidene chloride, fatty acid metal salts and the like. The amount of each powder to be added is 0.1 to 4 mass % and more preferably 0.3 to 3 mass % based on the mass of the toner.

[0137] As mentioned above, when a hydrotalcite compound is used as the compound having acid-adsorbing ability, the adhesion (contamination) of the hydrotalcite compound which adhesion is originated from irregularities and scratches caused by partial wear on the surface of the photoreceptor is easily caused and therefore such a defect that black points, white points and black lines originated from that adhesion appear on an image tends to be caused in the case of a conventional photoreceptor type.

[0138] For this, in the image forming method of the invention, the photoreceptor provided with the layer having charge-transferability and containing a siloxane compound having a crosslinking structure is used.

[0139] The details of the photoreceptor will be explained hereinbelow.

[0140] FIG. 2 to FIG. 6 show typical sectional views of the photoreceptor used in the image forming method of the invention. FIG. 2 to FIG. 4 show the case where the light-sensitive layer has a laminate structure and FIG. 5 and FIG. 6 show the case where light-sensitive layer has a monolayer structure.

[0141] In the example of FIG. 2, an intermediate layer 21 is disposed on the surface of a conductive support 24 and a charge generation layer 22 and a charge transfer layer 23 are disposed on the intermediate layer 21. The example of FIG. 3 has the same structure as the example of FIG. 2 except that a protective layer 25 is further formed on the charge transfer layer 23. In FIG. 4, an intermediate layer 21 is formed on the surface of the conductive support 24, a, charge transfer layer 23 and a charge generation layer 22 are disposed on the intermediate layer 21 and a protective layer 25 is further formed on the charge transfer layer 23. In FIG. 2 to FIG. 4, the intermediate layer may be formed or not formed.

[0142] The charge transfer layer 23 in the example of FIG. 2 and the protective layer 25 in FIG. 3 and FIG. 4 respectively correspond to the layer having charge transferability and containing a siloxane compound having a crosslinking structure.

[0143] In the example of FIG. 5, the intermediate layer 21 is disposed on the surface of the conductive support 24 and a charge generation/charge transfer layer 26 is disposed on the intermediate layer 21. The example of FIG. 6 has the same structure as the example of FIG. 5 except that a protective layer 25 is further formed on the surface.

[0144] The charge generation/charge transfer layer 26 in the example of FIG. 5 and the protective layer 25 in rig. 6 respectively correspond to the layer having charge-transferability and containing a siloxane compound having a crosslinking structure.

[0145] As the conductive support 24, those made of aluminum, SUS or the like and having a proper form such as a drum form, sheet form and plate form are used. However, the conductive support 24 is not limited to these materials.

[0146] The outer periphery of the conductive support 24 may be processed by anodic oxidation treatment to form an anodic oxide film as the intermediate layer 21. The anodic oxidation treatment in the case of using aluminum for the conductive support 24 may be performed by running anodic oxidation using the aluminum as the anode in an electrolytic solution, whereby an anodic oxide film can be formed on the surface. As the electrolytic solution used at this time, a sulfuric acid solution, oxalic acid solution or the like may be used.

[0147] In the meantime, the anodic oxide film as it stands is porous and chemically active and is therefore easily soiled and its resistance is largely fluctuated by environmental variation. It is therefore preferable to treat the oxide film by running a hydration reaction using pressure steam or in a boiled water (salts of metals such as nickel maybe added) to cause volumetric expansion and to convert the oxide into a more stable hydrate oxide, thereby carrying out pore-sealing treatment for sealing micropores of the oxide film.

[0148] The film thickness of the anodic oxide film is preferably 0.3 to 15 m. When the film thickness is less than 0.3 m, the barrier characteristics against intrusion is so poor that only insufficient effect is obtained. On the other hand, a film thickness exceeding 15 m causes a rise of residual potential in repeated use.

[0149] In addition, the anodic oxide film may be processed by acid solution treatment or boehmite treatment.

[0150] The acid solution treatment is carried out using an acidic processing solution consisting of phosphoric acid, chromic acid or hydrofluoric acid in the following manner.

[0151] Each proportion of phosphoric acid, chromic acid and hydrofluoric acid is in a range from 10 to 11 mass % in the case of phosphoric acid, in a range from 3 to 5 mass % in the case of chromic acid and in a range from 0.5 to 2 mass % in the case of hydrofluoric acid. The total concentration of these acids is preferably in-a range from 13.5 to 18 mass %. The treating temperature is 42 to 48 C. It is possible to form a thick film at a higher rate by maintaining high treatment temperature. The film thickness of the coating film is preferably 0.3 to 15 m. When the film thickness is less than 0.3 m, the barrier characteristics against intrusion is so poor that only insufficient effect is obtained. On the other hand, a film thickness exceeding 15 m causes a rise of residual potential in repeated use.

[0152] The boehmite treatment may be carried out by dipping the anodic oxide film in pure water kept at 90 to 100 C. for 5 to 60 minutes or by bringing the anodic oxide film into contact with 90 to 120 C. heating steam for 5 to 60 minutes. The film thickness of the coating film formed by the boehmite treatment is preferably 0.1 to 5 m.

[0153] After the boehmite treatment, anodic oxidation treatment may be carried out using an electrolytic solution reduced in coating film solubility such as adipic acid, boric acid, borates, phosphates, phthalates, maleates, benzoates, tartarates and citrates.

[0154] In the case of using the photoreceptor in a laser printer, the surface of the conductive support is preferably roughened so as to have a surface roughness of 0.04 m to 0.5 m in terms of arithmetic mean roughness Ra to prevent an interference fringe generated when laser light is applied. As a surface roughing method, wet honing performed by spraying abrasives suspended in water on the conductive support or centerless grinding in which the conductive support is pressed to rotating grinding stone to carry out grinding processing continuously is preferable. When Ra is less than 0.04 m, the surface of the conductive support is close to a mirror surface and the effect of preventing an interference fringe is not therefore obtained, whereas when Ra exceeds 0.5 m, an image quality is roughened even if the coating film is formed according to the invention, and therefore a surface roughness out of the above defined range is unsuitable.

[0155] It is to be noted that when non-interference light is used as a light source, the surface roughing for preventing an interference fringe is not particularly required and the generation of defects caused by the irregularities on the surface of the conductive support can be prevented, showing that the use of non-interference light is suitable for achieving longer life

[0156] Examples of materials used for the intermediate layer 21 besides the above anodic oxidation film include organic metal compounds such as organic zirconium compounds, e.g., zirconium chelate compounds, zirconium alkoxide compounds and zirconium coupling agents; organic titanium compounds, e.g., titanium chelate compounds, titanium alkoxide compounds and titanate coupling agents; organic aluminum compounds, e.g., aluminum chelate compounds and aluminum coupling agents; antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds and aluminum zirconium alkoxide compounds. Among these compounds, organic zirconium compounds, organic titanium compounds and organic aluminum compounds are preferably used because these compounds are decreased in residual potential and exhibit good electrophotographic characteristics.

[0157] Also, these compounds may be used by combining with a silane coupling agent such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, -glycidoxypropyltrimethoxysilane, -methacryloxypropyltrimethoxysilane, -aminopropyltriethoxysilane, -chloropropyltrimethoxysilane, -2-aminoethylaminopropyltrimethoxysilane, -mercaptopropyltrimethoxysilane, -ureidopropyltriethoxysilane or -3,4-epoxycyclohexyltrimethoxysilane.

[0158] Further, known binding resins which are conventionally used in the intermediate layer 21 maybe used. Examples of these binding resins include polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylenoxide, ethyl cellulose, methyl cellulose, ethylene/acrylic acid copolymers, polyamides, polyimides, casein, gelatin, polyethylene, polyesters, phenol resins, vinyl chloride/vinyl acetate copolymers, epoxy reins, polyvinylpyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid and polyacrylic acid. The proportion of these compounds may be optionally designed according the need.

[0159] Also, in the intermediate 21, an electron-transferable pigment may be used by mixing/dispersing it in an organic solvent. Examples of the electron-transferable pigment include organic pigments such as perylene pigments, bisbenzimidazoleperylene pigments, polycyclic quinone pigments, indigo pigments and quinacridone pigments; organic pigments such as bisazo pigments and phthalocyanine pigments having electron-attractive substituents such as a cyano group, nitro group, nitroso group and halogen atom; and inorganic pigments such as zinc oxide and titanium oxide as described in JP-A No. 47-30330. Among these pigments, perylene pigments, bisbenzimidazoleperylene pigments and polycyclic quinone pigments have high electron-transferability and are therefore desirably used. The electron-transferable pigments are used in an amount of 95 mass % or less and preferably 90 mass % or less based on the solid component of the intermediate layer 21 because the strength of the intermediate layer 21 is lowered, causing defects of the coating film if the amount is excessive.

[0160] As a method of mixing/dispersing the electron-transferable pigment, usual methods using a ball mill, roll mill, sand mill, attritor or ultrasonic wave are applied. The mixing and dispersing operation is carried out in an organic solvent. As the organic solvent, any solvent may be used as far as it dissolves organic metal compounds and resins and is neither gelled nor coagulated when mixing/dispersing the electron-transferable pigment.

[0161] For example, usual organic solvents such as methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene may be used either singly or by mixing two or more.

[0162] The thickness of the intermediate layer 21 is generally 0.1 to 20 m and preferably 0.2 to 10 m. As a coating method used when disposing the intermediate 21, usual methods such as a blade coating method, wire bar coating method, spray coating method, dip coating method, beads coating method, air knife coating method and curtain coating method may be used.

[0163] The resulting coating film is dried to obtain the intermediate layer 21. The drying is usually carried out at temperatures enabling solvents to be vaporized and a film to be formed. Particularly, the substrate processed by the above acidic solution treatment and boehmite treatment tends to have insufficient ability to conceal defects and it is therefore to form the intermediate layer 21.

[0164] Next, explanations will be furnished as to the protective layer 25. The protective layer of the electrophotographic photoreceptor to be used in the image forming method of the invention has charge-transferability and contains a siloxane compound having a crosslinking structure. The siloxane compounds are represented by the, following general formula (1).

[0165] where G represents an inorganic glassy network subgroup, D represents a flexible sub-unit and F represents a charge-transferable sub-unit.

[0166] Examples of F in the general formula (1) include, as a structure having photo carrier transferability, triarylamine type compounds, benzidine type compounds, arylalkane type compounds, aryl substituted ethylene type compounds, stilbene type compounds, anthracene type compounds, hydrazone type compounds, quinone type compounds, fluorenone compounds, xanthone type compounds, benzophenone type compounds, cyanovinyl type compounds and ethylene type compounds.

[0167] G in the general formula (1) is preferably a Si group having reactivity and gives rise to a crosslinking reaction among the parts of G to form a three-dimensional SiOSi bond, namely, an inorganic glassy network.

[0168] D in the general formula (1) serves to bond the above F for imparting charge-transferability, directly with the three-dimensional inorganic glassy network. D also works to impart a moderate flexibility to the inorganic glassy network which has high hardness, but is fragile in some respects thereby improving the strength required for a film.

[0169] To state in detail, as D, divalent hydrocarbon groups represented by C_nH_2n, C_nH_(2n-2) or C_nH_(2n-4) in the case where n represents an integer from 1 to 15, COO, S, O, CH₂C₆H₄, NCH, (C₆H₄)-(C₆H₄), combinations of these groups and those obtained by introducing'substituents may be used.

[0170] The compound represented by the general formula (1) may be obtained by a sol-gel method as described in JP-A No. 3-191358, for example.

[0171] Also, the compound represented by the general formula (1) preferably has a structure represented by the general formula (2).

[0172] wherein Ar¹ to Ar⁴ respectively represent a substituted or unsubstituted aryl group, Ar⁵ represents a substituted or unsubstituted aryl group or an arylene group, provided that one to four groups among Ar³ to Ar⁵ have a connector which can be connected to a connecting group represented by -D-G-D represents a flexible sub-unit, G represents an inorganic glassy network subgroup and is derived from a substituted silicon group having a hydrolyzable group represented by, particularly, Si(R₁)_(3-a)Q₀ where R₁ represents a hydrogen, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group and a denotes an integer from 1 to 3, and b denotes an integer from 1 to 4.

[0173] The compound represented by the general formula (2) exhibits particularly excellent high positive hole transferability and mechanical characteristics. Ar¹ to Ar⁴ in the general formula (2) respectively represent a substituted or unsubstituted aryl group and specifically, the following structures are exemplified.

[0174] Ar in the above general formula is selected from the structures shown below.

[0175] wherein R₆ is selected from a hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or with an alkoxy group having 1 to 4 carbon atoms or an unsubstituted phenyl group and an aralkyl group having 7 to 10 carbon atoms, R₇ to R₁₁ are respectively selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms and a halogen, m and s respectively denote 0 or 1 and X represents a substituent represented by -D-G which has been already shown in the definition of the general formula (1).

[0176] Also, Z is selected from the structures shown below.

[0177] wherein R₁₂ and R₁₃ respectively represent any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms and a halogen atom, q and r respectively denote an integer from 1 to 10 and t and t respectively represent an integer from 1 to 3.

[0178] W is selected from the following groups.

[0179] Wherein s denotes an integer from 0 to 3.

[0180] As specific examples of the structure of Ar⁵ in the general formula (2), any one of the structures of Ar¹ to Ar⁴ wherein m1 when k0 and any one of the structures of Ar¹ to Ar⁴ wherein m0 when k1 are given.

[0181] Specific examples of the compound represented by the general formula (2) are shown collectively in the following table by specifying each substituent. It is needless to say that the invention is not limited to the following compounds. Incidentally, the symbol obtained by adding the prefix (2)- to the number of each compound in the table shown below is designated as the symbol of the exemplified compound in this specification (for example, a compound having the number 27 is expressed as an exemplified compound (2)-27).

TABLE 1
Compound	k	Ar1	Ar2	Ar3	Ar4
1	0
2	0
3	0
4	0
5	0
Compound	k	Ar5	X
1	0		CHNCH2Si(OMe)2Me
2	0		CHN(CH2)3Si(OMe)3
3	0		CHN(CH2)3Si(OEt)3
4	0
5	0

[0182]

TABLE 2
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
6	0						O(CH2)3Si(OMe)3
7	0						O(CH2)3SiMe(OMe)2
8	0						O(CH2)3Si(OEt)3
9	0						CH2O(CH2)3Si(OMe)3
10	0						(CH2)3O(CH2)3Si(OMe)3

[0183]

TABLE 3
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
11	0						COO(CH2)3Si(OMe)3
12	0						CH2COO(CH2)3Si(OMe)3
13	0						(CH2)2COO(CH2)3Si(OMe)3
14	0						COO(CH2)3Si(OMe)3
15	0						CH2COO(CH2)3Si(OMe)3

[0184]

TABLE 4
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
16	0						(CH2)2COO(CH2)3Si(OMe)3
17	0						COO(CH2)3Si(OMe)3
18	0						CH2COO(CH2)3Si(OMe)3
19	0						(CH2)2COO(CH2)3Si(OMe)3
20	0						COO(CH2)3Si(OMe)3

[0185]

TABLE 5
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
21	0						COOCH2C6H4Si(OMe)3
22	0						COOCH2C6H4(CH2)3Si(OMe)3
23	0						CH2COO(CH2)3Si(OMe)3
24	0						CH2COOCH2C6H4Si(OMe)3
25	0						CH2COOCH2C6H4(CH2)2Si(OMe)3

[0186]

TABLE 6
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
26	0						(CH2)3COO(CH2)3Si(OMe)3
27	0						(CH2)3COOCH2_C6H4Si(OMe)3
28	0						CH2COOCH2C6H4(CH2)2Si(OMe)3
29	0						COO(CH2)3Si(OMe)3
30	0						COOCH2C6H4(CH2)3Si(OMe)3

[0187]

TABLE 7
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
31	0						(CH2)3COO(CH2)3Si(OMe)3
32	0						(CH2)2COOCH2C6H4(CH2)2Si(OMe)3
33	0						COO(CH2)3Si(OMe)3
34	0						COOCH2_C6H4Si(OMe)3
35	0						COO(CH2)3Si(OMe)3

[0188]

TABLE 8
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
36	0						COO(CH2)3Si(OMe)3
37	0						COO(CH2)3Si(OMe)3
38	0						COOCH2C6H4(CH2)3Si(OMe)3
39	0						CH2COO(CH2)3Si(OMe)3
40	0						CH2COOCH2C6H4(CH2)3Si(OMe)3

[0189]

TABLE 9
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
41	0						(CH2)3COO(CH2)3Si(OMe)3
42	0						(CH2)2COOCH2C6H4(CH2)3Si(OMe)3
43	0						COO(CH2)3Si(OMe)3
44	0						COOCH2C6H4(CH2)3Si(OMe)3
45	0						CH2COO(CH2)3Si(OMe)3

[0190]

TABLE 10
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
46	0						CH2COOCH2C6H4(CH2)3Si(OMe)3
47	0						(CH2)3COO(CH2)3Si(OMe)3
48	0						(CH2)3COOCH2C6H4(CH2)3Si(OMe)3
49	0						CHCHSi(OEt)3
50	0						CHCHCH2Si(OEt)3

[0191]

TABLE 11
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
51	0						CHCH(CH2)2Si(OMe)3
52	0						CHCH(CH2)3SiMe(OMe)2
53	0						CHCHCH2Si(OMe)2Me
54	0						CHCH(CH2)3Si(OEt)3
55	0						CHCH(CH2)3Si(OMe)3

[0192]

TABLE 12
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
56	0						CHCHC6H4Si(OMe)3
57	0						CHCHC6H4(CH2)2Si(OMe)3
58	0						CHCH(CH2)3Si(OMe)3
59	0						(CH2)3Si(OEt)3
60	0						(CH2)3Si(OEt)3

[0193]

TABLE 13
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
61	0						(CH2)4Si(OMe)3
62	0						(CH2)4SiMe(OMe)2
63	0						(CH2)4SiMe2(OMe)
64	0						(CH2)4Si(OEt)3
65	0						(CH2)6SiMe(OEt)2

[0194]

TABLE 14
Compound	k	Ar1	Ar2	Ar3
66	0
67	0
68	0
69	1
70	1
Compound	k	Ar4	Ar5	X
66	0			(CH2)12Si(OMe)3
67	0			(CH2)3C6H4(CH2)3Si(OMe)3
68	0			C2H4C4H6Si(OMe)3
69	1			CHN(CH2)3Si(OMe)3
70	1			CHN(CH2)3Si(OMe)3

[0195]

TABLE 15
Compound	k	Ar1	Ar2	Ar3
71	1
72	1
73	1
74	1
75	1
Compound	k	Ar4	Ar5	X
71	1			CHN(CH2)3Si(OMe)3
72	1			CHN(CH2)3Si(OMe)3
73	1			CHN(CH2)3Si(OMe)3
74	1
75	1			O(CH2)3Si(OMe)3

[0196]

TABLE 16
Compound	k	Ar1	Ar2	Ar3
76	1
77	1
78	1
79	1
80	1
Compound	k	Ar4	Ar5	X
76	1			O(CH2)3Si(OEt)3
77	1			CH2O(CH2)3Si(OMe)3
78	1			(CH2)3O(CH2)3Si(OMe)3
79	1			(CH2)4Si(OMe)3
80	1			(CH2)2C6H4Si(OMe)3

[0197]

TABLE 17
Compound	k	Ar1	Ar2	Ar3
81	1
82	1
83	1
84	1
85	1
Compound	k	Ar4	Ar5	X
81	1			(CH2)4Si(OMe)3
82	1			(CH2)4Si(OMe)3
83	1			(CH2)4Si(OMe)3
84	1			CHCH(CH2)2Si(OMe)3
85	1			CHCH(CH2)2Si(OMe)3

[0198]

TABLE 18
Compound	k	Ar1	Ar2	Ar3
86	1
87	1
88	1
89	0
90	0
Compound	k	Ar4	Ar5	X
86	1			CHCH(CH2)2Si(OMe)3
87	1			CHCH(CH2)2Si(OMe)3
88	1			CHCH(CH2)2Si(OMe)3
89	0			(CH2)2Si(OEt)3
90	0			(CH2)3Si(OEt)3

[0199]

TABLE 19
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
91	0						(CH2)2Si(OMe)2Me
92	0						(CH2)4Si(OMe)3
93	0						(CH2)12Si(OMe)3
94	0						(CH2)4Si(OEt)3
95	0						(CH2)2C6H4Si(OMe)3

[0200]

TABLE 20
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
96						(CH2)2C6H4(CH2)2Si(OMe)3
97						(CH2)4Si(OMe)3
98						(CH2)4Si(OMe)3
99						CHCHSi(OEt)3
100						CHCHCH2Si(OMe)2Me

[0201]

TABLE 21
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
101	0						CHCH(CH2)2Si(OMe)3
102	0						CHCH(CH2)2Si(OMe)2Me
103	0						CHCH(CH2)2SiMe2(OMe)
104	0						CHCH(CH2)3Si(OEt)3
105	0						CHCH(CH2)10Si(OMe)3

[0202]

TABLE 22
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
106	0						CHCHC6H4Si(OMe)3
107	0						CHCHC6H4(CH2)2Si(OMe)3
108	0						CHCH(CH2)2Si(OMe)3
109	0						CHN(CH2)3Si(OMe)3
110	0						CHN(CH2)3Si(OEt)3

[0203]

TABLE 23
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
111	0						CHNCH2Si(OMe)2Me
112	0						CHNC6H4(CH2)2Si(OMe)3
113	0						CHN(CH2)3Si(OMe)3
114	0						O(CH2)3Si(OMe)3
115	0						O(CH2)3Si(OEt)3

[0204]

TABLE 24
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
116	0						CH2O(CH2)3Si(OMe)3
117	0						(CH2)3O(CH2)3Si(OMe)3
118	0						CH2O(CH2)3Si(OMe)3
119	0						CH2COO(CH2)3Si(OMe)3
120	0						(CH2)2COO(CH2)3Si(OMe)3

[0205]

TABLE 25
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
121	0						(CH2)2COOCH2C6H4(CH2)3Si(OMe)3
122	0						CH2COOCH2C6H4(CH2)2Si(OMe)3
123	0						(CH2)3COO(CH2)3Si(OMe)3
124	0						(CH2)3COOCH2C6H4(CH2)2Si(OMe)3
125	0						CH2COOCH2C6H4(CH2)2Si(OMe)3

[0206]

TABLE 26
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
126	0						(CH2)2COO(CH2)3Si(OMe)3
127	0						(CH2)2COOCH2C6H4Si(OMe)3
128	0						(CH2)2COOCH2C6H4(CH2)3Si(OMe)3
129	0						CH2COO(CH2)3Si(OMe)3
130	0						(CH2)2COO(CH2)3Si(OMe)3

[0207]

TABLE 27
Compound	k	Ar1	Ar2	Ar3
131	0
132	0
133	0
134	0
135	0
	Compound	k	Ar4	Ar5	X
	131	0			(CH2)2COOCH2C6H4(CH2)3Si(OMe)3
	132	0			COO(CH2)3Si(OMe)3
	133	0			COOCH2C6H4(CH2)2Si(OMe)3
	134	0			CH2COOCH2C6H4(CH2)2Si(OMe)3
	135	0			(CH2)2COO(CH2)3Si(OMe)3

[0208]

TABLE 28
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
136	0						(CH2)2COOCH2C6H4(CH2)3Si(OMe)3
137	0						(CH2)2COO(CH2)3Si(OMe)3
138	0						(CH2)2COOCH2C6H4Si(OMe)3
139	0						(CH2)2COOCH2C6H4(CH2)2Si(OMe)3
140	0						CH2COO(CH2)3Si(OMe)3

[0209]

TABLE 29
Compound	k	Ar1	Ar2	Ar3
141	0
142	0
143	1
144	1
145	1
Compound	k	Ar4	Ar5	X
141	0			(CH2)2COO(CH2)3Si(OMe)3
142	0			(CH2)2COOCH2C6H4(CH2)3Si(OMe)3
143	1			(CH2)2Si(OEt)3
144	1			(CH2)3Si(OEt)3
145	1			(CH2)4Si(OMe)3

[0210]

TABLE 30
Compound	k	Ar1	Ar2	Ar3
146	1
147	1
148	1
149	1
150	1
Compound	k	Ar4	Ar5	X
146	1			(CH2)4SiMe(OMe)2
147	1			(CH2)4SiMe2(OMe)
148	1			(CH2)4Si(OEt)3
149	1			(CH2)2C6H4Si(OMe)3
150	1			(CH2)2C6H4(CH2)2Si(OMe)3

[0211]

TABLE 31
Compound	k	Ar1	Ar2	Ar3
151	1
152	1
153	1
154	1
155	1
Compound	k	Ar4	Ar5	X
151	1			(CH2)3Si(OMe)2Me
152	1			(CH2)4Si(OMe)3
153	1			CHCHSi(OEt)3
154	1			CHCHCH2Si(OMe)2Me
155	1			CHCH(CH2)2Si(OMe)3

[0212]

TABLE 32
Compound	k	Ar1	Ar2	Ar3
156	1
157	1
158	1
159	1
160	0
Compound	k	Ar4	Ar5	X
156	1			CHCH(CH2)2SiMe(OMe)2
157	1			CHCH(CH2)2SiMe2(OMe)
158	1			CHCH(CH2)2Si(OEt)3
159	1			CHCHC6H4Si(OMe)3
160	0			CHCHC6H4(CH2)2Si(OMe)3

[0213]

TABLE 33
Compound	k	Ar1	Ar2	Ar3
161	1
162	1
163	1
164	1
165	1
Compound	k	Ar4	Ar5	X
161	1			CHCHCH2Si(OMe)2Me
162	1			CHCH(CH2)2Si(OMe)3
163	1			CHNCH2Si(OMe)2Me
164	1			CHN(CH2)2Si(OEt)3
165	1			CHN(CH2)3Si(OMe)3

[0214]

TABLE 34
Compound	k	Ar1	Ar2	Ar3	Ar4
166	1
167	1
168	1
169	1
170	1
Compound	k	Ar5	X
166	1
167	1		CHNCH2Si(OMe)2Me
168	1		O(CH2)3Si(OMe)3
169	1		O(CH2)3SiMe(OMe)2
170	1		O(CH2)3Si(OEt)3

[0215]

TABLE 35
Compound	k	Ar1	Ar2	Ar3
171	1
172	1
173	1
174	1
175	1
Compound	k	Ar4	Ar5	X
171	1			CH2O(CH2)3Si(OMe)3
172	1			(CH2)3O(CH2)3Si(OMe)3
173	1			COO(CH2)3Si(OMe)3
174	1			COOCH2C6H4(CH2)2Si(OMe)3
175	1			CH2COO(CH2)3Si(OMe)3

[0216]

TABLE 36
Compound	k	Ar1	Ar2	Ar3
176	1
177	1
178	1
179	1
180	1
Compound	k	Ar4	Ar5	X
176	1			CH2COOCH2C6H4(CH2)2Si(OMe)3
177	1			(CH2)2COO(CH2)3Si(OMe)3
178	1			(CH2)2COOCH2C6H4(CH2)2Si(OMe)3
179	1			COOCH2C6H4(CH2)2Si(OMe)3
180	1			CH2COO(CH2)3Si(OMe)3

[0217]

TABLE 37
Compound	k	Ar1	Ar2	Ar3
181	1
182	1
183	1
184	1
185	1
	Compound	k	Ar4	Ar5	X
	181	1			CH2COOCH2C6H4Si(OMe)3
	182	1			CH2COOCH2C6H4(CH2)2Si(OMe)3
	183	1			(CH2)2COO(CH2)3Si(OMe)3
	184	1			(CH2)2COOCH2C6H4(CH2)2Si(OMe)3
	185	1			COO(CH2)3Si(OMe)3

[0218]

TABLE 38
Compound	k	Ar1	Ar2	Ar3
186	1
187	1
188	1
189	1
190	1
Compound	k	Ar4	Ar5	X
186	1			COOCH2C6H4Si(OMe)3
187	1			COOCH2C6H4(CH2)3Si(OMe)3
188	1			COO(CH2)3Si(OMe)3
189	1			COOCH2C6H4Si(OMe)3
190	1			COOCH2C6H4(CH2)3Si(OMe)3

[0219]

TABLE 39
Compound	k	Ar1	Ar2	Ar3	Ar4
191	1
192	1
193	1
194	0
195	0
	Compound	k	Ar5	X
	191	1		CH2COO(CH2)3Si(OMe)3
	192	1		(CH2)3COO(CH2)3Si(OMe)3
	193	1		(CH2)2COOCH2C6H4(CH2)2Si(OMe)3
	194	0		(CH2)3Si(OMe)2Me
	195	0		(CH2)3Si(OEt)3

[0220]

TABLE 40
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
196	0						(CH2)4Si(OMe)3
197	0						(CH2)4Si(OMe)2Me
198	0						(CH2)4SiMe2(OMe)
199	0						(CH2)4Si(OEt)3
200	0						(CH2)12Si(OMe)3

[0221]

TABLE 41
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
201	0						(CH2)2C6H4Si(OMe)3
202	0						(CH2)3C6H4(CH2)2Si(OMe)3
203	0						(CH2)4Si(OMe)3
204	0						CHCHSi(OMe)3
205	0						CHCHCH2Si(OMe)2Me

[0222]

TABLE 42
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
206	0						CHCH(CH2)2Si(OMe)3
207	0						CHCH(CH2)3SiMe(OMe3)2
208	0						CHCH(CH2)2SiMe2(OMe)
209	0						CHCH(CH2)2Si(OEt)3
210	0						CHCH(CH2)10Si(OMe)3

[0223]

TABLE 43
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
211	0						CHCHC6H4Si(OMe)3
212	0						CHCHC6H4(CH2)2Si(OMe)3
213	0						CHCH(CH2)2Si(OMe)3
214	0						CHN(CH2)3Si(OMe)3
215	0						CHN(CH2)3Si(OEt)3

[0224]

TABLE 44
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
216	0						CHNCH2Si(OMe)2Me
217	0						CHNC6H4(CH2)3Si(OMe)3
218	0						CHN(CH2)3Si(OMe)3
219	0						O(CH2)3Si(OMe)3
220	0						O(CH2)3Si(OMe)2Me

[0225]

TABLE 45
Compound	k	Ar1	Ar2	Ar3
221	0
222	0
223	0
224	1
225	1
Compound	k	Ar4	Ar5	X
221	0			O(CH2)3Si(OEt)3
222	0			CH2O(CH2)3Si(OMe)3
223	0			(CH2)3O(CH2)3Si(OMe)2Me
224	1			(CH2)4Si(OEt)3
225	1			(CH2)3Si(OEt)3

[0226]

TABLE 46
Compound	k	Ar1	Ar2	Ar3
226	1
227	1
228	1
229	1
230	1
Compound	k	Ar4	Ar5	X
226	1			CH2CH2(CH2)2Si(OMe)3
227	1			CH2CH2(CH2)2Si(OMe)3
228	1			CH2CH2CH2Si(OMe)2Me
229	1			CH2CH2C6H4Si(OMe)2Me
230	1			CHCH(CH2)2Si(OMe)3

[0227]

TABLE 47
Compound	k	Ar1	Ar2	Ar3
231	1
232	1
233	1
234	1
235	1
Compound	k	Ar4	Ar5	X
231	1			CHCH(CH2)2Si(OMe)3
232	1			CHCH(CH2)2Si(OMe)3
233	1			CHCHCH2Si(OMe)2Me
234	1			CHCHC6H4Si(OMe)3
235	1			CHN(CH2)3Si(OMe)3

[0228]

TABLE 48
Compound	k	Ar1	Ar2	Ar3
236	1
237	1
238	1
239	1
240	1
Compound	k	Ar4	Ar5	X
236	1			CHN(CH2)3Si(OMe)3
237	1			CHN(CH2)3Si(OMe)3
238	1			CHNCH2Si(OMe)2Me
239	1			CHNC6H4(CH2)2Si(OMe)3
240	1			O(CH2)3Si(OMe)3

[0229]

TABLE 49
Compound	k	Ar1	Ar2	Ar3
241	1
242	1
243	1
244	1
245	0
Compound	k	Ar4	Ar5	X
241	1			O(CH2)3Si(OEt)3
242	1			CH2O(CH2)3Si(OMe)3
243	1			CH2O(CH2)3Si(OEt)3
244	1			(CH2)3O(CH2)3Si(OMe)3
245	0			COO(CH2)3Si(OiPr)3

[0230]

TABLE 50
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
246	0						COOCH2C6H4(CH2)2Si(OiPr)3
247	0						CH2COO(CH2)3Si(OiPr)3
248	0						CH2COOCH2C6H4(CH2)2Si(OiPr)3
249	0						(CH2)2COO(CH2)3Si(OiPr)3
250	0						(CH2)2COOCH2C6H4(CH2)2Si(OiPr)3

[0231]

TABLE 51
Compound	k	Ar1	Ar2	Ar3
251	1
252	1
253	1
254	1
255	1
Compound	k	Ar4	Ar5	X
251	1			COO(CH2)3Si(OiPr)3
252	1			COOCH2C6H4(CH2)2Si(OiPr)3
253	1			CH2COO(CH2)3Si(OiPr)3
254	1			CH2COOCH2C6H4(CH2)2Si(OiPr)3
255	1			(CH2)2COO(CH2)3Si(OiPr)3

[0232]

TABLE 52
Compound	k	Ar1	Ar2	Ar3
256	1
257	0
258	0
259	0
260	0
Compound	k	Ar4	Ar5	X
256	1			(CH2)2COOCH2C6H4(CH2)2Si(OiPr)3
257	0			COO(CH2)3Si(OiPr)3
258	0			COOCH2C6H4(CH2)2Si(OiPr)3
259	0			CH2COO(CH2)3Si(OiPr)3
260	0			CH2COOCH2C6H4(CH2)2Si(OiPr)3

[0233]

TABLE 53
Compound	k	Ar1	Ar2	Ar3
261	0
262	0
263	1
264	1
265	1
Compound	k	Ar4	Ar5	X
261	0			(CH2)2COO(CH2)3Si(OiPr)3
262	0			(CH2)2COOCH2C6H4(CH2)2Si(OiPr)3
263	1			COO(CH2)3SiMe(OiPr)2
264	1			COOCH2C6H4(CH2)2SiMe(OiPr)2
265	1			CH2COO(CH2)3SiMe(OiPr)2

[0234]

TABLE 54
Compound	k	Ar1	Ar2	Ar3
266	1
267	1
268	1
269	0
270	0
Compound	k	Ar4	Ar5	X
266	1			CH2COOCH2C6H4(CH2)2SiMe(OiPr)2
267	1			(CH2)2COO(CH2)3SiMe(OiPr)2
268	1			(CH2)2COOCH2C6H4(CH2)2SiMe(OiPr)2
269	0			COO(CH2)3SiMe(OiPr)2
270	0			COOCH2C6H4(CH2)2SiMe(OiPr)2

[0235]

TABLE 55
Compound	k	Ar1	Ar2	Ar3	Ar4	Ar5	X
271	0						CH2COO(CH2)3SiMe(OiPr)2
272	0						CH2COOCH2C6H4(CH2)2SiMe(OiPr)2
273	0						(CH2)2COO(CH2)3SiMe(OiPr)2
274	0						(CH2)2COOCH2C6H4(CH2)2SiMe(OiPr)2