JP2021152607A - Image carrier unit and image forming apparatus - Google Patents

Abstract

To provide means that prevents the occurrence of dust dirt on and fogging of an image.SOLUTION: An image carrier unit comprises: an image carrier having a photo sensitive layer that contains a binder resin, a first charge transport material, and a second charge transport material; and a contact member that is in contact with a surface of the image carrier. When the weight average molecular weight of the binder resin in the photo sensitive layer is MP, the addition ratio of the binder resin is WL, the weight average molecular weight of the first charge transport material is MT1, the weight average molecular weight of the second charge transport material is MT2, the addition ratio of the first charge transport material is WT1, and the addition ratio of the second charge transport material is WT2, 199.5≤(MP×WL)/(MT1×WT1+MT2×WT2)≤231.9 is satisfied, and the Martens hardness of the image carrier is 151 MPa or more and 173 MPa or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to an image carrier unit and an image forming apparatus that form an image using an electrophotographic process.

In the conventional image carrier unit and image forming apparatus, the surface of the photosensitive drum as the image bearing uniformly charged by the charging roller is exposed by the exposure apparatus to form an electrostatic latent image, and the surface is statically charged by the developing roller. After developing an electro-latent image and forming a toner image as a developer image on the surface of a photosensitive drum, the toner image is transferred to a medium by a transfer roller and fixed by a fixing device. Further, the toner as a developer is attached to the photosensitive drum after the toner image is transferred to the medium, and the cleaning member removes the toner.

As the photosensitive drum, a laminated photoconductor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support is generally used. When forming a photosensitive layer of a laminated photoconductor having a charge generating layer and a charge transporting layer, a binder resin is used to disperse the compound in order to secure the film strength. Further, the charge transport layer is obtained by applying and drying a coating liquid obtained by dissolving or dispersing a charge transport substance and various binder resins in a solvent (see, for example, Patent Document 1).

JP-A-2007-179038

However, in the conventional technique, as the device becomes smaller and faster, the arrival time from the exposed part to the developed part of the photosensitive drum becomes shorter, so that the potential after exposure must be lowered to a desired potential in a short time. It's getting harder. If the potential after exposure of the photosensitive drum does not drop to the desired potential, the potential after exposure rises, especially after continuous energization in a high-temperature and high-humidity environment, the potential difference between the photosensitive drum and the developing roller becomes small, and the print density decreases. There is a problem.

If the amount of the charge transporting substance added is increased in order to lower the potential after exposure, that is, to increase the charge mobility from the charge generation layer to the surface of the charge transport layer, the charge transport layer is increased even if the charge mobility is increased. The elastic properties of the binder resin may be impaired, and the creep properties (strain resistance) may be deteriorated. At that time, the surface of the photosensitive drum is easily deformed at the contact portion with the contact member.

When the surface of the photosensitive drum is deformed, the contact member cannot follow the surface shape of the photosensitive drum, and the external additive of the toner as a developing agent slips through. The toner external additive that has passed through the abutting member is deposited and aggregated on the surface of the abutting member, and when it reaches a certain size, it collapses, and the disintegrated external additive agglomerate moves to the surface of the photosensitive drum, and the external addition The agent agglomerates inhibit the charging of the surface of the photosensitive drum by the charging roller, and the formed image has dust-like stains (hereinafter referred to as "dust stains") and toner on the surface of the photosensitive drum where the charging is inhibited. There is a problem that the phenomenon of adhesion (hereinafter referred to as "fog") may occur.

An object of the present invention is to solve such a problem, and an object of the present invention is to suppress the occurrence of dust stains and fog on an image.

Therefore, the present invention comprises an image carrier having a photosensitive layer containing a binder resin, a first charge transport material and a second charge transport material, and an abutting member that abuts on the surface of the image carrier. The weight average molecular weight of the binder resin in the photosensitive layer is MP, the addition ratio of the binder resin is WL, the weight average molecular weight of the first charge transport material is MT1, and the weight of the second charge transport material. When the average molecular weight is MT2, the addition ratio of the first charge transport material is WT1, and the addition ratio of the second charge transport material is WT2, 199.5 ≦ (MP × WL) / (MT1 × WT1 + MT2 × WT2). ) ≦ 231.9, and the Martens hardness of the image carrier is 151 [MPa] or more and 173 [MPa] or less.

The present invention in this manner has the effect of suppressing the occurrence of dust stains and fog on the image.

Schematic side sectional view showing the configuration of the developing apparatus in the embodiment. Schematic side sectional view showing the configuration of the image forming apparatus in the examples. A block diagram showing a control configuration of an image forming apparatus in an embodiment. Explanatory drawing of the method of measuring the resistance value of a developing roller in an Example Explanatory drawing of cleaning angle in Example Explanatory drawing which shows the structure of the photosensitive drum in an Example Explanatory drawing of dust stain in Example Explanatory drawing of method of measuring post-exposure potential of photosensitive drum in Example Explanatory drawing of solid pattern in Example Explanatory drawing of blank paper pattern in Example Graph of molecular weight distribution in Examples Explanatory drawing of charge transport layer in Example Explanatory drawing of positive afterimage in Example Explanatory drawing of action of charge transport layer in Example Explanatory drawing of the method of measuring Martens hardness in an Example Explanatory drawing of indentation test in Example

Hereinafter, examples of the image carrier unit and the image forming apparatus according to the present invention will be described with reference to the drawings.

FIG. 1 is a schematic side sectional view showing the configuration of the developing apparatus in the embodiment, and FIG. 2 is a schematic side sectional view showing the configuration of the image forming apparatus in the embodiment.

In FIG. 2, the image forming apparatus 10 forms a developer image on a medium, and is, for example, a printer, a facsimile machine, a copying machine, a multifunction device (MFP), or the like, but may be of any kind. .. In this embodiment, the image forming apparatus 10 will be described as being an electrophotographic printer that forms an image by an electrophotographic method. The image forming apparatus 10 may be an apparatus for forming a color image, but for convenience of explanation, it is assumed to be an apparatus for forming a monochrome image.

Inside the image forming apparatus 10, a paper cassette 21, an image forming unit 28, and a fixing device 27 are arranged along a transport path of a recording medium P as a medium.

The paper cassette 21 accommodates the recording medium P. The recording media P stacked and set on the paper cassette 21 are fed in a state of being separated one by one by the paper feed roller 31, transported in the medium transport direction indicated by the arrow B, and fed to the paper transport roller 32. Is done.

The image forming unit 28 has a developing device 20, forms a toner image as a developing agent image, and transfers the toner image to the recording medium P. The recording medium P fed to the paper transport roller 32 is fed by the paper transport roller 32 at a predetermined timing in the medium transport direction indicated by the arrow C, and is being conveyed along the transfer path, and the image forming unit 28 is being conveyed. The toner image formed by the above is transferred by the transfer roller 25.

The LED head 26 is an exposure apparatus including an LED (Light Emitting Diode) as a light emitting element.

The fuser 27 fixes the toner image transferred to the recording medium P by heat and pressure. When the recording medium P is sent to the fixing device 27, the fixing process is performed by the fixing device 27, and the toner image is fixed on the recording medium P.

The recording medium P on which the toner image is fixed is conveyed in the direction indicated by the arrow D, discharged by the paper ejection roller 33 in the direction indicated by the arrow E, and housed in a stacker outside the image forming apparatus 10.

As shown in FIG. 1, the developing apparatus 20 as an image carrier unit has a casing that internally accommodates a toner accommodating portion 22 as a developer accommodating unit and a toner 17 as a developing agent replenished from the toner accommodating portion 22. It is equipped with 23.

Further, the developing apparatus 20 has a photosensitive drum 13 as an electrostatic latent image carrier (image carrier), a developing roller 11 as a developing agent carrier arranged so as to face the photosensitive drum 13, and toner on the developing roller 11. A toner layer thickness regulating blade that forms a thin layer of a toner supply roller 12 as a developer supply member for supplying 17, a charging roller 14 as a charging member for charging the photosensitive drum 13, and a toner 17 supplied on the developing roller 11. The developing blade 15, the stirring members 24a, 24b and 24c for maintaining the fluidity of the toner 17 in the casing 23, and the cleaning blade 16 for scraping and recovering the transfer residual toner on the photosensitive drum 13. I have.

The cleaning blade 16 as a removing member has a contact portion that comes into contact with the surface of the photosensitive drum 13, and is plate-shaped to remove residues on the surface of the photosensitive drum 13 as the photosensitive drum 13 rotates. The removal member is not limited to the blade shape, and a roller-shaped cleaning roller may be used.

Further, the cleaning blade 16 is one of the contact members that come into contact with the surface of the photosensitive drum 13. Other abutting members include a developing roller 11 that abuts on the surface of the photosensitive drum 13.

The developing roller 11, the toner supply roller 12, the photosensitive drum 13, and the charging roller 14 rotate in the directions indicated by the arrows, respectively. The stirring members 24a, 24b, and 24c are crank-shaped rods, and rotate on the broken line shown in FIG. 1 in the direction indicated by the arrow.

Further, the LED head 26 shown in FIG. 2 exposes the surface of the photosensitive drum 13 based on the image data to form an electrostatic latent image.

FIG. 3 is a block diagram showing a control configuration of the image forming apparatus in the embodiment.

In FIG. 3, the image forming apparatus 10 is charged with a print control unit 30, an I / F control unit 36, an operation unit 42, a sensor group 43, a developing roller power supply 44, a toner supply roller power supply 45, and the like. It has a roller power supply 46, a developing blade power supply 47, a transfer roller power supply 51, a head drive control unit 52, a fixing control unit 53, a transfer motor control unit 54, and a drive control unit 55. ..

The print control unit 30 includes a microprocessor as a control means, a ROM (Read Only Memory) and a RAM (Random Access Memory) as a storage means, an input / output port, a timer, and the like, and is an I / F from a higher-level device such as a host computer. (Interface) Print data and control commands are received via the control unit 36, and the entire sequence of the image forming apparatus 10 is controlled to perform a printing operation.

The reception memory 37 temporarily records the print data input from the host device via the I / F control unit 36.

The image data editing memory 41 receives the print data recorded in the reception memory 37 and stores the image data formed by editing the print data, that is, the image data.

The operation unit 42 includes display means such as an LED for displaying the state of the image forming apparatus 10 and input means such as a switch for giving an instruction from the operator to the image forming apparatus 10.

The sensor group 43 includes various sensors for monitoring the operating state of the image forming apparatus 10, for example, a paper position detection sensor, a temperature / humidity sensor, a print density sensor, a toner remaining amount detection sensor, and the like.

The charging roller power supply 46 applies a voltage to the charging roller 14 according to the instruction of the print control unit 30 to charge the surface of the photosensitive drum 13.

The developing roller power supply 44 applies a predetermined voltage to the developing roller 11 in order to attach the toner 17 to the electrostatic latent image.

The toner supply roller power supply 45 applies a predetermined voltage to the toner supply roller 12 for supplying the toner 17 to the developing roller 11.

The developing blade power supply 47 applies a predetermined voltage to the developing blade 15 for forming a thin layer of toner 17 on the surface of the developing roller 11.

The transfer roller power supply 51 applies a predetermined voltage to the transfer roller 25 for transferring the toner image formed on the photosensitive drum 13 to the recording medium.

The charging roller power supply 46, the developing roller power supply 44, the toner supply roller power supply 45, the developing blade power supply 47, and the transfer roller power supply 51 are each member (charging roller 14, developing roller) according to the instructions of the print control unit 30. 11. The voltage applied to the toner supply roller 12, the developing blade 15, and the transfer roller 25) can be changed.

The head drive control unit 52 sends the image data recorded in the image data editing memory 41 to the LED head 26 shown in FIG. 2 to drive the LED head 26.

The fixing control unit 53 applies a voltage to the fixing device 27 as a fixing means in order to fix the transferred toner image on the recording medium. The fuser 27 includes a heater for melting the toner constituting the toner image on the recording medium, a temperature sensor for detecting the temperature, and the like. The fixing control unit 53 reads the sensor output of the temperature sensor, energizes the heater based on the sensor output, and controls the fixing device 27 so that the temperature becomes constant.

The transfer motor control unit 54 controls the paper transfer motor 34 for transporting the recording medium. The transfer motor control unit 54 transfers and stops the recording medium at a predetermined timing according to the instruction of the print control unit 30. The paper feed roller 31, the paper transport roller 32, and the paper discharge roller 33 are rotated by the paper transport motor 34. Then, the recording medium P shown in FIG. 2 is conveyed in the directions indicated by the arrows B to E.

The drive control unit 55 as a rotating unit drives a drive motor 35 for rotating the photosensitive drum 13. When the drive motor 35 is driven by the drive control unit 55, the photosensitive drum 13 is rotated in the direction indicated by the arrow, and the charging roller 14, the developing roller 11, and the toner supply roller 12 are rotated as shown in FIG. , Each of which is rotated in the direction indicated by the arrow.

Next, the main components of the developing apparatus 20 will be described in detail with reference to FIG.

First, the toner 17 will be described.

The toner 17 used in this example is a non-magnetic one-component negatively charged toner, and is an external additive such as an inorganic fine powder or an organic fine powder (hereinafter, external addition) to the toner mother particles containing at least a binder resin. It is called an agent). The binder resin is not particularly limited, but a polyester resin, a styrene-acrylic resin, an epoxy resin, or a styrene-butadiene resin is preferable. A mold release agent, a colorant, and the like are added to the binder resin, and other additives such as a charge control agent, a conductivity adjusting agent, a fluidity improving agent, and a cleaning property improving agent may be appropriately added. .. Further, the binder resin may be a mixture of a plurality of types, and in this example, a crystalline polyester resin having a crystal structure was used in addition to the plurality of amorphous polyester resins.

The average particle size of the toner 17 is 6.0 [μm] and the circularity is 0.96. A Coulter Multisizer 3 manufactured by Coulter Co., Ltd. was used for measuring the average particle size, and a flow-type particle image analyzer FPIA-3000 manufactured by Sysmex Corporation was used for measuring the circularity.

The release agent is not particularly limited, but is low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymer, microcrystallin wax, paraffin wax, aliphatic hydrocarbon wax such as Fishertropsh wax, polyethylene oxide wax. Oxides of aliphatic hydrocarbon waxes such as, or block copolymers thereof, waxes containing fatty acid esters such as carnauba wax and montanic acid ester wax as main components, and fatty acid esters such as deoxidized carnauba wax. Known examples include those obtained by deoxidizing a part or the whole. It is effective to add 0.1 to 20 parts by weight, preferably 0.5 to 12 parts by weight, based on 100 parts by weight of the binder resin, and a plurality of waxes may be used in combination. Is also preferable.

The colorant is not particularly limited, but dyes, pigments, etc. used as conventional colorants for black, yellow, magenta, and cyan toners can be used alone or in combination of two or more. For example, carbon black, iron oxide, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, Rhodamine-B base, solvent red 49, solvent red 146, pigment blue 15: 3, solvent blue 35, quinacridone, Examples thereof include Carmin 6B and Disuazoero. The content of this colorant is 2 to 25 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the binder resin.

As the charge control agent, a known one can be used. For example, in the case of a negatively charged toner, an azo-based complex charge control agent, a salicylic acid-based complex charge control agent, a calixarene-based charge control agent, and the like can be mentioned. The content of the charge control agent is 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the binder resin.

The external additive of the toner 17 is added for improving environmental stability, charge stability, developability, fluidity, and storage stability, and known ones can be used, and the content of the external additive is binding. 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, is added to 100 parts by weight of the resin. In this embodiment, several types of silica having an average particle size of 14 [μm] (positive and negative charging polarities) and colloidal silica having an average particle size of 110 [μm] are used in 100 parts by weight of the mother particles (negative). (Charged) and melamine (positively charged) having an average particle size of 200 [μm] were added so that the total amount was within the above range.

The charge amount (blow-off charge amount) of the toner 17 was measured by stirring the toner and the carrier by shaking. Here, as a carrier, a ferrite carrier "EF96-35" manufactured by Powder Tech Co., Ltd. was used, and a toner of 0.5 [g] and a carrier of 9.5 [g] were mixed. A mixture of toner and carrier (150 [mg]) is placed in a container and shaken using a shaker "YS-LD" manufactured by Yayoi Co., Ltd. The number of shakings was 200 [times / minute], and the shaking time was 300 seconds.

After shaking, using the powder charge measuring device "TB-203" manufactured by Kyocera Chemical Co., Ltd., suction is performed for 10 seconds with a blow pressure of 7.0 [kPa] and a suction pressure of -4.5 [kPa]. Is performed, and the PC (personal computer) is made to output the amount of electric charge and the amount of suction every 0.1 seconds. The charge amount Q / M per unit weight of the toner particles calculated from the average values of the charge amount and the suction amount output in the last 2 seconds of the suction time (10 seconds) is about -35 [μC / g]. there were. The measurement was performed at a temperature of 25 [° C.] and a relative humidity of [50%].

The developing roller 11 includes an elastic layer arranged on a conductive core metal as a shaft, and a surface layer covering the surface of the elastic layer.

The rubber hardness of the elastic layer in the roll shape is generally preferably Asker C hardness 55 to 80 [°]. If the Asker C hardness of the elastic layer is lower than 55 [°], if the developing apparatus 20 is not operated for a long period of time, a dent is generated at the contact portion between the photosensitive drum 13 and the developing blade 15 in the developing roller 11. There is a problem that horizontal streaks occur on the printed image. Further, when the Asker C hardness of the elastic layer is higher than 80 [°], the mechanical load applied to the developing roller 11 becomes large, and toner filming is likely to occur on the surface of the developing roller 11. In this example, the Asker C hardness of the elastic layer was set to 76 [°].

As the material of the elastic layer, a general rubber material such as silicone rubber or urethane can be used. When polyurethane is used as the elastic layer, it is preferably polyurethane mainly composed of a polyether polyol. The ether-based polyurethane is a so-called cast-type polyurethane obtained by reacting a polyol mainly composed of a polyether-based polyol with a polyisocyanate. This is to reduce the compression set. On the other hand, when ester polyurethane is used, it has poor hydrolysis characteristics and cannot be used stably for a long period of time.

When polyurethane is used as the elastic layer, examples of the isocyanate to be reacted with the polyol include trifunctional isocyanates such as triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, and bicycloheptane triisocyanate, and hexamethylene diisocyanate. Mixtures such as nelate-modified polyisocyanate and polypeptide MDI can be used.

Further, it may be a mixture of these trifunctional or higher functional polyisocyanates and a general bifunctional isocyanate compound. Examples of bifunctional isocyanate compounds are 2,4-toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), paraphenylenedi isocyanate (PPDI), 1,5-naphthalenediocyanate (NDI), 3,3- Examples thereof include dimethyldiphenyl-4,4-diisocyanate (TODI), modified compounds such as prepolymers having these isocyanates at both ends, and multimers.

The elastic layer is formed by adding carbon black to the rubber base material as described above and heat-curing it while maintaining the dispersed state of carbon. As a result, carbon black, which exhibits about 0.1 to 10 [Ω · cm] as an intrinsic resistance, ^{is dispersed in an elastomer (10 12} to 10 ¹⁶ [Ω · cm]), ^{which can be said to be an insulator, and 10 4} to 10 ⁸ [Ω]. The medium resistance region of [cm] can be formed so as to be stable.

In this example, the surface layer was formed by impregnating the surface layer portion of the elastic layer with a surface treatment liquid. The surface treatment liquid is an organic solvent in which at least an isocyanate component is dissolved. Examples of the organic solvent include methyl acetate, butyl acetate, and pentyl acetate. When such an organic solvent is used, for example, as an isocyanate component contained in the surface treatment liquid, an isocyanate compound such as 2,4-toluene diisocyanate (TDI) or 4,4-diphenylmethane diisocyanate (MDI), and the above-mentioned large amount A body, a denatured substance, or the like can be used.

The surface treatment liquid may contain a polyether polymer. Here, the polyether polymer is preferably soluble in an organic solvent, and preferably has active hydrogen and can react with an isocyanate compound to be chemically bonded. Suitable polyether polymers having active hydrogen include polymers having a hydroxyl group or an allyl group, and examples thereof include polyols and glycols used for terminal isocyanate prepolymers.

Further, the surface treatment liquid may contain a polymer selected from an acrylic fluorine-based polymer and an acrylic silicone-based polymer. Acrylic fluorine-based polymers and acrylic silicone-based polymers are soluble in a predetermined solvent and can react with an isocyanate compound to be chemically bonded. The acrylic fluorine-based polymer is, for example, a solvent-soluble fluorine-based polymer having a hydroxyl group, an alkyl group, or a carboxyl group, and examples thereof include a block copolymer of an acrylic acid ester and an alkyl acrylate and a derivative thereof. Further, the acrylic silicone-based polymer is a solvent-soluble silicone-based polymer, and examples thereof include a block copolymer of an acrylic acid ester and an acrylic acid siloxane ester and a derivative thereof.

Further, carbon black such as acetylene black may be further added to the surface treatment liquid as a conductivity-imparting material.

The total amount of the polyether polymer, the acrylic fluoropolymer and the acrylic silicone polymer in the surface treatment liquid is 10 to 70% by mass with respect to the isocyanate component. It is preferable to do so. If it is less than 10% by mass, the effect of retaining carbon black or the like in the surface treatment liquid becomes small. On the other hand, if it is more than 70% by mass, there is a problem that the electric resistance value increases or the isocyanate component is relatively reduced and an effective surface treatment layer cannot be formed.

By immersing the elastic layer in the above-mentioned surface treatment liquid to apply it and drying and curing it, the surface treatment liquid is impregnated into the surface layer portion of the elastic layer to form a surface layer.

The resistance value of the developing roller 11 was measured by the method shown in FIG. 4, and a high resistance meter (model number: 4339B) 65 manufactured by Hewlett-Packard Company was used. As shown in FIG. 4A, the developing roller 11 applies a load of W = 300 [g] to both ends in the axial direction to apply a load of W = 300 [g] to a metal roller 66 made of SUS (Steel Use Stainless) material having a diameter of 30 [mm]. Made contact. The metal roller 66 is rotated at a speed of 50 [rpm], a voltage of -100 [V] is applied to the core metal 61 of the developing roller 11, 100 points are measured per round of the developing roller 11, and the average value is measured by the roller. The resistance value was set to. At this time, the resistance value of the developing roller 11 ^{is preferably in the range of 1 × 10 4} to 1 × 10 ⁷ [Ω], and in this embodiment, ^{a developing roller having a resistance value of 1 × 10 5} [Ω] is used. ..

Note that FIG. 4B is a view of the developing roller 11 and the metal roller 66 viewed from the axial direction.

Next, the developing blade 15 and the cleaning blade 16 will be described.

The developing blade 15 in this embodiment is made of stainless steel, has a plate thickness of 0.08 [mm], is bent at a contact portion with the developing roller 11, and has a radius of curvature of 0 at the bent portion. It is .18 [mm], and the pressure (linear pressure) on the developing roller 11 is 40 [gf / cm].

In view of the setting conditions of the developing blade 15, it is necessary to examine the surface roughness, resistance value, etc. of the developing roller 11 in order to make the toner layer thickness and the toner charge amount on the developing roller 11 desired. As for the surface roughness of the developing roller 11 used in the embodiment of this embodiment, it is appropriate that the ten-point average roughness Rz (JIS B0601-1994) in the circumferential direction is 2 to 10 [μm].

The cleaning blade 16 used in this embodiment includes a plate-shaped elastic body and a conductive plate-shaped holder for holding the plate-shaped elastic body.

The material for forming the plate-shaped elastic body is not particularly limited, but an elastic composition is used so that the surface of the photosensitive drum 13 is not damaged when the residual toner is scraped off by sliding contact with the surface of the photosensitive drum 13. Is common. For example, a composition obtained by blending an appropriate additive with polyurethane, silicone resin, fluororesin, fluororubber, or the like can be mentioned. Of these, the polyurethane composition is preferable because it is excellent in mechanical strength, elastic pressure contactability, and the like.

The polyurethane composition can usually be obtained by using a polyisocyanate, a polyol, a curing agent and a catalyst.

The polyisocyanate is not particularly limited, and is, for example, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-tolylene diisocyanate). 2,6-TDI), 3,3'-tolyrene-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate uretidinedione (2,4) -TDI dimer), 1,5-naphthylene diisocyanate, metaphenylenediocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (hydrated MDI), carbodiimide-modified MDI, orthotoluidine diisocyanate, xylene Examples thereof include diisocyanates such as diisocyanate, paraphenylenediocyanate and lysine diisocyanate methyl ester, triisocyanates such as triphenylmethane-4,4', 4 ″ -triisocyanate, and polymeric MDI, which may be used alone or in combination of two or more. Of these, MDI is preferable from the viewpoint of abrasion resistance.

The polyol used together with the polyisocyanate is not particularly limited, and for example, polyester polyols such as polyethylene adipate (PEA), polybutylene adipate (PBA), and polyhexylene adipate, polycaprolactone, and polyoxytetra. Examples thereof include polyether polyols such as methylene glycol and polyoxypropylene glycol. These may be used alone or in combination of two or more. Of these, PBA is preferable because it has excellent wear resistance.

The curing agent used together with the polyisocyanate and the polyol is not particularly limited, and 1,4-butanediol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, 1,4-cyclohexanediol, and the like. Examples thereof include polyols having a molecular weight of 300 or less, such as 1,4-cyclohexanedimethanol, xylene glycol, triethylene glycol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, and 1,2,6-hexanetriol. These may be used alone or in combination of two or more.

The linear pressure of the cleaning blade 16 with respect to the photosensitive drum 13 is preferably 15 [gf / cm] or more and 30 [gf / cm] or less, and is set to 20 [gf / cm] in this example. Further, the cleaning angle was set to be 10 [°] or more and 15 [°] or less.

Here, the cleaning angle will be described with reference to FIG.

In FIG. 5, the free length of the cleaning blade 16 is L, the thickness of the cleaning blade 16 is t, the Young's modulus of the cleaning blade 16 is E, the set angle of the cleaning blade 16 is θ, and the cleaning blade 16 and the photosensitive drum 13 at the contact portion. When the contact angle of the cleaning blade 16 is α, the bite amount d of the cleaning blade 16 with respect to the photosensitive drum 13, and the load of the cleaning blade 16 with respect to the photosensitive drum 13 is N, the bite amount d is
d = NbL ³ /3EI ² ... Equation A (b is the length of the cleaning blade 16)
The cleaning blade 16 deflection angle (θ-α) is
tan (θ-α) = Nb 2 L 2 / 2EI ··· type B
Since I in the formulas A and B is the moment of inertia of area of the cleaning blade 16.
I = bt ^3/12
Will be.

Substituting this into equations A and B, the load N and the contact angle α are:
N = dEt ³ / 4L ³
α = θ-tan ^-1 (3d / 2L)
Therefore, this contact angle α is defined as the cleaning angle.

FIG. 6 is an explanatory diagram showing the configuration of the photosensitive drum in the embodiment.

As shown in FIG. 6A, the photosensitive drum 13 as an image carrier has a drum gear 71 and a drum flange 72, and as shown in FIG. 6B, the surface layer of the photosensitive drum 13 is cylindrical. The conductive support 74 processed into a mold has a laminated structure consisting of an undercoat layer 75, a charge generation layer 76, and a charge transport layer 77 in order from the surface, and the photosensitive layer 73 has a charge generation layer 76 and an electric charge. It is composed of a transport layer 77.

An undercoat layer 75 may be provided between the conductive support 74 and the photosensitive layer 73, which will be described later, in order to improve adhesiveness, blocking property, and the like.

As the undercoat layer 75, for example, a resin or a resin in which particles such as metal oxides are dispersed is used. Further, the undercoat layer 75 may be a single layer or may be provided with a plurality of layers.

Examples of the metal oxide particles used for the undercoat layer 75 include metal oxide particles containing one kind of metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, and iron oxide, calcium titanate, and the like. Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium titanate and barium titanate. One of these may be used alone, or two or more thereof may be used in any ratio and combination.

Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide or silicon oxide, or an organic substance such as stearic acid, polyol or silicone.

Any one of these treatments may be applied, and two or more of these treatments may be applied. As the crystal type of the titanium oxide particles, for example, rutile, anatase, brookite, or amorphous can be used. The titanium oxide particles may have only one type of crystal type, or may contain two or more types of crystal types in an arbitrary ratio and combination.

The particle size of the metal oxide particles is arbitrary as long as the effect of the present invention is not significantly impaired, but from the viewpoint of the characteristics of the binder resin and the like as the raw material of the undercoat layer 75 and the stability of the solution, the average primary particle size is Usually, it is preferably 10 [nm] or more, and usually 100 [nm] or less, preferably 50 [nm] or less. This average primary particle size can be measured by, for example, a transmission electron microscope (TEM).

The undercoat layer 75 is preferably formed by dispersing metal oxide particles in a binder resin. Such an undercoat layer 75 is, for example, a solution in which metal oxide particles are dispersed in a solution in which a binder resin is dissolved and the metal oxide particles are dispersed (hereinafter, appropriately referred to as "coating liquid for forming an undercoat layer". ) Is preferably applied. Examples of the binder resin used for the undercoat layer 75 include epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, and polyimide. Resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacrylic acid resin, polyacrylamide resin, polyvinylpyrrolidone resin, polyvinylpyridine resin, water-soluble polyester resin, nitrocellulose Cellular ester resin such as cellulose ester resin, cellulose ether resin, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelate compound, organic zirconium compound such as zirconium alkoxide compound, titanyl chelate compound, organic titanyl compound such as titanyl alkoxide compound. , Silane coupling agent and the like. One of these may be used alone, or two or more thereof may be used in any ratio and combination. Further, it may be used in a cured form together with a curing agent. Among them, alcohol-soluble copolymerized polyamides, modified polyamides and the like are preferable because they show good dispersibility and coatability.

As the configuration of the photosensitive layer 73, any configuration applicable to a known electrophotographic photosensitive member can be adopted. To give a specific example, it contains a so-called single-layer type photosensitive member having a single-layer photosensitive layer (that is, a single-layer type photosensitive layer) in which a photoconductive material is dissolved or dispersed in a binder resin, and a charge generating substance. Examples thereof include a so-called laminated photoconductor having a photosensitive layer (that is, a laminated photosensitive layer) formed by laminating a charge generating layer 76 and a charge transporting layer 77 containing a charge transporting substance. In general, it is known that a photoconductive material exhibits the same performance in terms of function regardless of whether it is a single-layer type or a laminated type.

The photosensitive layer of the electrophotographic photosensitive member of the present invention may be in any known form, but the mechanical properties, electrical characteristics, manufacturing stability, etc. of the electrophotographic photosensitive member may be comprehensively taken into consideration. A laminated electrophotographic photosensitive member is preferable. In particular, a forward-stacked photoconductor in which a charge generation layer 76 and a charge transport layer 77 are laminated in this order on a conductive support is more preferable.

When forming the charge transport layer of the function-separated photoconductor (that is, the laminated photoconductor) having the charge generation layer 76 and the charge transport layer 77 and the photosensitive layer of the single layer type photoconductor, usually in order to secure the film strength. , A binder resin (binding resin) is used to disperse the compound. The charge transport layer of the function-separated photoconductor can be obtained by applying and drying a coating liquid obtained by dissolving or dispersing a charge transport substance and various binder resins in a solvent. Further, the single-layer type photoconductor can be obtained by applying and drying a coating liquid obtained by dissolving or dispersing a charge generating substance, a charge transporting substance and various binder resins in a solvent.

Examples of the binder resin usually used for the charge generation layer 76 in the function-separated photoconductor include polyvinyl butyral resin, polyvinyl formal resin, partially acetalized polyvinyl butyral resin in which a part of butyral is modified with formal, acetal, or the like. Polyvinyl acetal resin, polyarylate resin, polycarbonate resin, polyester resin, modified ether polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, poly Acrylamide resin, polyamide resin, polyvinylpyridine resin, cellulose resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, casein, vinyl chloride-vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate Vinyl chloride-vinyl acetate copolymers such as copolymers, carboxyl-modified vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, styrene-butadiene copolymers, vinylidene chloride-acrylonitrile Select from insulating resins such as copolymers, styrene-alkyd resins, silicone-alkyd resins, and phenol-formaldehyde resins, and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylperylene. It can be used, but is not limited to these polymers. Further, one of these binder resins may be used alone, or two or more of these binder resins may be used in any ratio and combination.

Examples of the binder resin used for the charge transport layer 77 include polyvinyl acetal resin, polyarylate resin, polycarbonate resin, polyester resin, modified ether polyester resin, phenoxy resin, polyvinyl chloride resin, and vinylidene chloride resin. Polyvinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, polyacrylamide resin, polyamide resin, polyvinylpyridine resin, cellulose resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, casein, vinyl chloride -Vinyl acetate copolymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin, silicone-alkyd resin, phenol-formaldehyde resin, organic photoconductive resin and the like. The vinyl chloride-vinyl acetate-based copolymers include, for example, vinyl chloride-vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer and vinyl chloride-vinyl acetate-. It is a maleic anhydride copolymer or the like. Organic photoconductive resins include, for example, poly-N-vinylcarbazole, polyvinylanthracene and polyvinylperylene.

Among these, polyarylate resin and polycarbonate resin are preferable, and polyarylate resin is more preferable.

Those used as a charge transporting agent (charge transporting material) include, for example, any one or more (at least one or more) of the charge transporting substances. The type of the charge transporting substance is not particularly limited, and examples thereof include an aromatic amine derivative, a stilben derivative, a butadiene derivative, a hydrazone derivative, a carbazole derivative, an aniline derivative, and an enamin derivative. In addition, the charge transporting substance may be, for example, a compound in which any one or more of the above-mentioned aromatic amine derivatives are bound. Further, the charge transporting substance may be, for example, a polymer (electron donating material) having a group composed of the above-mentioned aromatic amine derivative or the like as a main chain or a side chain. Among them, the charge transporting substance is preferably an aromatic amine derivative, a stilben derivative, a hydrazone derivative, an enamin derivative, and a compound in which any one or more of them are bound, and the aromatic amine derivative and enamin are used. More preferably, it is a compound to which a derivative is bound.

Each layer constituting the photosensitive drum 13 is usually coated with a coating liquid containing the material constituting each layer on the conductive support 74 by using a known coating method, repeating the coating and drying steps for each layer, and sequentially coating the coating liquid. It is formed by going. As the solvent and dispersion medium used to dissolve the binder resin and prepare the coating liquid, for example, saturated aliphatic solvents such as pentane, hexane, octane and nonane, aromatic solvents such as toluene, xylene and anisole, chlorobenzene, etc. Halogenized aromatic solvents such as dichlorobenzene and chloronaphthalene, amide solvents such as dimethylformamide and N-methyl-2-pyrrolidone, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and benzyl alcohol, glycerin, Aliper polyhydric alcohols such as polyethylene glycol, chain, branched and cyclic ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, 4-methoxy-4-methyl-2-pentanone, methyl formate, ethyl acetate, n-butyl acetate Etc., methylene chloride, chloroform, halogenated hydrocarbon solvent such as 1,2-dichloroethane, diethyl ether, dimethoxyethane, tetrahydrofuran (hereinafter, appropriately referred to as "THF"), 1,4-dioxane, etc. Chain and cyclic ether solvents such as methyl cellsolve and ethyl cell solve, aproton polar solvents such as acetonitrile, dimethylsulfoxide, sulfolane, hexamethylphosphate triamide, n-butylamine, isopropanolamine, diethylamine, triethanolamine, Examples thereof include nitrogen-containing compounds such as ethylenediamine, triethylenediamine and triethylamine, mineral oils such as ligroin, water and the like, and those which do not dissolve the above-mentioned undercoat layer are preferably used. It should be noted that one of these may be used alone, or two or more thereof may be used in any ratio and combination.

In the case of the charge transport layer of the single-layer type photoconductor and the laminated type photoconductor, the coating liquid for layer formation has a solid content concentration of usually 5% by weight or more, preferably 10% by weight or more, and the upper limit thereof is , Usually 40% by weight or less, preferably 35% by weight or less. The viscosity of the coating liquid is usually 10 [mPa · s] or more, preferably 50 [mPa · s] or more, and the upper limit thereof is usually 500 [mPa · s] or less, preferably 400 [mPa · s]. It is as follows.

In the case of the charge generation layer of the laminated photoconductor, the solid content concentration is usually 0.1% by weight or more, preferably 1% by weight or more, and the upper limit thereof is usually 15% by weight or less, preferably 10% by weight. It is as follows. The viscosity of the coating liquid is usually 0.01 m [Pa · s] or more, preferably 0.1 [mPa · s] or more, and the upper limit thereof is usually 20 [mPa · s] or less, preferably 10 [. mPa · s] or less.

Examples of the coating method of the coating liquid include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, a curtain coating method and the like. However, other known coating methods can also be used. In addition, in these methods, 1 type may be used alone, and 2 or more types may be used in arbitrary combination. The coating liquid is dried by touch at room temperature (usually 25 ° C), and then heated in a temperature range of 30 [° C] or more and 200 [° C] or less, usually for 1 minute or more and 2 hours or less, without wind or in a blast. It is preferable to dry it. Further, the heating temperature may be constant or may be changed during drying.

The film thickness of the photosensitive layer of the single-layer type photoconductor is usually [5 μm] or more, preferably 10 [μm] or more, and the upper limit thereof is usually 100 [μm] or less, preferably 50 [μm] or less. The film thickness of the charge transport layer of the forward-laminated photoconductor is usually in the range of 5 [μm] or more and 50 [μm] or less, but is preferably 10 [μm] from the viewpoint of long life and image stability. ] Or more and 45 [μm] or less, more preferably 10 [μm] or more and 30 [μm] or less from the viewpoint of high resolution.

The operation of the above-described configuration will be described.

First, the operation of the developing device at the time of image formation will be described with reference to FIGS. 1, 2 and 3.

As the drive motor 35 controlled by the drive control unit 55 rotates, the photosensitive drum 13, the developing roller 11, and the toner supply roller 12 rotate in the directions indicated by the arrows in FIG.

In this embodiment, the printing speed of the image forming apparatus 10 is equivalent to 40 [ppm] (sheets / minute) for vertical printing on A4 paper as the recording medium P.

In the developing apparatus 20 shown in FIG. 1, the toner supply roller 12 provided with a foamed elastic layer which is a sponge-like elastic body rotates while carrying the toner 17 on the outer peripheral surface and in the cell, and reaches a contact portion with the developing roller 11. To arrive. A DC voltage of −330 [V] is applied to the toner supply roller 12 by the toner supply roller power supply 45. Further, a DC voltage of −200 [V] is applied to the developing roller 11 by the developing roller power supply 44. Then, the negatively charged toner 17 is supplied to the developing roller 11 due to the potential difference generated between the developing roller 11 and the toner supply roller 12.

The toner 17 supported on the surface of the developing roller 11 is thinned by the developing blade 15 to which a DC voltage of −330 [V] is applied by the power supply 47 for the developing blade.

Further, a DC voltage of −1000 [V] is applied to the charging roller 14 by the charging roller power supply 46. As a result, the surface of the photosensitive drum 13 is uniformly charged.

Then, the toner 17 carried by the developing roller 11 is supplied to the electrostatic latent image formed on the photosensitive drum 13 by the exposure of the LED head 26, and the electrostatic latent image is developed.

The toner 17 on the developing roller 11 that has not been supplied to the photosensitive drum 13 is scraped off by the toner supply roller 12 at the opposite portion of the toner supply roller 12.

The toner 17 developed on the photosensitive drum 13 and not transferred to the recording medium P and the external additive released from the toner matrix particles and adhering to the surface of the photosensitive drum 13 are conveyed to the contact portion of the cleaning blade 16. It is scraped off.

Next, the dust stain will be described with reference to FIG. 7.

When dust stains do not occur, as shown in FIG. 7A, the transfer residual toner and the toner externalizing agent 81 adhering to the surface of the photosensitive drum 13 are scraped off by the cleaning blade 16.

On the other hand, as shown in FIG. 7B, the toner external additive 81 adhering to the surface of the photosensitive drum 13 may not be sufficiently scraped off by the cleaning blade 16 and may slip through. The external additive 81 that has passed through the cleaning blade 16 is deposited on the surface of the cleaning blade 16 facing the photosensitive drum 13 and aggregates. The agglomerated external additive 82 disintegrates when it grows to a certain size, becomes an external additive aggregate 83, and falls from the surface of the cleaning blade 16 to the surface of the photosensitive drum 13. The external additive agglomerates 83 that have fallen on the surface of the photosensitive drum surface 13 have a size of several tens to several hundreds [μm], and the charging process is started by the charging roller 14 while adhering to the surface of the photosensitive drum 13. The surface of the photosensitive drum 13 to which the external additive agglomerates 83 is attached is not charged to a desired potential, and the toner 17 is developed and transferred onto the recording medium P in the developing process by the developing roller 11. NS. On the recording medium P, it appears as dust-like color dots (dust stains) having a size of several to several hundreds [μm].

Next, a method of measuring the post-exposure potential of the photosensitive drum 13 will be described with reference to FIG.

As shown in FIG. 8, the post-exposure potential of the photosensitive drum 13 excludes the toner 17, the developing roller 11, the toner supply roller 12, the developing blade 15, the cleaning blade 16, and the toner cartridge 22 as the toner accommodating portion from the developing device 20. Then, a probe 85 of a surface potential meter (Model 344) 84 manufactured by Trek Co., Ltd. was installed at a contact position between the photosensitive drum 13 and the developing roller 11, and the LED head 26 was fully exposed for measurement. The time for the surface of the photosensitive drum 13 to move from the exposure position by the LED head 26 to the development position by the developing roller 11 was 0.04 to 0.06 [s (seconds)].

The linear velocity of the photosensitive drum 13 at 0.04 [s (seconds)] is 234.0 [mm / sec], and the linear velocity of the photosensitive drum 13 at 0.06 [s (sec)]. Was 182.79 [mm / sec].

Next, a method for measuring fog will be described.

Here, fog means that the toner adheres to the background portion of the image, that is, the non-image portion by the toner having a low charge amount or the toner charged in the opposite polarity with respect to the normally charged toner. Further, a toner having a low charge amount that causes this fog or a toner charged with the opposite polarity is referred to as a fog toner.

To measure fog, a test pattern (blank paper) is printed on the recording medium P so that the print image density is 0%, and 3M's Scotch mending is applied to the portion of the surface of the photosensitive drum 13 from the developing portion to the transfer portion. After attaching and peeling off the tape (registered trademark), attach the unused mending tape and the peeled off mending tape to the excellent white paper manufactured by Oki Data Co., Ltd., and then attach the spectrophotometer manufactured by Konica Minolta Co., Ltd. This was done by measuring the color difference ΔE using CM-2600d. When a fog phenomenon occurs on the surface of the photoconductor drum 13, the toner 17 caused by the fog phenomenon adheres to the peeled mending tape. That is, the lower the fog level, the larger the value of ΔE.

Next, a positive afterimage of 13 cycles of the photosensitive drum will be described with reference to FIG.

The positive afterimage means that when an intermediate density image such as a halftone image is subsequently formed at an exposed portion of the photosensitive drum 13 that has formed an image with clear light and darkness, the previously formed image appears in the intermediate density image. It is a phenomenon.

FIG. 13 shows an example of an evaluation pattern for confirming the presence or absence of a positive afterimage in the photosensitive drum cycle. A solid bold character 101 is arranged at the upper end of the recording medium P, and a halftone pattern 102 is arranged at a position corresponding to one round of the photosensitive drum from the bold character 101. When the positive afterimage of the photosensitive drum cycle does not occur, the afterimage of the bold character 101 does not occur in the halftone portion 102 as shown in FIG. 13 (a), but when the potential VL after exposure is too low, FIG. 13 (b). As shown in the above, the surface potential of the portion printed with the bold character 103 does not rise completely at the time of the next charge, and the print density becomes high. As a result, a positive afterimage 105 is generated in the halftone portion 104 after one cycle of the photosensitive drum from the bold character.

Next, a printing test method performed to confirm the effect in this example will be described.

As for the test for confirming the presence or absence of dust stains, continuous paper passing was performed with the solid pattern 86 shown in FIG. The reason for continuous paper passing in a solid pattern (printed image density 100%) is that the amount of residual toner transferred increases, and the amount of toner 17 and the toner externalizing agent 81 collected by the cleaning blade 16 increases. The evaluation environment is temperature 25 [° C.], relative humidity 50 [%], 10,000 sheets, temperature 27 [° C.], relative humidity 80 [%], 10,000 sheets, temperature 10 [° C.], relative humidity 20 [° C.]. %] Was 10,000 sheets, for a total of 30,000 sheets. Further, a blank pattern (printed image density 0%) was printed every 1,000 sheets in order to confirm the presence or absence of the dust stain 87 shown in FIG.

In the print image density, printing with an area ratio of 100% at the time of solid printing on the entire surface in a printable range of a predetermined area (for example, one round of a photosensitive drum or one page of a print medium) is defined as 100% print image density. The print corresponding to the area of 0% with respect to the print image density of 100% is called the print image density of 0%.

The number of dots actually used in printing when the photosensitive drum rotates Cd, that is, the number of exposed dots is Cm (i), and the number of dots per rotation of the photosensitive drum, that is, regardless of the presence or absence of exposure. It is a dot that can be printed (potentially dots in printing) per rotation of the photosensitive drum, and if the number of dots used in the case of a solid image (solid image) is C0, the print image density is as follows. It is represented by.

Printed image density = [Cm (i) / (Cd × C0)] × 100 [%]
Note that Cd × C0 is the number of dots that can be printed (potentially dots in printing) when the photosensitive drum is rotated by Cd.

Further, in order to confirm the level of the positive afterimage, the pattern shown in FIG. 13A was printed every 1,000 sheets. Further, the fog toner on the photosensitive drum 13 was collected before continuous paper passing at a temperature of 27 [° C.] and a relative humidity of 80 [%] in a high temperature and high humidity environment, and ΔE was confirmed.

For the test for confirming the amount of increase in the post-exposure potential after continuous energization, the image forming apparatus and developing apparatus having the configuration shown in FIG. 8 were used in an environment of a temperature of 27 [° C.] and a relative humidity of 80 [%]. , The LED head 26 was fully exposed and the paper was continuously passed for 2 hours.

Regarding dust stains, it was judged that those that did not occur at all were effective in printing a total of 30,000 sheets in each environment. Further, regarding the increase in the potential after exposure, it was judged to be effective when the amount of increase in the potential after continuous energization was 20 [V] or less. The reason why the determination standard is set to 20 [V] or less is that when the amount of increase in the potential after exposure is larger than 20 [V], the print density decrease (particularly halftone) becomes remarkable.

Further, regarding fog in a high temperature and high humidity environment (temperature 27 [° C.], relative humidity 80 [%]), when ΔE is 1.5 or less, it is effective as the fog on the recording medium P is not noticeable. I decided.

Further, regarding the positive afterimage of 13 cycles of the photosensitive drum, the print density of the afterimage portion 105 and the halftone portion 104 shown in FIG. 13B was measured by X-Rite 528 manufactured by X-Rite, and the density difference was 0.02 or less. It was judged to be effective because the afterimage was not noticeable visually.

The test of this example was carried out by varying the molecular weight of the binder resin of the charge transport layer 77 of the photosensitive drum 13 and the molecular weight and the amount of the charge transport agent added to the charge transport layer 77.

In this example, a polyarylate resin was used as the binder resin for the charge transport layer 77. The polyarylate resin can be obtained by a known synthesis method (for example, the production method disclosed in JP-A-2018-172466).

As a method for adjusting the molecular weight of the binder resin, an interfacial polymerization method using a molecular weight adjusting agent was used. Examples of the molecular weight modifier include phenol, o, m, p-cresol, o, m, p-ethylphenol, o, m, p-propylphenol, o, m, p- (tert-butyl) phenol, and pentyl. Alkylphenols such as phenol, hexylphenol, octylphenol, nonylphenol, 2,6-dimethylphenol derivative, 2-methylphenol derivative; monofunctional phenols such as o, m, p-phenylphenol; chloride, butyric acid chloride, octyl Examples thereof include monofunctional acid halides such as acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride and their substitutes. Among these molecular weight modifiers, o, m, p- (tert-butyl) phenol, 2,6-dimethylphenol derivative, and 2-methylphenol derivative are preferable in terms of high molecular weight control ability and solution stability. Is. Particularly preferred are p- (tert-butyl) phenol, 2,3,6-trimethylphenol and 2,3,5-trimethylphenol.

In addition, the following method was used as the interfacial polymerization method. First, an alkaline aqueous solution of bisphenols is prepared as the aqueous phase, and then a polymerization catalyst and, if necessary, a molecular weight modifier (terminal sealant) are added. Further, the solvent for preparing the organic phase is mixed with dicarboxylic acid chloride, which is a raw material for polymerizing the dicarboxylic acid component, to prepare the organic phase. Then, the organic phase solution is mixed with the aqueous phase solution, and the interfacial polymerization reaction is carried out while stirring at 25 ° C. or lower for 1 to 5 hours to obtain a high molecular weight polyarylate. At this time, the high molecular weight polymer (reaction product) is present in the organic phase.

Further, in this example, a compound in which an aromatic amine derivative and an enamine derivative are bound was used as a charge transport agent.

The charge transport agent can be obtained by a known synthesis method (for example, the production method disclosed in JP-A-2018-172466). Further, the molecular weight of the charge transporting agent can be adjusted by changing the number of carbon atoms of the alkyl group, the alkoxy group, the phenyl group and the like by a known method.

The test results of this example are shown in Tables 1 and 2. In this example, the charge transport agent 1 as the first charge transport material is a compound using an aromatic amine derivative, and the charge transport agent 2 as a second charge transport material is a compound using an enamine derivative.

バインダー樹脂と電荷輸送剤の重量平均分子量(Ｍｗ)は、ＧＰＣ（ゲルパーミエイションクロマトグラフィー）で測定した。表１に、分子量分布のピークの分子量と、各ピークの面積割合（すなわち重量比）を記す。感光ドラム１３の表面に切り込みを入れた後、感光層７３を剥がし取り、剥がし取った感光層７３を約３[ｍｇ／ｌ]の濃度で、ＴＨＦで溶解したものを測定した。

The weight average molecular weight (Mw) of the binder resin and the charge transport agent was measured by GPC (gel permeation chromatography). Table 1 shows the molecular weight of the peaks of the molecular weight distribution and the area ratio (that is, weight ratio) of each peak. After making a cut in the surface of the photosensitive drum 13, the photosensitive layer 73 was peeled off, and the peeled photosensitive layer 73 dissolved in THF at a concentration of about 3 [mg / l] was measured.

In this example, THF, which is insoluble in the charge generation layer 76 and soluble in the charge transport layer 77, was selected as the solvent for dissolving the photosensitive layer 73.

To describe a specific measurement method, the peeled photosensitive layer 73 was put into THF and left in an environment of 40 ° C. for 1 hour to dissolve the charge transport layer 77.

Then, the solution in which the charge transport layer 77 was dissolved was taken out with a syringe, and then filtered through an HPLC pretreatment filter (chromatographic disk 25N, manufactured by Kurabo Industries Ltd.) having a pore size of 0.45 μm.

200 μL (microliter) of the filtered solution was taken out and measured with a GPC measuring machine.

In this embodiment, the film thickness of the charge transport layer 77 is 20 ± 1 μm, the film thickness of the charge generation layer 76 is 1 ± 0.2 μm, and the film thickness of the undercoat layer 75 is 1 ± 0.2 μm. Is used, and the film thickness of the charge transport layer 77 is remarkably thicker than the film thickness of the charge generation layer 76. That is, the main component of the peeled photosensitive layer 73 is the charge transport layer 77, and even if a part of the charge generation layer 76 is dissolved in THF, the main component of the filtered solution is contained in the charge transport layer 77. It is considered to be an ingredient.

The weight average molecular weight (Mw) of the binder resin and the charge transport agent in this example is measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. An example of more detailed measurement conditions is shown below.

Equipment: Gel permeation chromatograph system consisting of each unit of LC-20AD, SIL-20A HT, CBM-20A, RID-20A, CTO-20A manufactured by Shimadzu Corporation Column: TSKgel Super HM-M 6mm I. D. × 15 cm (manufactured by Tosoh Corporation) 2 Standard substances: Polystyrene (manufactured by Tosoh Corporation)
Flow velocity: 0.6 ml / min
Solvent: tetrahydrofuran (THF)
Temperature: 40 ° C
Detector: R. I, UV (254 nm)
The profile output as the weight average molecular weight distribution of the charge transport layer 77 is as shown in FIG. 11, and is based on the analysis results of the analysis software "LabSolutions" (manufactured by Shimadzu Corporation) attached to the gel permeation chromatograph system. , The peak molecular weight and area ratio (additional weight ratio) of each peak were obtained.

In the molecular weight distribution obtained by GPC measurement as shown in FIG. 11, the molecular weight showing the highest value on the vertical axis is defined as the peak molecular weight of each of the binder resin and the charge transport material. In addition, in FIG. 11, three peak molecular weights appear.

Further, in FIG. 11, the weight molecular weight is taken as an index on the horizontal axis. In the molecular weight distribution, the left side is the low molecular weight side and the right side is the high molecular weight side. Here, the horizontal axis of FIG. 11 is 1. The peak near E + 05 is the binder resin, 1. Let the two peaks near E + 03 be the peaks of the charge transport material, respectively.

Next, a method for measuring the Martens hardness will be described.

The Martens hardness in this example is a value measured in an environment of a temperature of 25 ° C. and a relative humidity of 50% using a micro hardness tester Nano Indenter G200 manufactured by Agilent Technologies.

FIG. 15 is an explanatory diagram of a method for measuring Martens hardness in this embodiment.

As shown in FIG. 15A, the photosensitive drum 13 is fixed to the holder 91, and the indenter 90 provided in the load control mechanism 92 is vertically loaded on the surface of the photosensitive drum 13. For the measurement, a pre-mounted Berkovich-diamond indenter having a facing angle of 145 degrees is used as the indenter 90. The Martens hardness is measured by an indentation test.

The indentation test will be described.

The measurement conditions are set as follows, and the load applied to the indenter 90 and the pushing depth under the load are continuously read, and each load [mN] is on the Y-axis and the depth [μm] is on the X-axis. Obtain a profile as shown in FIG. 16 plotted in.
[Measurement condition]
Allowable heat transfer rate 1 nm / s
Maximum pushing load 4mN
Load time required 25s
Load holding time 30s
Unloading time 25s
In FIG. 16, points G1 to G2 indicate a state in which the load applied to the indenter 90 increases, points G2 to G3 indicate a state in which the maximum indentation load by the indenter 90 is held, and points G3 to G4 are shown. Indicates a state in which the load due to the indenter 90 is unloaded.

In this embodiment, the Martens hardness is a value when the pushing load is pushed up to 4 mN, and is a value defined by the following formula from the pushing depth. Note that FIG. 15B shows a state when the indenter 90 is pushed into the photosensitive drum 13.

Martens hardness [N / mm ² ] = test load [N] / surface area of Vickers indenter under test load [mm ² ] ・ ・ ・ formula The toner used in this example is EDX measurement energy dispersive fluorescent X. It is measured by elemental analysis of the surface of the toner using an energy dispersive X-ray spectroscopy (EDX). In elemental analysis using EDX, for example, an energy dispersive fluorescent X-ray analyzer EDX-800HS manufactured by Shimadzu Corporation is used. In this case, for example, the analysis environment is set to a helium gas (He) atmosphere, and the X-ray tube voltage is set to 15 kV and 50 kV.

The toner of this example is attached with a plurality of types of silica as an external additive, and the amount of silicon detected by elemental analysis of the toner using EDX is in the range of 3.144 to 4.188% by weight. there were.

In Tables 1 and 2, regarding the four test items, post-exposure potential rise, dust stain, fog, and positive afterimage, those that were effective in the above-mentioned judgment criteria were "○" and those that were not effective were "○". × ”. Further, in the above-mentioned printing test results, those in which all four items were effective were considered to have long-term performance stability as the photosensitive drum 13, and were marked with "○" in the determination column.

The photosensitive drum 13 which does not generate dust stains, fog, and positive afterimages, suppresses the potential increase after exposure to 20 [V] or less, and has long-term performance stability, is described in Examples 1 to 7 shown in Table 1. Met.

In Examples 1 to 7, the product of the peak molecular weight A and the addition ratio B of the weight average molecular weight distribution of the binder resin represented by the formula (1), and the peak molecular weight and the addition ratio of the weight average molecular weight distribution of the charge transport agent. The ratio of the total product C × D + E × F was within the range of 199.5 or more and 231.9 or less.

A × B / (C × D + E × F) ・ ・ ・ Equation (1)
The Martens hardness of the photosensitive drum 13 was 151 [MPa] or more and 173 [MPa] or less. By increasing the Martens hardness of the photosensitive drum 13 in this way, the nip pressure between the photosensitive drum 13 and the developing roller 11 increases, and the triboelectric charge of the toner layer increases, resulting in improved fog.

That is, in Examples 1 to 7, the weight average molecular weight of the binder resin 88 of the charge transport layer 77 of the photosensitive drum 13 is MP, the addition ratio of the binder resin 88 is WL, and the weight average molecular weight of the first charge transport agent 89. MT1, the weight average molecular weight of the second charge transport agent 89 is MT2, the addition ratio of the first charge transport agent 89 is WT1, and the addition ratio of the second charge transport agent 89 is WT2.
(MP x WL) / (MT1 x WT1 + MT2 x WT2) ... Equation (2)
When
199.5 ≤ Equation (2) ≤ 231.9
And the Martens hardness of the photosensitive drum 13 was 151 [MPa] or more and 173 [MPa] or less.

From the above test results, it can be seen that the generation of dust stains and the increase in potential after exposure are contributed by the molecular weight of the binder resin of the charge transport layer 77, the molecular weight of the charge transport agent, and the addition amounts of each.

Comparative Examples 1 to 3 and 7 to 9 shown in Table 2 explain the reasons why the potential rise and dust stains occurred after exposure, respectively, in the explanatory view of the charge transport layer in the example of FIG. 12 and the example of FIG. It will be described with an explanatory diagram of the action of the charge transport layer in.

In FIG. 12, the charge transport layer 77 laminated on the charge generation layer 76 is mainly composed of the binder resin 88 and the charge transport agent 89.

The value of the formula (1) becomes large as in Comparative Examples 1 to 3 when the binder resin 88 has a large molecular weight, a small amount of the charge transporting agent is added, or a small molecular weight.

If the molecular weight of the binder resin 88 is increased in order to enhance the mechanical properties of the charge transport layer 77, which is the outermost layer of the photosensitive drum 13, side chains and the like that do not contribute to charge transfer to the resin increase. As shown in a), the number of paths for the charge of the charge transporting agent 89 generated in the charge generation layer 76 to move is reduced, and the post-exposure potential is increased. In addition, after continuous energization, the potential after exposure becomes even higher due to the influence of traps (deep energy levels created by impurities and lattice defects contained in the polymer) that hinder the movement of electric charges. Note that FIG. 14A shows a state in which the polymer chains of the binder resin 88 hinder the transfer of electric charges between the charge transporting agents 89, resulting in a delay.

Even when the molecular weight of the charge transport agent 89 is small or the amount added is small, as shown in FIG. 14 (b), the number of paths for charge transfer is reduced, so that the charge mobility is impaired and the post-exposure potential is increased. It gets higher. Note that FIG. 14B shows how the charge transfer is delayed because the amount of the charge transporting agent 89 is small.

The value of the formula (1) becomes small as in Comparative Examples 7 to 9 when the molecular weight of the binder resin 88 is small, the molecular weight of the charge transport agent 89 is large, or the amount added is large.

When the molecular weight of the binder resin 88 becomes small, as shown in FIG. 14C, the polymer chain of the binder resin 88 is short, so that the charge transport layer 77 has a pressure from the contact member (the arrow F in FIG. 14C). A large dent is generated with respect to the indicated pressure), and it becomes easy to be deformed. Along with the deformation of the charge transport layer 77, a slight gap is formed at the contact portion with the cleaning blade 16 shown in FIG. 7B, from which the toner external additive 81 slips through and an external additive aggregate 83 is generated. And generate dust stains.

When the molecular weight of the charge transporting agent 89 is large or the amount added is large, the amount of the charge transporting agent 89 existing between the molecules of the binder resin 88 increases as shown in FIG. It takes a long time to return to the original state after being deformed by receiving the pressure indicated by the arrow F of 14 (d), and it becomes difficult to return to the original state (plastic deformation becomes easy). As a result, a slight gap is formed at the contact portion with the cleaning blade 16, from which the toner external additive 81 slips through, an external additive agglomerate 83 is generated, and dust stains are generated.

It is considered that the deterioration of fog in Comparative Examples 6 and 7 shown in Table 2 is due to the decrease in the Martens hardness and the decrease in the nip pressure between the photosensitive drum 13 and the developing roller 11. As a result, the frictional force when the toner layer on the developing roller 11 comes into contact with the surface of the photosensitive drum 13 is reduced, and fog is exacerbated.

In Examples 1 to 7 and Comparative Examples 1 to 9, the addition ratio of the charge transporting agent 89 is about 40%, but in Comparative Examples 6 and 7, only the charge transporting agent having a large peak molecular weight is added. Therefore, the number of charge transporting agents 88 present in the charge transporting layer 77 is smaller than in other examples. As a result, it is considered that the binder resins 88 of Comparative Examples 6 and 7 are easily deformed by an external force, and the Martens hardness of the charge transport layer is lowered.

In other words, in order to increase the Martens hardness while maintaining the value of the formula (1) shown in Table 1 to be 199.5 or more and 231.9 or less so that the potential rise after exposure and dust stains do not occur. It can be seen that an appropriate amount of the charge transporting agent 89 having a small peak molecular weight should be added.

On the other hand, the reason why the positive afterimage deteriorated in Comparative Examples 4 and 5 was that the number of charge transport agents 89 in the charge transport layer 77 increased due to the increase in the amount of the charge transport agent 89 having a small peak molecular weight. This is because the mobility of the electric charge has increased and the potential after exposure has become too low. Since the potential after exposure was too low, the surface potential of the portion printed with the bold character 103 shown in FIG. 13B did not rise at the time of the next charge, and the print density became high.

As described above, from the results of Examples 1 to 7 of this Example, in order to suppress fog and positive afterimage while suppressing the potential rise after exposure and the generation of dust stains after continuous energization, the charge transport agent 89 is 2 Using the type, the above-mentioned equation (1)
199.5 ≤ Equation (1) ≤ 231.9
It can be seen that the Martens hardness of the photosensitive drum 13 should be 151 [MPa] or more and 173 [MPa] or less.

However, in this embodiment, of the two types of charge transporting agents 89, the charge transporting agent 2 having a smaller peak molecular weight than the charge transporting agent 1 has a peak molecular weight of 456 or more and 541 or less, and has an addition ratio of 10. % Or more and 15% or less.

This is because even if the addition ratio of the charge transport agent 2 is within the range of 10% or more and 15% or less, if the peak molecular weight is smaller than 456, the amount of the charge transport agent 2 added is large, and the potential after exposure drops too much, resulting in a worsening positive afterimage. do.

Further, even if the addition ratio of the charge transport agent 2 is within the range of 10% or more and 15% or less, if the peak molecular weight is larger than 541, the addition amount of the charge transport agent 2 is small, and the potential after exposure becomes too high, so that the print density is low. This is to become.

Further, if the addition ratio of the charge transport agent 2 is large (greater than 15%), the potential after exposure becomes too low, so that the print density becomes dark and the positive afterimage deteriorates.

Further, if the addition ratio of the charge transport agent 2 is small (less than 10%), the potential after exposure becomes too high and the print density becomes low.

Therefore, in this embodiment, the molecular weight peak of the charge transport agent 2 (second charge transport material) having a smaller molecular weight peak than that of the charge transport agent 1 (first charge transport material) is 456 or more and 541 or less, and the charge is charged. The amount of the transport agent 2 (second charge transport material) added was 10 [%] or more and 15 [%] or less.

The peak molecular weight is the peak molecular weight of the weight average molecular weight distribution measured by gel permeation chromatography (GPC). The addition ratio is the addition weight ratio [%] of the binder resin constituting the charge transport layer and the charge transport agent.

As described above, in this embodiment, it is possible to obtain the effect of suppressing the generation of dust stains and fog on the image formed by the developing apparatus.

In addition, the effect of suppressing the generation of positive afterimages can be obtained.

Further, it is possible to obtain the effect that the potential increase after exposure after continuous energization can be suppressed in the photosensitive drum.

In this embodiment, a direct transfer type monochrome printer with one developing device has been described as an example of an image forming device, but a color image forming device having a plurality of developing devices and an intermediate transfer type image forming device have been described. May be. Further, the image forming apparatus may be a copying machine, a facsimile apparatus, a multifunction device (MFP), or the like.

10 Image forming device 11 Developing roller 12 Toner supply roller 13 Photosensitive drum 14 Charging roller 15 Developing blade 16 Cleaning blade 17 Toner 20 Developing device 22 Toner accommodating part 23 Casing 25 Transfer roller 26 LED head 27 Fuser 28 Image forming unit 35 Drive motor 55 Drive control unit 71 Drum gear 72 Drum flange 73 Photosensitive layer 74 Conductive support 75 Undercoat layer 76 Charge generation layer 77 Charge transport layer

Claims (11)

An image carrier having a photosensitive layer containing a binder resin, a first charge transport material and a second charge transport material, and
An abutting member that comes into contact with the surface of the image carrier,
With
The weight average molecular weight of the binder resin in the photosensitive layer is MP, the addition ratio of the binder resin is WL, the weight average molecular weight of the first charge transport material is MT1, and the weight average molecular weight of the second charge transport material is MT1. Is MT2, the addition ratio of the first charge transport material is WT1, and the addition ratio of the second charge transport material is WT2.
199.5 ≤ (MP x WL) / (MT1 x WT1 + MT2 x WT2) ≤ 231.9
The filling,
The image carrier unit is characterized in that the Martens hardness of the image carrier is 151 [MPa] or more and 173 [MPa] or less. In the image carrier unit according to claim 1,
The molecular weight peak of the second charge transport material is smaller than that of the first charge transport material. The molecular weight peaks of the second charge transport material are 456 or more and 541 or less.
An image carrier unit characterized in that the amount of the second charge transport material added is 10 [%] or more and 15 [%] or less. In the image carrier unit according to claim 1 or 2.
An image carrier unit characterized in that the weight average molecular weight of the binder resin is 99792 or more and 11543 or less. In the image carrier unit according to any one of claims 1 to 3.
It has a contact portion that comes into contact with the surface of the image carrier, and is provided with a cleaning blade that removes residues on the surface of the image carrier as the image carrier rotates.
The image carrier unit is characterized in that the cleaning blade is in contact with the image carrier at a linear pressure of 15 [gf / cm] or more and 30 [gf / cm] or less. In the image carrier unit according to claim 4,
The image carrier is a rotating body and
An image carrier unit characterized in that the contact angle between the cleaning blade and the image carrier at the contact portion is 10 degrees or more and 15 degrees or less. In the image carrier unit according to claim 4 or 5.
An image carrier unit characterized in that the linear velocity of the image carrier is 234 [mm / sec] or less. The image carrier unit according to any one of claims 1 to 6.
The weight average molecular weight of the binder resin and the weight average molecular weights of the first charge transport material and the second charge transport material are the peak molecular weights of the weight average molecular weight analyzed by a GPC (gel permeation chromatography) apparatus. An image carrier unit characterized by this. An image carrier having a charge transport layer containing a binder resin, a first charge transport material and a second charge transport material, and
An abutting member that comes into contact with the surface of the image carrier,
With
The weight average molecular weight of the binder resin in the charge transport layer is MP, the addition ratio of the binder resin is WL, the weight average molecular weight of the first charge transport material is MT1, and the weight average of the second charge transport material. When the molecular weight is MT2, the addition ratio of the first charge transport material is WT1, and the addition ratio of the second charge transport material is WT2.
The peak molecular weight and area ratio of the binder resin, the first charge transport material, and the second charge transport material are determined by gel permeation chromatography measurement of the charge transport layer.
199.5 ≤ (MP x WL) / (MT1 x WT1 + MT2 x WT2) ≤ 231.9
The filling,
The image carrier unit is characterized in that the Martens hardness of the image carrier is 151 [MPa] or more and 173 [MPa] or less. In the image carrier unit according to claim 8,
The image carrier comprises a photosensitive layer containing a binder resin and two types of charge transporting materials.
The image carrier unit is characterized in that the gel permeation chromatography measurement uses a solution in which the photosensitive layer is dissolved in THF (tetrahydrofuran). In the image carrier unit according to claim 8 or 9.
The image carrier unit, wherein the charge transport layer is composed of the binder resin and the two types of charge transport materials. An image forming apparatus that forms a developer image.
An image forming apparatus comprising the image carrier unit according to any one of claims 1 to 10.

Images