JP2005241966A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a image forming method which provides high durability by suppressing image deletion, toner fusion on a photoreceptor, and contamination of a electrifying member in high-humidity environment even when the photoreceptor having high wear resistance is used. <P>SOLUTION: The image forming method includes: a step of electrifying a photoreceptor which has at least a photosensitive layer and a protection layer on a support being an image carrier; an electrostatic latent image forming step of forming an electrostatic latent image on the charge photoreceptor; a developing step of visualizing the electrostatic latent image by transferring toner carried on a toner image carrier to the electrostatic latent image; a transfer step of transferring the toner image formed on the image carrier to a transfer material; and a cleaning step of removing residual toner after transfer which is left on the photoreceptor after the transfer step from on the photoreceptor, wherein the image forming method is characterized in that the protection layer has 150 to 200 (N/mm<SP>2</SP>) universal hardness and a 44 to 65% elastic deformation rate and is supplied with fatty acid metal salt of 0.3 to 4.5 mass % in water content from a supply member. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an image forming method used in a recording method using an electrophotographic method, an electrostatic recording method or the like. More specifically, the present invention relates to an image forming method used in a copying machine, a printer, and a fax machine in which an electrostatic latent image formed on an electrostatic latent image carrier is developed with toner and then transferred onto a transfer material to form an image.

  Conventionally, an electrophotographic photoreceptor is often used as a function-separated photoreceptor in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical characteristics. As a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, since various electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning are directly applied to the surface of the photoreceptor to be used repeatedly, durability against them is required. .

  Specifically, durability against the occurrence of surface abrasion and scratches due to rubbing, and durability against deterioration of electrical characteristics such as sensitivity reduction and potential reduction are also required.

  Solving such problems of the conventional electrophotographic photosensitive member, and improving the abrasion resistance and scratch resistance by increasing the film strength, further, a highly durable photosensitive member, A photoconductor containing a curable resin in a surface layer is used as an electrophotographic photoconductor that exhibits very little change or deterioration in photoconductor characteristics such as an increase in residual potential and can exhibit stable performance even during repeated use. This has been proposed (see, for example, Patent Document 1).

  However, since these photoconductors with high wear resistance are less prone to scraping of the photoconductor, it is difficult to remove the charged product adhering to the surface by scraping the surface of the photoconductor with, for example, a cleaning blade. In particular, when the charging process is performed in a very small space between the charging member and the photosensitive member when used in a high humidity environment or when the charging member is in contact with the photosensitive member, the surface of the photosensitive member tends to undergo severe changes and oxidative degradation. Also, ozone generated in the charging process reacts with nitrogen in the air to form nitrogen oxides, and further reacts with moisture in the air to form nitric acid, which adheres to the surface of the photoreceptor and lowers the surface resistance of the photoreceptor. In the case of cleaning the transfer residual toner on the photosensitive member, particularly when cleaning with a blade, the blade is not stable and the transfer residual toner slips through the contact charging member. Surface is contaminated, charging failure is in the tendency uneven charging occurs, also fixation of the toner on the photosensitive member because it is difficult to cut the surface of the photosensitive member, the fusion is a problem that more likely to occur arises.

  It is known that these problems can be improved by applying a fatty acid metal salt typified by zinc stearate to the photoreceptor (for example, see Patent Documents 2 to 5).

JP 2002-82469 A JP-A-5-35155 JP 7-44076 A JP 2001-265040 A JP 2002-323837 A

  However, when photoconductors with high wear resistance are used, even if those fatty acid metal salts are applied to the photoconductor, the above-described problem-improving effect is insufficient, particularly in a high humidity environment. The problem has occurred.

  The present invention has been made in view of the above-mentioned problems. The object of the present invention is that even if a photoconductor having high wear resistance is used, image flow in a high humidity environment, toner fusion on the photoconductor, charging An object of the present invention is to provide a highly durable image forming method by suppressing contamination of members.

In order to achieve the above object, the present invention includes a step of charging a photosensitive member having a photosensitive layer and a protective layer on at least a support which is an image carrier, and an electrostatic for forming an electrostatic latent image on the charged photosensitive member. A latent image forming step, a developing step of transferring the toner carried on the toner carrying member to the electrostatic latent image for visualization, and a transferring step for transferring the toner image formed on the image carrying member to a transfer material; In the image forming method including the cleaning step of removing the transfer residual toner remaining on the photoconductor after the transfer step, the universal hardness value HU of the protective layer is 150 or more and 200 or less (N / mm ² ). And supplying the fatty acid metal salt having an elastic deformation rate of 44% to 65% and a moisture content of 0.3% to 4.5% from the supply member to the protective layer. Features.

According to the present invention, at least a step of charging a photosensitive member having a photosensitive layer and a protective layer on a support which is an image carrier, an electrostatic latent image forming step of forming an electrostatic latent image on the charged photosensitive member, and A development process for visualizing the toner carried on the toner carrying body by transferring the electrostatic latent image; a toner image formed on the image carrying body on the transfer material; In the image forming method having a cleaning step of removing the remaining transfer residual toner from the photosensitive member, the universal hardness value HU of the protective layer is 150 (N / m ² ) or more and 220 (N / m ² ) or less, and The fatty acid metal salt having an elastic deformation rate of 44% to 65% and a moisture content of 0.3% to 4.5% by mass is supplied to the protective layer from a supply member. Depending on the image forming method, Even when a highly durable photoconductor with a small amount is used, an extremely thin fatty acid metal salt film can be formed on the photoconductor surface by supplying the fatty acid metal salt as described above to the photoconductor surface. Since the discharge product generated in the process and adhered to the surface of the fatty acid metal salt having a film formed on the surface of the photosensitive member is easily removed from the surface of the photosensitive member by a cleaning blade or the like due to the scratching property of the fatty acid metal salt, It is possible to provide a highly durable image forming method in which image flow under high-humidity environment, toner adhesion to the photoconductor, and the like are suppressed.

  Embodiments of the present invention will be described below with reference to the accompanying drawings.

  FIG. 1 shows an example of a specific apparatus that can be used to carry out the image forming method of the present invention.

  In FIG. 1, reference numeral 1 denotes a photosensitive drum, and a primary charging roller 6, a developing device 7, and a transfer charging roller 2 are provided around the photosensitive drum. The photosensitive member 1 is charged by a primary charging roller 6 that contacts the photosensitive member. And it exposes by irradiating the photoreceptor 1 with the laser beam L with a laser generator. The electrostatic latent image on the photoreceptor 1 is developed with toner by the developing device 7 and transferred onto the transfer material 1 by the transfer roller 2 in contact with the photoreceptor via the transfer material. The transfer material on which the toner image is placed is conveyed to the fixing device 3 through the conveyance guide and is fixed on the transfer material. In addition, a part of the toner remaining on the photosensitive member is removed from the surface of the photosensitive member 1 by a cleaning process (illustrated by an elastic blade) 4 that contacts the photosensitive member 1, and a fatty acid metal salt is supplied to the photosensitive member. This is an image forming method including the member 9-1.

A feature of the present invention is that the photoreceptor 1 shown in FIG. 1 has a protective layer having a universal hardness value HU of 150 to 240 (N / mm ² ) and an elastic deformation ratio of 44% to 65%. And supplying the photoreceptor with a fatty acid metal salt containing water whose water content is 0.2% by mass or more and 4.0% by mass or less.

By using a photoconductor having a universal hardness value (hereinafter referred to as HU) of 150 to 240 (N / mm ² ) and an elastic deformation rate of 44% to 65% of the photoconductor having a protective layer, Mechanical deterioration of the surface of the photoconductor is suppressed, the amount of wear on the surface layer and the scratches on the photoconductor are reduced, and high durability of the photoconductor 1 is achieved.

  In general, the hardness of the film is higher as the amount of deformation with respect to external stress is smaller, and it is naturally considered that the electrophotographic photosensitive member having higher pencil hardness or Vickers hardness improves durability against mechanical deterioration. However, it has been found that the high hardness obtained by these measurements does not necessarily improve the durability, and the above range is good.

Although the HU and the elastic deformation rate cannot be captured separately, for example, when the HU exceeds 240 N / mm ² and the elastic deformation rate is less than 44%, the paper sandwiched between the cleaning blade, the charging, and the transfer roller Since the elastic force of the photoconductor is insufficient for powder, toner, etc., and if the elastic deformation rate is larger than 65%, the elastic deformation amount becomes small even if the elastic deformation rate is high. In particular, a large pressure is applied and scratches are easily generated, and the wear amount of the photosensitive member is also increased. Therefore, it is considered that the one with a high HU is not necessarily optimal as the photosensitive member.

Also, when the HU is less than 150 N / mm ² and the elastic deformation rate exceeds 65%, even if the elastic deformation rate is high, the amount of plastic deformation increases, and the paper sandwiched between the cleaning blade, the charging, and the transfer roller When the powder or toner is rubbed, scraping or fine scratches occur, and the durability life is shortened.

  HU (universal hardness value) and elastic deformation rate are the microhardness measuring device Fischerscope H100V (Fischer, Inc.) that applies continuous load to the indenter and directly reads the indentation depth under the load to obtain continuous hardness. ). The indenter used was a Vickers square pyramid diamond indenter with a face angle of 136 °.

  An outline of the output chart is shown in FIG. 2, and an example of measurement of the electrophotographic photosensitive member of the present invention is shown in FIG.

  2, the vertical axis represents the load (mN) and the horizontal axis represents the indentation depth h (μm). FIG. 3 shows the load increased stepwise (273 points with a holding time of 0.1 s for each point) up to 6 mN. , And then the load was reduced stepwise in the same manner.

  The HU (universal hardness value: hereinafter referred to as HU) of the protective layer of the present invention is defined by the following formula (1) from the indentation depth under the same load when indented at 2 mN.

HU = test load (N) / surface area of Vickers indenter at test load (mm ² )
= 0.002 / 26.43h ² (N / mm ² ) (1)
The elastic deformation rate is obtained from the amount of work (energy) performed by the indenter on the membrane, that is, the change in energy due to the increase or decrease of the load of the indenter on the membrane. The total work Wt (nW) is represented by the area surrounded by A-B-D-A in FIG. 1, and the elastic deformation work W (nW) is represented by the area surrounded by C-B-D-C. Is done.

Elastic deformation rate We = W / Wt × 100 (%) (2)
In order to bring the characteristics of the protective layer of the photoreceptor into the range as described above, the protective layer is preferably formed of a curable resin. This is because the use of the curable resin makes it easy to adjust the HU of the photoreceptor, particularly the elastic deformation rate, to the above-described range by adjusting the degree of cure of the curable resin.

  Curing and polymerization forms include addition by heat, radiation, light, and condensation reaction.

  In particular, by containing a compound obtained by polymerizing an unsaturated polymerizable functional group, the film strength is improved, and the surface layer of the photoconductor is prevented from being scraped by durability, so that high durability is achieved. That is, the unsaturated polymerization is a reaction in which an unsaturated group such as C═C, C≡C, C═O, C═N, C≡N, etc. is polymerized by radicals and ions. = C.

  By polymerizing and crosslinking these compounds having an unsaturated polymerizable functional group, the compound having an unsaturated polymerizable functional group in the photosensitive layer is shared in the three-dimensional crosslinked structure with at least two crosslinking points. Captured through binding.

  The compound having an unsaturated polymerizable functional group can be polymerized or crosslinked alone, or can be mixed with a compound having another polymerizable group, and any kind / ratio can be arbitrarily selected. Can be determined.

  When the functional group of the compound having an unsaturated polymerizable functional group and the other polymerizable compound is the same group or a group capable of polymerizing with each other, they both have a copolymerized three-dimensional crosslinked structure via a covalent bond. It is possible to take.

  When the two functional groups are functional groups that do not polymerize with each other, the photosensitive layer is a mixture of at least two or more three-dimensional cured products or other polymerizable compound monomers in the main component three-dimensional cured product, Alternatively, it is configured to contain the cured product, but it is possible to form an interpenetrating network (IPN), that is, an interpenetrating network structure by controlling the blending ratio / film forming method well. .

  As described above, since the surface layer of the photoconductor has a three-dimensional cross-linked structure, it is possible to provide a photoconductor capable of increasing the film strength and capable of forming an image with long-term durability.

  Specific examples of the unsaturated polymerizable functional group are shown below, but are not limited thereto.

上記中、Ｒは置換基を有しても良いメチル基、エチル基及びプロピル基等のアルキル基、置換基を有しても良いベンジル基及びフェネチル基等のアラルキル基及び置換基を有しても良いフェニル基、ナフチル基及びアンスリル基等のアリール基又は水素原子等を示す。

In the above, R has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. Or an aryl group such as a phenyl group, a naphthyl group and an anthryl group, or a hydrogen atom.

  Furthermore, the compound having an unsaturated polymerization functional group is preferably a hole transport compound. This is because, when it is a hole transport compound, injection of charges (holes) from the charge generation material occurs easily, and it is easy to suppress an increase in residual potential, deterioration in sensitivity, and potential fluctuation during repeated use.

  Although the example of a preferable positive hole transport compound is shown by the following general formula (1) below, it is not limited to these.

  P1 and P2 represent unsaturated polymerizable functional groups, and P1 and P2 may be the same or different. Z represents an organic residue which may have a substituent, and Y represents a hydrogen atom. a, b and d represent 0 or an integer of 1 or more. However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more. When a is 2 or more, P1 may be the same or different. When d is 2 or more, P2 may be the same or different. When b is 2 or more, Z may be the same or different.

  Here, "when a is 2 or more, P1 may be the same or different" means that different n types of unsaturated polymerizable functional groups are indicated as P11, P12, P13, P14, P15 ... pln, For example, when a = 3, the number of unsaturated polymerizable functional groups P1 directly bonded to the hole transporting compound A is the same, but two are the same and one is different (for example, P11, P11, and P12). However, this means that each of the three may be different (for example, P12, P15, and P17) ("If d is 2 or more, P2 may be the same or different" "When b is 2 or more, Z may be the same or different" means the same thing).

  A in the above general formula (1) represents a hole transporting group, and any group may be used as long as it exhibits hole transportability. A hydrogenated compound in which P1 or Z is replaced with a hydrogen atom (hole transportability) For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylamino) Phenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives and N-phenylcarbazole derivatives.

  Although the preferable example of a hole transportable compound is given to the following, it is not limited to these.

又、不飽和重合性官能基の重合／架橋を放射線により行うことが好ましい。

Moreover, it is preferable to carry out polymerization / crosslinking of the unsaturated polymerizable functional group by radiation.

  The greatest advantage of polymerization by radiation is that a polymerization initiator is not required, which makes it possible to produce a very high-purity three-dimensional photosensitive layer matrix and ensure good electrophotographic characteristics. In addition, the productivity is high because of an efficient polymerization reaction in a short time. Furthermore, since radiation is excellent in permeability, it can be mentioned that a blocking substance such as an additive is present in the layer or the influence of curing inhibition when forming a thick layer is very small.

  Examples of the radiation to be used include an electron beam and γ-ray, and an electron beam is preferable in terms of efficiency. In the case of electron beam irradiation, any type such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used as an accelerator. In the present invention, when irradiating an electron beam, the irradiation condition is very important in order to develop electric characteristics and durability. The acceleration voltage is preferably 300 kV or less, and optimally 150 kV or less. The dose is preferably in the range of 10 to 1000 kGy. When the dose is less than 10 kGy, the crosslinking is likely to be insufficient, and when it exceeds 1000 kGy, the photoreceptor is liable to deteriorate, so care should be taken.

  By forming the protective layer having the film characteristics as described above, a highly durable photoconductor can be provided. However, due to the influence of discharge products adhering to the surface of the photoconductor, image flow and toner on the photoconductor Since fusion is likely to occur, it is necessary to remove those discharge products, that is, to easily remove the discharge products adhering to the photoreceptor.

  For this purpose, it is necessary to supply a fatty acid metal salt having a water content of 0.3% by mass or more and 4.5% by mass or less from the supply member to at least the protective layer.

  By supplying the fatty acid metal salt as described above to the protective layer, it becomes possible to form a very thin fatty acid metal salt film on the surface of the protective layer, and the discharge product adheres to the film, The removal of the discharge product is easily removed by, for example, a cleaning process due to the rigidity of the fatty acid metal salt, and the discharge product is taken into the film, so that the hydrophobicity of the fatty acid metal salt causes the discharge product to be removed. It is presumed that moisture adsorption is hindered and resistance reduction is prevented, so that the generation of a flow image can be suppressed.

  When the water content of the fatty acid metal salt is less than 0.3% by mass, the adhesion to the protective layer is reduced, the formation of a film on the protective layer becomes insufficient and difficult, and the discharge product can be removed. When it becomes difficult and image flow occurs and the amount exceeds 4% by mass, the discharge product and moisture are easily adsorbed, resulting in low resistance and image flow. The water content of the fatty acid metal salt is more preferably 1.0% by mass or more and 4.0% by mass or less.

  The water content of the fatty acid metal salt was measured using an electronic moisture meter (MA40: manufactured by Sartorius Co., Ltd.). Specifically, the fatty acid metal salt to be measured is left in an environment of 30 ° C./80% for about 24 hours, the fatty acid metal salt is weighed (about 1 g, the initial mass is W1), and heated at 105 ° C. Measure the change in weight loss of the fatty acid metal salt while removing moisture, heat until this change in weight loss does not occur, set the mass when the weight change is completed as W2, and use the following measurement formula to determine the moisture content: Calculated.

Water content of fatty acid metal salt (% by mass) = ((W1-W2) / W1) × 100
Moreover, it is preferable that content of the metal contained in this fatty acid metal salt is 4.5 mass% or more and 12.0 mass% or less.

  If the metal content is less than 4.5% by mass, the amount of free fatty acid increases, the adhesion on the protective layer increases, and if the cleaning process is an elastic blade cleaning, the adhesion is free. Fatty acid increases the load on the blade and is liable to cause blade curling, and is preferably 12.0% by mass or more because the film property is lowered and image flow is liable to deteriorate.

  The method for measuring the metal content of the fatty acid metal salt was measured using a thermogravimetric apparatus (TGA7: manufactured by Perkin Elmer Co., Ltd.). Specifically, the fatty acid metal salt to be measured is weighed (initial mass X1), and the organic components are removed while heating up to 600 ° C. while gradually raising the temperature in a nitrogen atmosphere, and the residue remains at that time. The mass (X2) of the inorganic component was measured, and the metal content was calculated using the following formula.

Metal content of fatty acid metal salt (mass%) = (X2 / X1) × 100
Examples of the fatty acid metal salt having the above properties include calcium stearate, aluminum stearate, zinc stearate, sodium stearate, calcium laurate and the like, but more preferable properties are calcium stearate and aluminum stearate. Most preferred is calcium stearate.

  As a method of supplying the fatty acid metal salt from the supply member onto the protective layer, a method of supplying the fatty acid metal salt to the photoreceptor by containing the fatty acid metal salt in the toner and developing the toner is known. Due to the image ratio, pattern, durability, and triboelectric charging characteristics of the fatty acid metal salt, the supply to the photoreceptor cannot be performed stably, and there will be a part that is supplied and a part that is not supplied. It is difficult to solve. In addition, when using a highly durable photoreceptor as described above, it is necessary to increase the supply amount of the fatty acid metal salt, and a large amount of the fatty acid metal salt must be externally added to the toner. This is not preferable because the influence on the developability (density, fog characteristics, etc.) is increased.

  Therefore, in order to stably supply a certain amount of the fatty acid metal salt throughout the entire length of the photoreceptor, the member containing the fatty acid metal salt or the member supported on the surface is brought into contact with or in contact with the surface of the protective layer. Or the method etc. which supply this fatty acid metal salt suitably to the member which contacted and contacted the surface of the protective layer are mentioned. Among these, a particularly preferable supply method is to bring the elastic blade member in which the fatty acid metal salt is dispersed into contact with the surface of the protective layer, or to penetrate into the member in which the fatty acid metal salt is solidified and rotate while the surface of the protective layer is rotating. It is a method of supplying with the fur brush which contacts.

  In addition, a method that can be stably supplied over a long period of use, in particular, is a method in which a fatty acid metal salt enters a solid member and is supplied by a fur brush that contacts the surface of the protective layer while rotating. .

  The fatty acid metal salt forms an extremely thin film on the surface of the protective layer, so that discharge products that are causative substances such as image flow are easily removed. Since the coating is more easily formed by spreading on the surface of the protective layer, the above supply method is preferable.

  As a method for producing an elastic blade member, for example, in the case of a urethane elastic blade, a polyether polyol (alcohol) component (for example, polypropylene glycol or polyethylene glycol) and an isocyanate component (for example, toluene diisocyanate or hexamethylene diisocyanate) are mixed with NCO / After the fatty acid metal salt is added and dispersed in the components mixed so that the molar ratio of OH is 1, it is degassed under reduced pressure, poured into a blade mold, and heated at 80 to 100 ° C. for 30 to 60 minutes. By demolding, a fatty acid metal salt-dispersed elastic blade can be obtained.

  When the supply member is an elastic blade member in which the fatty acid metal salt is dispersed, the content of the fatty acid metal salt in the blade member is preferably 2% by mass or more and 10% by mass or less. If the amount is less than 2% by mass, the amount supplied to the protective layer is too small to obtain a sufficient effect, and if it exceeds 10% by mass, the elasticity of the elastic member tends to be hindered, and the blade is pressed against the surface of the protective layer. It is not preferable because the formation of a film by spreading the fatty acid metal salt due to is likely to be insufficient, and it is difficult to obtain a sufficient effect.

  The setting position of the supply member for supplying the fatty acid metal salt to the photoconductor is shown in FIG. 1 between the cleaning process and the charging process, but is not particularly limited to this position, for example, between the transfer process and the cleaning process (FIG. 4). Also, it may be between the charging process and the exposure process, or between the exposure process and the development process. However, since there is a high possibility that the toner image developed on the photoreceptor is disturbed between the development process and the transfer process, setting at that position is not preferable.

  Further, from the viewpoint of downsizing and space saving of the image forming apparatus, it is more preferable that the elastic blade member also serves as a cleaning blade at the time of the cleaning process.

  Further, the toner used is preferably a toner containing at least one kind of inorganic fine powder selected from strontium titanate, barium titanate or cerium oxide.

  In general, the above-mentioned inorganic fine powder has a polishing effect. For this reason, the fatty acid metal salt dispersed by polishing an elastic blade member in which the fatty acid metal salt in contact with the photoreceptor is dispersed is combined with the photoreceptor. Therefore, the fatty acid metal salt can be stably supplied to the surface of the protective layer, and even when supplied by a fur brush, the inorganic fine powder is applied to the surface of the fur brush. By adhering, the effect of polishing the solidified fatty acid metal salt is increased, and it is possible to stably supply the salt to the surface of the protective layer.

  Examples of the present invention are specifically shown below, but are not limited thereto.

First, production examples of the photoreceptor, toner, and fatty acid metal salt supply member used in the image forming method of the present invention are shown. In addition, the part in an Example represents a mass part.
Photoconductor Production Example 1)
An aluminum cylinder having a diameter of 30 mm × 357.5 mm is used as a support, and a paint composed of the following materials is applied to the support by a dip coating method and thermally cured at 140 ° C. for 30 minutes, and the film thickness is 18 μm. The conductive layer was formed.

Conductive pigment: SnO2 Coated barium sulfate 10 parts Resistance adjusting pigment: Titanium oxide 2 parts Binder resin: Phenol resin 6 parts Leveling material: Silicone oil 0.001 part Solvent: Methanol, methoxypropanol 0.2 / 0.8 15 Next, a solution prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymer nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was applied thereto by a dip coating method. Next, 4 parts of hydroxygallium phthalocyanine having strong peaks at 7.4 ° and 28.2 ° of black angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction, polyvinyl butyral (trade name) : ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) 2 parts and cyclohexanone 80 parts with 1 mm diameter glass beads After 4 hours dispersed in the stomach was sand mill to prepare a charge generation layer dispersion was added 80 parts of ethyl acetate. This was applied by a dip coating method to form a charge generation layer having a thickness of 0.2 μm.

  Then 7 parts of a styryl compound of the structural formula

及びポリカーボネート樹脂（ユーピロンＺ８００、三菱エンジニアリングプラスチックス（株）社製）１０部をモノクロロベンゼン１０５部及びジクロロメタン３５部の混合溶媒中に溶解して調整した電荷輸送層用塗料を用いて、前記電荷発生層上に電荷輸送層を形成した４層の感光体を作成した。このときの電荷輸送層の膜厚は１５μｍであった。

And a charge transport layer coating material prepared by dissolving 10 parts of polycarbonate resin (Iupilon Z800, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) in a mixed solvent of 105 parts of monochlorobenzene and 35 parts of dichloromethane. A four-layer photoreceptor having a charge transport layer formed on the layer was prepared. At this time, the thickness of the charge transport layer was 15 μm.

  Then the following structural formula:

の正孔輸送性化合物４５部をｎ−プロピルアルコール５５部に溶解し、１９部のポリテトラフルオロエチレン微粒子（テフロン、デュポン社）を添加して高圧分散機（マイクロフルイタイザー、Microfluidics 社製）にて分散し、表面保護層用塗料を調整した。この塗料を用いて、前記電荷輸送層上に保護層を塗布した後、酸素濃度１０ｐｐｍの雰囲気下で加速電圧１５０ｋＶ、線量５０ｋＧｙの条件で電子線を照射し、その後、同雰囲気下で感光体の温度が１５０℃になる条件下で５分間の加熱処理を行い、その後、通常雰囲気化で１４０℃で１時間の加熱乾燥を行い、膜厚４μｍの保護層を形成した電子写真感光体１を得た。
感光体製造例２）
感光体製造例１の正孔輸送性化合物４５部をｎ−プロピルアルコール５５部に溶解し、ポリテトラフルオロエチレン粒子を無添加の表面保護層用塗料を調整した以外は感光体製造例１と同様の感光体２を得た。
感光体製造例３）
感光体製造例１で電子線照射後の加熱を行わなかったこと以外は感光体製造例１と同様の感光体３を得た。
感光体製造例４）
感光体製造例１において表面保護層用の塗料の調整を下記の手順により作製した。

45 parts of the hole transporting compound is dissolved in 55 parts of n-propyl alcohol and 19 parts of polytetrafluoroethylene fine particles (Teflon, DuPont) are added to a high-pressure disperser (Microfluidizer, manufactured by Microfluidics). And the surface protective layer coating material was prepared. Using this paint, after applying a protective layer on the charge transport layer, it was irradiated with an electron beam in an atmosphere with an oxygen concentration of 10 ppm under an acceleration voltage of 150 kV and a dose of 50 kGy. An electrophotographic photosensitive member 1 having a protective layer having a film thickness of 4 μm is obtained by performing a heat treatment for 5 minutes under the condition of a temperature of 150 ° C., followed by heat drying for 1 hour at 140 ° C. in a normal atmosphere. It was.
Photoconductor production example 2)
Similar to Photoconductor Production Example 1, except that 45 parts of the hole transporting compound of Photoconductor Production Example 1 were dissolved in 55 parts of n-propyl alcohol, and a coating for a surface protective layer containing no polytetrafluoroethylene particles was prepared. Photoconductor 2 was obtained.
Photoconductor production example 3)
Photosensitive member 3 was obtained in the same manner as in photosensitive member manufacturing example 1 except that heating after electron beam irradiation was not performed in photosensitive member manufacturing example 1.
Photoconductor production example 4)
In Photoconductor Production Example 1, the coating material for the surface protective layer was prepared by the following procedure.

  Antimony-containing tin oxide fine particles having an average particle diameter of 0.02 μm (trade name: T-1, manufactured by Mitsubishi Materials Corporation), (3,3,3-trifluoropropyl) trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Manufactured by mixing 30 parts of 95% ethanol-5% aqueous solution with 300 parts, a solution dispersed in milling equipment for 1 hour is filtered, washed with ethanol, dried, and heated at 120 ° C. for 1 hour to oxidize The surface of tin fine particles was treated. Next, 25 parts of a curable acrylic monomer represented by the following structural formula as a photopolymerizable monomer,

光重合開始剤としての２，２−ジメトキシ−２−フェニルアセトフェノン５部、前記表面処理されたアンチモン含有酸化スズ粒子５０部及びエタノール３００部を混合してサンドミル装置で９６時間分散した分散液に、四フッ化エチレン樹脂粒子（商品名：ルブロンＬ−２、ダイキン工業（株）製）２０部を混合してサンドミル装置で８時間分散することにより保護層用の分散液を得て、４層の感光体上に浸漬コーティング法で塗布し、乾燥後、メタルハライドランプにて１０００ｍＷ／ｃｍ²の光強度で３０秒間紫外線照射することによって膜厚が４μｍの保護層を形成し、電子写真感光体４を作製した。
感光体製造例５）
感光体製造例１において表面保護層用の塗料の調整を下記の手順により作製した。

In a dispersion obtained by mixing 5 parts of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator, 50 parts of the surface-treated antimony-containing tin oxide particles and 300 parts of ethanol and dispersing for 96 hours in a sand mill apparatus, A dispersion for protective layer was obtained by mixing 20 parts of tetrafluoroethylene resin particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) and dispersing for 8 hours in a sand mill device. A dip coating method is applied onto the photoreceptor, and after drying, a protective layer having a thickness of 4 μm is formed by irradiating with an ultraviolet ray at a light intensity of 1000 mW / cm ² for 30 seconds with a metal halide lamp. Produced.
Photoconductor production example 5)
In Photoconductor Production Example 1, the coating material for the surface protective layer was prepared by the following procedure.

  32 parts of a hole transporting compound of the following structural formula (3),

下記構造式、８部を

The following structural formula, 8 parts

モノクロロベンゼン５０部及びジクロロメタン５０部の混合溶媒中に溶解し保護層用塗料を調整した。

A protective layer coating material was prepared by dissolving in a mixed solvent of 50 parts of monochlorobenzene and 50 parts of dichloromethane.

This coating solution was coated on the four-layered photoreceptor prepared in photoreceptor production example 1 to prepare photoreceptor 5 produced in the same manner as photoreceptor 1 except that the film thickness was 3 μm.
Photoconductor Production Example 6)
A photoconductor 6 similar to that of Photoconductor Production Example 2 was obtained except that the dose of the electron beam was 250 kGy in Photoconductor Production Example 2.
Photoconductor production example 7)
A photoconductor 7 similar to that of Photoconductor Production Example 1 was obtained except that, in Photoconductor Production Example 1, the electron beam dose was 25 kGy and heating after irradiation was not performed.

  The following table shows the elastic deformation rates and Hu values of the photoreceptors 1 to 7.

トナー製造例１）
・スチレンアクリル樹脂 １００部
（スチレン−ブチルアクリレート共重合比＝７８：２２）
・磁性体 １００部
・サリチル酸金属化合物 ２部
・エステルワックス ３部
上記をヘンシェルミキサーを用いて混合し、二軸押し出し混練機で溶融混練した後、ハンマーミルで粗粉砕し、ジェットミルで微粉砕した後、分級して平均粒径７μｍの着色粒子を得た。

Toner production example 1)
Styrene acrylic resin 100 parts (styrene-butyl acrylate copolymer ratio = 78: 22)
・ 100 parts of magnetic material ・ 2 parts of metal salicylate compound ・ 3 parts of ester wax Thereafter, classification was performed to obtain colored particles having an average particle diameter of 7 μm.

1.2 parts of hydrophobic silica (BET = 130 m ^{2 /} g) surface-treated with 100 parts by weight of silica having a primary particle diameter of about 7 nm and 20 parts of dimethyl silicone oil, and strontium titanate having an average particle diameter of 500 nm. Toner 1 was obtained by externally adding 2.5 parts of the inorganic fine powder with a Henschel mixer FM10B.
Toner production example 2)
1.2 parts of hydrophobic silica (BET = 130 m ^{2 /} g) surface-treated with 20 parts of dimethyl silicone oil and 100 parts by weight of silica having a primary particle size of about 7 nm are externally added to the colored particles using a Henschel mixer FM10B. Toner 2 was obtained.
Fatty acid metal salt supply member)
First, a fatty acid metal salt having a water content and a metal content shown in the following table was prepared as the fatty acid metal salt.

ポリオール成分とイソシアネート成分混合し、その混合成分に対して、６質量％の上記脂肪酸金属塩（Ｓ１〜Ｓ７）を分散させ、厚さ２ｍｍ、幅２０ｍｍ、長さ３００ｍｍの形状の金型に流し込み、８０℃で加熱を行い、脂肪酸金属塩分散のポリウレタンブレード（１−Ｓ１〜１−Ｓ７）を作製した。

A polyol component and an isocyanate component are mixed, 6 mass% of the fatty acid metal salt (S1 to S7) is dispersed in the mixed component, and poured into a mold having a thickness of 2 mm, a width of 20 mm, and a length of 300 mm, Heating was performed at 80 ° C. to prepare fatty acid metal salt-dispersed polyurethane blades (1-S1 to 1-S7).

  In the same manner as described above, a fatty acid metal salt S1-dispersed polyurethane blade (2-S1, 3-S1) was prepared using fatty acid metal salt S1 with a dispersion amount of 1% by mass and 12% by mass in the polyurethane blade.

Further, as a fur brush, as a fur brush, a nylon thread having a fiber thickness of 2.0 Tex is used, and the fiber density is 93 fibers / mm ² and is embedded in a base fabric with a W weave to form a sheet. A fur brush member (B1) having a diameter of 12 mm was prepared by spirally winding it on a core metal having a diameter of 2 mm.

  The fatty acid metal salt S1 is heated at 170 ° C., cooled to room temperature, made into a block state, and a fur brush and a solid fatty acid metal salt are added so that the B1 fur brush penetrates about 2 mm into the solid fatty acid metal salt. The set supply member (S1-B1) was produced.

  The fatty acid metal salt S2 is heated at 180 ° C., cooled to room temperature, made into a block state, and a fur brush and a solid fatty acid metal salt are added so that the B1 fur brush penetrates about 2 mm into the solid fatty acid metal salt. The set supply member (S2-B1) was produced.

  The fatty acid metal salt S3 is heated at 130 ° C., cooled to room temperature, brought into a block state, and a fur brush and a solid fatty acid metal salt are added so that the B1 fur brush penetrates about 2 mm into the solid fatty acid metal salt. The set supply member (S3-B1) was produced.

  The fatty acid metal salt S6 is heated at 160 ° C., cooled to room temperature, made into a block state, and a fur brush and a solid fatty acid metal salt are added so that the B1 fur brush penetrates about 2 mm into the solid fatty acid metal salt. The set supply member (S6-B1) was produced.

  The fatty acid metal salt S7 is heated at 240 ° C., cooled to room temperature, brought into a block state, and a fur brush and a solid fatty acid metal salt are added so that the B1 fur brush penetrates about 2 mm into the solid fatty acid metal salt. The set supply member (S7-B1) was produced.

  As an image forming apparatus for carrying out the image forming method of the present invention, an organic photoconductor digital copying machine using a laser beam (manufactured by Canon Inc .: GP405) was prepared. The outline of the apparatus is provided with a charging roller as charging means for the photosensitive member, and as a developing means a one-component developing device adopting a one-component jumping developing method in which the developer on the current photosensitive member and the photosensitive member are not in contact. The image forming apparatus includes a charging roller as a transfer unit, a blade cleaning unit, and a pre-charging exposure unit. Further, the photosensitive member charger, the cleaning means, and the photosensitive member are integrated units. The process speed is 210 mm / s. The device was modified as follows.

  First, the photoconductor and toner are replaced with the photoconductor and toner prepared above, and the drum potential is set to 250 V for development contrast and 180 V for back contrast, and charging and development from the dark and light potential on the drum. It was adjusted by changing the DC voltage.

  The control of the primary charging AC voltage is a sine wave with a frequency of 1.8 kHz, and the applied voltage is such that Vpp is variable so that constant current control is performed so that the AC current is 2.2 mA in the initial stage. .

Evaluation was performed using the image forming apparatus according to the following evaluation method.
Evaluation 1)
First, the photosensitive member 1 is used at a temperature of 30 ° C. and 80% environment, and only the cleaning blade is mounted on the photosensitive member as shown in FIG. 5, and the width between the blade and the photosensitive member is 10 mm as shown in FIG. About 0.1 g of various fatty acid metal salt powders are set to exist, and a photoreceptor as shown in FIG. 5 is rotated in the forward direction for 3 minutes (210 mm / s) with respect to the blade, A film of the fatty acid metal salt is formed.

Next, a cleaning blade and a photoreceptor having a fatty acid metal salt film formed by removing the fatty acid metal salt between the blade and the photoreceptor are prepared.
Evaluation 1-1) Image Flow Evaluation Only the charging roller is mounted on the above-described photosensitive member on which the film is formed, the frequency is a sine wave of 1.8 kHz, a DC voltage of −700 V, and an AC current of 2.5 mA. An AC voltage (Vpp) is applied for 3 minutes while rotating the photoconductor (210 mm / s) to produce a photoconductor having a charging history, and the photoconductor is subjected to the above image forming apparatus in an environment of 30 ° C./80%. And using toner 1 to draw a 1.5 mm ² hiragana character image and a 100 μm ² dot image, and observing the image with a 50 × optical microscope, Evaluation was performed according to the evaluation items.

  A: Both characters and dots are reproduced.

○: Characters are reproduced, but the dots are slightly blurred and blurred △: Characters are slightly blurred, blurred, and dots are hardly reproduced ×: Characters and dots are not reproduced, and characters can be read An almost white image can be obtained.
Evaluation 1-2) Evaluation of load on the blade The photosensitive member having the film formed thereon and the photosensitive member 1 having no film formed thereon were prepared, and Cefbon CMA (Central Glass ( Only a cleaning blade with a coating applied) is mounted, and a charging roller is applied with an AC voltage with a sine wave of 1.8 kHz and a DC voltage of −700 V and an AC current of 2.1 mA. Then, idling was performed for 15 seconds, and the torque of the photoreceptor after 15 seconds was measured with each photoreceptor, and evaluation was performed according to the following evaluation items.

A: Torque of the photoreceptor on which the film is formed is less than 1.5 times the torque of the photoreceptor on which the film is not formed. O: Torque of the photoreceptor on which the film is formed is 1 of the torque of the photoreceptor on which the film is not formed. .Times.5 times to less than 3.times .: The torque of the photoreceptor on which the film is formed is at least 3 times the torque of the photoreceptor on which the film is not formed. The fatty acid metal salts used in Examples and Comparative Examples are as follows. The results are summarized in a table.

評価２）
感光体１を用いて、図１に示すように、クリーニングブレードと帯電ローラの間の９−１の位置に、１−Ｓ１〜１−Ｓ７，２−Ｓ１，３−Ｓ１のウレタン弾性ブレードに脂肪酸金属塩を分散させた脂肪酸金属塩供給部材を、９−１のように感光体の回転方向と順方向に当接（感光体へのブレードの当接圧力は約３．３Ｎ）するように調節して当接させ、又、図４に示すように、転写ローラとクリーニングブレードの間の９−２の位置にＳ１−Ｂ１〜Ｓ７−Ｂ１の脂肪酸金属塩供給部材を、感光体へのファーブラシの侵入量が１．５ｍｍになるように調節して設置し、ファーブラシの回転方向が感光体と接触する部分において、感光体の回転方向と反対方向に回転させるように設定し（回転速度は感光体の回転速度の１／４に設定）、３２℃／８５％環境下で感光体上にトナーを３０秒に１秒間、ドラム長手全域に現像させるように現像、バックコントラストの時間制御を現像バイアスで調整し、転写を解除した状態で交流電流が２．５ｍＡの定電流制御の交流電圧を印加して、６０分間の空回転を行い、以下の評価項目に従い評価を行った。
評価２−１）画像流れ
６０分空回転後、３２℃／８５％環境下で感光体を２４時間放置し、上記の画像形成装置を用いて、１．５ｍｍ²の大きさの平仮名文字画像、１００μｍ²のドット画像の画出しを行い、その画像を５０倍の光学顕微鏡を用いて観察し、以下の評価項目に従い評価を行った。

Evaluation 2)
As shown in FIG. 1, using the photoreceptor 1, fatty acid is applied to the urethane elastic blades 1-S1 to 1-S7, 2-S1, and 3-S1 at the position 9-1 between the cleaning blade and the charging roller. The fatty acid metal salt supply member in which the metal salt is dispersed is adjusted so as to make contact with the rotation direction of the photosensitive member in the forward direction as shown in 9-1 (the contact pressure of the blade to the photosensitive member is about 3.3 N). Further, as shown in FIG. 4, the fatty acid metal salt supply members S1-B1 to S7-B1 are placed at the position 9-2 between the transfer roller and the cleaning blade, and the fur brush is applied to the photoconductor. Is adjusted so that the intrusion amount is 1.5 mm, and the fur brush is set to rotate in the direction opposite to the rotation direction of the photoconductor at the portion where the rotation direction of the fur brush is in contact with the photoconductor (rotation speed is (Set to 1/4 of the rotation speed of the photoreceptor), 32 ° C / In a 5% environment, the toner is developed on the photosensitive member for 1 second every 30 seconds, and the time control of the back contrast is adjusted by the developing bias so that the AC current is 2. An AC voltage of 5 mA constant current control was applied to perform idling for 60 minutes, and evaluation was performed according to the following evaluation items.
Evaluation 2-1) Image flow After rotating for 60 minutes, the photoconductor is left in a 32 ° C./85% environment for 24 hours, and a hiragana character image having a size of 1.5 mm ² using the above image forming apparatus, A dot image of 100 μm ² was imaged, the image was observed using a 50 × optical microscope, and evaluated according to the following evaluation items.

  A: Both characters and dots are reproduced.

○: Characters are reproduced, but the dots are slightly blurred and blurred △: Characters are slightly blurred, blurred, and dots are hardly reproduced ×: Characters and dots are not reproduced, and characters can be read An almost white image can be obtained.
Evaluation 2-2) Toner fusion After idling, the surface of the photosensitive member is observed with an optical microscope to confirm the presence or absence of toner fusion. Further, using the image forming apparatus, solid black, halftone, solid white in A4 size. Images were imaged and image defects due to toner fusion to the photoreceptor were evaluated according to the following evaluation items.

◎: No defective image is generated, and toner fusion is hardly confirmed even by microscopic observation. ○: Small black and white spots are confirmed only on a part of the image, and toner fusion is confirmed only on that part by microscopic observation. Δ: Several tens of small black and white spots are confirmed in the entire area of the image, and toner fusion is confirmed in the area even under microscopic observation. ×: Many rainy white and black spots are generated in the entire area of the image. Microscopic observation also confirms fusion over the entire area of the drum.

  The results of the fatty acid metal salt supply member, toner, and evaluations 2-1 and 2-2 used in Examples and Comparative Examples are summarized in the following table.

評価３）
上記画像形成装置で、図４に示す９−２の位置にＳ１−Ｂ１の脂肪酸金属塩供給部材を、感光体へのファーブラシの侵入量が１．５ｍｍになるように調節して設置し、トナーとしてトナー１を用い、２３℃／５％環境下で画像比率２％Ａ４横通紙１５万枚耐久を行い、ベタ黒、ハーフトーン画像、一次帯電の印加直流電圧を現像の直流電圧とほぼ同じにして、画像露光を行わないで、ハーフトーン濃度の画像（アナログハーフトーン）の画出しを行い、ドラム傷を以下の評価項目に従い評価を行った。

Evaluation 3)
In the image forming apparatus, the fatty acid metal salt supply member of S1-B1 is installed at a position 9-2 shown in FIG. 4 so that the amount of fur brush entering the photosensitive member is 1.5 mm. Using toner 1 as the toner, the image ratio is 2%, A4 horizontal paper is endured 150,000 sheets in an environment of 23 ° C / 5%, and the applied DC voltage for solid black, halftone image, and primary charge is almost equal to the DC voltage for development. In the same manner, an image having a halftone density (analog halftone) was drawn without performing image exposure, and drum scratches were evaluated according to the following evaluation items.

A: Vertical streak image due to flaws does not occur. B: Vertical streak image due to flaws is slightly confirmed only by analog halftone. Δ: Slightly confirmed as solid black. Many confirmed in analog halftone. X: Solid black, many confirmed in halftone image Examples, comparative examples, photoconductors used for evaluation, and results of evaluation 3 are summarized in the following table.

  The present invention is useful as an image forming method used in a recording method using an electrophotographic method, an electrostatic recording method, or the like.

1 is a diagram illustrating an example of a specific image forming apparatus of the present invention. It is a figure which shows an example of a film | membrane characteristic output chart. It is a figure which shows an example of the film | membrane characteristic measurement of a photoreceptor protective layer. 1 is a diagram illustrating an example of a specific image forming apparatus of the present invention. It is a figure which shows an example of the film formation method of the fatty-acid metal salt on a photoreceptor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Frame 3 Fixing device 4 Cleaning elastic blade 5 Transfer material 6 Primary charging roller 7 Developing device 8 Transfer charging roller 9-1 Blade type fatty acid metal salt supply member 9-2 Intrusion fur brush into solid fatty acid metal salt Supplied by 10 Fatty acid metal salts L Laser light

Claims (9)

A step of charging a photosensitive member having a photosensitive layer and a protective layer on at least a support which is an image carrier, an electrostatic latent image forming step of forming an electrostatic latent image on the charged photosensitive member, and a toner carrier A development process for transferring the carried toner to the electrostatic latent image for visualization, a transfer process for transferring the toner image formed on the image carrier to a transfer material, and a transfer residue remaining on the photoconductor after the transfer process In an image forming method having a cleaning step of removing toner from the photoreceptor,
The protective layer has a universal hardness value HU of 150 or more and 200 or less (N / mm 2), an elastic deformation rate of 44% or more and 65% or less, and the protective layer has a water content of 0.3 mass. % Or more and 4.5% by mass or less of a fatty acid metal salt is supplied from a supply member .
2. The image forming method according to claim 1, wherein the water content of the fatty acid metal salt is 1.0% by mass or more and 4.0% by mass or less.   3. The image forming method according to claim 1, wherein the metal content of the fatty acid metal salt is 4.5% by mass or more and 12.0% by mass or less.   The image forming method according to claim 1, wherein the fatty acid metal salt is calcium stearate or aluminum stearate.   The image forming apparatus according to any one of claims 1 to 4, wherein the supply member is a fur brush that enters a member obtained by solidifying the fatty acid metal salt and contacts the surface of the protective layer while rotating. Method.   The supply member supplies the fatty acid metal salt by bringing the elastic blade member containing the fatty acid metal salt dispersed on the surface of the protective layer into contact with the surface of the protective layer. 5. The image forming method according to any one of 4 above.   The image forming method according to claim 6, wherein the content of the fatty acid metal salt in the elastic blade member is 2 to 10% by mass.   8. The image forming method according to claim 6, wherein the elastic blade member is a cleaning blade that removes transfer residual toner from the photosensitive member.   9. The toner according to claim 1, wherein the toner contains at least a binder resin and a colorant, and further contains at least one inorganic fine powder selected from strontium titanate, barium titanate, or cerium oxide. The image forming method according to any one of the above.

Images