JP2009109861A - Image developing roller and manufacturing method therefor, process cartridge, and electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality developing roller which can suppress stripe images caused by long term contact with the developing blade, toner sticking to the developing roller at low temperatures and low humidities in its latter lifetime, and image fogging at high temperatures and high humidities. <P>SOLUTION: The developing roller has a resin layer formed around the shaft core, and a surface layer formed around this resin layer. The surface layer is formed, by using a heat curable ether ester polyurethane resin which has predetermined soft segment units, The ester concentration (Ec), the ether concentration (Etc), and the urethane concentration (Urc) of this heat-curable ether ester polyurethane resin satisfy relations: 8.0≤Ec≤11.2, 18.4≤Etc≤37.8, and 0.8≤Urc≤2.7, and JIS K 6253A hardness of this development roller is 26° or larger and 45° or smaller. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a developing roller used in contact with a photoreceptor incorporated in an electrophotographic apparatus such as a copying machine, a printer, and a facsimile receiving apparatus, a method for manufacturing the developing roller, and a process cartridge and an electrophotographic apparatus using the developing roller. It is about.

  Conventionally, as a developing method in an electrophotographic apparatus such as a copying machine, a printer, and a facsimile receiver, a two-component developing method and a one-component developing method are used. In recent years, a one-component developing system using a one-component toner has attracted attention because of demands for miniaturization and high performance.

  As a developing device using such a one-component toner, a developing roller is provided so as to close the opening of a toner container for storing the toner and to expose a part of the toner outside the container. The toner is supplied onto the surface of the developing roller by an elastic roller provided in contact with the developing roller in the toner container. Next, excess toner is removed by the developing blade to form the toner in a thin film on the developing roller, and at the same time, a predetermined amount of positive or negative triboelectric charge is given to the toner particles by rubbing. Further, the toner that is triboelectrically charged positively or negatively by the rotation of the developing roller is transported to the developing area of the exposed portion, where it adheres to the electrostatic image on the surface of the photoreceptor provided in contact with or in close proximity to perform development. As such a developing roller, a roller having a resin layer around the conductive shaft core and a surface layer on the outer periphery as required is used.

Further, the developing roller is required to satisfy the following various requirements.
To prevent toner sticking to the surface of the developing roller in order to output a stable image over a long period of time.
To have a low compression set in order to suppress image damage caused by deformation caused at a contact portion with the developing blade that contacts with a constant load.
-Appropriate chargeability is imparted to the toner.

  In recent years, there has been an increasing need for higher lifespan and higher image quality, and there is a method of making the developing roller flexible in order to prevent toner sticking to the developing roller at the end of the device life (Patent Document). 1). However, by softening the developing roller, the amount of deformation of the contact portion due to long-term contact with the developing blade increases, and image adverse effects such as image streaks due to roller deformation may deteriorate. Furthermore, there is a concern that initial toner fixation may occur due to an increase in the surface adhesive force of the surface layer of the developing roller.

  In addition, space-saving and low-cost image forming apparatuses have become widespread, and in recent years their use environment has fluctuated greatly. However, it is very difficult to achieve both image quality in both extreme environments such as high temperature and high humidity (temperature 30 ° C./humidity 85% RH) and low temperature low humidity (temperature 15 ° C./humidity 10% RH). There is a case. Specifically, when a developing roller is incorporated in a color printer compatible with high image quality in a high-temperature and high-humidity environment, fogging due to a decrease in frictional charging property to toner may occur. Furthermore, since the developing roller surface layer and the toner are softened, there is a concern that image defects due to roller deformation and initial toner fixation are likely to occur. On the other hand, in a low-temperature and low-humidity environment, the hardness of the developing roller surface layer and the toner increases, so that stress applied to the toner increases and the toner may adhere to the developing roller surface layer. In order to suppress the temperature dependence of hardness in the rubber member for electrophotography, a method using an ester polyol derived from 2,4-diethyl-1,5-pentanediol as a urethane raw material has been proposed (Patent Document 2). ing. In addition, a technique (Patent Document 3) that suppresses the temperature dependence of the resilience by specifying the molecular weight and ester concentration of the ester polyol is also cited.

  However, in the rubber member for electrophotography described in Patent Documents 2 and 3, since the JIS K 6253A hardness of the rubber member is high, the stress applied to the toner is strong, and there is a concern that the toner adheres to the surface layer of the developing roller. Furthermore, since the urethane raw material constituting the rubber member does not contain an electron donating group such as an ether group, fogging due to a decrease in frictional charging property to the toner may occur particularly under high temperature and high humidity.

In other words, in order to achieve a longer lifetime and higher image quality in electrophotographic apparatuses such as copying machines, printers, and facsimile receivers, the mechanical properties of the developing roller are extremely severe in various environments. I need to control it. Furthermore, at the same time, advanced control of toner charge imparting ability is required.
JP-A-11-212354 JP 2001-083855 A JP 2003-073440 A

  An object of the present invention is to develop a developing roller capable of simultaneously suppressing the deformation amount of the contact portion due to long-term contact with the developing blade and suppressing toner fixation on the surface layer of the developing roller when an image is repeatedly output under low temperature and low humidity. Is to provide. Another object of the present invention is to provide a high-quality developing roller capable of suppressing fogging caused by a decrease in frictional charging property to toner even under high temperature and high humidity. It is another object of the present invention to provide a method for producing such a developing roller, a high-quality and highly durable developing device using such a developing roller, and an electrophotographic apparatus.

  In view of the above-mentioned problems, the present inventors have suffered from image adverse effects caused by deformation of the contact portion due to long-term contact with the developing blade, toner fixation on the surface layer of the developing roller when an image is repeatedly output under low temperature and low humidity, Attempts were made to improve fogging under high temperature and high humidity. As a result, it has been found that the above object can be achieved by optimizing the blending ratio of the functional groups constituting the polyurethane resin used in the surface layer of the developing roller, the crosslinking point density such as the urethane concentration, and the JIS K 6253A hardness.

That is, the developing roller of the present invention has a resin layer around the shaft core, and a developing roller having a surface layer on the outer periphery of the resin layer.
The surface layer is formed using a thermosetting ether ester polyurethane resin having a unit of any of the following formulas (1) to (3),
The ester concentration (Ec), ether concentration (Etc) and urethane concentration (Urc) of the thermosetting ether ester polyurethane resin were measured by ESCA (X-ray photoelectron spectroscopy), the nitrogen element ratio, the C—C bond ratio, When defined by the following formulas (4) to (6) using the COO bond ratio and the CO bond ratio, 8.0 ≦ Ec ≦ 11.2, 18.4 ≦ Etc ≦ 37.8 and 0.8 ≦ In the range of Urc ≦ 2.7,
The developing roller has a JIS K 6253A hardness of 26 ° to 45 °.

A developing roller manufacturing method according to the present invention is the above-described developing roller manufacturing method,
Forming a coating film of the surface layer-forming paint on the outer periphery of the resin layer around the shaft core body, and curing the coating film to form a surface layer;
The surface layer forming paint is:
An ester polyol of 1000 ≦ Mn ≦ 6000 obtained using at least one polyhydric alcohol selected from 3-methyl-1,5-pentanediol, polycaprolactone diol and 1,3-butanediol;
2000 ≦ Mn ≦ 5500 prepolymer type having an ether group in the modified part and produced from at least one selected from diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and polymethylene polyphenylene polyisocyanate (polymeric MDI) It is characterized by containing isocyanate.

  The present invention also relates to a developing device for an electrophotographic apparatus, wherein the developing roller is provided in a process cartridge which is equipped with a developing roller and is detachable from the electrophotographic apparatus.

  Further, the present invention provides an electronic device that forms a thin layer of toner on the surface of a developing roller, contacts the developing roller with a photosensitive drum, and supplies the toner to the surface of the photosensitive member to form a visible image on the photosensitive member. The present invention relates to an electrophotographic apparatus comprising the developing roller.

  According to the developing roller of the present invention, it is possible to suppress image defects caused by deformation of a contact portion due to long-term contact with a developing blade and toner fixation when an image is repeatedly output under low temperature and low humidity. In addition, fogging can be controlled under high temperature and high humidity, and a high-quality image can be obtained. Furthermore, it is possible to provide a process cartridge and an electrophotographic apparatus capable of forming a long-life and high-quality image.

The developing roller of the present invention has a resin layer around the shaft core and a surface layer on the outer periphery thereof, and satisfies the following conditions.
(A) The surface layer is formed using the thermosetting ether ester polyurethane resin which has a unit in any one of said Formula (1) thru | or (3).
(B) The ester concentration (Ec), ether concentration (Etc) and urethane concentration (Urc) of the thermosetting ether ester polyurethane resin are 8.0 ≦ Ec ≦ 11.2 and 18.4 ≦ Etc ≦ 37.8. And 0.8 ≦ Urc ≦ 2.7. However, Ec, Etc, and Urc are the above formulas (4) to (4) using the nitrogen element ratio, the C—C bond ratio, the COO bond ratio, and the C—O bond ratio measured by ESCA (X-ray photoelectron spectroscopy). It is defined in 6).
(C) The developing roller has a JIS K 6253A hardness of 26 ° to 45 °.

  In the present invention, the surface layer is formed using a thermosetting ether ester polyurethane resin. Here, the polyurethane resin is not a name indicating a polymer having a single composition, but a general term for polymers including a urethane bond, and is composed of a hard segment and a soft segment such as a urethane bond, an allophanate bond, and a burette bond. . Polyurethane resins are generally classified as ester urethane resins, ether urethane resins, carbonate urethane resins, acrylic urethane resins, olefin urethane resins, etc., depending on the chemical bond type forming the soft segment. The ether ester polyurethane resin is composed of units in which a soft segment in a polymer contains an ether group and an ester group.

  Furthermore, it has a low compression set compared to thermoplastic urethane resin, can suppress the deformation of the developing roller due to the developing blade, and is thermosetting from the viewpoint of wear resistance and toner triboelectric chargeability. Type polyurethane resin.

  In addition, carbonate polyurethane resin, acrylic polyurethane resin, etc. have remarkably higher bond strength of soft segments in polyurethane resin than ether polyurethane resin and ester polyurethane resin. Therefore, when it is used for the surface layer of the developing roller, its hardness increases and stress applied to the toner increases.

  Moreover, the ether ester polyurethane resin in the present invention is characterized by having any unit of formulas (1) to (3). Such an ether ester polyurethane resin can be produced from at least one urethane raw material having any unit of formulas (1) to (3) as a main skeleton. These three types of units are units constituting the soft segment in the ether ester polyurethane resin. Generally, the structure of the soft segment of the polyurethane resin has a great influence on the physical properties of the polyurethane resin, in particular the mechanical properties. It is known. For example, various factors such as the ester concentration of polyester, the odd-even effect of the number of carbon atoms in the polymer main chain, the introduction of side groups such as methyl groups, terminal structures and branched structures contribute to the crystallinity of the soft segment, that is, the mechanical properties of polyurethane resin. Influence. In view of the above findings, the present inventors have conducted intensive studies, and as a result, have found that the effects of the present invention can be exhibited when at least one of the three types of units is contained. Although the detailed mechanism is unknown, since the raw material containing any one of the formulas (1) to (3) has a lower melting point than a general raw material, the crystallinity of the soft segment is appropriately controlled. It is expected that this contributed to the manifestation of the effects in the present invention.

  The presence of any one of the formulas (1) to (3) is determined by infrared spectroscopy (IR) method, pyrolysis gas chromatography (Pyr-GC) method after decomposition into components by hydrolysis, etc. The test piece collected from the surface layer can be analyzed and confirmed by a known method.

  Furthermore, the strict control of the functional group compounding ratio and the urethane concentration (Urc) shown in the ester concentration (Ec), the ether concentration (Etc) of the ether ester polyurethane resin is the most important point in manifesting the effects of the present invention. Specifically, control is performed so that 8.0 ≦ Ec ≦ 11.2, 18.4 ≦ Etc ≦ 37.8, and 0.8 ≦ Urc ≦ 2.7. In addition, the preferable upper limit and lower limit of each value are independent.

  The ester group has a strong intermolecular chain force and exhibits characteristics such as excellent wear resistance, Young's modulus and breaking strength, and thus contributes to imparting a low compression set to the surface layer. In addition, since the ether group has the highest occupied molecular orbital electron cloud that is electron donating, it contributes to imparting excellent negative chargeability to the toner. That is, by setting Ec to 8.0 or more, sufficient mechanical properties are obtained, the amount of deformation at the developing blade contact portion is reduced, and image defects such as image streaks and initial fixation are suppressed. On the other hand, by setting Ec to 11.2 or less, the relative ether concentration (Etc) in the polyurethane resin can be secured, and the stress on the toner due to the increase in the hardness of the surface layer can be reduced. Further, by setting Etc to 18.4 or more, sufficient triboelectric chargeability to the toner can be obtained. On the other hand, by making Etc 37.8 or less, it is possible to suppress a decrease in mechanical properties due to a relative decrease in the ester concentration (Ec).

  The urethane concentration (Urc) is a value indicating the density of cross-linking points in the ether ester polyurethane resin, and is a value proportional to mechanical properties such as storage elastic modulus. It is publicly known that, as a basic physical property of rubber, not only a polyurethane resin, mechanical properties increase in a low temperature and low humidity environment and mechanical properties decrease in a high temperature and high humidity environment. Further, since the urethane group has a lone electron pair in the nitrogen atom in the chemical bond, it contributes to imparting excellent negative chargeability to the toner. That is, by setting Urc to 0.8 or more, excellent toner charge imparting properties can be obtained with sufficient mechanical properties even in a high temperature and high humidity environment. On the other hand, by setting Urc to 2.7 or less, it is possible to suppress an increase in surface layer hardness under low temperature and low humidity, and to reduce stress applied to the toner.

  Furthermore, since the increase in the density of crosslinking points in the polyurethane resin may inhibit the crystallinity of the soft segment and lower the mechanical properties, the balance between the hard segment and the soft segment content is also an important point. That is, strict control of Ec, Etc, and Urc in the ether ester polyurethane resin is necessary to achieve optimization of mechanical properties and toner charge imparting properties in various environments in the present invention.

  Ec, Etc and Urc of the ether ester polyurethane resin are measured by a known method such as X-ray photoelectron spectroscopy called ESCA or XPS. The X-ray photoelectron spectroscopy using the soft X-ray as an excitation source is a non-destructive analysis method capable of identifying the elemental composition and chemical bonding state in the very vicinity of the surface of the developing roller surface layer. Details regarding the definition of Ec, Etc, and Urc of the surface layer measured by ESCA (X-ray photoelectron spectroscopy) in the present invention will be described later.

  In the present invention, the developing roller has a JIS K 6253A hardness in a range of 26 ° to 45 °. When the JIS K 6253A hardness is 26 ° or more, compression set can be suppressed, and an increase in deformation amount at the developing blade contact portion can be suppressed. Further, when the JIS K 6253A hardness is 45 ° or less, the stress applied to the toner can be reduced. Preferably they are 32 degrees or more and 39 degrees or less.

  When the full width at half maximum of the maximum peak obtained by measuring the thermosetting ether ester polyurethane resin by micro-sampling mass spectrometry (μ-MS) is L, 0.7 (min) ≦ L ≦ 2.5 Preferably it is in the range of (minutes). The maximum peak at which the thermal chromatogram obtained by μ-MS measurement is the maximum shows a very good correlation with the crosslinking point density of the polyurethane resin. Therefore, in the present invention, the maximum peak time was expressed as an index of crosslink point density, and a preferable range was found when the full width at half maximum (L) of the maximum peak intensity was handled as a crosslink point density distribution of urethane bonds. The distribution of the crosslinking point density of the ether ester polyurethane resin in the present invention is relatively broad, but when L is in the above range, the compression set and flexibility of the surface layer are in an appropriate balance relationship. Therefore, it is possible to contribute to both the reduction of the deformation amount of the developing roller and the reduction of stress on the toner at the contact portion with the developing blade.

  The values of Ec and Etc can be controlled by adjusting the polarity of the resin material, the carbon number of the soft segment main skeleton, the blending ratio of the soft segment containing an ether group and an ester group. Further, the value of Urc can be controlled by the crosslink density of the polyetherester polyurethane resin, and the JIS K 6253A hardness can be controlled by the values of Urc, Ec, Etc of the surface layer and the hardness of the resin layer. Can do.

  Examples of the thermosetting ether ester polyurethane resin include those obtained from polyol and isocyanate. In addition, both the polyol and the isocyanate may be sufficient as the raw material which made the main skeleton any unit of Formula (1) thru | or (3), and any one may be sufficient as it. Furthermore, as long as the values of Ec, Etc, and Urc are within the range defined in the present invention, the ether component and the ester component may be contained in both the polyol and the isocyanate, or may be contained in any one of them. Absent.

  Examples of the polyol include polyether polyol, polyester polyol, and mixtures thereof.

  The polyether polyol is not particularly limited, but a polyurethane ether polyol prepolymer is preferable since it has an excellent balance between mechanical properties and flexibility of the surface layer. Examples of the raw material polyether polyol include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), and a copolymer of THF and neopentyl glycol (PTXG).

  The polyester polyol is not particularly limited, but a polyester polyol obtained by direct esterification reaction or ring-opening polymerization reaction can be suitably used. Alternatively, a polyurethane polyol prepolymer obtained by extending a chain of polyester polyol and isocyanate can be suitably used. The polyester polyol synthesized by direct esterification is obtained by dehydrating and condensing a polybasic acid and a polyhydric alcohol as raw materials.

  Polybasic acids include adipic acid, isophthalic acid, tetrachlorophthalic anhydride, het acid, tetrabromophthalic anhydride, phthalic anhydride, hasophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, sebacine Acid, fumaric acid, trimellitic acid, dimer acid, maleic anhydride, 1,12-dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5- Examples include sodiosulfoisophthalic acid. Among these, adipic acid, isophthalic acid, terephthalic acid, and sebacic acid are particularly preferable because they are easily available.

  Examples of the polyhydric alcohol include 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, bisphenol A, glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2- Butyl-2-ethyl-1,3-propanediol, hydroxybivalylhydroxybivalate, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2 -Methyl-1,3-propanedio Can be exemplified Le, e.g., 2,4-diethyl-1,5-pentanediol as an example.

  Furthermore, among the polyester polyols synthesized by direct esterification reaction, those using 3-methyl-1,5-pentanediol and 1,3-butanediol from the polyhydric alcohols are particularly preferable. The above-mentioned substances show a specifically low melting point (-50 ° C., −77 ° C.) compared to the melting point of general polyhydric alcohol (−10 ° C. to 200 ° C.). Therefore, since it is easy to control the degree of crystallinity in the soft segment having an ester group in the polyurethane resin, it contributes to the suppression of increase in hardness, particularly under low temperature and low humidity, from the viewpoint of control of mechanical properties. Furthermore, polycaprolactone diol obtained by ring-opening polymerization reaction of ε-caprolactone or a polyester polyol synthesized by prepolymerizing polycaprolactone diol is particularly preferable. Among the polycaprolactone diols, those that are non-crystalline or have a low melting point are particularly preferred from the viewpoints of compatibility with isocyanate and solubility in solvents.

  The polyester polyol has an optimum Mn depending on the type of isocyanate used as the curing agent, the number average molecular weight (Mn), and the availability of urethane prepolymerization, but is preferably in the range of 1000 ≦ Mn ≦ 6000. By setting Mn to 1000 or more, it is possible to suppress an increase in cross-linking point density, that is, Urc, and to suppress an increase in surface layer hardness under low temperature and low humidity. Furthermore, it contributes to easily controlling Ec and Etc in the surface layer. On the other hand, when Mn is 6000 or less, an excessive decrease in Urc can be suppressed, an increase in compression set can be prevented, and initial toner adhesion due to excessive softening can be suppressed.

  Although it does not specifically limit as isocyanate, The following can be mentioned as an example. Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, carbodiimide-modified MDI, xylylene diisocyanate, trimethylhexamethylene diisocyanate, toluene diisocyanate, Naphthylene diisocyanate, paraphenyl diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, copolymers thereof, block bodies and mixtures thereof.

  Among those exemplified above, a prepolymer type isocyanate having an ether group and an ester group in the modified portion (soft segment portion) is particularly preferable because of compatibility with the polyol and easy adjustment of physical properties. As the raw material constituting the modified part having an ether group and an ester group, the same materials as those used for the polyol can be suitably used.

  The isocyanate is preferably produced from at least one selected from diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), and polymethylene polyphenylene polyisocyanate (polymeric MDI). The above three types of materials not only have good reactivity with polyols, but also can control excessive hardening caused by hard segments relatively easily compared to isocyanate raw materials such as toluene diisocyanate (TDI). Can do. Further, compared to isocyanate raw materials such as xylylene diisocyanate (XDI), it is relatively easy to maintain toughness, which is preferable from the viewpoint of controlling compression set. Particularly preferably, a prepolymer type isocyanate having an ether group in the modified part and produced from polymethylene polyphenylene polyisocyanate (polymeric MDI) is used. By using the polymeric MDI, the crosslinking point density distribution (L) in the polyurethane resin becomes relatively broad, which contributes to both the flexibility of the surface layer and the high level of compression set.

  Further, in the isocyanate compound in the present invention, the optimum Mn differs depending on whether or not urethane prepolymerization is possible and the type of polyol compound used for the reaction and Mn, but it is preferable to be in the range of 2000 ≦ Mn ≦ 5500. When Mn is 2000 or more, an increase in surface layer hardness under low temperature and low humidity can be suppressed by suppressing an increase in cross-linking point density, that is, Urc. Furthermore, it contributes to easily controlling Ec and Etc in the surface layer. On the other hand, when Mn is 5500 or less, an excessive decrease in Urc can be suppressed, an increase in compression set can be prevented, and initial toner adhesion due to excessive softening can be suppressed.

  It is particularly preferable that the isocyanate compound has an isocyanate index in the range of 1.0 to 1.5 with respect to the polyol compound. By being in the said range, the raise of the compression set by the production | generation of an unreacted substance and the raise of excessive hardness can be suppressed. The isocyanate index indicates the ratio ([NCO] / [OH]) between the number of moles of isocyanate groups in the isocyanate compound and the number of moles of hydroxyl groups in the polyol component.

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

  In the developing roller 1 of the present invention, as shown in FIG. 1, one or more resin layers 3 are fixed to the outer peripheral surface of a columnar or hollow cylindrical conductive shaft core 2, and the resin layer 3 has an outer peripheral surface. A surface layer 4 is laminated. Further, in addition to the case where the resin layer 3 and the surface layer 4 each have a single layer structure, a multilayer structure having different materials and compositions may be used.

  The conductive shaft core used in the developing roller of the present invention has a strength capable of supporting the upper resin layer and the surface layer and conveying the toner (developer) to the photosensitive member, and an electrode capable of moving the charged toner to the photosensitive member. As long as it has the conductivity which can become. Examples of the material include metals or alloys such as aluminum, stainless steel, and copper alloys; iron plated with chromium, nickel, and the like; and synthetic resins having conductivity.

  Further, as the conductive shaft core, a conductive shaft core material that has been subjected to rust prevention treatment such as plating or oxidation treatment can be used. Either electroplating or electroless plating can be used as the type of plating, but electroless plating is preferred from the viewpoint of dimensional stability. Examples of the electroless plating used here include nickel plating (Kanizen plating), copper plating, gold plating, and other various alloy plating. The plating thickness is preferably 0.05 μm or more, and the plating thickness is preferably 0.1 to 30 μm in consideration of the balance between work efficiency and rust prevention ability.

  Examples of the shape of the conductive shaft core include a rod-shaped body and a pipe-shaped body. A primer treatment layer may be formed on the surface as necessary. The outer diameter of the conductive shaft core is preferably in the range of 4 mm to 10 mm.

  The resin layer in the developing roller of the present invention has an appropriate elasticity so that the developing roller has an appropriate elasticity so that the toner on the surface formed in a thin film shape in contact with the developing blade can be supplied to the photoreceptor. It is preferable to have. Also, in order to reduce damage to the photoreceptor, developing blade, toner, etc. that come into contact with the developing roller, the hardness is low, and the generation of deformation due to the pressing force received from these is suppressed, and a high-quality image is obtained over a long period of time It is preferable that the compression set is small.

  The thickness of the resin layer is preferably 1 mm or more and 5 mm or less, and the hardness is preferably 20 ° or more and 45 ° or less according to JIS K 6253A hardness. When the resin layer has a thickness of less than 1 mm, or when the JIS K 6253A hardness exceeds 45 °, the press contact force with the photosensitive member may increase, and the deterioration of the toner may be promoted. If the thickness exceeds 5 mm, the apparatus may be increased in size and cost, and if the JIS K 6253A hardness is less than 20 °, image streaks may occur due to plastic deformation due to long-term pressure contact with other members. is there.

  The resin layer may be a foam or a solid body. Specific examples of the material include ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), epoxy. Rubber, urea rubber, melamine rubber, diallyl phthalate rubber, polycarbonate rubber, styrene-butadiene rubber (SBR), styrene rubber, fluoro rubber, silicone rubber, epichlorohydrin rubber, NBR hydride, polysulfide rubber, urethane rubber, etc. A rubber material can be mentioned. These can be used alone or in combination of two or more.

  It is preferable that the resin layer has conductivity and the developing roller has an electric resistance value of the semiconductor region. In order to have conductivity in the resin layer, it is preferable to contain a conductivity-imparting agent by an ionic conduction mechanism or an electronic conduction mechanism. As the conductivity-imparting agent, fine particles such as conductive metals such as graphite, carbon black, aluminum, and copper; conductive metal oxides such as zinc oxide, tin oxide, and titanium oxide can be used. These can be used alone or in combination of two or more. Among these, carbon black is preferable because it can be obtained relatively easily and good chargeability can be obtained.

The volume resistivity of the resin layer is preferably in the range of 1 × 10 ³ to 1 × 10 ¹¹ Ω · cm. If the volume resistivity of the resin layer is 1 × 10 ³ to 1 × 10 ¹¹ Ω · cm, the toner can be uniformly charged. A more preferable range of the volume resistivity of the resin layer is 1 × 10 ³ to 1 × 10 ⁸ Ω · cm. In addition, the value calculated | required with the following method is employable as the volume resistivity of the said resin layer.

An ultrahigh resistance meter R8340A (trade name, manufactured by Advantest) is used as the resistance meter, and measurement is performed under the following conditions.
Measurement mode: Program mode 5
(Charge and major 30 seconds, discharge 10 seconds)
Applied voltage: 100 (V)
Sample box: Sample box TR42 (trade name, manufactured by Advantest) for measuring ultrahigh resistance meter
Main electrode: Metal guard ring electrode having a diameter of 10 mm and a thickness of 10 mm: Metal having an inner diameter of 20 mm and an outer diameter of 26 mm and a thickness of 10 mm For the test piece, first, the resin layer material is made under the same conditions as in the molding of the resin layer. A flat test piece cured to the same thickness as the layer is prepared. Next, a test piece having a diameter of 30 mm is cut out from the test piece. On one side of the cut specimen, a vapor deposition film electrode (back electrode) is provided by performing Pt—Pd vapor deposition on the entire surface, and the main electrode film having a diameter of 15 mm is formed on the other surface by the same Pt—Pd vapor deposition film. A guard ring electrode film having an inner diameter of 18 mm and an outer diameter of 28 mm is provided concentrically. The Pt—Pd vapor deposition film is obtained by using a mild sputter E1030 (trade name, manufactured by Hitachi, Ltd.) and performing a vapor deposition operation for 2 minutes at a current value of 15 mA. The sample after the vapor deposition operation is used as a measurement sample.

  At the time of measurement, the main electrode having a diameter of 10 mm is placed so as not to protrude from the main electrode film having a diameter of 15 mm. Further, measurement is performed by placing a guard ring electrode having an inner diameter of 20 mm on the electrode film so as not to protrude from the guard ring electrode film having an inner diameter of 18 mm. The measurement is performed in an environment where the temperature is 23 ° C. and the relative humidity is 50%. Prior to the measurement, the measurement sample is left in the environment for 12 hours or more.

  In the above state, the volume resistance (Ω) of the test piece is measured. Next, when the measured volume resistance value is RM (Ω) and the thickness of the test piece is t (cm), the volume resistivity RR (Ωcm) of the test piece is obtained by the following equation.

RR (Ωcm) = π × 0.75 × 0.75 × RM (Ω) ÷ (4 × t (cm))
The surface layer is formed using the ether ester polyurethane resin described above. When two or more surface layers are formed, at least the outermost surface layer may be formed using the ether ester polyurethane resin described above.

  The surface layer may contain carbon black for imparting conductivity and controlling mechanical properties. The content of carbon black in the surface layer is 15 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the resin component of the surface layer, from the viewpoint of imparting conductivity in an appropriate range to the developing roller and controlling the mechanical properties. The following is preferable. When the carbon black content in the surface layer is 15 parts by mass or more, not only moderate conductivity can be obtained, but also compression set can be suppressed. On the other hand, the amount of 30 parts by mass or less is preferable because not only dispersion uniformity with respect to the resin component can be obtained, but also an increase in surface hardness can be suppressed, and a high-quality image can be obtained.

  As carbon black, since it has dispersion stability, oxidation-treated carbon black to which a surface functional group is imparted by oxidation treatment is preferable. The pH value of the oxidized carbon black is preferably 5.0 or less. Since the oxidized carbon black has a polar group on the surface, the affinity with the resin component forming the surface layer is improved. For this reason, even if carbon black is used within a range where sufficient conductivity can be imparted, it can be uniformly dispersed, aggregation over time can be suppressed, and image defects such as ghosts and occurrence of leaks can be suppressed. Can do.

  The average particle size of the carbon black can be set to, for example, 15 to 40 nm in consideration of maintaining the strength of the surface layer and taking into consideration appropriate conductivity. Further, the DBP oil absorption amount of carbon black can be set to, for example, 60 to 180 ml / 100 g for the same reason. As such carbon black, what was manufactured by the channel method, the furnace method, etc. can be used conveniently. Furthermore, you may mix | blend 2 or more types of carbon black according to a required physical property.

  The surface layer may contain spherical fine particles that form an uneven shape on the surface in order to impart an appropriate surface roughness to the surface of the developing roller. When the surface layer contains spherical fine particles, it becomes easy to make the surface roughness of the surface of the developing roller uniform, and at the same time, even when the surface layer is worn, the fluctuation of the surface roughness is reduced and the surface state is made constant. Can be held. The content of the spherical fine particles is preferably 15 to 100 parts by mass with respect to 100 parts by mass of the resin component in the surface layer.

  The spherical fine particles preferably have a volume average particle size of 8 to 30 μm. For measurement of the volume particle size of the fine particles, a LS-230 type laser diffraction particle size distribution measuring device (trade name) manufactured by Coulter, Inc., with a liquid module attached thereto can be used. For measurement, a small amount of surfactant is added to about 10 cc of water, about 10 mg of fine particles are added thereto, and the mixture is dispersed for 10 minutes with an ultrasonic disperser, and then measured under the conditions of a measurement time of 90 seconds and a single measurement. . The value measured by the above measurement method can be adopted as the value of the volume average particle diameter.

  Examples of the material of the spherical fine particles include urethane resin, polyester resin, polyether resin, polyamide resin, acrylic resin, and polycarbonate resin. These spherical fine particles can be produced, for example, by suspension polymerization or dispersion polymerization.

  In the surface layer, in addition to the above components, the filler, extender, vulcanizing agent, cross-linking agent, vulcanizing auxiliary, cross-linking auxiliary, antioxidant as long as the function of the above component is not impaired. Various additives such as anti-aging agent and processing aid can be contained.

  As thickness of a surface layer, 1-50 micrometers is preferable, More preferably, it is 3-30 micrometers. If the thickness of the surface layer is 1 μm or more, precipitation of low molecular weight components contained in the surface layer and the lower layer can be suppressed, and if it is 50 μm or less, the development roller is prevented from having high hardness, and the toner Can be suppressed. As a method of measuring the film thickness of the surface layer, it can be measured by cutting out the developing roller and observing cross-sectional observation. As a specific example, a measurement sample is prepared by cutting a point 5 mm from the both ends of the produced developing roller and a central portion in the longitudinal direction into a size of 1 mm thickness × 5 mm depth with a razor. A method of observing the cross section of each measurement sample using a digital microscope (trade name: VH-2450, Keyence Corporation) can be exemplified. By the above measuring method, measurement is performed for three different points in the circumferential direction of each developing roller, and the average of nine points can be set as the film thickness of the developing roller.

  In the production of the developing roller of the present invention, a resin layer is first formed on a conductive shaft core. As a molding method of the resin layer, a coating liquid is prepared from a composition (referred to as an uncured rubber composition) containing the uncured rubber component of the rubber, a conductivity imparting agent, and other components as necessary. The method of forming a coating film using this and hardening this can be mentioned. Examples of the coating method include a dip coating method, a blade coating method, a coating method using an annular coating tank, and a coating method using a ring-shaped coating head. Moreover, the method of shape | molding by the extrusion molding method and the metal mold | die method and hardening | curing can be mentioned using an uncured rubber composition. After the rubber component is cured, the resin layer can be molded by polishing to adjust the surface roughness.

  After forming the resin layer, the surface layer is formed. As a method for forming the surface layer, a composition containing the uncured binder resin and other surface layer materials (referred to as an uncured composition) is prepared, and a coating film is formed on the resin layer using the composition. The method of forming and hardening can be mentioned. For the preparation of the uncured composition, it is preferable to use a dispersion apparatus using beads such as a sand mill, a paint shaker, a dyno mill, and a pearl mill using methyl ethyl ketone, toluene, or alcohol as a solvent.

  A coating method such as spraying, dipping, or roll coating can be used for forming the coating film. A method of forming a coating film on the resin layer, drying, removing the solvent, and curing by heating. Can be used. Specifically, the curing may be either heating or electron beam irradiation.

  When forming the coating film by dip coating, it is preferable to use a liquid circulation type dip coating apparatus having a paint circulation mechanism shown in the schematic configuration diagram of FIG.

  An immersion tank 25 is provided in the coating apparatus shown in FIG. The dipping bath 25 has a cylindrical shape with an inner diameter slightly larger than the outer diameter of the roller 26 on which the resin layer is formed and a depth longer than the axial length of the roller 26, and is installed with the axial direction vertical. The An annular liquid receiving portion 27 is provided on the outer periphery of the upper end portion, and the liquid receiving portion is connected to the stirring tank 28 by a pipe 29 connected to the bottom surface thereof. On the other hand, the bottom of the immersion tank 25 is connected to a pump 31 that circulates the surface layer forming paint 30 via a pipe 33, and is further connected to the stirring tank 28 by a pipe 32 that connects the pump 31 and the stirring tank 28. The stirring tank 28 is provided with a stirring blade 34 for stirring the surface layer forming coating material 30 accommodated therein.

  This coating apparatus is provided with an elevating device 35 that raises and lowers the elevating plate 36 in the axial direction of the immersing tank in the upper part of the immersing tank, and the roller 26 suspended on the elevating plate 36 can enter and retract into the immersing tank. It has become.

  In order to form the surface layer on the resin layer using such a coating apparatus, the pump 31 is driven and the surface layer forming coating material 30 stored in the stirring tank 28 is passed through the pipes 32 and 33 and the immersion tank 25. To supply. The elevating device 35 is driven to lower the elevating plate 36, and the roller 26 enters the immersion tank 25 filled with the surface layer forming coating material 30. The surface layer forming coating material 30 overflowing from the upper end 25 a of the immersion tank due to the entrance of the roller 26 is received by the liquid receiving portion 27 and returned to the stirring tank 28 through the pipe 29. Thereafter, the elevating device 35 is driven to raise the elevating plate 36, the roller 26 is retracted from the immersion tank 25 at a predetermined speed, and a coating film is formed on the resin layer. During this time, the agitating blade 34 is rotated in the agitation tank 28 to agitate the surface layer forming coating material 30 to suppress sedimentation of the contents, and maintain the uniformity of the surface layer forming coating material 30.

  The roller 26 on which the coating film is formed is removed from the elevating plate 36, the coating film is dried and cured, and a surface layer is formed.

  The present invention also provides a process cartridge that includes the developing roller and is detachable from an electrophotographic apparatus. Further, according to the present invention, a thin layer of toner is formed on the surface of the developing roller, and the developing roller is brought into contact with the photosensitive drum to supply the toner to the surface of the photosensitive member. It is a photographic device. As in the electrophotographic apparatus shown in FIG. 2, the process cartridge can be an all-in-one process cartridge integrated with the photosensitive member 6, the cleaning blade 14, the waste toner container 13, and the charging device 12.

  FIG. 2 is a cross-sectional view showing a schematic configuration of an electrophotographic apparatus using the developing roller of the present invention and a process cartridge including the developing roller. In the electrophotographic apparatus of FIG. 2, an all-in-one process cartridge 5 including a developing device 10, a photoreceptor 6, a cleaning blade 14, a waste toner container 13 and a charging member 12 is detachably mounted. The developing device 10 includes a developing roller 1, a toner supply roller 7, toner 8, and a developing blade 9.

  The photosensitive member 6 rotates in the direction of the arrow, is uniformly charged by a charging member 12 for charging the photosensitive member 6, and the surface of the photosensitive member 6 is exposed by laser light 11 which is an exposure means for writing an electrostatic latent image on the photosensitive member 6. An electrostatic latent image is formed. The electrostatic latent image is developed by being applied with toner by the developing device 10 disposed in contact with the photoreceptor 6 and visualized as a toner image. Development is so-called reversal development in which a toner image is formed on the exposed portion.

  The visualized toner image on the photoreceptor 6 is transferred to a paper 22 as a recording medium by a transfer roller 17 as a transfer member. The paper 22 is fed into the apparatus through a paper feed roller 23 and a suction roller 24, and is transported between the photoconductor 6 and the transfer roller 17 by an endless belt-shaped transfer transport belt 20. The transfer / conveying belt is operated by a driven roller 21, a driving roller 16, and a tension roller 19. A voltage is applied to the transfer roller 17 and the suction roller 24 from a bias power source 18. The paper 22 to which the toner image has been transferred is subjected to fixing processing by the fixing device 15 and is discharged out of the device, thus completing the printing operation.

  On the other hand, the untransferred toner remaining on the photoconductor 6 without being transferred is scraped off by a cleaning blade 14 which is a cleaning member for cleaning the surface of the photoconductor 6 and stored in a waste toner container 13 for cleaning. The photoreceptor 6 repeatedly performs the above-described operation.

  The developing device 10 is a developer container that contains a non-magnetic toner 8 as a one-component developer, and a developer carrier that is located in an opening extending in the longitudinal direction in the developer container and is placed opposite to the photosensitive member 6. A developing roller 1 is provided to develop and visualize the electrostatic latent image on the photoreceptor 6.

  Further, as the developing blade 9, a member in which a rubber elastic body is fixed to a metal sheet metal, a member having a spring property such as a thin plate of SUS or phosphor bronze, or a member in which resin or rubber is laminated on the surface thereof is used. . Further, it is possible to control the toner layer on the developing roller by applying a voltage higher than the voltage applied to the developing roller 1 to the developing blade 9, and for this purpose, the developing blade 9 is made of SUS or phosphor bronze. It is preferable to use a thin plate. Note that a voltage is applied to the developing roller 1 and the developing blade 9 from the bias power source 18, but the voltage applied to the developing blade 9 is increased from 100 V to 300 V in absolute value with respect to the voltage applied to the developing roller 1. Is preferred.

  The developing process in the developing device 10 will be described below. Toner is applied onto the developing roller 1 by a toner supply roller 7 that is rotatably supported. The toner applied on the developing roller 1 is rubbed against the developing blade 9 by the rotation of the developing roller 1. Here, the toner on the developing roller is uniformly coated on the developing roller by the bias applied to the developing blade 9. The developing roller 1 is in contact with the photosensitive member 6 while rotating, and an electrostatic latent image formed on the photosensitive member 6 is developed with toner coated on the developing roller 1 to form an image.

  As a structure of the toner supply roller 7, a foamed skeleton-like sponge structure or a fur brush structure in which fibers such as rayon and polyamide are planted on the shaft core is used to supply the toner 8 to the developing roller 1 and to peel off the undeveloped toner. It is preferable from the point of taking. In this example, an elastic roller having a polyurethane foam on the core was used. The contact width of the toner supply roller 7 with respect to the developing roller 1 is preferably 1 to 8 mm, and the developing roller 1 is preferably provided with a relative speed at the contact portion.

  Hereinafter, the developing roller, the electrophotographic process cartridge, and the electrophotographic apparatus of the present invention will be described in detail, but the technical scope of the present invention is not limited thereto.

  First, although the production method of the resin layer roller in the Example and comparative example of this invention is illustrated and demonstrated concretely, this invention is not limited to these.

[Production of Resin Layer Roller 1]
As the shaft core body, a SUS304 φ8 core metal coated with a primer (trade name: DY35-051, manufactured by Toray Dow Corning) of about 1 μm and baked at 150 ° C. for 30 minutes was used.

A mixture of the following components was used as the base material for the liquid silicone rubber.
-Dimethylpolysiloxane (1) 50 parts by mass (vinyl groups are substituted at both ends, and 99 mol% or more of the main chain is a repeating unit of dimethylpolysiloxane. Weight average molecular weight (Mw) = 10,000)
-Dimethylpolysiloxane (2) 50 parts by mass (vinyl groups are substituted at both ends, and 99 mol% or more of the main chain is a repeating unit of dimethylpolysiloxane. Mw = 2,000,000)
Carbon black (1) 6 parts by mass (trade name: Raven 860 Ultra, manufactured by Columbian Chemical)
This base material was prepared by blending 10 ppm of an isopropanol solution of 2% by mass of chloroplatinic acid as a curing catalyst with respect to the total of dimethylpolysiloxanes (1) and (2). On the other hand, 3 parts by mass of methyl hydrogen polysiloxane in the base material (amount that SiH group is 1.1 mol with respect to a total of 1 mol of vinyl groups contained in dimethylpolysiloxane (1) and (2)) Was prepared. And these were mixed by mass ratio 1: 1, and it was set as the unvulcanized silicone rubber.

  Next, the shaft core was placed in a mold, and the unvulcanized silicone rubber was injected into a cavity formed in the mold. Subsequently, the mold was heated to cure and cure the unvulcanized silicone rubber at 150 ° C. for 15 minutes, and then demolded after cooling. Thereafter, the mixture was further heated at 180 ° C. for 1 hour to complete the curing reaction, and a resin layer was provided around the shaft core body. The diameter of the produced resin layer roller 1 was 16 mm.

[Production of Resin Layer Roller 2]
Resin layer roller in the same manner as the resin layer roller 1 except that 100 parts by mass of dimethylpolysiloxane (3) was used instead of 50 parts by mass of dimethylpolysiloxane (1) and 50 parts by mass of dimethylpolysiloxane (2). 2 was produced. The dimethylpolysiloxane (3) has vinyl groups substituted at both ends, 99 mol% or more of the main chain is a repeating unit of dimethylpolysiloxane, and Mw is 900,000.

[Production of Resin Layer Roller 3]
Resin layer roller 3 was produced in the same manner as resin layer roller 1 except that 6 parts by mass of carbon black (2) and 24 parts by mass of carbon black (3) were used instead of 6 parts by mass of carbon black (1). did. Carbon black (2) is Raven 3600 Ultra (trade name) manufactured by Columbia Chemical, and carbon black (3) is 50H (trade name) manufactured by Asahi Carbon Corporation.

[Production of resin layer roller 4]
Resin layer roller, except that 6 parts by mass of carbon black (2) and 20 parts by mass of carbon black (3) were used instead of 6 parts by mass of carbon black (1), and 15 parts by mass of silica (1) was further blended. The resin layer roller 4 was produced in the same manner as in No. 1. Carbon black (2) is Raven 3600 Ultra (trade name) manufactured by Columbia Chemical, and carbon black (3) is 50H (trade name) manufactured by Asahi Carbon Corporation. Silica (1) is Toroyama Leolosil MT-10 (trade name).

  Then, although the synthesis method of the prepolymer type polyol and isocyanate compound in the Example and comparative example of this invention is illustrated and demonstrated concretely, this invention is not limited to these.

[Synthesis of Prepolymer Type Polyol 1 (Pre-P1)]
・ 100 parts by mass of polytetramethylene glycol (trade name: PTG1000SN, manufactured by Hodogaya Chemical Co., Ltd.)
・ Isocyanate compound 25 parts by mass (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.)
The above components are mixed stepwise in a MEK solvent and reacted at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain an ether-modified prepolymer polyol 1 (Pre-P1) having a number average molecular weight Mn = 3,700. Obtained.

[Synthesis of Prepolymer Type Polyol 2 (Pre-P2)]
Polyester diol 100 parts by mass (consisting of adipic acid and 3-methyl-1,5-pentanediol. Mn = 500)
・ Isocyanate compound 24 parts by mass (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.)
The above components are mixed stepwise in a MEK solvent and reacted at 80 ° C. for 7 hours under a nitrogen atmosphere to produce an ester-modified prepolymer polyol 2 (Pre-P2) having a number average molecular weight Mn = 6,000. Obtained.

[Synthesis of Prepolymer Polyol 3 (Pre-P3)]
・ 100 parts by mass of polycaprolactone diol (trade name: L212AL, manufactured by Daicel Chemical Industries, Ltd.)
・ Isocyanate compound 47 parts by mass (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.)
The above components are mixed stepwise in a MEK solvent and reacted at 80 ° C. for 6 hours under a nitrogen atmosphere to produce an ester-modified prepolymer polyol 3 (Pre-P3) having a number average molecular weight Mn = 6,600. Obtained.

[Synthesis of Prepolymer Type Isocyanate 1 (Pre-BI1)]
・ 100 parts by weight of polypropylene glycol (trade name: Exenol 720, manufactured by Asahi Glass Co., Ltd.)
・ 95 parts by mass of polymethylene polyphenylene polyisocyanate (trade name: Cosmonate M-100, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 28 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain a prepolymer type isocyanate 1 (Pre-BI1) with Mn = 5,400 [of prepolymer type isocyanate 2 (Pre-BI2) Composition]
・ 100 parts by mass of polytetramethylene glycol (trade name: PTG1000SN, manufactured by Hodogaya Chemical Co., Ltd.)
・ 125 parts by mass of polymethylene polyphenylene polyisocyanate (trade name: Cosmonate M-200, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 48 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain prepolymer type isocyanate 2 (Pre-BI2) having Mn = 2,000.

[Synthesis of Prepolymer Type Isocyanate 3 (Pre-BI3)]
-Polypropylene glycol 100 parts by mass (trade name: Exenol 420, manufactured by Asahi Glass Co., Ltd.)
・ 90 parts by mass of polymethylene polyphenylene polyisocyanate (trade name: Cosmonate M-100, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 30 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain prepolymer type isocyanate 3 (Pre-BI3) having Mn = 2,600.

[Synthesis of Prepolymer Type Isocyanate 4 (Pre-BI4)]
Esterdiol 100 parts by mass (trade name: Adeka New Ace YT-101, manufactured by ADEKA Corporation, polyhydric alcohol raw material: 1,3-butanediol)
・ 100 parts by mass of polymethylene polyphenylene polyisocyanate (trade name: Cosmonate M-200, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 40 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain ester-modified prepolymer type isocyanate 4 (Pre-BI4) with Mn = 2,900.

[Synthesis of Prepolymer Type Isocyanate 5 (Pre-BI5)]
-Polypropylene glycol 100 parts by mass (trade name: Exenol 420, manufactured by Asahi Glass Co., Ltd.)
140 parts by mass of polymethylene polyphenylene polyisocyanate (trade name: Cosmonate M-100, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 54 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain a prepolymer type isocyanate 5 (Pre-BI5) with Mn = 1,800.

[Synthesis of Prepolymer Type Isocyanate 6 (Pre-BI6)]
・ 100 parts by weight of polypropylene glycol (trade name: Exenol 720, manufactured by Asahi Glass Co., Ltd.)
-Tolylene diisocyanate (TDI) 136 parts by mass (trade name: Cosmonate T-80, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 56 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain a prepolymer type isocyanate 6 (Pre-BI6) having Mn = 4,600.

[Synthesis of Prepolymer Type Isocyanate 7 (Pre-BI7)]
・ 100 parts by mass of polypropylene glycol (trade name: Exenol 1020, manufactured by Asahi Glass Co., Ltd.)
120 parts by mass of polymethylene polyphenylene polyisocyanate (trade name: Cosmonate M-100, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 28 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain a prepolymer type isocyanate 7 (Pre-BI7) having Mn = 5,800.

[Synthesis of Prepolymer Type Isocyanate 8 (Pre-BI8)]
・ 100 parts by weight of polypropylene glycol (trade name: Exenol 720, manufactured by Asahi Glass Co., Ltd.)
・ Isophorone diisocyanate (IPDI) 100 parts by mass (trade name: Takenate D140N, manufactured by Mitsui Chemicals Polyurethanes)
The above components were heated and reacted at 90 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, butyl cellosolve was added to a solid content of 70% by mass. Thereafter, 32 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain a prepolymer type isocyanate 8 (Pre-BI8) with Mn = 2,500.

  Then, although the preparation method of the coating liquid for surface layer formation in the Example and comparative example of this invention is specifically illustrated and demonstrated below, this invention is not limited to these.

"Preparation of surface layer forming coating liquid (1)"
・ 100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L212AL, manufactured by Daicel Chemical Industries, Mn = 1,200)
Pre-BI1 (Mn = 5,400) 226.8 parts by mass As a material for the coating liquid for forming the surface layer, the above components were mixed to obtain a resin component. Subsequently, 23 parts by mass of carbon black (trade name: X-55, manufactured by Asahi Carbon Co., Ltd.) and MEK are added to 100 parts by mass of the solid content of the resin component, and the mixture is agitated with an agitator motor at 400 rpm for 1 hour. Performed under conditions. Subsequently, MEK was further added so that the total solid content ratio was 32% by mass, and mixing and stirring was performed with a stirring motor at 700 rpm for 1 hour. Subsequently, the above mixed solution was uniformly dispersed with a horizontal dispersion NVM-03 (trade name, manufactured by IMEX) under conditions of a peripheral speed of 7 m / sec, a flow rate of 1 cc / min, and a dispersion temperature of 15 ° C. for 3 hours. In this dispersion, glass beads having a diameter of 1.5 mm (trade name: DMB503B, manufactured by Hotters Ballotinis) were used. Next, 45 parts by mass of urethane resin particles (trade name: Art Pearl CF-600T, manufactured by Negami Kogyo Co., Ltd.) are added as resin particles for adjusting the roughness to 100 parts by mass of the solid content of the resin component, and further for 1 hour. Uniformly dispersed. Next, this solution was prepared to a solid content of 23% by mass so that the film thickness of the surface layer after coating was 10 μm, and this solution was filtered through a 300-mesh net to form a surface layer-forming paint (1) It was.

"Preparation of surface layer forming coating liquid (2)"
Esterdiol 100 parts by mass (trade name: Adeka New Ace YT-101, manufactured by ADEKA Corporation, Mn = 1,000, polyhydric alcohol raw material: 1,3-butanediol)
・ Pre-BI2 (Mn = 2,000) 280.1 parts by mass The same as the surface layer forming coating liquid (1) except that the above components are mixed to form a resin component as the material of the surface layer forming coating liquid. The surface layer forming coating liquid (2) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (3)"
-100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L205AL, manufactured by Daicel Chemical Industries, Mn = 500)
・ Pre-BI1 (Mn = 5,400) 387.5 parts by mass The same as the surface layer forming coating solution (1) except that the above components are mixed into a resin component as the material of the surface layer forming coating solution. The surface layer forming coating liquid (3) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (4)"
Esterdiol 100 parts by mass (trade name: Adeka New Ace NS-2400, manufactured by ADEKA Corporation, Mn = 2,000, polyhydric alcohol raw material: 3-methyl-1,5-pentanediol)
-Pre-BI3 (Mn = 2,600) 106.8 parts by mass The same as the coating liquid for surface layer formation (1) except that the above components are mixed into a resin component as the material for the surface layer forming coating liquid. The surface layer forming coating liquid (4) was prepared by the method described above.

“Preparation of coating liquid for surface layer formation (5)”
-100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L220AL, manufactured by Daicel Chemical Industries, Mn = 1,900)
・ Pre-BI3 (Mn = 2,600) 111.6 parts by mass The same as the coating liquid for surface layer formation (1) except that the above components were mixed to form a resin component as the material for the surface layer forming coating liquid. The surface layer forming coating liquid (5) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (6)"
Pre-P1 (Mn = 6,600) 100 parts by mass Pre-BI4 (Mn = 1,800) 25.6 parts by mass As a material for the coating liquid for forming the surface layer, the above components were mixed to form a resin component The surface layer forming coating liquid (6) was prepared in the same manner as in the surface layer forming coating liquid (1) except for the above.

"Preparation of surface layer forming coating liquid (7)"
・ 100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L212AL, manufactured by Daicel Chemical Industries, Mn = 1,200)
・ Pre-BI3 (Mn = 2,600) 125.4 parts by mass ・ Pre-BI5 (Mn = 2,900) 53.7 parts by mass As a material for the coating liquid for forming the surface layer, the above components are mixed to form a resin component. A surface layer-forming coating liquid (7) was prepared in the same manner as in the surface layer-forming coating liquid (1) except that.

"Preparation of surface layer forming coating liquid (8)"
Pre-P2 (Mn = 3,700) 87.6 parts by mass Ester diol 12.4 parts by mass (trade name: Adeka New Ace NS-2400, manufactured by ADEKA Corporation, Mn = 2,000, polyhydric alcohol raw material : 3-methyl-1,5-pentanediol)
・ Pre-BI1 (Mn = 5,400) 69.3 parts by mass The same as the coating liquid for surface layer formation (1) except that the above components are mixed to form a resin component as the material for the surface layer forming coating liquid. The surface layer forming coating liquid (8) was prepared by this method.

"Preparation of surface layer forming coating liquid (9)"
・ 100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L212AL, manufactured by Daicel Chemical Industries, Mn = 1,200)
Pre-BI4 (Mn = 1,800) 148.9 parts by mass The same as the surface layer forming coating liquid (1) except that the above components were mixed to form a resin component as the material of the surface layer forming coating liquid The surface layer forming coating liquid (9) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (10)"
・ Pre-P2 (Mn = 3,700) 100 parts by mass ・ Pre-BI5 (Mn = 2,900) 46.8 parts by mass As a material for the coating liquid for forming the surface layer, the above components were mixed to form a resin component. The surface layer forming coating liquid (10) was prepared in the same manner as in the surface layer forming coating liquid (1) except for the above.

"Preparation of surface layer forming coating liquid (11)"
・ 100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L212AL, manufactured by Daicel Chemical Industries, Mn = 1,200)
・ Pre-BI6 (Mn = 4,600) 186.8 parts by mass The same as the coating liquid for surface layer formation (1) except that the above components were mixed into a resin component as the material for the coating liquid for surface layer formation. The surface layer forming coating liquid (11) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (12)"
・ Pre-P3 (Mn = 6000) 100 parts by mass ・ Pre-BI7 (Mn = 5,800) 47.8 parts by mass As the material of the coating liquid for forming the surface layer, the above components were mixed to form a resin component. The surface layer forming coating liquid (12) was prepared in the same manner as the surface layer forming coating liquid (1).

"Preparation of surface layer forming coating liquid (13)"
-100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L220AL, manufactured by Daicel Chemical Industries, Mn = 1,900)
Pre-BI8 (Mn = 2,500) 102.2 parts by mass The same as the surface layer forming coating liquid (1) except that the above components are mixed to form a resin component as the material of the surface layer forming coating liquid. The surface layer forming coating liquid (13) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (14)"
The surface layer forming coating liquid (14) was prepared in the same manner as the surface layer forming coating liquid (4). However, 13 parts by mass of carbon black (trade name: Special Black 5, manufactured by Degussa) was used instead of 23 parts by mass of carbon black (trade name: X-55, manufactured by Asahi Carbon Co., Ltd.).

"Preparation of surface layer forming coating liquid (15)"
The surface layer forming coating liquid (15) was prepared in the same manner as the surface layer forming coating liquid (4). However, instead of 23 parts by mass of carbon black (trade name: X-55, manufactured by Asahi Carbon Co., Ltd.), 15 parts by mass of carbon black (trade name: Special Black 5, manufactured by Degussa) was used.

"Preparation of surface layer forming coating liquid (16)"
The surface layer forming coating liquid (16) was prepared in the same manner as the surface layer forming coating liquid (4). However, 30 parts by mass of carbon black (trade name: MA-11, manufactured by Mitsubishi Chemical Corporation) was used instead of 23 parts by mass of carbon black (trade name: X-55, manufactured by Asahi Carbon Co., Ltd.).

“Preparation of coating liquid for surface layer formation (17)”
The surface layer forming coating liquid (17) was prepared in the same manner as the surface layer forming coating liquid (4). However, 32 parts by mass of carbon black (trade name: MA-11, manufactured by Mitsubishi Chemical Corporation) was used instead of 23 parts by mass of carbon black (trade name: X-55, manufactured by Asahi Carbon Co., Ltd.).

"Preparation of surface layer forming coating liquid (18)"
・ Pre-P1 (Mn = 6,600) 100 parts by mass ・ Pre-BI3 (Mn = 2,600) 30.3 parts by mass As a material of the coating liquid for forming the surface layer, the above components were mixed to form a resin component. The surface layer forming coating liquid (18) was prepared in the same manner as in the surface layer forming coating liquid (1) except for the above.

"Preparation of surface layer forming coating liquid (19)"
-100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L205AL, manufactured by Daicel Chemical Industries, Mn = 500)
・ Pre-BI2 (Mn = 2,000) 387.5 parts by mass The same as the surface layer forming coating liquid (1) except that the above components are mixed to form a resin component as the material of the surface layer forming coating liquid The surface layer forming coating liquid (19) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (20)"
Pre-P1 (Mn = 6,600) 100 parts by mass Pre-BI7 (Mn = 5,800) 40.9 parts by mass As a material for the coating liquid for forming the surface layer, the above components were mixed to form a resin component The surface layer forming coating liquid (20) was prepared in the same manner as in the surface layer forming coating liquid (1) except for the above.

"Preparation of surface layer forming coating liquid (21)"
Esterdiol 100 parts by mass (trade name: Adeka New Ace F13-35, manufactured by ADEKA Corporation, Mn = 1,000, polyhydric alcohol raw material: 1,4-butanediol)
・ Pre-BI8 (Mn = 2,500) 253.3 parts by mass The same as the surface layer forming coating solution (1) except that the resin component is mixed with the above components as the material of the surface layer forming coating solution. The surface layer forming coating liquid (21) was prepared by the method described above.

"Preparation of surface layer forming coating liquid (22)"
Pre-P1 (Mn = 6,600) 80.0 parts by mass Pre-P2 (Mn = 3,700) 20.0 parts by mass Pre-BI6 (Mn = 4,600) 32.6 parts by mass Surface layer The surface layer forming coating liquid (22) was prepared in the same manner as the surface layer forming coating liquid (1) except that the above components were mixed to form a resin component as the material of the forming coating liquid. .

"Preparation of surface layer forming coating liquid (23)"
Esterdiol 11.0 parts by mass (trade name: Adeka New Ace YG-108, manufactured by ADEKA Corporation, Mn = 900, polyhydric alcohol raw material: 1,6-hexanediol)
Pre-P2 (Mn = 3,700) 89.0 parts by mass Pre-BI1 (Mn = 5,400) 85.0 parts by mass As a material for the coating liquid for forming the surface layer, the above components are mixed to form a resin component A surface layer-forming coating solution (23) was prepared in the same manner as in the surface layer-forming coating solution (1) except that.

“Preparation of surface layer forming coating liquid (24)”
-100 parts by mass of liquid type polycaprolactone diol (trade name: Plaxel L220AL, manufactured by Daicel Chemical Industries, Mn = 1,900)
・ Pre-BI3 (Mn = 2,600) 68.2 parts by mass ・ Pre-BI5 (Mn = 2,900) 45.5 parts by mass As a material for the coating liquid for forming the surface layer, the above components are mixed to form a resin component. A surface layer-forming coating solution (24) was prepared in the same manner as in the surface layer-forming coating solution (1) except that.

  Subsequently, the production methods of the developing roller in Examples and Comparative Examples of the present invention will be specifically illustrated and described below, but the present invention is not limited to these.

[Example 1]
The surface layer forming paint (1) is placed in the apparatus shown in FIG. It was immersed and stopped for 10 seconds. Thereafter, the film was pulled up under conditions of an initial speed of 300 mm / s and an final speed of 200 mm / s and naturally dried for 60 minutes. Subsequently, the raw material of the surface layer was cured by heat treatment at 140 ° C. for 2 hours, and the developing roller (1) of Example 1 was produced. The results are shown in Table 1.

[Example 2]
A developing roller (2) of Example 2 was produced in the same manner as the developing roller (1) except that the resin layer roller 2 was used instead of the resin layer roller 1. The results are shown in Table 1.

[Example 3]
A developing roller (3) of Example 3 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (2) was used instead of the surface layer forming paint (1). The results are shown in Table 1.

[Example 4]
A developing roller (4) of Example 4 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (3) was used instead of the surface layer forming paint (1). The results are shown in Table 1.

[Example 5]
A developing roller (5) of Example 5 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (4) was used instead of the surface layer forming paint (1). The results are shown in Table 1.

[Example 6]
A developing roller (6) of Example 6 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (5) was used instead of the surface layer forming paint (1). The results are shown in Table 1.

[Example 7]
A developing roller (7) of Example 7 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (6) was used instead of the surface layer forming paint (1). The results are shown in Table 1.

[Example 8]
A developing roller (8) of Example 8 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (7) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 9]
A developing roller (9) of Example 9 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (8) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 10]
A developing roller (10) of Example 10 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (9) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 11]
A developing roller (11) of Example 11 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (10) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 12]
A developing roller (12) of Example 12 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (11) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 13]
A developing roller (13) of Example 13 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (12) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 14]
A developing roller (14) of Example 14 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (13) was used instead of the surface layer forming paint (1). The results are shown in Table 2.

[Example 15]
A developing roller (15) of Example 15 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (14) was used instead of the surface layer forming paint (1). The results are shown in Table 3.

[Example 16]
A developing roller (16) of Example 16 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (15) was used instead of the surface layer forming paint (1). The results are shown in Table 3.

[Example 17]
A developing roller (17) of Example 17 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (16) was used instead of the surface layer forming paint (1). The results are shown in Table 3.

[Example 18]
A developing roller (18) of Example 18 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (17) was used instead of the surface layer forming paint (1). The results are shown in Table 3.

[Example 19]
A developing roller (19) of Example 19 was produced in the same manner as the developing roller (11) except that the resin layer roller 3 was used instead of the resin layer roller 1. The results are shown in Table 3.

[Example 20]
A developing roller (20) of Example 20 was produced in the same manner as the developing roller (11) except that the resin layer roller 4 was used instead of the resin layer roller 1. The results are shown in Table 3.

[Comparative Example 1]
A developing roller (21) of Comparative Example 1 was produced in the same manner as the developing roller (1) except that the surface layer forming paint (18) was used instead of the surface layer forming paint (1). The results are shown in Table 4.

[Comparative Example 2]
A developing roller (22) of Comparative Example 2 was produced in the same manner as the developing roller (1) except that the resin layer roller 4 was used instead of the resin layer roller 1. The results are shown in Table 4.

[Comparative Example 3]
A developing roller (23) of Comparative Example 3 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (19) was used instead of the surface layer forming paint (1). The results are shown in Table 4.

[Comparative Example 4]
The same as the developing roller (1) except that the resin layer roller 3 is used instead of the resin layer roller 1 and the surface layer forming paint (20) is used instead of the surface layer forming paint (1). The developing roller (24) of Comparative Example 4 was produced by the method. The results are shown in Table 4.

[Comparative Example 5]
A developing roller (25) of Comparative Example 5 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (21) was used instead of the surface layer forming paint (1). The results are shown in Table 4.

[Comparative Example 6]
A developing roller (26) of Comparative Example 6 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (22) was used instead of the surface layer forming paint (1). The results are shown in Table 4.

[Comparative Example 7]
A developing roller (27) of Comparative Example 7 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (23) was used instead of the surface layer forming paint (1). The results are shown in Table 4.

[Comparative Example 8]
A developing roller (28) of Comparative Example 8 was produced in the same manner as the developing roller (2) except that the surface layer forming paint (24) was used instead of the surface layer forming paint (1). The results are shown in Table 4.

  Subsequently, ESCA measurement, μ-MS measurement, structural analysis, JIS K 6253A hardness measurement and GPC measurement method in Examples and Comparative Examples of the present invention, and Ec, Etc and Urc defined in the present invention will be described below. To do.

[Evaluation of developing roller / Evaluation of surface layer material]
(ESCA measurement method)
ESCA analyzer: Product name: Quantum 2000, manufactured by ULVAC-PHI Co., Ltd. Detection elements: C, N, O, Si
X-ray source: Monochrome AI Kα
Xray Setting: 100 μmφ (25 W (15 KV))
Photoelectron extraction angle: 45 ° Neutralization condition: Combined use of neutralization gun and ion gun Analysis area: φ100 μm
Pass Energy: 23.5eV
Step size: 0.1eV
In the present invention, Ec, Etc, and Urc are Cm, N, O, and atm% of Si element derived from the resin layer detected by quantitative analysis of ESCA measurement, and C 1s peak and N 1s peak detected by state analysis. It is determined from the area ratio. In the C 1s peak, the detection peak at 285.0 eV was assigned as the C—C bond, and the detection peak at 286.6 eV was assigned as the C—O bond, which was attributed to 289.3 eV. In the N 1s peak, the peak at 400.4 eV was assigned as the NH bond. In the O 1s peak, the detection peak at 532.4 eV was defined as C═O bond and Si—O bond, and the detection peak at 533.7 eV was assigned as C—O bond. In the Si 2p peak, the peak intensity at 102.5 eV was assigned as the Si—O bond.

  Here, since there is an excellent correlation with the quantitative ratio relationship of the abundance ratio of C—C bond, C—O bond and COO bond by state analysis of the ester concentration and ether concentration in the polyurethane resin and the C 1s peak, the present invention Used to define Ec and Etc. Specifically, Ec was defined by the following formula (4), and Etc was defined by the following formula (5). Further, since the N amount in the ether ester polyurethane resin is derived from the urethane group, the numerical value of N atm% was defined as Urc as shown in the following formula (6). In addition, the measurement of Ec, Etc, and Urc in the present invention was performed by measuring three points at different locations on the surface layer and using the average value.

  For example, as a result of quantitative analysis of elements in the surface layer of the developing roller (1), atm% of C, N, O and Si was 63.8, 1.2, 25.1 and 7.9%, respectively. Therefore, Urc is 1.2. In addition, the peak area ratios of C—C bond, C—O bond, and COO bond in the C 1s spectrum by state analysis of the developing roller (1) were 70.8%, 22.0%, and 6.2%, respectively. It was. From this value, the ratios of C—C, C—O and COO bonds in the surface layer of the developing roller (1) were 45.2%, 14.0% and 4.0%, respectively. When Ec and Etc were calculated based on this value, Ec and Etc of the developing roller (1) were 8.8 and 22.1, respectively.

(Surface layer structure analysis)
The structure of the surface layer of the obtained developing roller was analyzed by Fourier transform-infrared absorption (FT-IR) spectrum, pyrolysis GC-MS method, and ¹ H-NMR. Nicolet AVATAR360 FT-IR (trade name, manufactured by JASCO Corporation) was used for the FT-IR spectrum. ^{For 1} H-NMR, FT-NMR (trade name: DPX400) manufactured by Bruker was used, and the resonance frequency was 400 MHz, the measurement nuclide was ¹ H, the solvent used was deuterated chloroform, and the measurement temperature was room temperature. As a measurement sample, a toner and an external additive adhering to the surface of the developing roller were wiped off with a cloth soaked with isopropyl alcohol after image evaluation described later, and then the surface of the developing roller was thinly scraped with a biocutter.

For example, with respect to the developing roller (1), were evaluated in the FT-IR, an ether group (1100 cm ^-1), an ester group (1200 cm ^-1), the spectrum due to the urethane group (1710 cm ^-1) was confirmed . That is, it was confirmed that it was an ether ester polyurethane resin. In addition, alkaline hydrolysis with sodium hydroxide and thermal decomposition in a pressure-resistant decomposition vessel were performed, ether extraction operation was performed, and separation was performed with diol and dibasic acid. Then, when it evaluated by pyrolysis GC-MS and < ¹ > H-NMR, it was confirmed that it has the segment of Structural formula (1). The result in the developing roller produced by each Example and the comparative example is shown to Tables 1-4.

(Μ-MS measurement method)
The crosslink density of the surface layer of the developing roller in the present invention was measured by micro sampling mass spectrometry (μ-MS). An outline of micro sampling mass spectrometry is shown below. As the measurement sample, a surface layer after image evaluation described later was subjected to the same treatment as in the FT-IR analysis.

  For the measurement, an ion trap MS device mounted on Polaris Q (trade name, manufactured by Thermo Electron CO.) Was used. The sample is fixed to a filament located at the tip of the probe and inserted directly into the ionization chamber. After being kept in the chamber for 10 seconds, the sample was rapidly heated from room temperature (25 ° C.) to 1000 ° C. at a rate of temperature increase of 8.3 ° C./s, and the evaporated sample was ionized by electron beam irradiation and detected by a mass spectrometer. .

  Under a condition where the heating rate is constant, a thermal chromatogram similar to TG-MS having a mass spectrum called a total ion chromatogram (TIC) is obtained. In the present invention, the full width at half maximum of the time (temperature) at which the obtained thermal chromatogram becomes a maximum value is defined as L (min). In addition, although the peak obtained is an isocyanate-derived peak appearing on the low temperature side and two peaks derived from the polyol appearing on the high temperature side are detected, the decomposition temperature of the urethane bond is derived from a hard segment, that is, an isocyanate-derived peak. . Therefore, L in the present invention was calculated using an average value measured three times using a peak appearing on the low temperature side. The decomposition temperature is obtained by the following formula (7). For example, when μ-MS was evaluated for the developing roller (1) using the following formula (7), a maximum peak due to urethane bond decomposition was confirmed at 389.6 ° C., and L = 2.4 min. It was. The result in the developing roller produced by each Example and the comparative example is shown to Tables 1-4.

Decomposition temperature (° C) = [Maximum peak measurement time (s) × 60-10 (retention time)] × 8.3 ° C / s + 25 ° C (room temperature)
... Formula (7)
(Measurement method of JIS K 6253A hardness)
JIS K 6253A hardness of the developing roller is a rubber hardness meter constant pressure loader CL-150L (trade name: manufactured by Polymer Equipment Co., Ltd.) attached with a rubber hardness meter JA (trade name: manufactured by Polymer Equipment Co., Ltd.) Was measured at a load of 1 kg. There were a total of three measurement points at both ends and the center, and the simple (arithmetic) average of these was defined as the JIS K 6253A hardness of the developing roller. For example, the developing roller (1) has a left end portion of 26 °, a central portion of 26 °, and a right end portion of 26 °, and a simple average of 26 ° is defined as the JIS K 6253A hardness of the developing roller (1). The result in the developing roller produced by each Example and the comparative example is shown to Tables 1-4.

(Number average molecular weight of polyol and isocyanate)
A high-performance liquid chromatograph analyzer “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) in which two GPC columns “TSKgel SuperHM-M” (trade name, manufactured by Tosoh Corporation) were connected in series was used. The measurement sample was measured as a 0.1% by mass THF solution under the measurement conditions of tetrahydrofuran (THF) as a solvent, temperature 40 ° C., flow rate 0.6 ml / min, RI (refractive index) detector. A calibration curve was created using several types of monodisperse standard polystyrene (manufactured by Tosoh Corporation) as a standard sample for creating a calibration curve, and the number average molecular weight (Mn) from the retention time of the measurement sample obtained based on this Asked.

[Image evaluation]
[Evaluation of image streaks and initial toner fixing images by long-term development blade contact]
The developing roller was incorporated in an electrophotographic process cartridge, and this electrophotographic process cartridge was left in an environment of a temperature of 40 ° C. and a humidity of 95% RH for 20 days. Thereafter, the developing roller was remounted on a newly prepared electrophotographic process cartridge, and further left in an environment of a temperature of 30 ° C. and a humidity of 85% RH for 24 hours. Then, in the same environment, the electrophotographic process cartridge was incorporated into a modified printer LBP5500 (trade name) manufactured by Canon, and five solid white images were output under a bias condition of −150 V with respect to the developing bias. Thereafter, one solid black image was output under the same bias condition. The solid white and solid black images were evaluated under the following evaluation conditions for the deformation of the developing roller due to contact with the developing blade being left and the image layer adverse effect due to initial toner fixation. The result in the developing roller produced by each Example and the comparative example is shown to Tables 1-4.
A: No image defects such as fogging due to initial toner fixation are observed in the solid white image. In addition, almost no image streaks that appear to be caused by deformation can be confirmed.
B: No image defects such as fogging due to initial toner fixation are observed at all in the solid white image. In addition, the image streaks that are considered to be caused by deformation can be slightly confirmed.
C: Image defects such as fogging due to initial toner fixation are not observed at all in the solid white image. In addition, it is possible to clearly confirm image streaks that are considered to be caused by deformation.
D: Image defects such as fogging due to initial toner fixation are confirmed in the solid white image, and it does not disappear within 5 sheets of the initial solid white image output. In addition, it is possible to clearly confirm image streaks that are considered to be caused by deformation.

[Fog in a high temperature and high humidity environment (temperature: 30 ° C., humidity: 85% RH)]
After evaluation of image streaks due to long-term development blade contact and initial toner fixed image, fog was evaluated in the same environment. A white solid image was output under a bias condition of −150 V with respect to the development bias with respect to the blade bias, the printer was stopped during the output, and the toner adhering to the photoconductor was peeled off with a transparent adhesive tape. And the reflectance of the adhesive surface of a transparent adhesive tape was measured, and fog was evaluated from the fall of the reflectance. In addition, the reflection densitometer (Brand name: TC-6DS / A, Tokyo Denshoku Co., Ltd.) was used for the measurement of a reflectance. Evaluation was performed according to the following criteria from the average value at that time. The result in the developing roller produced by each Example and the comparative example is shown to Tables 1-4. In the evaluation of image streaks and initial toner fixing image, the developing roller for which initial toner fixing was confirmed was subjected to image evaluation after wiping off the toner fixed on the developing roller surface with a soft cloth.
A: The decrease in reflectance is less than 1%.
B: Decrease in reflectance is 1% or more and less than 2%.
C: Decrease in reflectance is 2% or more and less than 4%.
D: Decrease in reflectance is 4% or more.

[Evaluation of endurance fog in a low-temperature, low-humidity environment (temperature: 15 ° C., humidity: 10% RH)]
After fog evaluation in a high temperature and high humidity environment, the developing roller was incorporated into a new electrophotographic process cartridge, and the electrophotographic process cartridge was left in an environment of a temperature of 15 ° C. and a humidity of 10% RH for 24 hours. In the same environment, the electrophotographic process cartridge is installed in a modified Canon printer LBP5500 (trade name) in this environment, and continuous image output is performed at a printing rate of 1% under a bias condition of -200V with respect to the development bias. Went. Durability fog was evaluated by measuring the number of output sheets in which fog exceeding 3% was observed in the solid white portion, and performing the following evaluation criteria. In addition, the reflectance of the non-printed portion (reference) and the solid white portion of the print range is measured for every 1000 sheets of output using a Macbeth reflection densitometer. " The result in the developing roller produced by each Example and the comparative example is shown to Tables 1-4.
A: The fog of 3% or more is not confirmed even when printing 25000 sheets by continuous printing.
B: Fog of 3% or more was confirmed on continuous printing 20000 sheets or more and less than 25000 sheets.
C: Fog of 3% or more was confirmed on continuous printing of 10000 or more and less than 20000.
D: Fog of 3% or more was confirmed on less than 10,000 continuous prints.

  From Tables 1 to 3, it is clear that the developing rollers produced in Examples 1 to 20 have a good balance between the mechanical properties and the toner charge imparting properties of the developing rollers and can realize high-quality image formation. In particular, in the developing rollers produced in Examples 5 and 6, it is clear that the fogging under high temperature and high humidity, the durability fogging under low temperature and low humidity, and the suppression of image defects caused by deformation can be achieved at a high level. In the developing rollers produced in Examples 1 to 20, the values of Ec, Etc and Urc of the surface layer are in the range defined by the present invention, and the JIS K 6253A hardness of the developing roller is 26 ° to 45 °. . Further, the developing rollers produced in Examples 5 and 6 have a particularly good balance of Ec, Etc and Urc of the surface layer.

  On the other hand, the developing roller produced in Comparative Example 1 has a low JIS K 6253A hardness of the developing roller, so that not only image streaks with increased deformation at the developing blade contact portion were clearly confirmed, but also the surface layer The tackiness increased and initial toner fixation was confirmed. Since the developing roller produced in Comparative Example 2 has a high JIS K 6253A hardness, it has been confirmed that the stress applied to the toner increases and the durability fogging performance in a low temperature and low humidity environment is significantly deteriorated.

  Further, since the developing roller produced in Comparative Example 3 has a Urc value that is too high, the stress applied to the toner increases, and it is confirmed that the durability fogging performance in a low-temperature and low-humidity environment is significantly deteriorated as in Comparative Example 2. It was. Since the developing roller produced in Comparative Example 4 has a Urc value that is too low, not only image streaks with increased deformation at the developing blade contact portion were clearly confirmed, but also the adhesiveness of the surface layer increased, Initial toner adhesion was confirmed.

  Moreover, since the value of Ec was too high for the developing roller produced in Comparative Example 5, it was confirmed that fogging in a high temperature and high humidity environment was significantly deteriorated. Further, since at least one kind of raw material having a unit selected from the general formulas (1), (2) and (3) as a main skeleton is not contained, the mechanical properties are not optimized, and the developing blade contact portion is not A tendency for image streaks to deteriorate was confirmed. Since the developing roller produced in Comparative Example 6 has an Ec value that is too low, not only image streaks with increased deformation at the developing blade contact portion were clearly confirmed, but fogging in a high temperature and high humidity environment was significantly worsened. Confirmed to do.

  Further, since the developing roller produced in Comparative Example 7 has an Etc value that is too high, an image streak accompanying an increase in the amount of deformation at the developing blade contact portion is clearly confirmed by decreasing the relative Ec value. In addition, the adhesiveness of the surface layer increased and initial toner adhesion was confirmed. Since the developing roller produced in Comparative Example 8 has an Etc value that is too low, it was confirmed that the toner chargeability was lowered and fogging in a high temperature and high humidity environment was remarkably deteriorated.

  From the above, it is clear that by satisfying the conditions defined in the present invention, the fog at high temperature and high humidity, the durability fog at low temperature and low humidity, and the suppression of image defects caused by deformation can be achieved at the same time.

It is sectional drawing of an example of the developing roller of this invention. It is a schematic block diagram which shows an example of the electrophotographic apparatus of this invention. It is a schematic diagram of the liquid circulation type dip coating apparatus used for surface layer formation.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Developing roller 2 Shaft core body 3 Resin layer 4 Surface layer 5 Process cartridge 6 Photoconductor 7 Toner supply roller 8 Toner 9 Developing blade 10 Developing device 11 Laser beam 12 Charging member 13 Waste toner collection container 14 Cleaning blade 15 Fixing device 16 Driving roller 17 Transfer roller 18 Bias power supply 19 Tension roller 20 Transfer conveyance belt 21 Drive roller 22 Paper 23 Paper feed roller 24 Adsorption roller 25 Immersion tank 25a Immersion tank upper end 26 Roller 27 Liquid receiving part 28 Stirring tank 29 Tube 30 Surface layer Forming paint 31 Pump 32, 33 Pipe 34 Agitating blade 35 Lifting device 36 Lifting plate

Claims (9)

In the developing roller having a resin layer around the shaft core and a surface layer on the outer periphery of the resin layer,
The surface layer is formed using a thermosetting ether ester polyurethane resin having a unit of any of the following formulas (1) to (3),
The ester concentration (Ec), ether concentration (Etc) and urethane concentration (Urc) of the thermosetting ether ester polyurethane resin were measured by ESCA (X-ray photoelectron spectroscopy), the nitrogen element ratio, the C—C bond ratio, When defined by the following formulas (4) to (6) using the COO bond ratio and the CO bond ratio, 8.0 ≦ Ec ≦ 11.2, 18.4 ≦ Etc ≦ 37.8 and 0.8 ≦ In the range of Urc ≦ 2.7,
A developing roller, wherein the developing roller has a JIS K 6253A hardness of 26 ° to 45 °.

  When the full width at half maximum of the maximum peak obtained by measuring the thermosetting ether ester polyurethane resin by micro sampling mass spectrometry (μ-MS) is L, 0.7 (min) ≦ L ≦ 2.5 ( The developing roller according to claim 1, wherein the developing roller is in a range of minutes).   A polyol which is a raw material of the thermosetting ether ester polyurethane resin is obtained using at least one polyhydric alcohol selected from 3-methyl-1,5-pentanediol, polycaprolactone diol and 1,3-butanediol. The developing roller according to claim 1, wherein the developing roller is a polyester polyol, and the number average molecular weight (Mn) of the polyester polyol is in a range of 1000 ≦ Mn ≦ 6000.   The isocyanate which is a raw material of the thermosetting ether ester polyurethane resin has an ether group in the modified portion and is at least selected from diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and polymethylene polyphenylene polyisocyanate (polymeric MDI). The developing roller according to claim 1, wherein the developing roller is a prepolymer type isocyanate produced from one.   5. The developing roller according to claim 1, wherein the number average molecular weight (Mn) of an isocyanate which is a raw material of the thermosetting ether ester polyurethane resin is in a range of 2000 ≦ Mn ≦ 5500.   The developing roller according to claim 1, wherein the surface layer contains 15 parts by mass or more and 30 parts by mass or less of carbon black with respect to 100 parts by mass of the resin component of the surface layer. It is a manufacturing method of the developing roller according to claim 1,
Forming a coating film of the surface layer-forming paint on the outer periphery of the resin layer around the shaft core body, and curing the coating film to form a surface layer;
The surface layer forming paint is:
An ester polyol of 1000 ≦ Mn ≦ 6000 obtained using at least one polyhydric alcohol selected from 3-methyl-1,5-pentanediol, polycaprolactone diol and 1,3-butanediol;
2000 ≦ Mn ≦ 5500 prepolymer type having an ether group in the modified part and produced from at least one selected from diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and polymethylene polyphenylene polyisocyanate (polymeric MDI) A process for producing a developing roller, comprising isocyanate.   7. A process cartridge having a developing roller attached thereto and detachable from an electrophotographic apparatus, comprising the developing roller according to any one of claims 1 to 6.   An electrophotographic apparatus in which a thin layer of toner is formed on a surface of a developing roller, the developer roller is brought into contact with a photosensitive drum, and the toner is supplied to the surface of the photosensitive member to form a visible image on the photosensitive member. An electrophotographic apparatus comprising the developing roller according to any one of 1 to 6.

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