JP2008299246A - Developing roller, electrophotographic process cartridge, and electrophotographic image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing roller obtaining high image density from the beginning of use even in operating environment of high temperature and high humidity. <P>SOLUTION: The developing roller has a conductive shaft and an elastic layer formed on the outer peripheral surface of the conductive shaft. The elastic layer is composed of a resin composition containing urethan resin having an aromatic ring, and an aralkyl modified silicone compound expressed by a formula (1): (CH<SB>3</SB>)<SB>3</SB>SiO-(A)<SB>p</SB>-(B)<SB>q</SB>-(C)<SB>r</SB>-Si(CH<SB>3</SB>)<SB>3</SB>. In the formula (1), A, B and C respectively represent repeating units, and the arranged order of the repeating units A, B and C is optional. For example, C indicates the repeating unit expressed in a formula (4) wherein R3 to R7 are all hydrogen atoms and R2 is a propylene group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a developing roller, an electrophotographic process cartridge using the developing roller, and an electrophotographic image forming apparatus.

  As an image forming method for an electrophotographic apparatus such as a copying machine or an optical printer, a contact developing method using a non-magnetic one-component developer is known. The contact development method will be described in detail. First, a photosensitive member such as a rotatable photosensitive drum is uniformly charged by a charging means including a charging roller, and laser light or the like is applied to the uniformly charged surface of the photosensitive member. Is exposed to form an electrostatic latent image. Next, a developing roller having a developer thin film formed on the surface is opposed to the photosensitive member carrying the electrostatic latent image, and the photosensitive member and the developing roller are rotated with respect to each other. At this time, when a developing bias is applied to the developing roller, the developer moves from the developing roller to the electrostatic latent image on the photoreceptor, and the electrostatic latent image is visualized. Thereafter, the developer image on the photosensitive member is transferred to the recording material in the transfer portion, and fixed on the recording material by heating, pressurizing, or the like in the fixing portion, so that the image formation on the recording material is completed and the image formation is completed. It is discharged out of the device.

  In such an image forming method, examples of the developing device that supplies the developer to the electrostatic latent image carried by the photosensitive member include those having the following configuration.

  A developing roller is provided so as to close the opening of the developer container for storing the developer and to expose a part thereof to the outside of the container and to face the photosensitive member at the exposed part. In the developer container, there are provided a developer coating roller for supplying the developer to the developing roller, and a developing blade for forming the developer on the developing roller into a thin film and making the developer amount on the developing roller constant. The developing blade is installed in contact with the developing roller in the vicinity of the tip, for example, at a position not less than 0.1 mm and not more than 5.0 mm from the tip, and the developer supplied onto the developing roller by the developer coating roller. And formed into a thin film with a uniform thickness.

  In such a contact developing method using a non-magnetic one-component developer, the surface of the developing roller rubs against the developing blade, and therefore a material having high toughness is required as the material constituting the surface of the developing roller. . This is because if the material constituting the surface of the developing roller is poor in toughness, the surface of the developing roller is scraped and image defects occur when the developing roller is used for a long period of time. Further, the material constituting the surface of the developing roller is required to have flexibility. This is because, if the material constituting the surface of the developing roller is hard, when the developing roller is used for a long period of time, the developer is fused on the surface of the developing roller, resulting in image defects, so-called durable fusion. This is because the tendency to occur is high. That is, the contact pressure received by the developer is reduced at the contact portion between the developing roller and the developer application roller, the contact portion between the developing roller and the developing blade, and the contact portion between the developing roller and the photosensitive member. Otherwise, deterioration of the developer is promoted. This is because as the developer deteriorates, the developer tends to be fused on the surface of the developing roller.

  For these reasons, polyurethane resin, which is a resin having high toughness and flexible characteristics, is frequently used on the surface of the developing roller.

  However, a developing roller using a polyurethane resin has a problem that it is difficult to obtain a sufficient image density at the initial stage of durability when used in a high temperature and high humidity environment. This is presumably because the polyurethane resin has a slight hygroscopic property, so that the ability to impart charge to the developer tends to decrease in a high temperature and high humidity environment.

  Therefore, when used in a high temperature and high humidity environment, in order to obtain a sufficient image density from the beginning of the durability, it is considered that the moisture absorption of the polyurethane resin in the high temperature and high humidity environment should be reduced. As a specific method for reducing the moisture absorption of the polyurethane resin in a high temperature and high humidity environment, it is conceivable to add a hydrophobic silicone oil (silicone compound) to the polyurethane resin.

  In fact, various inventions of developing rollers in which silicone oil is added to resin or rubber have been disclosed. For example, a polysiloxane component can be added to a polyurethane resin to provide releasability without impairing the electrical properties of the polyurethane resin, to reduce the adhesion between the developing roller and the photoreceptor, and to reduce developer fusing. A developed developing roller is disclosed (see Patent Document 1). Further, a developing roller is disclosed in which silicone oil is added to fluororubber to impart releasability, improve the releasability of the developer, and reduce fusion of the developer (see Patent Document 2). .) In addition, a developing roller is disclosed in which silicone oil is added to a silicone graft acrylic polymer to reduce the coefficient of friction of the developing roller to reduce the fusion of the developer (see Patent Document 3).

  However, the above inventions are not aimed at reducing the moisture absorption of the developing roller, but are aimed at reducing the fusion of the developer to the developing roller by utilizing the releasability of the silicone oil. The above-mentioned patent document does not disclose a developing roller capable of obtaining a high image density from the initial use even in a high temperature and high humidity environment.

JP 2003-167398 A JP 09-230689 A JP 11-167273 A

  An object of the present invention is to provide a developing roller capable of obtaining a high image density from the initial use even in an environment of high temperature and high humidity, an electrophotographic process cartridge including the developing roller, and an image forming apparatus for electrophotography. is there.

Ｂは、下記化学式（３）で表される繰り返し単位を示し、

（式中、Ｒ１は、炭素数が２以上１８以下のアルキル基を示す。）
Ｃは、下記化学式（４）で表される繰り返し単位を示し、

（式中、Ｒ２は、炭素数が２または３のアルキレン基を示し、Ｒ３乃至Ｒ７は、各々独立に、炭素数が１以上４以下のアルキル基または水素原子を示す。）
ｐ及びｒは、各々独立に１以上の整数を示し、ｑは、０または1以上の整数を示す。） Since the silicone oil has heat resistance, weather resistance, and water repellency, the silicone oil is added to the elastic layer of the developing roller and used in a high temperature and high humidity environment. The study was carried out on the assumption that sufficient image density could be obtained from the above. In this research, a developing roller was produced by combining a non-reactive silicone compound and polyurethane resins having various molecular structures, and the obtained developing roller was evaluated. As a result, when an aralkyl-modified silicone compound modified with a methylstyryl group and a polyurethane resin having an aromatic ring are combined, the initial image density in a high-temperature and high-humidity environment is higher than that of a conventional developing roller. As a result, the present invention has been completed.
That is, the present invention that has solved the above problems is a developing roller having a conductive shaft and an elastic layer formed on the outer peripheral surface of the conductive shaft, wherein the elastic layer is a polyurethane having an aromatic ring. A developing roller comprising a resin and a resin composition containing an aralkyl-modified silicone compound represented by the following chemical formula (1):
(CH ₃ ) ₃ SiO · (A) _p · (B) _q · (C) _r · Si (CH ₃ ) ₃ (1)
(In the formula, A, B and C each represent a repeating unit, and the arrangement order of the repeating units A, B and C is arbitrary, A represents a repeating unit represented by the following chemical formula (2),

B represents a repeating unit represented by the following chemical formula (3),

(In the formula, R1 represents an alkyl group having 2 to 18 carbon atoms.)
C represents a repeating unit represented by the following chemical formula (4),

(Wherein R2 represents an alkylene group having 2 or 3 carbon atoms, and R3 to R7 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)
p and r each independently represents an integer of 1 or more, and q represents 0 or an integer of 1 or more. )

  When the developing roller of the present invention is used, a high image density can be obtained from the beginning of use even when used in a high temperature and high humidity environment.

  The reason why the image density at the initial stage of use is higher than that of the conventional developing roller in the specific combination under a high temperature and high humidity environment is considered as follows.

  That is, since the silicone compound (1) modified with a methylstyryl group has an aromatic ring derived from the methylstyryl group, it is considered that the compatibility with the polyurethane resin having an aromatic ring becomes very high. For this reason, the entire surface of the elastic layer of the developing roller is covered with a silicone compound, preventing the developing roller from absorbing moisture in a high temperature and high humidity environment, and preventing a decrease in the ability to impart charge to the developer. It is considered that a high image density can be obtained from the beginning.

Hereinafter, the present invention will be described in more detail.
[Development roller]
FIG. 1 shows a cross-sectional structure of an example of an embodiment of a developing roller according to the present invention. A developing roller 100 shown in FIG. 1 has a conductive shaft 1 and an elastic layer 2 formed on the outer peripheral surface of the conductive shaft 1. The elastic layer 2 is composed of a polyurethane resin having an aromatic ring and a resin composition containing an aralkyl-modified silicone compound represented by the following chemical formula (1).
(CH ₃ ) ₃ SiO · (A) _p · (B) _q · (C) _r · Si (CH ₃ ) ₃ (1)
In the above formula, A, B and C each represent a repeating unit, and the arrangement order of the repeating units A, B and C is arbitrary.

  A represents a repeating unit represented by the following chemical formula (2).

  B represents a repeating unit represented by the following chemical formula (3).

In the above formula, R1 represents an alkyl group having 2 to 18 carbon atoms.
When R1 is a long-chain alkyl group, it is preferable in that it has an action of increasing the hydrophobicity of the silicone compound, but it is not preferable in terms of low compatibility with the polyurethane resin. For this reason, when the carbon number of R1 is 19 or more, the compatibility between the aralkyl-modified silicone compound represented by the chemical formula (1) and the polyurethane resin is lowered, and the image density at the initial stage of use in a high temperature and high humidity environment is increased. It is difficult to obtain the effect.

  When R1 has 1 carbon, R1 represents a methyl group. That is, in this case, the repeating unit A and the repeating unit B are the same. In the aralkyl-modified silicone compound represented by the chemical formula (1), the presence of the repeating unit B is not essential, and q = 0 may be sufficient. That is, the compound which consists of the repeating unit A and the repeating unit C may be sufficient.

  C represents a repeating unit represented by the following chemical formula (4).

  In the above formula, R2 represents an alkylene group having 2 or 3 carbon atoms, and R3 to R7 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

  The repeating unit C has an alkylene group R2 having 2 or 3 carbon atoms, and R3 to R7 are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. As is well known, the aralkyl-modified silicone compound (1) has a helical structure in which the silicon-oxygen bond faces the inside of the helix and the functional group bonded to the silicon atom faces the outside of the helix. It has become. Accordingly, the alkylene group R2 and the aromatic ring connected to the alkylene group R2 have a three-dimensional structure arranged on the outer periphery of the helix. At this time, if the alkylene group R2 has 1 carbon atom, the aromatic ring is present in the very vicinity of the helical structure. In order to make such an aralkyl-modified silicone compound compatible with the polyurethane resin, it is necessary that the molecules of the polyurethane resin approach very close to the helical structure of the aralkyl-modified silicone compound. However, many methyl groups having low compatibility with the polyurethane resin are present on the outer periphery of the helix of the aralkyl-modified silicone compound. For this reason, when the number of carbon atoms of the alkylene group R2 is 1, the polyurethane resin cannot approach the aralkyl-modified silicone compound, the compatibility between the two decreases, and the initial image density in a high temperature and high humidity environment It is difficult to obtain the effect of increasing the value.

  When the number of carbon atoms of the alkylene group R2 is 5 or more, the direct effect has not been confirmed, but the distance between the helical structure of the siloxane bond and the aromatic ring becomes longer, so that the polyurethane resin also approaches the aralkyl-modified silicone compound. Is expected to be difficult. As a result, the density of the resin composition containing the polyurethane resin and the aralkyl-modified silicone compound is reduced, and water vapor in the use environment is liable to enter, and the effect of increasing the initial image density in a high temperature and high humidity environment. Is expected to be difficult to obtain.

  That is, when the aralkyl-modified silicone compound (1) and the polyurethane resin are close to each other at an appropriate distance, the compatibility between them is most improved. And even when used at high temperature and high humidity, it is considered that the effect that a high image density can be obtained from the beginning of use can be exhibited specifically. Therefore, the alkylene group R2 is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably a propylene group.

  R3 to R7 are preferably all hydrogen atoms, but some or all of R3 to R7 may be alkyl having 1 to 4 carbon atoms. When the number of carbon atoms in R3 is 5 or more, the direct effect is not confirmed, but a bulky alkyl group is present in the aromatic ring, so that compatibility with the polyurethane resin is reduced, and high temperature and It seems that it is difficult to obtain the effect of increasing the image density at the initial stage of use in a high humidity environment.

  In chemical formula (1), p and r each independently represent an integer of 1 or more, and q represents 0 or an integer of 1 or more.

  As described above, in the chemical formula (1), the arrangement order of the repeating units A, B, and C is arbitrary, p and r each independently represent an integer of 1 or more, and q represents 0 or an integer of 1 or more. . As described above, when q is 0, the repeating units contained in the aralkyl-modified silicone compound represented by the chemical formula (1) are two types, A and C. In the aralkyl-modified silicone compound represented by the chemical formula (1), the repeating unit B is not necessarily an essential component for obtaining the effects of the present invention. However, it is preferable that the repeating unit B is present in the aralkyl-modified silicone compound represented by the chemical formula (1) because the hydrophobicity of the silicone compound can be increased and moisture absorption of the developing roller in a high temperature and high humidity environment can be prevented.

  In addition, in a polymer containing a plurality of repeating units such as the aralkyl-modified silicone compound represented by the chemical formula (1), it is difficult to accurately identify p, q, and r of each repeating unit. Therefore, in the present invention, the degree of polymerization of the chemical formula (1) is shown with the weight average molecular weight Mw measured by the method described later.

  As is clear from the chemical formulas (1) to (4), the aralkyl-modified silicone compound represented by the chemical formula (1) is nonreactive with respect to isocyanate groups. That is, the aralkyl-modified silicone compound represented by the chemical formula (1) does not have an active hydrogen that reacts with an isocyanate group (hydrogen of a hydroxyl group or hydrogen of an amino group) or a reactive double bond such as a vinyl group. It does not have an epoxy group or a carboxyl group. Therefore, there is no possibility that the toughness of the obtained polyurethane resin is lowered and the characteristics of the polyurethane resin cannot be exhibited.

  A preferred molecular weight of the aralkyl-modified silicone compound represented by the chemical formula (1) is a weight average molecular weight of 2,000 or more and 20,000 or less. When the weight average molecular weight is 2,000 or more, the aralkyl-modified silicone compound is difficult to be raised on the surface of the developing roller. For this reason, the developing roller is not sticky, and the development of the developer from the developing roller to the photosensitive member is not performed well, and a high image density can be obtained from the beginning of use. When the weight average molecular weight of the aralkyl-modified silicone compound is 20,000 or less, an effect of increasing the image density at the initial stage of use in a high temperature and high humidity environment is easily obtained. This is not because, when the molecular chain of the aralkyl-modified silicone compound has an appropriate length, the molecular chain of the compound is easily entangled and the entire surface of the developing roller is easily covered with the silicone compound. It is guessed. A method for measuring the molecular weight of the aralkyl-modified silicone compound will be described later.

  A preferable content of the aralkyl-modified silicone compound represented by the chemical formula (1) contained in the elastic layer 2 is 0.1% by mass or more and 10% by mass or less with respect to the mass of the elastic layer. More preferably, it is 0.2 mass% or more and 5 mass% or less. When the addition amount of the aralkyl-modified silicone compound represented by the chemical formula (1) is 0.1% by mass or more, the effect of preventing moisture absorption of the developing roller in a high temperature and high humidity environment can be easily obtained. Compared to the above, the image density at the initial use can be increased. Further, when the addition amount of the aralkyl-modified silicone compound represented by the chemical formula (1) is 10% by mass or less, there is no risk that the surface of the developing roller becomes sticky, and the development of the developer from the developing roller to the photoreceptor is excellent. It is possible to obtain a high image density from the beginning of use.

  The content of the aralkyl-modified silicone compound can be easily known by pulverizing the elastic layer 2 in a frozen state, immersing it in an appropriate organic solvent, extracting the aralkyl-modified silicone compound, and measuring the mass. .

The polyurethane resin combined with the aralkyl-modified silicone compound represented by the chemical formula (1) is a polyurethane resin having an aromatic ring. In order to obtain such a polyurethane resin, a polyol and an isocyanate are required as raw materials for the polyurethane resin. It is also possible to add a chain extender to this. The following are mentioned as a polyol which is a raw material of a polyurethane resin.
Polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and mixtures thereof.

  The polyol may be prepolymerized by reacting with an isocyanate having an aromatic ring described below. Except for polyols prepolymerized with isocyanates having aromatic rings, generally used polyols do not have aromatic rings. Therefore, in order to introduce aromatic rings into the polyurethane resin of the present invention, aromatic rings are added to isocyanates. Need to be used.

  The isocyanate that can be used in the present invention is an isocyanate having an aromatic ring. Specific examples include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and naphthalene-1,5-diisocyanate (NDI). And mixtures thereof.

Examples of the chain extender that is a raw material of the polyurethane resin include the following.
Bifunctional low molecular diols such as ethylene glycol, 1,4-butanediol, 3-methylpentanediol; trifunctional low molecular triols such as trimethylolpropane, and mixtures thereof.

  In particular, among polyurethane resins, a polyether polyurethane resin using a polyether polyol has a smaller moisture absorption than a polyester polyurethane resin using a polyester polyol. Therefore, it is preferable for increasing the image density at the initial stage of use in a high temperature and high humidity environment.

In addition, although the elastic layer 2 uses the above-mentioned polyurethane resin as a main material, it may contain other resin components. Examples of other resin components include the following.
-Polyamide resin.
・ Urea resin.
・ Imide resin.
・ Melamine resin.
・ Fluorine resin.
・ Phenolic resin.
・ Polyester resin.
-Polyether resin.
·acrylic resin.
・ Natural rubber.
・ Butyl rubber.
-Acrylonitrile-butadiene rubber.
-Polyisoprene rubber.
-Polybutadiene rubber.
·silicone rubber.
-Styrene-butadiene rubber.
-Ethylene-propylene rubber.
-Ethylene-propylene-diene rubber.
・ Chloroprene rubber.
-At least two mixtures selected from the above.

  The molecular structure of the polyurethane resin used in the developing roller of the present invention and the aralkyl-modified silicone compound represented by the chemical formula (1) can be identified as follows. That is, the aralkyl-modified silicone compound and the polyurethane resin are isolated from the elastic layer 2 of the developing roller by appropriate means. Then, it identifies using analytical methods, such as pyrolysis GC / MS (gas chromatograph mass spectrometry), NMR (nuclear magnetic resonance spectroscopy), and IR (infrared absorption spectrum analysis).

The elastic layer 2 is blended with a conductivity-imparting agent such as an electron conductive material or an ionic conductive material, and has a volume resistivity of 1 × 10 ⁴ Ωcm to 1 × 10 ¹³ Ωcm, more preferably 1 ×. It may be adjusted to 10 ⁵ Ωcm or more and 1 × 10 ¹² Ωcm or less.

In addition, the value calculated | required with the following method is employable as the volume resistivity of the elastic layer 2. FIG.
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 measure 30 seconds, discharge 10 seconds)
-Applied voltage: 100 (V)
Sample box: Sample box TR42 (trade name, manufactured by Advantest) for measurement of ultrahigh resistance meter, main electrode is a metal with a diameter of 10 mm and a thickness of 10 mm, guard ring electrode is a metal with an inner diameter of 20 mm, an outer diameter of 26 mm and a thickness of 10 mm .
Test piece: First, a flat test piece is produced by curing the material of the elastic layer 2 to the same thickness as the elastic layer 2 under the same conditions as those for forming the elastic layer 2. 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))

Examples of the electronic conductive material used for imparting conductivity to the elastic layer 2 include the following.
Conductive carbon such as ketjen black EC, acetylene black; carbon for rubber such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, MT; carbon for color (ink) subjected to oxidation treatment; copper, silver, Metals such as germanium and metal oxides. Among these, carbon black [conductive carbon, carbon for rubber, carbon for color (ink)] is preferable because the conductivity can be easily controlled with a small amount.

Examples of the ion conductive material used for imparting conductivity to the elastic layer 2 include the following.
Inorganic ionic conductive materials such as sodium perchlorate, lithium perchlorate, calcium perchlorate and lithium chloride; organic ionic conductive materials such as modified aliphatic dimethylammonium ethosulphate and stearylammonium acetate.

  These conductivity-imparting agents are used in an amount necessary to adjust the elastic layer 2 to the above-described volume resistivity. Usually, the amount of the conductivity-imparting agent in the elastic layer 2 is 3% by mass or more and 30% by mass. Used in the following ranges. The volume resistivity can be measured by the method described above.

  In the developing roller 100, when the elastic layer 2 is a foam, a foamed shape is likely to appear in an image, and the strength of the elastic layer 2 is likely to be reduced. Therefore, a non-foamed (solid) layer is preferable. The layer thickness of the elastic layer 2 can usually be in the range of 0.5 mm to 5.0 mm. More preferably, it can be in the range of 1.0 mm to 4.0 mm.

  The developing roller 100 shown in FIG. 1 is a molding die in which a mixture of a raw material of the polyurethane resin, an aralkyl-modified silicone compound represented by the chemical formula (1), and a conductivity imparting agent is arranged in advance. After injection into the cavity, it can be made by heat-curing.

  FIG. 2 is a schematic sectional view showing an example of another embodiment of the developing roller according to the present invention. A developing roller 200 shown in FIG. 2 includes a conductive shaft 1, a resin layer 201 formed on the outer peripheral surface of the conductive shaft 1, and an elastic layer formed on the outer peripheral surface of the resin layer 201. 202. The elastic layer 202 of the developing roller 200 of the embodiment shown in FIG. 2 is the same as the elastic layer of the developing roller 100. Therefore, the description about the elastic layer 2 of the developing roller 100 is used for details regarding the material and volume resistivity of the elastic layer 202.

The resin layer 201 is made of a resin or rubber rich in elasticity in order to ensure a nip width with the photosensitive drum 21 (see FIG. 4) and to continue to output a uniform image and a stable image for a long time. Is preferred. Specifically, the following are suitable.
Natural rubber, butyl rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, polybutadiene rubber, silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, and mixtures thereof.
Among these, silicone rubber and ethylene-propylene-diene rubber are particularly preferable.

Similarly to the elastic layer 2 and the elastic layer 201, the resin layer 201 is blended with a conductivity-imparting agent such as an electronic conductive material or an ionic conductive material, and has a volume resistivity of 1 × 10 ⁴ Ωcm or more and 1 × 10 ^It may be ¹³ Ωcm or less. A more preferable range of the volume resistivity is 1 × 10 ⁵ Ωcm or more and 1 × 10 ¹² Ωcm or less. In addition, the value calculated | required by the measuring method similar to the elastic layer 2 can be employ | adopted for the volume resistivity of the resin layer 201. FIG.

The hardness of the resin layer 201 is preferably 25 to 70 degrees in terms of ASKER-C hardness.
The layer thickness of the resin layer 201 is preferably in the range of 0.5 mm to 5 mm, particularly 1.0 mm to 4.0 mm. The layer thickness of the elastic layer 202 is preferably 3 μm or more and 30 μm or less so as not to impair the flexibility of the resin layer 201.

  The layer thicknesses of the resin layer 201 and the elastic layer 202 are obtained by calculating the arithmetic average value when the cross section of the developing roller is enlarged and observed with a video microscope and measured five times while changing the observation field. The magnification is appropriately selected from 5 to 2000 times depending on the layer thickness of the measurement object.

  The developing roller 200 can be obtained by first forming the resin layer 201 on the outer peripheral surface of the shaft body 1 and then forming the elastic layer 202 on the outer peripheral surface of the resin layer 201.

The resin layer 201 can be formed by the following method 1) or 2).
1) A method including a step of injecting a raw material composition for forming the resin layer 201 into a cavity of a molding die in which the shaft body 1 is arranged in advance and heat-curing it;
2) A method including a step of forming a compound using a raw material composition for forming the resin layer 201, and a step of pressing the shaft body 1 into the tube after the compound is extruded into a tube shape.

  In either case of the above methods 1) and 2), after forming the resin layer 201 around the shaft body 1, it is adjusted to a predetermined outer diameter by cutting or polishing as necessary. Also good.

  Next, the elastic layer 202 is formed by spray coating or dip coating on the outer peripheral surface of the resin layer 201 with a paint prepared from the same raw material as the paint for forming the elastic layer 2, and then heat curing. Can be produced.

  The coating material for forming the elastic layer 202 is mixed by using a dispersing device such as a ball mill by mixing the raw materials and, if necessary, rough particles for adjusting the surface roughness of the developing roller. Can be prepared.

As said roughening particle | grains, what consists of the following materials can be used conveniently. These particles can be used alone or in combination.
-Rubber particles such as EPDM, NBR, SBR, CR, silicone rubber.
-Elastomer particles such as polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide based thermoplastic elastomer (TPE).
-Resin particles such as PMMA, polyurethane resin, fluorine resin, silicone resin, phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, polyacrylonitrile resin.

  The surface roughness of the developing roller is preferably adjusted so that the ten-point average roughness Rzjis according to JIS B0601: 2001 is 2 μm or more and 25 μm or less.

  The surface roughness of the developing roller can be expressed as an arithmetic average value of the measured values obtained by measuring the ten-point average roughness Rzjis at any nine positions per developing roller.

<Measurement method of molecular weight>
In the present invention, the weight average molecular weight of the aralkyl-modified silicone compound represented by the chemical formula (1) can be measured by gel permeation chromatography (GPC).

The GPC measurement conditions are described below.
The column is stabilized in a heat chamber at a temperature of 40 ° C., and tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute. About 50 to 200 μl of a THF sample solution of an aralkyl-modified silicone compound adjusted to a sample concentration of 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the aralkyl-modified silicone compound, the molecular weight is calculated from the relationship between the logarithmic value of a calibration curve prepared in advance using a monodisperse polystyrene standard sample and the number of counts (retention time). As a standard polystyrene sample for preparing a calibration curve, for example, the following is used.
Tosoh Corporation or Pressure Chemical Co. The molecular weights manufactured are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8 .6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ .
It is also appropriate to use at least 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns.
A combination of shodex GPC KF-801, 802, 803, 804, 805, 806, and 807 (all trade names) manufactured by Showa Denko KK can be used. Also, a combination of μ-styragels 500, 103, 104, and 105 (all trade names) manufactured by Waters may be used.

[Shaft]
The shaft 1 is made of a solid metal rod having a diameter of 4 mm or more and 10 mm or less formed of a material such as carbon steel, stainless steel, nickel chrome steel, nickel chrome molybdenum steel, chrome steel, or chromium molybdenum steel. Alternatively, a conductive resin obtained by kneading a conductive agent such as carbon black into a resin may be used. When a metal rod is used for the shaft body 1, the shaft body 1 can be plated or oxidized as a rust prevention measure. As the type of plating, either electroplating or electroless plating can be used. Electroless plating with excellent plating thickness uniformity is preferred. Examples of the electroless plating used here include nickel plating, copper plating, gold plating, Kanigen plating, and other various alloy plating. Ni-P, Ni-B, Ni-WP, and Ni-P-PTFE composite plating can be used as the type of nickel plating. Usually, the plating thickness is preferably 0.05 μm or more. A more preferable plating thickness considering the rust prevention effect, work efficiency, and price is usually 0.1 μm or more and 30 μm or less.

[Electrophotographic image forming apparatus]
The electrophotographic image forming apparatus of the present invention includes the following components.
An image carrier for carrying an electrostatic latent image.
A charging device for primarily charging the image carrier.
An exposure apparatus for forming an electrostatic latent image on a primary charged image carrier.
A developing device for developing the electrostatic latent image with a developer to form a developer image.
A transfer device for transferring the developer image to a transfer material.
The developing device has an electrophotographic process cartridge of the present invention as described below.

FIG. 3 is a cross-sectional view showing a schematic configuration of an example of an embodiment of the electrophotographic image forming apparatus of the present invention. FIG. 4 is an enlarged cross-sectional view of an example of an electrophotographic process cartridge mounted on the electrophotographic image forming apparatus shown in FIG.
The electrophotographic process cartridge shown in FIG. 4 includes a developing roller 24 and a developing blade 26. The developing roller 24 carries the developer in a state of facing the photosensitive drum 21 as an image carrier that carries an electrostatic latent image. The developing blade 26 regulates the layer thickness of the developer while frictionally charging the developer carried on the developing roller. Then, a developer thin film is formed on the surface of the developing roller 24, and the developing roller 24 is brought into contact with the photosensitive drum 21 as an image carrier to apply the developer to the surface of the image carrier, thereby electrostatic latent. Visualize the image as a developer image. As the developing roller 24, the developing roller of the present invention is provided.

  The photosensitive drum 21 as an image carrier for carrying the electrostatic latent image is uniformly provided by a charging member 22 connected to a bias power source (not shown) as a charging device for primarily charging the image carrier. Charged. The charging potential at this time is usually about -400V to -800V.

  Further, an electrostatic latent image is formed on the surface of the photosensitive drum 21 that is primarily charged by an exposure device for forming an electrostatic latent image. As the exposure means, either LED light or laser light 23 can be used. The surface potential of the exposed portion of the photosensitive drum 21 is usually about −100V to −200V.

  Next, the electrostatic latent image on the photosensitive drum 21 is developed by the electrophotographic process cartridge shown in FIG. 3 that can be attached to and detached from the image forming apparatus main body. At this time, the negatively charged developer is applied (developed) to the electrostatic latent image by the developing roller 24 incorporated in the electrophotographic process cartridge, and a developer image is formed. The electrostatic latent image is converted into the developer image. Is converted to At this time, a voltage of about −300 V to −500 V is normally applied to the developing roller 24 by a bias power source (not shown).

  Next, the developer image formed on the photosensitive drum 21 is primarily transferred to an intermediate transfer belt 27 as a transfer device for transferring the developer image to a transfer material. A primary transfer member 28 is in contact with the back surface of the intermediate belt 27, and a negative developer image is transferred from the photosensitive drum 21 to the intermediate transfer belt by applying a voltage of about +100 V to +1500 V to the primary transfer member 28. First transfer to 27. The primary transfer member 28 may have a roller shape or a blade shape.

  When the electrophotographic image forming apparatus is a full-color electrophotographic image forming apparatus as shown in FIG. 3, the above-described charging, exposure, development, and primary transfer processes are performed in yellow, cyan, magenta, This must be done for each black color. For this purpose, in the image forming apparatus shown in FIG. 3, one electrophotographic process cartridge containing the developer of each color is installed in a detachable manner with respect to the main body of the electrophotographic image forming apparatus. ing.

  The developing roller 24 faces the photosensitive drum 21 as an image carrier that carries an electrostatic latent image, and is normally in contact with the photosensitive drum 21 with a nip width of 0.5 mm or more and 3 mm or less. The developer supply roller 25 rotates in the rotation direction of the developing roller 25 with respect to a contact portion of the developing blade 26 that regulates the developer layer thickness while frictionally charging the developer in the developer container 34. It abuts on the upstream side and is rotatably supported.

  The charging, exposure, development, and primary transfer processes are sequentially executed with a predetermined time difference, and a state in which four color developer images for expressing a full-color image are superimposed on the intermediate transfer belt 27 is created. .

  The developer image on the intermediate transfer belt 27 is conveyed to a position facing the secondary transfer member 29 as the intermediate transfer belt rotates. At this time, the recording paper 32 is conveyed between the intermediate transfer belt 27 and the secondary transfer member 29 at a predetermined timing, and by applying a secondary transfer bias to the secondary transfer member 29, The developer image on the transfer belt 27 is transferred to the recording paper 32. At this time, the bias voltage applied to the secondary transfer member 29 is usually about + 1000V to + 4000V.

  The recording paper 32 onto which the developer image has been transferred by the secondary transfer member 29 is conveyed to the fixing device 31, and the developer image on the recording paper 32 is melted and fixed on the recording paper 32. Is discharged out of the electrophotographic image forming apparatus, thereby completing the printing operation.

  The developer remaining on the photosensitive drum 21 without being transferred from the photosensitive drum 21 to the intermediate transfer belt 27 is scraped off by a cleaning member 30 for cleaning the surface of the photosensitive drum 21, so that the surface of the photosensitive drum 21 is removed. Is cleaned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

(Synthesis of aralkyl-modified silicone compound)
Silicone compounds 1 to 12 used in this example were synthesized as follows. The structure of the repeating unit of the obtained silicone compounds 1-12 is shown in Tables 1-3.

(Synthesis example of silicone compound 1)
The following compounds were mixed:
-IPA solution of catalyst hexachloroplatinic (VI) acid (hexahydrate) (manufactured by Kishida Chemical Co., Ltd.) (concentration of hexachloroplatinum (VI) acid (hexahydrate): 2 wt%): 0.5 g;
Α-methylstyrene (Aldrich) 400 g;
-Toluene 2000g.
71.2 g of methyl hydrogen polysiloxane (trade name: KF9901, manufactured by Shin-Etsu Chemical Co., Ltd.) was gradually added dropwise to the above mixture using a dropping funnel so that the addition was completed in about 5 minutes. After completion of the dropwise addition, the mixture was heated to a temperature of 80 ° C. and stirred for 8 hours.

  Then, after air-cooling a reaction liquid to room temperature, activated carbon (5g) was added and it stirred at room temperature for further 2 hours. Next, after the activated carbon is filtered off, the container containing the reaction solution is decompressed to 5 mmHg and heated at 150 ° C. for 2 hours to remove the solvent and unreacted methylhydrogenpolysiloxane, and the target silicone. Compound 1 was obtained. The weight average molecular weight of the silicone compound 1 was 10,000. Table 1 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 1.

(Synthesis example of silicone compound 2)
Silicone compound 2 was obtained in the same manner as in the synthesis example of silicone compound 1 except that 400 g of α-methylstyrene was changed to 358 g of styrene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 2 was 10,000. Table 1 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 2.

(Synthesis example of silicone compound 3)
Silicone compound 3 was obtained in the same manner as in the synthesis example of silicone compound 1 except that 400 g of α-methylstyrene was changed to 448 g of α, 2-dimethylstyrene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 3 was 11,000. Table 1 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 3.

(Synthesis example of silicone compound 4)
Silicone compound 4 was obtained in the same manner as in the synthesis example of silicone compound 1 except that 400 g of α-methylstyrene was changed to 406 g of 3-methylstyrene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 4 was 10,000. Table 1 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 4.

(Synthesis example of silicone compound 5)
Silicone compound 5 was obtained in the same manner as in the synthesis example of silicone compound 1 except that 400 g of α-methylstyrene was changed to 552 g of 4-tertbutylstyrene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 5 was 12,000. Table 1 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 5.

(Synthesis example of silicone compound 6)
1-octadecene was added to 0.5 g of an IPA solution (hexachloroplatinum (VI) acid (hexahydrate) concentration: 2 wt%) of the catalyst hexachloroplatinic (VI) acid (hexahydrate) (manufactured by Kishida Chemical Co., Ltd.). (
434 g of Aldrich), 200 g of α-methylstyrene (Aldrich), and 2000 g of toluene were mixed. Next, 71.2 g of methyl hydrogen polysiloxane (trade name: KF9901, manufactured by Shin-Etsu Chemical Co., Ltd.) was gradually added dropwise to the mixture so that the addition was completed in about 5 minutes. After completion of the dropwise addition, the mixture was heated to a temperature of 80 ° C. and stirred for 8 hours.

  Then, after air-cooling a reaction liquid to room temperature, activated carbon (5g) was added and it stirred at room temperature for further 2 hours. Next, after the activated carbon is filtered off, the container containing the reaction solution is decompressed to 5 mmHg and heated at 150 ° C. for 2 hours to remove the solvent and unreacted methylhydrogenpolysiloxane, and the target silicone. Compound 6 was obtained. The weight average molecular weight of the silicone compound 6 was 16,000. Table 2 shows the structures of the repeating units A, B, and C in the chemical formula (1) of the silicone compound 6.

(Synthesis example of silicone compound 7)
Silicone compound 7 was obtained in the same manner as in the synthesis example of silicone compound 6 except that 434 g of 1-octadecene was changed to 290 g of 1-dodecene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 7 was 11,000. Table 2 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 7.

(Synthesis example of silicone compound 8)
The target silicone compound 8 was obtained in the same manner as in the synthesis example of silicone compound 6 except that 434 g of 1-octadecene was changed to 144 g of 1-hexene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 8 was 10,000. Table 2 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 8.

(Synthesis example of silicone compound 9)
A silicone compound 9 was obtained in the same manner as in the synthesis example of the silicone compound 6 except that 434 g of 1-octadecene was changed to 48 g of ethylene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 1 was 6,000. Table 2 shows the structures of the repeating units A, B and C in the chemical formula (1) of the silicone compound 9.

(Synthesis example of silicone compound 10)
Silicone compound 10 was obtained in the same manner as in the synthesis example of silicone compound 6 except that 434 g of 1-octadecene was changed to 482 g of 1-eicosene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 10 was 14,000. Table 2 shows the structures of the repeating units A, B, and C in the chemical formula (1) of the silicone compound 10.

(Preparation of silicone compound 11)
A silicone compound 11 was obtained in the same manner as in the synthesis example of the silicone compound 6 except that 200 g of α-methylstyrene was changed to 358 g of styrene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 11 was 12,000. Table 3 shows the structures of the repeating units A, B, and C in the chemical formula (1) of the silicone compound 11.

(Preparation of silicone compound 12)
A silicone compound 12 was obtained in the same manner as in the synthesis example of the silicone compound 9 except that 200 g of α-methylstyrene was changed to 358 g of styrene (manufactured by Aldrich). The weight average molecular weight of the silicone compound 12 was 8,000. Table 3 shows the structures of the repeating units A, B, and C in the chemical formula (1) of the silicone compound 12.

(Synthesis example of polyether polyol prepolymer (1))
-100 parts by mass of polytetramethylene glycol represented by chemical formula (5) (trade name: PTG1000SN, manufactured by Hodogaya Chemical Co., Ltd.);
-4,4'- diphenylmethane diisocyanate (abbreviation: MDI, brand name: Cosmonate MDI, manufactured by Mitsui Takeda Chemical Co., Ltd.) 18.7 parts by mass.
The above compounds were mixed stepwise in methyl ethyl ketone solvent.
The mixture was reacted at a temperature of 80 ° C. for 3 hours under a nitrogen atmosphere to obtain a polyether polyol prepolymer (1). The polyether polyol prepolymer (1) had a weight average molecular weight (Mw) of 10,000 and a hydroxyl value of 18.2 mgKOH / g.

(Preparation of elastic layer paint)
<Preparation example of paint 1 for elastic layer>
The following raw materials were prepared.
Polyether polyol prepolymer (1) 100 parts by mass Tolylene diisocyanate (abbreviation: TDI) 68 parts by mass (trade name: Cosmonate T-100 manufactured by Mitsui Takeda Chemical Co., Ltd.)
Silicone compound 1 2 parts by mass Methyl ethyl ketone (solvent) 300 parts by mass Carbon black (trade name: MA100, manufactured by Mitsubishi Chemical Corporation) 17 parts by mass Urethane resin particles (trade name: Art Pearl C600, manufactured by Negami Kogyo) 13 parts by mass Part of the above raw materials was mixed and stirred and dispersed with a ball mill to prepare elastic layer paint 1.

  The tolylene diisocyanate is a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.

<Preparation example of paint 2-12 for elastic layer>
Except having changed the silicone compound 1 into each of the silicone compounds 2-12, it carried out similarly to the preparation example of the coating material 1 for elastic layers, and obtained each of the coating materials 2-12 for elastic layers.

<Example of Preparation of Elastic Layer Coating 13>
Elasticity is the same as the preparation example of the paint 1 for elastic layer, except that 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) is changed to 60 parts by mass and 2 parts by mass of silicone compound 1 is changed to 10 parts by mass. A layer coating 13 was obtained.

<Example of Preparation of Elastic Layer Coating 14>
Elasticity is the same as the preparation example of the paint 1 for elastic layer, except that 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) is changed to 50 parts by mass and 2 parts by mass of silicone compound 1 is changed to 20 parts by mass. A layer coating 14 was obtained.

<Example of Preparation of Elastic Layer Coating 14>
Elasticity is the same as in the preparation example of the elastic layer coating material 1 except that 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) is changed to 46 parts by mass and 2 parts by mass of the silicone compound 1 is changed to 24 parts by mass. Layer coating 15 was obtained.

<Example of Preparation of Elastic Layer Coating 16>
Except for changing 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) to 69.6 parts by mass and changing 2 parts by mass of silicone compound 1 to 0.4 parts by mass, Similarly, the elastic layer coating material 16 was obtained.

<Example of Preparation of Elastic Layer Coating 17>
Except for changing 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) to 69.8 parts by mass and changing 2 parts by mass of silicone compound 1 to 0.2 parts by mass, Similarly, the elastic layer coating material 17 was obtained.

<Example of Preparation of Elastic Layer Coating 18>
Except for changing 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) to 69.9 parts by mass and changing 2 parts by mass of silicone compound 1 to 0.1 parts by mass, Similarly, the elastic layer coating material 18 was obtained.

<Preparation example of coating material 19 for elastic layer>
The following raw materials were prepared.
-Polyether polyol prepolymer (1) 100 parts by mass-1,5-naphthalene diisocyanate (abbreviation: NDI) 68 parts by mass (trade name: Cosmonate ND, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)
-Silicone compound 1 2 parts by mass-Methyl ethyl ketone (solvent) 200 parts by mass-Toluene (solvent) 100 parts by mass-Carbon black (trade name: MA100, manufactured by Mitsubishi Chemical Corporation) 17 parts by mass-Urethane resin particles (trade name: Art Pearl C600, manufactured by Negami Kogyo Co., Ltd. 13 parts by mass The above raw materials were mixed and stirred and dispersed with a ball mill to prepare an elastic layer coating material 19.

<Example of Preparation of Elastic Layer Coating 20>
Elasticity is the same as in the preparation example of the coating material 18 for the elastic layer except that 1,5-naphthalene diisocyanate is changed to m-xylylene diisocyanate (abbreviation: XDI, trade name: Takenate 500, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.). A layer coating 20 was obtained.

<Example of Preparation of Elastic Layer Coating 21>
Elasticity is the same as in the preparation example of the elastic layer coating material 1 except that 68 parts by mass of tolylene diisocyanate (abbreviation: TDI) is changed to 70 parts by mass and 2 parts by mass of the silicone compound 1 is changed to 0 parts by mass. A layer coating 21 was obtained.

<Example of Preparation of Elastic Layer Coating 22>
An elastic layer coating material 22 was obtained in the same manner as in the preparation example of the elastic layer coating material 1 except that the silicone compound 1 was changed to methylphenyl silicone oil (trade name: KF50-300cs, manufactured by Shin-Etsu Chemical Co., Ltd.).

  In addition, said methylphenyl silicone oil is a compound shown by following Chemical formula (6).

<Example of Preparation of Elastic Layer Coating 23>
The polyether polyol prepolymer (1) was changed to polypropylene glycol (trade name: Actol Diol-3000, manufactured by Mitsui Takeda Chemical Co., Ltd.). 1,5-naphthalene diisocyanate was changed to hexamethylene diisocyanate (abbreviation: HDI) (trade name: HDI, manufactured by Nippon Polyurethane Industry Co., Ltd.). Otherwise, the elastic layer coating material 22 was obtained in the same manner as in the preparation example of the elastic layer coating material 1.

Example 1
A shaft body (material: SUS304) having an outer diameter of 6 mm was installed in the cavity so as to be concentric with the cavity having a cylindrical cavity having an inner diameter of 12 mm. In the space between the mold cavity inner peripheral surface and the shaft outer peripheral surface, liquid conductive silicone rubber (manufactured by Toray Dow Corning Silicone Co., Ltd., ASKER-C hardness 40 degrees, volume resistivity 1 × 10 ⁵ Ω · cm product) Injected. This mold is placed in an oven at a temperature of 130 ° C. and heated for 20 minutes, and then the silicone rubber integrated with the shaft body is removed from the mold and heated in an oven at a temperature of 200 ° C. for 4 hours to obtain a secondary. Vulcanization was performed to form a roller having a 3 mm thick silicone rubber layer as a resin layer.

The roller was immersed in the elastic layer paint 1, and the elastic layer paint 1 was applied on the silicone rubber layer. It was dried in an oven at a temperature of 80 ° C. for 15 minutes, further heated in an oven at a temperature of 140 ° C. for 4 hours and cured to form an elastic layer on the silicone rubber layer to obtain a developing roller.
The thickness of the elastic layer of the obtained developing roller is 15 μm, the volume resistivity is 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis of the elastic layer obtained based on JIS B0601: 2001 of the obtained developing roller is 18 μm. The content of the silicone compound 1 in the elastic layer was 1% by mass [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.

  The polyurethane resin that constitutes the elastic layer of the developing roller of this embodiment has an aromatic ring derived from MDI and TDI. Moreover, this elastic layer contains the silicone compound 1 as an aralkyl modified silicone compound.

<Evaluation of image density>
The developing roller was evaluated using a color laser printer (trade name: Color LaserJet 4700, manufactured by Hewlett-Packard Company). Specifically, the magenta print cartridge for the color laser printer was modified and the developing roller was mounted on the magenta print cartridge. Prior to image output, the modified print cartridge was mounted on the color laser printer and left in a test environment at a temperature of 23 ° C./50% relative humidity for 24 hours. As the developer, a nonmagnetic one-component magenta developer mounted on the magenta print cartridge was used as it was. The recording paper used was CLC (color laser copier) paper (A4 size, basis weight = 81.4 g / m ² ) manufactured by Canon Inc.

  Next, one solid image was output on the entire surface of the recording paper leaving the 10 mm edge of the recording paper under each of the above test environments. The density of the output solid image was measured with a reflection densitometer RD918 (trade name, manufactured by Macbeth). The image density was measured at the intersections (three places in total) of three lines that divide the recording paper into four equal parts in the horizontal direction and three lines that divide the recording paper into four equal parts in the vertical direction. The arithmetic average value of the image densities at nine locations was taken as the image density under each test environment. Usually, if the solid image density is 1.00 or more, it is a level that can withstand normal use, preferably 1.10 or more, and more preferably 1.20 or more.

  Further, the image density was evaluated in the same manner as described above in two test environments of temperature 32 ° C./relative humidity 85% and temperature 35 ° C./relative humidity 85%. The results obtained are shown in Table 4.

(Example 2)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 2.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 2 was 1% by mass with respect to the mass of the elastic layer [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1].
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 3)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 3.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 3 was 1% by mass [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

Example 4
A developing roller was prototyped and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 4.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 4 was 1% by mass with respect to the mass of the elastic layer [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1].
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 5)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 5.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 5 was 1% by mass [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 6)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 6.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 6 was 1% by mass with respect to the mass of the elastic layer [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1].
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 7)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 7.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 7 was 1% by mass with respect to the mass of the elastic layer [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1].
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 8)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 8.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. In addition, the content of the silicone compound 8 was 1% by mass with respect to the mass of the elastic layer [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1].
Table 4 shows the evaluation result of the image density of the obtained developing roller.

Example 9
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 9.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound 9 was 1% by mass [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 10)
A developing roller was prototyped and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 11.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. Moreover, content of the silicone compound 10 was 1 mass% [2 / (100 + 68 + 2 + 17 + 13) * 100 = 1] with respect to the mass of this elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 11)
A developing roller was produced and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 12.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. Moreover, content of the silicone compound 11 was 1 mass% [2 / (100 + 68 + 2 + 17 + 13) * 100 = 1] with respect to the mass of this elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 12)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 13.
The thickness of the elastic layer of the obtained developing roller was 12 μm, the volume resistivity was 1 × 10 ¹¹ Ωcm, and the ten-point average roughness Rzjis was 20 μm. Moreover, content of the silicone compound 1 was 5 mass% [10 ÷ (100 + 60 + 10 + 17 + 13) × 100 = 5] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 13)
A developing roller was produced and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 14.
The thickness of the elastic layer of the obtained developing roller was 10 μm, the volume resistivity was 1 × 10 ⁹ Ωcm, and the ten-point average roughness Rzjis was 23 μm. Moreover, content of the silicone compound 1 was 10 mass% [10 ÷ (100 + 50 + 20 + 17 + 13) × 100 = 10] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 14)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 15.
The thickness of the elastic layer of the obtained developing roller was 7 μm, the volume resistivity was 5 × 10 ⁹ Ωcm, and the ten-point average roughness Rzjis was 25 μm. Moreover, content of the silicone compound 1 was 12 mass% [24 ÷ (100 + 46 + 24 + 17 + 13) × 100 = 12] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 15)
A developing roller was produced and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 16.
The thickness of the elastic layer of the obtained developing roller was 3 μm, the volume resistivity was 1 × 10 ¹¹ Ωcm, and the ten-point average roughness Rzjis was 13 μm. Moreover, content of the silicone compound 1 was 0.2 mass% [0.4 / (100 + 69.6 + 0.4 + 17 + 13) * 100 = 0.2] with respect to the mass of this elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 16)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 17.
The thickness of the elastic layer of the obtained developing roller was 30 μm, the volume resistivity was 1 × 10 ⁸ Ωcm, and the ten-point average roughness Rzjis was 2 μm. Moreover, content of the silicone compound 1 was 0.1 mass% [0.2 ÷ (100 + 69.8 + 0.2 + 17 + 13) × 100 = 0.1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 17)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 18.
The thickness of the elastic layer of the obtained developing roller was 10 μm, the volume resistivity was 1 × 10 ¹⁰ Ωcm, and the ten-point average roughness Rzjis was 20 μm. The content of the silicone compound 1 was 0.05% by mass with respect to the mass of the elastic layer [0.1 ÷ (100 + 69.9 + 0.1 + 17 + 13) × 100 = 0.05].
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 18)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 19.
The thickness of the elastic layer of the obtained developing roller was 20 μm, the volume resistivity was 1 × 10 ⁸ Ωcm, and the ten-point average roughness Rzjis was 12 μm. Moreover, content of the silicone compound 1 was 1 mass% [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 19)
A developing roller was produced and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 20.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹¹ Ωcm, and the ten-point average roughness Rzjis was 18 μm. Moreover, content of the silicone compound 1 was 1 mass% [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Example 20)
The following raw materials were prepared.
70 parts by mass of polypropylene glycol represented by the following chemical formula (7) (trade name: Actol Diol-3000, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Carbon black (trade name: MA100, manufactured by Mitsubishi Chemical Corporation) 19 parts by mass Tolylene diisocyanate 10 parts by mass (abbreviation: TDI, trade name: Cosmonate T-100, manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ 1 part by mass of silicone compound 1

The polypropylene glycol and carbon black were stirred with a ball mill to prepare dispersion A. Next, the tolylene diisocyanate and the silicone compound 1 were added to the dispersion A and stirred for 2 minutes to obtain a dispersion B. On the other hand, the shaft was placed in the cavity of the mold in the same manner as in Example 1, and the dispersion B was poured into a mold that had been heated to 115 ° C. in advance, and cured for 2 hours.
The polyurethane resin integrated with the shaft after curing was taken out of the mold and subjected to secondary crosslinking at 110 ° C. for 24 hours to obtain a roller. Next, the surface of the obtained roller is polished using a grindstone of No. 80 (trade name: PT, manufactured by Teiken) to obtain a developing roller having an elastic layer on the outer peripheral surface of the shaft body. It was.
The thickness of the elastic layer of the obtained developing roller was 6 mm, the volume resistivity was 1 × 10 ⁹ Ωcm, and the ten-point average roughness Rzjis of the elastic layer surface was 20 μm.
The content of the silicone compound 1 was 1% by mass [1 ÷ (70 + 19 + 10 + 1) × 100 (%)] with respect to the mass of the elastic layer.
The image density of the obtained developing roller was evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 1)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 21.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone compound was 0% by mass with respect to the mass of the elastic layer [0 ÷ (100 + 70 + 0 + 17 + 13) × 100 = 0].
Table 4 shows the evaluation result of the image density of the obtained developing roller.
In this comparative example, as is apparent from the formulation of the elastic layer coating material, the elastic layer does not contain a silicone compound.

(Comparative Example 2)
A developing roller was prototyped and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 22.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. The content of the silicone rubber compound 13 was 1% by mass [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Comparative Example 3)
A developing roller was prepared and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 23.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹¹ Ωcm, and the ten-point average roughness Rzjis was 18 μm. Moreover, content of the silicone compound 1 was 1 mass% [2 ÷ (100 + 68 + 2 + 17 + 13) × 100 = 1] with respect to the mass of the elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

(Comparative Example 4)
A developing roller was produced and evaluated in the same manner as in Example 1 except that the elastic layer coating material 1 was changed to the elastic layer coating material 10.
The thickness of the elastic layer of the obtained developing roller was 15 μm, the volume resistivity was 1 × 10 ¹² Ωcm, and the ten-point average roughness Rzjis was 18 μm. Moreover, content of the silicone compound 10 was 1 mass% [2 / (100 + 68 + 2 + 17 + 13) * 100 = 1] with respect to the mass of this elastic layer.
Table 4 shows the evaluation result of the image density of the obtained developing roller.

It is sectional drawing of the axial direction which shows a structure of an example of embodiment of the developing roller of this invention. It is sectional drawing of the axial direction which shows the structure of the other example of embodiment of the developing roller of this invention. 1 is a schematic cross-sectional view showing an example of an electrophotographic image forming apparatus of the present invention. 1 is a schematic cross-sectional view showing an example of an electrophotographic process cartridge of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Shaft body 2 Elastic layer 21 Photosensitive drum 22 Charging member 23 LED light or laser beam 24 Developing roller 25 Developer supply roller 26 Developing blade 27 Intermediate transfer belt 28 Primary transfer member 29 Secondary transfer member 30 Cleaning member 31 Fixing device 32 Recording Paper 34 Developer container 100 Developing roller 200 Developing roller 201 Resin layer 202 Elastic layer

Claims (7)

A developing roller having a conductive shaft and an elastic layer formed on the outer peripheral surface of the conductive shaft, wherein the elastic layer is represented by a polyurethane resin having an aromatic ring and the following chemical formula (1): A developing roller comprising a resin composition containing an aralkyl-modified silicone compound.
(CH ₃ ) ₃ SiO · (A) _p · (B) _q · (C) _r · Si (CH ₃ ) ₃ (1)
(In the formula, A, B and C each represent a repeating unit, and the arrangement order of the repeating units A, B and C is arbitrary, A represents a repeating unit represented by the following chemical formula (2),

B represents a repeating unit represented by the following chemical formula (3),

(In the formula, R1 represents an alkyl group having 2 to 18 carbon atoms.)
C represents a repeating unit represented by the following chemical formula (4),

(Wherein R2 represents an alkylene group having 2 or 3 carbon atoms, and R3 to R7 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)
p and r each independently represents an integer of 1 or more, and q represents 0 or an integer of 1 or more. ) The developing roller according to claim 1, further comprising a resin layer between the conductive shaft body and the elastic layer.   The developing roller according to claim 1, wherein the aralkyl-modified silicone compound contained in the elastic layer is 0.1% by mass or more and 10% by mass or less based on the mass of the elastic layer.   The developing roller according to claim 1, wherein R3 to R7 in the chemical formula (4) are all hydrogen atoms.   The developing roller according to claim 4, wherein R 2 in the chemical formula (4) is a propylene group.   A developing roller carrying a developer in a state of being opposed to an image carrier carrying an electrostatic latent image, and a developing blade for regulating the thickness of the developer while frictionally charging the developer carried on the developing roller; An electrostatic latent image is developed by forming a thin film of developer on the surface of the developing roller, and bringing the developing roller into contact with the image carrier and applying the developer to the surface of the image carrier. 6. An electrophotographic process cartridge that is visualized as an agent image, wherein the developing roller is the developing roller according to claim 1.   An image carrier for carrying an electrostatic latent image; a charging device for primarily charging the image carrier; an exposure device for forming an electrostatic latent image on the primary charged image carrier; An electrophotographic image forming apparatus comprising: a developing device for developing an electrostatic latent image with a developer to form a developer image; and a transfer device for transferring the developer image to a transfer material, An image forming apparatus for electrophotography, comprising the electrophotographic process cartridge according to claim 6 as the developing device.

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