JP2014228597A - Conductive elastomer member for electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive elastomer member for an electrophotographic device, which can exhibit stable electric characteristics.SOLUTION: The conductive elastomer member for an electrophotographic device is formed from a conductive elastomer produced by incorporating carbon black and graphite into a polyurethane elastomer using a specific polyester polyol.

Description

  The present invention relates to a conductive elastomer member for an electrophotographic apparatus.

2. Description of the Related Art Conventionally, electrophotographic apparatuses such as printers, copiers, facsimiles, and the like have been provided with an elastomer member that is partially or wholly formed of an elastomer. The elastomer member can be a roller, belt, or sheet. What has the shape of is known.
Further, as this type of elastomer member, a conductive elastomer member that contains a conductive filler such as carbon black or metal powder to give predetermined conductivity is known.
As the conductive elastomer member for electrophotographic apparatus, specifically, a developing member, a charging member, a transfer member, and the like are known. For example, a conductive elastomer member for charging a surface-supported toner. In the developing roller, an elastic layer is provided on the outer periphery of the core metal with a predetermined thickness, and the elastic layer is formed of the conductive elastomer.

  Such a conductive elastomer member for an electrophotographic apparatus exhibits conductivity when a conductive filler such as carbon black blended in the conductive elastomer forms a chain aggregate in the elastic layer. It is thought that

By the way, in recent years, in an electrophotographic apparatus, it has been carried out to refine the toner and improve the printing accuracy, and in liquids called carriers such as liquid paraffin, silicon oil, mineral oil, or vegetable oil, for example, A liquid developer in which toner finely divided to about 1 μm is dispersed has been used.
A liquid developing electrophotographic apparatus using this liquid developer is excellent in print quality, and is widely used in applications such as printing several hundred sheets or thousands of photographs or illustrations at a time.

However, the conductive elastomer member has a problem that when the voltage is continuously applied, the conductivity of the conductive elastomer gradually decreases (the electric resistance value increases). As described above, when the continuous operation for a long time is performed, the electrical characteristics may be changed.
In particular, in the case of a conductive elastomer member that plays a role of controlling the movement of toner, which is a charged particle, such as a developing roller, it becomes difficult to control the movement of the toner when the electric resistance of the elastic layer increases. There is a risk of image quality deterioration such as degradation.

Such In the invention described in Patent Document 1 to problems, DBP oil absorption amount is described to employ carbon black 71~168cm ³ / 100g as the conductive filler with graphite.

JP 2009-271328 A

Graphite has a particle size about one order of magnitude larger than that of carbon black, and exhibits metallic electrical characteristics. Therefore, by dispersing carbon black in a conductive elastomer member, a conductive network having the graphite as a relay point is formed. The conductive elastomer member can exhibit resistance stability during continuous energization as compared with the case where the conductive network is formed only with carbon black.
However, even when graphite and carbon black are used in combination, it may be difficult to cause the conductive elastomer member to exhibit sufficient resistance stability, and there has been a demand for further improvement.
Such a demand for the conductive elastomer member is strongly demanded particularly in a liquid developing electrophotographic apparatus having many opportunities for continuous use for a long time, but is used in a dry developing electrophotographic apparatus. The same applies to conductive elastomer members.
And this invention makes it a subject to satisfy such a request, and makes it the subject to provide the electroconductive elastomer member for electrophotographic apparatuses which can exhibit the stable electrical property.

The present inventor has intensively studied to solve the above problems, and has found a correlation between the charge accumulation in the conductive elastomer member and the temporal change in the resistance value.
In addition, the inventor found that the conductive elastomer member is electrically discontinuous with carbon black and graphite being separated from each other in angstrom order or nano order. Judging that the tunnel current is generated at the location, and that the accumulation of charges exceeding the allowable range due to continuous energization prevents the tunnel current from being interrupted is related to the temporal change in resistance value. To solve the above problems.
Then, the present inventor can form a conductive elastomer by dispersing a specific carbon black and graphite in a specific elastomer, so that a large amount of charge can be secured, and an excellent resistance to the conductive elastomer. The inventors have found that stability can be exhibited and have completed the present invention.

  That is, the present invention relating to a conductive elastomer member for an electrophotographic apparatus for solving the above problems is formed of a conductive elastomer containing a polyurethane elastomer obtained by reacting a polyol and a polyisocyanate and a conductive filler. A conductive elastomer member for an electrophotographic apparatus, wherein the polyol is a glycol (A1) having 4 or more carbon atoms having a side chain, a linear glycol (A2) having 2 or 3 carbon atoms, and a hydroxyl group. A polyester having a number average molecular weight of 2000 or more and 3000 or less and a hydroxyl value of 80 mg / KOHg or more and 88 mg / KOHg or less by reacting a glycol component (A) containing at least 3 glycols (A3) with adipic acid (B) Polyol, and the conductive elastomer is used as the conductive filler. It contains at least graphite and carbon black. When an AC voltage having an effective value of 500 mV is applied at a frequency ranging from 1 Hz to 20 kHz and the phase difference of the current with respect to the voltage is measured, the phase difference is −90 ° or more and −60 It has an electrical characteristic that the resistance value when the direct current of 100 μA is continuously applied for 5 hours is less than twice the resistance value immediately after the start of energization.

  According to the present invention, since the predetermined polyester polyol is adopted as the polyol of the polyurethane elastomer, the conductive elastomer member for an electrophotographic apparatus can exhibit resistance stability.

1 is a schematic perspective view showing a conductive elastomer member (developing roller) for an electrophotographic apparatus according to one embodiment.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings while illustrating a developing roller as a conductive elastomer member for an electrophotographic apparatus.

FIG. 1 is a perspective view showing a developing roller, and as shown in this perspective view, the developing roller 1 has a metal at the center to be provided in the electrophotographic apparatus in a state of being rotatable around an axis. A cored bar 2 made of a round bar is provided.
The developing roller 1 in this embodiment has an elastic body layer 3 provided on the outer periphery of the metal core 2 with a substantially constant thickness, and a surface layer 4 that covers the surface of the elastic body layer 3.
That is, the developing roller 1 in this embodiment is formed in a state where a cylindrical elastic body is mounted on the outer periphery of the cored bar 2.
The elastic layer 3 is provided so that the developing roller 1 exhibits desired elastic deformation by contact with another member, and the surface layer 4 is provided with a surface wear resistance and separation. It is provided on the outermost surface side of the developing roller 1 in order to improve moldability.

  Although the thickness of the elastic layer 3 and the thickness of the surface layer 4 vary depending on the electrophotographic apparatus in which the developing roller 1 of the present embodiment is incorporated, the thickness of the elastic layer 3 is usually as follows. The surface layer 4 has a thickness of 1 μm to 100 μm.

The electrical conductivity required for the developing roller of the present embodiment is not particularly limited, but is usually formed to have an electric resistance value of 1 × 10 ⁴ Ω or more and 1 × 10 ⁸ Ω or less. In general, the JIS A hardness is preferably about 10 to 60 °, and particularly preferably 20 to 50 °.

The developing roller applies an AC voltage having an effective value of 500 mV at a frequency ranging from 1 Hz to 20 kHz and measures the phase difference of the current with respect to the voltage, and the phase difference is −90 ° or more and −60 ° over the entire frequency region. It is important to be formed so that the resistance value is less than twice the resistance value immediately after the start of energization when a 100 μA DC current is continuously applied for 5 hours. is important.
The phase difference and the resistance value change are caused by applying electricity between the core metal and the stainless steel plate in a state where a load of 10 N in total is applied to one end of the core metal of the developing roller placed horizontally on the stainless steel plate. Can be measured.

According to the matter found by the present inventors, there is a positive correlation between the phase difference and the amount of change in the electric resistance value of the elastic layer before and after continuous energization, and in particular, the phase difference of the current with respect to the voltage is from 1 Hz. In any situation between 20 kHz, when the value shows a value exceeding −60 ° (for example, −50 °), the resistance value increases due to continuous energization.
Therefore, in order to obtain a developing roller having excellent electrical property stability, it is preferable to adjust the material used, the blending ratio, and the like of the elastic layer so that the phase difference measured by the measurement method falls within the above range. .
More specifically, the electrical characteristics of the developing roller can be obtained by the method described in the examples.
In addition, for example, in the case of a sheet-like conductive elastomer member other than the developing roller, a phase difference and a resistance value change are measured by applying electricity between the metal plates in the same manner as described above with being sandwiched between two metal plates. Can do.

The elastic layer is preferably formed of a predetermined material in that it is easy to impart the above characteristics to the developing roller.
Specifically, it is important that the elastic body layer 3 is formed of a conductive elastomer containing a polyurethane elastomer obtained by reacting a polyester polyol and a polyisocyanate, graphite, and carbon black.
More specifically, in the elastic layer 3, the conductive elastomer contains the carbon black in a proportion of 0.5% by mass to 1% by mass and the graphite 3% by mass to 5% by mass. is in a proportion of, DBP oil absorption amount of the carbon black is 175cm ^3/100 g or more 360 cm ^3/100 g or less, it is preferable that the average particle size of the graphite is 3μm or 10μm or less.

  In the elastic layer 3, the polyester polyol constituting the polyurethane elastomer is composed of a glycol (A1) having 4 or more carbon atoms having a side chain, and a linear glycol (A2) having 2 or 3 carbon atoms. And a glycol component (A) containing at least 3 hydroxyl groups (A3) and adipic acid (B) are reacted with adipic acid (B) to have a number average molecular weight of 2,000 to 3,000 and a hydroxyl value of 80 mg / KOHg to 88 mg / KOHg. It is important to be a polyester polyol.

Carbon black usually has a size of 1 μm or less (several tens of nm), whereas graphite usually has a size exceeding 1 μm, and its particle size is larger than that of carbon black. Some are larger than 1 order.

In addition, graphite has a crystal structure developed as compared with carbon black, its electronic state is semi-metallic, and usually the conductivity of the particles themselves is superior to that of carbon black.
Therefore, it is difficult to make the entire elastic layer relatively uniform with the above-mentioned medium resistance value using only graphite.
In the present embodiment, as described above, the DBP oil absorption value is large, and the elastic layer is imparted with stable electrical characteristics using carbon black having a developed structure.
However, when this carbon black is used in a large amount, the dispersion obtained by dispersing in the polyol has a high viscosity, so it is difficult to make the elastic layer have the above-mentioned medium resistance even with carbon black alone.
That is, in the present embodiment, the other side is complemented by the other side when imparting suitable electrical characteristics to the elastic body layer 3 by setting the contents of carbon black and graphite within the above ranges. .

  As the high structure carbon black exhibiting the DBP oil absorption amount as described above, for example, those commercially available under a designation such as ketjen black can be adopted, and the graphite is either natural graphite or artificial graphite. However, artificial graphite is preferable because it is easily available and the quality is more stable.

The DBP oil absorption amount is obtained by substituting the void volume in a constant mass of carbon black with liquid and using the volume as an index. Specifically, the amount of oil contained in 100 g of carbon black (cm ³ ), which can be measured by a method according to ASTM D3493-85a.

The elastic layer 3 preferably contains carbon black having a DBP oil absorption within the above range because the resistance value usually required for the developing roller is 1 × 10 ⁴ Ω to 1 × 10 ⁵ Ω. This is because it is easy for the developing roller to exhibit the above.
The carbon black has a DBP oil absorption value that is equal to or higher than the lower limit value of the range, so that the elastic layer 3 can easily exhibit stable conductivity, and the DBP oil absorption value is an upper limit value of the range. It has the advantage that the fluidity | liquidity excellent in the dispersion liquid obtained by disperse | distributing the said carbon black in a polyol can be exhibited by being below.
That is, the carbon black can be brought into a state suitable for allowing a simple molding method such as in-mold molding to be performed on a mixed liquid obtained by mixing polyisocyanate with the dispersion.

  In addition, the carbon black is contained in the conductive elastomer in a proportion of 0.5% by mass or more and 1% by mass or less because the carbon black is contained in an amount of 0.5% by mass or more. The conductivity of the carbon black can be more reliably exhibited, and by making the content of the carbon black 1% by mass or less, good fluidity can be exhibited in a dispersion in which the carbon black is dispersed in a polyol. Because.

The average particle diameter of the graphite used for forming the elastic body layer 3 is 3 to 10 μm because the average particle diameter of the graphite is 3 μm or more, so that the graphite is dispersed in the polyol together with the carbon black. This is because it is easy to impart good fluidity to the obtained dispersion liquid, and the formation of the elastic body layer 3 can be made easier. By making the average particle diameter of the graphite 10 μm or less, the conductivity of the elastic body layer is uniform. It is because it is easy to exhibit the property.
Moreover, it is preferable that the average particle diameter of graphite is 10 micrometers or less also in the point which makes the surface of an elastic body layer smooth easily.
For this reason, the average particle size of graphite is particularly preferably 4 μm or more and 6 μm or less.
The average particle diameter of the graphite means a cumulative 50% diameter (d50) in particle size distribution analysis by a laser diffraction / scattering method.

  The reason why the graphite is contained in the conductive elastomer at a ratio of 3% by mass or more and 5% by mass or less is that the conductive elastomer exhibits stable conductivity by containing the graphite by 3% by mass or more. This is because, by setting the graphite content to 5% by mass or less, good fluidity can be exerted on a dispersion obtained by dispersing the graphite together with carbon black in a polyol.

  In this embodiment, the polyurethane elastomer that forms an elastic layer together with such a conductive filler is obtained by reacting a polyester polyol and a polyisocyanate as described above.

  This polyester polyol is obtained by reacting the glycol component (A) and adipic acid (B) as described above, and the glycol component (A) includes a first glycol having 4 or more carbon atoms having a side chain. It contains at least (A1), a linear second glycol (C2) having 2 or 3 carbon atoms, and a third glycol (A3) having three or more hydroxyl groups.

(Primary glycol)
The first glycol (A1), which is one of the starting materials of the polyester polyol, is a main component in the glycol component (A) and is a glycol having 4 or more carbon atoms including side chains.
The first glycol preferably has 9 or less carbon atoms.
Examples of the first glycol (A1) include diols having 4 to 9 carbon atoms, and specific examples include 2-methylpropanediol, 3-methyl-1,5-pentanediol, and 3-methyl-2. , 4-pentanediol such as 3-methylpentanediol (abbreviation 3MPD), 2,2-dimethyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2,4- Examples include trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, and 2,4-diethyl-1,5-pentanediol.

  Moreover, as said 1st glycol (A1), a lactone ring-opening polymerization type | system | group polyester polyol can also be used, for example, a pentano-4-lactone type compound, a gamma-valerolactone type compound, 4,4-dimethyltetrahydro-2H. Examples include lactone ring-opening polymerization polyester polyols obtained by ring-opening polymerization of cyclic ester compounds (that is, lactones) containing a side chain such as a pyran-2-one compound.

When the developing roller of this embodiment is used in a liquid developing type electrophotographic apparatus, it is advantageous for forming an elastic body layer having excellent resistance to a carrier such as liquid paraffin, silicon oil, mineral oil, or vegetable oil. In this respect, it is preferable to employ any of 2-methylpropanediol and 3-methylpentanediol as the first glycol (A1), and it is particularly preferable to employ 3-methyl-1,5-pentanediol.
These first glycols may be used alone or in combination of two or more of the above exemplified compounds in the glycol component.

(Secondary glycol)
The second glycol having a straight chain structure having 2 to 3 carbon atoms is an effective component for exerting an effect of reducing compression set (residual strain suppression) on a conductive elastomer, and carrier resistance ( Swelling suppression) effect.
Examples of the second glycol (A2) include diols having 2 to 3 carbon atoms such as ethylene glycol (abbreviation EG) and 1,3-propylene glycol (1,3PD).
These second glycols may be used alone or in combination of two or more of the above-exemplified compounds in the glycol component.

(Third glycol)
The above-mentioned tertiary glycol (A3), which is a trifunctional or higher functional polyol having 3 or more hydroxyl groups, introduces a crosslinked structure into the conductive elastomer constituting the elastic layer and imparts an excellent restoring force against deformation to the elastic layer. It is an effective ingredient to do.
Further, when the developing roller of this embodiment is used in a liquid developing type electrophotographic apparatus, the third glycol can exert an effect of suppressing swelling due to the carrier in the elastic layer.

Examples of the third glycol include trifunctional compounds such as trimethylolpropane (abbreviation TMP), glycerin, pentaerythritol, and hexanetriol, or dimers such as trimethylolpropane and pentaerythritol (ditrimethylolpropane, dipentaerythritol). Stole), compounds having more than three functional groups such as saccharides such as sorbitol.
In these, it is preferable to employ | adopt trimethylol propane and glycerol as said 3rd glycol, and it is more preferable to employ | adopt trimethylol propane from the point of handling.
These third glycols may be used alone or in combination of two or more of the above-exemplified compounds in the glycol component.

The glycol component has a predetermined ratio of the first glycol (A1), the second glycol (A2), and the third glycol (A3) from the viewpoint of resilience to deformation of the elastic layer and, if necessary, carrier resistance. It is preferable to contain.
Specifically, the glycol component (A) contains the first glycol (A1) and the second glycol (A2) in a molar ratio of 90/10 to 30/70 ((A1) / (A2)). It is preferable that it is contained at a molar ratio of 80/20 to 50/50.
The triglyceride (A3) having three or more functional groups has a molar ratio [{(A1) + (A2)} / (A3) with respect to the total of the first glycol (A1) and the second glycol (A2). ] It is preferable to make it contain in a glycol component so that it may become 99/1-85/15, and it is especially preferable to make it contain in the glycol component by the said molar ratio of 97/3-90/10.

The glycol component and the adipic acid are preferably reacted at a molar ratio of 80/20 to 20/80, and the polyester polyol obtained by the reaction has a number average molecular weight of 2,000 to 3,000, and a hydroxyl value. It is important to carry out the reaction so that the concentration is 80 mg / KOHg or more and 88 mg / KOHg or less.
The number average molecular weight (Mn) of the polyester polyol can be measured by using a gel permeation chromatograph (GPC). For example, using GPC manufactured by Tosoh Corporation: “HLC-8020”, the column “G -4000 "," G-3000 ", and" G-2000 "(all manufactured by Tosoh Corporation) can be linked together, and the measurement can be performed by using chloroform as the mobile phase.
Moreover, the said hydroxyl value is a value calculated | required by the method according to JISK0070.

Such a polyester polyol can improve the dispersion state of the carbon black or the graphite in the elastic body layer.
Therefore, the elastic body layer of this embodiment is formed with more portions where the carbon blacks or the carbon black and the graphite are separated in angstrom order than the conventional elastic body layer. It will be in the state which shows large electrostatic capacitance compared with.
Therefore, the elastic layer of the present embodiment has a larger number of conductive paths due to the tunnel current than the conventional elastic layer and can secure a large amount of electric charge accumulated until the tunnel current is inhibited. Therefore, excellent resistance stability during continuous energization is exhibited.
Note that when the elastic layer is swollen by the carrier or the like, the interval between the conductive fillers may change, and the capacitance may be changed. However, the elastic layer of the present embodiment is as described above. In addition, a polyester polyol having excellent resistance to carriers is used for its formation.
Therefore, the developing roller of this embodiment has an advantage that resistance stability hardly changes depending on the carrier.
Therefore, it can be said that the developing roller of the present embodiment is preferably used in a liquid developing electrophotographic apparatus in that the effect can be exhibited more remarkably.

Although it does not specifically limit as said polyisocyanate which comprises a polyurethane elastomer with the above polyester polyols, Specifically, for example, 2, 4-tolylene diisocyanate (2,4-TDI), 2,6-tri-ethylene, for example. Range isocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 1,4-phenylene diisocyanate, poly Aromatic polyisocyanates such as methylene polyphenylene polyisocyanate, tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI) Aliphatic polyisocyanates such as lysine diisocyanate, norbornene diisocyanate methyl (NBDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), An alicyclic polyisocyanate such as H6XDI (hydrogenated XDI) or H12MDI (hydrogenated MDI), a carbodiimide-modified polyisocyanate of each of the above polyisocyanates, or an isocyanurate-modified polyisocyanate thereof can be employed.
In addition, these polyisocyanate can be used individually by 1 type or in combination of 2 or more types.

Among these, the polyisocyanate is preferably tolylene diisocyanate, and it is particularly preferable to use 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tolylene diisocyanate (2,6-TDI) in combination. preferable.
The polyisocyanate is most preferably a combination of 2,4-TDI and 2,6-TDI at a mass ratio of 7: 3 to 9: 1.

In order to obtain an elastic body layer that is excellent in resilience after elastic deformation and is hardly affected by the carrier, the polyisocyanate that constitutes the polyurethane elastomer together with the polyester polyol uses a polyisocyanate containing hexamethylene diisocyanate as a constituent component. It is preferable.
That is, as the polyisocyanate, a polyisocyanate generally called “modified HDI” or the like can be suitably used.
In addition, as the polyisocyanate in the present embodiment, a polyisocyanate in which a plurality of hexamethylene diisocyanates are bonded by an organic compound having two or more functional groups that react with isocyanate groups and the molecular ends are composed of hexamethylene diisocyanate is particularly preferable. .

This polyisocyanate may have a linear molecular structure without branching or may have a branched structure. In order to make the elastic body layer flexible with low hardness, It is preferable not to have a structure exhibiting rigidity such as an aromatic group or an alicyclic group.
That is, the organic compound that bonds hexamethylene diisocyanate to each other is preferably a substituted or unsubstituted saturated aliphatic hydrocarbon, and the polyisocyanate of the present embodiment is formed via this substituted or unsubstituted saturated aliphatic hydrocarbon. It is preferable that a plurality of hexamethylene diisocyanates are bonded and the bonds are made such that the molecular ends are hexamethylene diisocyanate.

The organic compound that binds hexamethylene diisocyanate to each other includes a molecular structure having at least one of a molecular structure having an ether bond in the main chain and a molecular structure having an alkyl group as a side chain. A glycol of 500 or less is preferred.
That is, the polyisocyanate of this embodiment is preferably one in which the isocyanate group of hexamethylene diisocyanate and the hydroxyl group of the glycol are bonded by a condensation reaction.

  More specifically, the polyisocyanate may be a multimer of hexamethylene diisocyanate as shown in the following structural formulas (1) and (2) (the following structural formula (1)) or a low molecular weight such as trimethylolpropane. Any one of adducts obtained by bonding glycol and hexamethylene diisocyanate by urethane bonds (the following structural formula (2)) or a mixture of one or more of these is preferable. It is preferable to use a mixture of one or more polyisocyanates represented by 1) and one or more polyisocyanates represented by the following structural formula (2).

  When a mixture containing a polyisocyanate represented by the following structural formula (1) and a polyisocyanate represented by the following structural formula (2) is employed as the polyisocyanate for constituting the polyurethane elastomer. Is preferably formed such that the number of polyisocyanate molecules represented by the following structural formula (1) is larger than the number of polyisocyanate molecules represented by the following structural formula (2).

In addition, as the polyisocyanate, a part of those represented by the structural formulas (1) and (2), or a polyhydric alcohol having an ether bond such as diethylene glycol instead of the whole, 2-ethyl- A polyhydric alcohol having a side chain alkyl group such as 1,6-hexanediol, or a polyhydric alcohol having both an ether bond and a side chain alkyl group such as dipropylene glycol and hexamethylene diisocyanate are urethane-bonded. You may employ | adopt the polyisocyanate couple | bonded by.
That is, a polyisocyanate having an isocyanate group at the molecular terminal obtained by bonding a hydroxyl group of these polyhydric alcohols and an isocyanate group of hexamethylene diisocyanate can also be suitably used as the polyisocyanate for constituting the polyurethane elastomer of this embodiment. .

In addition, the polyisocyanate of the present embodiment preferably has an average functional group number of 2.5 or more and 6.0 or less, and more preferably 3.0 or more and 5.8 or less. It is particularly preferably 5 or more and 5.5 or less.
Further, the polyisocyanate in this embodiment preferably has an NCO% of 12% or more and 20% or less.

In addition, the polyurethane elastomer for forming the elastic body layer 3 of the present embodiment can appropriately contain a polyol other than the polyester polyol, a chain extender, and the like as long as the physical properties of the elastic body layer are not substantially adversely affected. .
In addition, the elastic layer 3 of the present embodiment has a conductive filler other than the carbon black and the graphite, other inorganic fillers, and a silane coupling agent within a range that does not substantially adversely affect the physical properties of the elastic layer. , Plasticizers, antioxidants, anti-aging agents, ultraviolet absorbers, colorants, antibacterial agents and the like can be appropriately contained.

  The surface layer 4 formed on the outer periphery of the elastic layer 3 can be formed of the same material as the surface layer of a general developing roller, and the carbon is applied to a base polymer such as a fluororesin or a thermoplastic polyurethane. A resin composition containing a conductive filler such as black or graphite may be used.

  Furthermore, the cored bar 2 can be the same as a general developing roller, and the cored bar 2 is made of, for example, a metal such as copper, iron, aluminum, nickel, or an alloy thereof, or the like. , Hot dipping, electrolytic plating, electroless plating, and the like can be performed.

The developing roller 1 of this embodiment can be manufactured using the raw materials as described above, for example, as follows.
First, the core metal 2 is set at the center of a mold having a cylindrical cavity slightly larger than the outer diameter of the elastic layer 3 to be produced, and the polyester polyol, the polyisocyanate, and the carbon black described above are set. And the graphite are prepared, and the carbon black and the graphite are once dispersed in the polyester polyol using a mixer, a bead mill or the like to prepare a dispersion.
Next, a mixed liquid obtained by mixing the dispersion and the polyisocyanate is poured into the mold, and the mixed liquid is cured together with the mold to be cured in the mold, and then demolded and further heated. Post-crosslinking of the polyurethane elastomer is performed, and the outer diameter is adjusted by surface polishing to produce a semi-finished product in which the elastic body layer 3 is provided on the outer periphery of the cored bar 2.

  Further, for example, a coating liquid prepared to disperse a resin composition for forming a surface layer in a solvent so as to have an appropriate viscosity is applied to the surface of the semi-finished product and dried to develop the developing roller of this embodiment Can be produced.

At this time, since the polyester polyol is made of the starting material as described above, even when carbon black having a high DBP oil absorption amount is dispersed, the viscosity becomes low, and the workability in casting is improved. it can.
In addition, the developing roller 1 of the present embodiment has a long-time energization because the elastic layer 3 is formed of a conductive elastomer containing carbon black having a structure with a high DBP oil absorption amount and developed together with graphite. Even if the process is performed, there is little change in electrical characteristics, and the electrophotographic apparatus can exhibit a stable print quality.

  The electroconductive elastomer member for an electrophotographic apparatus of the present invention is suitably used not only in a liquid developing electrophotographic apparatus but also in a dry developing electrophotographic apparatus. Specifically, for example, a printer such as a laser beam printer, a copying machine, etc. It can be used for facsimiles.

The electroconductive elastomer member for an electrophotographic apparatus of the present invention is not limited to a member (developing member) such as a developing roller for adhering toner to a photoreceptor, and the conductivity changes by light irradiation. Examples thereof include a charging member such as a charging roller for charging the photoconductor, and a transfer member such as a transfer roller for transferring the toner adhering to the photoconductor to a transfer medium.
Further, in this embodiment, a developing roller formed using a material other than the conductive elastomer called a cored bar is cited as an example of the conductive elastomer member for an electrophotographic apparatus of the present invention. The formed belt-like or sheet-like member is also intended as a conductive elastomer member for an electrophotographic apparatus of the present invention, and is not particularly limited with respect to the form, like a roller-like member such as a developing roller. .

EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.

<Evaluation 1: Production of conductive roller>
A roller was produced as a conductive elastomer member for an electrophotographic apparatus.
And the following materials were used for preparation of this roller.

(Conductive filler)
Carbon black 1 (CB11):
Lion Corp. conductive carbon black (average particle diameter of 39.5nm, DBP oil absorption of 360cm ³ / 100g), trade name "Ketchen EC300J"

・ Carbon black 2 (CB12):
Manufactured by Mitsubishi Chemical Corporation conductive carbon black (average particle diameter 21 nm, DBP oil absorption 175cm ³ / 100g), trade name "# 3400"

・ Graphite 1 (GF11):
Natural graphite (average particle size 5μm) manufactured by Nippon Graphite Co., Ltd., trade name “UP5”

(Polyol)
Polyol 1 (PO11):
Glycol having 4 or more carbon atoms having side chain (A1): 3-methyl-1,5-pentanediol Linear glycol having 2 or 3 carbon atoms (A2): ethylene glycol Glycol having 3 or more hydroxyl groups (A3 ): Trimethylolpropane A polyol component (A) containing (A1) :( A2) :( A3) in a mass ratio of 100: 22.5: 18.0, and adipic acid (B) A polyester polyol having a number average molecular weight of 2000 and a hydroxyl value of 84.9 mg / KOHg obtained by reacting at a mass ratio of 100: 123.4 (A: B)

-Polyol 2 (PO12):
A low-branched polyol which is a polycondensation ester of diethylene glycol, trimethylolpropane and adipic acid (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Nitsporan N-4032”, average functional group number 2.35, hydroxyl value 60 mg / KOHg)

(Polyisocyanate)
-Polyisocyanate 1 (PI11):
Tolylene diisocyanate (mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate [(2,4-TDI) / (2,6-TDI) = 80/20 mass ratio]

(Roller sample formation: No. 1)
Dispersion so that the polyol 1 (PO11), the carbon black 1 (CB11), and the graphite 1 (GF11) have a mass ratio of 100: 0.6: 3.5 (PO11: CB11: GF11). After adjusting (DL1), the dispersion (DL1) and the polyisocyanate 1 (PI11) were mixed at a mass ratio of 100: 9.7 (DL1: PI11) to prepare a mixed solution.
A metal core having a diameter of 6 mm was charged in a molding die having an inner cylindrical space having an inner diameter of 20 mm and a length of 300 mm so as to pass through the center of the inner space, and the mixed liquid was cast.
Then, the mixed liquid is heated and cured together with a molding die to produce a molded product having a thickness (diameter) of 20 mm in which an elastic body layer is mounted on the outer periphery of the core metal, and the outer periphery of the molded product is polished to a roller. A sample was prepared.
The roller sample is formed so that the elastic layer has a thickness in the radial direction of 6 mm and a length in the axial direction of 23 cm so that the thickness (diameter) of the elastic layer forming portion is 18 mm. Produced.
And the said liquid mixture became a low-viscosity thing, and the casting operation | work was easy.
The final carbon black 1 (CB11) content in the elastic layer was 0.5 mass%, and the graphite 1 (GF11) content was 3.0 mass%.

(Electrical resistance stability evaluation)
A stainless steel plate having an area larger than the area of the elastic layer formed on the roller sample in plan view is prepared, the roller sample is placed on the stainless steel plate, and the elastic layer is made of stainless steel over the entire length. The roller sample was placed in contact with the upper surface of the plate.
In this state, the roller specimen is pressed against the stainless steel plate by applying a load of 5N (10N in total) to both ends of the metal core, and the outer peripheral surface of the elastic layer is applied to the stainless steel plate with a substantially constant nip width. Touched.
Then, a 100 μA direct current between the metal core and the stainless steel plate is continuously energized for 5 hours using a high-voltage power supply (manufactured by Trek Japan Co., Ltd., model name “610C”). The ratio (R1 / R0) of the resistance value (R1) 1 hour after the start of energization and the ratio (R5 / R0) of the resistance value (R5) 5 hours after the start of the energization were respectively evaluated.
A result is shown in following Table 1 with each resistance value (R0, R1, R5).

(Impedance measurement)
In the same manner as in the current resistance resistance evaluation, the core was pressed using a LCR meter (manufactured by Hioki Electric Co., Ltd., model name “3522-50”) in a state where the roller sample was pressed with a total load of 10 N. An AC voltage having an effective value of 500 mV was applied between gold and the stainless steel plate at a frequency ranging from 1 Hz to 20 kHz, and impedance measurement was performed to measure the phase difference of the current with respect to the voltage.
At this time, the delay angle of the current waveform with respect to the voltage waveform was between 1 Hz and 20 kHz, and between −90 ° and −60 °.
Table 1 below shows the smallest value of the delay angle (maximum value of the phase difference) among the delay angles of the current waveform with respect to the voltage waveform.

(No.2-No.23)
No. except that the types of carbon black used and the carbon black and graphite contents were changed as shown in Tables 1 to 3. A roller sample was prepared in the same manner as for No. 1 roller, and No. Evaluation was performed in the same manner as for one roller.
The results are shown in Tables 1-3.

In addition, No. 10, no. 12, no. 14, no. 16, no. 22, no. Regarding No. 23, an evaluation roller sample could not be obtained because the viscosity of the dispersion obtained by dispersing carbon black and graphite in a polyol was high and cast molding itself was difficult.
Therefore, it is preferable that the carbon black content is 0.5% by mass or more and 1% by mass or less and the graphite content is 3% by mass or more and 5% by mass or less in order to make the roller easy to manufacture. I understand that.

<Evaluation 2: Production of conductive roller>
A roller was produced as a conductive elastomer member for an electrophotographic apparatus.
And the following materials were used for preparation of this roller.

(Conductive filler)
Carbon black 1 (CB21):
Mitsubishi Chemical Co., Ltd. carbon black (particle diameter of 24nm, DBP oil absorption of about 45cm ³ / 100g), the trade name of "# 45L"

Carbon black 2 (CB22):
Mitsubishi Chemical Co., Ltd. carbon black (particle diameter of 23nm, DBP oil absorption of about 64cm ³ / 100g), the trade name of "# 47"

Carbon black 3 (CB23):
Mitsubishi Chemical Co., Ltd. carbon black (particle diameter of 24nm, DBP oil absorption of about 78cm ³ / 100g), the trade name of "# 44"

Graphite 1 (GF21):
Natural graphite (average particle size 5μm) manufactured by Nippon Graphite Co., Ltd., trade name “UP5”

(Polyol)
Polyol 1 (PO21):
Glycol having 4 or more carbon atoms having side chain (A1): 3-methyl-1,5-pentanediol Linear glycol having 2 or 3 carbon atoms (A2): ethylene glycol Glycol having 3 or more hydroxyl groups (A3 ): Trimethylolpropane A polyol component (A) containing a mass ratio of (A1) :( A2) :( A3) of 100: 5.8: 14.8, and adipic acid (B) Polyester polyol having a number average molecular weight of 2000 and a hydroxyl value of 86 mg / KOHg, which are reacted at a mass ratio of 100: 111.8 (A: B)

Polyol 2 (PO22):
A low-branched polyol which is a polycondensation ester of diethylene glycol, trimethylolpropane and adipic acid (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Nitsporan N-4032”, average functional group number 2.35, hydroxyl value 60 mg / KOHg)

(Polyisocyanate)
-Polyisocyanate 1 (PI21):
Tolylene diisocyanate (mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate [(2,4-TDI) / (2,6-TDI) = 80/20 mass ratio]

(No. 24 Formation of roller sample)
Dispersion so that the polyol 1 (PO21), the carbon black 1 (CB21), and the graphite 1 (GF21) have a mass ratio of 100: 1.9: 3.5 (PO21: CB21: GF21). After adjusting (DL2), this dispersion (DL2) and the polyisocyanate 1 (PI21) were mixed at a mass ratio of 100: 11.1 (DL2: PI21) to prepare a mixed solution.
A metal core having a diameter of 6 mm was charged in a molding die having an inner cylindrical space having an inner diameter of 20 mm and a length of 300 mm so as to pass through the center of the inner space, and the mixed liquid was cast.
Then, the mixed liquid is heated and cured together with a molding die to produce a molded product having a thickness (diameter) of 20 mm in which an elastic body layer is mounted on the outer periphery of the core metal, and the outer periphery of the molded product is polished to a roller. A sample was prepared.
The roller sample is formed so that the elastic layer has a thickness in the radial direction of 6 mm and a length in the axial direction of 23 cm so that the thickness (diameter) of the elastic layer forming portion is 18 mm. Produced.
And the said liquid mixture became a low-viscosity thing, and the casting operation | work was easy.
The final carbon black 1 (CB21) content in the elastic layer was 1.6 mass%, and the graphite 1 (GF21) content was 3.0 mass%.

(Electrical resistance stability evaluation)
A stainless steel plate having an area larger than the area of the elastic layer formed on the roller sample in plan view is prepared, the roller sample is placed on the stainless steel plate, and the elastic layer is made of stainless steel over the entire length. The roller sample was placed in contact with the upper surface of the plate.
In this state, the roller specimen is pressed against the stainless steel plate by applying a load of 5N (10N in total) to both ends of the metal core, and the outer peripheral surface of the elastic layer is applied to the stainless steel plate with a substantially constant nip width. Touched.
Then, a 100 μA direct current between the metal core and the stainless steel plate is continuously energized for 5 hours using a high-voltage power supply (manufactured by Trek Japan Co., Ltd., model name “610C”). The ratio (R1 / R0) of the resistance value (R1) 1 hour after the start of energization and the ratio (R5 / R0) of the resistance value (R5) 5 hours after the start of the energization were respectively evaluated.
The results are shown in Table 4 below together with each resistance value (R0, R1, R5).

(Impedance measurement)
In the same manner as in the current resistance resistance evaluation, the core was pressed using a LCR meter (manufactured by Hioki Electric Co., Ltd., model name “3522-50”) in a state where the roller sample was pressed with a total load of 10 N. An AC voltage having an effective value of 500 mV was applied between gold and the stainless steel plate at a frequency ranging from 1 Hz to 20 kHz, and impedance measurement was performed to measure the phase difference of the current with respect to the voltage.
At this time, the delay angle of the current waveform with respect to the voltage waveform was between 1 Hz and 20 kHz, and between −90 ° and −60 °.
Table 4 below shows the smallest value of the delay angle (maximum value of the phase difference) among the delay angles of the current waveform with respect to the voltage waveform.

(No. 25-26)
No. except that the types of carbon black used and the carbon black and graphite contents were changed as shown in Tables 4-6. A roller sample was prepared in the same manner as the 24 roller, and No. Evaluation was performed in the same manner as for 24 rollers.
The results are shown in Tables 4-6.
In Comparative Examples 16, 19, 22, and 23, it is possible to obtain roller samples that can be evaluated because the dispersion of carbon black and graphite dispersed in polyol has a high viscosity and cast molding itself is difficult. There wasn't.

In these tables, no. 1-8, No. 1 In 24-41, in the impedance measurement, the phase difference of the current with respect to the voltage is in the range of −90 ° to −60 °, which shows that the resistance stability is exhibited.
That is, it can be seen that according to the present invention, a conductive elastomer member for an electrophotographic apparatus having a stable electrical resistance value can be provided.
In the evaluation 1 DBP oil absorption using the following carbon black 175cm ^3/100 g or more 360 cm ^3/100 g, usually the resistance value of ^{1 × 10 4 Ω~1 × 10 5} Ω required for the developing roller stably It can also be understood from the above table.

  1: developing roller (conductive elastomer member for electrophotographic apparatus), 2: cored bar, 3: elastic layer, 4: surface layer

Claims (4)

A conductive elastomer member for an electrophotographic apparatus formed by a conductive elastomer containing a polyurethane elastomer obtained by reacting a polyol and a polyisocyanate, and a conductive filler,
A glycol in which the polyol contains at least a glycol having 4 or more carbon atoms (A1) having a side chain, a linear glycol having 2 or 3 carbon atoms (A2), and a glycol having 3 or more hydroxyl groups (A3). The component polyol (A) is a polyester polyol having a number average molecular weight of 2000 or more and 3000 or less and a hydroxyl value of 80 mg / KOHg or more and 88 mg / KOHg or less obtained by reacting the component (A) with adipic acid (B), and the conductive elastomer is the conductive filler. And at least graphite and carbon black. When an AC voltage having an effective value of 500 mV is applied at a frequency ranging from 1 Hz to 20 kHz and the phase difference of the current with respect to the voltage is measured, the phase difference is −90 ° or more and −60 The resistance value when the DC current of 100μA is continuously applied for 5 hours is Electrophotographic apparatus for conductive elastomer member, characterized in that it has an electrical characteristic that is twice or less the resistance value in the. The conductive elastomer, the carbon black in a proportion of 1 wt% or less than 0.5 wt%, DBP oil absorption of the carbon black is not more than 175cm ^3/100 g or more 360 cm ^3/100 g, and the graphite 2. The conductive elastomer member for an electrophotographic apparatus according to claim 1, wherein the graphite has an average particle diameter of 3 μm or more and 10 μm or less.   The electroconductive elastomer member for an electrophotographic apparatus according to claim 1 or 2, which is a roller having a cylindrical elastic body made of the electroconductive elastomer mounted on an outer periphery of a core metal.   4. A conductive elastomer member for an electrophotographic apparatus according to claim 3, which is a developing roller for a liquid developing electrophotographic apparatus.

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