JP2009008893A - Charging roll for electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charging roll for an electrophotographic apparatus excellently preventing adhesion of toner and external additives while maintaining its charging performance. <P>SOLUTION: The charging roll for an electrophotographic apparatus has a surface layer comprising a cured product of a UV-curable conductive composition containing (A) a monofunctional (meth)acrylate monomer having an ethylene oxide unit introduced into its molecular structure and (B) urethane (meth)acrylate. The mass ratio of the component (A) to the component (B) is preferably in a range of 20/80 to 80/20. The number of (meth)acryloyl groups contained in one molecule of the urethane (meth)acrylate (B) is preferably ≥6. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a charging roll for electrophotographic equipment.

  In recent years, electrophotographic apparatuses such as copying machines, printers, and facsimiles that employ an electrophotographic system have been widely used. In this type of electrophotographic apparatus, the surface of the photosensitive drum is charged in advance by a charging roll before the electrostatic latent image is formed.

  As charging methods for charging rolls, there are a DC charging method that facilitates energy saving and cost reduction by lowering the voltage of the power supply, and an AC / DC superimposed charging method that facilitates stable charging for higher speed and higher image quality. It has been known.

  The AC / DC superposition charging method has the problem of requiring two types of power supply, increasing the power supply capacity, and the problem of generating charging noise due to AC waves. The number of cases in which the DC charging method is adopted for the charging rolls is also increasing.

  As the charging roll, for example, an ion conductive rubber base layer is formed on the outer periphery of the shaft body, and in order to prevent toner and external additives from adhering to the outer periphery of the rubber base layer, a silicone resin or a fluorine resin is used. Those having a surface layer having a high releasability, etc. are known.

  In recent years, due to demands for low VOC and energy saving, the surface layer has been formed with ultraviolet curable resin or the like without suppressing the solvent as much as possible and without removing the solvent by heat treatment.

  For example, in Patent Document 1, a base layer made of conductive silicone rubber is formed on the outer periphery of a cored bar as a shaft body, and a surface layer is formed on the outer periphery of the base layer by ultraviolet-curing an ultraviolet curable conductive composition. A charging roll formed with is described.

  Specifically, the composition includes 50 parts by weight of trimethylolpropane ethylene oxide-modified triacrylate, 50 parts by weight of methoxypolyethylene glycol acrylate, 3 parts by weight of an ionic conductive agent, and 1 part by weight of a photoinitiator. Is disclosed.

JP 2006-274242 A

  However, conventionally known charging rolls have room for improvement in the following points.

  Recently, along with the shift to DC power supply due to lower prices of OA devices and the longer life of cartridges that lead to reduction in printing costs, OA devices are required to maintain high image quality for a longer time than before. . Along with this, charging rolls incorporated in OA equipment are also required to cope with this.

  However, the charging roll of Patent Document 1 has a relatively high surface tackiness (viscosity). Therefore, when the charging roll is used, the toner and external additives remaining on the photosensitive drum may adhere to the roll surface (filming), and it may be difficult to maintain stable charging performance for a long period of time. found.

  The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is to provide a charging roll for an electrophotographic apparatus having excellent adhesion resistance to toner and external additives while maintaining charging performance. It is to provide.

  In order to solve the above-mentioned problems, the charging roll for electrophotographic equipment according to the present invention comprises (A) a monofunctional (meth) acrylate monomer in which an ethylene oxide unit is introduced in the molecular structure, and (B) The gist is that it comprises a cured product of an ultraviolet curable conductive composition containing urethane (meth) acrylate.

  Here, the component (A) / component (B) (mass ratio) is preferably in the range of 20/80 to 80/20.

  The number of (meth) acryloyl groups contained in one molecule of the (B) urethane (meth) acrylate is preferably 6 or more.

  Moreover, the said ultraviolet curable conductive composition is good to contain the (C) ionic conductive agent.

  In addition, as a roll configuration of the charging roll, a configuration including a shaft body, a base layer formed on the outer periphery of the shaft body, and the surface layer formed on the outer periphery of the base layer, or a shaft body and a shaft body A configuration having a base layer formed on the outer periphery of the base layer, an intermediate layer formed on the outer periphery of the base layer, and the surface layer formed on the outer periphery of the intermediate layer is preferable.

  At this time, the surface layer preferably contains roughness forming particles.

  The surface layer of the charging roll for electrophotographic equipment according to the present invention is made of a cured product of an ultraviolet curable conductive composition containing a specific component (A) and a component (B).

  That is, by using the component (A), it becomes easy to lower the electric resistance value of the cured product, which is advantageous for securing charging performance. Further, by using the component (B), the hardness of the cured product becomes relatively high, the friction coefficient becomes small, and the tack property is lowered. Therefore, the adhesion resistance to the toner and the external additive is improved, and the chargeability is easily maintained for a long time.

  Therefore, according to the charging roll of the present invention, it is possible to maintain the image quality of OA equipment such as a printer and a copying machine in which it is incorporated for a long period of time.

  Here, when the component (A) / component (B) (mass ratio) is within a specific range, the balance of electrical resistance and adhesion resistance of the surface layer is excellent.

  Moreover, when the number of (meth) acryloyl groups contained in one molecule of the component (B) urethane (meth) acrylate is 6 or more, it is easy to ensure good adhesion resistance.

  Moreover, when the ultraviolet curable conductive composition contains (C) an ion conductive agent, it becomes easy to adjust the electric resistance of the cured product. Further, resistance unevenness is relatively less likely to occur.

  Further, when the surface layer contains roughness forming particles, the minute gap increases and the discharge portion increases, which contributes to uniform charge and improved charge amount.

  Hereinafter, the charging roll for electrophotographic equipment according to the present embodiment (hereinafter, also referred to as “the present charging roll”) will be described.

  FIG. 1 is a circumferential sectional view showing an example of the present charging roll. For example, as shown in FIG. 1, the charging roll 10 has a laminated structure in which a base layer 14 and a surface layer 16 are laminated in this order on the outer periphery of a shaft body 12.

  FIG. 2 is a circumferential sectional view showing another example of the present charging roll. The present charging roll 10 is not limited to the embodiment shown in FIG. 1, and as shown in FIG. 2, an intermediate layer 18 may be arbitrarily laminated between the base layer 14 and the surface layer 16.

  Each of the base layer, the surface layer, and the intermediate layer may be composed of a single layer or a plurality of layers. Preferably, the base layer, the surface layer, and the intermediate layer are preferably composed of a single layer from the viewpoint of simplifying the laminated structure and improving the roll productivity.

  Any shaft body may be used as long as it has conductivity. Specific examples include solid bodies made of metal such as iron, stainless steel, and aluminum, and a cored bar made of a hollow body. Moreover, you may apply | coat an adhesive agent, a primer, etc. to the surface of a shaft body as needed. The adhesive, primer, etc. may be made conductive as necessary.

  The base layer may be in any form of non-foam (solid) or foam (sponge). As the main material for forming the base layer, a rubber elastic material can be suitably used. Specific examples of the rubber elastic material include hydrin rubber, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), polynorbornene rubber, silicone rubber, butadiene rubber (BR), and isoprene rubber (IR). And natural rubber (NR), acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (H-NBR), and the like. These may be used alone or in combination.

  As the rubber elastic material, hydrin rubber, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR) and the like are preferable from the viewpoint of electrical resistance controllability, processability, and the like.

The base layer, for imparting conductivity, carbon black, _{graphite, c-TiO 2, c-} ZnO, c-SnO 2 (c- means conductive.), Ion conductive agent (quaternary ammonium salt, Conventionally known conductive agents such as borates and surfactants can be appropriately added to the above materials. Furthermore, if necessary, a foaming agent, a crosslinking agent, a crosslinking accelerator, a softening agent (oil) and the like may be appropriately added.

  In order to form the base layer on the outer periphery of the shaft body, the shaft body is coaxially installed in the hollow portion of the roll molding die, injected with the composition for forming the base layer, and heated and cured. Demolding (casting method), extruding the base layer forming composition on the surface of the shaft (extrusion method), etc. In addition, when a plurality of base layers are formed, an operation according to the above method may be repeated.

  Although the thickness of a base layer is not specifically limited, Preferably, it can select from the range of 0.1-10 mm, More preferably, it is 1-5 mm.

The volume resistivity of the base layer is preferably in the range of 10 ² to 10 ¹⁰ Ω · cm, more preferably 10 ³ to 10 ⁹ Ω · cm, and even more preferably in the range of 10 ⁴ to 10 ⁸ Ω · cm. You can choose from.

  In this charging roll, the surface layer is formed from a cured product of an uncured ultraviolet curable conductive composition (hereinafter, also simply referred to as “conductive composition”) containing a specific component. This surface layer can function as a protective layer on the roll surface.

  Here, the conductive composition contains (A) a monofunctional (meth) acrylate monomer and (B) urethane (meth) acrylate as specific components.

  In addition, in this invention, monofunctional means having one (meth) acryloyl group in 1 molecule of (meth) acrylate monomers. Polyfunctional means having two or more functional groups such as a (meth) acryloyl group involved in the photopolymerization reaction.

  (A) The monofunctional (meth) acrylate monomer has an ethylene oxide unit introduced in the molecular structure. This ethylene oxide unit contributes to an improvement in compatibility with an ionic conductive agent that may be contained in the conductive composition.

  The content of the ethylene oxide unit introduced into the molecular structure is preferably in the range of 1 to 98% by mass, more preferably 20 to 98, from the viewpoint of easily reducing the electric resistance of the cured product. It is good that it exists in the range of 40 mass%, More preferably in the range of 40-98 mass%.

  In addition, content of an ethylene oxide unit can be measured using NMR (nuclear magnetic resonance apparatus) etc., for example.

  (A) The monofunctional (meth) acrylate monomer may have one or more other units introduced into the molecular structure in addition to the ethylene oxide unit.

  Examples of the other units include alkylene oxide units having 3 to 20 carbon atoms, trimethylolpropane units, pentaerythritol units, ethylhexyl carbitol units, glycerin units, nonylphenol units, paracumylphenol units, bisphenol A units, Examples include units containing cyclic unsaturated structures such as styrene oxide units, isocyanuric acid units, bisphenol F units, phthalic acid units, and phenoxy units.

  Specific examples of the (A) monofunctional (meth) acrylate monomer include, for example, phenoxyethylene oxide modified acrylate (Chemical Formula 1 in Table 1), nonylphenol ethylene oxide modified acrylate (Chemical Formula 2 in Table 1), methoxyethylene oxide modified, and the like. Acrylate (Chemical Formula 3 etc. in Table 1), ethoxyethylene oxide modified acrylate (Chemical Formula 4 etc. in Table 1), 2 ethylhexyl ethylene oxide modified acrylate (Chemical Formula 5 in Table 1), butoxyethylene oxide modified acrylate (Chemical Formula 6 in Table 1), Examples thereof include ethylene oxide-modified cresol acrylate (Chemical 7 in Table 1 and the like). These may be contained alone or in combination of two or more.

  On the other hand, (B) urethane (meth) acrylate is a compound having both a urethane bond and a (meth) acryloyl group. Specific examples of the (B) urethane (meth) acrylate include, for example, a type in which a hydroxyl group-containing acrylate is directly added to an isocyanate compound, a type in which a hydroxyl group-containing acrylate is directly added to a polyisocyanate compound such as isocyanurate, and a polyol. A urethane (meth) acrylate such as a type in which a hydroxyl group-containing acrylate is added to a reaction product of an isocyanate compound can be exemplified. These may be contained alone or in combination of two or more.

  Examples of the isocyanate compound include pure MDI, crude MDI, and IPDI. Examples of the polyol include ester-based and ether-based polyols. Examples of the hydroxyl group-containing acrylate include hydroxyethyl acrylate, hydroxypropyl acrylate, and pentaerythritol triacrylate.

  Among these, urethane (meth) acrylates of a type in which a hydroxyl group-containing acrylate is added to a reaction product of a polyol and an isocyanate compound can be suitably used from the viewpoint of flexibility and strength.

  In addition, the number of (B) urethane (meth) acrylates contained in one molecule is preferably 6 or more, more preferably from the viewpoint of easily ensuring good adhesion resistance. 8 or more, and even more preferably 10 or more.

  The upper limit number of the (meth) acryloyl group is not particularly limited, but when the number of the (meth) acryloyl group is excessive, there is a tendency that the hardness increases and the flexibility decreases. It is done. Therefore, the number is preferably 20 or less.

  From the viewpoint of improving the balance of electrical resistance and adhesion resistance of the surface layer after curing, the conductive composition is preferably (A) component / (B) component (mass ratio), preferably 20 / It is good that it is in the range of 80-80 / 20, more preferably 25 / 75-75 / 25, and still more preferably 30 / 70-70 / 30.

  The conductive composition may contain other photopolymerization components as necessary in addition to the components (A) and (B).

  As other photopolymerization components, for example, a monofunctional (meth) acrylate monomer in which no ethylene oxide unit is introduced into the molecular structure, a polyfunctional (meth) acrylate in which an ethylene oxide unit is introduced into the molecular structure. Examples thereof include acrylate monomers and polyfunctional (meth) acrylate monomers in which ethylene oxide units are not introduced into the molecular structure.

  Further, the conductive composition is cured by photopolymerization with light such as ultraviolet rays, and contains a photopolymerization initiator.

  The photopolymerization initiator is not particularly limited, and any photopolymerization initiator can be used as long as it can be normally used.

  Specific examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, 2-methylbenzoin, benzyl, benzyldimethylketal, diphenyl sulfide, and tetramethylthiuram monosulfide. , Diacetyl, eosin, thionine, mihira-ketone, anthracene, anthraquinone, acetophenone, α-hydroxyisobutylphenone, p-isopropyl αhydroxyisobutylphenone, α · α 'dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone 2,2-dimethoxy-2-phenylacetophenone, methylbenzoyl formate, 2-methyl-1- [4- (methylthio) phenyl] .2.morpholino-propene, thioxanthone , Benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-monforinopropanone 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 1,2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyryl) titanium), -Hydroxy-2-methyl-1-phenylpropan-1-one, bisacylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, (η5-2,4-cyclopentadien-1-yl ) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-) and the like. These can be used alone or in combination of two or more.

  The lower limit of the content of the photopolymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the polymerization component contained in the conductive composition. Even more preferably, it is 1 mass part or more.

  On the other hand, the upper limit of the content of the photopolymerization initiator is preferably 50 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the polymerization component contained in the conductive composition. good.

  The conductive composition preferably further contains (C) an ion conductive agent as a preferred additive component. (C) When an ionic conductive agent is included, it is easy to adjust the electrical resistance of the surface layer, which is a cured product of the conductive composition. Further, resistance unevenness is relatively less likely to occur.

  The ionic conductive agent is not particularly limited, and any ionic conductive agent can be used as long as it can be used in the field of electrophotographic equipment.

Specific examples of the ionic conductive agent include, for example, quaternary ammonium perchlorate represented by Chemical Formula 8 (in the chemical formula 8, R ₁ , R ₂ , R ₃ , and R ₄ have 1 carbon atom) A borate represented by Chemical formula 9 (which represents a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group, xylyl group, etc.) In formula 9, R ₁ , R ₂ , R ₃ , R ₄ are alkyl groups having 1 to 18 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, phenyl group, xylyl group, etc. M ^{n +} is an alkali metal ion or an alkaline earth metal ion, and represents a lithium ion, a sodium ion, a potassium ion, a calcium ion, or the like. These may be used alone or in combination.

(Chemical formula 8)

(Chemical 9)

  The lower limit value of the content of the ionic conductive agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 100 parts by mass of the polymerization component contained in the conductive composition. More preferably, it is 1 mass part or more.

  On the other hand, the upper limit value of the content of the ionic conductive agent is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the polymerization component contained in the conductive composition. .

  The conductive composition preferably contains roughness forming particles. When the particles for roughness formation are included, irregularities are easily formed on the surface of the surface layer, which is a cured product of the conductive composition. For this reason, the minute gap formed between the surface of the surface of the charging roll and the surface of the photosensitive drum is increased, and the number of discharge portions is increased, which easily contributes to uniform charge and improved charge amount.

  Specific examples of the roughness forming particles include urethane particles, crosslinked polymethyl methacrylate particles, acrylic particles, urea resin particles, amide particles and other resin particles, rubber particles, silica particles, and the like. It can be illustrated as. These may be contained alone or in combination of two or more.

  The average particle diameter of the roughness forming particles can be selected to be an optimum value in consideration of the thickness of the surface layer described later.

  The average particle diameter of the roughness forming particles is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and still more preferably 5 to 15 μm.

  In addition to the above, the conductive composition may include a light stabilizer, a viscosity modifier, an anti-aging agent, a processing aid, a lubricant, a flame retardant, a plasticizer, a foaming agent, a filler, a crosslinking agent, and a crosslinking aid. 1 type, or 2 or more types of various additives, such as an agent, a dispersing agent, an antifoamer, a pigment, and a mold release agent, may be contained.

  The conductive composition described above has a viscosity (25 ° C.) of preferably 100,000 mPa · s or less, more preferably 10,000 mPa · s or less, from the viewpoint of good handleability. From the standpoint of excellent coating properties and the like, it is even more preferably 5000 mPa · s or less.

  From the viewpoint of adjusting the viscosity within the above range, the conductive composition is made of an organic solvent such as methyl ethyl ketone, toluene, acetone, ethyl acetate, butyl acetate, methyl isobutyl ketone (MIDK), THF, DMF, methanol, ethanol, etc. A solvent such as a water-soluble solvent may be appropriately contained. Further, it may be solventless.

  The conductive composition described above can be prepared by weighing various materials so as to have a desired composition and mixing them by a mixing means such as a stirrer or a sand mill. In addition, you may perform a defoaming process etc. after mixing during mixing.

  As a method for forming a surface layer on the outer periphery of the base layer or the intermediate layer using such a conductive composition, for example, various coating methods such as a roll coating method, a dipping method, and a spray coating method can be applied. .

  More specifically, for example, the conductive composition is applied on the surface of a roll body in which a base layer and an intermediate layer are arbitrarily formed on a shaft body by a roll coating method, and cured by irradiating ultraviolet rays. Examples of such a method include a method of immersing the roll body in a storage tank in which the conductive composition is stored, and a method of curing the roll body by irradiating it with ultraviolet rays. In the case of containing a solvent, in the case of containing a monomer component, heat treatment may be performed after ultraviolet curing.

  These coating methods may be used alone or in combination. The coating method may be repeated once or twice or more.

  The thickness of the surface layer is not particularly limited, but is preferably 0.01 to 100 μm, and more preferably 0.1 to 20 μm, from the viewpoint of hardly increasing the electrical resistance and suppressing the increase in roll hardness. Even more preferably, it may be selected from the range of 0.3 to 10 μm.

The volume resistivity of the surface layer is preferably 1 × 10 ⁴ to 1 × 10 ⁹ Ω · cm, more preferably 1 × 10 ⁵ to 1 × 10 ⁸ Ω · cm, from the viewpoint of the electrical resistance controllability of the roll. It can be selected from the range of cm.

  As described above, the charging roll may have an intermediate layer. The intermediate layer can function as a resistance adjustment layer.

  A rubber elastic material can be suitably used as the main material for forming the intermediate layer. Specific examples of rubber elastic materials include hydrin rubber (ECO), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), polynorbornene rubber, silicone rubber, butadiene rubber (BR), and isoprene rubber. (IR), acrylic rubber (ACM), chloroprene rubber (CR), urethane rubber, urethane elastomer, fluorine rubber, natural rubber (NR), acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (H-NBR) ) And the like. These may be used alone or in combination.

  As the rubber elastic material, silicone rubber, acrylonitrile-butadiene rubber, hydrin rubber, urethane elastomer, and the like are preferable from the viewpoints of electric resistance controllability, sag resistance, and the like.

The intermediate layer, for imparting conductivity, carbon black, _{graphite, c-TiO 2, c-} ZnO, c-SnO 2 (c- means conductive.), Ion conductive agent (quaternary ammonium salt, Conventionally known conductive agents such as borates and surfactants can be appropriately added to the above materials. Furthermore, if necessary, a foaming agent, a crosslinking agent, a crosslinking accelerator, a softening agent (oil) and the like may be appropriately added.

  In order to form the intermediate layer on the outer periphery of the base layer, the shaft body on which the base layer is formed is coaxially installed in the hollow portion of the roll molding die, and the intermediate layer forming composition is injected and heated. -After curing, the mold is removed (casting method), the intermediate layer forming composition is extruded on the surface of the base layer (extrusion method), and the like. In addition, when a plurality of intermediate layers are formed, an operation according to the above method may be repeated.

  Although the thickness of an intermediate | middle layer is not specifically limited, Preferably, it can select from the range of 0.001-2 mm, More preferably, it is 0.01-0.5 mm.

The volume resistivity of the intermediate layer is preferably in the range of 10 ⁴ to 10 ¹⁰ Ω · cm, more preferably 10 ⁵ to 10 ⁹ Ω · cm, and even more preferably in the range of 10 ⁶ to 10 ⁸ Ω · cm. You can choose from.

  Hereinafter, the present invention will be described in detail using examples.

1. Preparation of conductive composition used for surface layer of charging roll according to examples and comparative examples Weigh various materials so as to have a blending ratio (unit is part by mass) shown in Table 2 described later, and stir these with a stirrer. After mixing, each conductive composition used for the surface layer of the charging roll according to Examples 1 to 9 and Comparative Examples 1 and 2 was prepared by leaving it at room temperature for 24 hours (for defoaming).

Under the present circumstances, the various materials used at the time of preparation of each said electrically conductive composition are as follows.
・ Methoxyethylene oxide modified acrylate (CH ₂ ═CHCO (OCH ₂ CH ₂ ) _n OCH ₃ , n≈22) [manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester AM-230G”]
Phenoxyethyl ethylene oxide-modified acrylate _{(CH 2 = CHCO- (OCH 2} CH 2) 4 -O-C 6 H 5) [ manufactured by Toagosei Co., Ltd., "Aronix M101"]
- nonylphenol ethylene oxide modified acrylate _{(CH 2 = CHCO- (OCH 2} CH 2) 8 -C 6 H 4 -C 9 H 19) [ manufactured by Kyoeisha Chemical Co., Ltd., "LIGHT-ACRYLATE NP-8EA"]

-Urethane acrylate (1) (functional group number f = 6) [Daicel UCB, “Ebecryl 1290”]
Urethane acrylate (2) (functional group number f = 10) [Negami Kogyo Co., Ltd., “Art Resin UN904”]
Urethane acrylate (3) (functional group number f = 15) [manufactured by Negami Kogyo Co., Ltd., “Art Resin UN3320HS”]

Photoinitiator [Ciba Specialty Chemicals Co., Ltd., “Irgacure 127”]

・ Ionic conductive agent (trimethyloctadecyl ammonium perchlorate)

・ Urethane particles (Dainippon Ink & Chemicals, “Burnock CFB100”, average particle size 20 μm)

2. Characteristic Evaluation of Cured Product of Conductive Composition Next, property evaluation of the cured product of each obtained conductive composition was performed as follows.

(Coefficient of friction)
Each conductive composition was coated on a glass plate by the bar coating method, and then irradiated with ultraviolet rays to prepare each sheet-like cured product having a thickness of about 100 μm, a length of 100 mm, and a width of 100 mm. At this time, the distance between the UV lamp (mercury lamp type) of the UV irradiator (“UB031-2A / BM” manufactured by Igraphic Co., Ltd.) and each coated composition was 200 mm, and UV irradiation was performed for 50 seconds (UV intensity 100 mW / cm ² ).

  Next, using a friction coefficient measuring machine (“DFPM-S” manufactured by Kyowa Interface Science Co., Ltd.), the friction coefficient μs of each sheet-like cured product produced was measured under the measurement conditions of the tip: a hard sphere and a measurement load: 50 g. It was measured.

(Electric resistance)
A 1 cm square silver paste electrode was formed on the surface of each sheet-like cured product, and volume resistivity when 100 V was applied was measured according to JIS K6271 (double ring electrode method).

3. Production of charging roll for electrophotographic equipment (Preparation of composition for forming base layer)
First, 100 parts by mass of a hydrin rubber (manufactured by Daiso Corporation, “Epichromer CG102”), 1 part by mass of stearic acid (manufactured by Kao Corporation, “Lunac S-30”), and two types of zinc oxide (Mitsui) 5 parts by weight of Metal Industry Co., Ltd., 1.5 parts by weight of powder sulfur (manufactured by Tsurumi Chemical Industry Co., Ltd.), thiazole vulcanization accelerator (Ouchi Shinsei Chemical Industry Co., Ltd., “Noxeller DM ") 1.5 parts by mass, 0.5 parts by mass of thiuram vulcanization accelerator (manufactured by Ouchi Shinsei Chemical Co., Ltd.," Noxeller TS ") and 1 part by mass of trimethyloctadecyl ammonium perchlorate The composition for forming a hydrin rubber-based base layer was prepared by kneading with the above.

(Formation of base layer)
Next, the base layer-forming composition was poured into a cylindrical mold in which a core metal (diameter 6 mm) was set coaxially, heated at 180 ° C. for 45 minutes, cooled and demolded. Thereby, each roll body provided with the base layer (thickness 3 mm) which consists of a hydrin rubber type composition on the outer periphery of a metal core was produced.

(Formation of surface layer)
Next, using the roll coating method, each conductive composition is coated on the surface of each roll body, and irradiated with ultraviolet rays (ultraviolet intensity 100 mW / cm ² , irradiation for 50 seconds), and heat-treated at 130 ° C. for 30 minutes. Each conductive composition was cured. By the above operation, each surface layer (thickness 3 μm) was formed on the outer periphery of each base layer. This produced the charging roll (two-layer structure) which concerns on Examples 1-9 and Comparative Examples 1-2.

4). Charging roll characteristics evaluation (roll resistance)
Each charging roll is brought into line contact with the metal drum, and the metal drum is rotationally driven with a load of 500 g applied to both ends of the core metal of the roll, each charging roll is rotated at 30 rpm, and 500 V is applied. The electrical resistance between the metal core and the metal drum was measured as roll resistance.

(Adhesion resistance)
The adhesion resistance of the toner was evaluated by investigating filming. The evaluation was performed according to the following procedure.

  Each charging roll is incorporated in a cartridge of a color laser printer (“IPSIO CX-3000” manufactured by Ricoh Co., Ltd.), and a 5% printed character image (under an ambient temperature of 15 ° C. and a relative humidity of 10% RH) 15000 images were printed (images with 5% printed on the A4 paper area).

  After the endurance, using a mending tape (manufactured by Scotch, “810”), the surface of each charging roll was removed, and the concentration was measured with a Macbeth densitometer.

  At this time, when the density is 0.15 or less, the toner is hardly attached, and the adhesion resistance is “◎”. When the density is 0.16 to 0.2, However, when the density is 0.21 or more, the adhesion resistance is “x” because the toner adhesion is large.

(Chargeability)
Each charging roll was incorporated in a cartridge of a color laser printer (“IPSIO CX-3000” manufactured by Ricoh Co., Ltd.).

  Next, each photosensitive drum was rotated while being pressed against each charging roll, a voltage of DC-1200 V was applied, and the surface potential on the photosensitive drum at that time was measured. When the surface potential is −700 V or less, “◎” indicates that the charging property is excellent, and when the surface potential is more than −700 V to −600 V or less, “◯” indicates that the charging property is good. When the surface potential was more than −600 V, the chargeability was inferior, and “x” was assigned.

(Image evaluation)
Each charging roll is incorporated into a cartridge of a color laser printer (“IPSIO CX-3000” manufactured by Ricoh Co., Ltd.), and halftone images are output under conditions of an environmental temperature of 15 ° C. and a relative humidity of 10% RH. went. About the obtained initial image, the state of density unevenness was confirmed visually. A sample having no density unevenness was evaluated as “good”, and a sample having large density unevenness and could not withstand practical use was evaluated as “bad”.

  In Table 2, the evaluation result of the charging roll which concerns on an Example and a comparative example is shown collectively with the compounding ratio and material characteristic of the electroconductive composition for surface layer formation.

  Comparing Table 2 shows the following. That is, the surface of the charging roll according to Comparative Example 1 is made of a cured product of a conductive composition containing only the component (A) as a polymerization component.

  Therefore, it can be seen that although the resistance is low, the tackiness is high (the friction coefficient μs is high) and the toner adhesion resistance is poor.

  Moreover, the surface of the charging roll according to Comparative Example 2 is made of a cured product of a conductive composition containing only the component (B) as a polymerization component.

  Therefore, tackiness is low (friction coefficient μs is low) and filming is difficult to occur, but it has high resistance and is inferior in chargeability. As a result, it can be seen that a good image cannot be obtained.

  On the other hand, in each of the charging rolls according to the examples, each surface layer is a cured product of a conductive composition containing both the component (A) and the component (B) which are polymerization components defined in the present application. It has become.

  Therefore, it is possible to obtain a charging roll excellent in adhesion resistance to toner and external additives while maintaining charging performance by ensuring charging property by component (A) and lowering tackiness by component (B). Was confirmed.

  Therefore, according to such a charging roll, it can be said that the image quality of an OA device such as a printer or copying machine in which the charging roll is incorporated can be maintained at a high image quality for a long time.

  The embodiments and examples of the present invention have been described above, but the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention. is there.

It is a circumferential direction sectional view showing an example of a charging roll according to the present embodiment. It is a circumferential direction sectional view showing other examples of the charging roll according to the present embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Charging roll 12 Shaft body 14 Base layer 16 Surface layer 18 Intermediate layer

Claims (6)

The surface layer is
(A) a monofunctional (meth) acrylate monomer having an ethylene oxide unit introduced into the molecular structure;
(B) urethane (meth) acrylate,
A charging roll for an electrophotographic apparatus, comprising a cured product of an ultraviolet curable conductive composition comprising   2. The charging roll for an electrophotographic apparatus according to claim 1, wherein the component (A) / the component (B) (mass ratio) is in a range of 20/80 to 80/20.   3. The charging roll for an electrophotographic apparatus according to claim 1, wherein the number of (meth) acryloyl groups contained in one molecule of the (B) urethane (meth) acrylate is 6 or more.   The charging roll for an electrophotographic apparatus according to any one of claims 1 to 3, wherein the ultraviolet curable conductive composition contains (C) an ion conductive agent. A shaft body, a base layer formed on the outer periphery of the shaft body, and the surface layer formed on the outer periphery of the base layer, or
A shaft body, a base layer formed on an outer periphery of the shaft body, an intermediate layer formed on an outer periphery of the base layer, and the surface layer formed on an outer periphery of the intermediate layer. Item 5. The charging roll for electrophotographic equipment according to any one of Items 1 to 4.   The charging roll for an electrophotographic apparatus according to claim 1, wherein the surface layer includes particles for roughness formation.

Images