JP2009244463A - Elastic material for electrophotographic equipment, member for electrophotographic equipment, and method of manufacturing elastic material for electrophotographic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an elastic material for electrophotographic equipment which is improved in productivity by fast curability and superior in flexibility, and to provide a member for electrophotographic equipment using the same. <P>SOLUTION: The elastic material for electrophotographic equipment is formed of a cured body of a composition containing a photopolymerizable monomer and/or a photopolymerizable oligomer and rubber. A (meth)acrylate monomer is suitable as the photopolymerizable monomer, and a (meth)acrylate oligomer is suitable as the photopolymerizable oligomer. Chloroprene rubber, nitrile rubber, hydrin rubber, ethylene propylene (diene) rubber, natural rubber, etc., are preferrable as the rubber. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an elastic material for electrophotographic equipment, a member for electrophotographic equipment, and a method for producing an elastic material for electrophotographic equipment.

  In recent years, electrophotographic apparatuses such as copying machines, printers, and facsimiles that employ an electrophotographic system have been widely used. Inside these electrophotographic apparatuses, various conductive rolls such as a charging roll, a developing roll, a toner supply roll, and a transfer roll, and a conductive belt such as an intermediate transfer belt are incorporated.

  Conventionally, most of the elastic materials used for the conductive rolls and conductive belts have a prescription in which various rubbers are thermally cured with sulfur or peroxide in order to impart flexibility.

  Recently, in place of the rubber prescription, for example, as shown in Patent Document 1, a prescription for ultraviolet curing of an acrylate monomer has been proposed.

JP 2006-274242 A

  However, conventionally, elastic materials applied to members of electrophotographic equipment have room for improvement in the following points.

  That is, the conventional rubber formulation takes time for heat curing by the crosslinking reaction. In some cases, secondary curing may be required. Therefore, there was a problem that productivity was poor. In addition, there are disadvantages such as large consumption of heat energy and the need for a mold for molding, resulting in mold costs, mold maintenance costs, etc., resulting in high manufacturing costs.

  On the other hand, although the conventional UV curing formulation is capable of rapid curing, the cured product is relatively hard and brittle, and exhibits flexibility, but is inferior in high elastic recovery like rubber. there were. Therefore, when this material is used for a member of an electrophotographic apparatus, it is disadvantageous in terms of durability, and it is considered that an image defect after being left for a long time is caused.

  The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is that it is possible to improve productivity by rapid curability, and is excellent in flexibility and high elasticity recovery for electrophotographic equipment. It is to provide an elastic material. Another object of the present invention is to provide a member for an electrophotographic apparatus using the same.

  In order to solve the above-mentioned problems, the gist of the elastic material for electrophotographic equipment according to the present invention is a cured product of a composition containing a photopolymerizable monomer and / or photopolymerizable oligomer and rubber.

  Here, the photopolymerizable monomer is preferably a (meth) acrylate monomer, and the photopolymerizable oligomer is preferably a (meth) acrylate oligomer.

  The photopolymerizable monomer and / or the photopolymerizable oligomer may contain a photopolymerizable monomer and / or photopolymerizable oligomer having an ethylene oxide unit in the molecular structure.

  The rubber may contain one or more selected from chloroprene rubber, nitrile rubber, hydrin rubber, ethylene propylene (diene) rubber, and natural rubber.

  The composition may further contain an ionic conductive agent.

  An electrophotographic apparatus member such as a conductive roll for an electrophotographic apparatus and a conductive belt according to the present invention is summarized in that the elastic material for an electrophotographic apparatus is used.

  The method for producing an elastic material for an electrophotographic apparatus according to the present invention includes a step of irradiating a composition containing a photopolymerizable monomer and / or photopolymerizable oligomer and rubber with an active energy ray and curing the composition. Is the gist.

  The elastic material for electrophotographic equipment according to the present invention comprises a cured product of a composition containing a photopolymerizable monomer and / or photopolymerizable oligomer and rubber.

  Conventionally known rubber compositions (sulfur vulcanization system, peroxide cross-linking system, etc.) take time for heat curing by cross-linking reaction. On the other hand, a conventionally known ultraviolet curable composition using an acrylate monomer can be rapidly cured, but the cured product is relatively hard and brittle, or has poor elasticity recovery.

  On the other hand, the said composition can be hardened in a short time by irradiating active energy rays, such as an ultraviolet-ray and an electron beam. In addition, the composition contains a photopolymerization component and rubber, and since the photopolymerization component is bonded to the network in the rubber, the cured product is low in hardness and hardly sticky and has excellent flexibility. .

  Therefore, if the elastic material is applied to a member for an electrophotographic apparatus, the productivity of the member for an electrophotographic apparatus can be improved due to the fast curability. In addition, a member for an electrophotographic apparatus that is low in hardness, hard to stick and excellent in flexibility can be obtained.

  Here, the (meth) acrylate monomer and / or the (meth) acrylate oligomer are relatively many and have a wide range of material selection. Therefore, when the photopolymerizable monomer is a (meth) acrylate monomer and the photopolymerizable oligomer is a (meth) acrylate oligomer, the flexibility can be varied by adjusting hardness, anti-stickiness, etc. It is easy to improve the degree of freedom in material design.

  Further, when the photopolymerizable monomer and / or photopolymerizable oligomer has an ethylene oxide unit in the molecular structure, the electric resistance controllability of the elastic material can be improved.

  In particular, when a photopolymerizable monomer having an ethylene oxide unit in the molecular structure is used, the controllability on the low resistance side is excellent. Therefore, it can be suitably used for applications requiring a predetermined volume resistance, such as a charging roll, a developing roll, and an intermediate transfer belt of an electrophotographic apparatus.

  In addition, when the rubber is selected, since it is excellent in compatibility with the photopolymerization component, low hardness and low stickiness are easily exhibited. Therefore, the elastic material easily exhibits excellent flexibility and high elastic recovery.

  Moreover, when the said composition contains an ionic conductive agent, the resistance controllability of the said elastic material can be improved further.

  The electrophotographic apparatus member according to the present invention uses the above-described elastic material for electrophotographic apparatus. Therefore, it is excellent in the productivity of the member for electrophotographic equipment. In addition, a member for an electrophotographic apparatus that is low in hardness, hard to stick and excellent in flexibility can be obtained.

  Further, when a photopolymerizable monomer having an ethylene oxide unit in the molecular structure is used as the elastic material, the controllability on the low resistance side is excellent. Therefore, an electrophotographic apparatus member having a good volume resistance can be obtained.

  According to the method for producing an elastic material for an electrophotographic apparatus according to the present invention, a cured product of the composition can be obtained in a short time, and thus the productivity is excellent. In addition, an elastic material that is low in hardness and hardly sticky and has excellent flexibility can be obtained.

  Moreover, since a thermosetting facility is not required in the production line, the process is simplified, and this can also improve productivity. Since the consumption of thermal energy can be reduced, it can contribute to energy saving.

  Hereinafter, the electrophotographic apparatus elastic material according to the present embodiment (hereinafter also referred to as “the present elastic material”) and the electrophotographic apparatus member according to the present embodiment will be described.

1. This elastic material This elastic material consists of the hardened | cured material of the uncured composition containing a photopolymerization component and rubber | gum.

  The photopolymerization component is a photopolymerizable monomer and / or photopolymerizable oligomer that can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams.

  The composition may contain one or more photopolymerizable monomers and photopolymerizable oligomers. The photopolymerizable monomer or photopolymerizable oligomer may have one functional group involved in a photopolymerization reaction such as a (meth) acryloyl group (monofunctional) or two or more of the above functional groups. It may be (multifunctional).

  The photopolymerizable monomer and the photopolymerizable oligomer are preferably polyfunctional from the viewpoint that, when the crosslink density is high, the photopolymerizable component is combined in the rubber, so that it is easy to express a low shear property. And good.

  Specifically as a photopolymerizable monomer and a photopolymerizable oligomer, a (meth) acrylate monomer, a (meth) acrylate oligomer, etc. can be illustrated as a suitable thing.

  There are relatively many kinds of (meth) acrylate monomers and (meth) acrylate oligomers, and the range of material selection is wide. For this reason, the flexibility can be easily changed by adjusting the hardness, the settling resistance, etc., and the degree of freedom in material design can be improved.

  Specific examples of the photopolymerizable monomer include, for example, trimethylolpropane ethylene oxide-modified triacrylate, polyethylene glycol diacrylate, methoxy polyethylene glycol acrylate, polyethylene glycol dimethacrylate, 2 ethylhexyl carbitol acrylate, polyethylene glycol monoethyl ether methacrylate, Photopolymerization containing ethylene oxide units such as ethoxylated cyclohexane dimethacrylate, ethoxylated 2-methyl-1,3-propanediol diacrylate, ethoxylated polypropylene glycol dimethacrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, etc. Monomer and phenoxypolyethylene glycol acrylate , Paracumylphenoxyethylene glycol acrylate, paracumylphenol ethylene oxide modified acrylate, bisphenol A ethylene oxide modified diacrylate, propoxyethoxybisphenol A diacrylate, 9,9-bis (3-phenyl-4-acryloylpolyoxyethoxy) fluorene, ethoxylated Examples thereof include photopolymerizable monomers containing ethylene oxide units and cyclic unsaturated structural units such as isocyanuric acid triacrylate and nonylphenoxypolyethylene glycol acrylate. These may be used alone or in combination.

  Specific examples of the photopolymerizable oligomer include those having an ethylene oxide unit such as polyethylene polypropylene glycol diacrylate and polyethylene glycol diacrylate, carbonate acrylic oligomer, polytetramethylene glycol diacrylate, polycaprolactone diacrylate, and polyester acrylate. The thing etc. which do not have an ethylene oxide unit can be illustrated. These may be used alone or in combination.

  Of the above-described photopolymerizable monomers and photopolymerizable oligomers, those having an ethylene oxide unit in the molecular structure can be preferably used from the viewpoint of easily improving the electric resistance controllability of the elastic material. .

  The composition contains rubber in addition to the photopolymerization component. Specific examples of rubber include chloroprene rubber, nitrile rubber, hydrin rubber, urethane elastomer, ethylene propylene (diene) rubber, natural rubber, hydrogenated nitrile rubber, isoprene rubber, styrene-butadiene rubber, and acrylic rubber. Can do. These may be contained alone or in combination of two or more.

  Of the above-mentioned rubbers, chloroprene rubber, nitrile rubber, hydrin rubber, ethylene propylene (diene) rubber, natural rubber, and the like are preferable from the viewpoint of excellent compatibility with the photopolymerization component and ease of exhibiting flexibility. It can be used suitably.

  In the above composition, the ratio of the photopolymerization component and the rubber is not particularly limited. The ratio between the two can be adjusted in consideration of hardness, amount of settling, flexibility, and the like.

  The ratio of the photopolymerization component to the total mass of the rubber is preferably in the range of 3 to 70% by mass, more preferably in the range of 5 to 60% by mass, and even more preferably 10 to 50%. It is good if it is within the range of mass%.

  On the other hand, the ratio of the rubber to the total mass of the photopolymerization component and the rubber is preferably within a range of 30 to 97% by mass, more preferably within a range of 40 to 95% by mass, and even more preferably 50 to 90%. It is good if it is within the range of mass%.

  The said composition may contain various additives etc. as other components as needed.

  As said additive, the electrically conductive agent added in order to adjust the electroconductivity of this elastic material can be mentioned as a typical thing, for example. The conductive agent may be any of an ionic conductive agent such as a quaternary ammonium salt, and an electronic conductive agent such as carbon black or a conductive metal oxide. Preferably, an ionic conductive agent can be suitably used from the standpoint that resistance variation is small and resistance controllability is easily improved.

  In addition, when adding a electrically conductive agent, in order to acquire the effect fully, Preferably it exists in the range of 0.01-20 mass parts with respect to 100 weight part of photopolymerization components, More preferably, 0.05-15 Within the range of parts by mass, more preferably within the range of 0.1 to 10 parts by mass.

  Moreover, as said additive, a photoinitiator can be mentioned as a typical thing, for example. However, the photopolymerization initiator is necessary when the composition is ultraviolet-cured, but it is not necessary to add it when the electron beam is cured. The photopolymerization initiator is not particularly limited, and various commercially available products can be applied.

  In addition, when adding a photoinitiator, in order to acquire the effect fully, Preferably it exists in the range of 0.01-10 mass parts with respect to 100 mass parts of photopolymerization components, More preferably, it is 0.05. It is good to set it in the range of -8 mass parts, More preferably, you may be in the range of 0.1-5 mass parts.

  Examples of other additives include fillers, conductive agents, stabilizers, plasticizers, viscosity modifiers, anti-aging agents, processing aids, lubricants, flame retardants, foaming agents, crosslinking agents, crosslinking aids, and dispersing agents. Examples thereof include an antifoaming agent and a pigment.

  The elastic material is obtained by photocuring the uncured composition. Examples of photocuring include ultraviolet curing and electron beam curing. Preferably, UV curing is preferable from the viewpoint of simple equipment and excellent safety.

  The shape of the elastic material is not particularly limited, and various shapes such as a layer shape, a roll shape, and a tube shape can be adopted.

  The thickness of the elastic material can be varied in consideration of the shape, photocuring conditions, and the like.

  The thickness of the elastic material is preferably in the range of 0.1 μm to 10 mm, more preferably in the range of 0.5 μm to 8 mm from the viewpoint of taking advantage of the elastic body and being excellent in cured product characteristics. More preferably, it is in the range of 1 μm to 5 mm.

  The elastic material described above is basically produced by irradiating a composition containing a photopolymerizable monomer and / or photopolymerizable oligomer and rubber with an active energy ray and curing the composition. can do. This will be specifically described below.

  Until the above-mentioned photopolymerizable monomer and / or oligomer, rubber, and various additives such as a conductive agent and a photopolymerization initiator to be added as necessary are made uniform using a kneader or a biaxial kneader Kneading to prepare an uncured composition.

  Next, the prepared uncured composition is formed into a desired shape such as a layer, a roll, or a tube using an extrusion method, a casting method, a pressing method, or the like. Alternatively, the uncured composition is dissolved in a solvent to prepare a predetermined solution, and formed into a desired shape such as a layer, roll, or tube using spray coating, roll coating, spin coating, dip coating, etc. Can also

  Next, an uncured product formed into a desired shape is irradiated with an active energy ray such as an ultraviolet ray or an electron beam for an optimal amount of light and time according to the composition, and photocured. From the viewpoint of improving productivity by rapid curing, the conditions such as the amount of light are set so that the curing time is preferably within 3 minutes, more preferably within 2 minutes, and even more preferably within 1 minute. Good.

2. Electrophotographic apparatus member The electrophotographic apparatus member according to the present embodiment uses the elastic material as an elastic material constituting the member.

  Specific examples of the member for an electrophotographic apparatus include various conductive rolls such as a charging roll, a developing roll, a toner supply roll, and a transfer roll, and a conductive belt such as a transfer belt.

  For example, as a conductive roll, the structure by which the elastic body layer which has 1 layer or 2 layers or more of conductivity was laminated | stacked on the outer periphery of the shaft body can be illustrated, for example.

  Specific examples of the layer configuration include an intermediate layer such as a base layer and a resistance adjustment layer on the outer periphery of the shaft body, a layer configuration in which the surface layer is sequentially stacked, a layer configuration in which the base layer and the surface layer are sequentially stacked, and the like. Can do. Each layer may be composed of a single layer or a plurality of layers.

  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.

  Here, the conductive roll has an elastic layer formed of the elastic material. The elastic body layer formed from the elastic material may be disposed at any position in the roll layer configuration.

  Preferably, the base layer, the intermediate layer, and the like are formed of the elastic material from the viewpoints that the thickness is relatively large, low hardness and set resistance are required, and the advantage of flexibility is easily utilized.

  The thickness of the elastic layer formed from the elastic material is not particularly limited, but when used as a base layer, it is preferably about 0.1 to 3 mm. When used as an intermediate layer, the thickness is preferably about 0.01 μm to 1 mm. When used as a surface layer, the thickness is preferably about 0.1 μm to 100 μm.

  The material for forming the other elastic body layer is not particularly limited, and conventionally known elastic materials (various rubbers, various types of rubber, A material in which additives such as a conductive agent and roughness forming particles are added to a resin or the like as required can be appropriately selected and used.

  On the other hand, as a conductive belt, the structure which laminated | stacked the base material and the elastic body layer which has 1 layer or 2 layers or more of conductivity on the surface of a base material can be illustrated, for example. Moreover, the surface layer may be laminated | stacked on the surface of the elastic body layer as needed.

  Any substrate can be used as long as it can maintain tension. What is necessary is just to select suitably considering required rigidity. Specifically, polyimide, polyamideimide, polycarbonate, polytetrafluoroethylene and the like can be exemplified.

  Here, the conductive belt has an elastic layer made of the elastic material. The elastic body layer formed of the elastic material may be disposed at any position in the belt layer configuration.

  The thickness of the elastic layer formed from the elastic material is not particularly limited, but is preferably about 0.01 mm to 1 mm.

  The material forming the other elastic layer is not particularly limited, and conventionally known elastic materials (various rubbers, various rubbers, etc.) are used depending on the type of the conductive belt, the layer position where the other elastic layer is disposed, and the like. A material obtained by adding an additive such as a conductive agent to a resin or the like as necessary can be appropriately selected and used.

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

1. Production of elastic materials according to examples and elastic materials according to comparative examples (Examples 1 to 8)
Various materials were weighed so as to have a blending ratio (unit: parts by mass) shown in Table 1 described later, and these were kneaded for 30 minutes using a kneader to prepare each uncured composition.

  Subsequently, each obtained uncured composition was formed into a sheet using an extrusion method.

  Next, for Examples 3 to 6, and 8, each uncured product was irradiated with ultraviolet rays using an ultraviolet irradiator (“UB031-2A / BM” manufactured by Eye Graphic Co., Ltd., mercury lamp format). The cured product was UV cured.

Thus, sheet-like elastic materials (thickness: about 0.5 mm, length: 100 mm, width: 100 mm) according to Examples 3 to 6 and 8 were produced. At this time, the ultraviolet irradiation intensity was 120 mW / cm ² and the irradiation time was 30 seconds.

  In Examples 1, 2, and 7, each uncured product was irradiated with an electron beam using an electron beam irradiator (“MIWEL” manufactured by Mitsubishi Heavy Industries, Ltd.). Line cured.

  Thereby, sheet-like elastic materials (thickness: about 0.5 mm, length: 100 mm, width: 100 mm) according to Examples 1, 2, and 7 were produced. At this time, the electron beam irradiation intensity was 50 kGy, and the irradiation time was 1 second.

In addition, the various materials used at the time of preparation of the said composition are as follows.
(Photopolymerization component)
-Polytetramethylene glycol acrylate monomer [manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-PTMG65”, acrylic functional group number f = 2, molecular weight = 750]
Polytetramethylene glycol acrylate oligomer [Shin Nakamura Chemical Co., Ltd., “UA160TM”, acrylic functional group number f = 2, molecular weight = 1600]
-Ethylene oxide (EO) modified acrylate monomer [manufactured by Shin-Nakamura Chemical Co., Ltd., "NK Ester A-600", acrylic functional group number f = 2, molecular weight = 750, EO content 14 mol]
・ Ethylene oxide (EO) modified glycerin acrylate monomer [manufactured by Shin-Nakamura Chemical Co., Ltd., “A-CLY-9EO”, acrylic functional group number f = 3, molecular weight = 650, EO content 9 mol]

(Rubber component)
・ NBR <1> [Nippon DN202, manufactured by Nippon Zeon Co., Ltd.]
・ NBR <2> [Nippon ZEON Co., Ltd., "Nipol DN1072"]
・ CR [Electrochemical Industry Co., Ltd., “Denka Chloroprene M-40”]
ECO [Daiso Co., Ltd., “Epichromer CG-102”]
・ EPDM [manufactured by Sumitomo Chemical Co., Ltd., “Esprene 505”]
・ NR “RSS # 3]

(Conductive agent)
・ Carbon black (Electronic conductive agent) [Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.]
・ Tetrabutylammonium chloride (ionic conductive agent) [manufactured by Tokyo Chemical Industry Co., Ltd.]

Photoinitiator [Ciba Specialty Chemicals Co., Ltd., “Irgacure 819”]

(Comparative Example 1)
100 parts by mass of ECO (manufactured by Daiso Corporation, “Epichromer CG-102”), 1 part by mass of stearic acid (manufactured by Kao Corporation, “Lunac S-30”), and two types of zinc oxide (Mitsui Metal Industries ( 5 parts by mass), 3 parts by mass of an acid acceptor (manufactured by Kyowa Chemical Industry Co., Ltd., “DHT-4A”), 1.5 parts by mass of powder sulfur (manufactured by Tsurumi Chemical Co., Ltd.), and thiazole -Based vulcanization accelerator (Ouchi Shinsei Chemical Industry Co., Ltd., "Noxeller DM") 1.5 parts by mass, and Tyrium vulcanization accelerator (Ouchi Shinsei Chemical Industry Co., Ltd., "Noxeller TS") A hydrin rubber-based uncured composition was prepared by kneading 0.5 parts by mass and 1 part by mass of tetrabutylammonium chloride (ionic conductive agent, manufactured by Tokyo Chemical Industry Co., Ltd.) with a kneader.

  Next, the obtained uncured composition is press-molded and crosslinked (at 160 ° C. for 30 minutes), thereby forming a sheet-like elastic material according to Comparative Example 1 (thickness: about 0.5 mm, length: 100 mm, width: 100 mm). Produced.

(Comparative Example 2)
100 parts by weight of nitrile rubber (NBR) (manufactured by ZEON Corporation, “Nipol DN401”), 0.5 parts by weight of stearic acid (manufactured by Kao Corporation, “Lunac S-30”), and tetrabutylammonium chloride (Ion conductive agent, manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts by weight, zinc oxide (ZnO) 5 parts by weight, sulfenamide vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd., “Noxeller CZ- G ") 1 part by weight, 0.5 parts by weight of a dicarbamate vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd.," Noxeller BZ-P ") and 1 part by weight of powdered sulfur A nitrile rubber-based uncured composition was prepared by kneading with rubber.

  Next, the obtained uncured composition was press-molded and crosslinked (at 160 ° C. for 30 minutes) to produce a sheet-like elastic material according to Comparative Example 2 (the shape is the same as Comparative Example 1).

(Comparative Example 3)
By stirring X-34-264A / B (manufactured by Shin-Etsu Chemical Co., Ltd.), a silicone rubber-based uncured composition was prepared.

  Subsequently, the obtained uncured composition was press-molded and crosslinked (at 160 ° C. for 15 minutes) to produce a sheet-like elastic material according to Comparative Example 3 (the shape is the same as Comparative Example 1).

(Comparative Example 4)
50 parts by weight of urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., “UF8001”), 50 parts by weight of methoxytriethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., “MTG-A”), and acylphosphine as a polymerization initiator By stirring 5 parts by weight of fin oxide (manufactured by Ciba Specialty Chemicals, "IRGACURE819") and 2 parts by weight of tetrabutylammonium chloride (ionic conductive agent, manufactured by Tokyo Chemical Industry Co., Ltd.) An uncured composition was prepared.

Subsequently, the obtained uncured composition was irradiated with ultraviolet rays (irradiated with ultraviolet rays at an illuminance of 400 mW and an integrated light amount of 1000 mJ / cm ² using a Unicure UVH-0252C apparatus manufactured by Ushio Electric Co., Ltd.). A sheet-like elastic material (the shape is the same as in Comparative Example 1) was produced.

(Comparative Example 5)
By mixing 80 parts by weight of an aqueous solution (solid content 20%) in which a polyurethane resin (Daiichi Kogyo Seiyaku Co., Ltd., “Superflex 126”) is dispersed in water, and 20 parts by weight of tin oxide with a ball mill, A urethane-based uncured composition was prepared.

  Subsequently, the obtained uncured composition was dried and heated (at 150 ° C. for 10 minutes) to produce a sheet-like elastic material according to Comparative Example 5 (the shape is the same as that of Comparative Example 1).

2. Evaluation of Elastic Material According to Example and Elastic Material According to Comparative Example Next, the following evaluation was performed on the elastic material according to the obtained example and the elastic material according to the comparative example.

(Fast curing)
When each elastic material is produced, the case where the time required for the curing of the uncured composition is within 1 minute is considered as good fast curability, and the case where the time is over 1 minute is considered as fast curability. X was evaluated as inferior.

(hardness)
In accordance with JIS K6253, the surface hardness of each sheet-like elastic material was measured using an MD-1 hardness meter (manufactured by Kobunshi Keiki Co., Ltd., “Micro rubber hardness meter MD-1 type”).

(Elastic recovery rate)
Based on ISO14577-1, the surface of the sheet-like elastic material was measured under the following measurement conditions using a micro hardness tester (Fischer, microscope HS100), and η _IT [%] was determined. That is, when the indenter is pushed into the material surface with a constant test load using a microhardness meter, the total mechanical work W _total of the dent shown during the indentation work is expressed as the plastic deformation work W _plast of the dent. Only a small part is consumed. When the test load is unloaded, the remaining part is _released as the elastic return deformation work W _elast of the recess. If this mechanical work is defined as W = ∫Fdh, the relationship is as follows.
η _IT [%] = W _elast / W _{total
However, W total = W elast + W} plast
<Measurement conditions>
Indenter: Square-angled diamond indenter with a face angle of 136 ° Initial load: 0 mN
Maximum indentation load: 1mN (constant load)
Maximum load arrival time: 0.25 to 10 sec
Maximum load holding time: 30 sec
Drawing time: 0.25-10sec

(Electric resistance)
In accordance with JIS K6271, 10 mm square electrodes were formed on the surface of each sheet-like elastic material, and the electrical resistance value when 100 V was applied was measured.

(Measurement of tensile stress <TSb> at break and <Eb> at break of sheet elastic material)
In accordance with JIS K6251: 2004, using a tensile tester (AE-F strograph, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the tensile stress at break (TSb) and elongation at break (Eb) of the sheet-like elastic material were determined. It was measured.

  Table 1 summarizes the blending ratio and evaluation results when the elastic material according to the example and the elastic material according to the comparative example are manufactured.

  According to Table 1, the following can be understood. That is, it can be seen that the elastic material according to the example is excellent in fast curability, is relatively low in hardness and hardly sticky, has excellent flexibility, has a large TSb × Eb value, and is excellent in toughness.

3. Production of charging roll, developing roll and intermediate transfer belt for electrophotographic apparatus 3.1 Production of charging roll (Examples 1Tb to 8Tb)
As a charging roll according to Examples 1Tb to 8Tb, a base layer formed by photocuring each uncured composition prepared in Examples 1 to 8 and an acrylic fluorine-based surface layer are laminated in this order on the outer periphery of the cored bar. Each charging roll having the two-layer structure was manufactured by the following procedure. In addition, Example 1Tb-8Tb and Example 1-8 respond | correspond, respectively.

  Using the extrusion method, each uncured composition prepared in Examples 1 to 8 was extruded in the form of a roll onto the outer periphery of a core metal (made of SUS, outer diameter 6 mm, length 250 mm), and ultraviolet or electron beam was applied to this. Was applied to cure each composition with ultraviolet rays or electron beams to form a base layer having a thickness of 1 mm.

  Next, 50 parts by mass of a fluorine-modified acrylic binder (Dainippon Ink Chemical Co., Ltd., “Defensor TR230K”), 50 parts by mass of a fluororesin (Atofina Japan Co., Ltd., “Kyner 7201”), and conductivity An acrylic surface layer-forming composition was prepared by blending 100 parts by mass of titanium oxide (manufactured by Ishihara Techno Co., Ltd., “Typaque ET300W”) and 200 parts by mass of MEK, and dispersing the mixture using a sand mill.

  Next, the surface layer-forming composition was applied to the surface of each base layer by a roll coating method, and a heat treatment was performed at 100 ° C. for 30 minutes to form a surface layer having a thickness of 20 μm.

  This produced the charging roll which concerns on Example 1Tb-8Tb.

(Comparative Example 1Tb)
Using the casting method, the uncured composition prepared in Comparative Example 1 is formed into a roll shape on the outer periphery of the core metal, and heat-treated at 170 ° C. for 45 minutes to form a base layer having a thickness of 1 mm. did.

  Next, the surface layer-forming composition was applied to the surface of the base layer by a roll coating method, and heat-treated at 100 ° C. for 30 minutes to form a surface layer having a thickness of 20 μm.

  Thus, a charging roll according to Comparative Example 1Tb was produced.

(Example 1 Tm to 8 Tm)
As charging rolls according to Examples 1 to 8 Tm, the base layer of silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., “KE1350A / B”) based on the outer circumference of the core metal, each of the unrolled materials prepared in Examples 1 to 8 Each charging roll having a three-layer structure in which an intermediate layer formed by photocuring the cured composition and an acrylic fluorine-based surface layer were laminated in this order was produced by the following procedure. In addition, Example 1Tm-8Tm and Example 1-8 respond | correspond, respectively.

  Using the casting method, the silicone rubber base layer forming composition was formed into a roll shape on the outer periphery of the cored bar described above, and heat treated at 150 ° C. for 45 minutes to form a base layer having a thickness of 4 mm. .

  Next, using a roll coating method, a coating solution prepared by dissolving each uncured composition prepared in Examples 1 to 8 in a solvent is coated, and this is applied to the surface of the base layer, and then an ultraviolet ray or an electron beam. The composition was irradiated with UV or electron beam to form an intermediate layer having a thickness of 0.03 mm.

  Next, the surface layer-forming composition described above was applied to the surface of each intermediate layer by a roll coating method, and a heat treatment was performed at 100 ° C. for 30 minutes to form a surface layer having a thickness of 20 μm.

  Thereby, the charging roll which concerns on Example 1Tm-8Tm was produced.

(Comparative Example 2 Tm)
Extruding the uncured composition prepared in Comparative Example 2 into a tube shape using an extrusion method, covering this on the surface of the base layer prepared in Examples 1 Tm to 8 Tm, and heat-treating at 160 ° C. for 45 minutes Thus, an intermediate layer having a thickness of 0.03 mm was formed.

  Next, the surface layer-forming composition described above was applied to the surface of the intermediate layer by a roll coating method, and a heat treatment was performed at 100 ° C. for 30 minutes to form a surface layer having a thickness of 20 μm.

  Thus, a charging roll according to Comparative Example 2Tm was produced.

3.2 Production of developing roll (Examples 1Gb to 8Gb)
As a developing roll according to Examples 1Gb to 8Gb, a base layer formed by photocuring each uncured composition prepared in Examples 1 to 8 and a urethane surface layer are laminated in this order on the outer periphery of the core metal. Further, each developing roll having a two-layer structure was prepared by the following procedure. In addition, Example 1Gb-8Gb and Example 1-8 respond | correspond, respectively.

  Using the extrusion method, each uncured composition prepared in Examples 1 to 8 is extruded into a roll shape on the outer periphery of the above-described core metal, and irradiated with ultraviolet rays or electron beams, thereby irradiating each composition with ultraviolet rays. Alternatively, electron beam curing was performed to form a base layer having a thickness of 1 mm.

  100 parts by mass of a urethane resin (manufactured by Nippon Polyurethane, “Nipporan 5199”), 20 parts by mass of carbon black (manufactured by Denki Kagaku Kogyo Co., Ltd., “HS-100”), urethane particles (manufactured by Negami Kogyo Co., "Art Pearl C400BM") 15 parts by mass, MEK 400 parts by mass was added and dispersed and mixed using a sand mill to prepare a urethane-based surface layer forming composition.

  Next, the surface layer-forming composition was applied to the surface of each base layer by a roll coating method, and a heat treatment was performed at 130 ° C. for 30 minutes to form a surface layer having a thickness of 20 μm.

  This produced the developing roll which concerns on Example 1Gb-8Gb.

(Comparative Example 3Gb)
Using a casting method, the uncured composition prepared in Comparative Example 3 is formed into a roll shape on the outer periphery of the core metal, and heat-treated at 150 ° C. for 45 minutes to form a base layer having a thickness of 1 mm. did.

  Next, the surface layer-forming composition was applied to the surface of the base layer by a roll coating method, and heat-treated at 130 ° C. for 30 minutes to form a surface layer having a thickness of 20 μm.

  Thereby, a charging roll according to Comparative Example 3Gb was produced.

3.3 Preparation of intermediate transfer belt (Examples 1B to 8B)
As an intermediate transfer belt according to Examples 1B to 8B, each intermediate of a seamless structure in which an elastic layer formed by photocuring each uncured composition prepared in Examples 1 to 8 is laminated on the surface of a substrate. A transfer belt was produced by the following procedure. In addition, Example 1B-8B and Example 1-8 respond | correspond, respectively.

  First, 100 parts by mass of polyamide-imide resin (manufactured by Toyobo Co., Ltd., “HR-16NN”), 800 parts by mass of NMP (solvent), carbon black (manufactured by Denki Kagaku Kogyo Co., Ltd., “Denka Black HS-100” ]] 10 parts by mass was dispersed and mixed to prepare a polyamideimide resin dispersion solution.

  Next, the surface of the prepared cylindrical substrate (mold) is spray-coated with the polyamideimide resin dispersion solution, and the temperature is raised from room temperature to 250 ° C. over 2 hours, followed by heat treatment at 250 ° C. for 1 hour. gave.

  Next, air was blown between the base layer and the cylindrical base body (mold), the cylindrical base body (die) was extracted, and a cylindrical polyamideimide layer having a thickness of 0.1 mm and an inner peripheral length of 1000 mm was formed as the base layer. .

  Subsequently, each uncured composition prepared in Examples 1 to 8 was laminated on the surface of this base layer.

  Next, the obtained laminate was irradiated with ultraviolet rays or electron beams to cure each composition with ultraviolet rays or electron beams, thereby forming an elastic body layer having a thickness of 0.15 mm on the surface of the base layer.

  Subsequently, the intermediate transfer belt according to Examples 1B to 8B was manufactured by spray coating the laminate (silicone graft acrylic resin (manufactured by Toagosei Co., Ltd., “Symac US-350”)).

  In the production of the intermediate transfer belt according to Examples 1B to 8B, the uncured composition (only the photopolymerization component and no rubber component) prepared in Comparative Example 4 was laminated on the surface of the cylindrical polyamideimide layer.

  Next, the obtained laminate was irradiated with ultraviolet rays to cure each composition with ultraviolet rays, and an elastic body layer having a thickness of 0.15 mm was formed on the surface of the base layer.

  Thus, an intermediate transfer belt according to Comparative Example 4B was produced.

(Comparative Example 5B)
In the production of the intermediate transfer belt according to Examples 1B to 8B, the uncured composition prepared in Comparative Example 5 was laminated on the surface of the cylindrical polyamideimide layer.

  Next, the obtained laminate was heat-treated at 160 ° C. for 30 minutes to form an elastic body layer having a thickness of 0.15 mm on the surface of the base layer.

  Next, a surface layer was formed in the same manner as described above, and an intermediate transfer belt according to Comparative Example 5B was produced.

4). Evaluation of charging roll, developing roll, intermediate transfer belt 4.1 Roll evaluation (sag resistance)
<Charging roll>
A charging roll was pressed against the photoreceptor in the cartridge of a commercially available color laser printer (manufactured by Canon Inc., “Laser Shot LBP-2510”), and left in a 40 ° C. × 95% RH environment for 1 week. When it is incorporated in the above-mentioned apparatus, an image is taken out in a 15 ° C. × 10% RH environment, and when there is no image unevenness, streaks, spots, etc. by visual evaluation, ○, image unevenness, streaks, spots, etc. What was recognized was set as x.

(Stick resistance)
<Development roll>
The developing roll was assembled in a toner cartridge (Canon Corporation, EP-85 cyan) and left to stand for 2 weeks under conditions of 40 ° C. × humidity 95% RH, and then a solid image was printed. Then, the case where the image was left unacceptable was evaluated as ◯, and the image where the image was left unattended was evaluated as x.

(durability)
The charging roll was evaluated for durability as follows. That is, each charging roll was incorporated in a black cartridge of a commercially available color laser printer (manufactured by Canon Inc., “Laser Shot LBP-2510”).

  Next, with this color laser printer, 5000 half-tone images (A4 size) were printed in a black monochrome mode and in an environment of 15 ° C. × 10% RH.

  After the durability test, the appearance of the charging roll was confirmed. That is, when such an endurance test is performed, a phenomenon occurs in which an external additive such as silica removed from the toner adheres to the roll surface.

  Here, after the endurance test, there is little white powder on the roll surface, or there is a part where the white powder is slightly on the roll surface, or there is a slight white powder on the entire roll surface. Those with the same extent were marked as “good”. A white powder adhering to the entire roll surface and exceeding gray and appearing white was marked as “no durability”.

  On the other hand, the durability of the developing roll was evaluated as follows. In other words, it was incorporated into a commercially available color laser printer (“Laser Shot LBP-2510” manufactured by Canon Inc.), and after passing 5000 sheets of black solid images in an environment of 20 ° C. × 50% RH, at the edge. The case where there was no chipping and no toner leakage was rated as “◯”. The case where the edge was scraped and the toner was leaked was marked with x.

4.2 Belt evaluation (initial image)
Installed in a commercially available multifunction printer ("MPC-2500", manufactured by Ricoh Co., Ltd.), with no initial color misalignment or image unevenness in the initial image (solid image), with color misalignment or image unevenness X.

(durability)
Incorporated into a commercially available multifunction printer ("MPC-2500" manufactured by Ricoh Co., Ltd.) Color shift and wear debris between the back of the belt and the roller that stretches the belt in the image after 30,000 copies The case where no image defect (such as uneven spot density) caused by the convex deformation on the belt surface side caused by the agglomerates was confirmed, and the case where such image defect was confirmed was rated as x.

  Tables 2 to 5 show the evaluation results of the charging roll, the developing roll, and the intermediate transfer belt according to the example and the comparative example, respectively.

  According to Tables 2 to 5, the following can be understood. That is, the charging roll, the developing roll, and the intermediate transfer belt according to the example use the elastic material according to the example for the elastic layer on the surface of the base layer, the intermediate layer, and the base layer. Therefore, it can be said that it is excellent in productivity due to the rapid curability utilizing photocuring.

  Further, the elastic layer on the surface of the base layer, the intermediate layer, and the base layer is low in hardness and hardly sticky and has excellent flexibility. Therefore, it can be said that it is difficult to give stress to the toner and a good image quality can be obtained over a long period of 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.

Claims (9)

  An elastic material for electrophotographic equipment comprising a cured product of a composition containing a photopolymerizable monomer and / or photopolymerizable oligomer and rubber. The photopolymerizable monomer is a (meth) acrylate monomer,
The elastic material for electrophotographic equipment according to claim 1, wherein the photopolymerizable oligomer is a (meth) acrylate oligomer.   The electrophotographic monomer according to claim 1, wherein the photopolymerizable monomer and / or photopolymerizable oligomer includes a photopolymerizable monomer and / or photopolymerizable oligomer having an ethylene oxide unit in a molecular structure. Elastic material for equipment.   The said rubber | gum contains the 1 type (s) or 2 or more types selected from a chloroprene rubber, a nitrile rubber, a hydrin rubber, an ethylene propylene (diene) rubber, and a natural rubber in any one of Claim 1 to 3 characterized by the above-mentioned. Elastic material for electrophotographic equipment.   The elastic material for electrophotographic equipment according to any one of claims 1 to 4, wherein the composition contains an ionic conductive agent.   An electrophotographic apparatus member comprising the electrophotographic apparatus elastic material according to claim 1.   An electroconductive roll for electrophotographic equipment using the elastic material for electrophotographic equipment according to any one of claims 1 to 5.   An electroconductive belt for electrophotographic equipment, comprising the elastic material for electrophotographic equipment according to any one of claims 1 to 5.   A method for producing an elastic material for an electrophotographic apparatus, comprising a step of irradiating a composition containing a photopolymerizable monomer and / or photopolymerizable oligomer and rubber with an active energy ray and curing the composition.