JP2007256709A - Roll for electrophotographic equipment and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a roll for electrophotographic equipment which hardly causes failure in an image and can secure releasing property over a long term, and a manufacturing method by which the roll is more easily obtained than in the conventional method. <P>SOLUTION: The roll for electrophotographic equipment is equipped with a rubber layer on the outermost periphery of the roll, wherein the rubber of at least the surface part of the rubber layer has structure shown by chemical formula 1 and chemical formula 2. The roll is obtained by bringing (A) one or two or more kinds of compounds selected from compounds shown by X<SP>1</SP>(OX<SP>2</SP>)<SB>n</SB>(provided that X<SP>1</SP>shows a hydrogen atom, an alkali metal element, an alkaline earth metal element or an alkyl group, and X<SP>2</SP>shows a halogen atom and n shows the same integer as the valence of X<SP>1</SP>) and compounds having -CONX<SP>2</SP>- bonding in a molecule (provided that X<SP>2</SP>is a halogen atom) and (B) BF<SB>3</SB>into contact with the surface of the rubber layer containing the rubber having unsaturated bonding, and then washing away the surface of the rubber layer with a liquid containing water. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a roll for electrophotographic equipment and a method for producing the roll.

  In recent years, electrophotographic apparatuses such as copying machines, printers, and facsimiles that employ an electrophotographic system have been widely used. Usually, this type of electrophotographic apparatus incorporates a photosensitive drum, and a roll for an electrophotographic apparatus such as a charging roll, a transfer roll, a developing roll, and a toner supply roll is disposed around the photosensitive drum. Yes.

  In general, the roll for electrophotographic equipment needs to have releasability from toner. For this reason, a resin layer made of a fluororesin, a silicone resin, or the like that hardly adheres toner is often formed on the outermost periphery of the roll.

  Further, an attempt has been made to impart releasability to the toner by forming the outermost roll periphery as a rubber layer without subjecting the resin layer to surface treatment of the surface of the rubber layer.

  For example, Patent Document 1 discloses a roll for electrophotographic equipment in which a fluorine compound is chemically bonded to the rubber layer surface on the outermost periphery of the roll by atmospheric pressure plasma treatment.

  By the way, as a surface treatment method of rubber, for example, Patent Document 2 discloses a method in which a fluorine-based oligomer containing a fluoroalkyl group and a silane coupling agent are applied to the surface of a crosslinked rubber and then heat-treated. Yes. According to this method, it is said that the fluorine treatment effect can be stably exhibited even in the case of contact with a solvent.

  Patent Document 3 discloses a method of forming a treatment layer on a rubber surface using a treatment liquid containing a fluoroalkyl group-containing fluorine-based oligomer and a polyfunctional alkoxysilane. According to this method, it is said that antifouling properties can be imparted to the rubber surface.

  In Patent Document 4, the rubber surface is treated with an organic / inorganic halogenating agent such as chloroisocyanuric acid or acidified hypochlorite, and at the same time, it is treated with a static physical field and / or a high-frequency alternating physical field. A method is disclosed. According to this method, it is said that the adhesiveness of rubber can be improved.

  Patent Document 5 discloses a method in which a solution containing a halogen compound such as alkyl hypohalide or hypochlorite is applied to the surface of a polyolefin-based rubber and then vulcanized. According to this method, it is said that the adhesion to paints, adhesives, etc. can be improved.

JP 2003-165857 A JP 2004-67882 A JP 2003-253022 A JP-T 9-507690 JP-A-62-39638

  However, conventionally known rolls for electrophotographic equipment have the following problems.

  That is, the resin layer is harder than the rubber layer. Further, since a conductive agent such as carbon black is usually added to the resin layer in order to adjust the electric resistance, this also makes the resin layer harder.

  For this reason, when a conventional roll for electrophotographic equipment having a resin layer is used for a long time, the resin layer damages the photosensitive drum as a counterpart material or deteriorates the toner. As a result, there has been a problem that an image of the electrophotographic apparatus is defective.

  Further, when the interface strength between the resin layer and the lower layer is not sufficient, the resin layer is peeled off, and this also causes a problem that an image of the electrophotographic apparatus is defective.

  On the other hand, since the roll for electrophotographic equipment of Patent Document 1 performs plasma treatment on the surface of the rubber layer, an expensive processing apparatus is required. Therefore, there has been a problem that the manufacturing cost of the roll becomes high.

  In addition, the surface treatment methods of Patent Documents 2 and 3 have a problem that the releasability with respect to the toner cannot be ensured over a long period of time and the durability is poor. These methods use a fluorine-based oligomer having a relatively high molecular weight. Therefore, although it reacts with rubber, it is presumed that the film is formed because the molecular weight is large, and that the cause is that the coated treatment layer is peeled off from the interface or cracked.

  Moreover, the surface treatment method of Patent Document 4 requires a high reaction field to treat the rubber surface. Therefore, there has been a problem that the manufacturing cost of the roll becomes high.

  Moreover, even if the surface treatment method of Patent Document 5 is used, good images and long-term releasability cannot be ensured.

  Accordingly, the problem to be solved by the present invention is to provide a roll for an electrophotographic apparatus in which image defects do not easily occur over a long period of time and can ensure releasability with respect to toner. Another object is to provide a production method capable of easily obtaining the roll for an electrophotographic apparatus as compared with the conventional one.

  In order to solve the above-mentioned problems, the roll for electrophotographic equipment according to the present invention comprises a rubber layer containing rubber having an unsaturated bond on the outermost periphery of the roll, and the rubber on at least the surface portion of the rubber layer is And having the structure of Chemical Formula 2

On the other hand, the method for producing a roll for electrophotographic equipment according to the present invention is located on the outermost periphery of the roll, on the surface of a rubber layer containing rubber having an unsaturated bond,
(A) X ¹ (OX ² ) _n (where X ¹ is a hydrogen atom, alkali metal element, alkaline earth metal element or alkyl group, X ² is a halogen atom, and n is the same as the valence of X ¹⁾ And a compound having a —CONX ² — bond in the molecule (where X ² is a halogen atom),
(B) BF ₃ ,
A first step of contacting
The gist of the present invention is to have a second step of rinsing the surface of the rubber layer that has undergone the first step with a liquid containing water.

  In this case, the first step is preferably performed by bringing a treatment liquid containing the (A) and (B) into contact with the surface of the rubber layer.

  The roll for electrophotographic equipment according to the present invention includes a rubber layer on the outermost periphery of the roll. Therefore, compared with the case where the resin layer is provided on the outermost periphery of the roll, the roll surface is more flexible. Therefore, stress on the counterpart material can be greatly reduced, and image quality defects are unlikely to occur. Further, since the resin layer is not used in order to ensure releasability, image quality defects due to peeling or cracking of the resin layer do not occur.

  Further, the rubber in at least the surface portion of the rubber layer has the structures of Chemical Formula 1 and Chemical Formula 2. For this reason, it is possible to ensure releasability over a long period of time as compared with the conventional case, and the durability is excellent.

  Furthermore, the structures of Chemical Formula 1 and Chemical Formula 2 can be introduced by a relatively simple method. Therefore, the roll for electrophotographic equipment according to the present invention is easy to reduce the manufacturing cost as compared with the conventional roll, and is excellent in mass productivity.

  On the other hand, the method for producing a roll for electrophotographic equipment according to the present invention has the first step described above, and is derived from the compound (A) in the unsaturated bond portion of the rubber on at least the surface portion of the rubber layer. And a fluorine atom derived from the compound (B) are introduced. Moreover, since it has the said 2nd process, the hydroxyl group derived from water is further introduce | transduced into the part of the unsaturated bond of the said rubber | gum.

  Therefore, according to the method for manufacturing a roll for electrophotographic equipment according to the present invention, the roll for electrophotographic equipment can be obtained relatively simply and inexpensively without requiring large-scale equipment and expensive equipment.

  At this time, when the first step is performed by bringing the treatment liquid containing the compound (A) and the compound (B) into contact with the surface of the rubber layer, the step can be simplified. Can be performed efficiently.

  Hereinafter, the roll for an electrophotographic apparatus according to the present embodiment (hereinafter sometimes referred to as “main roll”), and the method for manufacturing the roll for electrophotographic apparatus according to the present embodiment (hereinafter referred to as “present manufacturing method”). Will be described in detail.

1. This roll This roll is provided with a rubber layer, and the rubber on the surface portion of this rubber layer has a specific molecular structure.

  In the present roll, the rubber layer is located on the outermost periphery of the roll. In other words, if the rubber layer is on the outermost periphery, this roll may have, for example, one rubber layer or one or more elastic layers under the rubber layer. May be.

  Further, the rubber layer may be formed thick enough to form, for example, a roll body, or may be formed in a thin film shape.

  The roll structure, the rubber layer, and the thickness of the elastic layer under the rubber layer are selected as appropriate in consideration of the purpose of the roll, the installation space inside the electrophotographic apparatus in which the roll is incorporated, and the type of electrophotographic apparatus. can do.

  As a specific configuration of the present roll, for example, a configuration having one rubber layer on the outer periphery of a conductive shaft made of metal or the like, or one or more elastic layers on the outer periphery of the shaft, A configuration having the rubber layer (for example, a film shape, a tube shape, etc.) on the outer periphery of the elastic layer can be exemplified.

  In the present roll, the rubber layer preferably contains mainly a rubber having an unsaturated bond (in the present application, “rubber” includes a thermoplastic elastomer, which will be omitted hereinafter). This is because, as will be described later, if the unsaturated bond of the rubber layer is used, the structures of Chemical Formula 1 and Chemical Formula 2 can be easily introduced into the molecular structure of rubber.

  Specific examples of the rubber include acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (H-NBR), butadiene rubber (BR), isoprene rubber (IR), and styrene-butadiene rubber (SBR). ), Epichlorohydrin rubber (ECO), acrylic rubber, chloroprene rubber (CR), butyl rubber, ethylene / propylene rubber, ethylene-propylene-diene rubber (EPDM), silicone rubber, urethane rubber, natural rubber, and the like. These may be contained alone or in combination of two or more.

  Of these, acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), styrene-butadiene rubber (SBR), epichlorohydrin rubber (ECO), and the like are preferable.

  In the rubber layer, a conductive agent (electronic conductive agent, ionic conductive agent), a filler, an extender, a reinforcing agent, an activator, a processing aid, a vulcanization accelerator, and a vulcanizing agent are added as necessary. In addition, one or more various additives such as an antioxidant, a plasticizer, a colorant, an ultraviolet absorber, and a foaming agent may be contained.

  As the proportion of the additive, conventionally known blending proportions can be appropriately adopted so that various additives can achieve their purpose.

  In addition, when it has an elastic layer in the lower layer of a rubber layer, the said rubber | gum etc. which contain the said additive arbitrarily can be illustrated as an elastic layer material. Moreover, when it has two or more elastic layers, each elastic layer may be the same material and composition, and a different material and composition may be sufficient as it.

  Here, the rubber of at least the surface portion of the rubber layer has the following structures 1 and 2. That is, among the rubbers contained in the rubber layer, the rubber existing at least on the surface portion has the following chemical structures 1 and 2 in the molecular structure.

Preferred examples of X ^{2 in} Chemical Formulas 1 and ² include Cl and F.

  At this time, it is preferable that the rubber having the structure of Chemical Formula 1 and Chemical Formula 2 (hereinafter referred to as “specific rubber”) exists so as to cover most of the surface of the rubber layer. However, it does not necessarily have to exist on the entire surface of the rubber layer. That is, the specific rubber may partially exist on the surface of the rubber layer as long as the effect of the present invention is achieved.

  The specific rubber may exist not only in the surface portion of the rubber layer but also in the rubber layer. In this case, the presence state of the specific rubber inside the rubber layer is not particularly limited.

  Specifically, for example, the specific rubber may be distributed so as to decrease or increase from the rubber layer surface toward the inside, or at a constant distance from the rubber layer surface to the inside. It may be distributed at almost the same existence ratio.

  In addition, it can confirm that it has the structure of the said Chemical formula 1 and Chemical formula 2 if the roll surface is analyzed by X-ray photoelectron spectroscopy (XPS), a nuclear magnetic resonance method (NMR), etc.

  The main roll can be suitably used as a conductive roll such as a developing roll, a charging roll, a toner supply roll, and a transfer roll.

2. This manufacturing method This manufacturing method is a method which can manufacture this roll which has the above-mentioned composition, and includes the following 1st processes and 2nd processes at least. Hereinafter, it demonstrates in order.

2.1 First Step In this production method, the first step is located on the outermost periphery of the roll and on the surface of the rubber layer containing rubber having an unsaturated bond, a specific (A) compound and a specific (B) It is a step of contacting at least a compound.

  In addition, the roll which has the rubber layer containing the rubber | gum which has an unsaturated bond before making the said specific compound contact can be prepared using a well-known method. For example, a method of extruding the rubber layer material described above on the surface of a conductive shaft optionally coated with a primer such as an adhesive, the rubber layer material described above is injected into a mold set with the conductive shaft. Examples of the method include removing the mold after heating and curing.

  In this case, when an elastic layer is formed below the rubber layer, one or more elastic layer materials described above are extruded or injection molded on the outer periphery of the conductive shaft, and then the outermost elastic layer surface is formed. Further, a rubber layer material may be applied by a roll coating method, a dipping method, a spray coating method, or the like, dried, and crosslinked.

Here, the compound (A) is X ¹ (OX ² ) _n (where X ¹ is a hydrogen atom, an alkali metal element, an alkaline earth metal element or an alkyl group, X ² is a halogen atom, and n is X represents a positive integer identical to the valence of X ¹ ), and a compound having a —CONX ² — bond in the molecule (where X ² is a halogen atom), or one or more A compound.

  Specific examples of the alkali metal element include lithium, sodium, and potassium.

  Specific examples of the alkaline earth metal element include magnesium and calcium.

  Specific examples of the alkyl group include a methyl group, an ethyl group, a tertiary butyl group, and a trifluoromethyl group. From the viewpoint of structural stability, a tertiary butyl group is preferable.

Specific examples of the halogen atom X ² include F, Cl, Br, and I. Preferably, F, Cl and the like are used from the viewpoint of being likely to be stably present on the rubber layer surface after the reaction.

More specifically, examples of the compound represented by X ¹ (OX ² ) _n include alkyl hypochlorides such as methyl hypochloride, ethyl hypochloride, tertiary butyl hypochloride, trifluoromethyl hypochloride, and methyl. Alkyl hypohalides such as hypofluoride, ethyl hypofluoride, tertiary butyl hypofluoride, alkyl hypofluoride such as trifluoromethyl hypofluoride, hypochlorous acid, lithium hypochlorite, hypochlorous acid, etc. Examples include hypochlorites such as sodium chlorate, magnesium hypochlorite, and potassium hypochlorite. These may be used alone or in combination of two or more.

More specifically, examples of the compound having a —CONX ² — bond in the molecule include acid imide halogen compounds such as N-chlorosuccinimide, N-chlorophthalimide, N-bromosuccinimide, N-bromophthalimide, and trichloro. Illustrative examples include isocyanuric halides such as isocyanuric acid and dichloroisocyanuric acid, and halogenated hydantoins such as dichlorodimethylhydantoin.

On the other hand, the compound (B) is a BF _3.

  The compound (A) and / or the compound (B) may be a single substance, or may be dissolved and / or dispersed in a liquid. That is, “contacting” in the first step includes not only the case where the compound itself is brought into direct contact with the surface of the rubber layer, but also the case where a liquid containing the compound is brought into contact.

  In the first step, the compound (A) and the compound (B) as described above are brought into contact with the surface of the rubber layer. In this case, the contact is a method in which either the compound (A) or the compound (B) is brought into contact with the surface of the rubber layer, and then the other compound is contacted (hereinafter referred to as “step contact method”). Or a method of contacting the compound (A) and the compound (B) almost simultaneously (hereinafter sometimes referred to as “simultaneous contact method”).

  Preferably, the contact is performed by the latter simultaneous contact method. This is because the process can be simplified and the surface treatment can be performed efficiently.

  Moreover, when using any of the above-mentioned step contact method and simultaneous contact method, a liquid containing at least each compound may be used. This is because there are advantages such as easy contact with the rubber surface uniformly.

  Specifically, for example, in the case of the above-described step contact method, a treatment liquid in which at least (A) compound or (B) compound is dissolved and / or dispersed in an appropriate aqueous solvent or organic solvent may be used. On the other hand, in the case of the simultaneous contact method, a treatment solution in which at least the (A) compound and the (B) compound are dissolved and / or dispersed in an appropriate aqueous solvent or organic solvent may be used.

  Specific examples of the aqueous solvent include water, and specific examples of the organic solvent include toluene, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, butyl acetate, hexane, methanol, ethanol, and propanol. And tertiary butanol, isopropyl alcohol, diethyl ether, N-methylpyrrolidone and the like. These may be used alone or in combination.

  Further, the content of the compound (A) and / or the compound (B) contained in the treatment liquid is particularly limited as long as the specific rubber can be finally present at least on the surface portion of the rubber layer. is not. It can be adjusted as necessary.

  In the case of the above-described step contact method, the content of the compound (A) contained in the treatment liquid containing the compound (A) can be specifically exemplified by, for example, 40 wt% as a preferable upper limit value. . On the other hand, as a preferable lower limit value that can be combined with this upper limit value, specifically, for example, 0.01 wt% can be exemplified.

  In the case of the step contact method, the content of the compound (B) contained in the treatment liquid containing the compound (B) is specifically exemplified by, for example, 40 wt% as a preferable upper limit value. Can do. On the other hand, as a preferable lower limit value that can be combined with this upper limit value, specifically, for example, 0.01 wt% can be exemplified.

  This is because when the content of the compound (A) or the compound (B) contained in each treatment liquid is within the above range, the balance between the reactivity to rubber and the rubber hardness is excellent.

  In the case of the simultaneous contact method, the content of the compound (A) contained in the treatment liquid containing the compound (A) and the compound (B) is specifically, for example, 40 wt% as a preferable upper limit value. Etc. can be illustrated. On the other hand, as a preferable lower limit value that can be combined with this upper limit value, specifically, for example, 0.01 wt% can be exemplified. Similarly, specific examples of the content of the compound (B) include 40 wt% as a preferable upper limit. On the other hand, as a preferable lower limit value that can be combined with this upper limit value, specifically, for example, 0.01 wt% can be exemplified.

  When the contents of the compound (A) and the compound (B) contained in the treatment liquid containing the compound (A) and the compound (B) are within these ranges, the balance between the reactivity to rubber and the rubber hardness, etc. It is because it is excellent in.

  In this case, specific examples of the preferable upper limit of the (A) compound / (B) compound (weight ratio) include, for example, 9 (90/10). On the other hand, specific examples of preferable lower limit values that can be combined with these preferable upper limit values include 0.01 (1/99).

  This is because when the (A) compound / (B) compound (weight ratio) is within these ranges, the balance between the reactivity to the unsaturated bond and the effect of introducing fluorine atoms is excellent.

  In the first step, the contact with the compound can basically be performed at around room temperature, but the contact temperature is appropriately adjusted as necessary within a range that does not adversely affect the production of the specific rubber. Also good.

  However, if the contact temperature is excessively high, the reaction proceeds excessively, and a tendency is observed such that the surface of the rubber layer is cracked or excessively hard. On the other hand, when the contact temperature is excessively lowered, the reaction with the rubber mainly constituting the rubber layer tends to decrease. Therefore, it is preferable to select the contact temperature in consideration of these.

  Further, the contact time with the compound varies depending on the concentration of the treatment liquid, but can be appropriately adjusted as necessary within a range that does not adversely affect the production of the specific rubber.

  However, if the contact time is excessively long, the roll production efficiency tends to decrease. On the other hand, when the contact time is excessively shortened, there is a tendency that the reaction with the rubber mainly constituting the rubber layer becomes insufficient. Therefore, it is preferable to select the contact time in consideration of these. Preferably, the contact time is in the range of 20 seconds to 60 seconds in consideration of productivity and reactivity.

  Moreover, the method of making the said process liquid contact the rubber layer surface is not specifically limited, A various method is employable. Specifically, for example, a method of immersing the roll in the treatment liquid, a method of applying the treatment liquid to the roll, a method of spraying the treatment liquid on the roll, and the like can be exemplified. These may be performed in combination of one or two or more.

  The first step can be performed in an inert gas such as nitrogen gas or argon gas, or in the atmosphere.

  By the above first step, the unsaturated bond contained in the rubber on the rubber layer surface portion is broken, and in the molecular structure of the rubber, a halogen atom derived from the compound (A), a fluorine atom derived from the compound (B) be introduced.

2.2 Second Step In this manufacturing method, the second step is a step of washing the surface of the rubber layer that has undergone the first step with a liquid containing water.

  Here, the method of washing the surface of the rubber layer with a liquid containing water is not particularly limited, and various methods can be employed. Specifically, for example, a method of immersing a roll in a liquid containing water, a method of spraying a liquid containing water on the roll, and the like can be exemplified. These may be performed in combination of one or two or more.

  Further, the washing time is not particularly limited and can be appropriately adjusted as necessary.

  However, if the washing time is excessively long, the roll production efficiency tends to decrease. On the other hand, if the washing time is excessively shortened, the reaction proceeds excessively due to the remaining treatment liquid, and the surface of the rubber layer tends to crack or become too hard. Therefore, it is only necessary to select the washing time with these points in mind.

  By this 2nd process, the (A) compound, (B) compound, etc. which have adhered to the surface of the rubber layer are washed away, and the roll surface becomes clean. Furthermore, hydroxyl groups are introduced into the molecular structure of the rubber on at least the surface portion of the rubber layer.

  In the first step, when a treatment liquid containing water is used, it is presumed that some hydroxyl groups are introduced into the molecular structure of the rubber also in the first step. In any case, according to this production method, a hydroxyl group derived from water is introduced into the molecular structure of the rubber on at least the surface portion of the rubber layer.

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

(Preparation of rubber composition)
100 parts by weight of butadiene rubber (BR) (manufactured by Zeon Corporation, “Nipol BR1220”), 0.5 parts by weight of stearic acid (manufactured by Kao Corporation, “Lunac S-30”), carbon black (Cabot -Japan Co., Ltd., "Show Black N220" 40 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 The rubber composition <1> was prepared by kneading with rubber.

  In the preparation of the rubber composition <1>, nitrile rubber (NBR) (manufactured by Nippon Zeon Co., Ltd., “Nipol DN401”) was used instead of butadiene rubber (BR), instead of 20 parts by weight of carbon black. A rubber composition <2> was prepared in the same manner except that 3 parts by weight of an ionic conductive agent (manufactured by Lion Corporation, “TBAHS”) was used.

  100 parts by weight of epichlorohydrin rubber (ECO) (manufactured by Daiso Corporation, “Epichromer CG102”), 1 part by weight of the stearic acid, 1 part by weight of the ionic conductive agent, and 2-mercaptoimidazoline (vulcanizing agent) By kneading 2 parts by weight (manufactured by Kawaguchi Chemical Industry Co., Ltd., "Accel 22S") and 5 parts by weight of an acid acceptor (manufactured by Kyowa Chemical Industry Co., Ltd., "DHT-4A") with a kneader A rubber composition <3> was prepared.

(Preparation of treatment liquid)
(A) Boron trifluoride-diethyl ether (containing 48 wt% of BF ₃ ) containing 5 g of tert-butyl hypochlorite (Tokyo Chemical Industry Co., Ltd.) as a compound and BF ₃ as a (B) compound , Manufactured by Kanto Chemical Co., Ltd.) was dissolved in 100 g of methyl ethyl ketone to prepare a treatment liquid <1>. The processing liquid <1> in (A) the concentration of hypochlorous acid tert- butyl 4.3 wt%, (B) the concentration of BF ₃ is 4.3wt%, (A) / ( B) ( weight ratio) Is 1.

A treatment liquid <2> was produced in the same manner as in the production of the treatment liquid <1> except that 0.1 g of tert-butyl hypochlorite and 20 g of boron trifluoride-diethyl ether were used. In the treatment liquid <2>, the concentration of (A) tert-butyl hypochlorite is 0.08 wt%, the concentration of (B) BF ₃ is 8.3 wt%, and (A) / (B) (weight ratio). Is 0.01.

A treatment liquid <3> was produced in the same manner as in the production of the treatment liquid <1> except that 9 g of tert-butyl hypochlorite and 2 g of boron trifluoride-diethyl ether were used. In the treatment liquid <3>, the concentration of (A) tert-butyl hypochlorite is 8 wt%, the concentration of (B) BF ₃ is 0.9 wt%, and (A) / (B) (weight ratio) is 9 It is.

In the preparation of the treatment liquid <1>, treatment liquid <4> was produced in the same manner except that 5 g of tert-butyl hypochlorite and 10 g of boron trifluoride-diethyl ether were used and 100 g of methyl ethyl ketone was not used. In the treatment liquid <4>, the concentration of (A) tert-butyl hypochlorite is 33 wt%, the concentration of (B) BF ₃ is 33 wt%, and (A) / (B) (weight ratio) is 1. .

A treatment liquid <5> was produced in the same manner as in the production of the treatment liquid <1> except that 1000 g of methyl ethyl ketone was used. In the treatment liquid <5>, the concentration of (A) tert-butyl hypochlorite is 0.05 wt%, the concentration of (B) BF ₃ is 0.05 wt%, and (A) / (B) (weight ratio). Is 1.

In the preparation of the treatment liquid <1>, treatment liquid <6> was similarly obtained except that 5 g of trichloroisocyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 5 g of tert-butyl hypochlorite. Was made. In the treatment liquid <6>, the concentration of (A) trichloroisocyanuric acid is 4.3 wt%, the concentration of (B) BF ₃ is 4.3 wt%, and (A) / (B) (weight ratio) is 1. is there.

  After adding 2 drops of acetic acid to 100 mL of a mixed solvent composed of 95% by volume of ethanol and 5% by volume of water, a fluoroalkyl group-containing compound represented by the following chemical formula 3 is added to the mixed solvent, Comparative treatment liquid <1> having a compound concentration of 1% by mass was produced.

In the preparation of the treatment liquid <1>, except that 5 g of the trichloroisocyanuric acid was used instead of 5 g of tert-butyl hypochlorite and 10 g of the boron trifluoride-diethyl ether was not used, Comparative treatment liquid <2> was prepared. In the comparative treatment liquid <2>, the concentration of (A) trichloroisocyanuric acid is 5 wt%, and the concentration of (B) BF ₃ is 0 wt%.

(Preparation of charging roll)
Example 1
After setting a metal shaft (diameter 6 mm) coated with an adhesive in the mold, the rubber composition <1> is injected into the mold, heated at 160 ° C. for 30 minutes and cured, and then demolded. did. As described above, a roll body having one rubber layer (thickness 4 mm) containing rubber having an unsaturated bond on the outer periphery of the conductive shaft was prepared.

  Next, the treatment liquid <1> was brought into contact with the surface of the rubber layer of the roll body for 60 seconds in an air atmosphere at 25 ° C. At this time, the contact was performed by immersing the roll body in the treatment liquid <1>.

  Next, the surface of the roll body in contact with the treatment liquid <1> was washed with water by immersing it in water for 30 seconds.

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

(Example 2)
A charging roll according to Example 2 was produced in the same manner as in Example 1, except that the rubber composition <2> was used instead of the rubber composition <1>.

(Example 3)
A charging roll according to Example 3 was produced in the same manner except that the rubber composition <3> was used instead of the rubber composition <1>.

Example 4
Example 1 is the same as Example 1 except that the rubber composition <2> was used instead of the rubber composition <1>, and the processing liquid <2> was used instead of the processing liquid <1>. Thus, a charging roll according to Example 4 was produced.

(Example 5)
Example 1 is the same as Example 1 except that the rubber composition <2> was used instead of the rubber composition <1>, and the processing liquid <3> was used instead of the processing liquid <1>. Thus, a charging roll according to Example 5 was produced.

(Example 6)
In Example 1, the same except that the rubber composition <2> was used instead of the rubber composition <1>, and the processing liquid <4> was used instead of the processing liquid <1>. Thus, a charging roll according to Example 6 was produced.

(Example 7)
The same as Example 1 except that the rubber composition <2> was used instead of the rubber composition <1>, and the processing liquid <5> was used instead of the processing liquid <1>. Thus, a charging roll according to Example 7 was produced.

(Example 8)
Example 1 is the same as Example 1 except that the rubber composition <2> was used instead of the rubber composition <1>, and the processing liquid <6> was used instead of the processing liquid <1>. Thus, a charging roll according to Example 8 was produced.

Example 9
In Example 1, the rubber composition <3> was used in place of the rubber composition <1>, a rubber layer was formed on the outer periphery of the conductive shaft, and a nitrile rubber (NBR) paint was further formed. A roll body in which a film-like rubber layer (rubber coating layer) (thickness: 100 μm) is further formed on the outer periphery of the lower rubber layer by fluorination treatment after crosslinking at 160 ° C. for 30 seconds. A charging roll according to Example 9 was produced in the same manner except that the above was prepared.

  The rubber paint is prepared by dissolving 100 g of the rubber composition <2> in 300 g of methyl ethyl ketone.

(Comparative Example 1)
In Example 1, the rubber composition <2> was used in place of the rubber composition <1>, the treatment liquid <1> was not brought into contact with the rubber layer surface, and the rubber layer surface was washed with water. A charging roll according to Comparative Example 1 was produced in the same manner except for the absence.

(Comparative Example 2)
A roll in which a film-like rubber layer is further formed on the outer periphery of the rubber layer in the same manner as in Example 9 except that the rubber composition <2> is used in place of the rubber composition <1> in Example 1. A charging roll according to Comparative Example 2 was produced in the same manner except that the body was prepared, the treatment liquid <1> was not brought into contact with the rubber layer surface, and the rubber layer surface was not washed with water.

(Comparative Example 3)
In Example 1 described above, the rubber composition <2> was used instead of the rubber composition <1>, a rubber layer was formed on the outer periphery of the conductive shaft, and then an acrylic resin (Sumitomo Chemical) was used. Co., Ltd., “LG6A”) 100 parts by weight Carbon for paint (Mitsubishi Chemical Co., Ltd., “MA100”) 20 parts by weight and acrylic particles (Negami Kogyo Co., Ltd., “Art Pearl G” -800 ") 15 parts by weight of a resin composition is diluted and dispersed to 20 wt% using methyl ethyl ketone, and this liquid is applied to form a film-like resin layer (thickness 30 μm) on the outer periphery of the lower rubber layer A charging roll according to Comparative Example 2 was produced in the same manner except that a roll body having a shape formed thereon was prepared. Since the roll surface is a resin layer, the charging roll according to Comparative Example 3 is not in contact with the treatment liquid <1> and washed with water.

(Comparative Example 4)
In Example 1, the rubber composition <2> was used in place of the rubber composition <1>, a rubber layer was formed on the outer periphery of the conductive shaft, and then a fluororesin (Daikin Industries) was used. 20 parts by weight of the coating carbon and 35 parts by weight of silica particles (manufactured by Tosoh Silica Co., Ltd., “Nipgel AZ-800”) with respect to 100 parts by weight of “Daiel Latex GL152” manufactured by Co., Ltd. A roll body in which a film-like resin layer (thickness 30 μm) was formed on the outer periphery of the lower rubber layer was prepared by diluting and dispersing the resin composition containing 20 wt% using methyl ethyl ketone and applying this liquid. A charging roll according to Comparative Example 4 was produced in the same manner except for the above point. Since the roll surface is a resin layer, the charging roll according to Comparative Example 4 is not contacted with the treatment liquid <1> and washed with water.

(Comparative Example 5)
In Example 1, the rubber composition <2> was used instead of the rubber composition <1>, except that the comparative processing liquid <1> was used instead of the processing liquid <1>. Thus, a charging roll according to Comparative Example 5 was produced.

(Comparative Example 6)
In Example 1, the rubber composition <2> was used instead of the rubber composition <1>, except that the comparative processing liquid <2> was used instead of the processing liquid <1>. Thus, a charging roll according to Comparative Example 6 was produced.

(Rubber structure on the surface of the rubber layer of the charging roll according to the embodiment)
About the charging roll which concerns on the produced said Example, the rubber structure of the rubber layer surface was investigated using XPS and NMR. As a result, it was confirmed that the rubber on the surface portion of the rubber layer had the structures of Chemical Formula 1 and Chemical Formula 2 (where X ² is Cl) in any of the Examples.

(Evaluation of each charging roll)
About each charging roll which concerns on an Example and a comparative example, the following 3 items were evaluated.

1. Roll surface hardness As reference data, the surface hardness of each charging roll was measured (N = 3) with an MD-1 hardness meter (manufactured by Kobunshi Keiki Co., Ltd., “Micro rubber hardness meter MD-1 type”).

2. Density unevenness Each charging roll is incorporated into a commercially available color laser printer (manufactured by Canon Inc., “LBP-2510”), and images are printed in an environment of 20 ° C. × 50% RH. went. At this time, there was no density unevenness in the halftone image, thin lines were broken, color unevenness, and no streak image were accepted, and those with density unevenness were rejected.

3. Adhesiveness of external additives after durability evaluation 2. Under the same conditions as described above, the image was passed through 1000 sheets (A4 size), and the subsequent roller appearance was confirmed. That is, when such durability evaluation is performed, a phenomenon occurs in which an external additive such as silica that has been removed from the toner adheres to the roll surface.

  Here, after the durability evaluation, there is almost no white powder on the roll surface, and there is no image disturbance, or the white powder adheres slightly on the roll surface, but there is no image disturbance. did. On the other hand, after durability evaluation, the white powder adhered on the roll surface, and the case where the adhesion nonuniformity produced in the image was made disqualified.

  Table 1 below summarizes the evaluation results.

  According to Table 1, the following can be understood. That is, it can be seen that none of the charging rolls according to Comparative Examples 1 to 6 has a hard roll surface, image defects, or sufficient releasability over a long period of time.

  On the other hand, any of the charging rolls according to Examples 1 to 9 has a structure in which the roll surface is flexible and has excellent releasability, so that image defects are hardly caused and sufficient for a long period of time. It can be seen that releasability can be secured.

  In addition, since the charging rolls according to Examples 1 to 9 do not have the resin layer, it can be said that image quality defects due to peeling or cracking of the resin layer hardly occur. Further, compared with the charging rolls according to Comparative Examples 3 and 4 having a resin layer, the repetition speed of static elimination and discharge is increased, and an improvement in charge imparting performance and charging performance to the toner can be expected.

  In addition, the charging rolls according to Examples 1 to 9 are subjected to extremely simple processes such as bringing a treatment liquid containing a specific compound into contact with the surface of the rubber layer located on the outermost periphery of the roll and washing with water. Obtainable.

  Therefore, it can be said that according to the method for manufacturing a charging roll according to the above-described embodiment, each charging roll having the above-described effects can be easily manufactured as compared with the conventional one.

  While the embodiments and examples of the present invention have been described above, 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.

Claims (3)

A roll for an electrophotographic apparatus, comprising a rubber layer containing a rubber having an unsaturated bond on the outermost periphery of the roll, wherein at least a surface portion of the rubber layer has a structure represented by the following chemical formula 1 and chemical formula 2.

Located on the outermost periphery of the roll, on the surface of the rubber layer containing rubber having an unsaturated bond,
(A) X ¹ (OX ² ) _n (where X ¹ is a hydrogen atom, alkali metal element, alkaline earth metal element or alkyl group, X ² is a halogen atom, and n is the same as the valence of X ¹⁾ And a compound having a —CONX ² — bond in the molecule (where X ² is a halogen atom),
(B) BF ₃ ,
A first step of contacting
And a second step of rinsing the surface of the rubber layer after the first step with a liquid containing water.   The said 1st process is by making the process liquid containing the said (A) and (B) contact the surface of the said rubber layer, The manufacture of the roll for electrophotographic apparatuses of Claim 2 characterized by the above-mentioned. Method.