JP2011013478A - Roll for image forming apparatus, method for producing the same and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a roll for an image forming apparatus having releasability over a longer period of time as compared with a roll comprising a fluorinated polyimide resin having no ether group in a main chain.SOLUTION: In the roll for an image forming apparatus, at least the outer surface of a surface layer comprises a fluorinated polyimide resin having an ether group in a main chain.

Description

  The present invention relates to a roll for an image forming apparatus, a manufacturing method thereof, and an image forming apparatus.

  In an image forming apparatus such as a copying machine, a printer, a facsimile, or an electrophotographic apparatus, an unfixed image or an untransferred image such as a toner image is fixed on a recording member such as a recording sheet by, for example, heating or electrostatic force. A fixing roll or an intermediate transfer roll made of a rotating body made of metal, plastic, rubber or the like to be transferred is used. For example, an elastic layer having elasticity and a surface layer having releasability are laminated and formed on a support made of aluminum, iron, stainless steel, or the like. Here, silicone rubber or the like is used as the elastic layer, and fluororubber or fluororesin is used as the surface layer. In particular, fluororesin is often used in terms of releasability.

  As a fixing device using the above-described roll, for example, a belt nip type has been proposed (for example, see Patent Document 1). The fixing device mainly includes a rotatable fixing roll and an endless belt that is arranged to contact the fixing roll and rotate according to the fixing roll. In the fixing operation using the fixing device having such a configuration, the contact portion between the fixing roll whose surface is heated and the endless belt is passed through a recording member such as a recording paper on which a toner image is formed, thereby allowing the toner to pass through. This is done by heat-fixing the image on the surface of the recording paper.

In this case, as the surface layer (release layer) of the fixing roll, PFA resin (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) is mainly used, and depending on the application, carbon may be dispersed to provide conductivity. Improved resins and resins improved in durability by mixing inorganic fillers such as SiO ₂ and BaSO ₄ are used.

  As a method not using a PFA resin as the surface layer (release layer), for example, a method using fluorinated polyimide has been proposed (see Patent Documents 2 to 4).

  In addition, since the surface layer (release layer) made of fluororesin is not directly adhered to the elastic layer made of silicone, a method of providing an adhesive layer such as a silane coupling agent after surface treatment such as excimer laser is adopted. Has been.

  On the other hand, rather than the partially fluorinated polyimides used in the past, fully fluorinated polyimide resin has been studied as a material for optical communication and has been developed for waveguide applications that utilize the transparency of light in the communication wavelength band. Have been studied (see Patent Documents 5 and 6).

JP-A-8-262903 Patent publication 3069041 JP 2000-137396 A Japanese Patent No. 4142465 Japanese Patent Publication No. 2737871 Japanese Patent No. 3085666

  An object of the present invention is to provide a roll for an image forming apparatus that has releasability over a long period of time compared to a case where the main chain is made of a fluorinated polyimide resin having no ether group.

  In order to achieve the above object, according to the present invention, the following roll for an image forming apparatus, a method for manufacturing the roll, and an image forming apparatus are provided.

[1] A roll for an image forming apparatus having a surface layer composed of a fluorinated polyimide resin having at least an outer surface having an ether group in the main chain.

[2] The fluorinated polyimide resin having an ether group in the main chain is a resin prepared from a fluorinated polyamic acid synthesized from a fully fluorinated acid anhydride and a fluorinated diamine. A roll for an image forming apparatus as described in 1.

[3] The perfluorinated acid anhydride has the following chemical formula (1) or (2):

  The fluorinated diamines are represented by the following chemical formula (3):

  The roll for an image forming apparatus according to [2], which is represented by

[4] The roll for an image forming apparatus according to [3], wherein the fluorinated diamines are any of those represented by the following chemical formulas (4) to (13).

[5] The roll for an image forming apparatus according to any one of [1] to [4], wherein the fluorinated polyimide resin having an ether group in the main chain is a resin having a perfluoroalkyl group in a side chain.

[6] The roll for an image forming apparatus according to any one of [1] to [5], further including a cylindrical elastic layer laminated on the back side of the surface layer.

[7] An image forming apparatus using the roll for image forming apparatus according to any one of [1] to [6].

[8] A columnar or cylindrical support or a laminate in which an elastic layer is laminated on the support are prepared, and a fully fluorinated acid anhydride and fluorinated diamines are prepared on the support or laminate. Fluorinated polyamic acid (fluorinated polyimide precursor solution) synthesized from the above is applied to form a coating film to be a surface layer, and then the formed coating film is heated and baked to form a surface layer. A method for manufacturing a roll for an image forming apparatus.

[9] The perfluorinated acid anhydride has the following chemical formula (1) or (2):

  The fluorinated diamines are represented by the following chemical formula (3):

  The manufacturing method of the roll for image forming apparatuses as described in said [8] which is represented by these.

[10] The method for producing a roll for an image forming apparatus according to [9], wherein the fluorinated diamines are any of those represented by the following chemical formulas (4) to (13).

[11] When forming the coating film on the laminate, the surface of the elastic layer constituting the laminate is irradiated with vacuum ultraviolet light having a wavelength of 180 nm or less before forming the coating film. The method for producing a roll for an image forming apparatus according to any one of [8] to [10], further comprising hydrophilizing the surface of the elastic layer.

[12] The method for manufacturing a fixing roll for image formation according to [11], wherein the vacuum ultraviolet light is emitted from a dielectric barrier discharge excimer lamp having a wavelength of 172 nm.

  According to the first to fifth aspects of the present invention, there is provided a roll for an image forming apparatus having releasability over a long period of time as compared with a case where the main chain is made of a fluorinated polyimide resin having no ether group. can do.

  According to the sixth aspect of the present invention, it is possible to provide a roll for an image forming apparatus that is further excellent in durability as compared with the case where the intermediate layer does not have an elastic layer.

  According to the seventh aspect of the present invention, it is possible to provide an image forming apparatus in which the smearing of the image is suppressed for a long period of time as compared with the case where the roll for the image forming apparatus having this configuration is not used.

  According to the eighth to tenth aspects of the present invention, it is possible to efficiently manufacture a roll for an image forming apparatus having releasability over a long period of time as compared with the case where the present configuration is not provided.

  According to the invention which concerns on Claims 11-12, after performing surface treatments, such as an excimer laser, the number of processes can be reduced compared with the method of providing adhesive layers, such as a silane coupling agent.

1 is a perspective view showing a roll for an image forming apparatus according to a first embodiment of the present invention (when a single surface layer is supported by a support). It is a longitudinal cross-sectional view of the roll for image forming apparatuses shown to FIG. 1A. It is a cross-sectional view of a roll for the image forming apparatus shown in FIG. 1A. It is a perspective view which shows the roll for the image forming apparatus which concerns on the 2nd Embodiment of this invention (when the multilayer of a surface layer and an elastic layer is supported by the support body). It is a longitudinal cross-sectional view of the roll for image forming apparatuses shown to FIG. 2A. It is a cross-sectional view of a roll for the image forming apparatus shown in FIG. 2A.

[Roll for Image Forming Apparatus According to First Embodiment]
FIG. 1A is a perspective view showing a roll for an image forming apparatus according to a first embodiment of the present invention (when a single surface layer is supported by a support). 1B is a longitudinal sectional view of a roll for the image forming apparatus shown in FIG. 1A. 1C is a cross-sectional view of the roll for the image forming apparatus shown in FIG. 1A.

  As shown in FIGS. 1A to 1C, a roll 10 for an image forming apparatus according to a first embodiment of the present invention is an image forming apparatus (not shown) that forms an image on a recording member (not shown). ), A roll 10 for an image forming apparatus used as a fixing roll or an intermediate transfer roll for fixing or transferring an unfixed image or an untransferred image on a recording member, and a cylinder that contacts the recording member at the time of fixing or transferring The surface layer 11 (or at least the outermost layer when the surface layer 11 itself comprises a plurality of layers) is made of a fluorinated polyimide resin having an ether group in the main chain. .

  In FIGS. 1A to 1C, as described above, a case where a cylindrical shape is used as the surface layer 11 is shown, but for example, a rectangular tube, an elliptical tube, or the like may be used. Moreover, although the case where the thing of a single layer was used as mentioned above was shown, for example, even if the surface layer 11 itself consists of a plurality of layers, it is composed of a single layer and has ether in the main chain from the inside to the outside. The content of the fluorinated polyimide resin having a group may be increased stepwise or in a gradient. In these cases, the outer surface needs to be composed of a fluorinated polyimide resin having an ether group in the main chain.

  Note that the roll 10 for the image forming apparatus according to the first embodiment may have a surface layer as a layer supported on a support 50 described later, for example, even if the surface layer 11 itself is composed of a plurality of layers. 11, for example, an elastic layer 12 (see FIG. 2A), which will be described later, or the like. For example, it is included in the case of not having an elastic layer or the like.

  The surface layer 11 of the roll 10 for the image forming apparatus according to the first embodiment (or at least the outermost layer when the surface layer 11 itself includes a plurality of layers) is a fluorine having an ether group in the main chain as described above. It is composed of a modified polyimide resin. Examples of such a fluorinated polyimide resin having an ether group in the main chain include a resin prepared from a fluorinated polyamic acid synthesized from a fully fluorinated acid anhydride and a fluorinated diamine. it can.

  When the roll for an image forming apparatus according to the present embodiment is used as a charged body using an electrostatic force such as a transfer roll (transfer body, transfer (contact charging) film), the surface of the roll 10 for the image forming apparatus When the conductive particles can be dispersed in the layer 11 and the roll of this embodiment is manufactured using a PI precursor solution or a fluorinated PI precursor solution (fluorinated polyimide varnish) as described later. It is preferable to add these conductive particles to the PI precursor solution or the fluorinated PI precursor solution.

Examples of the conductive particles include carbon black, carbon beads obtained by granulating carbon black, carbon fibers, carbon-based materials such as graphite, metals or alloys such as copper, silver, and aluminum, tin oxide, indium oxide, antimony oxide, Examples thereof include conductive metal oxides such as SnO ₂ —In ₂ O ₃ composite oxide, and conductive whiskers such as potassium titanate. Among these, carbon black particles are preferable because predetermined conductivity can be obtained with a small addition amount.

  Further, when the roll for the image forming apparatus of the present embodiment is used as a fixing roll (fixing body, fixing film), the releasability of the toner image adhering to the outer peripheral surface of the roll 10 for the image forming apparatus is improved. Therefore, it is also effective to add fine particles of a resin coating material having releasability to the PI precursor solution or the fluorinated PI precursor solution (fluorinated polyimide varnish).

  Examples of the resin coating material having such releasability include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). A fluororesin such as is preferred. In addition, carbon powder may be dispersed and contained in order to improve electrostatic offset.

  The fine particles of the fluororesin described above preferably have an average particle size of 0.1 μm to 5 μm, and more preferably have an average particle size of 0.1 μm to 1.0 μm.

Further, the surface layer 11 (or at least the outermost layer in the case of a plurality of layers) has semiconductivity, and its surface resistivity is preferably 10 ⁴ Ω / □ to 10 ¹² Ω / □, and the fixing roll Is more preferably 10 ⁴ Ω / □ to 10 ⁶ Ω / □, and the transfer roll is more preferably 10 ⁸ Ω / □ to 10 ¹² Ω / □.
The surface resistivity of the surface layer 11 is measured according to JIS K6911 using a circular electrode (for example, “UR probe” of Hiresta IP manufactured by Mitsubishi Yuka Co., Ltd.).

  Further, the surface layer 11 (at least the outermost layer in the case of a plurality of layers) preferably has a film thickness of 0.5 μm to 20 μm, and more preferably has a film thickness of 0.5 μm to 10 μm. If the thickness is less than 0.5 μm, the life may be shortened due to wear, and if it exceeds 20 μm, it may be difficult to cope with cardboard. Furthermore, the surface layer 11 (or at least the outermost layer in the case of a plurality of layers) preferably has a surface roughness Ra of 0.01 μm to 2 μm, and preferably has a surface roughness Ra of 0.01 μm to 0.5 μm. Further preferred.

[Roll for Image Forming Apparatus According to Second Embodiment]
FIG. 2A is a perspective view showing a roll for an image forming apparatus according to a second embodiment of the present invention (when a multilayer of a surface layer and an elastic layer is supported by a support). 2B is a longitudinal sectional view of a roll for the image forming apparatus shown in FIG. 2A. 2C is a cross-sectional view of the roll for the image forming apparatus shown in FIG. 2A.

  As shown in FIGS. 2A to 2C, the roll 20 for an image forming apparatus according to the second embodiment has a support 50 compared to the case of the roll 10 for an image forming apparatus according to the first embodiment. Regarding the layer formed on the surface, the roll 10 for the image forming apparatus according to the first embodiment is a single layer on the surface 11, but from a multilayer of the surface layer 21 and the elastic layer 22. The other points are basically the same as those in the first embodiment. Specifically, the roll 20 for an image forming apparatus according to the second embodiment is placed on a recording member in an image forming apparatus (not shown) that forms an image on the recording member (not shown). A roll 20 for an image forming apparatus used as a fixing roll or an intermediate transfer roll for fixing or transferring an unfixed image or an untransferred image, having a cylindrical elastic layer 22, and fixing on the elastic layer 22 Alternatively, it has a cylindrical surface layer 21 that contacts the recording member during transfer (in other words, the elastic layer 22 is provided on the back side of the surface layer 21), and the surface layer 21 (the surface layer 21 itself is composed of a plurality of layers). In this case, at least the outermost layer is composed of a fluorinated polyimide resin having an ether group in the main chain. Hereinafter, differences from the case of the first embodiment will be mainly described.

  The elastic layer 22 used in the roll 20 for the image forming apparatus according to the second embodiment is used for obtaining an image corresponding to cardboard. 2A to 2C, as described above, the case where a cylindrical member is used as the elastic layer 22 is shown, but for example, a rectangular tube, an elliptic tube, or the like may be used. Further, as in the case of the surface layer 21, the elastic layer 22 itself may be a plurality of layers.

  The elastic layer 22 (at least the innermost layer in the case of a plurality of layers) can be composed of silicone rubber, fluororubber, or the like. Among these, silicone rubber or fluororubber is preferable. As the silicone rubber, for example, silicone rubber such as HTV, LTV, and RTV can be suitably used. As the fluorine rubber, for example, VDF fluorine rubber, VDF-HFP fluorine rubber (binary or ternary), or the like can be suitably used. The thickness of the elastic layer 22 is preferably 100 μm to 3000 μm, and more preferably 150 μm to 1000 μm. If the thickness is less than 100 μm, the followability of deformation to an unfixed toner image may be deteriorated and image defects may be caused. If the thickness exceeds 3000 μm, the warm-up time during standby becomes long, resulting in an increase in power consumption. is there.

In addition, as described above, when the roll of the present embodiment is used as a charging body using an electrostatic force such as a transfer roll (transfer body, transfer (contact charging) film), the roll 20 for an image forming apparatus. The conductive particles can be dispersed in the surface layer 21 and the elastic layer 22, and the roll of the present embodiment using a PI precursor solution or a fluorinated PI precursor solution (fluorinated polyimide varnish) as described later Is preferably added to the PI precursor solution or the fluorinated PI precursor solution (fluorinated polyimide varnish). That is, the silicone rubber or fluororubber constituting the elastic layer 22 is preferably formed by dispersing conductive particles described later, inorganic fillers such as SiO ₂ and BaSO _{4, and the} like. By comprising in this way, the mechanical characteristic of the elastic layer 22 can be improved, or thermal conductivity and electrical conductivity can be improved. In this case, the optimum type and amount can be selected as appropriate.

Examples of the conductive particles include carbon black, carbon beads obtained by granulating carbon black, carbon fibers, carbon-based materials such as graphite, metals or alloys such as copper, silver, and aluminum, tin oxide, indium oxide, antimony oxide, Examples thereof include conductive metal oxides such as SnO ₂ —In ₂ O ₃ composite oxide, and conductive whiskers such as potassium titanate. Among them, it is preferable because a predetermined conductivity can be obtained with a small addition amount of carbon black particles.

[Support]
The support 50 is used to support the surface layers 11 and 21 and the surface layers 11 and 21 and the elastic layers 12 and 22 constituting the rolls 10 and 20 for the image forming apparatus.

  Examples of the shape of the support 50 include a columnar shape such as a columnar shape or a cylindrical shape such as a cylindrical shape. In general, the cross section is preferably a circular one as described above, but may have another cross section such as an ellipse. In the present embodiment, the “support 50 surface” means the outer peripheral surface of the support 50 when the support 50 is cylindrical, unless otherwise specified. When it is columnar, it means a surface parallel to the axial direction of the column.

  The support 50 is preferably made of a heat-resistant metal material such as aluminum, iron, and stainless steel. Moreover, you may comprise with heat resistant resins, such as a polyimide, polyamideimide, polybenzimidazole, a liquid crystal polymer, and polyphenylene sulfide, as needed.

  Although there is no restriction | limiting in particular as thickness of the support body 50, For example, 0.3 mm-3 mm are preferable and 0.3 mm-1 mm are more preferable.

[Method of manufacturing roll for image forming apparatus]
A roll manufacturing method for an image forming apparatus according to the present embodiment includes a columnar or cylindrical support, or a laminate in which an elastic layer is laminated on a support, and a complete fluorine on the support or laminate. A fluorinated polyamic acid (fluorinated polyimide precursor solution, in other words, a fluorinated polyimide varnish) synthesized from fluorinated acid anhydrides and fluorinated diamines is applied to form a coating film to be a surface layer (Hereinafter, it may be abbreviated as “fluorinated PI precursor coating film forming step”), and then heating and baking the formed coating film to form a surface layer (hereinafter referred to as “fluorinated PI resin”). A film (surface layer) forming step ”). In addition to the above steps, other steps such as a drying step of the fluorinated PI precursor coating film may be included as necessary.

  As a method for manufacturing a roll for an image forming apparatus according to the present embodiment, the roll 10 for the image forming apparatus is roughly fluorinated polyimide on the support 50 as in the case of the first embodiment. A case where only the surface layer 11 composed of a single layer is formed (when a single film (surface layer) of a fluorinated polyimide resin having an ether group in the main chain is directly formed on the support 50) and the second implementation In the case where the roll 20 for an image forming apparatus is composed of a plurality of layers of the elastic layer 22 and the surface layer 21 on the support 50 (after first forming the elastic layer 22 on the support 50) The surface layer 21 is formed by forming a fluorinated polyimide resin having an ether group in the main chain on the laminate of the support 50 and the elastic layer 22, and a plurality of layers (the elastic layer 22 and the surface are formed on the support 50. A row for an image forming apparatus having a layer 21) Divided into a case) to form a 20 will be described.

<When a roll for an image forming apparatus has only a surface layer on a support>
(Fluorinated PI precursor coating process)
In the fluorinated PI precursor coating film forming step, a fluorinated polyimide precursor solution is used to form a coating film on the surface of the support 50. Examples of the fluorinated polyimide precursor include a fully fluorinated dianhydride represented by the above chemical formulas (1) and (2) and a fluorinated diamine represented by the above chemical formulas (3) to (9). Kind is used. In addition, diamine is so preferable that a fluorination rate is high. As a solvent for dissolving the fluorinated PI precursor, a known aprotic polar solvent such as N-methylpyrrolidone, N, N-dimethylacetamide, acetamide, N, N-dimethylformamide or the like can be used. The concentration, viscosity, etc. of the fluorinated PI precursor solution can be selected as appropriate, and other materials or additions such as the above-mentioned conductive particles can be added to the fluorinated PI precursor solution as necessary. An agent or the like may be added.

  As a method of applying the fluorinated PI precursor solution to the surface of the support 50, although depending on the shape of the support 50, a dip coating method in which the support 50 is dipped in the fluorinated PI precursor solution and pulled up, an axial direction Are placed so as to be substantially parallel to the horizontal direction, and the fluorinated PI precursor solution is discharged onto the surface of the support 50 rotating in the circumferential direction from a nozzle or the like installed almost directly above the support 50. Utilizing a known method such as a flow coating method in which the support 50 or the nozzle is translated in the axial direction, and a blade coating method in which the coating film formed on the surface of the support 50 is metalized with a blade. Can do. In the flow coating method and the blade coating method, the coating film formed on the surface of the support 50 is formed in a spiral shape in the axial direction of the support 50, so that a seam can be formed. Since the solvent contained is slow to dry at room temperature, the seam is naturally smoothed.

(Fluorine PI precursor drying process)
In the fluorinated PI precursor drying step, it is preferable to remove the solvent contained in the coating film formed on the surface of the support 50 by heating and drying. The heating temperature is preferably equal to or lower than the boiling point of the solvent used. For example, when the solvent is N-methylpyrrolidone (NMP, boiling point 202 ° C.), the range is preferably 70 to 201 ° C., and the solvent is dimethylacetamide (DMAC, boiling point 165 ° C.). In this case, the range of 60 ° C to 164 ° C is preferable. More preferably, after heating at 60 ° C. to 125 ° C., which is 125 ° C. or less at which imidation starts, to remove water that adversely affects fluorination dissolved in the solvent, heating is performed at a temperature below the boiling point of the solvent. It is preferred to remove the solvent by step heating. As the temperature of the second stage, for example, when the solvent is N-methylpyrrolidone (NMP, boiling point 202 ° C.), a range of 125 ° C. to 201 ° C. is preferable, and the solvent is dimethylacetamide (DMAC, boiling point 165 ° C.). In some cases, a range of 125 ° C to 164 ° C is preferred. The heating time varies depending on the concentration and film thickness of the applied coating film, but the heating time at each stage is preferably about 10 to 120 minutes. When the coating film formed on the surface of the support 50 is dripped due to the influence of gravity during drying, the support 50 may be heated and dried while rotating at about 10 to 60 rpm with the axial direction horizontal. preferable.

(Fluorinated PI resin film (surface layer) formation process)
Formation of the fluorinated PI film by heating the coating film dried through the fluorinated PI precursor drying step may be carried out in the temperature range from the boiling point of the solvent to about 400 ° C. for about 20 to 120 minutes. preferable. At that time, it is preferable that the temperature is increased stepwise or slowly at a constant speed until the above temperature is reached, and more preferably, heating and film formation are performed at two or three stages of temperature. In addition, since a firm film | membrane is formed, the one where final temperature is higher, it is preferable to heat at 340 degreeC or more. The roll 10 for the image forming apparatus thus obtained may be subjected to end slit processing, punching drilling processing, tape winding processing, and the like as necessary.

<When a roll for an image forming apparatus has an elastic layer and a surface layer on a support>
When the roll for the image forming apparatus has the elastic layer 22 and the surface layer 21 on the support, the elastic body 22 is previously laminated and formed on the columnar or cylindrical support 50, and the surface of the elastic body 22 is formed. The surface layer 21 is coated with a fluorinated polyamic acid (fluorinated polyimide precursor solution, in other words, a fluorinated polyimide varnish) prepared using a fully fluorinated acid anhydride and a fluorinated diamine. Form. However, the silicone elastic body usually used as the elastic body 22 has a strong water repellency, and even if a fluorinated polyamic acid is applied, the water repellent cannot be applied uniformly. Therefore, it is necessary to make the surface of the elastic body 22 hydrophilic in order to form a uniform coating film. As the hydrophilization method, UV ozone treatment, excimer laser irradiation, application of a coupling agent corresponding to an adhesive, or the like is used. Among these, excimer laser irradiation is excellent as a method for hydrophilization because a coating film made of a material having high water and oil repellency can be formed directly on the silicone elastic layer. However, in the case of excimer laser irradiation, the cost is high and the productivity is not always satisfactory. Therefore, in this embodiment, instead of excimer laser irradiation, a dielectric barrier discharge excimer lamp with a wavelength of 172 nm is irradiated while rotating the laminated body of the support 50 and the elastic body (silicone elastic body) 22. Therefore, it has become possible to realize a hydrophilic treatment at a lower cost and higher productivity than an excimer laser. The surface of the elastic body (silicone elastic body) 22 irradiated with the 172 nm excimer lamp is hydrophilized by the covalent bond between Si and O being cut.

  After the surface of the elastic body has been hydrophilized (hereinafter, may be abbreviated as “hydrophilic surface hydrophilization process”), “the roll for the image forming apparatus has only the surface layer on the support. In the same way as in the case of “fluorinated PI precursor coating film forming process”, “fluorinated PI precursor drying process”, “fluorinated PI resin film (surface layer) forming process”, etc., the fluorinated PI resin film (Surface layer 21) is formed, and roll 20 for an image forming apparatus is obtained. The roll 20 for the image forming apparatus thus obtained may be further subjected to end slit processing, punching drilling processing, tape winding processing, and the like as necessary. Hereinafter, the “hydrophilization process of the elastic body surface” will be described in more detail.

(Hydrophilization process of elastic body surface)
When a silicone elastic body is used as the elastic body 22, the silicone elastic body has high water repellency and it is difficult to apply a material for forming the surface layer 21 without performing surface treatment. Therefore, it is necessary to break the covalent bond between Si and O to make it hydrophilic. However, since the covalent bond between Si and O is as large as 105.4 kcal / mol, strong energy is required. is necessary. For surface modification, it is preferable to use a method of irradiating an excimer lamp while rotating a roll with a silicone elastic body at a constant speed using a dielectric barrier discharge excimer lamp having a wavelength of 172 nm. Since the surface treatment is performed by rotating the roll at a constant speed, the entire surface of the elastic layer 22 can be uniformly modified. Since light with a wavelength of 172 nm is rapidly attenuated in the atmosphere, it is preferable to use the distance between the irradiation surface of the lamp and the surface of the elastic layer 22 as close as possible, and a distance of 1 mm to 10 mm is often used. . Note that, in an oxygen-free state under a vacuum atmosphere or a nitrogen atmosphere, there is little attenuation of light intensity, and thus there is practically no limitation on the distance between the lamp irradiation surface and the elastic layer 22 surface. An excimer laser may be used instead of the excimer lamp.

  After the above-mentioned “hydrophilization process of the elastic body surface”, “fluorinated PI precursor coating film formation process”, “when the roll for the image forming apparatus has only the surface layer on the support”, “ Through the “fluorinated PI precursor drying step”, “fluorinated PI resin film (surface layer) forming step” and the like, the fluorinated PI resin film (surface layer 21) is formed, and the roll 20 for the image forming apparatus is obtained. However, in the “fluorinated PI resin film (surface layer) forming step”, if the heat resistance of the applied elastic body 22 is insufficient, the temperature at which the imidization reaction proceeds is not less than the boiling point of the solvent. Formation of a fluorinated PI resin film (surface layer) is possible. For example, when NMP is used as the solvent, it may be 202 ° C. or higher, and the heat resistance temperature of the elastic body 22 to be applied is at least 202 ° C.

[Image forming apparatus]
Next, an image forming apparatus using the image forming roll of the present embodiment will be described. The image forming apparatus according to the present embodiment may be any known image forming apparatus that can use the image forming roll according to the present embodiment. An image fixing apparatus having such a configuration will be described below.

    The image forming apparatus (image fixing apparatus) of the present embodiment includes a heat fixing roll used as the fixing roll of the present embodiment, an endless belt stretched by a group of rolls such as a pressure roll, and the like. The heat-fixing roll is provided with, for example, a halogen lamp with an output of 850 W as a heat source. Further, a temperature sensor is appropriately disposed on the surface, the surface temperature is measured, and the halogen lamp is feedback controlled by the temperature controller based on the measurement signal, so that the surface of the heat fixing roll is adjusted to 150 to 180 ° C. It is like that. When this image fixing device is used, first, a toner image is transferred onto a recording member such as a recording sheet by a transfer device and conveyed to a fixing roll. The toner image is fixed on the recording member by the pressure applied by the pressure roll and the heat applied by the halogen lamp to the heat fixing roll.

  Hereinafter, the roll for the image forming apparatus of the present invention and the manufacturing method thereof will be described in more detail with reference to examples. Note that the present invention is not limited in any way by the following examples.

  Here, in Examples 1 to 5, in the case of a roll for an image forming apparatus in which a single layer of a surface layer is formed on a support, Examples 6 to 10 are an elastic layer and a surface layer on the support. In the case of a roll for an image forming apparatus in which multiple layers are formed, Comparative Examples 1 and 2 each show a case where a resin having no ether group in the main chain is used as the fluorinated polyimide resin.

Example 1
Application | coating of the solution containing the fluorinated PI precursor to the support body 50 surface was implemented as follows using the flow coat apparatus. The fluorinated PI precursor solution includes an acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and an aromatic diamine (4FMPD: tetrafluoro-1, N-methylpyrrolidone solution of fully fluorinated polyamic acid composed of (3-phenylenediamine) was used. As the support 50, an iron cylinder having an outer diameter of 30 mm, a length of 500 mm, and a thickness of 0.5 mm was prepared. Next, the N-methylpyrrolidone solution of the above-mentioned fully fluorinated polyamic acid was applied to the surface of the support 50 using a flow coat apparatus. Next, heating film formation was performed using a heating furnace (inert oven) purged with nitrogen. Heating is performed at 120 ° C. for 30 minutes, followed by heating at 200 ° C. for 30 minutes, 250 ° C. for 30 minutes, 300 ° C. for 30 minutes, and finally heating at 380 ° C. for 30 minutes. A roll 10 for an image forming apparatus coated with a defect-free fully fluorinated PI resin film (surface layer 11) was obtained by forming a fluorinated PI resin film (surface layer 11) having a thickness of 1 μm.

(Example 2)
The fluorinated PI precursor comprises acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and aromatic diamine (8FODA: 2,2 ′, 3, 3 ′, 5,5 ′, 6,6′-octafluoro-4,4′-diaminodiphenyl ether) A roll 10 for an image forming apparatus coated with a surface layer 11) was obtained.

(Example 3)
The fluorinated PI precursor comprises acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and aromatic diamine (6FMDA: 4,4 ′-(hexa). A roll 10 for an image forming apparatus coated with a defect-free fully fluorinated PI resin film (surface layer 11) was obtained in the same manner as in Example 1 except that it was composed of fluoroisopropylidene) dianiline). .

Example 4
The fluorinated PI precursor comprises acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and aromatic diamine (13FPD: 1,4-diamino-2 A roll for an image forming apparatus coated with a fully fluorinated PI resin film (surface layer 11) having no defects in the same manner as in Example 1 except that it comprises -tridecafluoro-n-hexylbenzene) 10 was obtained.

(Example 5)
The fluorinated PI precursor comprises acid anhydride (P6FDA: 3,6-bis (trifluoromethyl) -1,2,4,5-benzenetetracarboxylic dianhydride) and aromatic diamine (8FODA: 2,2). Complete defect-free fluorination in the same manner as in Example 1, except that it consists of ', 3,3', 5,5 ', 6,6'-octafluoro-4,4'-diaminodiphenyl ether) A roll 10 for an image forming apparatus covered with the PI resin film (surface layer 11) was obtained.

(Example 6)
An iron cylinder (thickness: 0.5 mm) having an outer diameter of 30 mm and a length of 500 mm was used as the support 50. After applying a primer as an adhesive layer to this surface, silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd.) was 1 mm thick. A roll with an elastic layer was formed. Next, using a dielectric barrier discharge excimer lamp (light intensity 50 mW) having a wavelength of 172 nm on the surface of the elastic layer (silicone elastic layer) 22, the laminate of the support 50 and the elastic body 22 is rotated at a speed of 10 rpm. However, excimer vacuum ultraviolet light was irradiated. The distance between the irradiation surface of the excimer lamp and the silicone elastic layer was fixed to 5 mm, and light irradiation was performed for 3 minutes while purging nitrogen. Next, the fluorinated PI precursor solution (the fully fluorinated polyamic acid N-methylpyrrolidone solution used in Example 1) was applied to the surface of the elastic layer 21 using a flow coater. Next, heating film formation was performed using a heating furnace (inert oven) purged with nitrogen. Heating is performed at 120 ° C. for 30 minutes, followed by heating at 200 ° C. for 30 minutes, 250 ° C. for 30 minutes and 280 ° C. for 120 minutes, and a 1 μm thick fluorinated PI resin film (surface layer) 21) was formed, and a roll 20 for an image forming apparatus was obtained which was coated with a fully fluorinated PI resin film (surface layer 21) having no defects.

(Example 7)
The fluorinated PI precursor comprises acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and aromatic diamine (8FODA: 2,2 ′, 3, 3 ′, 5,5 ′, 6,6′-octafluoro-4,4′-diaminodiphenyl ether) in the same manner as in Example 6 with a thickness of 1 μm and complete defect-free fluorination A roll 20 for an image forming apparatus covered with the PI resin film (surface layer 21) was obtained.

(Example 8)
The fluorinated PI precursor comprises acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and aromatic diamine (6FMDA: 4,4 ′-(hexa). A roll for an image forming apparatus coated with a fully fluorinated PI resin film (surface layer 21) having a thickness of 1 μm and having no defects exactly as in Example 6 except that it comprises fluoroisopropylidene) dianiline) 20 was obtained.

Example 9
The fluorinated PI precursor comprises acid anhydride (10FEDA: 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride) and aromatic diamine (13FPD: 1,4-diamino-2 -Tridecafluoro-n-hexylbenzene) Image formation covered with a fully fluorinated PI resin film (surface layer 21) having a thickness of 1 μm and having no defects exactly as in Example 6. The roll 20 for apparatuses was obtained.

(Example 10)
The fluorinated PI precursor comprises acid anhydride (P6FDA: 3,6-bis (trifluoromethyl) -1,2,4,5-benzenetetracarboxylic dianhydride) and aromatic diamine (8FODA: 2,2). Except that it consists of ', 3,3', 5,5 ', 6,6'-octafluoro-4,4'-diaminodiphenyl ether), the defect was found in a thickness of 1 μm in the same manner as in Example 6. A roll 20 for an image forming apparatus covered with a completely non-fluorinated PI resin film (surface layer 21) was obtained.

(Comparative Example 1)
The fluorinated PI precursor has the following chemical formula (14):

  An acid anhydride represented by the formula (6FDA: 2,2-bis (3,4-anhydrodicarboxyphenyl) -hexafluoropropane) and an aromatic diamine represented by the chemical formula (5) (TFDB: 2,2 ′) An image forming apparatus coated with a partially fluorinated PI resin film (surface layer 21) having a thickness of 1 μm and having no defects in the same manner as in Example 6 except that -bis (trifluoromethyl) benzidine) A roll 20 was obtained. However, this partially fluorinated polyimide film is rigid and lacks flexibility because it does not have an ether bond.

(Comparative Example 2)
The fluorinated PI precursor has the following chemical formula (15):

  An acid anhydride represented by the formula (NTCDA: naphthalene-1,4,5,8-tetracarboxylic dianhydride) and an aromatic diamine represented by the above chemical formula (4) (6FMDA: 2,2′-bis Except for comprising (trifluoromethyl) benzidine), an image forming apparatus coated with a partially fluorinated PI resin film (surface layer 21) having a thickness of 1 μm and having no defects exactly as in Example 6. A roll 20 was obtained. However, this partially fluorinated polyimide film is rigid and lacks flexibility because it does not have an ether bond.

(Evaluation test)
Each of the rolls for the image forming apparatus using each fluorinated polyimide resin obtained in Examples 1 to 10 and Comparative Examples 1 and 2 was used as a fixing roll, respectively, as a color composite machine (trade name: DocuCentre C7600: manufactured by Fuji Xerox Co., Ltd.). ), And a durability test and image quality evaluation were conducted by continuously feeding 200,000 sheets. In the fixing device incorporating the semiconductive rolls of Examples 1 to 10, good durability and image quality were obtained even after continuous feeding of 200,000 sheets, but the semiconductive rolls of Comparative Examples 1 and 2 were incorporated. In the fixing device, good durability was obtained even after continuous feeding of 200,000 sheets. However, since the toner releasability is poor, the toner adhering to the roll adheres to the surface of the recording medium. The eyes are stained, and good image quality cannot be obtained over a long period of time.

DESCRIPTION OF SYMBOLS 10 Roll for image forming apparatuses 11 Surface layer 20 Roll for image forming apparatuses 21 Surface layer 22 Elastic layer 50 Support body

Claims (12)

  A roll for an image forming apparatus having a surface layer composed of a fluorinated polyimide resin having at least an outer surface having an ether group in the main chain.   The image according to claim 1, wherein the fluorinated polyimide resin having an ether group in the main chain is a resin prepared from a fluorinated polyamic acid synthesized from a fully fluorinated acid anhydride and a fluorinated diamine. Roll for forming equipment. The fully fluorinated acid anhydride has the following chemical formula (1) or (2):

The fluorinated diamines are represented by the following chemical formula (3):

The roll for an image forming apparatus according to claim 2, which is represented by: The roll for an image forming apparatus according to claim 3, wherein the fluorinated diamine is one represented by the following chemical formulas (4) to (13).

  The roll for an image forming apparatus according to claim 1, wherein the fluorinated polyimide resin having an ether group in the main chain is a resin having a perfluoroalkyl group in a side chain.   The roll for an image forming apparatus according to claim 1, further comprising a cylindrical elastic layer laminated on the back side of the surface layer.   An image forming apparatus using the roll for an image forming apparatus according to claim 1. Prepare a columnar or cylindrical support, or a laminate in which an elastic layer is laminated on the support,
On the support or laminate, a fluorinated polyamic acid (fluorinated polyimide precursor solution) synthesized from a fully fluorinated acid anhydride and fluorinated diamines is applied to form a coating film that becomes a surface layer. A method for producing a roll for an image forming apparatus, comprising forming and then heating and baking the formed coating film to form a surface layer. The fully fluorinated acid anhydride has the following chemical formula (1) or (2):

The fluorinated diamines are represented by the following chemical formula (3):

The method for producing a roll for an image forming apparatus according to claim 8, wherein The method for producing a roll for an image forming apparatus according to claim 9, wherein the fluorinated diamine is one represented by the following chemical formulas (4) to (13).

  When forming the coating film on the laminate, before forming the coating film, the surface of the elastic layer constituting the laminate is irradiated with vacuum ultraviolet light having a wavelength of 180 nm or less to form an elastic layer. The method for producing a roll for an image forming apparatus according to claim 8, further comprising hydrophilizing the surface of the image forming apparatus.   The method for manufacturing a fixing roll for image formation according to claim 11, wherein the vacuum ultraviolet light is emitted from a dielectric barrier discharge excimer lamp having a wavelength of 172 nm.

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