JP2017068034A - Electrophotographic member, fixing device, and image forming apparatus - Google Patents

Abstract

An object of the present invention is to provide an electrophotographic member having excellent adhesiveness between a surface layer and an elastic layer. SOLUTION: An electrophotographic image forming apparatus has a substrate 4, an elastic layer 3 containing silicone rubber on the substrate 4, and a surface layer 1 on the elastic layer 3, the surface layer 1 containing at least fluororubber as a binder. In the member, a surface layer 1 and an elastic layer 3 are bonded via an adhesive layer 2 containing polyimide silicone, and the elastic modulus of the adhesive layer 2 is 0.3 MPa or more and 110 MPa or less. [Selection diagram] Fig. 1

Description

  The present invention relates to an electrophotographic member and a fixing device used in the field of fixing technology in an electrophotographic image forming apparatus (hereinafter simply referred to as “image forming apparatus”) such as a copying machine and a printer.

  Toner images obtained by the image forming apparatus are formed on various recording materials. Among these, paper most frequently used as a recording material has irregularities due to paper fibers on the surface, and a toner image is formed on the irregularities. The unfixed toner particles formed on the paper are crushed by being heated while being pressed by the electrophotographic member and fixed on the surface of the paper.

  Generally as an electrophotographic member, a multilayer body comprising an elastic layer containing silicone rubber and a surface layer containing fluorine rubber as a binder formed thereon is used. Since the surface layer containing fluororubber as a binder is flexible, it follows the unevenness existing on the paper well, and also makes good contact with the toner particles located in the recesses on the surface and applies a pressing force to the toner particles. Can do. Therefore, such an electrophotographic member can obtain a high-quality fixed image.

  As such an electrophotographic member, Patent Document 1 describes an electrophotographic member having a surface layer including a sea phase containing fluororubber and an island phase made of a silicone compound having a crosslinked structure.

  On the other hand, the electrophotographic member is required to have high adhesion between the surface layer and the elastic layer. If the adhesion between the surface layer and the elastic layer is weak, the surface layer may be peeled off from the elastic layer while being used as an electrophotographic member, and the surface layer may partially float, and the lifted portion may break. is there. Therefore, it is important to ensure adhesion between the surface layer and the elastic layer.

  Therefore, it is common practice to provide an adhesive layer between the surface layer and the elastic layer. As an adhesive layer of an electrophotographic member, Patent Document 2 describes an adhesive layer containing an organopolysiloxane resin formed by a reaction between a silane coupling agent and a polyalkylene glycol.

JP 2011-158892 A JP 2008-176293 A

  However, as a result of the study by the present inventors, when the adhesive layer according to Patent Document 2 is employed in an electrophotographic member having an elastic layer containing silicone rubber and a surface layer containing fluorine rubber as a binder, sufficient adhesion is achieved. I could not get sex.

  Therefore, an object of the present invention is to provide an electrophotographic member having excellent adhesion between a surface layer and an elastic layer. Another object of the present invention is to provide a fixing device and an image forming apparatus that can stably obtain a high-quality image.

  According to the present invention, there is provided a base material, an elastic layer containing silicone rubber on the base material, and a surface layer on the elastic layer, and the surface layer contains at least fluoro rubber as a binder. The surface layer and the elastic layer are bonded via an adhesive layer containing polyimide silicone, and the elastic modulus of the adhesive layer is 0.3 MPa or more and 110 MPa or less. An electrophotographic member is provided.

  In addition, according to the present invention, there is provided a fixing device having a fixing member and a pressure member disposed to face the fixing member, wherein one or both of the fixing member and the pressure member are selected. A fixing device is provided that is the above-described electrophotographic member.

  Furthermore, according to the present invention, there is provided an image forming apparatus comprising the above fixing device.

  According to the present invention, an electrophotographic member having excellent adhesion between the surface layer and the elastic layer can be obtained.

  In addition, according to the present invention, it is possible to provide a fixing device and an image forming apparatus capable of stably obtaining a high-quality image.

(A) It is a general | schematic cross-section block diagram of an example of the member for electrophotography which has a belt shape. (B) It is a schematic cross-sectional block diagram of an example of the member for electrophotography which has a roller shape. 1 is a schematic cross-sectional configuration diagram of an example of a fixing device according to an embodiment of the present disclosure. 1 is a schematic cross-sectional configuration diagram of an example of an image forming apparatus according to an embodiment of the present invention. It is explanatory drawing of the measuring method of adhesive force. 4 is an IR analysis result of an adhesive layer according to Example 1. 4 is an IR analysis result of an adhesive layer according to Example 2. It is IR analysis result of the contact bonding layer which concerns on Example 7. FIG. It is IR analysis result of the contact bonding layer concerning the comparative example 1. It is IR analysis result of the contact bonding layer concerning the comparative example 2.

  As a result of studying to solve the above-mentioned problems, the inventor of the present invention contains polyimide silicone in the adhesive layer, and by making the elastic modulus of the adhesive layer within a predetermined numerical range, the adhesion between the elastic layer and the surface layer is improved. It was found that it can be secured. That is, the present inventors have newly found that the elastic modulus of the adhesive layer containing polyimide silicone affects the adhesiveness of both. And it discovered that the adhesiveness of both became favorable by making the elasticity modulus of the adhesive layer containing polyimide silicone into 0.3 MPa or more and 110 MPa or less, ie, a low elasticity modulus compared with the conventional adhesive layer. .

  The present inventor considers the reason why such an adhesive layer is excellent in adhesion between the surface layer and the elastic layer as follows. The adhesive layer made of the organopolysiloxane resin described in Patent Document 2 has a large elastic modulus far from the elastic modulus of the surface layer and the elastic layer. Specifically, the elastic layer containing a general silicone rubber has an elastic modulus of 1 MPa or less, and the elastic modulus of a surface layer containing fluororubber as a binder is 10 MPa or less, whereas the adhesive layer made of an organopolysiloxane resin is For example, it is about 600 MPa (refer to Comparative Example 2 described later). In this case, the deformation amount of the adhesive layer is relatively small compared to the deformation of the surface layer and the elastic layer, which occurs when an external force is applied to the electrophotographic member. It is considered that stress is likely to occur at the interface between the layer and the elastic layer. As a result, separation between layers tends to occur at those interfaces. On the other hand, the elastic modulus of the adhesive layer according to one embodiment of the present invention is 0.3 MPa or more and 110 MPa or less, which is lower than that of the conventional adhesive layer, and is closer to the elastic modulus of the surface layer or the elastic layer. Is. Therefore, when an external force is applied to the electrophotographic member, each layer of the electrophotographic member is deformed to the same extent, and stress is unlikely to concentrate on the interface between the surface layer and the adhesive layer and the interface between the adhesive layer and the elastic layer. Guessed. As a result, in the electrophotographic member according to the embodiment of the present invention, separation between the layers hardly occurs and good adhesiveness is obtained.

[Electrophotographic materials]
The electrophotographic member according to an embodiment of the present invention has a belt shape or a roller shape.

  FIG. 1A is a schematic cross-sectional configuration diagram of an example of an electrophotographic member having a belt shape, and FIG. 1B is a schematic cross-sectional configuration diagram of an example of an electrophotographic member having a roller shape. Each of the electrophotographic members shown in FIG. 1 has an elastic layer 3 containing silicone rubber on a base material 4 and a surface layer 1 on the elastic layer 3. The layer 3 is bonded via an adhesive layer 2 containing polyimide silicone. The layer structure of the electrophotographic member is not limited to this, and may be a structure of five or more layers including another intermediate layer on the substrate 4.

(Adhesive layer)
The adhesive layer 2 contains polyimide silicone and has an elastic modulus of 0.3 MPa or more and 110 MPa or less. When the elastic modulus of the adhesive layer 2 is 0.3 MPa or more, the adhesive layer 2 has a sufficiently high strength. Further, when the elastic modulus of the adhesive layer 2 is 110 MPa or less, the elastic modulus of the adhesive layer 2 is sufficiently close to the elastic modulus of the surface layer 1 and the elastic layer 3, and good adhesiveness is obtained in the electrophotographic member. Can do. In order to obtain better adhesiveness, the elastic modulus of the adhesive layer 2 is preferably 3 MPa or more and 4 MPa or less.

  The polyimide silicone preferably has a polyimide structure and a dimethylsiloxane structure in the molecule.

  The elastic modulus of polyimide silicone can be lowered by increasing the silicone rate. The silicone rate is preferably 4 or more and 20 or less, particularly 9 or more and 11 or less. The siliconization rate of the polyimide silicone can be determined by the ratio (Si / N) of the silicon element existing ratio to the nitrogen element existing ratio obtained by XPS analysis.

  The adhesive layer 2 is formed by coating the elastic layer 3 with a coating solution in which polyimide silicone before thermosetting is dissolved in a solvent (hereinafter sometimes referred to as “coating solution for the adhesive layer”) and drying the coating solution. It can be formed by applying a coating for forming a surface layer, which will be described later, and thermally curing them.

  The polyimide silicone before thermosetting can be manufactured using a well-known technique (refer patent 4590443).

  As the polyimide silicone before thermosetting, a polyimide having any unit represented by the following formulas (1) to (3) and any unit represented by the following formulas (4) to (6): Silicone may be mentioned.

  In formulas (4) to (6), a to f are each an integer of 1 to 100.

  Moreover, the coating liquid in which the polyimide silicone before thermosetting was melt | dissolved in the solvent is marketed. Specific examples are given below. “SMP-4001”, “SMP-5005-PGMEA” (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

  Although the thickness of the contact bonding layer 2 is not specifically limited, It is preferable that they are 0.1 micrometer or more and 5.0 micrometers or less.

[Elastic layer]
The elastic layer 3 contains silicone rubber. The elastic layer 3 is particularly preferably a cured product of an addition reaction type liquid silicone rubber.

  The elastic modulus of the elastic layer 3 is preferably 0.3 or more and 1 MPa or less. When the elastic modulus of the elastic layer 3 is 1 MPa or less, since the surface hardness of the electrophotographic member is sufficiently low, the followability of the electrophotographic member to the irregularities on the paper surface is good. When the elastic modulus of the elastic layer 3 is 0.3 MPa or more, the strength of the electrophotographic member is sufficiently increased.

  The thickness of the elastic layer 3 can be appropriately designed from the viewpoint of contributing to the surface hardness of the electrophotographic member and securing the nip width. When the electrophotographic member has a belt shape, the thickness of the elastic layer 3 is preferably 100 μm or more and 500 μm or less, particularly 200 μm or more and 400 μm or less. When the electrophotographic member has a roller shape, the thickness of the elastic layer 3 is preferably 300 μm or more and 10 mm or less, and particularly preferably 1 mm or more and 5 mm or less.

[Surface layer]
The surface layer 1 contains fluororubber as a binder. Fluoro rubber includes binary copolymers of vinylidene fluoride and hexafluoropropylene, terpolymers of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, vinylidene fluoride having ether groups and tetrafluoroethylene Mention may be made of terpolymers with perfluoroalkyl vinyl ethers. Among these, the fluoro rubber is preferably a fluoro rubber having an ether group.

  The surface layer 1 containing fluororubber can be formed by crosslinking these fluororubber precursor polymers using a crosslinking aid by a known method. The fluororubber precursor polymer preferably has two or more iodine or bromine in the molecule as a radical reaction site. Moreover, what has an allyl group as a crosslinking adjuvant is preferable. The crosslinking reaction is considered to be carried out by an extraction reaction of iodine atom or bromine atom in the precursor polymer and a radical reaction to the allyl group in the crosslinking aid. Examples of such a crosslinking aid include triallyl cyanurate and triallyl isocyanurate, and triallyl isocyanurate is particularly preferably used. Although the compounding quantity of a crosslinking adjuvant is not specifically limited, It is preferable that they are 2 mass parts or more and 20 mass parts or less with respect to 100 mass parts of fluororubber precursor polymers.

  The fluorine concentration of the fluororubber is preferably 65% by mass or more. By including a cross-linked product of fluororubber having a high fluorine concentration in the surface layer 1 as described above, a better toner releasability can be imparted to the surface layer 1. The fluorine content here is the content (% by mass) of fluorine atoms in the precursor polymer. The fluorine content is determined by burning a precursor polymer sample in a cylinder filled with oxygen, collecting the fluorine in the sample in an absorbing solution (1% by mass aqueous sodium hydroxide), and then quantifying the fluorine by ion chromatography. Can be obtained. For combustion of the sample, a cylinder type chlorine content tester “Model 1009” manufactured by Yoshida Seisakusho Co., Ltd. can be used.

  Such a fluororubber precursor polymer can be synthesized by a known method. Such a fluororubber precursor polymer is commercially available. Specific examples are given below.

  “DAIEL G-801” (fluorine content = 66 mass%), “DAIEL G-902” (fluorine content = 71 mass%), “DAIEL LT-252” (fluorine content = 65 mass%), “DAIEL LT-302 "(fluorine content = 65 mass%) (all are trade names, manufactured by Daikin Industries, Ltd.).

  “Viton GBL200S” (fluorine content = 67.7 mass%), “Viton GBL600S” (fluorine content = 67.7 mass%), “Viton GF200S” (fluorine content = 70.2 mass%), “Viton” “GF600S” (fluorine content = 70.2 mass%), “Viton GLT200S” (fluorine content = 64 mass%), “Viton GLT600S” (fluorine content = 64 mass%), “Viton GFLT200S” (fluorine content) = Viton GFLT600S "(fluorine content = 67 mass%) (all are trade names, manufactured by DuPont Co., Ltd.).

  The elastic modulus of the surface layer 1 containing fluororubber as a binder is usually 10 MPa or less due to the properties of the material. The elastic modulus of the surface layer 1 is preferably 1 MPa or more and 10 MPa or less, more preferably 3 MPa or more and 4 MPa or less, although it depends on the type of the fluororubber.

  The surface layer 1 preferably has a matrix (sea phase) containing the above-described fluororubber and a domain (island phase) containing a silicone compound.

  The silicone compound is preferably a silicone surfactant (polysiloxane surfactant) having a polyoxyalkylene structure which is a hydrophilic group and a dimethylpolysiloxane structure which is a hydrophobic group, from the viewpoint of toner releasability. .

Silicone surfactants can be classified into the following three types of structures, taking dimethylpolysiloxane as an example;
(I) A side chain modified type having a structure in which polyoxyalkylene is bonded to a side chain of a dimethylpolysiloxane skeleton represented by the following formula (7):

(Ii) A terminal-modified type having a structure in which polyoxyalkylene is bonded to the terminal of a dimethylpolysiloxane skeleton represented by the following formula (8).

(Iii) A copolymer type having a structure in which dimethylpolysiloxane and polyoxyalkylene are alternately and repeatedly bonded as represented by the following formula (9).

  In formulas (7) to (9), m, n, l, j and k are each an integer of 1 or more, p to w are each an integer of 1 or more, and R and R ′ are each a hydrogen atom Or it is a hydrocarbon group.

  Among these, the copolymer type silicone surfactant of (iii) is preferable because it has the best dispersibility with respect to fluororubber.

  The silicone surfactant preferably further has a carbon-carbon unsaturated bond at both ends of the molecular chain. It is considered that the crosslinking in the domain is performed by a reaction at the unsaturated bond site of the silicone-based surfactant and the unsaturated bond site of the crosslinking aid, a reaction between methyl groups of dimethylpolysiloxane, or the like. Further, crosslinking by radical reaction may be performed at the interface between the fluororubber as a matrix and the silicone surfactant as a domain.

Viscosity at 25 ° C. of the silicone-based surfactant, 100 mm ² / s or more 25000 mm ² / s or less, in particular, it is preferable 3000 mm ² / s or more 5000mm is ² / s or less.

The HLB value of the silicone-based surfactant is preferably 1 or more and 10 or less, particularly 1 or more and 5 or less. The HLB value can be obtained by the Griffin method. The HLB value by the Griffin method is determined by the following calculation formula (A) from the content (mass%) of the hydrophilic group in the surfactant, and indicates the degree of hydrophilicity or lipophilicity of the surfactant.
HLB value = 20 × (mass% of hydrophilic group) (A)
Examples of such silicone surfactants include “FZ-2203” (viscosity 4500 mm ² / s, HLB value 1), “FZ-2207” (viscosity 3500 mm ² / s, HLB value 3) manufactured by Toray Dow Corning. ), “FZ-2208” (viscosity 20000 mm ² / s, HLB value 7) and “FZ-2154” (viscosity 110 mm ² / s, HLB value 8).

  The content of the silicone surfactant is preferably 20 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the fluororubber.

  Such a surface layer 1 can be formed by applying a solution containing the fluororubber having an ether bond and the silicone surfactant and curing the coating film.

  The domain diameter of the surface layer 1 is preferably 1 μm or more and 20 μm or less. The diameter of the domain is measured by electron microscope observation. In an image obtained by magnifying the cross section of the surface layer 1 with a scanning electron microscope at a magnification of 4000 (vertical 24 μm × horizontal 30 μm), 20 domains are randomly selected and the major axis of the domain is measured. Among the measured values, the major axis is an arithmetic average value of 14 measured values excluding three values on the largest side and the smallest side. Further, when the number of domains in the image is 19 or less, all domains are set as measurement targets. In consideration of the resolution of the apparatus, a domain having a major axis of 0.3 μm or more is set as a measurement target.

The surface layer 1 may contain an ionic liquid as another component. Examples of ionic liquids include Cl ⁻ , Br ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) N. ^- ionic liquids having any anion selected from the group consisting of is preferred. These anions play an important role in producing fluororubbers with low surface tackiness, and include Cl ⁻ , Br ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ^- and _{(CF 3 SO 2) (C} 4 F 9 SO 2) N - by the action of any of the anions selected from the group consisting of, that lower surface of the adhesive fluorine rubber after crosslinking The applicant has found. Although the mechanism of action has not been clarified, it is considered that the cross-linking points of the fluororubber precursor polymer are slightly increased and the rubber surface tackiness is reduced due to the high anion electronegativity. As a mechanism for increasing the cross-linking point of the fluororubber precursor polymer, the one having a high electronegativity of anion has H ⁺ acceptability, and when the fluororubber is cross-linked, it promotes deHF from the polymer chain, It is conceivable that crosslinking proceeds at the unsaturated bond portion formed in the chain. On the other hand, for example, even when a silicone rubber is produced by crosslinking a mixture of a silicone polymer and an ionic liquid having these anions, the effect of reducing the adhesiveness of the surface of the silicone rubber is not recognized.

  In addition, an ionic liquid means the salt which exists in a liquid state also at normal temperature (25 degreeC). Usually, inorganic salts such as NaCl are in a liquid state at a high temperature of about 800 ° C. or higher. This is considered because the ion size is small and the interaction between ions is very strong. On the other hand, specific organic ions are in a liquid state even at a low temperature such as around room temperature. In general, a liquid state at 100 ° C. or lower is often called an ionic liquid. Certain organic ions are considered to be in a liquid state at a low temperature because the ion size is large and the interaction between ions is weaker than that of inorganic ions.

  As general characteristics of the ionic liquid, it is considered that the vapor pressure is low, non-volatile, non-flammable and high in heat resistance, and is relatively suitable for applications used at high temperatures such as electrophotographic members.

  Specific examples of the ionic liquid include imidazolium salts, pyrrolidinium salts, pyridinium salts, ammonium salts, phosphonium salts, sulfonium salts and the like, and can be roughly classified as follows according to the type of cation. Imidazolium salts, pyrrolidinium salts, and pyridinium salts, wherein the cation is a cyclic compound containing nitrogen. Ammonium salt, phosphonium salt, sulfonium salt whose cation is aliphatic.

  The ionic liquid is preferably an imidazolium salt, a pyrrolidinium salt or a pyridinium salt made of a cyclic compound whose cation contains nitrogen. This is because the cation is considered to have higher heat resistance than that of an aliphatic cation.

  Although the compounding quantity of an ionic liquid is not specifically limited, It is preferable that they are 0.001 mol (mol) or more and 0.03 mol (mol) or less with respect to 100 mass parts of fluororubbers.

  The thickness of the surface layer 1 is preferably 10 μm or more and 100 μm or less.

[Method for producing electrophotographic member]
The electrophotographic member can be produced, for example, as follows.

  First, the elastic layer 3 is formed on the substrate 4. Examples of a method for forming the elastic layer 3 include a method in which a raw material composition of silicone rubber is uniformly applied on the substrate 4 by means such as a ring coating method and a blade coating method, and then heated and cured. Further, a method of injecting a silicone rubber raw material composition into a mold and heat-curing, a method of heat-curing after extrusion molding, and a method of heat-curing after injection molding can be used.

  Next, the above-mentioned coating liquid for the adhesive layer is coated on the elastic layer 3 and dried. As a method for coating the coating liquid for the adhesive layer, known methods such as spray coating, slit coating, blade coating, roll coating, and dip coating can be used. The coating liquid may be dried by heating as necessary. Prior to coating the coating liquid for the adhesive layer, the surface of the elastic layer 3 may be irradiated with ultraviolet rays.

  Next, the coating material for forming the surface layer is applied on the dried film of the coating liquid for the adhesive layer and dried. The coating for forming the surface layer includes the above-described fluororubber precursor polymer, the silicone surfactant as necessary, triallyl isocyanurate as the crosslinking aid, and if necessary, It is a paint in which an ionic liquid is dissolved in a solvent. The solvent is preferably a ketone solvent from the viewpoint of solubility.

  The laminated body thus produced is subjected to primary crosslinking by electron beam irradiation or heating, and further subjected to secondary crosslinking by heating, thereby curing the polyimide silicone and crosslinking the fluororubber precursor polymer. Heating at the time of primary crosslinking and secondary crosslinking may be performed in a normal atmosphere or in an inert gas. In addition, when primary crosslinking is performed by heating, a peroxide such as benzoyl peroxide is added to the coating material for forming the surface layer. In this way, the adhesive layer 2 and the elastic layer 3 can be formed.

  When primary crosslinking is performed by electron beam irradiation, it can be performed under conditions of an acceleration voltage of 50 kV to 150 kV and an irradiation current of 1 mA to 20 mA. Moreover, when performing primary bridge | crosslinking by heating, heating can be performed on the conditions for 30 second-1 hour at the temperature of 100 degreeC or more and 200 degrees C or less. Secondary crosslinking can be performed by heating in an oven at a temperature of 150 ° C. or higher and 250 ° C. or lower for 10 minutes to 24 hours. Since the elastic modulus of the adhesive layer 2 increases as the degree of crosslinking of the polyimide silicone increases, it is preferable to appropriately adjust the conditions for primary crosslinking and secondary crosslinking within the above ranges.

[Fixing device]
A fixing device according to an embodiment of the present invention is a fixing device having a fixing member and a pressure member disposed to face the electrophotographic member, and any one selected from the fixing member and the pressure member. One or both of them is the above-described electrophotographic member. The fixing member and the pressure member may have either a roller shape or a belt shape.

  FIG. 2 is a schematic cross-sectional configuration diagram of an example of a fixing device according to an embodiment of the present invention. In the fixing device 114, a fixing roller 5 as a fixing member and a pressure belt 6 as a pressure member are arranged. In this example, the above-described electrophotographic member is used for the fixing roller 5.

  The fixing roller 5 is heated by a halogen heater 7 disposed inside. The pressure belt 6 is stretched by an entrance roller 8, a separation roller 9, and a steering roller 10. The separation roller 9 presses the pressure belt 6 against the fixing roller 5. The steering roller 10 is movable and corrects the shift of the pressure belt 6. A pressure pad 11 is disposed between the entrance roller 8 and the separation roller 9. The pressure pad 11 presses the pressure belt 6 against the fixing roller 5.

  The fixing roller 5 is rotated at a predetermined peripheral speed in the arrow direction by a driving source (not shown), and the pressure belt 6 is also rotated in the arrow direction accordingly. The surface temperature (fixing temperature) of the fixing roller 5 is maintained at a set temperature by controlling the output to the halogen heater 7 based on the temperature measured by the thermistor 12 on the surface temperature of the fixing roller 5. . The fixing temperature is not particularly limited, but is usually 130 ° C. or higher and 220 ° C. or lower.

  The toner image formed on the recording material such as paper is sandwiched and conveyed between the fixing roller 5 and the pressure belt 6, and the heat from the halogen heater 7, the fixing roller 5, the pressure belt 6, and the like. It is fixed by the pressure of. Contamination of the paper filler and toner component adhering to the surface of the fixing roller 5 moves to the surface of the metal recovery roller 13 and is wiped off by the cleaning web 15. The cleaning web 15 is pressed against the collection roller 13 by the web roller 14.

[Image forming apparatus]
FIG. 3 shows an image forming apparatus 100 in which the fixing device 114 described above is mounted as a fixing device that heats and fixes an unfixed toner image on a recording material as an example of an image forming apparatus according to an embodiment of the present invention. FIG. The image forming apparatus 100 is a color printer using an electrophotographic system.

  The image forming apparatus 100 applies color to a sheet-like recording material P based on an electrical image signal input from an external host device 200 such as a personal computer or an image reader to a control circuit unit (control means) 101 on the image forming apparatus side. Perform image formation. The control circuit unit 101 includes a CPU (arithmetic unit), a ROM (storage unit), and the like, and exchanges various electrical information with the host device 200 and an operation unit (not shown) of the image forming apparatus 100. Further, the control circuit unit 101 comprehensively controls the image forming operation of the image forming apparatus 100 in accordance with a predetermined control program and a reference table.

  Y, C, M, and K are four image forming units that form yellow, cyan, magenta, and black toner images, respectively, and are arranged in the order of Y, C, M, and K from the bottom in the image forming apparatus 100. Has been. Each of the image forming units Y, C, M, and K includes an electrophotographic photosensitive drum 51 as an image carrier, and a charging device 52 and a developing device 53 as process means that act on the electrophotographic photosensitive drum 51. And a cleaning device 54 and the like. The developing device 53 of the yellow image forming unit Y contains yellow toner as a developer, and the developing device 53 of the cyan image forming unit C contains cyan toner as a developer. The developing device 53 of the magenta image forming unit M stores magenta toner as a developer, and the developing device 53 of the black image forming unit K stores black toner as a developer. An optical system 55 that forms an electrostatic latent image by exposing the electrophotographic photosensitive drum 51 to light is provided corresponding to the four color image forming portions Y, C, M, and K. A laser scanning exposure optical system is used as the optical system.

  In each of the image forming units Y, C, M, and K, the electrophotographic photosensitive drum 51 uniformly charged by the charging device 52 is subjected to scanning exposure based on image data from the optical system 55. Thereby, an electrostatic latent image corresponding to the scanning exposure image pattern is formed on the surface of the electrophotographic photosensitive drum 51. These electrostatic latent images are developed as toner images by the developing device 53. That is, for example, a yellow toner image corresponding to a yellow component image of a full-color image is formed on the electrophotographic photosensitive drum 51 of the yellow image forming unit Y.

  The toner images formed on the electrophotographic photosensitive drums 51 of the image forming units Y, C, M, and K are intermediate transfer that rotates at substantially constant speed in synchronization with the rotation of the electrophotographic photosensitive drums 51. The images are superimposed and sequentially transferred onto the body 56 in a predetermined alignment state. As a result, an unfixed full-color toner image is synthesized and formed on the intermediate transfer member 56. In this embodiment, an endless intermediate transfer belt is used as the intermediate transfer member 56. The intermediate transfer belt 56 is composed of three rollers, a driving roller 57, a secondary transfer roller facing roller 58, and a tension roller 59. It is wound and stretched, and is driven by a driving roller 57.

  A primary transfer roller 60 is used as a primary transfer unit of the toner image from the electrophotographic photosensitive drum 51 of each image forming unit Y, C, M, K to the intermediate transfer belt 56. A primary transfer bias having a polarity opposite to that of the toner is applied to the primary transfer roller 60 from a bias power source (not shown). As a result, the toner images are primarily transferred from the electrophotographic photosensitive drums 51 of the image forming portions Y, C, M, and K to the intermediate transfer belt 56.

  After the toner image is primarily transferred from the electrophotographic photosensitive drum 51 to the intermediate transfer belt 56 in each of the image forming units Y, C, M, and K, the toner remaining on the electrophotographic photosensitive drum 51 is removed by the cleaning device 54. Removed.

  The above process is performed for each color of yellow, cyan, magenta, and black in synchronization with the rotation of the intermediate transfer belt 56, and the primary transfer toner images of the respective colors are sequentially superimposed on the intermediate transfer belt 56. It should be noted that the above process is performed only for the target color during image formation of only a single color (monochromatic mode).

  On the other hand, the recording material P in the recording material cassette 61 is separated and fed by the feeding roller 62 at a predetermined timing. Then, the recording material P is transferred at a predetermined timing by the registration roller pair 63 at a predetermined timing, and the transfer nip portion that is a pressure contact portion between the intermediate transfer belt 56 portion and the secondary transfer roller 64 wound around the secondary transfer roller facing roller 58. It is conveyed to. The primary transfer toner image formed on the intermediate transfer belt 56 is collectively transferred onto the recording material P by a bias having a polarity opposite to that of a toner applied from a bias power source (not shown) to the secondary transfer roller 64 (secondary transfer). Transcription).

  The secondary transfer residual toner remaining on the intermediate transfer belt 56 after the secondary transfer is removed by the intermediate transfer belt cleaning device 65. The unfixed toner image secondarily transferred onto the recording material P is fixed onto the recording material P by the fixing device 114, and is sent out to the discharge tray 67 through the discharge path 66 as a full color print.

  Hereinafter, details of the present invention will be described by way of examples. Prior to the examples, various evaluation methods will be described.

Example 1
[Production of fixing roller]
Aluminum with an outer diameter of 77 mm with an adhesive applied to the central part of a cylindrical mold with an inner diameter of 80 mm, the inner surface of which was previously treated with a mold release agent (water-diluted solution of die-free ME-313 manufactured by Daikin Industries, Ltd.) A hollow cylindrical cored bar made of metal was placed, and an addition reaction type liquid silicone rubber was injected into the outer periphery of the core bar and heated at a temperature of 130 ° C. for 1 hour. Thereafter, it was demolded and subjected to secondary crosslinking for 4 hours at a temperature of 200 ° C., and an elastic layer containing silicone rubber having a thickness of 1.5 mm was formed on the outer peripheral portion of the core metal.

Next, the surface of the elastic layer was irradiated with ultraviolet rays in the atmosphere using an ultraviolet lamp installed at a distance of 10 mm from the surface of the elastic layer while rotating the roller with the elastic layer in the circumferential direction. As the ultraviolet lamp, a low-pressure mercury ultraviolet lamp (trade name: GLQ500US / 11, manufactured by Harrison Toshiba Lighting Co., Ltd.) was used. Irradiation with ultraviolet rays was performed such that the integrated light amount at a wavelength of 185 nm was 150 mJ / cm ² .

  Next, while rotating this ultraviolet-treated roller with an elastic layer in the circumferential direction, on the peripheral surface of the elastic layer, a coating solution in which polyimide silicone before thermosetting is dissolved in a solvent (trade name: SMP-4001, Shin-Etsu Chemical Co., Ltd.) was spray-coated so that the film thickness after drying was 3 to 4 μm. Then, this roller was heat-dried at 100 degreeC.

  On the other hand, three types of coating material for forming the surface layer shown in Table 1 were dissolved in 186 g of methyl ethyl ketone. 1 was prepared. Table 2 shows the trade names of the materials in Table 1.

  Next, while rotating the roller in the circumferential direction, the coating No. was applied onto the dried coating film of the coating liquid for the adhesive layer. 1 was spray-coated so that the film thickness after drying was 50 μm. Next, while rotating the roller at 300 rpm, the surface of the coating film was irradiated with an electron beam at an acceleration voltage of 150 kV, an irradiation current of 15 mA, and a workpiece transfer speed of 0.5 m / min in an atmosphere having an oxygen concentration of 10 ppm. A device manufactured by Iwasaki Electric Co., Ltd. was used as the electron beam irradiation device. Thereafter, the adhesive layer and the surface layer were formed by heating for 24 hours in an oven at a temperature of 180 ° C., thereby forming a fixing roller according to Example 1.

  The surface layer of the obtained fixing roller was cut out, and the cross-section was observed with a scanning electron microscope (trade name: JSM-2000, manufactured by JEOL Ltd.) at an acceleration voltage of 15 kV and a magnification of 4000 times. As a result, the matrix-domain structure was confirmed. It was done. In addition, elemental analysis was performed by designating domains and matrix positions with EDS (trade name: JED-2000, manufactured by JEOL Ltd.) under conditions of an acceleration voltage of 5 to 15 kV and a magnification of 4000 times. As a result, a large number of Si atoms were found in the domain and F atoms were found in the matrix. Therefore, it was confirmed that the domain was a silicone surfactant and the matrix was fluororubber.

[Measurement of adhesive strength]
The measurement of the adhesive force was performed according to the 90 ° peel adhesion strength test defined by Japanese Industrial Standard (JIS) K 6854-1: 1999.

  A method for measuring the adhesive force will be described with reference to FIG.

  First, both ends of the produced fixing roller were sandwiched and held from the outside by bearing bearings (not shown) that are rotatable in the R direction in the drawing.

  Next, a polyimide tape having a width of 1 cm was attached to the surface of the surface layer along the circumferential direction of the fixing roller. Then, the fixing roller was cut with a razor so as to reach the elastic layer surface from the surface of the release layer along a side substantially parallel to the circumferential direction of the fixing roller of the adhered polyimide tape. A cut was similarly made at one end H of the polyimide tape. The standard of the depth of cut at this time is 100 μm to 1 mm, and the standard of the circumferential length of the cut is 50 to 90 mm from the peeling end H.

  Next, at one end H of the polyimide tape, the surface layer is forcibly peeled off from the interface portion between the surface layer and the elastic layer using a razor, and the peeled end H ′ is placed on the fixing roller at a digital force gauge ( Nidec Sympo Co., Ltd., Model No .: FGX-5) (not shown). Then, an average load (gf) between a distance of 1 cm and 7 cm was measured by pulling up at a constant speed (5 cm / min) in the vertical direction F from directly above the rotation axis of the fixing roller. The evaluation results are shown in Table 3.

  At this time, until the peeled distance reaches at least 70 mm, it is important that the peeling direction F is maintained at 90 ° with respect to the tangential direction of the main body of the fixing roller at the root of the peeling end H ′. It is. A specific method for maintaining 90 ° is as follows. First, when the peeled end H ′ is pinched with a force gauge, the peeled surface portion is pinched so as to be 90 °. Next, the fixing roller is pulled at a constant moving speed (5 cn / min) from directly above the rotation axis of the fixing roller, and at the same time, the moving speed at the tangent to the fixing roller is equal to the moving speed in the vertical direction F. The fixing roller may be rotated in the R direction in the figure.

  Further, after the prepared fixing roller was heated in an oven at 200 ° C. for 7 days, the adhesive force was measured in the same manner. This is an accelerated deterioration test assuming that the fixing roller is mounted on the image forming apparatus. The evaluation results are also shown in Table 3.

  In addition, about the Example 5-10 mentioned later and Comparative Examples 1-2, the adhesive force after leaving high temperature is not evaluated.

[Measurement of elastic modulus of adhesive layer]
First, a sample for evaluating the adhesive layer was prepared. A coating liquid in which a SUS foil is wound around the outer peripheral surface of an aluminum hollow cylindrical core metal having an outer diameter of 80 mm, and polyimide silicone having a high silicone ratio before thermosetting is dissolved in a solvent on the outer peripheral surface. (Trade name: SMP-4001, manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated so that the film thickness after drying was 3 to 4 μm to form a coating film of the coating solution. The membrane was heat dried at 100 ° C. Next, a polyimide sheet having a thickness of 50 μm was attached to the surface of the coating film. Next, while rotating the roller at 300 rpm, the surface of the polyimide sheet was irradiated with an electron beam at an acceleration voltage of 150 kV, an irradiation current of 15 mA, and a workpiece transfer speed of 0.5 m / min in a nitrogen atmosphere with an oxygen concentration of 10 ppm. (Electron beam irradiation device: manufactured by Iwasaki Electric Co., Ltd.) The polyimide silicone in the coating film was primarily crosslinked. Subsequently, it was heated in an oven at a temperature of 180 ° C. for 24 hours to be secondarily crosslinked to form an adhesive layer. Then, the sample for the adhesive layer evaluation in which the adhesive layer was formed on the SUS foil was produced by peeling off the polyimide sheet on the surface. The polyimide sheet is pasted and the electron beam is irradiated by pasting the polyimide having the same density as the surface layer (about 1.4 g / cm ³ ) on the adhesive layer instead of the surface layer. This is to make the electron beam irradiation conditions substantially the same as when the surface layer is on the adhesive layer.

  Then, with a nanoindenter (manufactured by MTS Systems, Nano Indenter G200 type), Hardness having an indentation depth of 100 to 200 nm was measured at 10 locations on the surface of the sample for adhesive layer evaluation, and the average value thereof was determined as the elasticity of the adhesive layer. Rate (MPa). The measurement was performed under the following measurement conditions using a Barkovic indenter and a continuous stiffness measurement method (Continuous Stiffness Measurement (CSM) mode) using a DCM head.

<Measurement conditions>
Measurement temperature Room temperature Surface Approach Velocity (approach speed of the indenter near the surface of the measurement point) 10 nm / s
Depth Limit (maximum indentation depth) 2000nm
Strain Rate Target (constant constant strain rate) 0.05 1 / s
Harmonic Displacement Target (target value of displacement amplitude) 1nm
Frequency target (vibration frequency) 75Hz
Surface Approach Distance (distance to sample surface approached by indenter at high speed) 1000 nm
Poisson Ratio (Poisson's ratio) 0.25.

  The evaluation results are shown in Table 3.

[Calculation of silicone conversion rate of polyimide silicone in adhesive layer]
The sample for adhesive layer evaluation was analyzed by XPS (manufactured by ULVAC PHI, Quantum 2000, measurement area φ: 100 μm, excitation condition: 25 W × 15 kV, detector angle: 45 °). The abundance ratio (atomic%) of each detected element was determined, and the ratio of the abundance ratio of silicon based on silicone to the abundance ratio of nitrogen based on imide bonds (Si / N) was calculated as the silicone rate. The evaluation results are shown in Table 3.

[Measurement of elastic modulus of surface layer]
Hardness was measured at 10 locations on the surface of the prepared fixing roller in the same manner as the elastic modulus of the adhesive layer, and the average value was taken as the elastic modulus (MPa) of the surface layer. The evaluation results are shown in Table 3.

[Measurement of elastic modulus of elastic layer]
At the center in the longitudinal direction of the produced fixing roller, a sample having a thickness of 10 to 30 mm square on the surface of the fixing roller and a total thickness in the thickness direction of the fixing roller was cut out. The surface layer and the adhesive layer were removed from the surface of this sample to expose the surface of the elastic layer. For removal of the surface layer and the adhesive layer, methods such as polishing with a lapping film, an ion milling method and a microtome method can be used alone or in combination. Hardness was measured at 10 locations on the surface of this sample in the same manner as the elastic modulus of the adhesive layer, and the average value was taken as the elastic modulus (MPa) of the elastic layer. The elastic modulus of the elastic layer was 0.35 MPa.

(Example 2)
Except having changed the coating liquid in which the polyimide silicone before thermosetting was melt | dissolved in the solvent into another coating liquid (brand name: SMP-5005-PGMEA, the Shin-Etsu Chemical Co., Ltd. make), it carried out similarly to Example 1. A fixing roller and an adhesive layer evaluation sample were prepared. These were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 3)
Except for changing the material of the surface layer forming coating material to the four types of materials shown in Table 1, the coating material No. In the same manner as paint No. 1, paint no. 2 was prepared. As a paint for forming the surface layer, paint No. A fixing roller was produced in the same manner as in Example 1 except that No. 2 was used, and was used for evaluation. The evaluation results are shown in Table 3.

Example 4
Except having changed into the coating liquid (trade name: SMP-5005-PGMEA, the Shin-Etsu Chemical Co., Ltd. product) the coating liquid with which the polyimide silicone before thermosetting was melt | dissolved in the solvent, it carried out similarly to Example 3. A fixing roller was prepared and used for evaluation.

(Example 5)
Except for changing the material of the coating material for forming the surface layer to two kinds of materials shown in Table 1, paint No. In the same manner as paint No. 1, paint no. 3 was prepared. As a paint for forming the surface layer, paint No. A fixing roller was produced in the same manner as in Example 1 except that No. 3 was used, and was used for evaluation. The evaluation results are shown in Table 3.

(Example 6)
Except having changed into the coating liquid (trade name: SMP-5005-PGMEA, the Shin-Etsu Chemical Co., Ltd. product) the coating liquid with which the polyimide silicone before thermosetting was melt | dissolved in the solvent, it carried out similarly to Example 5. A fixing roller was prepared and used for evaluation. The evaluation results are shown in Table 3.

(Example 7)
[Production of fixing roller]
Except for changing the material of the surface layer forming coating material to the four types of materials shown in Table 1, the coating material No. In the same manner as paint No. 1, paint no. 4 was prepared.

  Next, similarly to Example 1, a roller on which a dry coating film of the coating liquid for the adhesive layer was formed was produced. With respect to this roller, while rotating the roller itself in the circumferential direction, the coating No. 1 was applied on the dried coating film of the coating liquid for the adhesive layer. 4 was spray-coated so that the film thickness after drying was 50 μm. Next, this roller was heated at 150 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration of 10 ppm (primary crosslinking). Thereafter, the mixture was heated in an oven at 180 ° C. for 24 hours (secondary crosslinking) to form an adhesive layer and a surface layer, and a fixing roller according to Example 7 was produced. The adhesive strength and elastic modulus of the surface layer of this fixing roller were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Preparation of sample for adhesive layer evaluation]
A coating solution (trade name: SMP) in which a SUS foil is wound around the outer peripheral surface of an aluminum hollow cylindrical metal core having an outer diameter of 80 mm, and polyimide silicone before thermosetting is dissolved in a solvent on the outer peripheral surface. -5005-PGMEA (manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated so that the film thickness after drying was 3 to 4 μm to form a coating film of the coating solution. Thereafter, the individual coating films were heat-dried at 100 ° C. Next, the dried roller was heated at 150 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration of 10 ppm to primarily crosslink the polyimide silicone in the coating film. Subsequently, it was heated in an oven at a temperature of 180 ° C. for 24 hours to perform secondary crosslinking to form an adhesive layer, and an adhesive layer evaluation sample in which an adhesive layer was formed on a SUS foil was produced. The elastic modulus and the siliconization rate of this adhesive layer evaluation sample were measured in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 8)
Except having changed into the coating liquid (trade name: SMP-5005-PGMEA, the Shin-Etsu Chemical Co., Ltd. product) the coating liquid with which the polyimide silicone before thermosetting was melt | dissolved in the solvent, it carried out similarly to Example 7. A fixing roller and an adhesive layer evaluation sample were prepared. These were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 9
Except for changing the material of the surface layer forming coating material to the four types of materials shown in Table 1, the coating material No. In the same manner as paint No. 1, paint no. 5 was produced. As a paint for forming the surface layer, paint No. A fixing roller was prepared and evaluated in the same manner as in Example 1 except that No. 5 was used. The evaluation results are shown in Table 3.

(Example 10)
Except having changed into the coating liquid (trade name: SMP-5005-PGMEA, the Shin-Etsu Chemical Co., Ltd. product) the coating liquid with which the polyimide silicone before thermosetting was melt | dissolved in the solvent, it carried out similarly to Example 9. A fixing roller was prepared and used for evaluation. The evaluation results are shown in Table 3.

(Comparative Example 1)
A coating solution in which a polyimide silicone before thermosetting is dissolved in a solvent is used as a coating solution in which a low silicone rate is dissolved as a polyimide silicone before thermosetting (trade name: SMP-2003-PGMEA, Shin-Etsu Chemical Co., Ltd.) A sample for evaluating the fixing roller and the adhesive layer was obtained in the same manner as in Example 1 except that the product was manufactured by the same company. These were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Comparative Example 2)
Other than using a coating liquid (trade name: MEGUM W3295, manufactured by ROHM AND HAAS) whose main component is a silane coupling agent instead of a coating liquid in which polyimide silicone before thermosetting is dissolved in a solvent In the same manner as in Example 1, a fixing roller and an adhesive layer evaluation sample were obtained. These were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 11)
The adhesive layer evaluation samples according to Examples 1, 2, and 7 and Comparative Examples 1 and 2 were further subjected to the following IR analysis and XPS analysis, as well as SEM observation and EDS analysis.

[IR analysis and XPS analysis]
The ATR measurement (total reflection absorbance measurement) of the sample for evaluating the adhesive layer was performed under the conditions of a resolution of 4 cm ⁻¹ and a total number of times of 4 times. As a measuring device, a Perkin Elmer Frontier FTIR spectrophotometer manufactured by PerkinElmer Japan Co., Ltd. was used.

  In XPS, each adhesive layer was analyzed under the conditions of measurement area φ: 100 μm, excitation condition: 25 W × 15 kV, detector angle: 45 ° as measurement conditions, and the state of chemical bonding of carbon atoms was examined. As a measuring device, Quantum2000 manufactured by ULVAC PHI was used.

[IR analysis and XPS analysis results]
FIG. 5 shows the IR analysis result of the adhesive layer according to Example 1, FIG. 6 shows the IR analysis result of the adhesive layer according to Example 2, FIG. 7 shows the IR analysis result of the adhesive layer according to Example 7, and FIG. FIG. 8 shows the IR analysis result of the adhesive layer according to 1 and FIG. 9 shows the IR analysis result of the adhesive layer according to Comparative Example 2.

In the adhesive layers according to Examples 1, 2, 7 and Comparative Example 1, a peak based on the polyimide structure and a peak based on the dimethylsiloxane structure were observed. Specifically, for the polyimide structure, a peak based on aromatic C—H stretching vibration near 2970 cm ⁻¹ , a peak based on C═O stretching vibration near 1780 cm ⁻¹ and 1720 cm ^−1, and aroma near 1500 cm ^−1. a peak based on the family C-C stretching vibration, 1390 cm ^-1 vicinity to the aromatic ring -N <peak based on the stretching vibration, a peak based on C-O stretching vibration in the vicinity of 1220 cm ^-1, an aromatic ring in the vicinity of 720 cm ^-1 - A peak based on N <deflection vibration was observed. The dimethyl siloxane structure, a peak based on CH ₃ stretching vibration in the vicinity of 2890cm ^-1, a peak based on Si-C stretching vibration in the vicinity of 1250 cm ^-1, a peak based on Si-O-Si stretching vibration in the vicinity of 1100～1000Cm ^-1 , A peak based on Si—C stretching vibration was observed in the vicinity of 790 cm ⁻¹ .

On the other hand, in the adhesive layer according to Comparative Example 2, no peak based on the polyimide structure was observed, and a peak based on the silicone resin obtained by curing the silane coupling agent was observed. Specifically, a peak based on Si—O—Si stretching vibration was observed near 1100 to 1000 cm ⁻¹ .

  From the XPS analysis results, the adhesive layers according to Examples 1, 2, 7 and Comparative Example 1 are considered to be based on C = O of the polyimide structure in the vicinity of the bond energy of 287.5 eV with respect to the 1s orbit of the carbon atom. Peak was observed.

  On the other hand, the peak considered to be based on C = O of the polyimide structure was not recognized about the contact bonding layer concerning the comparative example 2.

  As described above, from the results of IR analysis and XPS analysis of the adhesive layer, it was confirmed that the adhesive layers of Examples 1, 2, 7 and Comparative Example 1 had a polyimide structure and a dimethylsiloxane structure.

[SEM observation and EDS analysis]
The dispersion state of the surface layer sample was observed using a scanning electron microscope (JSM-5600LV manufactured by JEOL Ltd., high vacuum mode, acceleration voltage: 15 kV, measurement magnification: 1000 times). Further, it was also examined by performing elemental mapping of silicon with an energy dispersive X-ray analyzer (JED-2200 manufactured by JEOL Ltd., minicup EDS detector).

[Results of SEM observation and EDS analysis]
Moreover, in the SEM observation result of the adhesive layer of Examples 1-10 and Comparative Example 1, the phase separation structure was not seen in the adhesive layer, and the uneven distribution of silicon was not recognized from the EDS analysis result. Therefore, in polyimide silicone, it is considered that the polyimide structure and the dimethylsiloxane structure do not exist as separate molecules but exist in the same molecule.

  In the above examples, the measurement of the elastic modulus of the adhesive layer, the calculation of the silicone rate, the XPS analysis, the SEM observation, and the EDS analysis were performed using the separately prepared adhesive layer evaluation sample. It is also possible to produce a sample from which only the adhesive layer has been appropriately removed from the fixing roller as described below and perform the above analysis.

  First, in the longitudinal center of the fixing roller manufactured at the longitudinal center of the fixing roller, a sample having a thickness of 10 to 30 mm square on the surface of the fixing roller and a total thickness in the thickness direction of the fixing roller is cut out. Most of the cut surface layer and elastic layer of this sample are removed by prepolishing with a lapping film while confirming with a stereomicroscope. At this time, it is preferable that both the surface layer and the elastic layer remain about several μm. Next, in this sample, the remaining portions of the surface layer and the elastic layer are respectively removed by an ion milling method or a microtome method. The sample consisting only of the adhesive layer thus obtained can be attached to a SUS plate and evaluated as described above.

  IR analysis can also be performed by nano IR using a sample cut from the fixing roller.

DESCRIPTION OF SYMBOLS 1 Surface layer 2 Adhesive layer 3 Elastic layer 4 Base material 5 Fixing roller 6 Pressure belt

Claims (10)

A substrate;
An elastic layer comprising silicone rubber on the substrate;
A surface layer on the elastic layer,
The surface layer is an electrophotographic member containing at least fluororubber as a binder,
The surface layer and the elastic layer are bonded via an adhesive layer containing polyimide silicone,
An electrophotographic member, wherein the adhesive layer has an elastic modulus of 0.3 MPa to 110 MPa.   The electrophotographic member according to claim 1, wherein the elastic modulus of the surface layer is 10 MPa or less.   The electrophotographic member according to claim 1, wherein the elastic modulus of the elastic layer is 0.3 or more and 1 MPa or less.   The member for electrophotography according to claim 1, wherein the polyimide silicone has a polyimide structure and a dimethylsiloxane structure in the molecule.   The electrophotographic member according to claim 4, wherein the silicone ratio of the polyimide silicone is 4 or more and 20 or less.   The electrophotographic member according to any one of claims 1 to 5, wherein the adhesive layer has an elastic modulus of 3 MPa or more and 4 MPa or less.   The electrophotographic member according to claim 6, wherein the surface layer has a matrix containing the fluororubber and a domain containing a silicone-based surfactant.   The electrophotographic member according to claim 7, wherein the silicone surfactant has a dimethylpolysiloxane structure and a polyoxyalkylene structure.   A fixing device having a fixing member and a pressure member disposed opposite to the fixing member, wherein one or both selected from the fixing member and the pressure member is any one of claims 1 to 8. A fixing device comprising the electrophotographic member according to claim 1.   An image forming apparatus having an image forming unit for forming an unfixed toner image on a recording material and a fixing device for fixing the toner image, wherein the fixing device is the fixing device according to claim 9. An image forming apparatus.