WO2008044643A1 - Tube en polyimide, son procédé de production, procédé de production d'un vernis en polyimide et ceinture de fixation - Google Patents
Tube en polyimide, son procédé de production, procédé de production d'un vernis en polyimide et ceinture de fixation Download PDFInfo
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- WO2008044643A1 WO2008044643A1 PCT/JP2007/069587 JP2007069587W WO2008044643A1 WO 2008044643 A1 WO2008044643 A1 WO 2008044643A1 JP 2007069587 W JP2007069587 W JP 2007069587W WO 2008044643 A1 WO2008044643 A1 WO 2008044643A1
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- polyimide
- boron nitride
- varnish
- tube
- repeating unit
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/20—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat
- G03G15/2003—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat
- G03G15/2014—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat using contact heat
- G03G15/2053—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/08—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder
- B29C41/085—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder by rotating the former around its axis of symmetry
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/20—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat
- G03G15/2003—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat
- G03G15/2014—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat using contact heat
- G03G15/2053—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating
- G03G15/2057—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating relating to the chemical composition of the heat element and layers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G2215/00—Apparatus for electrophotographic processes
- G03G2215/20—Details of the fixing device or porcess
- G03G2215/2003—Structural features of the fixing device
- G03G2215/2016—Heating belt
- G03G2215/2035—Heating belt the fixing nip having a stationary belt support member opposing a pressure member
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G2215/00—Apparatus for electrophotographic processes
- G03G2215/20—Details of the fixing device or porcess
- G03G2215/2003—Structural features of the fixing device
- G03G2215/2048—Surface layer material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Definitions
- the present invention relates to a polyimide tube, and more particularly, to a polyimide tube excellent in tensile strength and elastic modulus in addition to having high thermal conductivity.
- the present invention also relates to a method for producing the polyimide tube, a polyimide varnish used for producing the polyimide tube, and a fixing belt using the polyimide tube as a belt base material.
- an image exposure process is performed on a photoconductor.
- a transfer step of transferring onto a transfer material such as a sheet; a fixing step of fixing an unfixed toner image on the transfer material by means such as heating and pressing; and untransferred toner remaining on the photoreceptor Each process such as cleaning process to be removed;
- a method is generally used in which an unfixed toner image on a transfer material is heated and pressed to be fused onto the transfer material.
- a heating / pressurizing unit a fixing roller and a pressure roller are opposed to each other, and a transfer material on which an unfixed toner image is placed is passed between them.
- a method of heating with a built-in fixing roller has been adopted.
- the fixing roller has a structure in which a cylindrical cored bar is used as a base, the outer surface thereof is coated with rubber or resin having excellent releasability, and a heating source such as an electric heater is disposed in the hollow. .
- the fixing roller having such a structure requires a relatively long waiting time to raise the surface temperature of the fixing roller to the fixing temperature by the heating means arranged in the hollow.
- a fixing belt 1 composed of a thin endless belt is used.
- the heating means (heater) 2 More specifically, the heater 2 and the pressure roller 3 are opposed to each other through a thin fixing belt 1, and a material to be transferred 4 on which an unfixed toner image 5 is formed is pressed between the heater 2 and the pressure roller 3. Heat with heater 2. As a result, the unfixed toner image 5 on the transfer material 4 is fused on the transfer material 4.
- the heater 2 is fixed, and the fixing belt 1 and the pressure roller 3 rotate in opposite directions.
- the pressure roller 3 a structure in which a rubber layer and a fluororesin layer are arranged in this order on a metal core is generally used. A system using a pressure belt instead of the pressure roller 3 has been developed.
- the unfixed toner image 5 on the transfer material 4 is heated by the heater 2 through the thin fixing belt 1, so that the fixing unit can reach a predetermined fixing temperature in a short time. And waiting time after power-on becomes extremely short.
- a fixing belt used in such a fixing method is required to have excellent heat resistance, mechanical strength, releasability, and the like.
- a fixing belt in consideration of the above-mentioned required performance, a belt in which a polyimide tube made of an endless belt is used as a base and a fluororesin layer is provided on the outer surface thereof has been widely used.
- fixing belts based on polyimide tubes are composed of polyimide resin and fluororesin with low thermal conductivity, so fixing speed is increased, fixing temperature is lowered, full-color toner fixability, etc.
- the thermal conductivity there is a need for improved thermal conductivity. If the thickness of the polyimide tube is reduced to improve the thermal conductivity of the fixing belt, the mechanical strength will decrease, and the fixing belt will tend to wrinkle, crush, crack, etc. due to rotation during fixing. .
- Patent Document 1 Japanese Patent Laid-Open No. 62-3980
- an inner layer made of a polyimide resin composition containing a heat conductive filler is formed on the inner peripheral surface of an endless belt made of polyimide resin.
- Endless belts have been proposed.
- the endless belt has an insufficient effect of improving the thermal conductivity in the thickness direction because the endless belt made of a polyimide resin as a base material has insufficient thermal conductivity.
- the endless belt requires an inner layer forming step, which increases the cost.
- Patent Document 2 JP-A-3-25478 discloses a polyimide resin, carbon black, An endless film comprising a resin composition containing an inorganic filler such as silicon carbide or silica is disclosed.
- the fixing belt based on this endless film can lower the fixing temperature to some extent, but when the blending ratio of the inorganic filler is increased, the elongation rapidly decreases. Therefore, each example of Patent Document 2 only shows an endless belt-like polyimide film in which carbon black, silicon carbide or silica is contained in polyimide resin at a low blending ratio of 1 to 5% by weight. It is. If the blending ratio of the inorganic filler to the polyimide resin is too low, it is difficult to sufficiently increase the thermal conductivity of the polyimide tube.
- JP-A-8-80580 discloses a polyimide tube comprising a resin composition containing an inorganic filler having excellent thermal conductivity such as boron nitride (boron nitride) in polyimide resin.
- a fixing belt having a base material is disclosed.
- Patent Document 3 has a wide disclosure regarding the proportion of boron nitride! /, In order to obtain a fixing belt having sufficient thermal conductivity, in practice, boron nitride is used at a high ratio. It was necessary to make it contain.
- the thermal conductivity of the fixing belt cannot be sufficiently increased, and it is difficult to achieve the required performance such as higher fixing speed. . Further, if the content of boron nitride in the polyimide resin is too low, the elastic modulus is not sufficiently high, so that the fixing belt is liable to be twisted or crushed at the end.
- Patent Document 4 discloses that 100 parts by weight of a polyimide resin contains 0.;! To 100 parts by weight of carbon nanotubes and a thermal conductivity of 0.30 W / mK or more. A polyimide tubular product (polyimide tube) is disclosed. Thus, Patent Document 4 Although there is a very wide disclosure regarding the mixing ratio of carbon nanotubes, in each example, in order to obtain a polyimide tube with a high thermal conductivity of 0.50-0.55 W / m'K, It is shown that it is necessary to increase the mixing ratio of carbon nanotubes to 30 to 50 parts by weight. However, as specifically shown in each example of Patent Document 4, when the compounding ratio of the carbon nanotubes is increased, the mechanical strength such as the tear strength of the polyimide tube is remarkably lowered.
- Patent Document 1 Japanese Patent Application Laid-Open No. 62-3980
- Patent Document 2 JP-A-3-25478 (corresponding to US Pat. No. 5,182,606)
- Patent Document 3 JP-A-8-80580
- Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-123867
- An object of the present invention is to provide a polyimide tube excellent in tensile strength and elastic modulus in addition to having high thermal conductivity.
- the object of the present invention is a polyimide that has a high tensile strength and a high elastic modulus, and is less susceptible to problems such as torsional deformation, cracking at the end, and crushing when used as a base material for a fixing belt. Is to provide a tube
- Another object of the present invention is to provide a method for producing a polyimide tube excellent in the above-mentioned various characteristics. Moreover, the subject of this invention is providing the manufacturing method of the polyimide varnish used for manufacture of this polyimide tube.
- Still another problem of the present invention is that the use of a polyimide tube having excellent properties as a base material significantly improves the fixing speed, the fixing temperature, and the fixing ability of a full-color toner.
- the object of the present invention is to provide a fixing belt that is less prone to problems such as torsional deformation, cracking at the end, and crushing.
- the present inventors as a filler in polyimide resin, boron nitride and acicular substance (acicular filler) on the basis of the total composition volume, Is a polyimide tube composed of a polyimide resin composition dispersed at a specific rate. I came up with it.
- the polyimide tube of the present invention has a low level of boron nitride in the polyimide resin to prevent a decrease in tensile strength, and a high level of thermal conductivity and elastic modulus by using acicular substances in a specific ratio. Hold on!
- the polyimide tube of the present invention contains boron nitride and acicular substances in a specific ratio, the tensile strength in the circumferential direction and the axial direction is high, and the elastic modulus is also at a high level. The torsional deformation, cracking at the end, and crushing of the fixing belt based on the tube are suppressed.
- the polyimide tube of the present invention is a method in which an organic solvent solution (polyimide varnish) containing a polyimide precursor, boron nitride and an acicular substance is applied to the surface of a cylindrical or cylindrical mold by a dipping method ( A method of forming a coating layer by spirally winding a polyimide varnish around an outer surface or an inner surface of a core body using a dispenser (dispenser method);
- boron nitride and needle-like substances can be oriented in the circumferential direction to increase the tensile strength in the circumferential direction.
- a polyimide tube having a high tensile strength and elastic modulus in the circumferential direction and in the axial direction and a particularly high mechanical strength in the circumferential direction is used during driving when used as a base material for a fixing belt.
- a polyimide resin in which 5 to 23.5% by volume of boron nitride and acicular substances;! To 15% by volume are dispersed in the polyimide resin as a filler based on the total volume of the composition.
- a polyimide tube composed of the composition is provided.
- the discharge roller polyimide varnish of the dispenser supply part which is in contact with the outer surface or the inner surface of the core is continuously supplied.
- the dispenser supply unit is moved relatively in the direction of the rotation axis of the core body.
- the polyimide varnish strength organic solvent contains a polyimide precursor and a filler composed of boron nitride and an acicular substance as a solid content, and boron nitride in the total volume of the solid content.
- a polyimide varnish having a content ratio of 5-23.5% by volume and a needle-shaped substance content of 1 to 15% by volume is provided.
- the filler contains boron nitride and an acicular substance, the organic solvent is an organic amide solvent, and the following steps 1 and 2:
- Step 1 of mixing a needle-shaped substance, a dispersing agent, and an organic amide solvent to prepare a dispersion containing the needle-shaped substance;
- a method for producing a polyimide varnish for producing a polyimide tube comprising the step 2 of mixing the dispersion, boron nitride and a polyimide precursor.
- the polyimide tube is used as a belt base material, and the outer peripheral surface of the belt base material has a layer structure in which a fluororesin layer is provided directly or via an adhesive layer.
- a fuser belt is provided.
- the present invention it is possible to provide a polyimide tube excellent in tensile strength and elastic modulus in addition to high thermal conductivity. Since the polyimide tube of the present invention is excellent in the above-mentioned characteristics, when it is used as a base material for a fixing belt, the fixing speed is increased, the fixing temperature is lowered, and the fixing property of a full color toner is remarkably improved. Obtain the belt with the force S.
- the polyimide tube of the present invention has a high tensile modulus in the circumferential direction and axial direction and a high elastic modulus, when used as a base material for a fixing belt, it is twisted, cracked at the end, and crushed. Etc. are suppressed.
- the fixing belt based on the polyimide tube of the present invention is less likely to crack or tear.
- FIG. 1 is an explanatory view showing a fixing method using a fixing belt.
- FIG. 2 is a cross-sectional view showing a layer structure of an example of a fixing belt.
- FIG. 3 is a cross-sectional view showing a layer structure of another example of the fixing belt.
- FIG. 4 is an explanatory diagram regarding a method of applying a polyimide varnish by a dispenser method.
- thermosetting polyimide resin also referred to as “condensation type polyimide resin”
- thermoplastic polyimide resin can be used as the polyimide resin.
- the polyimide tube of the present invention is preferably formed from a thermosetting polyimide resin from the viewpoint of heat resistance, tensile strength, elastic modulus, and the like.
- a polyimide tube made of a thermosetting polyimide resin is composed of an organic solvent solution of a polyimide precursor (also referred to as “polyamide acid” or “polyamic acid”! /, U), hereinafter referred to as “polyimide varnish”! /, U) Is applied to the outer surface of the cylindrical mold or the outer surface or inner surface of the cylindrical mold, dried and heated. Then, the force S is obtained by the method of hardening.
- a polyimide precursor also referred to as "polyamide acid” or “polyamic acid”! /, U
- polyimide varnish hereinafter referred to as "polyimide varnish”! /, U
- the thermosetting polyimide resin is preferably a condensation-type wholly aromatic polyimide resin from the viewpoints of heat resistance and mechanical strength.
- the thermosetting polyimide resin include acid dianhydrides such as pyromellitic dianhydride, 3, 3 ', 4, 4'-diphenyltetracarboxylic dianhydride, and oxydiphthalic dianhydride.
- Polyimide precursors were synthesized by polymerization reaction of diamines such as 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4, A'-diaminobenzanilide, and resornoresin xydianiline in organic solvents.
- An example is an organic solvent solution (polyimide varnish) of this polyimide precursor that is shaped into a tube shape and then heated and dehydrated and closed.
- polyimide varnish commercially available products can be used in addition to those synthesized independently.
- the thickness, outer diameter, length, and the like of the polyimide tube can be appropriately selected according to the desired mechanical strength and application.
- the thickness of the polyimide tube is usually 30 to 80 mm 111, preferably 40 to 70 mm 111, more preferably.
- the outer diameter is usually 50 to 60 mm, and the outer diameter is usually 10 to 60 mm, preferably 15 to 50 mm.
- the length of the polyimide tube can be appropriately set according to the size of the transfer material such as copy paper.
- the polyimide resin (imidized resin) used in the present invention may be a homopolymer or a copolymer.
- the polyimide resin is a homopolymer, its chemical structure is represented by the following formula (A)
- Polyimide resin B having a repeating unit represented by:
- the tensile strength and elastic modulus of the polyimide tube are highly balanced.
- polyimide resins A to C are each independent, and certain! / Can be used as a mixture of two or more.
- the polyimide resin having these repeating units A to C can be obtained by a method of imidizing after forming into a tube using a polyimide precursor corresponding to each of them.
- a polyimide resin having a repeating unit A 3, 3 ', 4, ⁇ ' -diphenyltetracarboxylic dianhydride and ⁇ -phenylenediamine are used as monomers.
- V a polyimide precursor is synthesized, a tube is formed using a polyimide varnish containing the polyimide precursor, and then imidized.
- the acid dianhydride component and the diamine component are used in an approximately equimolar ratio (hereinafter the same).
- a polyimide precursor is synthesized using pyromellitic dianhydride and 4,4'-diaminodiphenyl ether as monomers, and the polyimide precursor is synthesized.
- the tube may be formed using the polyimide varnish contained and then imidized.
- the polyimide resin ⁇ ⁇ ⁇ ⁇ ⁇ to C is a force S that can be used by blending two or more kinds, and at that time, blends a polyimide resin having excellent rigidity and a polyimide resin having excellent flexibility. It is preferable. From such a viewpoint, as the blend, for example, a blend of polyimide resin A and polyimide resin B and a blend of polyimide resin A and polyimide resin C are preferable. In these blends, the proportion of polyimide resin A is preferably 25 to 95% by weight, and the proportion of polyimide resin B or polyimide resin C is preferably 5 to 75% by weight.
- Polyimide copolymer 4 having a repeating unit represented by:
- These polyimide copolymers 1 to 5 can be used alone or in combination of two or more. These polyimide copolymers can be obtained by a method of imidizing after forming into a tube using a polyimide precursor corresponding to each.
- polyimide copolymer 1 having a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B)
- 3 3 ', 4 Polyimide precursor is synthesized using, diphenyltetracarboxylic dianhydride, p-phenylenediamine and 4, ⁇ ⁇ ⁇ -diaminodiphenyl ether, and a tube using a polyimide varnish containing the polyimide precursor. After molding, imidization may be performed. Acid dianhydride component and diamine formation The ratio with minutes is approximately equimolar (hereinafter the same).
- the proportion of the repeating unit (A) is preferably 25 to 99 mole 0/0
- the proportion of the repeating unit (B) preferably 1 ⁇ 75 mol%.
- polyimide copolymer 2 having a repeating unit represented by the formula (D) and a repeating unit represented by the formula (B)
- 3 3 ', 4 Polyimide precursors were synthesized using, diphenyltetracarboxylic dianhydride, 4,4'-diaminobenzanilide and p-phenylenediamine, and polyimide varnish containing the polyimide precursor was used. Then, after forming the tube, it may be imidized.
- the ratio of the repeating unit (D) is preferably 25 to 99 mol%
- the ratio of the repeating unit (B) is preferably 1 it is a 75 mole 0/0.
- the polyimide copolymer 4 having the repeating unit represented by the formula ( ⁇ ) and the repeating unit represented by the formula (F), 3, 3 ′, 4 After synthesizing a polyimide precursor using ⁇ -diphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride and ⁇ -phenylenediamine, and forming a tube using a polyimide varnish containing the polyimide precursor What is necessary is just to imidize.
- the proportion of the repeating unit ( ⁇ ) is preferably 25 to 99 mol%
- the proportion of the repeating unit (F) is preferably 1 to 75 mol%. %.
- a polyimide copolymer 5 having a repeating unit represented by the formula ( ⁇ ) and a repeating unit represented by the formula (G)
- 3, 3 ', 4 -Diphenyltetracarboxylic dianhydride, ⁇ -phenylenediamine and resorcinoxydianiline were used to synthesize a polyimide precursor, and a polyimide varnish containing the polyimide precursor was used for After forming the tube, it may be imidized.
- the proportion of the repeating unit (A) is preferably 25 to 99 mol%
- the proportion of the repeating unit (G) is preferably 1 to 75 mol%. 0/0.
- a force may be employed in which a fluororesin dispersion is applied to the outer peripheral surface and sintered at a high temperature. Copolymers and blends thereof have heat resistance sufficient to withstand such high-temperature sintering!
- Boron nitride (hereinafter abbreviated as “BN”, which has the force S) is known as graphite structure type hexagonal BN (h— BN) and cubic cubic BN (c— BN). Either the force S or the present invention can be used. These boron nitrides can be used alone or in combination of two or more. Boron nitride has a true specific gravity of 2.26 g / cm.
- the average particle size of boron nitride measured by the laser scattering method is preferably 0 ⁇ ;! to ⁇ ⁇ , more preferably 0.5 to 10111. If the average particle size of boron nitride is too small, it tends to agglomerate and may be difficult to disperse in the polyimide resin. If the average particle size of boron nitride is too large, the smoothness of the surface may be impaired when the thickness of the polyimide tube is reduced.
- the content ratio of boron nitride in the polyimide resin composition is 5 to 23.5% by volume, preferably 10 to 20% by volume, based on the total volume of the composition. If the boron nitride content is too low, the thermal conductivity of the polyimide tube and the fixing belt based on the polyimide tube will decrease. If the boron nitride content is too high, the mechanical strength such as tensile strength will decrease.
- the polyimide resin composition means a resin composition in which boron nitride and an acicular substance are dispersed in an imidized polyimide resin.
- boron nitride and an acicular substance are mixed at a predetermined mixing ratio in an organic solvent solution (raw material polyimide varnish) of a polyimide precursor corresponding to the polyimide resin.
- a tube may be formed using the polyimide varnish added in step 1 and imidized.
- Boron nitride can be treated with a surface treatment agent such as a coupling agent in order to increase dispersibility in the polyimide varnish and adhesion to the polyimide resin.
- a coupling agent a known silane coupling agent or titanate coupling agent can be used.
- the acicular substance used in the present invention typically means an acicular filler, and specifically includes fibrous substances such as carbon nanotubes and minute acicular crystals (Wys power).
- Means a substance consisting of Specific examples of acicular substances include carbon nanotubes, titanium oxide, zinc oxide, potassium titanate, aluminum borate, carbide, nitride nitride, magnesium sulfate, calcium silicate, calcium carbonate, and graphite. It is done.
- These acicular substances can be used alone or in combination of two or more.
- carbon nanotubes are preferable from the viewpoint of thermal conductivity.
- the length and diameter of the acicular substance are not particularly limited, but the length is usually about 0.;! To about 200 m, and the diameter is usually about 0.01 to about 10 m. However, it is preferable in consideration of the step of applying the polyimide precursor solution and the thickness of the coating film.
- the length of the acicular material is preferably 0.5 to 50 111.
- the diameter of the acicular material is preferably 0.05-5111. Acicular substances can be used alone or in combination of two or more.
- the carbon nanotube used as the acicular substance in the present invention (hereinafter abbreviated as "CNT” has a force S) refers to a single sheet of graphite (sometimes called darafen or graphen sheet).
- CNT carbon nanofibers with a fiber diameter of 1 ⁇ m or less, and carbon nanotubes with many cup-shaped carbon materials with open bottoms, etc. included.
- the method for producing the carbon nanotube is not particularly limited, but a carbon nanotube produced by a vapor phase growth method in which the diameter of the carbon nanotube is controlled and excellent in mass productivity is preferable.
- the diameter of the carbon nanotube is usually 300 nm or less, preferably 200 nm or less, and the length is usually 50 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
- the diameter and length can be measured by, for example, a laser scattering method or a scanning electron microscope. If the diameter and length of the carbon nanotube is too large, the polyimide varnish The dispersibility with respect to tends to decrease. If the diameter and length of the carbon nanotube are too large, the mechanical strength may be lowered, and the surface smoothness may be impaired.
- the content ratio of the carbon nanotubes in the polyimide resin composition is 1 to 15% by volume, preferably 2 to 10% by volume, and more preferably 2 to 5% by volume based on the total volume of the composition. If the carbon nanotube content is too low, the thermal conductivity of the polyimide tube and the fixing belt based on the polyimide tube is lowered, and the combined use effect with boron nitride is reduced. If the carbon nanotube content is too high, the mechanical strength may decrease.
- the carbon nanotubes may be treated with a surface treatment agent as described above if desired.
- the polyimide resin composition when the volume% of boron nitride is X and the volume% of a needle-like substance such as carbon nanotube is y, the polyimide resin composition has the following formula (1)
- boron nitride and the acicular material are dispersed in the respective volume% satisfying the above relationship in order to highly balance various properties such as thermal conductivity, tensile strength, and elastic modulus.
- the polyimide resin composition has the following formula (2) when the volume% of boron nitride is X and the volume% of the needle-like substance is y.
- the boron nitride and the acicular material are dispersed in each volume% satisfying the above relationship in order to further balance various properties such as thermal conductivity, tensile strength, and elastic modulus. .
- a polyimide tube is formed by applying a polyimide varnish containing a polyimide precursor, boron nitride, and a needle-like substance to the outer surface of a cylindrical mold or the outer surface or the inner surface of a cylindrical mold, drying, and then curing by heating. It can obtain by the method of making it. After drying the polyimide varnish coating layer, heat cure with the tube containing the polyimide precursor attached to the mold surface. At the time when it is solidified to such a strength that it can hold the structure or the structure as a tubular product, the polyimide precursor tube is removed from the mold and then cured by heating.
- the polyimide precursor When the polyimide precursor is heated from a maximum temperature of 350 ° C to 450 ° C, the polyamic acid is dehydrated and closed to form a polyimide. If necessary, various additives such as other inorganic fillers can be added to the polyimide varnish as long as the object of the present invention is not impaired.
- the method for applying the polyimide varnish is not particularly limited.
- the polyimide varnish is applied to the outer surface of a columnar or cylindrical mold by a dubbing method, and then the outer diameter of the mold is set outside the mold.
- a method of forming a coating film having a desired film thickness by passing a die having a large inner diameter is mentioned.
- a coating film having a desired film thickness may be formed by applying polyimide varnish to the inner surface of the cylindrical mold and passing through a die having an inner diameter smaller than the inner diameter of the mold.
- the polyimide tube of the present invention can effectively suppress torsional deformation of the fixing belt, collapse due to buckling, and the like when used as a base material of the fixing belt. It is preferable because it is possible. In order to increase the mechanical strength in the circumferential direction, it is preferable to orient boron nitride and the acicular substance in the circumferential direction.
- the dispenser method is a method in which a polyimide resin is continuously supplied from a discharge port of a dispenser supply unit that is in contact with an outer surface or an inner surface of a core while rotating the core that is a molding die. At that time, by moving the dispenser supply section in the direction of the rotation axis of the core body, a polyimide varnish is spirally wound around the outer surface or the inner surface of the core body to form a coating layer, and then And a method for producing a polyimide tube in which the coating layer is removed from the core after the coating layer is solidified or cured.
- FIG. 4 is an explanatory diagram of the dispenser method.
- the polyimide varnish is continuously supplied from the supply unit 21 of the dispenser while rotating the columnar or cylindrical core body 24 in the circumferential direction.
- the discharge port 22 of the supply unit 21 is brought into contact with the outer surface of the core body 24.
- the discharge port 22 of the dispenser supply unit 21 is in contact with the inner surface thereof.
- the polyimide varnish may be supplied by touching.
- the supplied polyimide varnish is spirally formed.
- the coating layer 23 is formed by winding.
- the dispenser supply unit 21 is moved in the direction of the rotation axis of the core body 24.
- the dispenser supply unit 21 may be moved in the direction of the rotation axis while rotating the core body 24.
- the polyimide varnish wound spirally joins adjacent portions to form a uniform coating layer.
- the discharge port 22 of the dispenser supply section is usually a nose.
- the surface of the core body 24 is adjusted by adjusting the moving speed of the dispenser and the rotation speed of the core body 24 so that the polyimide varnishes wound and applied in a spiral form come into contact with each other to form a uniform coating layer. Apply polyimide varnish without any gaps. After this coating step, the coated polyimide varnish is heat-cured (imidized) by a conventional method to form a strong thin tube-like film. Thereafter, by taking out the tube from the core, it is possible to obtain a polyimide tube. After the coating process, the solidified tube is demolded until the coating layer that does not completely imidize has enough strength to maintain the structure of the tube, and the tube is heat-cured after demolding (imidization). Let me let you.
- the polyimide varnish contains a polymide precursor, boron nitride, and acicular substance as solids in an organic solvent, and the boron nitride content in the total volume of the solids is 5%.
- the viscosity of the polyimide varnish at 25 ° C. is preferably 100 to 15,000 poise (10 to 1500 Pa-s), more preferably 100 to 3000 boise (10 to 300 Pa-s).
- the shape of the core used is preferably a columnar shape or a cylindrical shape.
- Materials for the core used in the present invention include metals such as aluminum, aluminum alloy, iron and stainless steel; ceramics such as alumina and carbon carbide; heat resistance such as polyimide, polyamideimide, polybenzimidazole and polybenzoxazole. Resin; and the like.
- a release agent composed of silicone oil or the like, or to coat the core with a ceramic.
- ceramics include silica, alumina, zirconium oxide, silicon nitride coated by a sol-gel method; alumina coated by a thermal spraying method, zirconium oxide; aluminum nitride coated by a sputtering method, and the like.
- ceramic coating by the zonore gel method which does not require an expensive apparatus and is easy to perform coating, is preferable.
- a slightly darker color! / Part may be formed and a striped pattern may be formed.
- the film may be uneven.
- the striped pattern is generated when the discharge port of the dispenser supply section and the polyimide varnish layer spirally applied to the core are in contact with each other, and the moving speed V (mm / sec) and the rotational speed R of the core are R. (Rotation / second) and (V / R) ⁇ 3.0 (mm / number of rotations). Generation of stripes and irregularities can be prevented by the stirring effect.
- This relational expression is preferably (V / R) ⁇ 1.5 (mm / number of revolutions).
- a plastics tube, a rubber tube, a metal tube, or the like can be used for the discharge port of the dispenser supply unit.
- a plastics tube, a rubber tube, a metal tube, or the like can be used for the discharge port of the dispenser supply unit.
- polytetrafluoroethylene especially polytetrafluoroethylene
- a tube made of (PTFE) or a tetrafluoroethylene / perfluoroalkyl butyl ether copolymer (PFA) is preferable because it has an appropriate rigidity and hardly scratches the surface of the core.
- a polyimide varnish used for manufacturing a polyimide tube can be prepared by mixing each component.
- a polyimide varnish can be prepared by adding boron nitride and a needle-like substance to a polyimide varnish, pre-stirring with a stirrer, blending with a roll mill, and vacuum degassing.
- the filler contains boron nitride and an acicular substance, the organic solvent is an organic amide solvent, and the following steps 1 and 2:
- Step 1 of mixing a needle-shaped substance, a dispersing agent, and an organic amide solvent to prepare a dispersion containing the needle-shaped substance;
- a process for producing a polyimide varnish for producing a polyimide tube which comprises the step 2 of mixing the dispersion, boron nitride and a polyimide precursor solution.
- organic amide solvents include N methyl 2-pyrrolidone, N cyclohexyl lu 2-pyrrolidone, N methyl 8-pyrrolidone compounds such as N-methyl pyrrolidone; N-cycloalkyl pyrrolidone compounds; N, N dimethylformamide Amide compounds such as N, N dimethylacetamide; N, N-dialkylimidazolidinone compounds such as 1,3 dialkyl 1-2 imidazolidinone; Tetraalkylurea compounds such as tetramethylurea; Hexamethyl phosphate-removing amide Oxaalkyl phosphate triamide compounds; and the like. Of these, N-methyl-2-pyrrolidone is preferred.
- dispersant various dispersion stabilizers can be used as long as they have a function of enhancing the dispersion stability of particles such as fillers in an organic amide solvent.
- Such dispersing agents include various surfactants in addition to those commercially available as dispersing agents.
- a polymer type dispersant is preferable from the viewpoint of dispersibility and dispersion stability.
- Polymer type dispersants range from low molecular weight oligomer types to high molecular weight types.
- the number average molecular weight (according to GPC measurement) of the polymer type dispersant is preferably ⁇ 1,000-500,000.
- Examples of the polymer type dispersant include Ajimoto PB-711 and Ajisper PB-821 (both are basic functional group-containing copolymers) manufactured by Ajinomoto Fine Techno Co., Ltd .; DISPERBYK manufactured by BYK Chemie —161, DISPERBYK—163, DISPERBYK—164, DIS PERBYK—182 (all are block copolymers); Polybulol pylori manufactured by Wako Pure Chemical Industries, Ltd.
- the dispersant is usually added in a proportion of 0.;! To 20% by weight, preferably 0.3 to 10% by weight, with respect to the needle-like substance such as carbon nanotube. If the amount of the dispersant added is too small, the dispersibility and dispersion stability will not be sufficiently improved. If it is too large, the dispersant may remain in the fired polyimide tube and cause a decrease in strength. is there.
- the dispersion of the needle-like substance can be prepared by adding a needle-like substance such as carbon nanotube and a dispersant to the organic amide solvent, stirring with a stirrer, and mixing.
- the solid content concentration of the acicular substance is preferably ;! to 70% by weight, more preferably 3 to 50% by weight.
- a polyimide varnish can be prepared by adding boron nitride and a needle-like substance dispersion to a polyimide precursor solution (raw varnish), blending with a roll mill, and stirring and mixing with a stirrer. . It is also possible to employ a method in which the raw material varnish and boron nitride are blended by a roll mill, and then a needle-like substance dispersion is added and stirred and mixed with a stirrer. Any other method may be employed as long as it can efficiently disperse boron nitride and the acicular substance in the raw material varnish.
- the polyimide tube of the present invention can be used as a base material of a fixing belt mounted on a fixing unit in an electrophotographic image forming apparatus.
- the fixing belt of the present invention is composed of a polyimide resin composition in which boron nitride 5 to 23.5% by volume and acicular substance 1 to 15% by volume are dispersed in a polyimide resin on the basis of the total volume of the composition. It is preferable that a polyimide tube is used as a belt base material, and a fluororesin layer is provided on the outer peripheral surface of the belt base material directly or via an adhesive layer.
- fluororesin that forms the fluororesin layer preferably have excellent heat resistance in order to enable continuous use of the fixing belt at a high temperature.
- Fluoroethylene PTFE
- PFA perfluoroalkylbi Nyl ether copolymer
- FEP tetrafluoroethylene / hexafluoropropylene copolymer
- the fluororesin layer can be formed using a pure fluororesin, but can contain a conductive filler in order to prevent offset due to charging.
- a conductive filler can also be contained in the intermediate layer.
- the fluororesin layer is provided to impart releasability to the fixing belt and prevent the toner on the transfer material such as recording paper from adhering to the surface of the fixing belt.
- a conductive filler is added to a fluororesin to impart conductivity, an offset phenomenon due to charging can be prevented.
- the conductive filler is not particularly limited, and examples thereof include conductive carbon black such as ketjen black; metal powder such as aluminum;
- the average particle size of the conductive filler is preferably 0.5 m or less in order to obtain stable and uniform conductivity.
- the content of the conductive filler is usually about 0.;! To 5% by weight. If the content of the conductive filler is increased, the conductivity level of the fluororesin layer becomes too high, and the charge of the toner may flow to the fluororesin layer, which may reduce the suction force between the transfer material and the toner. is there.
- the fluororesin layer may be formed by a method in which a varnish containing a fluororesin is applied and sintered. A force that can be applied S As another method, a method of covering a fluororesin tube may be employed.
- the thickness of the fluororesin layer is usually 1 to 30 111, preferably 5 to 15 mm.
- the fixing belt can be provided with an adhesive layer as an intermediate layer in order to improve the adhesion between the polyimide tube and the fluororesin layer.
- the adhesive layer can be made to contain a conductive filler.
- the adhesive layer is preferably composed of a heat resistant resin from the viewpoint of heat resistance.
- the resin constituting the adhesive layer is not particularly limited. For example, a mixture of a fluororesin and a polyamideimide resin, a mixture of a fluororesin and a polyethersulfone resin, or the like is preferable.
- a conductive filler is included in the adhesive layer, the shielding effect against frictional charging on the inner surface of the fixing belt and the antistatic effect on the outer surface can be enhanced, and offset can be effectively prevented.
- the blending ratio of the conductive filler is usually 0.5 to 10% by weight, preferably about 1 to 5% by weight.
- the thickness of the adhesive layer is usually about 0.;! ⁇ 20 111, preferably about !! ⁇ 10 m.
- the fixing belt of the present invention has a structure in which a fluororesin layer is provided directly or via an adhesive layer on the outer peripheral surface of a heat-cured (imidized) polyimide tube.
- a fluororesin layer is formed, if the fluororesin is sintered at a high temperature, a tube is formed by drying and removing the solvent in the polyimide tube manufacturing process, and directly or via an adhesive layer. After the fluororesin layer is formed, the polyimide tube can be heated and cured simultaneously with the sintering of the fluororesin.
- the fixing belt of the present invention has a two-layer structure in which a fluororesin layer 13 is formed on the outer peripheral surface of the polyimide tube 11, as shown in a cross-sectional view in FIG.
- the polyimide tube 11 has a three-layer structure in which a fluororesin layer 13 is formed on the outer peripheral surface of the polyimide tube 11 via an adhesive layer 12.
- a resin layer or a rubber layer other than the adhesive layer may be additionally disposed in the intermediate layer.
- the polyimide tube of the present invention is excellent in thermal conductivity and also in elastic modulus with high circumferential and axial tensile strengths.
- the mechanical strength in the circumferential direction increases due to the orientation of boron nitride and the acicular substance.
- the thermal conductivity of the polyimide tube of the present invention is preferably 0.50 W / m'K or more, more preferably 0.52 W / mK or more, and particularly preferably 0.54 W / mK or more.
- Circumferential direction of the tensile strength of the polyimide tube of the present invention preferably 225N / mm 2 or more, more rather preferably has a 230N / mm 2 or more, a tensile strength in the axial direction, preferably 208N / mm 2 or more, more Preferably it is 210 N / mm 2 or more.
- Elastic modulus of the polyimide tube of the present invention the good Mashiku 138N / mm 2 or more, more preferably 140 N / mm 2 or more.
- the polyimide tube of the present invention is used as a base material for a fixing belt, it is possible to obtain a fixing belt in which torsional deformation, cracking at the end, crushing, and the like are suppressed.
- the thermal diffusivity was measured using a periodic heating method thermal diffusivity measuring device (FTC-1) manufactured by ULVAC-RIKO, and the obtained thermal diffusivity was multiplied by the specific heat and density of the polyimide tube.
- the thermal conductivity was calculated (measurement temperature 23 ° C).
- the specific heat of the polyimide tube was measured according to JIS K 71 12 (Method A) using a METTLER electronic balance AE-240 (measurement temperature 23 ° C.).
- the tensile strength of the polyimide tube is obtained by cutting a specimen from the polyimide tube and using the autograph “AGS — 500D” manufactured by Shimadzu according to JIS K 7161 at two locations in the circumferential direction and the axial direction. s, measured at a distance between chucks of 30 mm.
- the elastic modulus of the polyimide tube is obtained by cutting a sample piece from the polyimide tube and using an autograph “AGS-5 00D” manufactured by Shimadzu Corporation in accordance with JIS K 7161 at two locations in the circumferential direction and the axial direction. / s, measured at a chuck distance of 30 mm.
- the elastic modulus is the average of the measured values in the circumferential direction and the axial direction.
- an aluminum cylinder with an outer diameter of 20 mm ⁇ coated with ceramics is used, and while rotating the core, the nozzle (discharge port) set in the dispenser supply section is connected to the core. The outer surface of the core was brought into contact.
- Solid raw material polyimide varnish (“U-Varnish S-301” manufactured by Ube Industries, Ltd., specific gravity 1.446; polyimide precursor varnish that forms a polyimide resin having a repeating unit represented by the formula (A)) Boron nitride (“Mitsui Chemical Co., Ltd.“ MBN-010T ”, graphite structure type BN, specific gravity 2.27) 10% by volume, carbon nanotube (Showa Denko“ VGCF ”, diameter 150 ⁇ ⁇ , long 8 m, specific gravity 2.0) 5% by volume was added, pre-stirred with a stirrer, compounded with a three-roll mill, and then vacuum degassed to obtain a polyimide varnish containing the above components.
- the nozzle While the polyimide varnish is quantitatively supplied from the nozzle of the dispenser supply unit to the outer surface of the core body, the nozzle is moved at a constant speed in the rotational axis direction of the core body to apply the polyimide varnish. Went.
- a PTFE tube with an inner diameter of 2 mm and an outer diameter of 4 mm was used as the nozzle for the dispenser supply section. The nozzle is brought into contact with the position 20 mm from the right end of the core, and the supply of the polyimide varnish is started.When the nozzle reaches the position 20 mm from the left end of the core, the supply of the polyimide varnish is stopped, and the nozzle is Separated from the surface.
- the polyimide tube thus obtained had a thickness of 50 m, an outer diameter of 20.15 mm, and a length of 250 mm.
- a polyimide tube was produced in the same manner as in Example 1, except that boron nitride was changed to 15% by volume and carbon nanotubes were changed to 2% by volume in Example 1.
- a polyimide tube was prepared in the same manner as in Example 1, except that boron nitride was changed to 15% by volume and carbon nanotubes were changed to 3.5% by volume in Example 1.
- a polyimide tube was produced in the same manner as in Example 1, except that boron nitride was changed to 15% by volume and carbon nanotubes were changed to 5% by volume in Example 1.
- a polyimide tube was produced in the same manner as in Example 1, except that boron nitride was changed to 20% by volume and carbon nanotubes were changed to 2% by volume in Example 1.
- a polyimide tube was produced in the same manner as in Example 1, except that boron nitride was changed to 20% by volume and carbon nanotubes were changed to 3.5% by volume in Example 1.
- a polyimide tube was produced in the same manner as in Example 1, except that boron nitride was changed to 25% by volume and carbon nanotubes were changed to 0% by volume.
- a polyimide tube was produced in the same manner as in Example 1 except that in Example 1, boron nitride was changed to 20% by volume and carbon nanotubes were changed to 0% by volume. [0135] [Comparative Example 3]
- a polyimide tube was produced in the same manner as in Example 1, except that boron nitride was changed to 30% by volume and carbon nanotubes were changed to 0% by volume.
- Each of the polyimide varnishes of Examples 1 to 6 and Comparative Examples 1 to 3 has a viscosity of about 500 to 3000 boises measured with a B-type viscometer at a liquid temperature of 25 ° C and a rotational speed of the mouth of 6 rpm. Met. The results are shown in Table 1.
- the polyimide tube of the present invention has a high level of tensile strength and tensile modulus in addition to excellent thermal conductivity, and in particular, the tensile strength in the circumferential direction is high in the axial direction. It tends to be higher than the degree.
- the present invention by using boron nitride and a needle-like material such as carbon nanotube in combination, various characteristics are highly balanced and a polyimide tube having high mechanical strength in the circumferential direction is obtained. be able to.
- Example 2 a polyimide tube was produced in the same manner as in Example 2 except that the raw material polyimide varnish was used instead of “U-Varnish S-301” manufactured by Ube Industries. The resulting polyimide tube had the same thermal conductivity, circumferential tensile strength, axial tensile strength, and elastic modulus as those in Example 2.
- Example 2 a coating layer of polyimide varnish is formed on the surface of the core body by the dispenser method, and then heat curing (imidation) is not performed in that state in steps from 100 ° C to 200 ° C. The solvent was removed by heating to form a solidified polyimide layer.
- an adhesive layer was formed by a dating method using a primer containing 3% by weight of conductive carbon black.
- the resin that forms the adhesive layer is polyamideimide, It was a dispersion (made by DuPont Japan Limited, product number 855-003) made of a mixture of PTFE, PFA and the like.
- a fluororesin layer was formed on the adhesive layer by applying 0.7% by weight of conductive carbon black to a fluororesin dispersion (product number 855-405, manufactured by DuPont Japan Limited). . After sintering the polyimide layer and the fluororesin layer at 400 ° C., the core was pulled out to obtain a fixing belt. The thickness of each layer of the obtained fixing belt was 50 m for the polyimide resin layer, 5 m for the adhesive layer, and 10 m for the fluororesin layer.
- a fixing unit composed of the above fixing belt and pressure roller was incorporated into a fixing unit of a commercially available electrophotographic copying machine (15 sheets printed per minute). During continuous printing of 30,000 sheets, no abnormality such as torsional deformation, cracking at the end, or crushing was found on the fixing belt.
- a polyimide tube was produced in the same manner as in Example 1 except that this polyimide varnish was used. The results are shown in Table 2.
- This polyimide varnish contains "U varnish S-301” and “Pyre ML RC-5019” in a solids weight ratio of 10:90, and boron based on the total solid content. It contains 20% by volume of nitride and 5% by volume of carbon nanotubes.
- a polyimide tube was produced in the same manner as in Example 1 except that this polyimide varnish was used. The results are shown in Table 2.
- a carbon nanotube dispersion was prepared in the same manner as in Example 12, except that it was changed to 8.00-96.0].
- a polyimide varnish was prepared in the same manner as in Example 12 except that this carbon nanotube dispersion was used, and then a polyimide tube was prepared using the polyimide varnish. The results are shown in Table 2.
- the polyimide tube of the present invention has a tensile strength. In addition, since it has an excellent elastic modulus, it exhibits excellent properties as a base material for a fixing belt disposed in a fixing unit of an electrophotographic image forming apparatus. Therefore, the polyimide tube of the present invention can be used as a base material for a fixing belt.
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP20070829325 EP2072581B1 (en) | 2006-10-11 | 2007-10-05 | Polyimide tube, method for production thereof, method for production of polyimide varnish, and fixing belt |
AT07829325T ATE503802T1 (de) | 2006-10-11 | 2007-10-05 | Polyimidrohr, herstellungsverfahren dafür, verfahren zur herstellung eines polyimidlacks und fixierband |
JP2008538705A JP5491031B2 (ja) | 2006-10-11 | 2007-10-05 | ポリイミドチューブ、その製造方法、ポリイミドワニスの製造方法、及び定着ベルト |
DE200760013585 DE602007013585D1 (de) | 2006-10-11 | 2007-10-05 | Polyimidrohr, herstellungsverfahren dafür, verfahren zur herstellung eines polyimidlacks und fixierband |
US12/444,951 US8263199B2 (en) | 2006-10-11 | 2007-10-05 | Polyimide tube, method for production thereof, method for production of polyimide varnish, and fixing belt |
CN2007800379105A CN101522808B (zh) | 2006-10-11 | 2007-10-05 | 聚酰亚胺管、其制备方法、聚酰亚胺清漆的制备方法、以及定影带 |
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US (1) | US8263199B2 (ja) |
EP (1) | EP2072581B1 (ja) |
JP (1) | JP5491031B2 (ja) |
CN (1) | CN101522808B (ja) |
AT (1) | ATE503802T1 (ja) |
DE (1) | DE602007013585D1 (ja) |
TW (1) | TW200829652A (ja) |
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Cited By (14)
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JP2010085450A (ja) * | 2008-09-29 | 2010-04-15 | Ube Ind Ltd | シームレスベルトおよびシームレスベルトの製造方法 |
JP2010092008A (ja) * | 2008-09-10 | 2010-04-22 | Sumitomo Electric Ind Ltd | 定着用ベルト |
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US20100279045A1 (en) * | 2007-12-25 | 2010-11-04 | Sumitomo Electric Industries, Ltd. | Polyimide tube, process for producing the same and fixing belt |
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US9335689B2 (en) | 2011-11-29 | 2016-05-10 | Sumitomo Electric Industries, Ltd. | Polyimide tube, method for producing same, and fixing belt |
JP2013114068A (ja) * | 2011-11-29 | 2013-06-10 | Sumitomo Electric Ind Ltd | ポリイミドチューブ、その製造方法、及び定着ベルト |
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JP7407501B2 (ja) | 2017-03-17 | 2024-01-04 | 三菱ケミカル株式会社 | ポリイミド積層体 |
JP2019045677A (ja) * | 2017-09-01 | 2019-03-22 | 富士ゼロックス株式会社 | 無端ベルト、画像形成装置、無端ベルトユニット、及びポリイミド樹脂成形体 |
JP2019045727A (ja) * | 2017-09-04 | 2019-03-22 | 富士ゼロックス株式会社 | 赤外光定着装置用管状体、赤外光定着装置、及び画像形成装置 |
JP2019178223A (ja) * | 2018-03-30 | 2019-10-17 | 山形県 | カーボンナノチューブ複合樹脂成形体及びその製造方法 |
JP7053015B2 (ja) | 2018-03-30 | 2022-04-12 | 山形県 | カーボンナノチューブ複合樹脂成形体の製造方法 |
Also Published As
Publication number | Publication date |
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JPWO2008044643A1 (ja) | 2010-02-12 |
EP2072581A4 (en) | 2009-11-04 |
JP5491031B2 (ja) | 2014-05-14 |
US20100055365A1 (en) | 2010-03-04 |
TW200829652A (en) | 2008-07-16 |
EP2072581B1 (en) | 2011-03-30 |
DE602007013585D1 (de) | 2011-05-12 |
EP2072581A1 (en) | 2009-06-24 |
ATE503802T1 (de) | 2011-04-15 |
US8263199B2 (en) | 2012-09-11 |
CN101522808A (zh) | 2009-09-02 |
CN101522808B (zh) | 2011-09-28 |
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