JP2009092785A5 - - Google Patents

Description

Heat fixing belt and image fixing device

The present invention relates to an image fixing device of an image forming apparatus such as a copying machine or a laser beam printer . The present invention also relates to a fixing belt incorporated in the image fixing apparatus.

  Conventionally, in an image forming apparatus such as a copying machine or a laser beam printer, a heat roller method is often used as a method for thermally fixing an unfixed toner image formed on a sheet-like transfer material such as copy paper or OHP in an image forming unit. Has been. However, in recent years, the film fixing method shown in FIG. 8 has become mainstream from the viewpoint of energy saving.

In the image fixing apparatus 70 of the film fixing system, a seamless fixing belt is used in which a release layer such as a fluororesin is laminated on the outer surface of a heat resistant film such as polyimide. There will be described based one example thereof in FIG.

In the image forming apparatus 70 of the film fixing type, a belt guide 72 and a ceramic heater 73 are disposed inside the fixing belt 71, and the position between the pressure roll 74 and the fixing belt 71 pressed against the ceramic heater 73 is undecided. The copy paper 77 on which the contact toner image 78 is formed is sequentially fed, and the toner is heated and melted and thermally fixed on the copy paper. In such an image forming apparatus 70, the toner is substantially directly heated by the ceramic heater 73 via the extremely thin film-like fixing belt 71. Therefore, the contact surface N (nip surface) between the fixing belt 71 and the pressure roll 74. Reaches a predetermined fixing temperature instantly. Therefore, such an image forming apparatus 70 has a short waiting time from when the power is turned on until it reaches a fixable state, and also has low power consumption. For this reason, such an image forming apparatus 70 is widely used from home use to industrial use. In FIG. 8, reference numeral 75 denotes a thermistor, reference numeral 79 denotes a fixed toner image, and reference numeral 76 denotes a cored bar portion of the pressure roll 74.

Incidentally, in the image forming apparatus of the conventional film fixing method, as described above, is fixing belt heated through the ceramic heater, the toner image is fixed on its surface, the heat conductivity of the fixing belt It becomes an important point. However, when the fixing belt to try to improve the thinned thermal conductivity, Ri is Na difficult speed mechanical properties is reduced, the ceramic heater is disadvantageously damaged ease Kunar. In order to solve such a problem, in recent years, a method has been proposed in which a heating element is provided on the fixing belt itself and the fixing belt is directly heated by supplying power to the heating element to fix the toner image (for example, Patent References 1 to 5). This type of image forming apparatus has an even shorter waiting time from when the power is turned on until it reaches a fixable state, further reducing power consumption, and is excellent in terms of speeding up thermal fixing.
JP 2000-066539 A JP 2004-281123 A Japanese Patent Laid-Open No. 06-202513 JP-A-10-142972 JP 2000-058228 A

  However, many problems still remain in such a new type image forming apparatus, and such a new type image forming apparatus has not yet been put into practical use.

  For example, the belt heater system described in the above patent document has the following problems. In this application, in describing the fixing method of the electrophotographic image forming process, the fixing method shown in FIG. 8 is referred to as “film fixing method”, the fixing method described in the above patent document is referred to as “belt heater method”, and the method of this application is referred to as “fixing method”. This will be described as “heat-generating fixing belt system”.

  In the belt heater type fixing belt heater, a heat generating layer is formed by mixing a conductive material such as carbon powder or metal powder with a heat-resistant insulating base material such as polyimide or silicone rubber. For this reason, it is difficult to obtain a heating element having a uniform heating region. Patent Document 5 discloses a thin film resistance heating element formed mainly of carbon nanotubes and carbon microphone coils as a heating element material, and a toner heat fixing member using the thin film resistance heating element. Yes. However, when the heating element material is formed only of carbon nanotubes or carbon microcoils, increasing the mixing amount of carbon nanotubes or the like in order to reduce the volume resistivity, the mechanical characteristics of the heating element are drastically reduced. There is a problem and it is very difficult to produce a heating resistor having a low volume resistivity.

  Patent Documents 1 and 3 describe forming a fixing belt heater by a centrifugal molding method. However, such a molding method has a problem that it is difficult to mass-produce a fixing belt having a small inner diameter (10 to 20 mm), and cannot cope with a reduction in cost of a laser beam printer or the like.

Further, Patent Documents 1, 2 and 4, as a method for supplying power to the tubular belt heater having a heat generating layer, is described a direct feed roll or a bar-shaped electrode or a method that makes contact with a brush electrode to the heat generating layer Yes. However, the method in which the power feeding member is brought into direct contact with the heat generating layer has a serious problem in terms of durability and power feeding stability due to the severe wear of the resistance heating element layer.

The present invention has been made in view of the above problems, has a very uniform heat generation region, can stably supply power, has a very short standby time after power-on, can perform a quick start, and consumes power. An object of the present invention is to provide a highly safe image fixing apparatus capable of suppressing electric power and performing high-speed fixing.

The heat-generating fixing belt according to the first invention includes a resistance heating element layer , an insulating layer , a release layer, and an electrode. The electrodes are a pair of electrodes for supplying power to the resistance heating element layer . Moreover , this electrode is formed from the polyimide resin containing electroconductive particle and a metal supplementary agent.

The heat generating and fixing belt according to the second invention is the heat generating and fixing belt according to the first invention, and the conductive particles are formed of core particles and a metal shell . The metal shell covers the core particles .

Heating fixing belt according to the third aspect of the present invention is the heat generation fixing belt according to the second invention, the core particles, Ru least one particle der selected from the group consisting of carbon, of glass and ceramics. In addition, the metal shell, Ru Tei is formed from silver.

A heat-generating fixing belt according to a fourth invention is the heat-fixing belt according to any one of the first to third inventions , wherein the metal supplement is (a) a pyrimidine thiol compound represented by the following chemical formula (1): (B) At least one compound selected from a triazine dithiol compound represented by the following chemical formula (2) and (c) an imidazole compound having a mercapto group.

（式（１）中、Ｒ１、Ｒ２、Ｒ３及びＲ４のうち少なくとも１つはＳ−Ｈ又はＳ−Ｍであり、Ｍは金属又は置換若しくは無置換のアンモニウムである）

(In the formula (1), at least one of R1, R2, R3 and R4 is SH or SM, and M is a metal or substituted or unsubstituted ammonium)

（式（２）中、Ｒ５、Ｒ６及びＲ７のうち少なくとも１つはＳ−Ｈ又はＳ−Ｍであり、Ｍは金属又は置換若しくは無置換のアンモニウムである）

(In formula (2), at least one of R5, R6, and R7 is SH or SM, and M is a metal or substituted or unsubstituted ammonium.)

The exothermic fixing belt according to the fifth invention is the exothermic fixing belt according to the fourth invention, wherein the imidazole compound having a mercapto group is 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, From 2-mercapto-5-methylimidazole, 5-amino-2-mercaptobenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methoxybenzimidazole and 2-mercaptobenzimidazole-5-carboxylic acid At least one imidazole compound selected from the group consisting of:

A heat-generating fixing belt according to a sixth aspect of the present invention is the heat-generating fixing belt according to any one of the first to fifth aspects, wherein the electrode is formed from a polyimide precursor solution containing conductive particles and a metal scavenger. Yes. The metal scavenger is added in an amount of 0.01% by weight to 10% by weight with respect to the solid content of the polyimide precursor solution.

An exothermic fixing belt according to a seventh invention is the exothermic fixing belt according to the sixth invention , wherein the polyimide precursor solution comprises at least one aromatic diamine and at least one aromatic tetracarboxylic dianhydride. Polymerized in an organic polar solvent.

An exothermic fixing belt according to an eighth invention is the exothermic fixing belt according to any of the first to seventh inventions, wherein the resistance heating element layer is selected from the group consisting of carbon nanofibers, carbon nanotubes, and carbon microcoils. at least one electrically conductive material is, strands made of nickel particles (hereinafter "filamentary nickel particles" hereinafter) and the polyimide resin is dispersed with continuous shape three-dimensionally. The filamentary nickel particles preferably have the shape shown in FIG. This is because filamentary nickel particles are entangled with carbon nanofibers and the like, and the resistance of the resistance heating element layer is reduced.

A heat generating fixing belt according to a ninth aspect of the present invention is the heat generating fixing belt according to any one of the first to eighth aspects , wherein the release layer is at least selected from the group consisting of fluororesin, silicone rubber and fluororubber. It consists of one resin or rubber.

Heating belt according to the tenth invention is a heating fixing belt according the first invention in any of the ninth invention, Ru further includes an elastic layer. The elastic layer is made of at least one of silicone rubber and fluororubber. The release layer is provided in contact with the outer surface of the elastic layer.

Image fixing apparatus according to an eleventh invention comprises a heating fixing belt, and a power supply means. The heat generating fixing belt is a heat generating fixing belt according to any one of the first to tenth inventions. The power supply means is provided to supply power through the electrode of the heat generating fixing belt.

The heating fixing belt according to the present invention, the electrode is formed of a polyimide resin containing conductive particles and a metal scavenger. For this reason, in this heat-generating fixing belt, the electrode is excellent in heat resistance , mechanical properties, durability, adhesion to the base material, and the like, and high flexibility is maintained even if the electrode is a thick film of 50 μm to 125 μm . Further, even when electrodes are provided at both ends of the heat fixing belt, the heat fixing belt can follow high speed rotation.

In addition, when electrodes are provided at both ends of the heat-generating fixing belt, the electrodes reinforce both ends of the heat-fixing belt, and therefore, breakage from the end portions of the heat-generating fixing belt can be prevented.

In addition, when a polyimide precursor solution is used as a raw material for the polyimide resin during the production of the heat fixing belt, a smooth and tough electrode having a low electric resistance value can be formed. For this reason, the contact resistance of the electrode with respect to the power supply terminal can be reduced, and the wear resistance and durability of the electrode are improved, and stable power supply is realized .

In the production of the heat fixing belt, when a polyimide precursor solution is used as a raw material for a polyimide resin and an imidazole compound containing a mercapto group is used as a metal scavenger, the imidazole compound containing a mercapto group works as a metal scavenger. In addition, since it acts as an imidizing agent, the imidization efficiency of the polyimide precursor can be improved.

Further, in manufacturing of the heating fixing belt, when a metal shell particles as conductive fine particles, it is possible to greatly reduce the manufacturing cost.

When the insulating layer is a polyimide resin , the heat-generating fixing belt can be continuously used even in a high temperature range of 180 to 250 ° C. which is a fixing temperature range.

In addition, when carbon nanomaterials and filamentary nickel particles are added to the resistance heating element layer, the volume resistivity is highly accurate in a wide range by changing the mixing ratio of the carbon nanomaterial and filamentary nickel particles. An exothermic fixing belt can be designed.

Further, in the image fixing apparatus according to the present invention, it is possible to heat the fixing belt itself by without requiring such a conventional special ceramic heater or the like, to power directly to the resistance heating layer of the heating fixing belt . For this reason, this image fixing apparatus has high thermal efficiency, and there is no waiting time after the power is turned on, and a quick start is possible .

  Next, embodiments of the present invention will be described in detail.

Figure 1 is Ri schematic sectional view der fever fixing belt according to an embodiment of the present invention, FIG. 2 is an external perspective view of a heating fixing belt according to an embodiment of the present invention.

As shown in FIGS . 1 and 2 , the heat fixing belt 10 according to an embodiment of the present invention includes a first insulating layer 1, a resistance heating element layer 2, a second insulating layer 3, a release layer 4, and an electrode 5. It is composed of. The electrodes 5 are formed outside the both end portions of the heat generating and fixing belt 10.

3 is a schematic cross-sectional view of a heating fixing belt according to another embodiment of the present invention.

As shown in FIG. 3 , the heat fixing belt 20 according to another embodiment of the present invention includes a first insulating layer 21, a resistance heating element layer 22, a second insulating layer 23, a release layer 24, and an electrode 25. Is done . The electrodes 25 are formed inside both end portions of the heat fixing belt 20.

1 and 3, stable adhesion between the second insulating layer 3, 23 and the release layer 4, 24 by providing a primer layer between the second insulating layer 3, 23 and the release layer 4,24 It is preferable to make it. In heating fixing belt 10, 20 according to the embodiment of the present invention, all the matrix resin and the resin forming the insulating layer 1,3,21,23 of the resistance heating layer 2, 22 and the electrodes 5, 25 is a polyimide resin is there. By adopting such a configuration, it is possible to obtain the heat-resistant fixing belts 10 and 20 that are safe and highly durable and have excellent characteristics such as heat resistance, mechanical characteristics, and electrical characteristics of the polyimide resin.

Further, in FIGS. 1 and 3, electrodes 5, 25 may be formed directly as a conductive coating film on the both end portions of the heating fixing belt 10, 20. By providing such electrodes 5 and 25 , the power supply member can be brought into contact with the individual electrodes 5 and 25 from the inside or the outside of the heat fixing belts 10 and 20 , and the resistance heating element layers 2 and 22 can be stably supplied with power. The resistance heating element layers 2 and 22 can generate heat.

In heating fixing belt 10, 20 according to an embodiment of the present invention, the feed roll, a metal brush, or the power supply member such as a metal bar feeding in contact with the electrodes 5 and 25 to the electrode 5, 25 is carried out, The heat generating fixing belts 10 and 20 generate heat. Incidentally, FIG. 1, the first heat conductive insulating layer 1 in the heating fixing belt 10 shown in FIG. 2, regardless of the fixing condition, the insulating layer 1 only purpose of satisfying the sufficient mechanical properties of the heating fixing belt 10, The thickness of 3 can be determined. The outer surface of the thermally conductive filler insulating layer formed of a mixed polyimide resin is second efficiency heat of the resistance heating layer 2 that Ru is used as the insulating layer 3 may heating fixing belt 10, such as boron nitride preferably from the viewpoint of Ru was conducted to, preferably in terms of quick start or energy saving.

Heat generating fixing belts 10 and 20 according to an embodiment of the present invention preferably have an inner diameter of 10 mm to 100 mm for use in laser beam printers, and an inner diameter of 40 mm to 150 mm for high speed fixing applications such as copying machines. Are preferably used.

In the embodiment of the present invention, the electrodes 5 and 25 are formed by imide conversion of a polyimide precursor in a conductive paint containing conductive particles, a metal scavenger, and a polyimide precursor solution.

Conductive coating material according to an embodiment of the present invention includes conductive particles and metal capture agent and a polyimide precursor solution. Incidentally, the conductive coating material, after fabricating a pre polyimide precursor solution, that the polyimide precursor solution by mixing conductive fine particles, then adding a metal capture agent dissolved in a solvent to the polyimide precursor solution it is possible to produce Ri by the. Moreover, preferably obtained by reacting a diamine or its derivative and a tetracarboxylic dianhydride or its derivative in a polar solvent as a polyimide precursor solution.

In the embodiment of the present invention, the conductive fine particles are preferably metal fine particles having high conductivity such as platinum, gold, silver, nickel, palladium, and the like. (Hereinafter referred to as “core-shell type conductive fine particles”) is more preferable.

The conductive fine particles are core - when a shell-type conductive fine particles, it is possible to reduce the cost or weight of the conductive coating material. In the core-shell type conductive fine particles, the core particles are not particularly limited , but are preferably inorganic particles such as carbon, glass and ceramics from the viewpoints of cost and heat resistance. Further, as the inorganic fine particles, those having an arbitrary shape such as a scale shape, a needle shape, or a resin shape can be used. From the viewpoints of dispersibility, stability and weight reduction when mixed with the polyimide precursor solution, hollow and foamed fine particles are more preferable.

The metal shell which more than 80% of the surface area of the inorganic fine particles are coated with silver is preferred core particles. Further, the metal shell is more preferable that more than 90% of the surface area of the inorganic fine particles are core particles are coated, more preferably those which are covered at least 95%. This is because when the core particle coverage of the metal shell is less than 80%, the conductivity is lowered. The metal shell may be a single layer or two or more layers. Further, the remaining surface of the core particle may be coated with another conductive metal within a range not impairing the properties of the present invention. Examples of other conductive metals include noble metals such as platinum, gold, and palladium, and base metals such as molybdenum, nickel, cobalt, iron, copper, zinc, tin, antimony, tungsten, manganese, titanium, vanadium, and chromium. .

  Next, the average particle diameter of the core-shell type conductive fine particles is preferably 1 μm or more and 50 μm or less. When the average particle diameter of the core-shell type conductive fine particles is 1 μm or more, it is preferable that the core-shell type conductive fine particles hardly aggregate. Further, when the core-shell type conductive fine particles are 50 μm or less, the surface roughness of the obtained coating film or film is preferably not so large.

The surface of the inorganic fine particle as a method for coating a metal is not particularly limited, for example, electrolytic plating, electroless plating, vacuum deposition, a method such as sputtering.

Metal scavengers can be used in the embodiment of the present invention, pyrimidine thiol compound represented by chemical formula (1), a triazine thiol compound represented by the following chemical formula (2) and (c) a mercapto group It is an imidazole compound .

（式（１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４のうち少なくとも１つはＳ−Ｈ又はＳ−Ｍであり、Ｍは金属又は置換若しくは無置換のアンモニウムである）

(In formula (1), at least one of R1, R2, R3, and R4 is S — H or S — M , and M is a metal or substituted or unsubstituted ammonium . )

（式（２）中、Ｒ５、Ｒ６、Ｒ７のうち少なくとも１つはＳ−Ｈ又はＳ−Ｍであり、Ｍは金属又は置換若しくは無置換のアンモニウムである）

(In Formula (2), at least one of R5, R6, and R7 is S — H or S — M , and M is a metal or substituted or unsubstituted ammonium . )

The pyrimidine thiol compound is not particularly limited, has a pyrimidine skeleton, and has at least one SH (thiol) or SM (metal salt of thiol or substituted or unsubstituted ammonium salt). Any compound may be used. Further, metals include, but are not limited to, lithium, sodium, alkali metals such as potassium, magnesium, alkaline earth metals such as calcium, copper, etc. are exemplified. For example, 2-mercaptopyrimidine (2MP), 2-hydroxy-4-mercaptopyrimidine, 4-hydroxy-2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine, 2-thiobarbituric acid, 4-hydroxy-2-mercapto-6-methylpyrimidine, 4,6-dimethyl-2-pyrimidinethiol (DMPT), 4,5 -Diamino-2,6-dimercaptopyrimidine, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine and the like. These may be used alone or in combination.

The triazine thiol compound is not particularly limited , and has a triazine skeleton and a compound having at least one SH (thiol) or SM (metal salt of thiol or substituted or unsubstituted ammonium salt). If it is. Metal atom is not particularly limited, for example, lithium, sodium, alkali metals such as potassium, magnesium, alkaline earth metals such as calcium, copper, etc. are exemplified. For example, 2-amino-1,3,5-triazine-4,6-dithiol (ATDT), 2-allylamino-4,6-dimercapto-1,3,5-triazine, 2-diallylamino-4,6- Dimercapto-1,3,5-triazine, 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine (DBDMT), 2-phenylamino-4,6-dimercapto-1,3 , 5-triazine, trithiocyanuric acid (TTCA), trithiocyanuric acid monosodium salt, trithiocyanuric acid trisodium salt (TTCA-3Na), and the like. These may be used alone or in combination.

The imidazole compounds having a mercapto group include, for example, 2-mercaptobenzimidazole, 2-mercapto-imidazole, 2-mercapto-1-methylimidazole, 2-mercapto-5-methylimidazole, 5-amino-2 -Mercaptobenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methoxybenzimidazole, 2-mercaptobenzimidazole-5-carboxylic acid and the like. Imidazole compounds having these mercapto group may be used alone or may be used in combination.

Next, Oite, the polyimide precursor solution to an embodiment of the present invention preferably has a viscosity of less than 1,000 poise. If the viscosity is 1,000 poise or more, it is difficult to uniformly disperse the conductive fine particles, which is not preferable.

As a method for producing a polyimide precursor solution is not particularly limited, a method of reacting a diamine or its derivative and a tetracarboxylic dianhydride or its derivative in a polar solvent may be convenient.

Examples of the diamine that can be used Oite to the embodiment of the present invention, for example, para-phenylenediamine (PPD), meta-phenylene diamine (MPDA), 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4 '-Diaminobiphenyl, 3,3'-dimethyl-4,4'-biphenyl, 3,3'-dimethoxy-4,4'-biphenyl, 2,2-bis (trifluoromethyl) -4,4'-diamino Biphenyl, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane (MDA), 2,2-bis- (4-aminophenyl) propane, 3,3′-diaminodiphenylsulfone (33DDS), 4,4 '-Diaminodiphenylsulfone (44DDS), 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfide 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether (34 ODA), 4,4′-diaminodiphenyl ether (ODA), 1,5-diaminonaphthalene, 4,4′-diaminodiphenyldiethylsilane, 4, 4′-diaminodiphenylsilane, 4,4′-diaminodiphenylethylphosphine oxide, 1,3-bis (3-aminophenoxy) benzene (133APB), 1,3-bis (4-aminophenoxy) benzene (134APB), 1,4-bis (4-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] sulfone (BAPSM), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS), 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane (BA P), 2,2-bis (3-aminophenyl) 1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) 1,1,1,3,3 , 3-hexafluoropropane, aromatic diamines such as 9,9-bis (4-aminophenyl) fluorene, aliphatic diamines such as tetramethylene diamine and hexamethylene diamine, cyclohexane diamine, isophorone diamine, norbornane diamine, bis (4 Examples include alicyclic diamines such as -aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane. Moreover, it does not interfere at all even if these are mixed and made to react. Among them, preferable diamines are paraphenylenediamine (PPD), metaphenylenediamine (MPDA), 4,4′-diaminodiphenylmethane (MDA), 3,3′-diaminodiphenylsulfone (33DDS), and 4,4′-diaminodiphenylsulfone. (44DDS), 3,4'-diaminodiphenyl ether (34 ODA), 4,4'-diaminodiphenyl ether (ODA), 1,3-bis (3-aminophenoxy) benzene (133APB), 1,3-bis (4- Aminophenoxy) benzene (134APB), bis [4- (3-aminophenoxy) phenyl] sulfone (BAPSM), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS), 2,2-bis [4- (4-Aminophenoxy) phenyl] propane (BAP ) It is.

Examples of the tetracarboxylic dianhydride which can be used suitably Oite to the embodiment of the present invention, pyromellitic dianhydride (PMDA), 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3′4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2 ′, 3,3′-benzophenone tetra Carboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), bis (3,4 -Dicarboxyphenyl) Lufone dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), 4, 4 '-(hexafluoroisopropylidene) diphthalic anhydride, oxydiphthalic anhydride (ODPA), bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfoxide dianhydride , Thiodiphthalic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride and 9,9-bis [4- (3,4'- Aromatic tetracarboxylic dianhydrides such as dicarboxyphenoxy) phenyl] fluorene dianhydride, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3, 4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride. These may be reacted with alcohols such as methanol and ethanol to form ester compounds. Moreover, it does not interfere at all even if these are mixed and made to react. The Particularly preferable tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'- biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4 Examples include '-benzophenone tetracarboxylic dianhydride (BTDA), 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), and oxydiphthalic anhydride (ODPA).

The polar solvents which can be suitably used for Oite to the embodiment of the present invention, for example, N, N- dimethylformamide, N, N- dimethylacetamide, N, N- diethylacetamide, N- methyl-2-pyrrolidone 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphoric triamide, 1,2-dimethoxyethane, diglyme, triglyme and the like. Preferred solvents are N, N-dimethylacetamide (DMAC) and N-methyl-2-pyrrolidone (NMP). These solvents can be used alone or as a mixture or mixed with other solvents such as toluene, xylene, that is, aromatic hydrocarbons.

When the conductive paint according to the embodiment of the present invention is manufactured, a resin such as polyamideimide or polyethersulfone may be added within a range not impairing the properties of the present invention.

In addition, in the production of the conductive paint according to the embodiment of the present invention, the method for adding the conductive fine particles and the method for adding the metal scavenger are not particularly limited. In addition to the method of adding conductive fine particles to the polyimide precursor solution, the conductive fine particles may be added in advance when producing the polyimide precursor solution.

  The addition amount of the metal scavenger is preferably 0.01% by weight or more and 10% by weight or less based on the solid content of the polyimide precursor solution. If it is less than 0.01% by weight, the metal cannot be captured. Moreover, when there are more addition amounts of a metal supplement agent than 10 weight% with respect to the solid content of a polyimide precursor, electroconductive fine particles may aggregate abundantly and is unpreferable.

Further, in the production of the conductive paint according to the embodiment of the present invention, the filler, the pigment, the pigment dispersant, the solid lubricant, the anti-settling agent, the leveling agent, the surface conditioning are within the range not impairing the properties of the present invention. Agent, moisture absorbent, anti-gelling agent, antioxidant, UV absorber, light stabilizer, plasticizer, anti-coloring agent, anti-skinning agent, surfactant, antistatic agent, antifoaming agent, antibacterial agent Well-known additives such as a fungicide, a preservative, and a thickener may be added.

Conductive coating film according to the embodiment of the present invention is formed of a conductive coating material according to the embodiment of the present invention has been heat treated.

As a method for forming a conductive coating film of conductive paint, well known to those skilled in the art the general manner degassed conductive paint as necessary, after processing such as filtering, doctor conductive coating blading, screen printing, casting, and a method of molding by moving the die and the like to apply a predetermined thickness. Then, after heating and drying the conductive coating film, the conductive coating film is heated gradually or stepwise to 300 ° C~450 ° C, and imidization of the polyimide precursor in the conductive coating Make it progress. At this time, a chemical imidation method in which a dehydrating agent and an imidization catalyst of a stoichiometric amount or more are added to the conductive coating to advance imidization of the polyimide precursor may be used in combination. The conductive paint according to the embodiment of the present invention is excellent in adhesion to a base material, and can form a strongly integrated conductive paint thin film by completing imidization after coating on the base material. .

Although the film thickness of the conductive paint thin film which concerns on embodiment of this invention can be determined arbitrarily, it is about 1 micrometer-125 micrometers normally. When the conductive paint according to the embodiment of the present invention is used, a highly flexible conductive paint thin film can be obtained even if the film thickness is 50 μm to 125 μm. In the embodiment of the present invention, “highly flexible” is formed on a cylinder having a diameter of 5 mm on a flexible substrate such as a conductive film, Kapton (registered trademark) film, or Upilex (registered trademark) film. Even if the conductive paint thin film is wound, it means that there is no problem such as cracking or generation of cracks.

The volume resistivity of the conductive paint thin film according to the embodiment of the present invention is preferably 2 × 10 ⁻⁶ Ωcm or more and 1 × 10 ² Ωcm or less. When the conductive coating thin film has a volume resistivity in this range, when a conductive path is formed by screen printing or the like, or a conductive film that is formed as a coating film on the power supply terminal connection part of an electric circuit, so-called an energizing medium, so-called This is because excellent conductivity can be maintained even when used as an electric wire or an electric circuit.

Next , in the embodiment of the present invention, in the resistance heating element layers 2 and 22 of the heat fixing belts 10 and 20 , the carbon nanomaterial and the filamentous metal fine particles are substantially uniformly in the matrix resin made of polyimide resin. It exists in a distributed manner. The carbon nanomaterial is preferably at least one conductive substance selected from the group consisting of carbon nanofibers, carbon nanotubes, and carbon microcoils. Such a carbon nanomaterial has a fiber diameter of several nm to several hundred nm, a fiber length of several μm to several tens of μm, and a bulk density of 0.01 to 0.3 g / cm ³ . The specific surface area is 10 to 100 m ² / g. Among these, carbon nanofibers are particularly preferable conductive materials, and those having a fiber diameter of 20 to 200 nm and a fiber length of 0.1 to 10 μm are particularly preferable. It is because it is easy to disperse | distribute uniformly to a polyimide precursor solution.

Further, in the embodiment of the present invention, as described above, it is an essential condition that the resistance heating element layers 2 and 22 contain the filamentous metal fine particles together with the carbon nanomaterial. Image fixing devices such as laser beam printers require the ability to heat-fix unfixed toner images on A4 size paper at a rate of 30 to 40 sheets per minute, so that the fixing unit generates 500 to 1500 W of heat. This is because a uniform heat generation surface is required. Note that it is difficult to control such heat generation characteristics only with the carbon nanomaterial. This is because in order to obtain a low electrical resistance of several ohms by mixing only carbon nanomaterials, it is necessary to mix a large amount of carbon nanomaterials with the solid content of the polyimide precursor. This is because the mechanical characteristics of the resistance heating element layers 2 and 22 are remarkably deteriorated. Therefore, in order to achieve both the calorific value necessary for such characteristics and sufficient mechanical characteristics, it is essential to include filamentous metal fine particles having higher conductivity than the carbon nanomaterial together with the carbon nanomaterial. .

Examples of the filamentous metal fine particles include acicular crystal silver particles , aluminum particles, and nickel particles . In addition, nickel fine particles having a shape in which strands are three-dimensionally connected are more preferable . The nickel fine particles have an average particle diameter of 0.1 to 5.0 μm, a specific surface area of 1.0 to 100 m ² / g, and have a shape in which strands are three-dimensionally connected as shown in the photograph of FIG. has, by intertwined carbon nanomaterial and linear, it is possible to form a low resistance heat generating layer 2, 22, because it is possible to form the resistance heating element layer 2, 22 having a uniform volume resistivity It is.

In the embodiment of the present invention, it is preferable that the conductive material in the resistance heating element layers 2 and 22 is oriented in a certain direction. The carbon nanomaterial used in the embodiment of the present invention has a fiber diameter of 20 to 200 nm and a fiber length of 0.1 to 10 μm. When these carbon nanomaterials are mixed in a polyimide precursor solution and simply cast on a glass plate, the vertical and horizontal directions vary. And when a polyimide precursor is imide-converted in this state, there exists a problem that the dispersion | variation in the resistance value of the film formed becomes large. Moreover, it is necessary to mix more carbon nanomaterials compared with the case where the carbon nanomaterials are oriented, which inevitably leads to a decrease in mechanical properties of the resistance heating element layers 2 and 22 .

  Therefore, it is preferable that these carbon nanomaterials are oriented substantially in one direction, that is, the individual fibers of the carbon nanomaterial are bundled in the length direction. This is because the electrical resistance value can be lowered with a small amount of carbon nanomaterial mixed, and uniform heat generation characteristics can be obtained.

As shown in FIG. 7, a conductive composition 64 containing a polyimide precursor is applied to the outer surface of a cylindrical mold 61 , and a ring-shaped die 62 is run outside the cylindrical mold 61 to conduct the conductive composition. When the conductive composition coating 63 of the object 64 is formed on the outer surface of the cylindrical mold 61, the nickel fine particles having a shape in which the carbon nanomaterials and strands in the conductive composition coating 63 are three-dimensionally connected are obtained. The ring-shaped dies 62 are aligned in one direction toward the traveling direction and are oriented. Thereafter, the conductive composition coating 63 is dried and the imidization of the polyimide precursor is completed, whereby the most preferable resistance heating element layers 2 and 22 solidified in a state where the carbon nanomaterials and nickel fine particles are oriented are formed. Can be molded.

In this way, by aligning the carbon nanomaterial uniformly and mixing the carbon nanomaterial and the filamentous metal fine particles, it is possible to finely adjust the volume resistivity with a small amount of conductive material, and the resistance heating element layer without reducing the mechanical properties of the 2,22, it is possible to obtain a uniform volume resistivity, the heating fixing belt 10, 20 having excellent durability.

In the embodiments of the present invention, for the purpose of improving the conductive properties, etc., various shapes and particle sizes of graphite, carbon black, carbon nanotubes, carbon microcoils, metal particles such as nickel powder and silver powder, stainless steel powder, etc. metal alloy particles, tungsten carbide and tantalum carbide, intermetallic compounds such as tungsten boride, the conductive particles of the metal-coated powder or the like, such as silver-coated carbon, for the purpose of heat conduction improvement, alumina, boron nitride, aluminum nitride, silicon carbide, titanium oxide, a non-conductive particles such as silica, potassium titanate fibers for the purpose of improving mechanical properties such as needle-like titanium oxide, aluminum borate whisker, tetrapod-like zinc oxide whisker, sepiolite, glass fiber, etc. Viscous minerals such as fibrous particles, montmorillonite, talc, etc. No problem be added to the degree.

Moreover, in preferable embodiment of this invention, it is preferable that the abundance of the carbon nanomaterial and the filament-like metal fine particles in the resistance heating element layers 2 and 22 is 5 to 50 vol% with respect to the polyimide solid content. . More preferably, it is the range of 10-40 vol%. If the abundance is less than 5 vol%, the volume resistivity varies greatly and it is difficult to obtain a uniform heat generation region. On the other hand, if the abundance is 50 vol% or more, the mechanical properties and durability of the resistance heating element layers 2 and 22 are undesirably lowered. Further, the mixing ratio of the carbon nanomaterial and the filamentous metal fine particles can be arbitrarily selected according to the volume resistivity of the resistance heating element layers 2 and 22 and the desired amount of heat generation. Since the heat generation amount in the heat generating fixing belts 10 and 20 is in the range of about 500 to 1500 W, the heat generation amount is determined according to the specifications such as the inner diameter, thickness, and length (copy paper size A4 or A3) of the heat fixing belts 10 and 20. Can be adjusted.

In the embodiment of the present invention, the resin forming the matrix resin of the resistance heating element layers 2 and 22 and the insulating layers 1, 3, 21, and 23 includes at least one aromatic diamine and at least one aromatic tetracarboxylic acid. it is preferably made from an acid dianhydride and a polyimide resin obtained polyimide precursor obtained are polymerized in an organic polar solvent and imidization.

In the embodiment of the present invention, the aromatic diamine is paraphenylene diamine, and the aromatic tetracarboxylic dianhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. Particularly preferred. Polyimide resins obtained from these monomers are tough excellent mechanical properties, rather name is softened or melted it as resistive heating element layer 2,22 thermoplastic resin even when the temperature is elevated, excellent It is because it has heat resistance.

Such polyimide precursor solution, Ru obtained by reacting in the usual 90 ° C. or less and an aromatic tetracarboxylic dianhydride and an aromatic diamine in an organic polar solvent. In addition , the solid content concentration in the solvent can be appropriately adjusted depending on the mixing ratio of the conductive substance or the coating conditions. The preferable range is 10-30 mass%.

  In addition, when aromatic tetracarboxylic dianhydride and aromatic diamine are reacted in an organic polar solvent, the viscosity of the solution increases depending on the polymerization state. Can be used from. It is usually used at a viscosity of 1 to 5000 poise depending on manufacturing conditions and working conditions.

In addition, in order to apply | coat to the surface of a metal mold | die by the casting method, it is preferable that the viscosity of a conductive composition is the range of 10-1500 poise. More preferably, it is the range of 50-1000 poise. Also, when the insulating layer 3, 23 on the outside of the resistance heating element layer 2,22 in heating the fixing belt 10 and 20 according to the embodiment of the present invention is provided, boron nitride on the insulating layer 3, 23, titanate potassium, titanium oxide, aluminum nitride, alumina, silicon carbide, preferably thermally conductive material having an electrical insulation property such as silicon nitride Ru are mixed. This is because heat conductivity can be imparted and a uniform heat generating surface can be obtained. The viscosity of the insulating polyimide precursor solution for forming the insulating layers 3 and 23 is also preferably 50 to 1000 poise.

In the embodiment of the present invention, the release layers 4 and 24 of the heat generating fixing belts 10 and 20 may be made of at least one resin or rubber selected from the group consisting of fluororesin, silicone rubber, and fluororubber. preferable. In a heat-generating fixing belt used for a monochrome printer, a release layer made of a fluororesin is preferable. Also, among fluororesins, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) are used alone or in combination. More preferably, it is used.

The release layers 4 and 24 made of a fluororesin are preferably 5 to 30 μm thick, and more preferably 10 to 20 μm thick. In addition, a primer is preferably applied between the insulating layers 3 and 23 and the release layers 4 and 24 in order to stabilize the adhesion. Moreover, it is preferable that the thickness of the primer layer is 2-5 micrometers.

The thickness of the resistance heating element layers 2 and 22 of the heat generating fixing belts 10 and 20 necessary for obtaining a desired amount of electric heat generation is set based on factors such as the amount of conductive material mixed and the inner diameter of the heat generating belts 10 and 20. Can do. The insulating layers 1, 3, 21 , and 23 are layers that maintain the mechanical characteristics of the fixing belts 10 and 20 , and preferably have a thickness of 20 μm to 80 μm. The mechanical properties and heat conduction properties of the insulating layers 1, 3, 21 , and 23 are generally contradictory properties, but a heat conductive material such as boron nitride is mixed into the insulating layers 1, 3 , 21, and 23. If the thickness is optimized, both characteristics can be satisfied.

When a full-color image is thermally fixed, it is necessary to sufficiently fuse and mix the four colors of red, blue, yellow, and black toners, and to fix the intermediate colors and shades clearly. For this reason, it is preferable that the elastic layer is formed near the surface of the fixing belt. Specifically, in the heat-generating fixing belt 10 shown in FIG. 1, an elastic layer such as silicone rubber is directly provided on the outer surface of the second insulating layer 3 or the surface of the resistance heating element layer 2 , and further on the outer surface of the elastic layer. A release layer such as a fluororesin is preferably provided.

Further, this elastic layer is preferably soft and has a low rubber hardness. Specifically, silicone rubber having a JIS-A hardness of 3 to 50 degrees is suitable. The thickness of the elastic layer is preferably in the range of 100 to 500 μm. In the embodiment of the present invention , since the fixing belt itself generates heat by power feeding, the heat generation efficiency is high even in a structure in which an insulating layer, an elastic layer, and a release layer are laminated. No, you can get high image quality.

Furthermore, when the insulating layers 1 , 3 , 21 , 23 , the resistance heating element layers 2 , 22 and the release layers 4 , 24 are molded , the polyimide precursor in the resistance heating element layers 2, 22 , polyimide precursor in 3,21,23 were respectively in a semi-cured state, a fluororesin dispersion or the like is applied to its outer surface, after drying, the resistance heat generating layer 2, 22 and the insulating layer 1,3,21,23 preferably carried out completion of imidization of the polyimide precursor in and the baking of the fluororesin release layer 4 simultaneously. This is because it is and the child to enhance the adhesion of each layer. Moreover, since both the imidization temperature of the polyimide precursor and the firing temperature of the fluororesin are performed at a high temperature of 350 ° C. to 400 ° C., each heat treatment step can be shortened by treating these simultaneously. The thermal efficiency at the time of manufacture can be improved . In the case for forming a release layer 4, 24 on the outer surface of the insulating layer 3 and 23, in order to stabilize the adhesion strength, it is preferable to interpose a primer layer.

Note that the semi-cured state, the conductive composition or an insulating polyimide precursor solution, after being dried at a temperature of 80 to 120 ° C, refers to a state of being heated at a temperature of up to 200 to 250 ° C. In such a case, the polyimide precursor is in a state before imidization is completed. Moreover, processing time required until the state is 30 minutes to 2 hours.

Next, the image fixing apparatus heating fixing belt 10, 20 is incorporated according to an embodiment of the present invention based on the FIG. This image fixing device is in contact with a heat generating fixing belt 31 , a belt support 32 made of a heat-resistant insulating resin disposed inside the heat generating fixing belt 31, a pressure roll 36, and an electrode 34 of the heat generating fixing belt 31. And a roll feed terminal 33 for supplying power . Roll feeding terminal 33 for feeding power to the resistance heating element layer in contact with the electrodes 34 of the heating fixing belt 31. Incidentally, the shaft 37 of the pressure roll 36 is coupled to a drive motor (not shown). Reference numeral 38 denotes a power source, and reference numeral 39 denotes a lead wire. Further, the belt guide plates 35 play a role of a stopper when the heating fixing belt 31 meanders. As the material of the belt support 32 and the belt guide plates 35, polyphenylene sulfide, polyamideimide, polyether ether ketone, the heat-resistant resin such as liquid crystal polymer is used preferably. 4B is a cross-sectional view taken along the line II of FIG . 4A .

In the image fixing apparatus according to this embodiment, the pressure roll 36 with a driving source, the pressure roll 36 pressure contact the heating fixing belt 31 has the driven nip portion N between the heating fixing belt 31 and pressure roll 36 Then, the copy paper 40 on which the unfixed toner image 41 is formed is sequentially fed, and the unfixed toner image 41 is thermally fixed to the copy paper 40 .

The heat-generating fixing belt according to the present invention will be described more specifically with reference to the following examples. In addition, evaluation of the implementation product was performed on the conditions shown below using the measuring device shown below.

(1) Measurement of volume resistivity Using a digital multimeter Model 7562 (manufactured by Yokogawa Electric), the volume resistivity of the heat-generating fixing belt was measured with a four-wire probe.

(2) Measurement of temperature distribution The temperature distribution of the heat-generating fixing belt during heat generation was measured with a thermotracer TH1101 (manufactured by NEC Sanei).

(3) If there is no evaluation otherwise noted the conductive paint, 120 ° C30 minutes conductive paint drying furnace was cast on a glass plate, the coating after forming the coating film was dried 200 ° C30 minutes The film was released, and then the film was fixed to a metal frame and heated at 250 ° C. for 30 minutes, 300 ° C. for 30 minutes, and 350 ° C. for 30 minutes to imidize the film to produce a conductive film . Thereafter, the conductive film was evaluated as follows.

( 3-1 ) Volume resistivity
The volume resistivity of the conductive film was measured according to JIS K7194 using Mitsubishi Chemical's Loresta-GP MCP-T610.

( 3-2 ) Flexibility When a conductive film or a conductive coating film formed on a flexible substrate such as a Kapton film or an Upilex film is wrapped around a 5 mm diameter cylinder, the conductive film or the conductive property In the case where there was no problem such as cracking of the coating film or generation of cracks , it was rated as ○. Crack the conductive film or the conductive coating film, when or cracks, it was △. Moreover, it was set as x when a conductive film or a conductive coating film was not formed in the first place. In addition, the evaluation result of each Example is shown in Table 1, Table 2, and Table 3.

Polyimide precursor solution RC5063 (manufactured by IST Corporation, composition BPDA / PPD, solid content 17.5 wt%) and silver-coated carbon powder 8.77 g (AG / GCM-10, manufactured by Mitsubishi Materials, average) Particle diameter 10 μm) was added and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical) and 0.018 g of 2-mercaptopyrimidine (2MP) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.1% relative to the solid content of the polyimide precursor solution) were added to the solution. 25 wt%) was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5019 (commercially available from IST Corporation, composition PMDA / ODA, solid content 15.5 wt%) and stirred for 15 minutes. . Next , a solution in which 0.016 g of 2-mercaptopyrimidine (2MP) (0.25 wt% based on the solid content of the polyimide precursor solution) was dissolved in 10 g of N-methyl-2-pyrrolidone was added to the solution. A conductive paint was prepared by stirring for 8 hours . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

8.77 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5063 and stirred for 15 minutes. Next , 0.018 g of 4,6-dimethylpyrimidine-2-thiol (DMPT) (manufactured by Wako Pure Chemical Industries) in 10 g of N-methyl-2-pyrrolidone (0% based on the solid content of the polyimide precursor solution) was added to the solution. .25% by weight) solution prepared by dissolving the mixture, to prepare a conductive coating and stirred for 8 hours. Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Next , 0.016 g of 4,6-dimethylpyrimidine-2-thiol (DMPT) in 10 g of N-methyl-2-pyrrolidone (0.25 wt% based on the solid content of the polyimide precursor solution) was added to the solution. The dissolved solution was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

8.77 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5063 and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) (manufactured by Alfa Aesar) 0.018 g (of the polyimide precursor solution) were added to the solution. A solution in which 0.25% by weight of the solid content was dissolved was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.016 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

8.77 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5063 and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine (DBDMT) (manufactured by Wako Pure Chemical Industries) 0.018 g A solution in which (0.25% by weight with respect to the solid content of the polyimide precursor solution) was dissolved was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Subsequently , 0.016 g (DBDMT) of 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine (DBDMT) was added to 10 g of N-methyl-2-pyrrolidone. A solution in which 0.25% by weight of the solid content was dissolved was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

8.77 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5063 and stirred for 15 minutes. Next , 0.018 g of trithiocyanuric acid (TTCA) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.25 wt% based on the solid content of the polyimide precursor solution) was dissolved in 10 g of N-methyl-2-pyrrolidone. The solution was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Next , a solution in which 0.016 g of trithiocyanuric acid (TTCA) (0.25 wt% based on the solid content of the polyimide precursor solution) was dissolved in 10 g of N-methyl-2-pyrrolidone was added to the solution, and 8 The conductive paint was produced by stirring for a period of time . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

To 40 g of polyimide precursor solution RC5063, 13.15 g of the silver-coated carbon powder of Example 1 was added and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.018 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

11.65 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5019 and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.016 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

To 40 g of polyimide precursor solution RC5063, 5.64 g of silver-coated carbon powder of Example 1 was added and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.018 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

To 40 g of the polyimide precursor solution RC5019, 4.99 g of the silver-coated carbon powder of Example 1 was added and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.016 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 1.

8.77 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5063 and stirred for 15 minutes. Then , 1035 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.0035 g (based on the solid content of the polyimide precursor solution) 0.05 wt%) was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Then , 1031 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.0031 g (based on the solid content of the polyimide precursor solution) 0.05 wt%) was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Then , 10 g of N-methyl-2-pyrrolidone and 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine (DBDMT) 0.37 g of polyimide precursor solution were added to the solution. A solution in which 6.0% by weight) was dissolved was added and stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

To 500ml separable flask, N- methyl-2-pyrrolidone 326.96g and 4,4'-diaminodiphenyl ether (ODA; manufactured by Wako Pure Chemical Industries, Ltd.) was poured 27.99G, 4,4'-diaminodiphenyl ether with all The mixture was stirred until dissolved, and then 45.05 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA; manufactured by Daicel Chemical Industries) was added, and the contents were stirred for 24 hours to form a solid. A polyimide precursor solution having a content of 17% by weight was prepared. 8.5 g of the silver-coated carbon powder of Example 1 was added to 40 g of this polyimide precursor solution and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.017 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then, by heat-treating the conductive paint to obtain flexible high conductivity film. The evaluation results are shown in Table 2.

To 500ml separable flask, N, N- dimethylacetamide (Wako Pure Chemical) 31.03 g, ethanol (Wako Pure Chemical) 8.82 g, and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 30.84 g was added and stirred at 80 ° C. for 2 hours to completely dissolve. Next , 19.16 g of 4,4′-diaminodiphenyl ether was added to this solution, and the content was stirred at 80 ° C. for 2 hours to prepare a polyimide precursor solution having a solid content of 46.7% by weight. To 5 g of this polyimide precursor solution, 2.92 g of silver-coated carbon powder of Example 1 was added and stirred for 15 minutes. Next , 0.523 g of N, N-dimethylacetamide and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.0023 g (based on the solid content of the polyimide precursor solution) were added to the solution. In addition , a solution in which 0.1 wt% was dissolved was added and stirred for 8 hours to prepare a conductive paint . Then, this conductive paint is cast on an upilex film (manufactured by Ube Industries, thickness 50 μm), dried at 120 ° C. for 30 minutes, 200 ° C. for 30 minutes, then 250 ° C. 30 minutes, 300 ° C. 30 minutes, 350 C. for 30 minutes, and a conductive coating film was formed on the upilex film. The evaluation results are shown in Table 2.

To 40 g of polyimide precursor solution RC5063, 2.5 g of silver-coated hollow glass powder (AG / GB, manufactured by Mitsubishi Materials, average particle size 30 μm) was added and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.018 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

To 22 g of the polyimide precursor solution RC5019, 2.22 g of the silver-coated hollow glass powder of Example 20 was added and stirred for 15 minutes. Next , 10 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.016 g (based on the solid content of the polyimide precursor solution) were added to the solution. 0.25 wt%) was added , and the mixture was stirred for 8 hours to prepare a conductive paint . Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

To 5 g of polyimide precursor solution RC5019, 4.07 g of silver powder (AgC-A, manufactured by Fukuda Metal Foil Powder, average particle size: 3.1 μm) was added and stirred for 15 minutes. Next , 2.519 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.0019 g (in the solid content of the polyimide precursor solution) were added to the solution. A solution in which 0.25% by weight) was dissolved was added and stirred for 8 hours to prepare a conductive paint. Then, this conductive paint is cast on a Kapton film (made by DuPont, thickness 2 mil), dried at 120 ° C. 30 minutes, 200 ° C. 30 minutes, then 250 ° C. 30 minutes, 300 ° C. 30 minutes, 350 ° C. 30 minutes. Baked sequentially at 400 ° C. for 60 minutes to form a conductive coating film on the Kapton film. The evaluation results are shown in Table 2.

To 5 g of the polyimide precursor solution RC5063, 4.71 g of silver powder (AgC-A, manufactured by Fukuda Metal Foil Powder Co., Ltd., average particle size: 3.1 μm) was added and stirred for 15 minutes. Then , to the solution, 2.5 g of N-methyl-2-pyrrolidone and 2-amino-1,3,5-triazine-4,6-dithiol (ATDT) 0.0022 g (in the solid content of the polyimide precursor solution) A solution in which 0.25% by weight) was dissolved was added and stirred for 8 hours to prepare a conductive paint. Then, this conductive coating was formed and heat-treated in the same manner as in Example 22 to form a conductive coating film on the Kapton film. The evaluation results are shown in Table 2.

To 5 g of polyimide precursor solution RC5019, 4.07 g of silver powder (AgC-A, manufactured by Fukuda Metal Foil Co., Ltd., average particle size: 3.1 μm) was added and stirred for 15 minutes. Next , a solution in which 0.0019 g of 2-mercaptopyrimidine (2MP) (0.25 wt% based on the solid content of the polyimide precursor solution) was dissolved in 2.5 g of N-methyl-2-pyrrolidone in the solution. It was added, to prepare a conductive coating and stirred for 8 hours. Then, this conductive coating was formed and heat-treated in the same manner as in Example 22 to form a conductive coating film on the Kapton film. The evaluation results are shown in Table 2.

To 5 g of polyimide precursor solution RC5063, 4.71 g of silver powder (AgC-A, manufactured by Fukuda Metallic Foil, average particle size 3.1 μm) was added and stirred for 15 minutes. Next , a solution in which 0.0022 g of 2-mercaptopyrimidine (2MP) (0.25 wt% based on the solid content of the polyimide precursor solution) was dissolved in 2.5 g of N-methyl-2-pyrrolidone in the solution. It was added, to prepare a conductive coating and stirred for 8 hours. Then, this conductive coating was formed and heat-treated in the same manner as in Example 22 to form a conductive coating film on the Kapton film. The evaluation results are shown in Table 2.

8.77 g of silver-coated carbon powder of Example 1 was added to 40 g of polyimide precursor solution RC5063 and stirred for 15 minutes. Next , 0.114 g of trithiocyanuric acid trisodium salt (TTCA-3Na) 15% by weight aqueous solution (manufactured by Fluka) in 10 g of N-methyl-2-pyrrolidone was added to the polyimide precursor solution. a solution of a 0.25 wt%) added to solid content, to prepare a conductive coating and stirred for 8 hours. Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Next , 0.128 g of trithiocyanuric acid trisodium salt (TTCA-3Na) 0.128 g (trithiocyanuric acid trisodium salt is added to the solid content of the polyimide precursor solution in 10 g of N-methyl-2-pyrrolidone. a solution of a 0.25 wt%) for adding, to prepare a conductive coating and stirred for 8 hours. Then , the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 2.

To 40 g of the polyimide precursor solution RC5063, 8.77 g of the silver-coated carbon powder of Example 1 was added and stirred for 15 minutes. Then, to the solution, (manufactured by Wako Pure Chemical) 10 g of N- methyl-2-pyrrolidone to 2-mercaptobenzimidazole (2MBZ) 0.018g (0.25 wt% based on the solids content of the polyimide precursor solution) A solution in which was dissolved was added and stirred for 8 hours to prepare a conductive paint . Then, the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 3.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Then, the solution was dissolved in 10g of N- methyl-2-pyrrolidone 2-mercapto benzoimidazole MIG tetrazole (2NBZ) 0.016g (0.25 wt% based on the solids content of the polyimide precursor solution) It was added, to prepare a conductive coating and stirred for 8 hours. Then, the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 3.

To 77 g of polyimide precursor solution RC5063, 8,77 g of silver-coated carbon powder of Example 1 was added and stirred for 15 minutes. Then, to the solution, dissolved in 10g of N- methyl-2-pyrrolidone 2-mercapto-1-methylimidazole (2MMZ) 0.018g (0.25 wt% based on the solids content of the polyimide precursor solution) The solution was added and stirred for 8 hours to prepare a conductive paint . Then, the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 3.

7.77 g of the silver-coated carbon powder of Example 1 was added to 40 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Subsequently, to the solution, dissolved in 10g of N- methyl-2-pyrrolidone 2-mercapto -1 one-methylimidazole (2MMZ) 0.016g (0.25 wt% based on the solids content of the polyimide precursor solution) solution while handling, to prepare a conductive coating and stirred for 8 hours. Then, the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 3.

To 40 g of polyimide precursor solution RC5063, 2.5 g of the silver-coated hollow glass powder of Example 20 was added and stirred for 15 minutes. Then, to the solution, a solution obtained by dissolving the 10g of N- methyl-2-pyrrolidone 2-mercaptobenzimidazole (2MBZ) 0.018g (0.25 wt% based on the solids content of the polyimide precursor solution) In addition , the mixture was stirred for 8 hours to prepare a conductive paint . Then, the conductive paint was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 3.

To 22 g of the polyimide precursor solution RC5019, 2.22 g of the silver-coated hollow glass powder of Example 20 was added and stirred for 15 minutes. Then, to the solution, a solution obtained by dissolving the 10g of N- methyl-2-pyrrolidone 2-mercaptobenzimidazole (2MBZ) 0.018g (0.25 wt% based on the solids content of the polyimide precursor solution) In addition , the mixture was stirred for 8 hours to prepare a conductive paint . Then, the conductive coating was heat-treated to obtain a highly flexible conductive film. The evaluation results are shown in Table 3.

In a 500 ml separable flask, 31.03 g of N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries), 8.82 g of ethanol (manufactured by Wako Pure Chemical Industries) and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 30 .84 g was added and stirred at 80 ° C. for 2 hours to completely dissolve. Next, 19.16 g of 4,4′-diaminodiphenyl ether was added to this tetracarboxylic acid ester compound solution and stirred at 80 ° C. for 2 hours to prepare a polyimide precursor solution having a solid content of 46.7% by weight. did. Then, 2.92 g of silver-coated carbon powder of Example 1 was added to 5 g of this polyimide precursor solution and stirred for 15 minutes. The solution was then to the solution, obtained by dissolving 0.5g of N, N-dimethylacetamide 2-mercaptobenzimidazole (2MBZ) 0.0023g (0.1 wt% based on the solids content of the polyimide precursor solution) It was added, to prepare a conductive coating and stirred for 8 hours. Then, this conductive paint is cast on a Upilex film (manufactured by Ube Industries, thickness 50 μ), dried at 120 ° C. for 30 minutes and at 200 ° C. for 30 minutes, and then at 250 ° C. for 30 minutes, 300 ° C. for 30 minutes, 350 C. C. for 30 minutes, and a conductive coating film was formed on the Upilex (registered trademark) film. The evaluation results are shown in Table 3.

4.07 g of the silver powder of Example 22 was added to 5 g of the polyimide precursor solution RC5019 and stirred for 15 minutes. Then, the solution was dissolved in 2.5g of N- methyl-2-pyrrolidone 2-mercaptobenzimidazole (2MBZ) 0.0019g (0.25 wt% based on the solids content of the polyimide precursor solution) It was added, to prepare a conductive coating to 8 hours撹絆. Then, this conductive paint is cast on a kabuton (registered trademark) film (manufactured by DuPont, thickness 50 μm), dried at 120 ° C. for 30 minutes and at 200 ° C. for 30 minutes, and then at 250 ° C. for 30 minutes, 300 ° C. for 30 minutes. Sintered at 350 ° C. for 30 minutes and 400 ° C. for 60 minutes to form a conductive coating film on the kabuton film. The evaluation results are shown in Table 3.

In this embodiment, the heat generating fixing belt 10 having the structure shown in FIG. 1 was manufactured as shown below, and then a fixing test of the heat generating fixing belt was performed.

<Production of heat generating belt>
(1) Production of Conductive Composition for Resistance Heating Element Layer A polyimide precursor solution (polyimide varnish “Pyre-ML RC5063”, manufactured by IS Corporation) was prepared. This polyimide precursor solution is obtained by polymerizing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride “BPDA” and paraphenylenediamine “PPD” in N-methyl-2-pyrrolidone (NMP). The solid content concentration was 17.5 wt%. And in this polyimide precursor solution , 20 vol% carbon nanofibers (VGCF-H, manufactured by Showa Denko) and 13 vol% filamentary nickel fine particles (TYPE210, manufactured by Inco) with respect to the solid content of the polyimide precursor solution , Was added and stirred for 1 hour, and then the mixture was filtered through No. 150 SUS mesh to prepare a conductive composition for a resistance heating element layer having a viscosity (23 degrees C, measured by B type viscometer) 800 poise. did. The true density of the carbon nanofiber (VGCF-H) is 2.0 g / cm ³ , and the true density of the filamentary nickel fine particles (TYPE 210) is 8.9 g / cm ³ .

(2) was prepared polyimide varnish "Pyre-ML RC5063" as polyimide precursor solution for forming a first insulating layer for manufacturing a polyimide precursor solution for the first insulating layer (I.S.T Co.). Incidentally, the solid content concentration of the polyimide precursor solution is 17.5 wt%, a viscosity (by 23 ° C, B type viscometer) was 850 poise. Hereinafter, this polyimide precursor solution is referred to as “a polyimide precursor solution for the first insulating layer”.

(3) was prepared polyimide varnish "Pyre-ML RC5063" as polyimide precursor solution for forming a second insulating layer produced in the second insulating layer-forming polyimide precursor solution (I.S.T Co.). Then, boron nitride powder (Mitsui Chemical "MBN-010T") is mixed with the polyimide precursor solution at 20 wt% with respect to the solid content concentration of the polyimide precursor solution to prepare a polyimide precursor solution for the second insulating layer. did. Note that the second insulating layer polyimide precursor solution has a viscosity of B-type viscometer at 23 ° C was 880 poise.

(4) Molding of the first insulating layer An aluminum cylindrical mold having an outer diameter of 30 mm and a length of 500 mm, which is coated with a silicon oxide coating agent by a dipping method and baked. Was covered with a silicon oxide film. The average surface roughness of this cylindrical mold was Rz 0.2 μm. Then, by immersion casting process shown in FIG. 7, the first insulating layer polyimide cylindrical aluminum mold was immersed from the lower end to 400mm part cylindrical aluminum mold the polyimide precursor solution for the first insulating layer after the precursor solution was applied, the outside of the aluminum cylindrical mold so as to run by inserting a ring-shaped die from the top of an aluminum cylindrical mold side, the thickness after imidization becomes 70 [mu] m 1 An insulating layer cast film was formed.

Thereafter, an aluminum cylindrical mold in which the first insulating layer cast film was formed, dried placed in 60 minutes in an oven at 120 ° C, allowed to warm for 30 minutes to a temperature of 200 ° C, the same temperature in taken out of the oven after held for 15 minutes, cooled to room temperature (25 ° C), to obtain a semi-cured first insulating layer belt.

(5) Molding of the resistance heating element layer is then immersed cylindrical aluminum mold which semi-cured first insulating layer belt is molded to the resistance heating layer for the conductive composition, immersing the casting method of FIG. 7 Was cast with a ring die so that the thickness after imide conversion was 35 μm. Next, as in the heat treatment of the first insulating layer, this aluminum cylindrical mold was placed in an oven at 120 ° C. and dried for 60 minutes, and then heated to 200 ° C. over 30 minutes. Holding for 15 minutes, a semi-cured conductive layer laminated belt in which a semi-cured conductive layer was laminated on the outer surface of the first insulating layer was obtained.

(6) Molding of second insulating layer Next, the both ends of the semi-cured conductive layer laminated belt are masked, and the aluminum cylindrical mold is immersed in the polyimide precursor solution for the second insulating layer, as shown in FIG. A semi-cured second insulating layer cast film was formed by an immersion casting method so that the thickness after imidization was 15 μm. Next, as in the heat treatment of the resistance heating element layer, this aluminum cylindrical mold was placed in an oven at 120 ° C. and dried for 60 minutes, and then heated to a temperature of 200 ° C. over 30 minutes. and held for 15 minutes to obtain a semi-cured second insulating layer laminated belt second insulating layer in a semi-cured state on the outer surface of the semi-cured state conductive layer are laminated.

(7) Molding of conductive paint thin film electrode
The conductive paint prepared in Example 1 was formed to a thickness of 30 μm on the resistance heating layer body exposed portions at both ends of the semi-cured second insulating layer laminated belt , and dried at 120 ° C. for 30 minutes and 200 ° C. for 30 minutes in a drying oven. Subsequently, it was heated at 250 ° C. for 30 minutes to obtain a semi-cured conductive paint thin film electrode forming belt.

(8) Molding of the fluororesin primer layer Masking the electrode exposed part of the semi-cured conductive paint thin film electrode molding belt, immersing it in the fluororesin primer solution and pulling it up at a predetermined speed results in a thickness of about 4 μm. After coating, the substrate was dried at a temperature of 150 ° C. for 20 minutes and then cooled to room temperature again to obtain a primer molding belt.

(9) Molding of Release Layer Next, PTFE dispersion (manufactured by DuPont: “Teflon (registered trademark)” 855-510) as a release layer material was prepared . After masking only the lower primer forming belt, it was immersed in PTFE dispersion a cylindrical aluminum mold primer forming belt is molded to a position where the primer layer is applied. Thereafter, the aluminum-made cylindrical mold pulled up at a predetermined speed, the PTFE dispersion was coated to a thickness of 15 [mu] m, to obtain a fluororesin coating belt. Thereafter, the masking is removed from the fluororesin-coated belt, and the fluororesin-coated belt is dried at 200 ° C. for 10 minutes, then heated to 400 ° C. over 30 minutes, and heated at the same temperature for 20 minutes to sinter the PTFE resin. When the resistance heating element layer in a semi-cured state, the first insulating layer, and imidization of the second insulating layer and the conductive polyimide precursor coating film electrode in complete simultaneously, to obtain a heating fixing belt.

This heat generating fixing belt is shown in FIG . The heat generating fixing belt has an inner diameter of 30 mm, a thickness of the first insulating layer of about 70 μm, a thickness of the resistance heating element layer of about 35 μm, a thickness of the second insulating layer of about 15 μm, and the outermost layer. The release layer had a thickness of about 15 μm and a total thickness of 140 μm.

<Evaluation of heat generating belt>
( 1 ) Measurement of volume resistivity
The volume resistivity of a heat-generating fixing belt having a total length of 285 mm in which the length of the electrodes at both ends was 25 mm was measured using a digital multimeter Model 7562. The volume resistivity in the length direction of the heat generating fixing belt was 36 × 10 ⁻⁴ Ωcm.

( 2 ) Measurement of exothermic temperature distribution
A power supply terminal was attached to the conductive paint thin film electrode , and a heat generation test was performed by the method shown in FIG. The power supply terminals were clipped to the conductive paint thin film electrodes on both ends of the heat generating fixing belt. As shown in FIG. 5, a variable voltage regulator 52 was connected to the power source 51, and power was supplied from the power source 51 to the conductive paint thin film electrode 5 while setting the voltage by the variable voltage regulator 52 . Specifically, first, the variable voltage regulator is set so that the surface of the heat-generating fixing belt (the surface of the release layer) becomes 220 ° C. while observing the surface temperature of the heat-generating fixing belt by first setting the thermotracer to the standard mode. After the output voltage of 52 was adjusted and the surface reached 220 ° C., power supply was continued in this state, and the temperature distribution at that time was measured. The output voltage at this time was 45V. Thereafter, the power supply was stopped, and the heat fixing belt was naturally cooled until it reached room temperature.

Next, the thermotracer was switched to the time trace mode, and the temperature rise change of the heat generating fixing belt for 10 seconds from the start of energization was observed and recorded. When the heating element surface temperature in the length direction 10 seconds after the start of energization was read from the recorded data, the maximum temperature was 210.8 degrees C, the minimum temperature was 208 degrees C, and the temperature distribution was within 3 degrees C. . That is, a uniform heat generation increase characteristic could be confirmed. In particular, there was almost no temperature difference between the power supply terminals of the heat generating fixing belt, and very uniform heat generation characteristics were obtained.

( 3 ) Evaluation of incorporation into an image fixing apparatus A heat fixing belt was incorporated into the image fixing apparatus shown in FIG. 4 and a toner image fixing test was conducted. The fixing temperature was subjected to setting to sheet passing test at 200 ° C by a thermistor, sharp fixed image can fix immediately the power-on was obtained. In addition, stable power feeding was possible without any wear or poor contact with the electrodes .

In this embodiment, a heat-generating fixing belt formed with a silicone elastic layer will be described.

(1) Production of heat-generating belt intermediate body A heat-generating fixing belt intermediate body that has been imidized by heating the semi-cured conductive paint thin film electrode forming belt produced in item (7) of Example 36 to 400 ° C. Obtained. However, the conductive coating material used was prepared in Example 23.

(2) Silicone rubber elastic layer molding
Primer was applied to the surface of the second insulating layer the resistance heating layer exposed portion of the heating fixing belt intermediate masking. Specifically, as a primer, a mixture of A and B2 liquids of trade name “XP-81-405” manufactured by GE Toshiba Silicone Co., Ltd. in a ratio of 1: 1 in advance is used for the second insulating layer of the heat fixing belt intermediate. After uniformly applying to the outer surface with a brush, the exothermic fixing belt intermediate was dried at room temperature for 20 minutes, then placed in an oven at 150 ° C. and dried for 20 minutes. Thereafter, liquid silicone rubber (trade name “XE15-B7354” A and B2 liquids manufactured by GE Toshiba Silicones Co., Ltd., in a ratio of 1: 1 in advance is applied to the outside of the surface on which the primer of the heat generating fixing belt intermediate is applied using a ring die. The mixed liquid rubber) was applied in a thickness of 300 μm. Then, remove the masking from the heating fixing belt intermediate the primary vulcanization at a temperature of 150 ° C 10 minutes after Tsu line, and heated 4 hours at a temperature of the heating fixing belt intermediate further 200 degrees C, the liquid Secondary vulcanization of silicone rubber was performed. As a result, an elastic layer laminated belt in which silicone rubber was molded to a thickness of 300 μm on the outer surface of the heat generating belt intermediate was produced. The test piece produced under the same vulcanization conditions had a rubber hardness of 30 degrees.

(3) Release layer molding of outer surface of elastic layer laminated belt The silicone rubber surface of the elastic layer laminated belt was lightly roughened with # 500 sandpaper, and the surface was washed with alcohol. Next, a liquid primer (PR-990CL manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was applied to the silicone rubber surface and dried at room temperature for 10 minutes. Next, the elastic layer laminated belt was immersed in a PFA dispersion (trade name PFA920HP plus “ENA-162-8” manufactured by DuPont) adjusted to a viscosity of 200 centipoise, and then the elastic layer laminated belt was moved to a predetermined speed. The elastic layer laminated belt was coated with PFA dispersion so that the final thickness of the release layer was 15 μm . And that after the elastic layer laminated belt was dried for 30 minutes at room temperature, placed in an oven at 330 ° C, to prepare a heating fixing belt elastic layer of interest are stacked by baking 15 minutes.

This heat-generating fixing belt had an inner diameter of 30 mm and a total thickness of 440 μm. When this heat fixing belt was incorporated in an image fixing apparatus and a full color image was thermally fixed, a good image was obtained. That is, it was confirmed that this heat generating fixing belt can be suitably used as a fixing belt for full-color images.

In the present embodiment, a heat-generating fixing belt shown in FIG. 2 in which a conductive paint thin film electrode is formed inside the heat-generating fixing belt will be described.

(1) Molding of first insulating layer A semi-cured first insulating layer belt was obtained under the same conditions as in item (4) of Example 36.

(2) resistance shaping of the heating element layer Next, the semi-cured first first insulating layer Cut Example 36 (5) semi-cured conductive under the same conditions as the section 30mm portion from the lower end of the mold insulating layer belt A layer laminated belt was produced. However, the resistance heating element layer has been formed each 30mm long at both ends of the semi-cured first insulating layer belt.

(3) Following the molding of the second insulating layer, examples 36 to all the surface of the semi-cured conductive layer laminated belt (6) term second insulating layer polyimide precursor solution under the same conditions as was applied semi-cured first A two-insulating layer laminated belt was obtained.

(4) Molding of fluororesin primer layer and molding of release layer Fluorine is applied to the entire surface of the semi-cured second insulating layer laminated belt of item (3) before under the same conditions as those in Examples 36 (8) and (9). perform molding of the molding and the release layer of the resin primer, after the fluororesin coating belt and dried at 200 ° C 10 minutes, the temperature was raised in 30 minutes up to 400 ° C, the PTFE resin by heating at the same temperature for 20 minutes Completed firing and imidization of semi-cured resistance heating element layer and polyimide precursor in insulating layer at the same time, and after cooling , the molded product was demolded from an aluminum cylindrical mold and a release layer was laminated I got a belt.

(5) Molding of conductive paint thin film electrode The conductive paint prepared in Example 2 was applied to the portions where the resistance heating element layers were exposed at both ends inside the release layer laminated belt prepared in the previous section (4). It was coated and molded to a thickness of 25 μm, and the conductive paint was dried in a drying furnace at 120 ° C. for 30 minutes and 200 ° C. for 30 minutes . Next , the release layer laminated belt is inserted into a mold and heated successively at 250 ° C. for 30 minutes, 300 ° C. for 30 minutes and 350 ° C. for 30 minutes to convert the polyimide precursor in the conductive coating into an imide, thereby obtaining a heat generating fixing belt. It was.

As described above, in the heat-fixing belt in which the conductive paint thin-film electrodes are provided at both inner ends of the heat- fixing belt , a power supply roll is arranged on the inner side and power is supplied from the conductive paint thin-film electrode to the resistance heating element layer. The amount of generated heat was obtained, and a clear fixed image was obtained. The heating fixing belt thus provided with an electrode on the inner side, which is electrically safe for feeding rolls can be stored therein. The step such as masking in the manufacturing process of the heating fixing belt can provide a heating fixing belt at a low cost because it is unnecessary.

Heating fixing belt according to the embodiment of the present invention as described above, holds the conductive and flexible excellent as evidenced by Tables 1 to 3, a flexible, heat resistance and mechanical possessed by polyimide A conductive paint thin film electrode having characteristics, and the resistance heating element layer of the heat fixing belt according to the embodiment of the present invention includes a conductive material such as carbon nanofiber, carbon nanotube, and carbon microcoil, and a strand. since the nickel particles having a three-dimensionally continuous shape is formed of a polyimide resin is dispersed, electrical, to provide a mechanically and chemically highly stable and durable heating fixing belt and the image fixing device it can.

It is sectional drawing of the heat-generating fixing belt which concerns on one Embodiment of this invention. It is the external appearance schematic of FIG . It is sectional drawing of the heat-generating fixing belt which concerns on another embodiment of this invention. 1 is a schematic cross-sectional view of an image fixing device according to an embodiment of the present invention. It is a figure for demonstrating the heat_generation | fever temperature distribution measuring method of the heat fixing belt which concerns on embodiment of this invention. It is a microscope picture of the nickel fine particle in which the strand connected in three dimensions. It is the schematic for demonstrating the immersion casting method. 1 is a schematic view of a film fixing device .

1, 21 First insulation layer 2 , 22 Resistance heating element layer 3 , 23 Second insulation layer 4 , 24 Release layer 5 , 25 Electrode 10 , 20 , 31 Heat generation fixing belt 32 Belt support 33 Roll feed terminal 35 Belt guide Plate 36 Pressure roll 38 , 51 Power supply 40 Copy paper 41 Unfixed toner image N Nip part

Claims (11)

A resistance heating element layer ;
An insulating layer ;
A release layer ,
An electrode formed of a polyimide resin containing a pair of electrodes conductive particles and metal scavenger to power the resistive heating element layer
A heat-generating fixing belt comprising:   The heat-generating fixing belt according to claim 1, wherein the conductive particles are formed of core particles and a metal shell that covers the core particles. The core particles are at least one of the particles of carbon, selected from the group consisting of glass and ceramics,
The heat generating fixing belt according to claim 2, wherein the metal shell is made of silver. The metal scavenger is selected from (a) a pyrimidine thiol compound represented by the following chemical formula (1), (b) a triazine dithiol compound represented by the following chemical formula (2) and (c) an imidazole compound having a mercapto group. The heat-fixing belt according to claim 1 , wherein the heat-fixing belt is at least one compound.

(In the formula (1), at least one of R1, R2, R3 and R4 is SH or SM, and M is a metal or substituted or unsubstituted ammonium)

(In formula (2), at least one of R5, R6, and R7 is SH or SM, and M is a metal or substituted or unsubstituted ammonium.) The imidazole compound having a mercapto group includes 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 2-mercapto-5-methylimidazole, 5-amino-2-mercaptobenzimidazole, 2- The heat fixing according to claim 4, which is at least one imidazole compound selected from the group consisting of mercapto-5-nitrobenzimidazole, 2-mercapto-5-methoxybenzimidazole and 2-mercaptobenzimidazole-5-carboxylic acid. belt. The electrode is formed from a polyimide precursor solution containing the conductive particles and the metal scavenger,
The metal scavengers, heating fixing belt according to any of claims 1 through 3 is added 0.01% by weight to 10% by weight relative to the solid content of the polyimide precursor solution. The polyimide precursor solution, heating fixing according to <br/> claim 6 obtained by polymerizing the at least one aromatic diamine and at least one aromatic tetracarboxylic acid dianhydride in an organic polar solvent belt. In the resistance heating element layer, at least one conductive material selected from the group consisting of carbon nanofibers, carbon nanotubes, and carbon microcoils, and nickel particles having a shape in which strands are three-dimensionally connected are dispersed. The heat-generating fixing belt according to any one of claims 1 to 7, comprising a polyimide resin. The heat-generating fixing belt according to any one of claims 1 to 8, wherein the release layer is made of at least one resin or rubber selected from the group consisting of fluororesin, silicone rubber, and fluororubber. An elastic layer made of at least one of silicone rubber and fluororubber;
The release layer, heating the fixing belt according to claim 1 which is provided in contact with the outer surface of the elastic layer 9. The heat-generating fixing belt according to any one of claims 1 to 10,
An image fixing device comprising: a power supply means for supplying power to the electrode of the heat generating fixing belt.