JP3069041B2 - Fixing film, method of manufacturing the same, fixing device, and image forming apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing film for fixing an image in an image forming apparatus such as a copying machine, a facsimile, a printer, and the like, a method of manufacturing the same, a fixing device, and an image forming apparatus.

[0002]

2. Description of the Related Art Conventionally, a heat roller fixing method has been widely used as a means for fixing a developed image on a recording paper by a developer (developer). However, this heat roller fixing method has a problem that a warm-up time until the heat roller reaches a predetermined fixing temperature is long.

Accordingly, the applicant of the present invention has disclosed Japanese Patent Application Laid-Open No. 63-313.
No. 182, Japanese Patent Application Laid-Open No. 2-157878, etc. propose a fixing method using a heat-resistant film (hereinafter referred to as a "SURF method"). In the SURF method, a resistance heating layer is provided on a substrate made of a material having a high thermal conductivity such as alumina, and heat is applied to an unfixed image via a heat-resistant fixing film while being pressed by a pressure roller, thereby forming a developer. (Toner) is fused and fixed on the recording material.

[0004] The heat-resistant fixing film to be used is generally a two-layer film, and in order to reduce the heat capacity,
The total thickness of the film is set to 500 μm or less, preferably 300 μm or less. For example, a laminate of a polyimide layer having a thickness of 30 μm as a base layer and a fluororesin PTFE (polytetrafluoroethylene) layer having a thickness of 10 μm as a release layer is used. Such SURF system is
Unlike the heat roller method, only the pressure contact portion between the heating element and the pressure roller is heated instead of the entire system, so that there is an advantage that the time required to reach the fixing temperature is short and no extra heat is required.

[0005] Such a fixing film is manufactured, for example, as follows. That is, a polyimide resin precursor (polyamic acid solution) is applied to the inner peripheral surface of a cylinder (die), and a traveling body such as a bullet or a sphere is caused to travel in the cylinder. Next, the polyamic acid is imidized, and the polyimide resin film is taken out of the cylinder. Subsequently, a fluororesin solution in which a conductive substance is dispersed is spray-coated on the outer surface of the film to form a conductive fluororesin layer. A fixing film is manufactured as described above (Japanese Patent Laid-Open No. 3-130149).

However, the fixing film having a conductive fluororesin layer on the outer surface manufactured as described above is used as a fixing film used in a field where a higher toner fixing property is required, for example, a color copier. In this case, the surface layer of the film is hard to follow the step caused by the fiber on the surface of the recording material, for example, the paper, so that the film cannot follow the step, and a fixing difference occurs due to the unevenness of the surface of the paper, thereby causing minute gloss unevenness.

In view of this, Japanese Patent Application Laid-Open No. H5-154963 proposes a belt-shaped fixing film in which a layer made of silicone rubber or fluorine rubber is formed on the outermost layer, that is, the surface in contact with the toner.

[0008]

SUMMARY OF THE INVENTION However, SUR
When the fixing speed is 60 mm / sec or more, the heat capacity of the film is large in the F type apparatus, so that the supply of heat cannot catch up, an offset phenomenon occurs, and the fixing may be difficult. When a two-layer film is used as described above, the polyimide layer may be thinned. However, since the polyimide itself slides on the heater surface and wears, the polyimide layer should be thinned to 25 μm or less from the viewpoint of durability. Was difficult.

Further, as the fixing film is made thinner, pinholes are more likely to be generated during film formation, and there is a problem that a leak with a resistance heating element of a ceramic heater is induced at the time of fixing.

Further, in order to improve the flexibility of the fixing film, a thermoplastic resin such as a fluororesin or a silicone resin is dispersed and mixed with the polyimide resin. There is a problem that wrinkles occur due to the flexibility provided.

On the other hand, in a fixing film in which a layer made of silicone rubber or fluorine rubber is formed on the outermost layer, an inorganic filler added for the purpose of imparting fluidity to the toner, such as silica, is mechanically slid. There is a problem that the life is short because the abrasion easily occurs, or the charge control agent or the like causes the chemical bond to be cut and deteriorates easily.

Accordingly, a first object of the present invention is to provide excellent releasing properties and lubricity, no offset phenomenon even at high speed fixing, and durability (abrasion resistance and mechanical strength). It is an object of the present invention to provide a fixing film, a fixing device, and an image forming apparatus having the same, which are excellent in the above.

A second object of the present invention is to prevent the offset phenomenon from occurring even if continuous fixing is performed at a high speed for a long time without causing a decrease in the releasability and lubricity (the releasability and lubricity). An object of the present invention is to provide a fixing film having high durability, a fixing device, and an image forming apparatus provided with the fixing film and the fixing device.

A third invention of the present invention is to provide a fixing film which is flexible and does not generate wrinkles and has no pinhole, a fixing device provided with the fixing film, and an image forming apparatus. is there.

A fourth object of the present invention is to provide a highly durable fixing film which has excellent fixability without causing uneven gloss and is less likely to be scratched or deteriorated, a method for producing the same, and a fixing device provided with the fixing film. An apparatus and an image forming apparatus are provided.

[0016]

Means for Solving the Problems The present inventor has made various studies in order to achieve the above object, and as a result, completed the present invention.

According to a first aspect of the present invention, a heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and the fixing film is interposed therebetween. A fixing device for applying heat to the recording material to heat and melt the visible image, and then fixing the visible image on the recording material by separating the fixing film and the recording material; The present invention relates to a fixing device, wherein a material containing a fluorinated polyimide as a main component is used for a film.

According to a second aspect of the present invention, a heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-fusible developer, and the fixing film is interposed therebetween. A fixing device for applying heat to the recording material to heat and melt the visible image, and then fixing the visible image on the recording material by separating the fixing film and the recording material; A fixing device characterized in that the film is a film having a multilayer structure in which a film is laminated using a plurality of materials, and at least the outermost layer and / or the innermost layer is made of a material containing fluorinated polyimide as a main component. .

A third invention relates to the fixing device according to the second invention, wherein the fixing film has a rubber layer as an intermediate layer.

A fourth invention relates to the fixing device according to the second invention, wherein the fixing film has a silicone rubber layer and / or a fluorine rubber layer as an intermediate layer.

According to a fifth aspect of the present invention, a heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and the fixing film is interposed therebetween. A fixing device for applying heat to the recording material to heat and melt the visible image, and then fixing the visible image on the recording material by separating the fixing film and the recording material; The present invention relates to a fixing device, wherein a material containing fluorinated polyimide as a main component is used for a surface layer of a pressure roller for adhering a film.

The sixth invention relates to the fixing device according to any one of the first to fifth inventions, wherein the material containing fluorinated polyimide as a main component is a single material of fluorinated polyimide.

According to a seventh aspect of the present invention, there is provided the fixing method according to any one of the first to fifth aspects, wherein the material containing a fluorinated polyimide as a main component is a material containing a fluorinated polyimide as a main component and a fluororesin dispersed and mixed. Related to the device.

According to an eighth aspect of the present invention, the fluorinated polyimide has the formula (I)

[0025]

Embedded image And / or the formula (II)

[0026]

Embedded image The present invention relates to the fixing device according to any one of the first to seventh inventions, which is a polyimide compound containing a repeating unit represented by the following formula:

According to a ninth aspect of the present invention, a heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and supported by a heat-meltable developer, and the fixing film is interposed therebetween. The fixing film used in a fixing device for fixing a developed image on a recording material by applying heat to the recording material to heat and melt the developed image, and then separating the fixing film and the recording material. And a fixing film comprising a material containing fluorinated polyimide as a main component.

According to a tenth aspect of the present invention, a heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-fusible developer, and the fixing film is interposed therebetween. The fixing film used in a fixing device for fixing a developed image on a recording material by applying heat to the recording material to heat and melt the developed image, and then separating the fixing film and the recording material. And a fixing film having a multilayer structure in which a plurality of materials are stacked, wherein at least the outermost layer and / or the innermost layer is made of a material containing fluorinated polyimide as a main component.

The eleventh invention relates to the fixing film according to the tenth invention, which has a rubber layer as an intermediate layer.

The twelfth invention relates to the fixing film of the tenth invention, which has a silicone rubber layer and / or a fluorine rubber layer as an intermediate layer.

The thirteenth invention relates to the fixing film according to any one of the ninth to twelfth inventions, wherein the material containing fluorinated polyimide as a main component is a single material of fluorinated polyimide.

A fourteenth invention is the fixing method according to any one of the ninth to twelfth inventions, wherein the material containing fluorinated polyimide as a main component is a material containing fluorinated polyimide as a main component and a fluororesin dispersed and mixed. About the film.

According to a fifteenth aspect, the fluorinated polyimide is
Formula (I)

[0034]

Embedded image And / or the formula (II)

[0035]

Embedded image The present invention relates to a fixing film according to any one of the ninth to fourteenth inventions, which is a polyimide compound containing a repeating unit represented by the formula:

According to a sixteenth aspect of the present invention, a heat-resistant fixing film is brought into close contact with a visible image carrying surface of a recording material on which an unfixed visible image is formed and carried by a heat-meltable developer, and the fixing film is interposed therebetween. A fixing device for applying heat to the recording material to heat and melt the visible image, and then fixing the visible image on the recording material by separating the fixing film and the recording material; The film has a multilayer structure of at least three layers composed of at least a polyimide resin layer, a rubber layer and a silicone resin layer or a fluorine resin layer, the innermost layer being the polyimide resin layer, the intermediate layer being a rubber layer, and the outermost layer being a silicone resin. The present invention relates to a fixing device comprising a fixing layer or a fluororesin layer.

The seventeenth invention relates to the fixing device according to the sixteenth invention, wherein the rubber layer of the fixing film comprises a silicone rubber layer and / or a fluorine rubber layer.

According to an eighteenth aspect of the present invention, a heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and the fixing film is interposed therebetween. The fixing film used in a fixing device for fixing a developed image on a recording material by applying heat to the recording material to heat and melt the developed image, and then separating the fixing film and the recording material. Having a multilayer structure of at least three layers consisting of at least a polyimide resin layer, a rubber layer and a silicone resin layer or a fluorine resin layer, the innermost layer is the polyimide resin layer, the intermediate layer is a rubber layer,
The present invention relates to a fixing film, wherein the outermost layer is formed of a silicone resin layer or a fluororesin layer.

The nineteenth invention relates to the fixing film of the eighteenth invention, wherein the rubber layer comprises a silicone rubber layer and / or a fluoro rubber layer.

According to a twentieth aspect, a rubber solution is applied to the outer surface side of the innermost film, and then a cylindrical body is extrapolated to the film and the cylindrical body is moved relatively to the film. A method for producing a fixing film according to the eleventh, twelfth, eighteenth, or nineteenth invention, wherein a rubber layer as an intermediate layer is formed, and then an outermost layer is formed.

A twenty-first invention is characterized in that a rubber solution is spray-coated on the outer surface side of the innermost film to form a rubber layer as an intermediate layer, and then the outermost layer is formed by spray coating. The present invention relates to a method for producing a fixing film according to the eleventh, twelfth, eighteenth, or nineteenth invention.

The twenty-second invention relates to the method for producing a fixing film according to the twentieth or twenty-first invention, wherein a rubber layer is formed, vulcanized, and then the outermost layer is coated and formed by heating.

According to a twenty-third aspect of the present invention, the vulcanization and the curing are simultaneously performed by heating after the rubber layer coating and the outermost layer coating are completed. The present invention relates to a method for manufacturing a fixing film.

The twenty-fourth invention relates to the method for producing a fixing film according to the twenty-second or twenty-third invention, wherein the secondary vulcanization is carried out.

The twenty-fifth invention relates to an image forming apparatus provided with the fixing device according to any one of the first to eighth, sixteenth, and seventeenth inventions.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

Preferred fluorinated polyimides for use in the fixing film of the present invention are represented by formula (II), which is a fluorinated polyimide comprising a repeating unit represented by formula (I) (hereinafter referred to as "6FDA / TFDB polyimide"). A fluorinated polyimide comprising a repeating unit represented by the following formula (I) and a repeating unit represented by the formula (II): . These fluorinated polyimides include:
Other repeating units may be contained within a range not to impair the object of the present invention.

6FDA / TFDB polyimide (I) has the formula (III)

[0049]

Embedded image 2,2'-bis (trifluoromethyl) -4 represented by
4′-diaminobiphenyl (hereinafter referred to as “TFDB”) and formula (IV)

[0050]

Embedded image Formula (V) produced by polymerizing 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (hereinafter referred to as “6FDA”) represented by the following formula:

[0051]

Embedded image 6FDA / TFDB polyamic acid represented by the following formula:

On the other hand, PMDA / TFDB polyimide (II)
FDB (III) and formula (VI)

[0053]

Embedded image (VII) formed by polymerizing pyromellitic anhydride (hereinafter referred to as “PMDA”) represented by the following formula:

[0054]

Embedded image Can be produced by imidizing the PMDA / TFDB polyamic acid represented by the formula:

A specific method of the above process can be performed by a known technique described in, for example, Macromolecules, Vol. 24, No. 18, 5001 (1991).

The fixing film of the present invention may be a single-layer film made of a material containing fluorinated polyimide as a main component, or a film made of a material containing fluorinated polyimide as a main component and another material. It may be a film having a laminated structure with a layer composed of This laminated structure can be a laminated structure of two or more layers as long as the film thickness is not too large.

As the fixing film of the present invention having this laminated structure, for example, a layer composed of a material containing fluorinated polyimide as a main component as a base layer (layer on the heating body side) and a release layer (layer on the recording material side) As), there is a film in which a fluororesin PTFE layer is laminated. Since the fluorinated polyimide has lubricity in addition to the original durability, it can be made thinner (less than 25 μm) than the conventional polyimide, and the durability (abrasion resistance and mechanical strength) ) And good fixing can be achieved without causing an offset phenomenon even at a high fixing speed. Also, PTFE
Is inexpensive, so that the cost can be reduced in terms of material as compared with the case where the fixing film is formed of a single layer of fluorinated polyimide.

As the fixing film of the present invention having another laminated structure, for example, a conventional polyimide layer as a base layer (layer on the heating body side) and a fluorinated polyimide as a release layer (layer on the recording material side) are mainly used. A film in which layers made of materials as components are laminated is exemplified. Since the fluorinated polyimide itself has the same mold release properties as the fluororesin, and the thickness of the film can be reduced due to the inherent durability of the fluorinated polyimide, the offset phenomenon does not occur even at a high fixing speed. A fixing film capable of fixing and having excellent durability (abrasion resistance and mechanical strength) can be provided. Further, as the base layer, a belt-shaped or cylindrical metal film can be used. It is preferable that the metal has a high Young's modulus.

In addition to the above fixing film, a material mainly composed of fluorinated polyimide can be used for the surface layer of the pressure roller. Thereby, the releasability of the roller side is improved, and the durability thereof can also be improved.

The material containing a fluorinated polyimide as a main component in the present invention may be a fluorinated polyimide alone, but is more preferably a fluorinated polyimide in which a fluororesin is dispersed and mixed.

By dispersing and mixing the fluororesin, the contact angle of the fixing film is hardly reduced even when continuous fixing is performed at a high speed for a long time, so that the releasability and lubricity are not reduced (the releasing property is not reduced). As a result, the offset phenomenon does not occur. Further, since the fluororesin is a thermoplastic resin, the fixing film is provided with flexibility, does not generate wrinkles, and enables good fixing. Further, since a pinhole is hardly generated at the time of film formation, a fixing film having no pinhole can be obtained. This is because even if a pinhole occurs once during film formation, softening occurs during imidization, and the pinhole disappears.

Further, when the fluororesin is dispersed and mixed on the surface of the fixing film, a large amount of wax adheres to the fixing film when fixing is performed using a toner containing wax, and a minute amount of fine particles adheres to the surface of the fixing film. And is uniformly dispersed and adhered, so that when absorbed by a recording material such as paper, there is no occurrence of a pool of wax so as to appear as a stain.

The fluororesin used in the present invention includes ethylene tetrafluoride-perfluoroalkoxyethylene copolymer (hereinafter referred to as "PFA resin"),
Hexafluoropropylene resin (hereinafter referred to as “FEP resin”), polytetrafluoroethylene (hereinafter “PTF”)
E ". Is preferred. The mixing ratio with the fluorinated polyimide is 5 to 100 parts by weight of the fluorinated polyimide.
~ 50 parts by weight are preferred. When the amount is less than 5 parts by weight, a sufficient contact angle, for example, a contact angle exceeding 80 degrees cannot be obtained, which is insufficient to maintain the releasability. On the other hand, when the amount exceeds 50 parts by weight, the thermoplasticity is large. It becomes too much and causes stress relaxation, which is not preferable as a fixing film. In the above-mentioned method of mixing the fluororesin, for example, in a step described below, imidization is carried out after dispersing and mixing in a polyamide solution to produce the fixing film of the present invention.

Since the fluorinated polyimide of the present invention has a fluorine atom in the bone nucleus, it has a very high affinity for a fluororesin. Therefore, the fluororesin is very well dispersed and mixed in the fluorinated polyimide. When a fluororesin is dispersed in a conventional polyimide having no fluorine atom, it cannot be uniformly dispersed.

The fixing film of the present invention includes a furnace,
A conductive substance such as carbon black such as thermal or Ketjen black or graphite may be dispersed and mixed. As a result, it is possible to prevent electrostatic offset, prevent charging of the film surface (prevent the developer from scattering on the film before fixing), and the like.

Next, another embodiment of the fixing film of the present invention will be described. The fixing film of the present embodiment is a fixing film having a multilayer structure of three or more layers composed of at least a polyimide resin layer, a rubber layer, and a silicone resin layer or a fluorine resin layer, wherein the innermost layer is a polyimide resin layer,
A fixing film characterized in that the intermediate layer is composed of a rubber layer and the outermost layer is composed of a silicone resin layer or a fluororesin layer. As the rubber layer, a silicone rubber layer or a fluorine rubber layer is preferable. The rubber layer of the intermediate layer, for example, in order to increase the adhesive strength with the outermost fluororesin layer,
A fluorine rubber layer may be provided on the silicone rubber layer, and a fluorine resin layer may be laminated on the fluorine rubber layer. Further, in order to increase the adhesive strength with the outermost silicone resin layer, a silicone rubber layer may be provided on the fluorine rubber layer, and the silicone resin layer may be laminated on the silicone rubber layer. Further, instead of either or both of the innermost polyimide resin layer and the outermost silicone resin layer or the fluororesin layer, a layer made of a material containing the above-mentioned fluorinated polyimide as a main component may be provided.

The fluororesin is a resin having at least a tetrafluoroethylene repeating unit in the main chain or a fluoroalkoxy group and / or a fluoroalkyl group in the side chain having at least a tetrafluoroethylene repeating unit in the main chain. The resin can be arbitrarily selected from fluororesins conventionally used for a fixing surface layer material, such as a resin having the same or a resin in which the fluoroalkyl group is a methyltrifluoride group.

The silicone resin may be a dispersion commercially available from Toray or Shin-Etsu Chemical, and the fluororesin may be a liquid coating material such as a dispersion commercially available from Daikin Industries, Ltd. or the like. .

The silicone rubber is used in a liquid state, and includes, for example, a commercially available silicone rubber made at room temperature (silicone RTV rubber). The fluororubber is used in the form of a solution (including a dispersion). For example, commercially available FKM (VDF
-Binary and ternary copolymers of HFP fluororubber)
Latex and the like.

The polyamic acid as a precursor of the above-mentioned polyimide resin can be obtained by reacting tetracarboxylic dianhydride or a derivative thereof with substantially equimolar amounts of diamine in an organic polar solvent. Can be used.

The above tetracarboxylic dianhydride includes:
Examples include those represented by the following general formula (VIII).

[0072]

Embedded image In the formula, R is a tetravalent organic group, which is aromatic, aliphatic, cycloaliphatic, a combination of aromatic and aliphatic, or a substituted group thereof.

For example, pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, , 2'-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-
Dicarboxyphenyl) sulfone dianhydride, perylene-
3,4,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
And ethylene tetracarboxylic dianhydride.

Examples of the diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane,
3'-dichlorobenzidine, 4,4'-diaminodiphenylsulfide-3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4 ' 1-biphenyldiamine, benzidine, 3,3 '
-Dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminophenylsulfone, 4,4'-
Diaminodiphenyl sulfide, 4,4′-diaminodiphenylpropane, 2,4-bis (β-amino-tert-butyl) toluene, bis (p-β-amino-tert-butylphenyl) ether, bis (p-β- Methyl-δ-aminophenyl) benzene, bis-p- (1,1-dimethyl-
5-amino-pentyl) benzene, 1-isopropyl-
2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, di (p-aminocyclohexyl) methane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, Diaminopropyltetramethylene, 3-methylheptamethylenediamine,
4,4-dimethylheptamethylenediamine, 2,11-
Diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-
Methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-
Methylnonamethylenediamine, 2,11-diaminododecane, 2,17-diaminoeicosadecane, 1,4-diaminocyclohexane, 1,10-diamino-1,10
-Diamino-1,10-dimethyldecane, 1,12-diaminooctadecane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, piperazine, H ₂ N
(CH ₂ ) ₃ O (CH ₂ ) ₂ O (CH ₂ ) NH ₂ , H ₂ N (C
H ₂ ) ₃ S (CH ₂ ) ₃ NH ₂ , H ₂ N (CH ₂ ) ₃ N (C
H ₃ ) (CH ₂ ) ₃ NH _{2 and the} like.

In the method for producing a fixing film of the present embodiment, the organic polar solvent used at the time of synthesizing the polyamic acid has a dipole whose functional group does not react with tetracarboxylic dianhydride or diamine. .
And, besides being inert to the reaction system and acting as a solvent for the product polyamic acid,
It must act as a solvent for at least one of the reaction components, preferably both. In particular, N, N-dialkylamides are useful as the organic polar solvent, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide and the like having low molecular weights. These can be easily removed from the polyamic acids and polyamic acid moldings by evaporation, displacement or diffusion. Further, as an organic polar solvent other than the above,
N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-methyl-2-pyrrolidone, pyridine, tetramethylenesulfone, dimethyltetramethylenesulfone, etc. Is mentioned. These may be used alone or in combination.

Further, cresol.
Phenols such as phenol and xylenol, benzonitrile, dioxane, butyrolactone, xylene, cyclohexane, hexane, benzene, toluene and the like can be used alone or in combination. However, the addition of water is not preferred. That is, since polyamic acid is hydrolyzed to have a low molecular weight by the presence of water, it is necessary to synthesize polyamic acid under substantially anhydrous conditions.

The polyamic acid is obtained by reacting the above tetracarboxylic dianhydride (A) with the diamine (B) in an organic polar solvent. At that time, the monomer concentration (the concentration of (A) + (B) in the solvent) is set according to various conditions. However, usually 5 to 30% by weight
(Hereinafter abbreviated as “%”). Further, the reaction temperature is preferably set to 80 ° C or lower, particularly preferably 5 to 50 ° C. The reaction time is suitably about 0.5 to 10 hours.

By reacting the acid dianhydride component raw material and the diamine component raw material in an organic polar solvent as described above, a polyamic acid is generated, and the solution viscosity increases as the reaction proceeds. In the present invention, the logarithmic viscosity is 0.5
It is preferable to synthesize the above polyamic acid and use it. That is, a polyimide belt formed by using a polyamic acid having a logarithmic viscosity of 0.5 or more is particularly superior to a belt having less reliability against thermal deterioration. The logarithmic viscosity of the polyamic acid is a value obtained by measuring the polyamic acid solution with a capillary viscometer and calculating from the following equation.

Logarithmic viscosity = (In (t ₁ / t ₀ )) / C t ₁ : Fall time of solvent, t ₀ : Fall time of solution C: Concentration (g / dl) Such a polyamic acid solution is used. When the viscosity is high, the solution is diluted with an appropriate solvent to reduce the viscosity. The viscosity of the polyamic acid solution is set according to, for example, the coating thickness, the inner diameter of the cylinder, the solution temperature, the shape of the running body, and the like. Measurement value). The polyamic acid concentration in the polyamic acid solution is
From the viewpoint of the effect, the content is preferably set to 5 to 30% as described above, and particularly preferably 10 to 20%.

In the method of manufacturing the fixing film of this embodiment, a silicone rubber or a fluororubber and an organic polar solvent solution of polyamic acid obtained as described above are used. A fixing film having the above multilayer structure can be manufactured.

As a first manufacturing method, for example, there is the following embodiment. First, a polyimide resin film is prepared according to a conventional method. As a method for producing this polyimide resin film, for example, first, a polyamic acid is applied to the inner peripheral surface of a cylinder. The coating method includes (i) a method in which the cylinder is immersed in a polyamic acid solution and then lifted up, and (ii) a polyamic acid solution is supplied near one end of the cylinder to form a bullet-shaped or spherical traveling body. There are two methods of running along the inner peripheral surface of the cylinder, and the method is appropriately selected according to the situation and the like. Examples of the bullet-shaped or spherical traveling body include those made of metal, hard plastic, and hard glass. As a method of traveling the traveling body, the traveling body travels by using compressed air pressure, gas explosion force, or the like. There are methods such as biasing, pulling the traveling body using a pulling wire or the like, and running the vehicle under its own weight (standing upright the cylinder and traveling the traveling body by its own weight). In the above method (i), after applying the polyamic acid solution to the inner peripheral surface of the cylinder, a bullet-shaped or spherical traveling body may be caused to travel along the inner peripheral surface of the cylinder, if necessary.

Subsequently, the polyamic acid applied in this manner is heated to be imidized. Heating in this imidization is performed by first heating at 80 to 180 ° C for 20 to 60 minutes to remove the solvent, and then heating at 250 to 400 ° C for 20 to 20 minutes.
Heating for 60 minutes is performed. As a result, the ring-closing water and the like generated during the imidization are evaporated, and the imidization is completely performed. As described above, a polyimide resin film is obtained, and the polyimide resin film is taken out of the cylinder. In this case, the polyimide resin film is preferably formed to have a thickness in the range of 10 to 100 μm.

Next, a silicone rubber solution or a fluorine rubber solution is applied to the outer peripheral surface of the polyimide resin film. When applying the solution on the outer peripheral surface of the polyimide resin belt, the polyimide resin belt may be fitted into a cylinder having an outer diameter slightly smaller than the inner diameter of the polyimide resin belt. Then, the cylindrical body is extrapolated and arranged on the belt coated with the solution. Next, the cylinder or the belt is run, or both are run in opposite directions to make the coating thickness uniform.

When the above-mentioned silicone rubber solution is applied, it is left at 20 to 150 ° C. for 1 to 24 hours and cured to form a silicone rubber intermediate layer. On the other hand, when a fluororubber solution is applied,
For 10 to 30 minutes to remove the solvent, then 200
The fluororubber intermediate layer is formed by heating at ~ 350 ° C for 1-60 minutes. In this case, the thickness of the silicone rubber intermediate layer and the fluorine rubber intermediate layer is 100 to 50.
Preferably, it is formed so as to be within the range of 0 μm.

Finally, a silicone resin solution or a fluororesin solution is applied on the rubber intermediate layer on the outer peripheral surface of the film. When applying the solution on the outer peripheral surface of this film,
This film may be inserted into a cylinder having an outer diameter slightly smaller than the inner diameter of the film. Then, the cylindrical body is extrapolated to the film coated with the solution. Next, the cylinder or the film is run, or both are run in opposite directions to make the coating thickness uniform. 380 when any resin solution is used.
The outermost layer can be formed by heating at ４００400 ° C. for 10 to 30 minutes. The outermost layer is preferably formed to have a thickness in the range of 5 to 100 μm.

As a second method for manufacturing the fixing film of the present embodiment, for example, the following embodiment is available. First, a silicone rubber solution or a fluorine rubber solution is spray-coated with a spray gun or the like on the outer peripheral surface of a polyimide resin film obtained by a conventionally known method, so as to be uniformly applied. Next, in the case of applying a silicone rubber solution, the silicone rubber intermediate layer is formed by allowing the mixture to stand at a temperature of 20 to 150 ° C. for 1 to 24 hours to cure. On the other hand, in the case of applying a fluororubber solution, the solvent is removed by heating at 80 to 150 ° C. for 10 to 30 minutes, and then at 200 to 350 ° C. for 1 hour.
By heating for 〜60 minutes, a fluorine rubber intermediate layer is formed. The gun used for the spray coating is not particularly limited, but a smaller nozzle diameter is preferable for uniform coating, for example, a nozzle diameter of 0.1 to 2 mm.
Are preferred. Further, the spray pressure is 1.0 to 5.0.
It is preferable to set within the range of kg / cm ² . In other words, if the spray pressure is too low, the spray-coated solution will not dry well and cracks and pinholes will be easily formed in the formed outer layer.On the other hand, if the spray pressure is too high, solution clogging tends to occur at the nozzle tip. It is not preferable from the viewpoint of coating operation.

Subsequently, a silicone resin solution or a fluororesin solution is applied in the same manner.
The outermost layer is formed by heating at ４００400 ° C. for 10 to 30 minutes. The outermost layer is preferably formed to have a thickness in the range of 5 to 100 μm.

In the above-mentioned first and second production methods, the curing treatment was sequentially performed. However, if the rubber layer is likely to be softened and deteriorated by excessive heating, the outermost layer is applied while the intermediate layer is wet. You may heat simultaneously. In addition, the outermost layer is formed after the intermediate layer is formed and vulcanized, or vulcanization and curing are simultaneously performed by heating after the application of the intermediate layer and the outermost layer are completed. You may. Furthermore, secondary vulcanization may be performed as necessary. 200 ~
Heat at 350 ° C. for 1-60 minutes. This secondary vulcanization
The purpose is to prevent the degradation of the releasability caused by the decomposition products generated in the primary vulcanization adhering to the outermost layer surface.

In the first and second manufacturing methods described above,
Prior to forming a fluorine rubber layer or a silicone rubber layer on the outer peripheral surface of the polyimide resin film, to improve the adhesive strength between the polyimide resin film layer and the fluorine rubber layer or the silicone rubber layer (intermediate layer) Next, it is preferable to form an intermediate layer after surface-treating the outer peripheral surface of the polyimide resin film. Examples of the surface treatment method include wet treatment such as alkali treatment, primer treatment, ultrasonic treatment, and etching treatment, and dry treatment such as corona treatment, plasma treatment, ultraviolet (UV) irradiation treatment, electronic treatment, and laser treatment. These processing methods are performed alone or in combination. Among the above treatments, alkali treatment, primer treatment, corona treatment,
Plasma treatment and UV irradiation treatment are preferred in terms of workability.
Similarly, in order to improve the adhesive strength between the interlayer and the outermost layer, it is preferable to form the outermost layer after performing the same surface treatment as described above after the formation of the intermediate layer.

Next, the configuration of the fixing device of the present invention will be described. FIGS. 1, 2 and 3 are schematic explanatory views of a film heating type fixing device (image heating fixing device). FIG.
2 is a schematic longitudinal sectional view of a pressing portion, FIG. 2 is a schematic longitudinal sectional view of a pressing roller portion, and FIG. 3 is a schematic plan view of a heating body. 1 is a fixing film of the present invention. 4 is a heater (ceramic heater) fixedly supported by the support (3)
It is. The fixing film (1) is brought into close contact with the heating element (4) with a pressure roller (2) and is slid and conveyed. A heating element (4) and a pressure roller (2) sandwiching the fixing film (1)
A recording material (P) on which an image is to be fixed as a material to be heated is placed between the fixing film (1) and the pressure roller (2) in the pressure contact nip portion (N) (fixing nip portion) formed by The sheet is introduced and pinched and transported together with the fixing film (1).
Thereby, the heat of the heating element (4) is applied to the recording material (P) via the fixing film (1), and the unfixed visible image (T ₁ ) (toner image) on the recording material (P) is changed. Heat fixing is performed on the surface of the recording material (P). The recording material (P) that has passed through the press nip (N) is separated from the surface of the fixing film (1) and conveyed.

The heating element (4) of the fixing device according to the present invention has a longitudinal direction perpendicular to the transport direction (a) of the heat-resistant fixing film (1) or the recording material (P) as the material to be heated. An elongated substrate having heat resistance, insulation, and good thermal conductivity; a resistance heating element (6) formed along the longitudinal direction of the substrate at the center in the short side of the surface of the substrate; Electrodes (6a, 6b) at both longitudinal ends of the resistance heating element, a heat-resistant overcoat layer (7) for protecting the surface of the heating element on which the resistance heating element is formed, and heating provided on the back side of the substrate (5). It consists of a temperature sensing element (8) such as a thermistor that detects body temperature,
It is a linear heating element with low heat capacity as a whole. This heating element (4) has a surface on the side of the resistance heating element (6) pressed with a pressure roller (1).
Toward the 02) side, the support (3) having rigidity and heat insulation is adhesively held and fixedly disposed.

The heating element (4) comprises a resistance heating element (6)
When the power is supplied to the electrodes (6a, 6b) at both ends, the resistance heating element (6) generates heat over its entire length, thereby increasing the temperature. At this time, the temperature of the heating element is detected by the temperature detecting element (8), and the detected temperature is fed back to a temperature control circuit (not shown) so that the resistance of the heating element (4) is maintained at a predetermined temperature. The energization of the heating element (6) is controlled. That is, at the time of fixing, energization to the resistance heating element (6) is controlled so that the detection output of the temperature detecting element (8) becomes constant.

[0093]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A 6FDA / TFDB polyimide was prepared as follows. 6
FDA / TFDB polyamic acid is commercially available from Aftei Co., Ltd. This 6FDA / TFDB polyamic acid was used only for imidization to prepare 6FDA / TFDB polyimide. A polyamic acid solution is applied to the surface or the inner surface of a stainless steel pipe having a predetermined diameter, and the solution is applied to an inert gas such as nitrogen.
The temperature was raised stepwise to ° C to imidize. Gradual heating is performed at 70 ° C for 2 hours, 160 ° C for 1 hour, and 250 ° C for 3 hours.
Performed for 0 minute at 350 ° C. for 1 hour. The temperature was raised according to the method described in the above-mentioned literature. The analysis was performed in the same manner as in the above-mentioned literature, and the fact that imidization was completed was confirmed by IR
And NMR were used to determine the positions of functional groups and protons using DSC.
As a result, it was confirmed that the glass transition points were respectively in agreement with the literature values. A fixing film having a film thickness of 20 μm was obtained.

The developer was prepared as follows.

Preparation of aqueous medium A: 710 g of ion-exchanged water
450 g of 0.1 M Na ₃ PO ₄ aqueous solution
TK homomixer (manufactured by Tokushu Kika Kogyo)
And stirred at 13000 rpm. 1.0M
68 g of CaCl ₂ aqueous solution is gradually added, and Ca ₃ (P
An aqueous medium A containing O ₄ ) ₂ was obtained.

Preparation of Polymerizable Monomer Composition B: Styrene 1
66 g, n-butyl acrylate 34 g, copper funurolanine pigment 15 g, ditertiary butyl salicylic acid metal compound 3 g, saturated polyester (acid value 11, peak molecular weight 8500) 10 g, monoester wax (Mw 50
0, Mn400, viscosity 6.5 mPs, SP value 8-6) 4
0 g of the mixture was heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer. In this, 10 g of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved, and the polymerizable monomer composition B was dissolved.
Was prepared.

Preparation of Toner: The above-mentioned polymerizable monomer composition B was charged into the above-mentioned aqueous medium A, and was subjected to 10000 rpm using a TK homomixer at 60 ° C. and in an N ₂ atmosphere.
The mixture was stirred at pm for 20 minutes to granulate the polymerizable monomer composition B. Thereafter, the mixture was heated to 80 ° C. while being stirred with a paddle stirring blade and reacted for 10 hours. After completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered,
After washing with water and drying, polymer particles were obtained. Obtained particles 10
The specific surface area by the BET method is 100 m with respect to 0 parts by weight.
2.0 parts by weight of ² / g of hydrophobic titanium oxide was externally added,
A toner having an average particle size of 6.2 μm was obtained.

With 7 parts by weight of the toner thus obtained, 93 parts by weight of a 35 μm silicone-coated ferrite carrier were mixed to obtain a developer.

A fixing device (FIGS. 1 to 3) of the present invention provided with the above-mentioned cylindrical fixing film (diameter: 45 mm, film thickness: 20 μm) was mounted on a fixing section of a commercially available full-color copying machine CLC800 (manufactured by Canon). Using the above developer, the image was fixed at a fixing speed of 133 mm / sec. The fixing film was a film of fluorinated polyimide alone, and fixing was performed using an endless belt. As a result, even in a single color or a plurality of colors, by setting the fixing temperature to 200 ° C., it was possible to fix satisfactorily without causing an offset phenomenon.

Example 2 An image was fixed in the same manner as in Example 1 except that a commercially available PMDA / TFDB polyimide prepared from a PMDA / TFDB acid amide solution was used as a fixing film. As in Example 1, no offset phenomenon occurred, and good results were obtained.

Example 3 An image was fixed in the same manner as in Example 1 except that a pulverized toner based on a polyester resin manufactured by Sharp Melt used in CLC800 was used as the toner. As in Example 1, no offset phenomenon occurred, and good results were obtained.

Example 4 An image was fixed in the same manner as in Example 1 except that a two-layer film was used as the fixing film. This fixing film was formed by laminating a 20 μm thick fluorinated polyimide layer as a base layer and a 10 μm thick fluororesin PTFE layer as a release layer.

Since the fluorinated polyimide has lubricity in addition to the original durability, it is possible to make the film thickness smaller (to 20 μm) than that of the conventional polyimide. Also, no offset phenomenon occurred and good results were obtained. Further, since PTFE is inexpensive, a part of the fixing film is made of fluorinated polyimide, so that the cost can be reduced as compared with the case of the first embodiment.

Example 5 An image was fixed in the same manner as in Example 1 except that a fluorinated polyimide in which a PFA resin was dispersed and mixed was used. 30 parts by weight of P per 100 parts by weight of fluorinated polyimide
After the FA resin was dispersed and mixed in the polyamide solution, imidization was performed.

The offset phenomenon does not occur, and A4
500,000 sheets of paper were successfully fixed. After fixing, the contact angle of the fixing film was 80 degrees.

Example 6 An image was fixed in the same manner as in Example 5 except that a commercially available PMDA / TFDB polyimide prepared from a PMDA / TFDB amide solution in which a PFA resin was dispersed and mixed was used. As in the case of Example 5, no offset phenomenon occurred, and good results were obtained.

Example 7 An image was fixed in the same manner as in Example 5, except that a ground toner made of a polyester resin made of Sharp Melt used in CLC800 was used as the toner. As in the case of Example 5, no offset phenomenon occurred, and good results were obtained.

Example 8 An image was fixed in the same manner as in Example 5 except that a two-layer film was used as the fixing film. This fixing film is composed of a fluorinated polyimide layer having a thickness of 20 μm as a base layer and a fluororesin PTFE having a thickness of 10 μm as a release layer.
The layers were formed by lamination.

Example 9 An image was fixed in the same manner as in Example 5 except that a two-layer film was used as the fixing film. In this fixing film, the following resin layer having a thickness of 10 μm was formed as a release layer on a fluorinated polyimide layer having a thickness of 15 μm as a base layer. That is, a fluorinated polyimide 10
A weight ratio (PFA / PTFE) of PFA resin and PTFE resin corresponding to a total amount of 30 parts by weight with respect to 0 parts by weight.
= 3/7 to form a resin layer dispersed and mixed with the fluorinated polyimide. In fixing the image, the same result as in Example 5 was obtained.

Example 10 Substantially equimolar amounts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine were N-methyl-2-pyrrolidone (hereinafter referred to as "NMP"). ) (Monomer concentration 20%), and reacted at 20 ° C. for 5 hours to obtain a rotational viscosity of 35,000 poise (measured with a B-type viscometer).
A polyamic acid solution having a logarithmic viscosity of 2.8 was prepared. Next, to 100 parts by weight of this solution (hereinafter abbreviated as "parts"), 33 parts of NMP was added for dilution, and the mixture was further heated to 50 ° C. to obtain a polyamic acid solution having a viscosity of 150 poise.

The above polyamic acid solution was treated with an inner diameter of 50 mm,
It is applied to the inner peripheral surface of a stainless steel cylinder having a thickness of 5 mm and a length of 500 mm and having an inner peripheral surface smoothed, and using a bullet-shaped traveling body having an outer diameter of 49.4 mm at a speed of 50 mm / min by a self-weight traveling method. By running, the polyamic acid solution was uniformly applied to the inner peripheral surface of the cylinder. After applying, 70
After drying at 60 ° C. for 60 minutes, the temperature was raised from 70 ° C. to 300 ° C. at a rate of 0.8 ° C./min. Then, at 300 ° C, 6
The mixture was heated for 0 minutes to remove the solvent, remove the ring-closing water and imidize, and then cooled to room temperature to form a polyimide resin film.

Next, the open ends at both ends of the cylinder were plugged, and the polyimide resin belt was peeled from the cylinder by taking out air from a small through-hole provided beforehand near the opening of the cylinder. The polyimide resin film was cut off at both ends and had an outer diameter of 5 mm.
0mm, inner diameter 49.94mm, length 450mm, thickness 3
It was a 0 μm film.

A silicone-based primer was uniformly spray-coated on the outer peripheral surface of the polyimide resin film thus obtained, and air-dried for 30 minutes to form a primer layer. The polyimide resin film on which the primer layer was formed was fitted to the outer periphery of a stainless steel cylinder having an outer diameter of 49.92 mm, an inner thickness of 5 mm, and a length of 500 mm and having a smooth outer peripheral surface. Then, RTV silicone rubber (K) is applied to the outer peripheral surface of the polyimide resin film.
E-1400, manufactured by Shin-Etsu Chemical Co., Ltd.)
1400, manufactured by Shin-Etsu Chemical Co., Ltd.). At this time, the silicone rubber solution was run along the outer peripheral surface of the polyimide resin film fitted in the cylinder at a speed of 50 mm / min by a self-weight running method using a cylindrical running body having an inner diameter of 50.3 mm, and the silicone rubber solution was made of polyimide resin. The film was uniformly applied to the outer peripheral surface of the film. After application, 25 ℃, humidity 5
The film was left at 0% RH for 12 hours to obtain a film in which a silicone rubber layer was provided around the polyimide resin film. Further, in the same manner, a silicone-based primer was uniformly spray-coated on the outer peripheral surface of the film and air-dried for 30 minutes to form a primer layer. Further, a silicone resin solution obtained by adding a curing agent (manufactured by Toshiba Silicone) to a silicone resin (manufactured by Toshiba Silicone) is applied, and 380 to 400
Heat at 10 ° C. for 10-30 minutes.

The total thickness of the obtained film was 300 μm, of which the thickness of the silicone rubber layer was 260 μm and the thickness of the silicone resin layer was 10 μm.

The fixing film manufactured as described above is set as an endless belt in a color image fixing device, and the fixing device is attached to an image forming device (CL manufactured by Canon Inc.).
C800), and fixing was performed. As a result, an image having good toner fixability and no fine gloss unevenness was obtained.

Example 11 The outer surface of a polyimide resin film produced in the same manner as in Example 10 was uniformly spray-coated with a silicone primer and air-dried for 30 minutes to form a primer layer.

Next, RTV silicone rubber (KE-1)
400, manufactured by Shin-Etsu Chemical Co., Ltd.) and a curing agent (CAT-140)
0, manufactured by Shin-Etsu Chemical Co., Ltd.).
The solution was diluted with 1,1,1-trichloroethane so as to be 0%, and this solution was spray-coated with a spray gun on the outer peripheral surface of the primer-treated polyimide resin film. Then, at 25 ° C and 50% RH, 12
After leaving for a time, a film having no unevenness on the intermediate layer surface was obtained.

Next, in order to form an outermost layer, a silicone-based primer was uniformly spray-coated and air-dried for 30 minutes to form a primer layer. Subsequently, a silicone resin solution obtained by adding a curing agent (manufactured by Toshiba Silicone) to the silicone resin (manufactured by Toshiba Silicone) is applied, and 380 to 400
It heated at 10 degreeC for 10 to 30 minutes, and implemented simultaneously with vulcanization. Furthermore, it heated at 250 degreeC for 60 minutes, and implemented secondary vulcanization. In addition, the spray coating is performed by repeating the spray coating 30 times with the discharge amount reduced, the air pressure is set to 2 kg / cm ² or more, and the spray coating is performed to obtain a predetermined film thickness. The film thickness varies).

The total thickness of the obtained film was 200 μm, of which the thickness of the silicone rubber layer was 160 μm.

The fixing film manufactured as described above is set as an endless belt in a color image fixing device, and the fixing device is attached to an image forming device (CL manufactured by Canon Inc.).
C800), and fixing was performed. As a result, an image having good toner fixability and no fine gloss unevenness was obtained.

Example 12 The outer peripheral surface of a polyimide resin film produced in the same manner as in Example 10 was spray-coated with a fluorine rubber solution (Dye Latex GLS-213, manufactured by Daikin Co., Ltd.) using an air spray gun. Thereafter, the mixture was heated at 100 ° C. for 15 minutes, further heated from 100 ° C. to 300 ° C. at a rate of 2 ° C./min, and then heated at 300 ° C. for 5 minutes and cooled to room temperature. A film having a fluororubber layer having no unevenness on the outer peripheral surface was obtained on the outer periphery of the polyimide resin film.

Further, Daikin Industries, Ltd.
ND1 (50% solids FEP (tetrafluoroethylene-hexafluoropropylene copolymer)) was spray-coated with an air spray gun. afterwards,
Heated at 380-400 ° C for 10-30 minutes.

The total thickness of the obtained fixing film was 200 μm.
m, of which the thickness of the fluororubber layer was 155 μm.

The fixing film manufactured as described above is set as an endless belt in a color image fixing device, and this fixing device is attached to an image forming device (CL manufactured by Canon Inc.).
C800), and fixing was performed. As a result, an image having good toner fixability and no fine gloss unevenness was obtained.

Example 13 The outer surface of a polyimide resin film produced in the same manner as in Example 10 was uniformly spray-coated with a silicone primer and air-dried for 30 minutes to form a primer layer.

Next, RTV silicone rubber (KE-1)
400, manufactured by Shin-Etsu Chemical Co., Ltd.) and a curing agent (CAT-140)
0, manufactured by Shin-Etsu Chemical Co., Ltd.).
The solution was diluted with 1,1,1-trichloroethane so as to be 0%, and this solution was spray-coated with a spray gun on the outer peripheral surface of the primer-treated polyimide resin film. Thereafter, the film was allowed to stand at 25 ° C. and 50% RH for 12 hours to obtain a film having no unevenness on the surface of the intermediate layer.

Next, ND1 (FEP (tetrafluoroethylene-hexafluoropropylene copolymer) having a solid content of 50%) manufactured by Daikin Industries, Ltd. was spray-coated on the fluororesin using an air spray gun. Then 3
Heated at 80-400 ° C for 10-30 minutes. In addition, the spray coat reduces the discharge amount and the air pressure is 2 kg / c.
Spray coating was repeated 30 times at m ² or more to obtain a predetermined film thickness. (If a predetermined thickness is formed at one time, the film thickness varies due to insufficient drying.)

The total thickness of the obtained fixing film was 200 μm.
m, of which the thickness of the silicone rubber layer is 160 μm
And the thickness of the outermost fluororesin layer was 10 μm.

The fixing film produced as described above is set as an endless belt in a color image fixing device, and this fixing device is mounted on an image forming device (CL, manufactured by Canon Inc.).
C800), and fixing was performed. As a result, an image having good toner fixability and no fine gloss unevenness was obtained.

[0131]

As is apparent from the above description, according to the present invention, by using a fluorinated polyimide for the fixing film, the fluorinated polyimide itself has not only the durability but also the releasability equivalent to that of the fluororesin. Since it has lubricating properties, it is not necessary to separate the functions as a conventional fixing film and take a laminated structure of a base layer and a release layer, and the total thickness can be reduced to 20 μm or less, resulting in low heat capacity. Even when the fixing speed is as high as 130 mm / sec or more,
Good fixing becomes possible without causing the offset phenomenon.

By forming the fixing film into a laminated structure and forming a fluorinated polyimide layer as a base layer, the fluorinated polyimide has lubricity equivalent to that of a fluororesin in addition to its original durability, and therefore has a sliding surface. Even if it moves, the amount of abrasion is small, the durability of the fixing film can be improved, and the film thickness can be further reduced, so that good fixing can be performed without causing an offset phenomenon.

By forming the fixing film into a laminated structure and forming a fluorinated polyimide layer as a release layer, the fluorinated polyimide itself has the same releasability as a fluororesin, and has a film thickness due to the inherent durability of the polyimide. Therefore, it is possible to provide a fixing film capable of performing excellent fixing without causing an offset phenomenon and having excellent durability.

By using a material in which a fluorinated polyimide is used as a main component and a fluororesin is dispersed and mixed for the fixing film, the releasability and lubricity can be maintained even when continuous fixing is performed at a high speed for a long time. It is possible to obtain a fixing film which does not lower, does not cause an offset phenomenon, has flexibility and does not generate wrinkles, and has no pinhole.

Further, since the fluororesin is dispersed and mixed on the surface of the fixing film, even if a large amount of wax adheres to the fixing film when fixing is performed using a toner containing wax, a minute And is uniformly dispersed and adhered, so that when absorbed by a recording material such as paper, there is no occurrence of a pool of wax so as to appear as a stain.

In the fixing belt of the present invention, since the rubber layer is formed on the intermediate layer, the surface layer of the film follows the step caused by the fibers on the recording material, for example, the paper surface, and is fixed according to the unevenness of the paper surface. Since there is no difference, there is no occurrence of minute gloss unevenness. Furthermore, since the outermost layer is formed of a silicone resin, a fluororesin, or a fluorinated polyimide, it may be mechanically scratched with a substance such as silica, or may cause a chemical bond to be cut by a charge control agent or the like. Since there is no deterioration, the life is very long. Further, according to the production method of the present invention, such a fixing film can be formed with a uniform thickness for each layer, and an excellent fixing film having these characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic longitudinal sectional view of a pressurized portion of a fixing device of the present invention.

FIG. 2 is a schematic longitudinal sectional view of a pressure roller portion of the fixing device of the present invention.

FIG. 3 is a schematic plan view of a heating element of the fixing device of the present invention.

[Explanation of symbols]

1 the fixing film 2 pressure roller 3 support 4 heater 5 substrate 6 resistive heating elements 6a, 6b electrodes 7 heat-resistant overcoat layer 8 thermometric element N press nip P the recording material T ₁ unfixed visualized image T ₂ fixed image a Transport direction

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) G03G 15/20 101 B29D ⁷ /00-7/01 B29K 79:00

Claims (25)

(57) [Claims] 1. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and supported by a heat-fusible developer, and the recording medium is interposed through the fixing film. A fixing device for fixing a developed image on a recording material by applying heat to the material to heat and melt the developed image, and then separating the fixing film and the recording material, wherein the fixing film is fluorinated. A fixing device comprising a material containing polyimide as a main component. 2. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and the recording medium is passed through the fixing film. A fixing device for fixing a developed image on a recording material by applying heat to heat and melt the developed image, and then separating the fixing film and the recording material, wherein the fixing film has a plurality of fixing films. A film having a multilayer structure laminated by using a material, wherein at least an outermost layer and / or
Alternatively, a fixing device in which a material containing fluorinated polyimide as a main component is used for an innermost layer. 3. The fixing device according to claim 2, wherein the fixing film has a rubber layer as an intermediate layer. 4. The fixing device according to claim 2, wherein the fixing film has a silicone rubber layer and / or a fluorine rubber layer as an intermediate layer. 5. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and said recording medium is passed through said fixing film. A fixing device for fixing a developed image on a recording material by applying heat to heat and melt the developed image, and then separating the fixing film and the recording material, wherein the fixing film is adhered to the fixing device. A material containing fluorinated polyimide as a main component is used for a surface layer of the pressure roller. 6. The fluorinated polyimide-based material is a single material of the fluorinated polyimide.
6. The fixing device according to any one of items 5 to 5. 7. The fixing device according to claim 1, wherein the material containing fluorinated polyimide as a main component is a material containing fluorinated polyimide as a main component and a fluororesin dispersed and mixed. 8. The fluorinated polyimide having the formula (I): And / or a repeating unit represented by the formula (II): The fixing device according to claim 1, wherein the fixing device is a polyimide compound containing a repeating unit represented by the formula: 9. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and supported by a heat-fusible developer, and the recording medium is interposed through the fixing film. The fixing film used in a fixing device for fixing a developed image on a recording material by applying heat to the material to heat and melt the developed image, and then separating the fixing film and the recording material, A fixing film comprising a material containing fluorinated polyimide as a main component. 10. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and said recording medium is passed through said fixing film. The fixing film used in a fixing device for fixing a developed image on a recording material by applying heat to the material to heat and melt the developed image, and then separating the fixing film and the recording material, A fixing film having a multilayer structure in which a plurality of materials are laminated, wherein at least the outermost layer and / or the innermost layer is made of a material containing fluorinated polyimide as a main component. 11. The fixing film according to claim 10, further comprising a rubber layer as an intermediate layer. 12. The method according to claim 1, wherein the intermediate layer has a silicone rubber layer and / or a fluorine rubber layer.
0 fixing film. 13. The material containing fluorinated polyimide as a main component is a single material of fluorinated polyimide.
13. The fixing film according to any one of items 12 to 12. 14. The material according to claim 9, wherein the material containing fluorinated polyimide as a main component is a material containing fluorinated polyimide as a main component and a fluororesin dispersed and mixed.
Item 7. The fixing film according to item 1. 15. A fluorinated polyimide having the formula (I): And / or a repeating unit represented by the formula (II): The fixing film according to any one of claims 9 to 14, which is a polyimide compound containing a repeating unit represented by the following formula: 16. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and said recording medium is passed through said fixing film. A fixing device for fixing a developed image on a recording material by applying heat to the material to melt the developed image, and then separating the fixing film and the recording material,
The fixing film has a multilayer structure of at least three layers consisting of at least a polyimide resin layer, a rubber layer, and a silicone resin layer or a fluorine resin layer, the innermost layer is the polyimide resin layer, the intermediate layer is a rubber layer, and the outermost layer is A fixing device comprising a silicone resin layer or a fluororesin layer. 17. The fixing device according to claim 16, wherein the rubber layer of the fixing film comprises a silicone rubber layer and / or a fluorine rubber layer. 18. A heat-resistant fixing film is brought into close contact with a developed image carrying surface of a recording material on which an unfixed developed image is formed and carried by a heat-meltable developer, and said recording medium is passed through said fixing film. The fixing film used in a fixing device for fixing a developed image on a recording material by applying heat to the material to heat and melt the developed image, and then separating the fixing film and the recording material, It has a multilayer structure of at least three layers composed of at least a polyimide resin layer, a rubber layer, and a silicone resin layer or a fluorine resin layer, the innermost layer being the polyimide resin layer, the intermediate layer being a rubber layer, and the outermost layer being a silicone resin layer or a fluorine layer. A fixing film comprising a resin layer. 19. The fixing film according to claim 18, wherein the rubber layer comprises a silicone rubber layer and / or a fluorine rubber layer. 20. After applying a rubber solution to the outer surface side of the innermost film, a cylinder is extrapolated to the film and the cylinder is moved relatively to the film to form an intermediate layer. The rubber layer is formed, and then the outermost layer is formed.
A method for producing the fixing film as described above. 21. A rubber layer as an intermediate layer is formed by spray-coating a rubber solution on the outer surface side of the innermost film, and then the outermost layer is formed by spray-coating. 20. The method for producing a fixing film according to claim 18, 18 or 19. 22. The method for producing a fixing film according to claim 20, wherein a rubber layer is formed and vulcanized, and then the outermost layer is coated and formed by heating. 23. The method for producing a fixing film according to claim 20, wherein the vulcanization and the curing are simultaneously performed by heating after the coating of the rubber layer and the coating of the outermost layer are completed. . 24. The method for producing a fixing film according to claim 22, wherein secondary vulcanization is performed. 25. An image forming apparatus comprising the fixing device according to any one of claims 1 to 8, 16, and 17.