JPH10340018A - Member for fixation, fixing device using the same, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesive strength between a carrier and a fluororesin layer forming an outermost layer by providing a layer which has fluororesin and silicone modified polyimide between the carrier and the fluororesin layer which forms the outermost layer. SOLUTION: This member for fixation which has layers on the carrier has the adhesion layer 102 having 1st fluororesin and silicone modified polyimide and the outermost layer 104 formed of 2nd fluororesin. Namely, this member for fixation is composed of the fluororesin so that the outermost layer 104 and adhesion layer 102 has their border in slanting structure through the compatibility of the adhesion layer 102 with the fluororesin at the time of thermal fusion between the silicone modified polyimide having good adhesive strength with metal and the fluororesin of the outermost layer 104. The 1st fluororesin and 2nd fluororesin are preferably superior in heat resistance for continuous use above 200 deg.C by the heating of the fixation member. Further, a filler and other resin may properly be mixed with the outermost layer 104.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heating and cooling cycle and a heating apparatus used in a fixing unit of a copying apparatus, a printer and other various image forming apparatuses which are always subjected to mechanical pressure welding. The present invention relates to a fixing member such as a roll or a belt, a fixing device using the fixing member, and an image forming method using the fixing device.

[0002]

2. Description of the Related Art In a copying apparatus, a printer and other various image forming apparatuses used in an electrophotographic system, a method for fixing a toner image formed on a sheet usually includes a heating element such as a lamp inside. A method is adopted in which a toner image is fused on a support by passing a carrier, such as paper, on which a toner image is formed between two pairs of rotating bodies that are heated by being arranged and pressed against each other. .

As an example of a fixing device used in such a method, there is a hot roll fixing device as shown in FIG. 1, and this hot roll fixing device comprises a pair of a heating roll 1 and a pressure roll 11. Consists of Heating roll 1
Is a fluorine-based material such as fluorine rubber, silicone rubber, polytetrafluoroethylene (PTFE), or a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA) on the surface of a cylindrical hollow metal core 2 such as aluminum or iron. An outermost layer 4 made of a heat-resistant elastomer such as a resin or a heat-resistant resin having excellent release properties is covered. A heating element 21 such as a halogen lamp is disposed inside the heating roll 1 so as to have a function of a heating roll.

On the other hand, the pressure roll 11 is made of aluminum,
An outermost layer 14 made of a heat-resistant elastomer or a heat-resistant resin having the same or different type as that of the heating roll 1 and excellent in releasability is coated on the surface of a hollow cylindrical core 12 made of iron or the like. The heating roll 1 and the pressure roll 11 are pressed against each other by a spring or the like. In the figure, reference numeral 27 denotes an inlet, 28 denotes an outlet, and 29 denotes a release agent application device for applying a release agent to the surface of the heating roll 1.

In this heat roll fixing device, a paper 31 having a toner image 32 on its surface is conveyed between a heating roll 1 and a pressure roll 11, and after the toner image 32 is fixed on the paper 31, an outlet is formed. The paper is conveyed from between a pair of rolls via.

[0006] The fixing member coated on the surface of the carrier such as a roll may have a phenomenon such as a hot offset in which a part of the fused toner image adheres to the rotating body, or the toner image may not be separated from the rotating body together with the carrier. It is required that phenomena such as winding around the rotating body do not occur as much as possible.

On the other hand, since the cycle of heating and cooling, in which the apparatus is heated to a high temperature of 200.degree. C. when the apparatus is in operation and cooled to room temperature when the apparatus is stopped, is repeated, it is required that the apparatus withstand this cycle. ing. Further, on the outermost surface of the rotating body, the fixing members which are opposed to each other are in pressure contact with each other, and the separation claw for preventing the winding of the paper is always in pressure contact. Exposure and constant stress.

Accordingly, the heat-resistant elastomer or heat-resistant resin having excellent releasability coated on the rotating body of the fixing device is limited to silicone-based or fluorine-based polymer materials such as fluororubber, silicone rubber and fluororesin. Have been.
However, these polymer materials have good releasability, but have low adhesion to a carrier such as a metal, and it is difficult to directly cover them as a surface layer when manufacturing a heating roller.

Therefore, as a method of coating a fluororesin having low adhesiveness on a carrier surface, a method of interposing an adhesive member called a primer between the fluororesin layer and the metal surface has been proposed.

For example, in the case where a PFA resin is used as a fluororesin, Japanese Patent Application Laid-Open No. 57-177067 discloses a polyimide precursor obtained by a reaction between pyromellitic anhydride and diaminodiphenyl ether or diaminodiphenyl ether or diaminodiphenylmethane. A method has been proposed in which a hollow cored bar and a PFA resin layer are bonded via a bonding primer containing a PFA resin. JP-A-63-112677 discloses an aromatic polyimide precursor obtained by reacting pyromellitic anhydride and 4,4'-diaminodiphenyl sulfone as main components in a mixed solvent of a water-soluble organic solvent and water. Or a product obtained by neutralizing the free carboxylic acid with an amine or PF
Adhesive primer containing resin A, hollow core metal and P
A method of adhering to an FA resin layer has been proposed.

In the case of using a PTFE resin instead of a PFA resin as a fluororesin, US Pat.
No. 049,863 contains PTFE, colloidal silica, and polyamideimide (PAI).
Shown is a primer having an AI ratio of 1: 9, which may be applied to grid blasting, flame spraying of metal or metal oxide or frit coating,
Alternatively, it has been proposed to coat a metal core roll surface-treated with phosphoric acid or chromic acid so that the dry film thickness is 2 to 15 μm. US Patent 3,8
No. 01,379, 5-20% PT was added to the aluminum substrate after the core roll surface was treated with hot water or steam.
It has been proposed to coat FE-containing poly (arylene sulfide). Canadian Patent 88
7, 122 proposes coating with a gradient structure using PAI and PTFE. Further, in British Patent 1,512,495, P containing PTFE powder
It is proposed that the minimum ratio of PTFE to PAI in the AI coating is 1: 7.

Japanese Patent Application Laid-Open No. 64-1534 discloses an example of a fixing member used in an electrophotographic image forming apparatus in which a fluororesin layer and a carrier such as a metal are adhered by a primer. There has been proposed a fluororesin-coated cylindrical part obtained by heating and fusing a tube made of a thermofluid fluororesin containing a filler to a cylindrical part which has been surface-treated with a primer containing a fluororesin in advance. Also, JP-A-4-8543 and JP-A-4-4.
JP-A-5931 and JP-A-4-78533 propose a fluororesin-coated cylindrical part obtained by heating and fusing a fluororesin tube to a cylindrical part having a primer layer containing a polyparapanoic acid resin or a polyimide resin. I have.

These primers are mainly composed of a heat-resistant resin such as polyamide, polyimide, polyamide-imide, polyarylene sulfide, etc., and the carrier and the fluororesin are bonded using the above-mentioned bonding primer. In the case or in a fixing member in which a fluororesin layer and a carrier such as a metal are adhered by a primer, the adhesion between the fluororesin layer and the carrier such as a metal provides good results in an initial stage, but the electrophotographic method is used. Under the severe use conditions of the fixing member used in the image forming apparatus, there is a problem that deterioration with time occurs, and the carrier and the fluororesin are easily peeled off with time, and a long life cannot be obtained. ing.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a fixing member used in an electrophotographic image forming apparatus, which comprises a carrier and a fixing member. An adhesive layer having excellent heat resistance, adhesion to the carrier, and adhesion to the fluororesin layer is provided between the fluororesin layer and the fluororesin layer even under the severe conditions described above. In particular, an object of the present invention is to provide a fixing member which is hardly peeled off from metal and has excellent durability.

[0015]

As a result of intensive studies, the inventors have found that a layer having a fluororesin and a silicone-modified polyimide is provided between the metal carrier and the fluororesin layer forming the outermost layer. As a result, it was found that the adhesiveness between the metal carrier and the fluororesin layer forming the outermost layer was improved, and the present invention was completed.

That is, the present invention provides a fixing member having a layer on a carrier, wherein the layer comprises an adhesive layer having a first fluororesin and a silicone-modified polyimide;
And the outermost layer made of a fluororesin.

In the fixing member according to the present invention, the adhesive layer is made compatible with the fluororesin when the silicone-modified polyimide having excellent adhesion to metal and the fluororesin of the outermost layer are heat-fused to form an adhesive layer. Is composed of fluorocarbon resin so that the boundary of the metal forms an inclined structure, so that the adhesion between metal and fluorocarbon resin is improved as compared with the conventional fixing member, and heat resistance, heat cycle resistance, stress resistance, etc. are improved. Has excellent action.

Therefore, according to the present invention, there is provided a fixing member for use in an electrophotographic image forming apparatus, which can be used under severe conditions such as being constantly exposed to heating and cooling cycles and mechanical stress. In addition, there is provided a fixing member which is excellent in durability as compared with a conventional fluororesin-coated fixing member using a primer without causing a change with time or exfoliation of a fluororesin from a metal for a long period of time.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The carrier may be based on an inorganic material, or may be based on a heat-resistant resin containing an inorganic material as a filler. Examples of the inorganic material include metals having good heat conductivity, such as aluminum, copper, and nickel, alloys such as stainless steel, silver alloys, and nickel alloys, and ceramics.
Examples of the heat-resistant resin containing an inorganic material as a filler include metals, SiO ₂ , TiO ₂ , Al ₂ O ₃ , MgO,
Heat resistant resins such as polyamides, polyamideimides, polyimides, polyarylene sulfides, and polyethers to which inorganic oxides such as CaO and Fe ₂ O _3, and fine particles of SiC (silicon carbide) and BN (boron nitride) are added.

When an inorganic material is added to the heat-resistant resin as a filler, the content of the inorganic material as the filler in the carrier is preferably 0.1% by weight or more and 50% by weight or less, and more preferably 1% by weight or more. More preferably, it is not more than 30% by weight. In addition, the average particle diameter of the inorganic material as a filler,
It is desirable to set it to a range of 5 μm or less. If the average particle size exceeds 5 μm, there is a possibility that the particles may easily fall off from the heat-resistant resin. Further, in consideration of dispersibility, those having an average particle diameter of 0.001 μm or more are more preferable.

When the carrier is made of an inorganic material such as a metal, the carrier is provided in the form of, for example, a roll of a hollow metal core or a belt of a Ni electroformed sheet. When composed of resin, the carrier is provided in the form of, for example, a belt of a polyimide film or the like, but is not limited thereto.
The surface of the carrier may be subjected to a surface treatment to firmly adhere the adhesive layer. For example, in the case of a metal surface, a degreasing treatment using an organic solvent or the like and a roughening treatment by sandblasting or the like can be performed.

Next, the adhesive layer among the layers formed on the carrier will be described. The adhesive layer of the present invention has a first fluororesin and a silicone-modified polyimide.

The first fluororesin of the present invention is preferably a resin having excellent heat resistance in order to heat the fixing member so that it can be continuously used at 200 ° C. or higher.
E, PFA, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and the like are preferable. Among them, PFA is particularly preferable in that it has excellent durability against mechanical stress.

The fluororesin is blended with the primer in the form of a powder or a dispersion. The fluororesin in the primer is melted by the heat applied when forming the outermost layer to compatibilize the fluororesin in the outermost layer. And it mix | blends for the purpose of making the density | concentration of the fluororesin of the boundary of an outermost layer and an adhesive layer form a gradient structure, and a fluororesin and a primer adhere firmly.

The silicone-modified polyimide of the present invention includes the following general formula (1) containing a polysiloxane unit:
And those obtained by reacting as a monomer at least one of a diamine represented by the following general formula (2) containing a tetracarboxylic dianhydride represented by and a polysiloxane unit. General formula (1)

[0026]

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In the formula, R ₁ is a trivalent aliphatic group or aromatic group, the acid anhydride skeleton is a 5- or 6-membered ring, and has 6 to 50 carbon atoms. R ₂ and R ₃ are a monovalent aliphatic group or an aromatic group, and R ₂ and R ₃ may be different from each other. n
Represents an integer of 1 to 100. Specifically, as R ₂ and R ₃ , an aliphatic group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group and an aromatic group such as a phenyl group are used. Among them, a methyl group, an ethyl group and a phenyl group are preferred. Further, n is preferably in the range of 1 to 10 from the viewpoint of adhesiveness to the carrier and heat resistance. General formula (2)

[0028]

Embedded image

In the formula, R ₄ and R _{5 each} have a divalent carbon number of 1 to 1.
0 aliphatic group or an aromatic group having 6 to 50 carbon atoms,
R ₄ and R ₅ may be different from each other. R ₆ and R ₇ are a monovalent aliphatic group or an aromatic group, and R ₆ and R ₇ may be different from each other. n represents an integer of 1 to 100. Specifically, examples of R ₄ and R ₅ include a methylene group, an ethylene group, and a phenylene group, and a phenylene group is preferable from the viewpoint of heat resistance. Examples of R ₆ and R ₇ include an aliphatic group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an iso-butyl group and a tert-butyl group, and an aromatic group such as a phenyl group. Groups, ethyl groups and phenyl groups are preferred. Further, from the viewpoint of adhesiveness to the carrier and heat resistance, n
Is preferably in the range of 1 to 10.

As the combination of the monomer components, a tetracarboxylic dianhydride represented by the general formula (1) and another diamine, or a diamine represented by the general formula (2) and another tetracarboxylic dianhydride, or There is a combination of a tetracarboxylic dianhydride represented by the general formula (1) and a diamine represented by the general formula (2).

Other tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′,
3,3′-benzophenonetetracarboxylic dianhydride,
2,3,3 ', 4-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride , Naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7
-Tetracarboxylic dianhydride, 4,8-dimethyl-1,
2,3,5,6,7-hexahydronaphthalene-1,
2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,
6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, 2,3,6
7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3, 3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4-diphenyltetracarboxylic dianhydride 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3"
-P-terphenyltetracarboxylic dianhydride, 2,
3,3 ", 4" -p-terphenyltetracarboxylic dianhydride,

2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (2,3-
Dicarboxyphenyl) ether dianhydride, bis (2,
3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3
8,9-tetracarboxylic dianhydride, perylene-3,
4,9,10-tetracarboxylic dianhydride, perylene-
4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,1
0-tetracarboxylic dianhydride, cyclopentane-1,
2,3,4-tetracarboxylic dianhydride, pyrazine-
2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride,
Examples include, but are not limited to, 4,4'-oxydiphthalic dianhydride.

Other diamines include 3,3
3′-dimethyl-4,4′-diaminobiphenyl, 4,
6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 4,4′-methylenedi-o-toluidine, 4,
4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino-diphenyl propane,
3,3′-diamino-diphenylpropane, 4,4′-
Diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4 '
-Diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,
3'-diamino-diphenyl ether, benzidine,
3,3′-diaminobiphenyl, 3,3′-dimethoxybenzidine, 4,4 ″ -diamino-p-terphenyl,
3,3 "-diamino-p-terphenyl,

Bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl) -4-aminopentyl)
Benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,
6-diaminonaphthalene, 2,4-bis (β-amino-
t-butyl) toluene, 2,4-diaminotoluene, m
-Xylene-2,5-diamine, p-xylene-2,5
-Diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, 1,4-diamino -Cyclohexane, piperazine, methylenediamine, ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, hepta Methylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4
-Dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylnonamethylenediamine,
Decamethylenediamine, 1,10-diamino-1,10
-Dimethyldecane, 2,11-diaminododecane, 1,
Examples include, but are not limited to, 12-diaminooctadecane, 2,17-diaminoicosane, 1,3-bis (3-aminophenoxy) benzene.

Since these silicone-modified polyimides have better adhesiveness to inorganic materials such as metals than polyimide which is a heat-resistant resin conventionally used for the adhesive layer, the carrier and the adhesive layer are firmly bonded. It is blended for the purpose of binding.

The compounding ratio of the first fluororesin and the silicone-modified polyimide is from 90:10 to 1 by weight.
It is preferably in the range up to 0:90, and 70:30
More preferably in the range from 30:70 to 30:70.
If the compounding ratio of the first fluororesin exceeds 90% by weight, the adhesiveness between the carrier and the adhesive layer is impaired, while if the compounding ratio of the silicone-modified polyimide exceeds 90% by weight, the fluorine of the outermost layer This is because the adhesiveness between the resin and the adhesive layer is impaired.

In the adhesive layer of the present invention, a filler may be appropriately compounded in order to improve the strength of the adhesive layer. These fillers can be used as long as the adhesion between the carrier and the adhesive layer and between the adhesive layer and the fluororesin layer and the degree of releasability required as a fixing member are not impaired.

As the filler, metal or SiO_Two, TiO
_Two, Al_TwoO_Three, MgO, CaO, Fe_TwoO_ThreeSuch as nothing
Oxide, SiC (silicon carbide), BN (boron nitride),
Si _ThreeN_FourUsing fine particles of inorganic materials such as (silicon nitride)
Can be Among them, excellent heat resistance and durability,
Fe is inexpensive,_TwoO_Three(Bengara) especially
preferable. When adding an inorganic filler to the adhesive layer, the adhesive layer
Content of the inorganic filler is 0.1% by weight or more and 50% or more.
% By weight or less, preferably 1% by weight or more and 30 weights
More preferably, the amount is not more than%. Also, inorganic filler
It is desirable to set the average particle size of the
Good. If the average particle size exceeds 5 μm, it will come off the adhesive layer.
It may be easy to drop. In addition, consider dispersibility
In this case, those having an average particle diameter of 0.001 μm or more are more preferable.
Good.

The adhesive layer of the present invention comprises the above-mentioned silicone-modified polyimide or its precursor and the above-mentioned fluororesin powder or its dispersion,
Dissolves in water-soluble organic solvents such as pyrrolidone, furfuryl alcohol, butanol, isopropanol, and ethanol.
It is formed by applying the adhesive primer solution obtained by mixing to the surface of the carrier. In order to improve the dispersibility of the fluororesin, a surfactant such as polyoxyethylene phenyl ether may be added.

The silicone-modified polyimide may be mixed with the bonding primer solution in a polyimide state in which aromatic tetracarboxylic dianhydride and diamine, which are monomers, are completely dehydrated and condensed. You may mix | blend with the adhesive primer in the state of the polyamic acid which is the precursor which carried out dehydration condensation. From the viewpoint of processability and handleability, it is preferable to blend the polyamic acid into the adhesive primer.

As a coating method, a dip method, a spin method, a spray method, a roll coating method and the like can be used, but a dip method and a spray method are preferred. The film thickness is 1 to 50 μm
Is more preferable, and the range of 5 to 20 μm is more preferable. Drying is performed by heating or air drying.

Next, of the layers formed on the carrier, the second
The outermost layer made of the above fluororesin will be described.

As the second fluororesin forming the outermost layer of the present invention, a resin having excellent heat resistance is preferable in order to heat the roller so that it can be continuously used at a temperature of 200 ° C. or higher. In terms of durability against stress and releasability,
Perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer, polytetrafluoroethylene, hexafluoropropylene-tetrafluoroethylene copolymer, and polyhexafluoropropylene are particularly preferred.

In the outermost layer of the present invention, a filler or other resin may be appropriately blended in order to enhance the durability against heat stress such as abrasion and the heat resistance. These fillers and other resins can be used as long as the adhesion between the carrier and the adhesive layer and between the adhesive layer and the fluororesin layer and the degree of releasability required for the fixing member are not impaired.

As the filler, metal or SiO_Two, TiO
_Two, Al_TwoO_Three, MgO, CaO, Fe_TwoO_ThreeSuch as nothing
Oxide, SiC (silicon carbide), BN (boron nitride),
Si _ThreeN_FourUsing fine particles of inorganic materials such as (silicon nitride)
Can be Among them, mechanical resistance such as heat resistance and wear
In terms of excellent resistance to tress, Si
C, BN, Si_ThreeN_FourIs particularly preferred. Inorganic filler
When added to the outer layer, the content of inorganic filler in the outermost layer
Preferably, the amount is from 5% by weight to 50% by weight.
More preferably, the content is 5% by weight or more and 15% by weight or less.
New The average particle size of the inorganic filler depends on the required film thickness.
It is desirable to set the range appropriately to 10 μm or less.
No. If the average particle size exceeds 10 μm, it will fall off the outermost layer
May be easier to do. Also consider the dispersibility
For example, those having an average particle diameter of 0.001 μm or more are more preferable.
New

As other resins, heat-resistant resins such as polyamide, polyimide, polyamideimide, polybenzimidazole, polyarylene sulfide, polyether, polyketone, aromatic polyester, and silicone resin can be used. From the viewpoint that the moldability is not impaired, a polymer in which either a perfluoroalkyl group or a fluorine-substituted aromatic ring is introduced into the skeleton of a silicone resin or these heat-resistant resins is particularly preferable. When another resin is added to the outermost layer, the content of the other resin in the outermost layer is preferably from 1% by weight to 50% by weight, more preferably from 5% by weight to 20% by weight. . The softening point of the other resin due to heat is preferably equal to or higher than the softening point of the fluororesin.

The outermost layer of the present invention is formed by forming the adhesive layer and then coating the adhesive layer with the fluororesin layer in a dry or wet state. The outermost layer made of a fluororesin is formed by uniformly applying a fluororesin powder or a dispersion of the fluororesin powder by a method such as a dipping method or a spray method, and then baking at a temperature at which the fluororesin melts, or a fluororesin tube. Is formed by heat shrinking.

The thickness of the outermost layer is preferably from 0.1 to 100 μm, more preferably from 5 to 40 μm. If the thickness is too small, the release layer on the surface is worn out over a long period of use, and the adhesive layer and the surface of the metal core roll are exposed, so that the releasability is greatly reduced. Also, if it is too thick, thermal conductivity will deteriorate,
It takes a long time to warm up.

The fixing device of the present invention is a fixing device for heating and fixing a toner image on a transfer member, wherein the fixing member in contact with the toner image on the transfer member has a layer on a carrier. As this layer, there is an adhesive layer having a first fluororesin and a silicone-modified polyimide, and an outermost layer made of a second fluororesin.

It is preferable that the fixing member that comes into contact with the toner image on the transfer member has a heating source. As a fixing device that heats and fixes the toner image on the transfer member, a heating device may be used. A fixing device including a pressing belt that presses the roll and the heating roll and a pressing roll that presses the pressing belt from behind. A fixing device including a heating roll and a pressure roll that presses the heating roll. A fixing device including a heating belt and a pressing member that presses the heating belt from the inside and a pressing roll at a position facing the pressing member. There is a fixing device that includes a heating belt and a pressing member that presses the heating belt from the inside and a pressing roller that is provided at a position facing the pressing member via a pressing belt.

That is, in the above-mentioned fixing device, an adhesive layer having a first fluororesin and a silicone-modified polyimide and a second fluororesin are formed on a heating roll or a heating belt in contact with a toner image on a transfer member. And an outermost layer.

The image forming method of the present invention comprises the steps of forming a latent image on a latent image holding member, developing the latent image using a developer, transferring the developer onto a transfer member, And fixing the image on the transfer member.

In the step of fixing the developed image on a transfer member, a layer is provided on a carrier, and the layer includes an adhesive layer having a first fluororesin and a silicone-modified polyimide, and a second fluororesin. There is no particular limitation as long as a fixing member having an outermost layer composed of Each of these steps is a general step itself, and is described in, for example, JP-A-56-40868, JP-A-49-91231, and the like. The image forming method of the present invention can be carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.

[0054]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of Adhesive Primer Solution) Water, N-methyl-2-pyrrolidone and furfuryl alcohol were mixed in 4: 2: 1, respectively.
20 parts by weight of a polyamic acid represented by the following formula (3) as a precursor of a silicone-modified polyimide, and a concentration of 60 wt% of PFA particles (average particle diameter: 0.2 μm) dispersion per 100 parts by weight of a solvent mixed at a ratio of Was added and 11 parts by weight of Fe ₂ O ₃ (tongue, particle size: 0.1 μm) as an inorganic filler was added, and then uniformly mixed and dispersed to prepare an adhesive primer solution.

[0056]

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(Preparation of Heating Roll 1 in FIG. 1) As a carrier, an aluminum hollow metal core 2 having an outer diameter of 50 mmφ, which has been subjected to a degreasing treatment and a roughening treatment by sandblasting, is prepared, and the above-mentioned adhesive primer solution is applied by spraying. 150
After drying at 5 ° C. for 5 minutes to form an adhesive layer, a PFA powder resin paint is uniformly applied by an electrostatic coating method, and a curing process and a PFA film forming process are performed at 375 ° C. for 30 minutes. Was formed. After firing, the surface was polished with a polishing film to obtain a heating roll 1. In addition, the film thickness after drying of the primer solution was 11 to 13 μm, and all the film thicknesses after forming the PFA film were 47 to 52 μm.

(Evaluation of Heating Roll 1 in FIG. 1) Using this heating roll 1, the peel strength between the metal surface and the adhesive layer was measured. The peel strength was evaluated by a peel test using a load cell shown in FIG. The peeling test method using a load cell means that the surface of the heating roll 1 as a test object is cut in a circumferential direction to a width of 1 cm with a knife, and the outermost layer 104 and a part of the adhesive layer 102 of the metal core 100 as a carrier are removed. Peeling is performed, and the end 106 is attached to a chuck of a peeling tester, and the strength at the time of peeling at 90 ° in the circumferential direction is measured. Table 1 shows the results. Further, the heating roll 1 was placed in a fixing unit having the same configuration as that of FIG. 1 of a copying machine (Vision 550: manufactured by Fuji Xerox Co., Ltd.), and a paper passing durability test was performed at a surface temperature of 200 ° C. Did not occur.

[0059]

[Table 1]

Example 2 Preparation of a heating roll 1 and preparation of a heating roll 1 were carried out in exactly the same manner as in Example 1 except that the precursor of the silicone-modified polyimide was changed to a polyamic acid represented by the formula (4) in the preparation of the adhesive primer solution. An evaluation was performed. Table 1 shows the measurement results of the peel strength.
Shown in Further, in the paper passing durability test, no abnormality occurred even for 500,000 sheets.

[0061]

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Example 3 The preparation of the heating roll 1 and the preparation of the heating roll 1 were carried out in exactly the same manner as in Example 1 except that the precursor of the silicone-modified polyimide was changed to the polyamic acid represented by the formula (5) in the preparation of the adhesive primer solution. An evaluation was performed. Table 1 shows the measurement results of the peel strength.
Shown in Further, in the paper passing durability test, no abnormality occurred even for 500,000 sheets.

[0063]

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Example 4 A heating roll 1 was prepared and evaluated in exactly the same manner as in Example 1 except that a method of heat shrinking the PFA tube and fusing it was used in forming the outermost layer made of a fluororesin. Table 1 shows the evaluation results of the peel strength. Further, in the paper passing durability test, no abnormality occurred even for 500,000 sheets.

Example 5 (Preparation of Heating Belt 6 in FIG. 3)
O ₂ fine particles (primary particle diameter about 20 nm)
Prepare a 0.2 mm thick polyimide film belt added at a ratio of 0% by weight, apply the same adhesive primer solution as in Example 3 by spraying, and dry at 150 ° C. for 5 minutes to form an adhesive layer. After that, a PFA powder resin paint was uniformly applied by an electrostatic coating method, and a hardening treatment and a PFA film formation treatment were carried out at 350 ° C. for 40 minutes to form an outermost layer. After firing, the surface was polished with a polishing film to obtain a heating belt 6. The film thickness after drying the primer was 11 to 13 μm
Thus, all the film thicknesses after forming the PFA film are 47 to 5
It was 2 μm.

(Preparation of Heating Belt 6 in FIG. 3) Using this heating belt 6, the peel strength between the belt surface and the adhesive layer was measured. Evaluation of the peel strength was performed by a peel test method using a load cell shown in FIG. The peeling test method using a load cell means that the surface of the heating belt 6 as a test object is circumferentially cut into a width of 1 cm with a knife, and the outermost layer 204 and a part of the adhesive layer 202 of the belt 200 as a carrier are peeled off. The end 206 is attached to a chuck of a peeling tester to measure the strength when peeled at 90 ° in the circumferential direction. Table 1 shows the results. Copier (Viva
ce550: Fuji Xerox Co., Ltd.) was replaced with a fixing unit having the same configuration as that of FIG. 3, the heating belt 6 was arranged in the fixing unit, and a paper passing durability test was performed at a surface temperature of 200 ° C. No abnormalities occurred even with 500,000 sheets.

Comparative Example 1 (Preparation of Adhesive Primer Solution) Pyromellitic anhydride and 4,4'-
A primer solution for adhesion was prepared in the same manner as in Example 1 except that a conventional polyimide precursor represented by the following formula (6) produced by reacting diaminodiphenylsulfonic acid was used.

[0068]

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(Preparation of Heating Roll 1 in FIG. 1) In the same manner as in Example 1, a hollow cored bar 2 made of aluminum having an outer diameter of 50 mmφ, which had been subjected to degreasing and sandblasting, was prepared as a carrier. The primer solution is applied by spraying and dried at 150 ° C. for 5 minutes to form an adhesive layer. Then, a PFA powder resin paint is uniformly applied by an electrostatic coating method, and cured at 375 ° C. for 30 minutes, followed by curing.
The outermost layer was formed by performing FA film formation processing. After firing, the surface was polished with a polishing film to obtain a heating roll 1. The film thickness after drying of the primer solution was 10 to 12 μm, and all the film thicknesses after forming the PFA film were 46 to 51 μm.

(Evaluation of Heating Roll 1 in FIG. 1) Evaluation was performed in the same manner as in Example 1. Table 1 shows the peel strength evaluation results.
Shown in In the paper passing durability test, peeling occurred between the carrier and the adhesive layer when the number of sheets exceeded 300,000.

Comparative Example 2 A heating roll 1 was prepared and evaluated in exactly the same manner as in Comparative Example 1, except that the PFA tube was heat-shrinked and fused to form an outermost layer made of a fluororesin. Table 1 shows the evaluation results of the peel strength. In the paper passing durability test, peeling occurred between the carrier and the adhesive layer when the number of sheets exceeded 280,000.

Comparative Example 3 Preparation of a heating roll 1 and preparation of a heating roll 1 were carried out in exactly the same manner as in Example 3 except that no dispersion of PFA particles (average particle size: 0.2 μm) was used in the preparation of the adhesive primer solution. An evaluation was performed. Table 1 shows the peel strength evaluation results.
Shown in In the paper passing durability test, peeling occurred between the outermost layer and the adhesive layer when the number of sheets exceeded 180,000.

Comparative Example 4 (Preparation of Heating Belt 6 in FIG. 3) As in Example 5, SiO ₂ fine particles (primary particle diameter of about 20 n
Using a 0.2 mm thick polyimide film belt to which m) was added as a filler at a ratio of 20% by weight, the same adhesive primer solution as in Comparative Example 1 was applied by spraying.
After drying at 50 ° C. for 5 minutes to form an adhesive layer, PFA
A powdered resin coating was uniformly applied by an electrostatic coating method, and a hardening treatment and a PFA film-forming treatment were carried out at 350 ° C. for 40 minutes to form an outermost layer. After firing, the surface was polished with a polishing film to obtain a heating belt 6. The film thickness after drying of the primer was 10 to 13 μm, and all the film thicknesses after forming the PFA film were 46 to 50 μm.

(Evaluation of Heating Belt 6 in FIG. 3) Evaluation was performed in the same manner as in Example 7. Table 1 shows the peel strength evaluation results.
Shown in In the paper passing durability test, peeling occurred between the carrier and the adhesive layer when the number of sheets exceeded 280,000.

[0075]

According to the fluorine-coated fixing member of the present invention, the adhesive layer has a remarkably improved adhesiveness to an inorganic material such as a metal as compared with the conventional one, and has a high heat resistance, heat cycle resistance, stress resistance and the like. Are better. Therefore, even under severe conditions such as a cycle of heating and cooling or constant exposure to mechanical stress, the adhesive layer is unlikely to change with time, and it is possible to exfoliate between a carrier such as a metal and the fluororesin for a long time. There is an effect that the fixing member does not exist, the life is greatly extended as compared with the conventional fixing member, and the reliability can be improved and the running cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a conventional heat roller type fixing device.

FIG. 2 shows PFA bonded to a carrier via an adhesive layer.
It is a figure which shows the outline | summary of the peeling strength test which evaluates the adhesive strength of resin by a peeling test.

FIG. 3 is a schematic cross-sectional view showing an example of a belt-incorporated fixing device used in a fixing method according to a fifth embodiment of the present invention. It is.

DESCRIPTION OF SYMBOLS 1 Heating roll 2 Hollow core 4, 14, 104, 204 Outermost layer 6 Heating belt 11 Pressing roll 12 Hollow core 13 Elastic layer 21, 22, 26 Heater 23 Pressing pad 24 Belt driving roll Reference Signs List 25 belt transport roll 27 inlet 28 outlet 29 release agent coating device 31 paper 32 toner image 100, 200 carrier 102, 202 adhesive layer 106, 206 end of outermost layer

Claims (11)

[Claims] 1. A fixing member having a layer on a carrier, characterized in that the layer has an adhesive layer having a first fluororesin and a silicone-modified polyimide, and an outermost layer made of a second fluororesin. Fixing member. 2. The silicone-modified polyimide is reacted with at least one of a tetracarboxylic dianhydride represented by the following general formula (1) and a diamine represented by the following general formula (2) as a monomer. The fixing member according to claim 1, wherein the fixing member is obtained. General formula (1) In the formula, R ₁ is a trivalent aliphatic group or aromatic group, the acid anhydride skeleton is a 5- or 6-membered ring, and has 6 to 50 carbon atoms. R ₂ and R ₃ are monovalent aliphatic groups or aromatic groups;
₂ and R ₃ may be different from each other. n is 1 to 100
Represents an integer. General formula (2) In the formula, R ₄ and R ₅ are a divalent aliphatic group having 1 to 10 carbon atoms or an aromatic group having 6 to 50 carbon atoms, and R ₄ and R ₅ may be different from each other. R ₆ and R ₇ are a monovalent aliphatic group or an aromatic group, and R ₆ and R ₇ may be different from each other. n represents an integer of 1 to 100. 3. The fixing member according to claim 1, wherein the adhesive layer contains an inorganic filler. 4. The fixing member according to claim 3, wherein the content of the inorganic filler in the adhesive layer is 0.1% by weight or more and 50% by weight or less. 5. The method according to claim 1, wherein the compounding ratio of the first fluororesin to the silicone-modified polyimide in the adhesive layer is in a range from 90:10 to 10:90. The fixing member as described in the above. 6. The inorganic filler has an average particle size of 5 μm.
The fixing member according to claim 3, wherein: 7. The fixing member according to claim 1, wherein the first fluororesin is a perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer. 8. The resin wherein the second fluororesin is selected from perfluoroalkylvinyl ether-tetrafluoroethylene copolymer, polytetrafluoroethylene, hexafluoropropylene-tetrafluoroethylene copolymer, and polyhexafluoropropylene. The fixing member according to claim 1, wherein: 9. The method according to claim 1, wherein the outermost layer is a layer formed by applying a fluororesin powder or a dispersion, followed by firing, or a layer formed by thermally shrinking the fluororesin tube. The fixing member according to claim 1. 10. A fixing device for fixing a toner image on a transfer body by heating the toner image, wherein a fixing member in contact with the toner image on the transfer body has a layer on a carrier, A fixing device comprising: an adhesive layer having the first fluorine resin and a silicone-modified polyimide; and an outermost layer made of a second fluorine resin. 11. A step of forming a latent image on a latent image holding member,
Developing the latent image using a developer, transferring the developer onto a transfer member, and fixing the developed image on a transfer member. The developed image is transferred by using a fixing member having an adhesive layer having a first fluororesin and a silicone-modified polyimide, and an outermost layer made of a second fluororesin as the layer. An image forming method comprising the step of contact fixing on a body.