JP2000330405A - Fixing member and its production as well as fixing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesion property of a fluororesin to a base material of a fixing member, to enhance paper releasability and wear resistance and to make image quality higher by constituting a high-polymer composition layer from a tight contact layer containing the cyclic fluororesin having a functional group and the outermost layer containing the cyclic fluororesin free of the functional group. SOLUTION: The high-polymer composition layer consists of the tight contact layer containing the cyclic fluororesin having the functional group and the outermost layer containing the cyclic fluororesin free of the functional group. In such a case, a fixing roll 1 is constituted by providing the inside of a cylindrical arbor 1a with a heater lamp 1d, forming an elastic material layer 1b on its outer peripheral surface and further, forming a release layer 1c on the outermost periphery. A pressurizing roll 2 to be arranged in pressurized contact with this fixing roll 1 is constituted by providing the inside of a cylindrical arbor 1a with a heater lamp 2d, forming an elastic material layer 2b on its outer peripheral surface and further, forming a release layer 2c on the outermost periphery. The release layers 1c and 2c are constituted of the previous tight contact layers and the outermost layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing member used in an electrophotographic image forming apparatus, a method for manufacturing the same, and a fixing apparatus, and more particularly, to a fixing member suitable for forming a high-quality full-color image.

[0002]

2. Description of the Related Art In recent years, even in an electrophotographic image forming apparatus, stable use of the apparatus has been promoted from the viewpoint of preventing deterioration of the installation environment of the apparatus and effective use of resources, ensuring high reliability, and There is a need to reduce costs. As one of the measures, it has been studied to eliminate the supply of release oil to the surface of a fixing member such as a fixing roll or a fixing belt. However, if the supply of the releasing oil is eliminated, the releasing property and the abrasion resistance of the fixing member deteriorate.

In particular, a soft roll used for fixing a color image has a remarkable effect of a release agent on abrasion. If a release agent is not supplied, the surface of the soft roll made of silicone rubber or fluororubber becomes several hundred sheets. Scratches and abrasion may occur due to the degree of copying, making it unusable. For this reason, it has been considered that the outermost layer of the soft roll is made of a resin other than rubber, particularly a fluororesin having abrasion resistance.

On the other hand, a heat and pressure type fixing device has a fixing nip in which a fixing roll and a pressure roll are arranged to face each other, and the unfixed toner image is fixed on recording paper by the fixing nip.
Roll-type fixing devices are widely used. For fixing a color image, a soft roll having an elastic layer such as silicone rubber having a thickness of about 1 to 5 mm is used as a fixing roll. In this soft roll, the recording paper on which the unfixed toner image is placed is inserted into the fixing nip and deformed due to the unevenness of the toner, and when the recording paper having the fixed image exits the fixing nip, the deformation will return to the original shape. As a result, the roll is distorted. For this reason, inconveniences such as the recording paper wrapping around the roll via the molten toner and the offset of the molten toner to the roll occur.

On the other hand, in order to obtain a high-quality color fixed image, it is important that the surface of the fixing roll follows the thickness unevenness (formation unevenness) of the recording paper and makes uniform contact over the entire unfixed toner image. It is. If the surface of the fixing roll does not contact uniformly, the degree of melting of the toner in the unfixed toner image becomes non-uniform, causing uneven gloss of the fixed image and lowering the image quality. However, fluororesins generally have a lower elastic modulus than silicone rubber or fluororubber, are less likely to be distorted, and are less likely to follow the formation unevenness of recording paper. Therefore, when the outermost layer is made of a fluororesin, it is important to make the outermost layer as thin as possible so that it can follow the formation unevenness of the roll surface. The thickness of the fluororesin layer depends on the toner material, the elastic layer of the fixing roll, the outer diameter of the fixing roll, and the like, but is usually preferably 30 μm or less.

In order to fix a color image at a high speed and to reduce power consumption, a fixing belt having a release layer formed on a thin metal or a heat-resistant resin such as polyimide is used. When a belt-type fixing device having a fixing nip is used, it is required that the heat capacity of the belt be smaller and the heat conduction be better. Therefore, when a fluororesin layer is formed on such a fixing belt, it is important to make the layer as thin as possible.

In view of the conventional fixing member using a fluororesin, Japanese Patent Publication No. 43-1555 discloses that a fixing roll surface is coated with polytetrafluoroethylene resin (PTFE), It has been proposed to coat a silicone rubber elastic body and further coat PTFE thereon. Japanese Patent Publication No. 58-43740 discloses a fixing member in which a silicone rubber elastic layer is formed around a cored bar, and a perfluoroalkyl vinyl ether copolymer (PFA) whose ether group is specified is coated around the layer. Proposed.

JP-A-55-31494 discloses that a core metal pretreated with a fluoroprimer is coated with perfluoroalkyl vinyl ether copolymer (PFA) particles by an electrostatic coating method, and then the PFA particle layer is coated. 300-425 ° C
To obtain a fluororesin layer having a thickness of 12 to 120 [mu] m. JP-A-63-29838
No. 2 proposes a method of coating a core resin with a fluororesin dispersion liquid (dispersion) such as PTFE, PFA, and FEP, followed by melting and firing.

Japanese Patent Application Laid-Open No. Sho 63-218982 discloses that a fluororesin tube is held in a stretched state, a liquid silicone rubber is injected into the tube, vulcanized and fired to form a fluororesin layer and fixed. It is proposed to get a roll. Japanese Patent Application Laid-Open No. 6-95545 discloses that a specific silicone rubber is interposed between a silicone rubber layer and a fluororesin layer to improve the adhesiveness and to increase the adhesive strength between the silicone rubber layer and the fluororesin layer. Proposed.

However, in these manufacturing methods, 50 μm is required.
When a fluororesin thin film having a thickness of m or less is formed, defects such as pinholes are generated, or a large molding pressure and a large stretching force are required, so that practical use has been difficult. In particular, it was extremely difficult to form a uniform thin film of 30 μm or less.

As described above, since an aliphatic fluororesin is generally insoluble in a solvent, it has been difficult to form a uniform coating film by coating. However, a method has been proposed in which a perfluoropolymer having an alicyclic structure in its main chain is dissolved in a solvent of a perfluoro compound and coated (JP-A-63-238111, JP-A-63-260932). No.). These are cyclic polymers called cycle polymers and amorphous polymers that do not have a melting point.Some of them can be coated by dissolving them in a solvent. There is an advantage that can be formed.

These polymers having a fluorinated aliphatic ring structure have poor adhesion to a substrate such as a fixing member for electrophotography, and easily peel off even if the substrate is coated. For this reason, it has been difficult to form an outermost layer having a thickness of 30 μm or less on a fixing roll or a fixing belt even with this type of fluororesin.

[0013]

[Problems to be solved by the present invention]
Eliminates the above problems, improves the adhesion of the fluororesin to the base material of the fixing member, and excels in paper release properties, abrasion resistance, and high-quality full-color images even when little release oil is used. It is an object of the present invention to provide a fixing member for electrophotography, a method for manufacturing the same, and a heating / pressing fixing device which enable the fixing.

[0014]

The present invention has succeeded in solving the above-mentioned problems by employing the following constitution. (1) In a fixing member for electrophotography having a polymer composition layer on a substrate, the polymer composition layer includes an adhesion layer containing a cyclic fluororesin having a functional group, and a cyclic layer having no functional group. An electrophotographic fixing member comprising an outermost layer containing a fluororesin.

(2) The electron according to (1), wherein the cyclic fluororesin is at least one resin selected from the group represented by the following general formulas (1) to (4). Fixing member for photography.

[0016]

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[0017]

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[0018]

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[0019]

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(3) A cyclic fluororesin wherein the functional group is a carboxylic acid group, a sulfonic acid group, or an alkoxysilyl group, or an ester thereof is used.
The fixing member for electrophotography according to (1) or (2).

(4) The fixing member for electrophotography according to any one of (1) to (3), wherein an elastic layer is interposed between the base material and the adhesion layer. . (5) The fixing member for electrophotography according to (4), wherein the elastic layer is filled with inorganic fine particles or organic fine particles.

(6) The fixing member for electrophotography according to any one of (1) to (5), wherein abrasion-resistant fine particles are added to the outermost layer. (7) The wear resistant fine particles are SiC, SiO ₂ , BN, A
The electrophotographic fixing member according to (6), wherein the fixing member is at least one type of fine particles selected from the group consisting of l ₂ O ₃ , TiN, and CF.

(8) The above (1) to (8), wherein a heat-resistant elastomer is blended with the outermost layer of the cyclic fluororesin.
The fixing member for electrophotography according to any one of (7) and (8). (9) The fixing member for electrophotography according to (8), wherein the heat-resistant elastomer has a higher elastic modulus than the cyclic fluororesin and is soluble in a solvent. (10) The fixing member for electrophotography according to any one of (1) to (9), wherein the cyclic fluororesin of the outermost layer is crosslinked.

(11) The thickness of the polymer composition layer is from 1 to 30.
The fixing member for electrophotography according to any one of the above (1) to (10), which is in a range of μm. (12) The fixing member for electrophotography according to (11), wherein the thickness of the adhesion layer is 1 μm or less. (13) The base material is a metal, glass or ceramic cylindrical roll, or a heat-resistant resin or metal endless belt, wherein (1) to
The fixing member for electrophotography according to any one of (12).

(14) In the method of manufacturing an electrophotographic fixing member for forming a polymer composition layer on a substrate, a solution in which a cyclic fluororesin having a functional group is dissolved in a solvent is used on the substrate. A method for producing a fixing member for electrophotography, wherein an outermost layer is formed using a solution in which a cyclic fluororesin having no functional group is dissolved in a solvent.

(15) The method for producing a fixing member for electrophotography according to (14), wherein after forming an elastic layer on the base material in advance, the adhesion layer and the outermost layer are formed. (16) The elastic layer is subjected to a primer treatment with a coupling agent in advance, and then the adhesion layer is formed.
(15) The method for producing a fixing member for electrophotography according to (15). (17) After forming the adhesion layer, using a solvent to dissolve the cyclic fluororesin having a functional group of the adhesion layer to make it thinner,
Next, the (1) is characterized in that the outermost layer is formed.
4) The method for producing a fixing member for electrophotography according to any one of the above (16) to (16).

(18) An electrophotographic fixing device comprising means for forming a fixing nip by arranging a fixing member and a pressure member to face each other and transferring a transfer sheet having an unfixed toner image to the fixing nip. A fixing device using the fixing member according to any one of (1) to (13).

(19) The fixing device according to (18), wherein a fixing nip is formed by using a fixing roll as the fixing member and a pressing roll as the pressing member. (20) The fixing device according to (18), wherein a fixing nip is formed by using a fixing belt as the fixing member and a pressing roll as the pressing member. (21) The fixing device according to (18), wherein a fixing nip is formed by using a fixing roll as the fixing member and a pressing belt as the pressing member. (22) The fixing device according to (18), wherein a fixing nip is formed by using a fixing belt as the fixing member and a pressing belt as the pressing member.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides an electrophotographic fixing member comprising an adhesive layer containing a cyclic fluororesin having a functional group and an outermost layer containing a cyclic fluororesin having no functional group on a substrate of an electrophotographic fixing member. By providing this, the adhesion of the fluororesin to the base material of the fixing member or the elastic layer coated thereon is improved, and even when little release oil is used, the paper has excellent release properties and abrasion resistance, In addition, it enables full-color high image quality.

The cyclic fluororesin used in the present invention is not particularly limited as long as it has a functional group which is soluble in a solvent and has an adhesive property to the substrate of the fixing member for electrophotography. The cyclic fluororesin having a functional group and the cyclic fluororesin having no functional group used in the present invention may be the same resin except for the presence or absence of a functional group, or may be a combination of different resins.

Specific examples of the cyclic fluororesin that can be used in the present invention include fluororesins having an aliphatic ring structure in the main chain and represented by the general formulas (5) to (8). it can. Examples of the functional group include a carboxylic acid group, a sulfonic acid group, and an alkoxysilyl group, and an ester thereof can also be used. This cyclic fluororesin has a weight molecular weight of 20,000 to 500,000 as measured by gel permeation chromatography (GPC),
Preferably, the range of 50,000 to 300,000 is appropriate. This is because the above resin having a molecular weight in this range is most suitable for coating the fixing member.

In the fixing member of the present invention, first, an adhesion layer made of a cyclic fluororesin having a functional group is formed on a substrate or an elastic layer coated thereon. As a solvent for dissolving this cyclic fluororesin, a solvent of a perfluoro compound such as perfluoro (2-butyltetrahydrofuran) (FC-75: trade name, manufactured by 3M) or perfluorobenzene (Afludo: trade name, manufactured by Asahi Glass Co., Ltd.) is preferable. It is. The dilution concentration is 0.1
-50% by weight, preferably 0.5-20% by weight.

The method for forming the adhesion layer on the substrate is not particularly limited. However, in order to reduce the thickness of the polymer composition layer consisting of the adhesion layer and the outermost layer to a thickness of 30 μm or less and to ensure the uniformity of the outermost layer, a method of coating the above solution on a substrate is preferable. The coating method is not particularly limited as long as the surface of the outermost layer becomes uniform. Specifically, a dipping method, a spin method, a spray method, a roll coating method and the like can be exemplified. After coating, the coating is dried to form an adhesion layer on the substrate. For drying, after drying at room temperature, raise the temperature slowly in the lower temperature range than the boiling point of various solvents,
It is preferable to evaporate the solvent so as to prevent air bubbles from entering and heat and dry.

As the base material of the fixing member of the present invention, in addition to metal, glass, ceramics and the like, heat-resistant rubber such as silicone rubber and fluorine rubber, and heat-resistant resin such as fluorine resin and polyimide can be used. The adhesion layer may be formed directly on the surface of these substrates, or the adhesion layer may be formed on an elastic layer formed on the substrate. The formation of the adhesion layer to the substrate or the elastic layer is performed by chemical bonding via the functional group of the cyclic fluororesin. Note that a primer treatment such as a silane coupling agent may be previously performed on the base material or the elastic layer.

Next, an outermost layer made of a cyclic fluororesin having no functional group is formed on the adhesion layer. As the solvent for dissolving the cyclic fluororesin having no functional group, as in the case of the fluororesin having a functional group, perfluoro (2-butyltetrahydrofuran) (trade name: FC-75, manufactured by 3M) or perfluorobenzene (trade name) : Aflud, manufactured by Asahi Glass Co., Ltd.)
And the like are preferred. The dilution concentration is 0.1
-50% by weight, preferably 0.5-20% by weight.

The method of forming the outermost layer is not particularly limited, but it is preferable to coat the above solution on the adhesion layer, as in the case of forming the adhesion layer. The coating method is not particularly limited as long as the surface becomes uniform as in the case of forming the adhesion layer, and examples thereof include a dip method, a spin method, a spray method, and a roll coating method. After coating, it is dried to form the outermost layer. Drying may be carried out at room temperature, followed by pre-baking at a temperature lower than the boiling point of various solvents to slowly raise the temperature.

The outermost layer of the present invention may contain a filler for improving abrasion resistance and releasability. Filler is Si
At least one selected from the group consisting of C, SiO ₂ , BN, Al ₂ O ₃ , TiN, and CF is used by blending it with a cyclic fluororesin solution having no functional group. The particle size of the filler is appropriately determined according to the thickness of the outermost layer. The filling amount is in the range of 1 to 50% by weight, preferably 1 to 10% by weight of the outermost layer.

In the conventional method of forming a fluororesin tube, it was difficult to form a high-quality fluororesin layer having a thickness of 30 μm or less, and a high-quality fixed image could not be obtained. However, in the fixing member of the present invention, since the fluorine-containing polymer composition layer can be formed by the solution coating method, it is easy to form a submicron to several tens of microns thin layer. The thickness of the fluorine-containing polymer composition layer of the present invention is preferably from 1 to 30 μm to obtain a high-quality fixed image.

Further, since the fixing member of the heating and pressing type fixing device is usually heated to 140 to 200 ° C., when the operating temperature of the fixing member is increased or the operating time is prolonged, the cyclic fluorine having the functional group of the adhesive layer may be used. A part of the resin may re-melt and move to the outermost layer, and eventually the functional groups may be exposed on the surface. Therefore, in the present invention, it is desirable to make the adhesion layer thin, and the thickness of the adhesion layer is 1 μm or less, preferably 0.01 μm or less.
It is appropriate to set it in the range of 0.5 μm.

In order to make the adhesive layer a thin layer having a thickness of 1 μm or less, after forming the adhesive layer on the base material, the adhesive layer is immersed in a solvent such as perfluoroalkane, perfluoroalkylamine, or perfluoro (alkyltetrahydrofuran). Dissolve. Note that it is preferable to apply ultrasonic waves during immersion to accelerate dissolution. By this dissolution, most of the cyclic fluororesin having a functional group is removed except for the part chemically bonded to the base material, and the adhesion layer can be made extremely thin. Then, the outermost cyclic fluororesin can strongly adhere to this extremely thin adhesion layer.

Further, since the cyclic fluororesin formed by the solution coating method can be dissolved in a solvent of a perfluoro compound, the outermost layer is flawed or abraded, and a fixing roll or a fixing belt which has reached the end of its service life is By dissolving and removing the outermost layer with the above solvent and coating the substrate with the outermost layer again, a fixing roll or a fixing belt can be manufactured.

The cyclic fluororesin layer produced in this manner has higher tensile strength and yield strength than conventional fluororesin layers (PTFE, PFE) and is durable.
It is possible to provide a highly reliable fixing member. Further, the conventional fluororesin needs to be heated to about 300 ° C. or more and melted and fired, and there is a possibility that the rubber or resin used as the base of the fixing member may be deteriorated. However, in the solution coating method of the present invention, Since the solvent can be dried and coated at a low temperature, the restrictions on the base material are reduced.

Further, in the conventional method using a resin dispersion or a dispersion type solution, there has been a problem that the fluororesin particles to be dispersed float up on the surface due to the sintering temperature and fall off or peel off to shorten the life. In the present invention, since the cyclic fluororesin layer can be formed by the solution coating method, a uniform layer can be easily formed, so that the above problem does not occur.

In the fixing member of the present invention, a heat-resistant elastic layer such as silicone rubber or fluorine rubber is provided on the outer periphery of a hollow roll made of metal or the like, or on the surface of a belt made of a heat-resistant resin. To form a soft roll or soft belt. In such a fixing member, the outermost layer of the fixing member is deformed while the recording paper on which the toner image is placed is inserted into the fixing nip and is heated and fixed, and when the recording paper is discharged from the fixing nip, the elastic layer is formed. Of the material tends to return to its original shape due to the elasticity of the material. This elasticity serves to suppress winding and offset of the recording paper.

However, the fluororesin generally has a lower elastic modulus than silicone rubber or fluororubber and is less likely to be distorted. If the fluororesin layer of the fixing member is thick, it cannot be deformed, and the distortion is transmitted to the elastic layer. Can not. Then, the above-mentioned elastic layer does not function, and there is a problem that winding and offset occur. Therefore, in the present invention, it is important to reliably transmit the above-mentioned strain to the elastic body layer and to prevent winding and offset by setting the thickness of the cyclic fluororesin layer to 1 to 30 μm, preferably 5 to 20 μm. is there.

When a high-quality color fixed image is to be obtained using the above-mentioned soft roll or the like, the roll surface follows the thickness unevenness (formation unevenness) existing on the recording paper to cover the entire unfixed toner image. It is important that the contact be uniform throughout. If the surfaces of the rolls do not contact uniformly, the degree of melting of the toner in the unfixed toner image varies, resulting in uneven gloss in the fixed image. Fluororesin generally has a lower elastic modulus than silicone rubber or fluoro rubber,
It is difficult to follow such formation unevenness of the recording paper. Therefore, in the present invention, it is desirable that the thickness of the cyclic fluororesin layer be within the above range so that it can follow the formation unevenness.

Further, in order to fix a color image at high speed and not to increase power consumption, a fixing belt in which an annular fluororesin layer is formed on a thin metal film or a heat-resistant resin film such as polyimide is used. It is desirable to form a relatively long fusing nip. At that time, the smaller the heat capacity of the belt is, the better the heat conductivity is. Therefore, when a fluororesin is formed on the fixing belt, it is preferable to make the fixing belt as thin as possible. From this viewpoint as well, the thickness of the cyclic fluororesin layer is preferably set in the above range.

The fixing member is used at a relatively high temperature, but when the rotation of the fixing member is stopped due to a paper jam or the like, the state in which the fixing member is in pressure contact with the pressure roller or the pressure belt at a high temperature is maintained, and the fixing member in the fixing nip is maintained. Deformation may not be recoverable in a short time. In such a case, when the cause of a failure such as a paper jam is removed and restarted, the deformation of the fixing member appears as a mark on the fixed image. In order to prevent this, in the present invention, an elastomer may be added to a cyclic fluororesin having no functional group in the outermost layer to impart elasticity, or the strength may be increased by crosslinking the cyclic fluororesin to increase the strength. Good.

The elastomer is not particularly limited as long as it has a higher elastic modulus than the cyclic fluororesin and is soluble in a solvent, but fluorine rubber and silicone rubber can be used. The fluororubber is a vulcanizable and elastic fluoropolymer, and a conventionally known fluororubber can be used. For example, V
Binary fluororubbers of DF-HFP (vinylidene fluoride-propylene hexafluoride) and ternary fluororubbers of VDF-HFP-TFE (vinylidene fluoride-propylene hexafluoride-tetrafluoroethylene) may be mentioned. As the vulcanization method, any of amine vulcanization, polyol vulcanization and peroxide vulcanization can be used, but polyol vulcanization is most stable and easy to produce. VDF-HFP-TF
Among the ternary fluororubbers of E, there are resinous ones depending on the compounding ratio, and among them, those which are soluble in a solvent may be selected.

Ketones are often used as the solvent for dissolving the fluororubber, and methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) are suitable. They may be used alone or in combination. The dilution concentration is suitably in the range of 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

As the silicone rubber, vinyl methyl silicone rubber, methyl silicone rubber, phenyl methyl silicone rubber, fluorosilicone rubber and the like can be used as raw materials. The vulcanization method includes a thermal vulcanization type (HTV) in which an organic oxide is crosslinked and a room temperature vulcanization type (RT
V), a low temperature vulcanization type (LTV) silicone rubber which is crosslinked by addition polymerization using a platinum catalyst can be used. Formally, silicone rubber powder or the like can also be used. As the solvent for dissolving the silicone rubber, benzene, toluene, xylene and the like are suitable, and they may be used alone or in combination. The dilution concentration is 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

When the outermost layer is formed by mixing an elastomer, a solution in which a cyclic fluororesin is dissolved in a solvent of a perfluoro compound and the above-mentioned elastomer solution are mixed, and coated on the adhesion layer on the substrate. In general, the two solutions are generally immiscible, and it is preferable to coat immediately after stirring well or with stirring. The ratio of the cyclic fluororesin solution to the elastomer solution is 95: 5
The range of 40:60, preferably 90:10 to 70:30 is good. As a coating method, a dip method, a spin method, a spray method, a roll coating method, or the like can be used.

For chemically cross-linking the cyclic fluororesin,
As described in JP-A-6-56936, a crosslinkable fluoropolymer composition comprising a polymer having a fluorinated aliphatic ring structure and having a maleimide group or a -NH ₂ group in the molecule is prepared. Heat crosslinking can be performed by using as a crosslinking agent. Further, as described in JP-A-7-268031, a polymer having a fluorinated aliphatic ring structure having an amidine group or imidoylamidine group at the terminal of the main chain or side chain, or a polymer having a main chain or side chain. A polymer having a fluorine-containing alicyclic structure having a cyano group at a terminal is cross-linked by reacting with ammonia and a polymer having a fluorine-containing alicyclic structure having a cyano group at a terminal of a main chain or a side chain. After coating the solution, it can be cross-linked by contacting with ammonia gas to react.

Further, as described in JP-A-9-144420, a polymer having a fluorine-containing alicyclic structure having a functional group and a compound represented by the formula R ¹ _m R ² _n Si (OR ³ ) _4-mn
(Wherein R ¹ and R ² are the same or different non-hydrolyzable groups, R ³ is an alkyl group, m and n are integers from 0 to 3 satisfying 0 ≦ m + n ≦ 3) Can be cross-linked via a coupling agent having a hydrolyzable group (a site capable of reacting with the partially hydrolyzed condensate) and a non-hydrolyzable group.

Next, the base material of the fixing member used in the present invention will be described. The base material may be a metal roll body such as aluminum, iron, copper, etc., a glass roll body, a ceramic roll body, a metal belt body such as aluminum, iron, copper, etc., or a heat resistant resin belt body such as polyimide. Can be used. In addition,
An elastic layer can be provided on these substrates.

When silicone rubber or fluorine rubber is used as the elastic layer, a general-purpose layer can be used. For example, examples of the silicone rubber include vinyl methyl silicone rubber, methyl silicone rubber, phenyl methyl silicone rubber, and fluorosilicone rubber. Examples of the fluorine rubber include vinylidene fluoride rubber, ethylene tetrafluoride / propylene rubber, ethylene tetrafluoride / perfluoromethyl vinyl ether rubber, phosphazene rubber, fluoropolyether, and other fluorine rubbers. These may be used alone or in combination of two or more.

The elastic layer may contain various inorganic or organic fillers. As the inorganic filler, carbon black, titanium oxide, silica, silicon carbide, talc, mica, kaolin, iron oxide, calcium carbonate, calcium silicate, magnesium oxide, graphite, silicon nitride, boron nitride, iron oxide, aluminum oxide, Magnesium carbonate and the like. Also, as the organic filler, polyimide,
Polyamide imide, polyether sulfone, polyphenylene sulfide and the like can be mentioned. In addition, a fluororesin such as PTFE and PFE can be used as a special elastic body. As the rubber elastic body, those having relatively high rebound resilience are good, and those having 40% or more, preferably 50% or more are effective, and among them, silicone rubber is the best.

The fixing device of the present invention is not particularly limited as long as it melts the powder toner for electrophotography by heating and pressing to fix the toner on the recording paper. FIG. 1 shows a fixing device of a two-roll type. The fixing roll 1 has a cylindrical core 1a.
Has a heater lamp 1d inside, an elastic layer 1b formed on the outer peripheral surface thereof, and a release layer 1c formed on the outermost periphery. The pressure roll 2 which is pressed against the fixing roll 1 is provided with a heater lamp 2d inside a cylindrical cored bar 2a, forms an elastic layer 2b on the outer peripheral surface thereof, and further has a release layer 2c on the outermost peripheral side. Is formed. The release layer 1c of the fixing roll 1 and the release layer 2c of the pressure roll 2 are composed of the adhesion layer and the outermost layer of the present invention. A pressure of 1 to 15 kg / cm ² , preferably 3 to 10 kg / cm ² is applied between the fixing roll 1 and the pressure roll 2. The recording paper 3 having the unfixed toner image 4 is inserted into a fixing nip composed of a fixing roll 1 and a pressure roll 2 and fixed. In the figure, 5 is an oil supply device, 6 is a cleaning device, 7 is a separation claw, and 8 is a temperature sensor.

FIG. 2 shows a fixing roll and a pressure belt type fixing device. The fixing roll 1 is provided with a heater lamp 1d inside a cylindrical cored bar 1a, an elastic layer 1b formed on the outer peripheral surface thereof, and a release layer 1c formed on the outermost peripheral side. The release layer 1c of the fixing roll 1 is composed of the adhesion layer and the outermost layer of the present invention. The pressing belt 9 is stretched by a plurality of rolls, and at least one of the plurality of rolls is in pressure contact with the fixing roll 1 via the pressing belt 9. Further, a fixed pressure pad 10 is provided on a part of the inside of the pressure belt 9 so as to be in pressure contact with the fixing roll 1. The recording paper 3 having the unfixed toner image 4 is inserted and fixed between the fixing roll 1 and the pressure belt 9. The surface layer of the pressure belt 9 can also be constituted by the adhesion layer and the outermost layer of the present invention. In addition,
In the figure, 5 is an oil supply device, 6 is a cleaning device,
7 is a separation claw, and 8 is a temperature sensor.

FIG. 3 shows a fixing device of a fixing belt type and a pressure roll type. The fixing belt 11 includes a cylindrical core 12a.
Roll 12 with heater lamp 12d inside
And a plurality of other rolls. The pressure roll is obtained by forming an elastic layer 2b on the outer peripheral surface of a cylindrical cored bar 2a and further forming a release layer 2c on the outermost periphery. At a part inside the fixing belt 11, there is provided a pressure contact member 13 that presses against the pressure roll 2 via the fixing belt 11. The recording paper 3 having the unfixed toner image 4 is a fixing belt 11
And between the pressure roll 2 and the fixing. The surface layer of the fixing belt 11 and the release layer 2c of the pressure roll 2 are composed of the adhesion layer and the outermost layer of the present invention. In the figure, 5
Is an oil supply device, 6 is a cleaning device, 7 is a separation claw, and 8 is a temperature sensor.

FIG. 4 shows a fixing belt and a pressure belt type fixing device. The fixing belt 11 and the pressure belt 14
At least one is stretched by a plurality of rolls, at least one of which is a heating roll 12 provided with a heater lamp 12d inside a cylindrical cored bar 12a, and a pressurization having an elastic layer 15b formed on the outer peripheral surface of the cylindrical cored bar 15a. Roll 15. The fixing belt 11 and the pressing belt 14 are sandwiched between the heating roll 12 and the pressing roll 15 and are pressed between the other two rolls to form a fixing nip in a certain range of the belt. The recording paper 3 having the unfixed toner image 4 is
1 and the belt 14 are inserted and fixed. In addition, the surface layer of the fixing belt 11 and the surface layer of the pressure belt 14 are configured by the adhesion layer and the outermost layer of the present invention. In addition,
In the figure, 5 is an oil supply device, 6 is a cleaning device,
7 is a separation claw, and 8 is a temperature sensor.

[0062]

EXAMPLES Example 1 (1) Preparation of Fixing Roll Preparation of Coating Solution for Release Layer As a coating solution for an adhesion layer composed of a cyclic fluororesin having a functional group, a carboxyl group was added to a perfluoro solvent. (Asahi Glass Co., Ltd., Cytop (trade name) CTX1)
09MP) was used. As a coating solution for the outermost layer made of a cyclic fluororesin having no functional group, a solution of a cyclic fluororesin dissolved in a perfluoro solvent at a concentration of 9% by weight (Cytop (trade name) CTX, manufactured by Asahi Glass Co., Ltd.)
109SP).

Preparation of Base Roll A hollow core made of aluminum having an outer diameter of 32 mm was prepared as a base material, and an HTV silicone rubber having a rubber hardness of 55 ° was coated thereon as an elastic layer to a thickness of 3 mm. To produce a base roll.

Formation of Adhesion Layer The above-mentioned coating solution for the adhesion layer is applied to a base roll by a dip coating method, dried for 30 minutes at room temperature, and then dried with hot air at 90 ° C. lower than the boiling point of 100 ° C. of the solvent. The solvent was evaporated. Then, the entire base roll is immersed in perfluorooctane so that the thickness of the adhesion layer is 0.1 μm.
m and ultrasonic cleaning to obtain a very thin adhesion layer.

Formation of Outermost Layer The coating solution for the outermost layer was applied to a roll having an adhesion layer by dip coating and dried for 30 minutes at room temperature. The solvent was volatilized by drying with hot air for 1 hour, and further dried at 180 ° C. for 1 hour to form an outermost layer. The coating solution for the outermost layer is further diluted with a perfluoro solvent, and the thickness of the outermost layer is adjusted to 5 by adjusting the pulling speed of the roll.
It was adjusted to μm to obtain a fixing roll. Further, by repeatedly forming the outermost layer, the thickness is reduced to 10 μm and 20 μm.
μm and 30 μm fixing rolls were produced. Hereinafter, fixing rolls having outermost layers having thicknesses of 5 μm, 10 μm, 20 μm, and 30 μm are referred to as fixing rolls 1-5 and 1-1, respectively.
0, fixing roll 1-20 and fixing roll 1-30.

(2) Preparation of pressure roll A hollow core made of aluminum was prepared as a base material, and a base roll coated with HTV silicone rubber having a rubber hardness of 55 ° to a thickness of 1 mm as an elastic layer was prepared. Then, an adhesion layer and an outermost layer were formed in the same manner as in the fixing roll. The thickness of the adhesion layer was about 0.1 μm or less, and the thickness of the outermost layer was adjusted to 10 μm.

(3) Evaluation method by actual machine The above-mentioned fixing roll and pressure roll were mounted on the two-roll fixing device of FIG. 1 so that the fixing nip width was 6 mm, and the actual machine was evaluated. 800 W and 700 W halogen lamps (1d, 2d) were provided as heater lamps inside the fixing roll and the pressure roll, and the fixing temperature was set to 150 ° C. and the fixing speed was set to 100 mm / sec. Fuji Xerox J paper was used as the recording paper, and Fuji Xerox color fuser oil was used as the release agent oil on both roll surfaces in an amount of 1 μl.
/ A4 paper size. The toner was used by adding 5% of wax to a cyan toner manufactured by Fuji Xerox Co., Ltd. The copier was evaluated using the electrophotographic apparatus A Color 635 (manufactured by Fuji Xerox Co., Ltd.) in which the fixing roll pair was partially modified.

Evaluation of Sheet Peelability The unfixed toner image is a belt-shaped solid image formed at a position from 5 mm to 55 mm in the leading end of the recording sheet in the transport direction, and has a toner density of 2.0 mg / cm ^2. . In the evaluation of the releasability of the recording paper, whether the paper was cleanly peeled off from the heating roll was visually evaluated. ：: Peeled cleanly without any concern. △: Slightly peeled off while being hung on a roll ×: Wound on a roll

Image Quality Evaluation The recording paper was changed to L paper manufactured by Fuji Xerox Co., Ltd., and the unfixed toner image was a solid image of 25 mm square, and the toner density was 0.5 mg / cm ² . The image quality was evaluated by visually observing the unevenness of gloss in the image while changing the angle of illumination. ：: Gloss unevenness cannot be discriminated. Δ: Gloss unevenness can be slightly discriminated, but there is no problem in practical use. X: Gloss unevenness is clearly recognized.

Evaluation of abrasion resistance The recording paper used was J paper manufactured by Fuji Xerox Co., Ltd., and the unfixed toner image was an image having an area ratio of 10% composed of characters and pictures. The average toner density of the image portion was 0%. 0.5mg / cm
^{And 2} . For the evaluation of abrasion resistance, the presence or absence of a defect such as a flaw of a fixing roll was observed on the fixed image while passing many unfixed toner images. ：: No defects occurred in the fixed image after passing 10000 sheets, and observation of the fixing roll surface showed no change in the surface such as generation of scratches, wrinkles, falling off rubber, and abrasion. Defects did not occur in the fixed image and the surface of the fixing roll was observed, and slight changes in the surface such as scratches, wrinkles, falling off of rubber, and abrasion were observed, but there was no problem in practical use. Defects occur in the fixed image within 10,000 sheets. Observation of the surface of the fixing roll clearly shows changes in the surface such as scratches, wrinkles, falling off rubber, and abrasion.

(4) Evaluation Results As shown in Table 1, the fixing rolls 1-5 and 1-
No. 10 and the fixing roll 1-20 were evaluated as "good" in the evaluation of the releasability of the paper without any concern, and "good" in the image quality evaluation (non-uniform gloss) because the non-uniform gloss was not discriminated.
The abrasion resistance evaluation was such that no fixed image defect was generated even after passing 10000 sheets, and the surface of the fixing roll was observed by observing the surface of the fixing roll, such as scratches, wrinkles, falling off rubber, and abrasion. It was good because there was no problem.

In the evaluation of the releasability of the paper, the fixing roll 1-30 barely peeled off while being slightly stuck on the roll, and the evaluation was poor. Therefore, the evaluation of the abrasion resistance was as follows. The fixing image did not have any defect even after passing 10000 sheets, and the surface of the fixing roll was observed by observing the surface of the fixing roll.
Since there was no change in the surface such as generation of wrinkles, falling off of the rubber, abrasion, etc., it was evaluated as ○.

Example 2 (1) Preparation of Fixing Roll Preparation of Coating Solution for Release Layer The same coating solution for the adhesion layer as used in Example 1 was used. The coating solution for the outermost layer was prepared by mixing the following fluororubber solution and the following primer in a weight ratio of 50: 50: 5 to the same cyclic fluororesin solution as in Example 1. .

The fluororubber solution was prepared by adding a ternary polyol vulcanized fluororubber (G-602, manufactured by Daikin Industries, Ltd.) to 3 m.
The mixture is cut into small pieces of about m cubes, and is gradually poured into a solvent in which methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK) are mixed at a weight ratio of 80:20, and is stirred to be completely dissolved. A rubber solution was prepared. The primer is tetraethoxysilane (KB, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent.
E04) was used.

Formation of Adhesion Layer A thickness of 0.1 μm was formed on the base roll in the same manner as in Example 1.
The following adhesion layer was obtained. Formation of the outermost layer The coating solution for the outermost layer is applied to a roll having an adhesion layer by a dip coating method, and is dried at room temperature for 30 minutes, and then heated with hot air at 90 ° C lower than the boiling point of the solvent at 100 ° C. After drying for an hour, the solvent was volatilized, and further dried at 220 ° C. for 3 hours to form an outermost layer.

The coating solution for the outermost layer was further diluted with a perfluoro solvent, or the thickness of the outermost layer was adjusted to 10 μm by adjusting the pulling speed of the roll to obtain a fixing roll. Observation of the surface showed a mosaic pattern in which a transparent resin layer and a white rubber layer were mixed. Also,
By repeatedly forming this outermost layer, the thickness becomes 2
Fixing rolls of 0 μm and 30 μm were also prepared. Hereinafter, fixing rolls having the outermost layer thicknesses of 10 μm, 20 μm, and 30 μm are referred to as fixing rolls 1-10, 1-20, respectively.
This is referred to as a fixing roll 1-30.

(2) Preparation of Pressure Roll The same roll as in Example 1 was prepared. (3) Evaluation method using actual machine In the actual machine evaluation of the first embodiment, the same fixing device, toner, recording paper, release agent oil, and electrophotographic apparatus as in the first embodiment were used, except that the above fixing roll was changed. Example 1
In the same manner as in the above, the evaluation of the releasability, the image quality and the abrasion resistance of the paper were performed.

(4) Evaluation Results As shown in Table 1, the fixing roll 2-10 and the fixing roll 2
-20 and the fixing rolls 2-30 were all evaluated as good because the releasability evaluation of the paper was cleanly peeled off without any concern, and the image quality evaluation (non-uniform gloss) was positive because gloss unevenness could not be determined. The abrasion resistance evaluation was such that no defects occurred in the fixed image even after passing 10000 sheets, and the surface of the fixing roll was observed, and there was no change in the surface such as generation of scratches, wrinkles, falling off of rubber, and abrasion. ○, no problem at all.

Comparative Example 1 (1) Preparation of Fixing Roll As in Example 1, an aluminum hollow core was 3 m thick.
After forming an elastic layer of m, a heat-shrinkable tube (manufactured by Gunze Industries, Ltd.) made of a tetrafluoroethylene / perfluoroalkylvinyl ether copolymer (PFA) having a thickness of 30 μm is fixed via a primer layer, and separated. A fixing layer was obtained by forming a mold layer.

(2) Production of Pressure Roll As in Example 1, an aluminum hollow core was 1 m thick.
After forming the elastic layer of m, a heat-shrinkable tube made of PFA (manufactured by Gunze Industries) having a thickness of 30 μm was fixed via a primer layer to obtain a pressure roll.

(3) Evaluation method using actual device The same fixing device as in Example 1 was used in the evaluation of the actual device of Example 1 except that the above-mentioned fixing roll and pressure roll were changed.
Using a toner, a recording paper, a release agent oil, and an electrophotographic apparatus, the same as in Example 1, the evaluation of the peelability of the paper, the evaluation of the image quality,
The abrasion resistance was evaluated.

(4) Evaluation Results As shown in Table 1, in the evaluation of the releasability of the paper, the paper was wrapped around the fixing roll, and the result was x. In the image quality evaluation (the unevenness of the gloss), the unevenness of the gloss was clearly recognized. X.
In the abrasion resistance evaluation, no defect was generated in the fixed image even after passing 10000 sheets, and the surface of the fixing roll was observed and no change was observed such as scratches, wrinkles, falling off of rubber, and abrasion. So it was ○.

Comparative Example 2 (1) Preparation of Fixing Roll As in Example 1, an aluminum hollow core was 3 m thick.
After forming an elastic layer of m, a binary peroxide-based fluororubber having a thickness of 30 μm (G-80, manufactured by Daikin Industries, Ltd.)
2) was fixed via a primer layer to form a release layer to obtain a fixing roll.

(2) Production of Pressure Roll As in the case of the first embodiment, a hollow core made of aluminum was 1 m thick.
After forming an elastic layer of m, a binary peroxide-based fluororubber having a thickness of 30 μm (G-80, manufactured by Daikin Industries, Ltd.)
2) was fixed via a primer layer to obtain a pressure roll.

(3) Evaluation method using actual device The same fixing device as in Example 1, except that the above-described fixing roll and pressure roll were used in the evaluation of the actual device of Example 1,
Using a toner, a recording paper, a release agent oil, and an electrophotographic apparatus, the same as in Example 1, the evaluation of the peelability of the paper, the evaluation of the image quality,
The abrasion resistance was evaluated.

(4) Evaluation Results As shown in Table 1, in the evaluation of the releasability of the paper, the paper was cleanly peeled without winding the paper around the fixing roll, and the image quality evaluation (non-uniform gloss) was evaluated as having non-uniform gloss. Since it could not be discriminated, it was ○. However, the abrasion resistance evaluation was 10,000.
When the sheets were passed, a streak-like defect occurred in the fixed image, and when the surface of the fixing roll was observed, a fatal scratch occurred on the circumference. Therefore, the test was stopped.

[0087]

[Table 1]

[0088]

According to the present invention, by adopting the above-described structure, the adhesion of the fluororesin to the base material and the elastic layer of the fixing member is improved, and even when the release oil is scarcely used, the paper is released. It has excellent moldability and abrasion resistance and enables high-quality full-color fixed images. In particular, by selecting a cyclic fluororesin that is soluble in a solvent and forming a film by a liquid coating method, it is possible to make the fluororesin layer thinner, and as a result, the thickness of the full-color toner image or transfer paper is caused by unevenness. The distortion of the surface of the fixing member is reliably transmitted to the underlying elastic layer. In short, the outermost layer of the fixing member can be reliably deformed and restored following the distortion, so that a high-quality full-color fixed image can be stably obtained. Now you can do it.
In addition, by providing an adhesion layer made of a cyclic fluororesin having a functional group, it is possible to secure adhesion to the base material and the elastic layer, and to form the outermost layer with an inert cyclic fluororesin having no functional group. Thereby, the releasing property and abrasion resistance of the fixing member are secured, and the fixing member can be stably used for a long period of time.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a two-roll type fixing device according to one embodiment of the present invention.

FIG. 2 is a conceptual diagram of a fixing roller and a pressure belt type fixing device according to another embodiment of the present invention.

FIG. 3 is a conceptual diagram of a fixing belt and a pressure roll type fixing device according to still another embodiment of the present invention.

FIG. 4 is a conceptual diagram of a fixing belt and a pressure belt type fixing device according to another embodiment of the present invention.

[Explanation of symbols]

1 fixing roll, 1a cylindrical core, 1b elastic layer,
1c release layer, 1d heater lamp, 2 pressure roll,
2a cylindrical core, 2b elastic layer, 2c release layer, 2d
Heater lamp, 3 recording paper, 4 unfixed toner image, 5 oil supply device, 6 cleaning device, 7
Separation claw, 8 temperature sensor, 9 endless pressure belt, 10 pressure pad, 11 endless fixing belt,
12 heating roll, 12a cylindrical core, 12d heater lamp, 13 pressure contact member, 14 endless pressure belt, 15 pressure roll, 15a cylindrical core, 15b elastic layer.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Daisuke Okuda 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture F-Xerox Co., Ltd. F-term (reference) 2H033 BB05 BB08 BB26

Claims (13)

[Claims] 1. An electrophotographic fixing member having a polymer composition layer on a substrate, wherein the polymer composition layer has an adhesion layer containing a cyclic fluororesin having a functional group and a functional group. And an outermost layer containing a non-cyclic fluororesin. 2. The electrophotographic device according to claim 1, wherein the cyclic fluororesin is at least one resin selected from the group represented by the following general formulas (1) to (4). Fixing member. Embedded image Embedded image Embedded image Embedded image 3. An electrophotographic fixing member according to claim 1, wherein an elastic layer is interposed between said base material and said adhesive layer. 4. An electrophotographic fixing member according to claim 1, wherein wear-resistant fine particles are added to said outermost layer. 5. The fixing member for electrophotography according to claim 1, wherein a heat-resistant elastomer is blended into the outermost layer of the cyclic fluororesin. 6. The fixing member for electrophotography according to claim 1, wherein the outermost cyclic fluororesin is crosslinked. 7. The polymer composition layer has a thickness of 1 to 30 μm.
The fixing member for electrophotography according to any one of claims 1 to 6, wherein m is in a range of m. 8. The fixing member for electrophotography according to claim 7, wherein the thickness of the adhesion layer is 1 μm or less. 9. A method for producing a fixing member for electrophotography, wherein a polymer composition layer is formed on a substrate,
Forming an adhesion layer using a solution in which a cyclic fluororesin having a functional group is dissolved in a solvent, and forming an outermost layer thereon using a solution in which a cyclic fluororesin having no functional group is dissolved in a solvent. A method for producing a fixing member for electrophotography. 10. The method of manufacturing an electrophotographic fixing member according to claim 9, wherein an elastic layer is formed on the base material, and then an adhesion layer and an outermost layer of the polymer composition layer are formed. Method. 11. The method for producing a fixing member for electrophotography according to claim 10, wherein the polymer composition layer is formed after the elastic layer is previously subjected to a primer treatment with a coupling agent. 12. After forming the adhesion layer, a cyclic fluororesin having a functional group of the adhesion layer is dissolved using a solvent to reduce the thickness, and then the outermost layer is formed. Item 12. The method for producing an electrophotographic fixing member according to any one of Items 9 to 11. 13. A fixing device for electrophotography, comprising: a fixing member and a pressure member arranged opposite to each other to form a fixing nip, and a unit for transferring a transfer sheet having an unfixed toner image to the fixing nip. Item 10. A fixing device using the fixing member according to any one of Items 1 to 8.