JP6174349B2 - Endless cyclic resin film having a metal thin film - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a composite endless annular film in which a metal thin film is laminated on an endless annular resin film with high adhesion and is suitably used as a fixing belt in an image forming apparatus such as a copying machine, a printer, or a facsimile machine. Furthermore, this invention relates to the manufacturing method of the said composite endless annular film.

  2. Description of the Related Art Image forming apparatuses such as copying machines, printers, and facsimiles use fixing devices that heat and fix toner images transferred to paper or the like. In this fixing device, conventionally, the fixing belt is heated by a method using a heating roller (external roller heating method) as an external heating technique, or a method in which a heater provided inside the fixing belt is brought into contact with the fixing belt and heated. In recent years, an induction heating method has been developed in which the fixing belt is heated from the outside by induction heating in order to reduce power consumption and realize energy saving.

  Generally, a resin film such as polyimide is used for the fixing belt. However, it is necessary to laminate a metal thin film on the resin film as an object to be heated in the fixing belt heated by an induction heating method. However, resin films, particularly polyimide films, have a problem of low adhesion to the metal layer. Therefore, conventionally, a technique for improving the adhesion between a resin film and a metal layer in a fixing belt heated by an induction heating method has been reported.

  For example, in Patent Document 1, a conductive metal thin film layer is formed on a resin film, and copper electroplating is performed using this as a cathode to form a copper thick film layer. A technique for enhancing the above is disclosed. In Patent Documents 2 and 3, as a technique for improving the adhesion between the resin film and the metal layer, a conductive material such as metal particles is displaced on one surface of the resin film, and electrolysis is performed using the conductive material as a cathode. A method of laminating a metal layer directly on a resin film by plating is disclosed.

  However, when a metal thin film layer is formed by performing electroplating using a conductive material or conductive metal layer unevenly distributed on the surface of the resin film as an electrode, metal particles such as nickel having a large heat capacity are added to the resin film. As a result, the heat capacity of the fixing belt is increased, resulting in poor energy saving performance. Furthermore, since metals such as nickel and polyamic acid are likely to form a complex, the imidization reaction during the production of the resin film is suppressed, resulting in a decrease in the physical properties of the resin film and a significant increase in the viscosity of the raw material varnish. There is a disadvantage that production becomes difficult. In addition, it is known that when copper is added as a conductive substance, the physical properties of the resin film are significantly deteriorated.

  In Patent Document 4, a polyimide precursor liquid is molded on the outer surface of a polyimide tubular molding core, and before the imide conversion, metal powder is attached to the polyimide precursor molding outer surface to form a metal anchor layer, and then the imide conversion. Then, a method of forming a metal thin film layer on the surface of the metal anchor layer is disclosed. However, since the polyimide precursor is very fragile and difficult to handle, it is not easy to efficiently attach the metal powder to the polyimide precursor.

  Although the adhesion between the resin film and the metal layer is improved by various surface treatments disclosed in these documents, the adhesion is still not satisfactory. From such a background, a metal thin film is laminated on an endless annular resin film with high adhesion, and development of a composite endless annular film that is suitably used as a fixing belt in an image forming apparatus has been desired.

JP 2003-13257 A JP 2003-327723 A JP 2002-248705 A JP 2002-292766 A

  An object of this invention is to provide the technique which improves the adhesiveness of a metal thin film and a resin film in the composite endless annular film by which the metal thin film is laminated | stacked on the resin film.

  The present inventor made intensive studies to solve the above problems, and by exposing at least a part of the filler contained in the endless cyclic resin film to the outer surface, irregularities were formed, and on the surface having the irregularities. It has been found that when the metal thin film is laminated, the adhesion between the metal thin film and the endless cyclic resin film is remarkably improved. The present invention has been completed by further studies based on this finding.

That is, this invention provides the composite endless cyclic | annular film and its manufacturing method hung up below. Item 1. A composite endless annular film in which a metal thin film is laminated on an endless annular resin film, wherein the endless annular resin film contains a filler,
At least a part of the filler contained in the endless cyclic resin film is exposed on the outer surface to form irregularities,
A composite endless annular film, wherein a metal thin film is laminated on the outer surface of the endless annular resin film on which irregularities are formed.
Item 2. Item 2. The composite endless annular film according to Item 1, wherein the filler is exposed on the outer surface of the endless annular resin film by ion bombardment or polishing.
Item 3. Item 3. The composite endless annular film according to Item 1 or 2, wherein the filler is acicular.
Item 4. Any one of Items 1 to 3, wherein the filler is at least one selected from the group consisting of titanium oxide, aluminum borate, alumina, silica, talc, calcium carbonate, barium sulfate, aluminum hydroxide, carbon, and nickel. A composite endless annular film as described in 1.
Item 5. Item 5. The composite endless annular film according to any one of Items 1 to 4, which is used as a fixing member in an image forming apparatus.
Item 6. The manufacturing method of the composite endless cyclic | annular film on which the metal thin film was laminated | stacked on the endless cyclic resin film including the following 1st-3rd process;
A first step of preparing an endless cyclic resin film containing a filler;
The second step of removing the resin on the outer surface of the endless annular resin film obtained in the first step to expose at least part of the filler on the outer surface to form irregularities, and the second step. A third step of laminating a metal thin film on the outer surface of the endless annular resin film.
Item 7. Item 7. The manufacturing method according to Item 6, wherein the second step is performed by ion bombardment or polishing.
Item 8. Item 8. The production method according to Item 6 or 7, wherein the filler is acicular.
Item 9. Any one of Items 6 to 8, wherein the filler is at least one selected from the group consisting of titanium oxide, aluminum borate, alumina, silica, talc, calcium carbonate, barium sulfate, aluminum hydroxide, carbon, and nickel. The production method described in 1.
Item 10. Item 10. The manufacturing method according to any one of Items 6 to 9, wherein the composite endless annular film is a fixing member in an image forming apparatus.

  According to the composite endless annular film of the present invention, the adhesion between the metal thin film and the endless cyclic resin film is remarkably improved. Can be provided with excellent durability without peeling off.

It is a schematic diagram for showing the concept of a major axis and a minor axis about the filler used by the present invention.

1. Composite endless cyclic resin film The endless cyclic resin film of the present invention is a composite endless cyclic film in which a metal thin film is laminated on an endless cyclic resin film containing a filler, on the outer surface on which irregularities of the endless cyclic resin film are formed. The metal thin film is laminated, and the irregularities on the outer surface of the endless cyclic resin film are formed by exposing at least a part of the filler contained in the endless cyclic resin film on the outer surface of the endless cyclic resin film. It is characterized by that. Hereinafter, the endless cyclic resin film of the present invention will be described in detail.

The resin used for the preparation of the endless annular resin film having the irregularities formed on the outer surface thereof is not particularly limited as long as it exhibits heat resistance, Examples of the resin include polyimide, aromatic polyamide, thermotropic liquid crystal polymer, polyester, polyethylene terephthalate, polyethersulfone, polyetheretherketone, polysulfone, polyimideamide, polybenzimidazole, and polyetherimide. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these resins, polyimide is excellent in properties such as heat resistance, flex resistance, flexibility, and dimensional stability, and is preferably used in the present invention. A polyimide is obtained by, for example, synthesizing a polyamic acid (polyimide precursor) from an acid anhydride and an amine compound and imidizing the polyamic acid with heat or a catalyst. The acid anhydride used for the synthesis of the polyimide is not particularly limited. For example, biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, Examples thereof include aromatic tetracarboxylic dianhydrides such as oxydiphthalic dianhydride, diphenylsulfone tetracarboxylic dianhydride, hexafluoroisopropylidene diphthalic dianhydride, and cyclobutane tetracarboxylic dianhydride. In addition, the diamine compound used for the synthesis of polyimide is not particularly limited. For example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4 ′. -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7 -Diamino-dimethyldibenzothiophene-5,5'-dioxide, 4,4'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 1,4-bis And aromatic diamines such as (4-aminophenoxy) benzene.

  Although there is no restriction | limiting in particular about the thickness of the said endless cyclic resin film, For example, 20-120 micrometers, Preferably it is 30-110 micrometers, More preferably, 40-90 micrometers is mentioned.

  In the present invention, the endless annular resin film having irregularities formed on the outer surface thereof is formed by exposing at least a part of the filler to the outer surface in an endless annular resin film containing a filler.

  The shape of the filler is not particularly limited, and examples thereof include needles, spheres, plates, spindles, fibers, and irregular shapes. Among these, the needle shape is preferable from the viewpoint of further improving the adhesion between the metal thin film and the resin film. Further, a combination of a needle-like filler and a spherical or amorphous filler can also be used. When using a combination of a needle-like filler and a spherical or amorphous filler, these ratios are not particularly limited, but from the viewpoint of further improving the adhesion between the metal thin film and the resin film, for example, The spherical or amorphous filler is 10 to 80 parts by weight, preferably 10 to 70 parts by weight, and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the needle-like filler.

  About the magnitude | size of the said filler, what is necessary is just to set suitably according to the shape, For example, the average of a major axis is 1-30 micrometers, and the average of a minor axis is 0.1-2 micrometers. In this specification, the average value of the major axis and the minor axis of the filler is taken with a magnification of 1,000 to 50,000 times using an electron microscope (manufactured by Hitachi, Ltd., SEM, S-4800). And it calculates | requires by measuring the filler in the obtained micrograph using a ruler, and calculating the average of the major axis and the minor axis of 20 fillers. Further, in the present specification, the minor axis is a combination of two parallel lines in contact with the outside of the filler particles in the micrograph so as to sandwich the filler particles, and the shortest interval among these combinations The distance between two parallel lines (dotted line in FIG. 1). On the other hand, the major axis is two parallel lines that are perpendicular to the parallel line that determines the minor axis, and two parallel lines that are the longest interval among the combinations of two parallel lines that contact the outside of the filler particles ( It is the distance of the broken line in FIG. The rectangle formed by these four lines is sized to fit the filler particles just within it.

  More specifically, if the filler is needle-shaped, spindle-shaped, or fibrous, the average of the long diameter (fiber length) is 1 to 30 μm, preferably 2 to 20 μm, and the short diameter (fiber diameter). An average is 0.1-2 micrometers, Preferably 0.2-1.5 micrometers is mentioned.

  Moreover, when the said filler is spherical shape or indefinite shape, an average particle diameter is 0.1-5 micrometers, Preferably 0.2-3 micrometers is mentioned. In this specification, an average particle diameter shows the volume average diameter measured with a laser diffraction type particle size distribution meter.

Although the specific gravity of the filler contained in an endless cyclic resin film is not specifically limited, For example, what has a higher specific gravity than resin used for an endless cyclic resin film can be used. By using the filler having such a specific gravity, it can be displaced on one surface of the resin film, and the filler can be efficiently exposed on the outer surface of the endless cyclic resin film. As the specific gravity is higher than the resin used in the endless resin film, for example, a true specific gravity of 2 to 6 g / cm ^3, preferably include fillers 2.5~5g / cm ^3.

As the specific surface area of the filler, for example, 1 to 100 m ² / g, preferably include 1-20 m ² / g.

  Specific examples of the filler include inorganic fillers such as zirconium oxide, magnesium sulfate, barium sulfate, aluminum borate, alumina, titanium oxide, silica, potassium titanate, wollastonite, carbon, talc, and calcium carbonate; nickel, Examples thereof include metal fillers such as cobalt and aluminum. Among these, titanium oxide, aluminum borate, alumina, silica, talc, calcium carbonate, barium sulfate, aluminum hydroxide, carbon, nickel are exemplified as preferred fillers, titanium oxide, aluminum borate, alumina, silica, talc, Calcium carbonate is exemplified as a more preferable filler.

  In the present invention, the filler in the endless cyclic resin film may be dispersed in the film or may be unevenly distributed on the outer surface as long as at least part of the filler is exposed on the outer surface. In the present invention, since unevenness is formed by exposing at least part of the filler on the outer surface of the endless cyclic resin film, the filler is contained in a state of being offset on the outer surface of the endless cyclic resin film. The filler can be efficiently exposed by removing the resin on the outer surface. Examples of the method for localizing (displacement) the filler on the outer surface of the endless cyclic resin film include a method in which the filler is added to a solution containing the resin or a precursor thereof and then centrifugally molded.

  Here, the state in which the filler is displaced on the outer surface of the endless cyclic resin film means that in the endless cyclic resin film, the content of the filler present on the outer surface of the film is larger than the content of the filler present inside the film. This does not necessarily indicate that the filler is present only on the outer surface of the film.

  The endless cyclic resin film having irregularities formed on the outer surface is first prepared an endless cyclic resin film containing a filler, then the resin on the outer surface of the endless cyclic resin film is removed, Manufactured by exposing at least a portion.

  Preparation of an endless cyclic resin film containing a filler can be appropriately performed based on known conditions. For example, if polyimide is used as a resin, a solution containing a polyamic acid synthesized from an acid anhydride and a diamine compound is used. The filler is added to the mixture, and then subjected to centrifugal molding. Thereafter, the temperature is raised between 100 to 450 ° C. at a speed of 1.5 to 2.5 ° C./min in a hot air oven, and the temperature is set to 400 to 450 ° C. for 10 to 60 minutes. Preferably, by performing the heat treatment for 20 to 40 minutes, the polyamic acid is imidized by the heat treatment and converted into polyimide, whereby an endless cyclic polyimide film can be obtained.

  The amount of the filler added is not particularly limited, but from the viewpoint of forming irregularities that can further improve the adhesion to the metal thin film on the outer surface of the endless cyclic resin film, the resin or its The filler is 2 to 30 parts by weight, preferably 3 to 20 parts by weight, and more preferably 5 to 20 parts by weight per 100 parts by weight of the precursor.

  In the centrifugal molding, the heating condition of the rotating drum (mold) is appropriately set according to the type of resin to be used or its precursor, for example, 0.5 to 1.5 ° C./min, preferably When the temperature is raised at a rate of 0.7 to 1.0 ° C./min and reaches 100 to 120 ° C., preferably 110 to 120 ° C., the temperature is maintained.

  In the centrifugal molding, the rotation conditions of the rotary drum may be set as appropriate according to the size of the rotary drum, the type of resin or filler used, and the like, for example, 10 to 120G, preferably 30 to 70G. In the state where the centrifugal force is applied, 90 to 180 minutes, preferably 120 to 160 minutes can be mentioned. More specifically, for example, when a rotating drum having a diameter of about 6 cm is used, it is 60 to 180 rad / second, preferably 80 to 160 rad / second, 90 to 180 minutes, preferably 120 to 160 minutes. It is done.

  The method for removing the resin on the outer surface of the endless cyclic resin film containing the filler is not particularly limited as long as at least a part of the filler can be exposed on the outer surface of the endless cyclic resin film, but for example, ion bombardment Treatment, polishing treatment and the like.

  In the ion bombardment treatment, a gas for generating plasma is introduced into a vacuum vessel, and a high frequency discharge or a direct current discharge is performed to generate a plasma to ionize the gas, which is outside the endless annular resin film containing a filler. This is done by hitting the surface.

In the ion bombardment process, for the setting conditions such as the degree of vacuum, the type of plasma generating gas, the plasma output, the atmospheric temperature, the processing time, etc. What is necessary is just to set suitably so that a filler can be exposed. For example, the degree of vacuum (atmospheric pressure after the introduction of the plasma generating gas) is not particularly limited as long as plasma generation is possible and an effective ion bombardment effect can be obtained, and can be appropriately selected from conventionally known conditions. However, it is usually 1 × 10 ⁻⁴ to 1 × 10 ⁰ Torr. As the plasma generating gas, an inert gas such as Ar or Ne may be used, or an active gas such as oxygen or nitrogen may be used. A mixed gas of an inert gas and an active gas may be used. Examples of the plasma output include 10 to 500 W. The ambient temperature may be in a range where the removal of impurities and the effect of plasma can be ensured, and a range of 25 to 400 ° C., preferably 50 to 200 ° C. is usually mentioned. Moreover, about processing time, it can set suitably according to a vacuum degree, the kind of gas, plasma output, etc., for example, 1 to 120 minutes, Preferably 10 to 60 minutes are mentioned.

  In the polishing process, various polishing methods using a conventionally known polishing tool, an abrasive, and the like can be employed. Examples thereof include polishing with lapping cloth and lapping.

  Polishing with the polishing cloth can be performed by polishing the outer surface of the endless annular resin film containing the filler using the polishing cloth. Abrasive cloth paper is made by applying an adhesive to a flexible cloth, paper, resin film, or other base material, and then bonding an abrasive made of silicon carbide, alumina, gold sand, glass powder, or the like. . A well-known thing can be used for an abrasive cloth, for example, the particle size of abrasive | polishing material is # 12- # 15000, Preferably it is # 40- # 3000, More preferably, it is # 60- # 2000. The polishing process using the polishing cloth can be carried out using a known polishing apparatus. The polishing conditions are not particularly limited as long as the filler can be exposed on the outer surface of the endless cyclic resin film, and can be appropriately set based on conventionally known processing conditions. For example, the endless cyclic resin film Rotational speed of 50 to 3000 mm / sec, preferably 200 to 1500 mm / sec, pressing 0.01 to 0.3 MPa, preferably 0.05 to 0.2 MPa, pressing part moving speed 1 to 50 mm / sec, preferably 1 to A condition of 30 mm / sec is mentioned.

The wrapping process can be performed using an apparatus called a lapping machine or a wrapping machine. More specifically, an endless annular resin film containing a filler is placed on a flat table (called a lapping table or lapping platen), and abrasive grains (between the outer surface of the resin film and a polishing tool (lapping)) A filler is exposed on the outer surface of the endless annular resin film by placing a lapping material) and polishing it by sliding it from above the tool or applying pressure to both the tool and the lapping table. In general, silicon carbide, alumina, diamond or the like is used as the wrap material. In addition, the lapping treatment includes wet lapping in which a working fluid (lapping solution) is added to the lapping agent and dry lapping in which lapping material is embedded in the lapping table and polished, and any method is adopted in the present invention. Also good.

  In the present invention, from the viewpoint of efficiently exposing the filler, ion bombardment treatment and polishing treatment with abrasive cloth are exemplified as preferred methods, and ion bombardment treatment is exemplified as a more preferred method.

  By performing the surface treatment, at least a part of the filler can be exposed on the outer surface of the endless cyclic resin film, thereby forming irregularities on the film surface. The outer surface having the irregularities of such an endless cyclic resin film has a surface roughness (Ra) of usually 0.01 to 10 μm, preferably 0.1 to 5 μm, and can improve the adhesion to the metal thin film. it can.

Lamination of a metal thin film on an endless annular resin film having irregularities The composite endless annular film of the present invention is prepared by laminating a metal thin film on the outer surface on which irregularities of an endless cyclic resin film are formed.

  In the composite endless annular film of the present invention, a metal underlayer may be provided between the metal thin film and the endless annular resin film, if necessary, in order to laminate the metal thin film by electrolytic plating. The metal for forming the metal underlayer is not particularly limited, but preferably nickel, cobalt, aluminum and the like can be mentioned. The method for forming the metal underlayer is not particularly limited, and examples thereof include electroless plating, sputtering, and vapor deposition plating, and preferably electroless plating and sputtering. Although it does not restrict | limit especially about the thickness of a metal base layer, For example, 0.05-3 micrometers, Preferably 0.1-2 micrometers is mentioned.

  The metal thin film is a part to be heated by electromagnetic induction heating. The method for laminating the metal thin film on the surface of the endless annular resin film on which the irregularities are formed is not particularly limited, but from the viewpoint of low cost, manufacturing simplicity, etc., an electrolytic plating method is preferable.

  The type of metal thin film is not particularly limited as long as it can generate heat by electromagnetic induction heating, but examples thereof include metals such as copper, nickel, aluminum, iron, tin, zinc, chromium, gold, and silver. From the viewpoint of imparting excellent conductivity at low cost, copper is preferably used. The metal thin film may be composed of a single metal selected from one of these metals, or composed of an alloy composed of a combination of two or more of these metals. It may be.

  About the thickness of a metal thin film, although it sets suitably according to the kind etc. of metal to be used, 5-30 micrometers is mentioned, for example, Preferably 7-20 micrometers is mentioned.

  Further, in the composite endless annular film of the present invention, a metal protective layer is provided on the surface of the metal thin film (the surface opposite to the surface in contact with the endless annular resin film) in order to impart durability, oxidation resistance, and the like. It may be done. The metal forming the metal protective layer is not particularly limited, but preferably nickel is used. As a method for forming the metal protective layer, a conventionally known method such as a general electroless plating method or an electrolytic plating method can be adopted, and the electrolytic plating method can be mentioned as a preferable method from the viewpoint that it can be manufactured at low cost. Although it does not restrict | limit especially about the thickness of a metal protective layer, For example, 0.05-50 micrometers, Preferably 0.1-10 micrometers is mentioned.

  Further, in the composite endless annular film of the present invention, a resin layer made of a fluororesin having wear properties, triboelectric charging properties, etc. may be laminated on the surface of the metal thin film or the surface of the metal protective layer. Examples of the fluororesin include tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotriethylene. Fluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc. are mentioned. These fluororesins may be used individually by 1 type, and may be used in combination of 2 or more type. Although there is no restriction | limiting in particular about the thickness of the resin layer which consists of a fluororesin, For example, 2-30 micrometers, Preferably 5-20 micrometers is mentioned.

2. Use of the composite endless annular film of the present invention The composite endless annular film of the present invention is suitably used as a fixing member (fixing belt, fixing roll) in an image forming apparatus such as a copying machine, a printer or a facsimile.

  Specifically, the fixing member made of the composite endless annular film of the present invention is arranged as a belt-shaped or roll-shaped fixing unit in various image forming apparatuses, and is composed of a rubber roller or the like while being heated by an induction heating method. It is installed so as to face and press against the pressure roller. In the image forming apparatus, a transfer object on which a toner image is transferred passes between a belt-shaped or roll-shaped fixing unit and a pressure roller, and unfixed toner is heated and melted in the belt-shaped or roll-shaped fixing unit. Then, the image is formed by fixing on the transfer object.

3. Manufacturing method of composite endless annular film of the present invention The composite endless annular film of the present invention is manufactured through the following first to third steps.
First step of preparing an endless cyclic resin film containing a filler, removing the resin on the outer surface of the endless cyclic resin film obtained in the first step to expose at least part of the filler on the outer surface to form irregularities And a third step of laminating a metal thin film on the outer surface of the endless cyclic resin film obtained in the second step.

  About the raw material used at the said 1st-3rd process, process conditions, etc., it is as the above-mentioned "1. composite endless annular film".

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples.

Example 1
Preparation of endless cyclic polyimide film 144.6 g of biphenyltetracarboxylic dianhydride (BPDA) and 53.2 g of p-phenylenediamine (PPD) were subjected to a condensation polymerization reaction in 802.2 L of N-methylpyrrolidone solvent to obtain a solid content of 18 A weight% polyamic acid solution (viscosity 5.1 Pa · s; B-type viscometer (TVB-10M (Toki Sangyo Co., Ltd.), rotor M3, rotation speed 12 rpm, measurement temperature 23 ° C.) was obtained. , Acicular titanium oxide (FTL-400, true specific gravity 4.2 g / cm ³ , fiber diameter D = 0.71 μm, fiber length L = 9.72 μm, specific surface area 2.4 m ² / g, Ishihara Sangyo ( 9 g, N-methylpyrrolidone 445 g as a solvent was added, and uniform dispersion was performed with a homodisper. %, The filler concentration in the solid content was 4.8% by weight.

Next, 73.2 g of the dispersion was poured into a rotary drum for centrifugal molding, and centrifugal molding was performed under the following conditions.
Rotating drum : A metal rotating drum with an inner diameter of 61.54 mm and a width of 520 mm was used, and the rotating drum was placed on two rotating rollers and arranged to rotate with the rotation of the rollers.
Heating temperature : A far-infrared heater is disposed on the outer surface of the rotating drum, and the inner surface temperature of the rotating drum is raised to 110 ° C. at 1 ° C./min. When the temperature reaches 110 ° C., this temperature is maintained. did.
First, 73.2 g of the dispersion was uniformly applied to the inner surface of the rotating drum while the rotating drum was rotated, and heating was started. For heating, the temperature of the inner surface of the rotating drum was raised to 110 ° C. at 1 ° C./min, and the rotating drum was rotated while maintaining that temperature for 60 minutes. The rotating speed of the rotating drum gradually accelerated with heating, and was maintained when it reached 80 rad / s. After the heating and rotation were completed, the solid endless annular film was taken out from the rotating drum. The resin constituting the obtained endless cyclic film was a polyamic acid containing 16% by weight of N-methylpyrrolidone.

  The obtained endless cyclic polyamic acid film was inserted into a hollow tubular mold having an outer diameter of 60.00 mm and a width of 450 mm, and this was put in a 100 ° C. hot air drying furnace and heated to 450 ° C. at 2 ° C./min. Furthermore, it heated at the temperature for 30 minutes. Thus, the polyamic acid was imidized and the remaining solvent was removed to obtain an endless cyclic polyimide film. The thickness of the obtained endless cyclic polyimide film was 69 μm.

The obtained endless annular polyimide film was again inserted into a hollow tubular mold having an outer diameter of 60.00 mm and a width of 450 mm, and while rotating this, an ion bombard treatment apparatus (a sputter apparatus for plastic films (SBH manufactured by ULVAC, Inc.) −5215RD)), the outer surface of the endless cyclic polyimide film was treated for 30 minutes using argon gas as the atmosphere gas under the conditions of a high-frequency output of 200 W, a temperature of 70 ° C., and a degree of vacuum of 1 × 10 ⁻³ Torr. After the ion bombardment treatment, the surface roughness (Ra) of the endless cyclic polyimide film was measured and found to be 0.324 μm. The obtained endless cyclic polyimide film was subjected to the outer side by X-ray photoelectron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis) using a scanning X-ray photoelectron spectrometer (manufactured by ULVAC-PHI) after ion bombardment. The surface was analyzed. As a result, a peak of titanium was confirmed, and it was shown that titanium oxide as a filler was exposed on the outer surface of the polyimide resin film.

Formation of Metal Underlayer A metal underlayer made of nickel was formed on the endless cyclic polyimide film prepared above (with ion bombarding) under the following conditions.
<Metal underlayer formation (i): electroless plating method>
First, the endless cyclic polyimide film prepared above was immersed in a 30% by weight palladium chloride aqueous solution for 10 minutes, and palladium was supported on the outer surface on which the irregularities of the endless cyclic polyimide film were formed.
Next, 25 g of nickel sulfate, 25 g of sodium hypophosphite, and 50 g of sodium pyrophosphate were dissolved in 1 L of ion-exchanged water and 5% of an endless cyclic polyimide film in which palladium was supported on an aqueous solution adjusted to pH 10 with ammonia water. A metal underlayer made of nickel having a thickness of 1 μm was formed by immersion for 1 minute and electroless nickel plating.

The metal underlayer formed on the endless annular polyimide film laminated with a metal thin film was used as a cathode, and electrolytic copper plating was performed under the following conditions, and a metal thin film made of copper was laminated on the outer surface of the endless annular polyimide film.
An endless polyimide film laminated with a metal thin film was immersed as a cathode in a copper electrolyte adjusted to a temperature of 25 ° C., and electrolysis was performed at a cathode current density of 1 A / dm ² for 10 minutes using a pure copper plate as the anode. . As a result, a composite endless annular film in which a metal thin film made of copper was laminated on the outer surface of the endless annular polyimide film was obtained. In the composite endless annular film, the thickness of the metal thin film made of copper was 10 μm.

Example 2
A composite endless annular film was produced under the same conditions as in Example 1 except that the addition amount of acicular titanium oxide as a filler was 18 g and N-methylpyrrolidone 505 g as a solvent. In Example 2, the solid concentration in the dispersion obtained by dispersing the filler in the polyamic acid solution was 13% by weight, and the filler concentration in the solid was 4.8% by weight.

Example 3
Instead of using acicular titanium oxide as the filler, a composite endless annular film was produced under the same conditions as in Example 1 above, except that particulate titanium oxide (average particle size = 0.39 μm) was used. . The metal underlayer was formed by the following metal underlayer formation (ii) method. Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a titanium peak was confirmed, and titanium oxide as a filler was exposed on the outer surface of the polyimide resin film. It was shown that
<Metal Underlayer Formation (ii): Sputtering>
A sputtering apparatus (a sputtering apparatus for plastic films (SBH-5215RD) manufactured by ULVAC, Inc.) uses argon gas as an atmosphere gas, a high frequency output of 1.5 kW, a temperature of 25 ° C., and a vacuum of 6.0 × 10 ⁻³ Torr. For 30 minutes to form a metal underlayer.

Example 4
The above examples except that instead of using acicular titanium oxide as a filler, particulate titanium oxide (average particle size = 0.40 μm: titanium oxide whose surface was modified to enhance dispersibility) was used. A composite endless annular film was produced under the same conditions as in 1. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a titanium peak was confirmed, and titanium oxide as a filler was exposed on the outer surface of the polyimide resin film. It was shown that

Example 5
Instead of using acicular titanium oxide as a filler, except that particulate aluminum borate (true specific gravity 3.0 g / cm ³ , average particle size = 2.3 μm: manufactured by Shikoku Kasei Kogyo Co., Ltd.) is used. Produced a composite endless annular film under the same conditions as in Example 1 above. The metal underlayer was formed by the method of metal underlayer formation (ii). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA as in Example 1, an aluminum peak was confirmed, and aluminum borate as a filler was exposed on the outer surface of the polyimide resin film. It was shown that.

Example 6
A composite endless annular film was used under the same conditions as in Example 1 except that particulate hydrophobic precipitated silica (average particle size = 4.5 μm) was used instead of acicular titanium oxide as a filler. Manufactured. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a silicon peak was confirmed, and hydrophobic precipitated silica as a filler was found on the outer surface of the polyimide resin film. It was shown to be exposed.

Example 7
Instead of using acicular titanium oxide as a filler, particulate hydrophilic precipitated silica (average particle size = 4.2 μm) was used, and a composite endless annular film was produced under the same conditions as in Example 1 above. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a silicon peak was confirmed, and hydrophilic precipitated silica as a filler was found on the outer surface of the polyimide resin film. It was shown to be exposed.

Example 8
Instead of using acicular titanium oxide as a filler, except that particulate barium sulfate (true specific gravity 4.5 g / cm ³ , average particle size = 0.3 μm, specific surface area 15 m ² / g) was used, A composite endless annular film was produced under the same conditions as in Example 1 above. The metal underlayer was formed by the method of metal underlayer formation (ii). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a barium peak was confirmed, and barium sulfate as a filler was exposed on the outer surface of the polyimide resin film. It was shown that

Example 9
A composite endless annular film was produced under the same conditions as in Example 1 except that particulate aluminum hydroxide (average particle size = 0.66 μm) was used instead of acicular titanium oxide as a filler. did. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, an aluminum peak was confirmed, and aluminum hydroxide as a filler was exposed on the outer surface of the polyimide resin film. It was shown that.

Example 10
Instead of using acicular titanium oxide as a filler, a composite endless annular film was produced under the same conditions as in Example 1 above, except that particulate alumina (average particle size = 2.68 μm) was used. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, the peak of alumina was confirmed, and alumina as a filler was exposed on the outer surface of the polyimide resin film. It was shown that.

Example 11
Instead of using acicular titanium oxide as a filler, a composite endless annular film was produced under the same conditions as in Example 1 except that carbon (average particle size = 0.16 μm) was used. The metal underlayer was formed by the method of metal underlayer formation (ii).

Example 12
A composite endless annular film was produced under the same conditions as in Example 2 except that the treatment with the abrasive cloth shown below was performed instead of the ion bombardment treatment. In addition, when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film was measured after the treatment with the polishing cloth, it was 1.936 μm. The metal underlayer was formed by the method of metal underlayer formation (ii). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a titanium peak was confirmed, and titanium oxide as a filler was exposed on the outer surface of the polyimide resin film. It was shown that
<Treatment with abrasive cloth>
The endless annular polyimide film thus obtained was again inserted into a hollow tubular mold having an outer diameter of 60.00 mm and a width of 450 mm, and while rotating this, the outer surface was applied by # 120 abrasive cloth using a polishing apparatus. Was polished. The treatment was performed at an endless cyclic polyimide film rotation speed of 47 cm / sec, a pressure of 0.1 MPa, and a pressing portion moving speed of 5 mm / sec.

Example 13
A composite endless annular film was produced under the same conditions as in Example 12 except that # 800 abrasive cloth was used in the treatment with the abrasive cloth. In addition, when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film was measured after the treatment with the polishing cloth, it was 0.365 μm. The metal underlayer was formed by the method of metal underlayer formation (ii). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a titanium peak was confirmed, and titanium oxide as a filler was exposed on the outer surface of the polyimide resin film. It was shown that

Example 14
A composite endless annular film was produced under the same conditions as in Example 13 except that # 2000 abrasive cloth was used in the treatment with the abrasive cloth. In addition, when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film was measured after the treatment with the polishing cloth, it was 0.199 μm. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, a titanium peak was confirmed, and titanium oxide as a filler was exposed on the outer surface of the polyimide resin film. It was shown that

Example 15
A composite endless annular film was produced under the same conditions as in Example 12 above, except that particulate nickel (average particle size: 2.5 μm) was used instead of acicular titanium oxide as the filler. In addition, it was 2.97 micrometers when the surface roughness (Ra) of the outer surface of an endless cyclic polyimide film was measured after grinding | polishing cloth paper processing. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA similarly to Example 1, the peak of nickel was confirmed and nickel which is a filler was exposed on the outer surface of the polyimide resin film. It was shown that.

Comparative Example 1
A composite endless annular film was produced under the same conditions as in Example 1 except that the addition of the filler and the ion bombardment were not performed. In addition, it was 0.042 micrometers when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film before forming a base metal layer was measured. The metal underlayer was formed by the method of metal underlayer formation (ii).

Comparative Example 2
A composite endless annular film was produced under the same conditions as in Example 1 except that the ion bombardment treatment was not performed. In addition, when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film before forming the base metal layer was measured, it was 0.363 μm. The metal underlayer was formed by the method of metal underlayer formation (ii). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, no titanium peak was confirmed, and no filler was exposed when ion bombardment was not performed. It has been shown.

Comparative Example 3
A composite endless annular film was produced under the same conditions as in Example 1 except that the following atmospheric pressure plasma treatment was performed instead of the ion bombardment treatment. In addition, when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film after the atmospheric pressure plasma treatment was measured, it was 0.26 μm. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, no titanium peak was confirmed, and no filler was exposed when atmospheric pressure plasma treatment was performed. It has been shown.
<Atmospheric pressure plasma treatment>
The obtained endless annular polyimide film was again inserted into a hollow tubular mold having an outer diameter of 60.00 mm and a width of 450 mm, and while rotating this, it was installed in an atmospheric pressure plasma processing apparatus (manufactured by Enercon) and plasma of argon was obtained. Atmospheric pressure plasma treatment was performed under the condition of 364 W / m ² / min as a gas species.

Comparative Example 4
A composite endless annular film was produced under the same conditions as in Example 11 above, except that the following atmospheric pressure plasma treatment was performed instead of the ion bombardment treatment. In addition, when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film after the atmospheric pressure plasma treatment was measured, it was 0.026 μm. The metal underlayer was formed by the method of metal underlayer formation (i).

Comparative Example 5
Acicular titanium oxide (FTL500 true specific gravity 4.2 g / cm ³ , fiber diameter D = 1.24 μm, fiber length L = 18.3 μm, specific surface area 1.5 m ² / g manufactured by Ishihara Sangyo Co., Ltd.) as a filler A composite endless annular film was produced under the same conditions as in Example 1 except that the following excimer UV treatment was performed. In addition, it was 0.379 micrometer when the surface roughness (Ra) of the outer surface of the endless cyclic polyimide film after the excimer UV treatment was measured. The metal underlayer was formed by the method of metal underlayer formation (i). Moreover, about the obtained endless cyclic polyimide film, when the outer surface was analyzed by ESCA in the same manner as in Example 1, the titanium peak was not confirmed, and the filler was not exposed when the excimer UV treatment was performed. Indicated.
<Excimer UV treatment>
The obtained endless cyclic polyimide film was again inserted into a hollow tubular mold having an outer diameter of 60.00 mm and a width of 450 mm, and while rotating this, an excimer UV irradiation device (USHIO Inc.) Excimer UV light was irradiated in an air atmosphere. The irradiation intensity directly under the excimer lamp was 2 W / cm ² and the irradiation time was 2 minutes.

Evaluation of adhesion In the composite endless annular film produced in Example 1-15 and Comparative Example 1-5, in order to evaluate the adhesion between the metal thin film (copper layer) and the resin film (polyimide resin), the following The test was conducted.

  Each composite endless annular film is stretched at a tension of 2 N / cm on a total of three rolls, one roll (diameter 20 mm), a drive roll (diameter 20 mm) and a tension roll (diameter 20 mm) that can be heated to 230 ° C. The outer peripheral speed of the composite endless annular film was continuously rotated at 100 mm / second for 72 hours. Next, the rotation was stopped, the composite endless annular film was cut open, and 10 strip test pieces having a width of 10 mm and a length of 100 mm were produced. Using this strip-shaped test piece, peel strength (adhesion strength, N / cm) between the resin film and the metal thin film using a peel tester (TRIBOGEARTYPE: 17 JIS P8139 compliant peel rate 200 mm / min, manufactured by Shinto Kagaku Co., Ltd.) Was measured. The peel strength (adhesion strength, N / cm) was obtained by calculating the average value of 10 strip-shaped test pieces.

Results The results obtained are shown in Table 1 below. From this result, the adhesion between the endless cyclic polyimide film and the metal thin film is obtained by exposing at least a part of the filler to the outer surface of the endless cyclic polyimide film containing the filler to form irregularities and laminating the metal thin film thereon. Was significantly improved (Examples 1 to 15 and Comparative Example 2). Moreover, it was shown that the ion bombardment process and the polishing process by abrasive cloth paper are excellent as the surface treatment method for exposing the filler (Examples 1 to 15 and Comparative Examples 3 to 5). Furthermore, it was shown that the adhesion between the endless cyclic polyimide film and the metal thin film is further improved by performing ion bombardment using titanium oxide, aluminum borate, silica, and carbon as fillers (Example 1). -7, 11).

  As a result of the surface analysis (ESCA) of the endless cyclic polyimide film after the ion bombardment treatment or the polishing cloth treatment, a peak indicating that each filler is present on the outer surface was observed, but atmospheric pressure plasma treatment or excimer UV was observed. No peak was observed in the treatment. That is, it was shown that the filler was exposed on the outer surface of the endless cyclic polyimide film by performing ion bombardment or abrasive cloth treatment.

Claims (8)

A composite endless annular film in which a metal thin film is laminated on an endless annular resin film,
The endless cyclic resin film contains a filler,
The filler is at least one selected from the group consisting of titanium oxide, aluminum borate, alumina, silica, talc, calcium carbonate, barium sulfate, aluminum hydroxide, and carbon;
At least a part of the filler contained in the endless cyclic resin film is exposed on the outer surface to form irregularities,
A metal thin film is laminated on the outer surface on which the unevenness of the endless annular resin film is formed,
A composite endless annular film characterized by that.   The composite endless annular film according to claim 1, wherein the filler is exposed on the outer surface of the endless annular resin film by ion bombardment or polishing.   The composite endless annular film according to claim 1, wherein the filler has a needle shape. It is used as a fixing member in the image forming apparatus, the composite endless tubular film according to any one of claims 1-3. The manufacturing method of the composite endless cyclic | annular film on which the metal thin film was laminated | stacked on the endless cyclic resin film including the following 1st-3rd process;
A first step of preparing an endless cyclic resin film containing at least one filler selected from the group consisting of titanium oxide, aluminum borate, alumina, silica, talc, calcium carbonate, barium sulfate, aluminum hydroxide, and carbon ;
The second step of removing the resin on the outer surface of the endless cyclic resin film obtained in the first step to expose at least a part of the filler on the outer surface to form irregularities, and the second step obtained A third step of laminating a metal thin film on the outer surface of the endless annular resin film. The manufacturing method according to claim 5 , wherein the second step is performed by an ion bombardment process or a polishing process. The manufacturing method of Claim 5 or 6 whose said filler is acicular. The manufacturing method according to claim 5 , wherein the composite endless annular film is a fixing member in an image forming apparatus.