JP2000248086A - Durable/heat-resistant seamless tubular film and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a seamless tubular film especially free from dimensional change and occurrence of wrinkle in use under pressure at a high temperature and under rotating and driving conditions and to provide its use. SOLUTION: This durable/heat-resistant seamless tubular film comprises 85-99 pts.wt. of a heat-resistant resin having >=70 deg.C heat distortion temperature (e.g. polyimide, fluororesin) and 15-1 pt.wt. of aluminum borate as main components. The durable/heat-resistant seamless tubular film having semiconduction comprises further 1-30 wt.% (based on the resin) of electroconductive carbon black besides the main components. These films are effectively used as a member for transporting an article under pressure at a high temperature and effectively used especially as an intermediate transfer belt 5 also used for fixation in color copying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an improved durability.
The present invention relates to a heat-resistant seamless tubular film and its use, and solves problems such as generation of wrinkles and dimensional changes, which are observed when a belt-shaped belt is repeatedly used for a long time under high temperature and pressure.

[0002]

2. Description of the Related Art When articles are sandwiched between rolls or placed on a belt and transported, particularly when the transport is performed in an environment under high temperature and pressure, the heat resistance of the rolls and the belt itself is important. Of course, it is an extremely important condition that there is no occurrence of wrinkles or dimensional changes, which are observed with repeated use for a long period of time. The degree of these wrinkles and dimensional changes differs depending on the type of the article and the transport accuracy. For example, with regard to multicolor printing using toner copying technology, when using a fixing and intermediate transfer method that performs transfer and fixing simultaneously using a long belt, even slight wrinkles,
Also, dimensional changes are not allowed. This is because the color image fixed on the paper may be misaligned (improper registration) or may have uneven fixing (density unevenness), thereby deteriorating the image quality. In particular, image quality is extremely important in recent years when color copying has become widespread, and it has been demanded that a long-term copying does not allow a drastic change in image quality. It is a fact.

Further, as a material of a fixing belt used under pressure and heat in a toner copying apparatus or a material of a fixing and intermediate transfer belt, a fluorine resin or a thermosetting polyimide is mainly used. This is due to its high heat resistance, excellent mechanical strength, chemical resistance, and excellent releasability.
However, the fact is that it is becoming impossible to answer the above-mentioned request.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems at once. In other words, even under repeated use for a long time under high temperature and pressure, it was obtained as a result of various studies in order to find a seamless tubular film made of resin without wrinkles or dimensional changes, etc., which is solved by the following means. Things.

[0005]

That is, according to the present invention, first, as described in claim 1, 85 to 99 parts by weight of a heat-resistant resin having a heat distortion temperature of 70 ° C. or more and 15 to 1 part of aluminum borate.
This can be achieved by providing a durable and heat-resistant seamless tubular film whose main component is parts by weight. The tubular film is effective for use as, for example, a fixing member of a toner copying machine. (Claim 6)

On the other hand, there is also provided a durable and heat-resistant seamless tubular film in which the conductive carbon black is further contained in an amount of 1 to 30% by weight based on 85 to 99 parts by weight of the heat-resistant resin. As a result, the tubular film according to claim 1 is provided with an electrical property of semi-conductivity. When the semi-conductivity is also provided, various obstacles due to static electricity can be prevented, and conversely, It can be easily charged by performing an external charging operation. Further, if the charge is maintained for a certain period of time, it is easy to remove the charge. The charging and discharging operations are effective for use as a fixing and intermediate transfer belt in a toner copying machine, for example. (Claim 7)

In the first and second aspects, more preferably, a resin (a heat-resistant resin having a heat distortion temperature of 70 ° C. or more) which is a matrix component is a thermosetting polyimide or a fluorocopolymer. It also provides that. (Claim 4)

Aluminum borate contained in a heat-resistant resin as a matrix resin is a seamless tubular film in which the content (dispersion) of the aluminum borate is large on the front surface (relative to the back surface) and is dispersed in an inclined manner. It also provides a dispersion state of aluminum borate, which is preferable. (Claims 1 to 4) The present invention will be described in detail in the following embodiments.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a heat-resistant resin having a heat distortion temperature of 70 ° C. or more, which is a matrix resin constituting a durable and heat-resistant seamless tubular film (hereinafter simply referred to as an SL film) of the present invention, will be described in detail.

In the above resin, the heat deformation temperature is 70 °
C, preferably 100 ° C. and high heat resistance. First, the heat distortion temperature here is JIS K72
It is the Vicat softening temperature measured at the center load of 18.5 kg / cm ² according to the definition of 06. And heat resistance is 100
Even when used continuously at a temperature of 150 ° C. or more, preferably 150 ° C. or more, without load, the mechanical properties, chemical properties, and the like do not substantially change.

As described above, the SL film is particularly heated at a high temperature (for example, 70 ° C. or more), under pressure and in a belt shape (at least two or more rollers or the like) to rotate to move the article. This is because, when it is used for a long period of time by repeatedly moving it, it basically has at least the properties necessary for solving problems such as wrinkles and dimensional changes. Therefore, even if the other resin contains aluminum borate, it cannot be used because it is extremely insufficient in terms of dimensional change required by the present invention and wrinkles, as well as long-term repeated use. Will be.

The heat-resistant resin to be used is SL
It is necessary to have the property that it can be easily formed into a film and that it can be bent freely.Specifically, for example, polyphenylene sulfide, polyethylene naphthalate, polyether sulfone, polyether ketone, polyphenylene sulfide, polyarylate, aromatic polyamide , Fluorine-based resin, thermoplastic or thermosetting polyimide, and the like.
Among these, a fluororesin, a thermoplastic or thermosetting polyimide is preferable, and a thermosetting polyimide is more preferable.

The thermoplastic or thermosetting polyimide is:
More specifically, it is as follows. First, thermoplastic polyimide has thermoplasticity while having an imide group unlike thermosetting polyimide. Therefore, the resin itself melts or softens at a predetermined temperature or higher, and can be directly extruded. This characteristic ether bond (two or more) in the main chain, alkylene linkages (C ₃ or higher), even seen in the polyimide having a functional group that provides flexibility between the molecules, such as a carbonyl group. Specifically, for example, pyromellitic dianhydride, 2, 2 ', 3, 3'-biphenyltetracarboxylic dianhydride, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, bis ( Organic acid dianhydride such as 2,3-dicarboxyphenyl) methane dianhydride and bis [4
-{3- (4-aminophenoxy) benzoyl} phenyl] ether, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy)
Phenyl] sulfone, 2,2′-bis [4- (3-aminophenoxy) phenyl] propane, and an equivalent of an organic diamine in an organic polar solvent (N-methylpyrrolidone N,
(N-dimethylacetamide, etc.) while stirring. In this reaction, polycondensation to a polymer having a required molecular weight and imide ring closure after the polycondensation are performed, and the polyimide reacts at once. The extrusion temperature for the SL film is about 300 to 400 ° C.

On the other hand, thermosetting polyimide does not melt in a polyimide state. Therefore, the molding into an SL film is performed in two steps of first performing molding at the stage of a precursor having thermoplasticity, that is, polyamic acid, and then separately performing imidization. Examples of the polyimide include the above-mentioned organic acid dianhydride and P-phenylenediamine, 4,4′-diaminodiphenyl, 4,4 ′
-Equivalent amount of an organic diamine such as diaminodiphenylmethane, 4,4'-diaminophenyl ether is gradually reacted in an organic solvent while stirring. The reaction here is a polycondensation reaction for obtaining a polyamic acid having a desired molecular weight, and must not be accompanied by a ring closing reaction to imidization. For this purpose, it is necessary to maintain a low temperature and gradually react. The above-mentioned examples are polyimides having no amino group, but so-called polyamide imides containing an amino group can also be used. Polyamide imide uses tricarboxylic monoanhydride as an organic acid, and organic diamine is obtained by a polycondensation reaction in an organic solvent in an equivalent amount in combination with those exemplified above. The polyimide resin has a heat deformation temperature of 200 to 400 ° C. and a heat resistance of about 250.
~ 350 ° C.

[0015] The fluororesin is a generally known thermoplastic homo- or copolymer-type fluororesin. Of these, a resin which meets the above conditions is selected and used. It is a perfluoro copolymer. Specifically, a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, a copolymer of tetrafluoroethylene and hexafluoropropylene, a copolymer of tetrafluoroethylene and ethylene, and a copolymer of tetrafluoroethylene and hexafluoropropylene 3 with perfluoroalkyl vinyl ether
And the like. The heat distortion temperature of these polymers is about 70-110 ° C, and the heat resistance is about 150-260.
° C.

Next, aluminum borate will be described. This is because the tubular film made of only the heat-resistant resin specified as described above, especially when it is used continuously in a belt form under heating and pressurization for a longer period of time, is inevitably wrinkled, since the problem of dimensional change is inevitable. , To solve this problem at once. This makes it possible to obtain a high-performance SL film substantially free of wrinkles and dimensional changes. Therefore, even if other generally known fillers such as silicon nitride, silicon carbide, potassium titanate, mica, and glass flakes provide the above-mentioned effects, they can obtain the SL film having a very high level according to the present invention. I can't do things. That is, what can solve the problem of the present invention at a sufficiently satisfactory level is that the heat-resistant resin and aluminum borate are inevitably bonded only when they are inevitably bonded.

Aluminum borate has a general chemical formula of 9
Al₂O₃・ 2B₂O₃Or 2Al ₂O₃・ B₂O₃so
Non-crystalline powder or needle-like crystals (whiskers) shown
It is misplaced. The powder diameter (average) of the powder is about 0.1
３０30 μm, preferably 1-20 μm, for the whisker
If the fiber length is about 5-40 μm, preferably 10-30 μm
m, and its diameter is 0.3-1.5 μm, preferably
It is 0.5 to 1 μm. And when blending,
Equivalent action and effect for both crystalline powder and acicular crystals
It is not necessary to use a mixture of both.
But that is not to deny it.

Although aluminum borate is basically blended as it is, it may be surface-treated with, for example, a silane coupling agent prior to blending. The coupling agent includes an aminosilane type, an epoxysilane type, a perfluorosilane type and the like, and it is better to determine which one is better in consideration of compatibility with the matrix resin and the like.

Next, the conductive carbon black according to claim 2 will be described. As described above, the electrical characteristics of semi-conductivity are imparted by the blending of the toner. However, this results in obtaining a functional member having newly added electrical characteristics. In addition to the further improvement of such applications, it is advantageous to develop the use in new fields.

Specifically, the carbon black generally has an average particle diameter of 1 to 500 μm and a volume resistance of about 10 μm.
^{It is 1} to 10 ⁴ Ω · cm. For example, acetylene black, ketchin black, oil furnace black, thermal black and the like can be exemplified. Among these, oil funnel black having higher conductivity is preferable. This has good compatibility with the above-mentioned matrix resin and aluminum borate, and may be used in a small amount. As a result, the dispersibility is good, so that a higher quality and higher performance SL film can be obtained. The electric resistance of the obtained semiconductive SL film is in the range of 10 ⁵ to 10 ¹⁴ Ω · cm, preferably 10 ⁷ to 10 ¹² Ω · cm. This is because the characteristics are well balanced in the effects of charging, discharging, and preventing static electricity.

Next, the composition of each of the above components will be described.
First, the compounding amount is in claim 1, the specified heat-resistant resin is 85 to 99 parts by weight, preferably 88 to 97 parts by weight, and aluminum borate is 15 to 1 part by weight, preferably 12 to 3 parts by weight. It is better to This is because when aluminum borate exceeds 15 parts by weight, wrinkles and dimensional changes are improved, but it is not only difficult to form itself into an SL film, but also it is difficult to use it in a belt form. This is because there is a danger that cracks may occur during the rotation of the belt, eventually leading to cutting. Conversely, when the amount is less than 1 part by weight, not only the wrinkles and the disadvantage of dimensional change are not substantially improved, but also there is no improvement in repeated use for a longer period.

On the other hand, the compounding amount of the conductive carbon black in claim 2 is 1 to 30% by weight, preferably 3 to 25% by weight based on 85 to 99 parts by weight of the heat resistant resin. When the content is less than 1% by weight, the desired upper limit of 10 ¹⁴ Ω · cm required for the obtained SL film is obtained.
On the other hand, when the content is 30% by weight or more, the dispersion is not sufficiently performed at a high level. As a result, the resistance value varies, and the moldability of the SL film becomes poor.

In general, the addition of conductive carbon black to a resin imparts a desired semiconductivity, but the semiconductivity often changes after long-term use. This is especially true for continuous use under heating. In the heat-resistant resin according to the present invention as well, a tendency is observed although the degree of the change varies. However, it was also found that when used in combination with aluminum borate, this change was greatly improved, and an unexpected effect of maintaining more stable semiconductivity was also obtained.

The method of compounding the above components is not particularly limited. Generally, a predetermined amount of each component powder is first mixed using a hybridization system, a ball mill or the like. In order to further improve the dispersion, the mixture is kneaded using a twin-screw extruder in some cases to obtain pellets.
When semiconductive carbon black is used in combination, it is preferable to mix and disperse in the following procedure. First, after mixing the heat-resistant resin powder and the carbon black, aluminum borate powder is added to the mixture, and the mixture is similarly mixed.
Finally, the three-component mixed powder is kneaded by a twin-screw extruder to obtain a sufficiently dispersed pellet. However, when the heat-resistant resin is a thermosetting polyimide, it is mixed at the stage of polyamic acid. Here, mixing in a solid state using the polyamic acid powder itself has a high risk of forming due to an imidization reaction during the mixing process. Therefore, with respect to the polyimide resin, it is particularly preferable to use a method in which aluminum borate or semiconductive carbon black is mixed in a solution state using a polyamic acid dissolved in an organic polar solvent.

In addition, when mixing the above-mentioned components, addition of trace amounts of various additives and further modification are not limited. For example, in order to further improve the dispersibility between components, addition of an interfacial lubricant, particularly a fluorine-based interfacial lubricant, can be exemplified.

Next, when the above components are mixed and dispersed, they are formed (molded) into a desired SL film. For example, there are the following two methods.

There are a dry molding method and a wet molding method. The dry molding method is a method in which a thermoplastic polymer in the heat-resistant resin becomes a matrix resin, and is directly melt-extruded and molded from an annular die in a state in which substantially no organic solvent is present, and thus the resin is dispersed in the resin. The aluminum borate or the conductive carbon black is uniformly dispersed throughout without taking a gradient dispersion state. On the other hand, in the wet molding method, primary molding is performed in advance in a plasticized state or a solution state in the presence of an organic solvent, and finally, the solvent and the like are removed to form a target SL film. Here, the primary molding, especially in the plasticized composition, can be molded into a tube while casting toward the outer periphery of the metal drum, or can be directly extruded from an annular die.
In a solution state, a centrifugal casting method in which the solution is poured into a metal drum and molded while rotating is preferable.

In the SL film by the centrifugal casting method,
Particularly, aluminum borate contained therein is contained more in the front surface portion than in the back surface portion, and exists in a state of being dispersed as a whole as a whole. When the conductive carbon black is used in combination, the aluminum borate has the same tendency, however, the carbon black has a very small tendency to disperse in a gradient, and is rather uniformly dispersed.

As described above, SL by the centrifugal casting method is particularly used.
The films differ in the dispersion state of aluminum borate and conductive carbon black. Generally, it is preferable that the particles are uniformly dispersed throughout. However, in order to solve this more effectively in the problem of the present invention,
As described above, it is more effective that the compound is contained in two dispersed forms. This is due to the fact that aluminum borate has a large gradient on the surface, and the carbon black is uniformly dispersed. With a SL film having a smaller amount of aluminum borate, wrinkles and dimensional changes can be more effectively reduced. What can be improved. In addition, the effects of charging and discharging can be further enhanced, and a more stable electric resistance value can be maintained. This is a surprising effect,
The mechanism is not clear. It is conceivable that the prevention of wrinkles and dimensional changes of the SL film is in particular in the improvement of the properties of its surface portion, and the charging and discharging are not because the uniform electric resistance value as a whole works more easily. It is thought.

The organic solvent used in the wet molding method is selected from those which swell or dissolve in the heat-resistant resin (polyamic acid in the case of a thermosetting polyimide). It is necessary to use a completely soluble organic solvent and its amount.

For example, the most preferable thermosetting polyimide is a centrifugal casting method, which is exemplified as follows. First, the starting materials are subjected to a polycondensation reaction in the organic solvent to obtain a polyamic acid solution. Aluminum borate or / and conductive carbon black are mixed and dispersed therein. Next, SL of desired size (diameter and width)
Select a metal drum corresponding to the film. Then, a predetermined amount of the polyamic acid solution is poured into the drum, and the drum is heated from the outside and starts rotating. When spinning at a predetermined temperature (generally a temperature slightly higher than the boiling point of the organic solvent and lower than the imidization temperature) for a predetermined time, the solvent is gradually evaporated and uniformly removed over the entire inner surface, and the polyamic acid is solidified. Shaped as endless tubular film. Then, the film was peeled off from the drum, and then fitted into a cylindrical mold, and the whole was put into a heating oven. The temperature was gradually raised to about 250 ° C. at first, and then 400 ° C.
Temperature gradually (secondary molding). During this time, an imidization reaction is gradually performed to obtain an SL film using a thermosetting polyimide as a matrix, and the entire process is completed. The cylindrical mold used in the secondary molding is effective for performing the secondary treatment while mainly maintaining the shape, and is not essential. Also, when a heat resistant resin other than the thermosetting polyimide is molded by the centrifugal casting method, it is desirable to perform the molding in accordance with the procedure for the polyimide.

[0032] Regardless of the dry molding method or the wet molding (mold) method, other molding conditions are not particularly limited, as long as appropriate conditions are selected for the selected composition. However, particularly in the dry molding method, it is preferable that the melt molding from the annular die is extruded at room temperature and is taken out substantially without stretching.

The obtained SL film is used as a roller by fitting it to a roller core material, and is used as a belt by being stretched over two or more rollers. Since it is resistant to use and has excellent chemical resistance as well as mechanical strength, it can be used regardless of the type of article to be handled.
As a specific application, for example, after a toner image is transferred to paper in a copying machine using toner, a visible image on a photosensitive drum is transferred to the belt in a fixing belt that is fixed by heat fusion.
It fixes the toner image that has been transferred almost simultaneously as it is in a hot-melt state, transfers it to the supplied paper at once, and fixes it by fusing. In addition, intermediate transfer and fixing, which are particularly effective for multicolor printing, are described. The use of an intermediate transfer belt system, which is performed almost simultaneously with one belt, may be used. When used as a roller or a belt, the surface thereof may be coated with a fluororesin, except for those using a fluororesin. This is to improve the releasability, and is more effective in terms of handling articles, workability, and the like.

[0034]

The present invention will be described in more detail with reference to the following examples together with comparative examples. The dimensional changes and wrinkles in the examples were measured as follows. * Dimensional change: Each of the obtained SL films (test belts) was stretched on the measuring device shown in FIG. 1 and the nip pressure (vs. the test belt) was 10 × 10 ⁵ (Pa) and the predetermined temperature (ceramic 100m below heater (described in each example)
The change in dimensions at the time of continuous rotation for 24 hours at a speed of m / sec (the percentage of expansion / contraction relative to the original size, + indicates elongation, and-indicates shrinkage). The tension of the belt was 3 kgf. * Wrinkle: After the dimensional change measurement, the occurrence of wrinkles (waves) is observed by visual inspection. ◎ indicates complete absence, ○ indicates faintly observed, and X indicates clearly observed. Indicated. In the apparatus, 1 is a test belt, 2 is a ceramic heater (fixed) for stretching and heating,
Reference numeral 3 denotes a tension / rotation roller (vertical movement-tension adjusting mechanism), and reference numeral 4 denotes a nip (receiving) roller (vertical movement-nip pressure adjusting mechanism).

Example 1 First, an equivalent of pyromellitic dianhydride and 4,4'-diaminobiphenyl ether was subjected to a polycondensation reaction in a dimethylacetamide solvent at room temperature to obtain a polyamide having a solid content of 11.9% by weight. 3 kg of acid solution was synthesized. Then, 580 g of this was collected, and aluminum borate whiskers (9Al ₂ O ₃ 2B ₂ O ₃ , average fiber length 10 to 30 μm, average fiber diameter 0.5 to 1.0 μ)
m, and a tensile strength of 800 kgf / mm ² ) (1.4 g, 2% by weight based on the solid matter) were added thereto with sufficient stirring. This is called solution A.

On the other hand, a centrifugal casting machine having the following structure was prepared. * A metal drum having a predetermined inner diameter and width, and having a mirror-finished inner surface (bearers are provided around both sides to prevent liquid leakage). * The drum is mounted on two variable rotary rollers with built-in heaters, and adopts an indirect rotation method in which the drum rotates by the rotation of the rollers. * The drum is heated externally by a far-infrared heater. * The removal of the vapors evaporated by heating is performed by disposing a suction / discharge device that suctions and discharges air while supplying air to a horizontally long, detachable supply / discharge nozzle provided at the center of the inside of the drum.

Then, 56 g of the liquid A was collected and uniformly cast (inner diameter 80 mm, width 400 mm) into the metal drum of the centrifugal casting machine which slowly rotated. After the casting, the supply / discharge nozzle was operated, and the rotation was gradually accelerated together with the heating of the drum. When the rotation reached 400 rpm, the temperature was raised to 140 ° C. while maintaining the rotation (drum internal temperature). Molding was performed for 120 minutes under this rotation and temperature. Then, the solid tubular film was peeled from the drum and taken out. The obtained film was a polyamic acid film containing some dimethylacetamide (solvent).

Next, in order to remove the solvent remaining with the imidation, the obtained polyamic acid film was subjected to R _Z = 5.0 μm, outer diameter 77 mm, and length 350 mm.
Was inserted in contact with the surface of the cylindrical mold, and the whole was put into a hot-air dryer. Then, the temperature is gradually raised, and when the temperature reaches 300 ° C., the temperature is further raised to 450 ° C. for 20 minutes at that temperature.
Was reached and heated at that temperature for 30 minutes. Finally, it was cooled to room temperature and extracted from the mold. The resulting film was a completely imidized polyimide SL film. The thickness of the film is 60 ± 5 μm, inner diameter 77 m
m, the length was 350 mm, and both surfaces were extremely smooth. When the cross section of the SL film was observed with an electron microscope, it was confirmed that the number of dispersed aluminum borate whiskers was larger at the surface than at the back, and that the whisker was dispersed as a whole.

The dimensions of the polyimide SL film and the occurrence of wrinkles were measured, and are shown in Table 1.

[0040]

[Table 1]

Example 2 580 g of 3 kg of a polyamic acid solution having a solids concentration of 11.9% by weight obtained by a polycondensation reaction using the same raw materials as in Example 1 was sampled and separately mixed in advance. A mixed powder of 11 g of conductive carbon black of oil furnace (Mitsubishi Chemical Co., Ltd. MA-100) and 1.4 g of aluminum borate whisker (same as in the example) was gradually added with stirring and thoroughly mixed and dispersed. did. Hereinafter, this mixed polyamic acid solution is referred to as a B solution.
The mixing ratio of the polyamic acid and the carbon black is 8
6.25% by weight to 13.75% by weight, and the aluminum borate whisker is 2% by weight based on the polyamic acid.
Met.

Next, 175 g of the solution B was sampled and molded by the centrifugal casting machine in Example 1 to obtain the polyamide acid seamless tubular film having the two components. However, the molding conditions in this case were as follows, and the other operations were the same as in Example 1. -Metal drum: 260 mm inside diameter, 500 mm width-Rotation speed: 150 rpm-Ultimate heating temperature: 120 ° C

Next, in the same manner as in Example 1, the polyamic acid film obtained above was inserted into a cylindrical mold and heat-treated for imidization and complete removal of the residual solvent. However, the cylindrical mold had R _Z = 5.0 μm, an outer diameter of 250 mm, and a length of 400.
mm, and the heating maintenance time at 300 ° C. and 450 ° C. was 20 minutes and 30 minutes, respectively. The film cooled and removed from the mold is a polyimide SL film that has been completely imidized and desolventized as in Example 1,
And both sides are smooth, thickness is 60 ± 5μm, inner diameter 2
50 mm, length 400 mm, volume resistance value is 5 × 10 ¹⁰
Ω · cm. In addition, when the cross section of the SL film was observed with an electron microscope, aluminum borate whiskers were more distributed on the surface than carbon black, and were scattered as a whole. However, it was confirmed that the carbon black was almost uniformly dispersed as a whole, even though the carbon black was slightly larger on the surface. Table 1 summarizes the measurement results.

(Example 3) (When polyamideimide is used as a heat-resistant resin) An equivalent of trimellitic anhydride and 4,4'-diaminodiphenylmethane is heated in N-methylpyrrolidone to carry out a polycondensation reaction. 500 g of a polyamideimide solution was obtained (solid concentration 28% by weight). Hereinafter this is referred to as a PAI stock solution. Next, 156 g of the PAI stock solution was collected, and 6.85 g of the same conductive carbon black as in Example 1 was first added thereto.
A slight amount of a fluorine-based interfacial lubricant (EF-TOP) for improving dispersibility and 43 g of N
After adding and mixing -methylpyrrolidone (for dilution), 2.65 g of aluminum borate whisker (Example 1) was gradually added with stirring, and finally, the mixture was put in a ball mill and sufficiently mixed and dispersed. Hereinafter, this is referred to as liquid C. The compounding ratio of each component was 94.28% by weight and 5.72% by weight for the polyamideimide and aluminum borate whisker, respectively, and 13.56% by weight of the conductive carbon black to the polyamideimide. .

Next, 185 g of the liquid C was collected and centrifugally molded using the centrifugal casting machine in Example 1. However, the metal drum used had an inner diameter of 170 mm and a width of 500 mm, the molding conditions were a rotation speed of 100 rpm, and the ultimate heating temperature was 150.
C. for 60 minutes and 260.degree. C. for 40 minutes.

The polyamideimide SL film obtained above had R _Z = 1 μm, a thickness of 115 ± 3 μm, and an outer diameter of 17 μm.
0 mm and a volume resistance value of 1 × 10 ¹⁰ Ω · cm. Also for this, the dimensional accuracy and wrinkles were measured in the same manner as in Example 1, and are summarized in Table 1.

Example 4 As a heat-resistant resin, a copolymer of ethylene and tetrafluoroethylene (ETF) was used.
E) (heat deformation temperature 104 ° C, heat resistance 170 ° C)
First, Ketjen black is added as a conductive carbon black, and the mixture is blended in a nitrogen gas atmosphere using a hybridization system. Subsequently, the same aluminum borate whisker as in Example 1 is added to the blend. Subsequently, the same blending was performed. Then, in order to further completely mix the three-component blend powder and to easily form the SL film, a twin-screw extruder (barrel temperature 2)
70 to 310 ° C.) and obtained as pellets while kneading. The mixing ratio of the above three components is as follows: ETFE and aluminum borate are 90% by weight and 10% by weight, respectively.
Ketchin black was 7.2% by weight based on ETFE.

Then, an SL film was formed from the pellet under the following conditions. That is, an annular die (temperature: 300 ° C.) having an inner diameter of 163 mm and a nozzle width of 0.1 mm is supplied to a single-screw extruder (barrel temperature: 270 to 310 ° C.) having a head, and extruded in a tubular shape. While passing through the sizing sleeve, the tube was cooled from the inside of the tube and pulled substantially without stretching. The obtained SL film had a thickness of 150 ± 5 μm, an inner diameter of 160 mm, a volume resistance value of 5 (± 1) × 10 ¹⁰ Ω · cm, and both surfaces were smooth. In addition, when the cross section of this SL film was observed with an electron microscope, ketchin black and aluminum borate were mutually uniformly dispersed between ETFE. This SL film was also measured for dimensional changes and wrinkles and summarized in Table 1.

(Comparative Example 1) (Comparison with Example 1) First, 57.2 g of 1.5 kg of the polyamic acid solution synthesized in Example 1 was collected and injected into the centrifugal molding machine in Example 1. Then, centrifugal casting was performed under the same conditions to obtain an endless film of polyamic acid. Next, the film was fitted into a cylindrical mold in the same manner as in Example 1, and heated to completely imidize and remove the solvent. The obtained polyimide single SL film had a thickness of 60 ± 4 μm and an inner diameter of 77.0.
mm and a width of 350 mm. Then, dimensional changes and wrinkles were measured in the same manner, and the results are summarized in Table 1.

Comparative Example 2 (Comparison with Example 4) In Example 4, except that aluminum borate whiskers were not added, the mixture was dispersed and pelletized under the same conditions as in Example 4 and pelletized. To form an SL film. The film showed some undulations. To correct this, the film was fitted into a cylindrical mold and heat-treated at 120 ° C. This heat treatment is wavy correction,
Although effective for measuring dimensional stability, it was not performed in Example 4. The obtained SL film has smoothness on the front and back sides without waving, and has a thickness of 151 ± 4 μm, an inner diameter of 159.1 mm, and a volume resistance value of 5 (1 ±) × 10 ¹⁰ Ω ·.
cm. However, for dimensional changes and wrinkles, see Table 1.
As shown in FIG.

(Example 5) (Example of use as fixing and intermediate transfer belt) From 3 kg of the polyamic acid solution synthesized in Example 1,
160 g was collected, and the same carbon black and aluminum borate as in Example 2 were added thereto in the same procedure.
The mixture was sufficiently mixed and dispersed. However, the addition amount of both components is doubled to 24
g and 3.2 g. Hereinafter, this is referred to as liquid D.

Next, 460 g of the solution D was collected and molded by the same procedure using the centrifugal casting machine in Example 1 to obtain a seamless tubular film of polyamic acid. However, the molding conditions in this case were as follows. -Metal drum: 520 mm inside diameter, 500 mm width-Rotation speed: 160 rpm-Ultimate heating temperature: 130 ° C

Next, the obtained polyamide acid seamless tubular film was inserted into a cylindrical mold and heated. However, the cylindrical mold has R _Z = 5.0 μm, an outer diameter of 510 mm, and a length of 450.
mm, and the respective heating maintenance times at 300 ° C. and 450 ° C. were 20 minutes and 30 minutes. It was cooled and removed from the mold to obtain a polyimide SL film. This is the same as Example 1, and has a thickness of 60 ± 5 μm, an inner diameter of 510 mm, a length of 450 mm, and the same volume resistance of 5 × 1.
It was 0 ¹⁰ Ω · cm.

Next, the following materials were coated on the surface of the polyimide SL film in order to impart an appropriate release property. That is, an emulsion of tetrafluoroethylene and perfluoroalkyl vinyl ether copolymer is spray-coated on the surface of the film, and then the coated film is placed in a hot-air dryer at 380 ° C. to form an emulsion medium. Bake with evaporation.
The thickness of the coated copolymer is 7 ± 0.
It was 4 μm, and it was sufficiently adhered. This coating S
The volume resistance value of the L film was 5.1 × 10 ¹⁰ Ω · cm, and no difference was observed between the L film and the SL film before coating.

Then, the above-mentioned coated polyimide SL
The film was used as a fixing and intermediate transfer belt for a multicolor toner copier. Its usage is shown in the schematic side view of FIG. In the figure, 5 is a belt made of the SL film,
This is the feed roller R1, R2 and the heat roller HR.
It is stretched over a book and rotates repeatedly in the direction of the arrow. Multicolor printing by the machine is performed by the following mechanism. First, a visual image of blue toner based on C (blue) color-separated is formed on the photosensitive drum 6. This is immediately transferred to the surface of the belt 5 charged negatively by the charger 6a. The same operation is performed in the order of M → Y → B. In the last transfer of B, all of the four colors (●●●●) are reproduced on the belt 5, and this is the heat roller HR and the receiving roller R3 which are on standby.
And the toner image is softened or melted. Then, it is pressed against a copy sheet fed in a timely manner from one side, reproduced on the copy sheet, and the copying is completed. The copy sheet is discharged as a copied sheet 10a. The belt 5 that has completed the heat fixing is neutralized by the neutralizer 11.
The surface of the belt 5 is cleaned by the cleaner 12, and charging, transfer and heat fixing are repeated again, and color copying is performed.

[0056]

As described above, the present invention has the following advantages.

In particular, improvements in dimensional change under heating and pressurization, wrinkles, etc. were observed, and it became possible to stably and repeatedly use for a longer period of time.

Since the dimensional change and the improvement in wrinkles are measured with extremely high precision, a member having higher functionality,
For example, especially in a color copying machine employing an intermediate transfer method,
Dramatic improvement in performance has been achieved for performing transfer and fixing with a single belt. Of course, the use of only the heat-fixing belt (or roller) in the copying machine provides a further effect. Further, the present invention is also effective for use of transport rollers, belts, and the like in other applications.

[Brief description of the drawings]

FIG. 1 Measurement device for dimensional change and wrinkles (side view)

FIG. 2 is a schematic view of a color copier equipped with a fixing and intermediate transfer belt (side view).

[Explanation of symbols]

 Reference Signs List 1 Test belt (SL film) 2 Stretching and heating ceramic heater 3 Stretching and rotating roller 5 Fixing and intermediate transfer belt 6-9 Photosensitive drum (4 colors) 6a-9a Charger HR Heater roller (heat fixing section) 10 Copy paper 11 Static eliminator

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G03G 15/20 101 G03G 15/20 101 4J002 // B29C 41/04 B29C 41/04 4J043 (72) Inventor Tsuneo Miyamoto 163 Morikawahara-cho, Moriyama-shi, Shiga Prefecture Gunze Co., Ltd. Research and Development Department Shiga Research Laboratory (72) Inventor Takashi Kuraoka 163 Morikawahara-cho, Moriyama City, Shiga Prefecture Gunze Co., Ltd. Shiga Research Laboratory R & D Department F-term (reference) 2H032 BA09 BA18 DA04 DA13 2H033 BA12 BA17 BA19 BA20 BE03 3F024 AA07 AA11 CA04 CA08 4F071 AA26 AA27 AA60 AB03 AB27 AH04 AH16 BC01 BC05 4F205 AA16 AA40 AB16 AB18 AB25 AC05 AE10 AG08 AG16 GA02 GE01 GM01 GE03 GE04 GE02 FD117 GM00 GM01 4J043 PA02 QB26 QB31 RA05 RA35 SA06 SB01 TA13 TA14 TA21 TA22 UA12 1 UA122 UA131 UA132 UA151 UA171 UB011 UB012 UB021 UB121 UB131 UB141 UB151 UB152 UB301 UB401 UB402 VA011 VA021 VA022 VA031 VA041 VA042 VA061 VA062 VA082 XA16 XA19 XB34 YA06 ZA31 ZB47

Claims (7)

[Claims] 1. A heat-resistant resin having a heat deformation temperature of 70 ° C. or more.
A durable and heat-resistant seamless tubular film comprising 5 to 99 parts by weight and 15 to 1 part by weight of aluminum borate as main components. 2. A durable and heat-resistant seamless tubular film characterized in that the heat-resistant resin further contains 1 to 30% by weight of conductive carbon black. 3. The durable and heat-resistant seamless tubular film according to claim 1, wherein the thermosetting polyimide is a heat-resistant resin. 4. The durable and heat-resistant seamless tubular film according to claim 1, wherein the perfluoro copolymer polymer is a heat-resistant resin. 5. The durable and heat-resistant seamless tubular film according to claim 1, wherein a large amount of aluminum borate is present on the surface portion and dispersed as a whole. 6. The durable and heat-resistant seamless tubular film according to claim 1, which is a toner fixing member. 7. The durable and heat-resistant seamless tubular film according to claim 2, which is a toner fixing and intermediate transfer belt.