JP2005138450A - Method for producing tubular molding of polyimide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a tubular polyimide molding good in shape which reduces the nonuniformity of shrinkage stress and prevents wrinkling. <P>SOLUTION: In the method for producing the tubular polyimide molding, in a process in which the precursor of the polyimide molding, after being externally engaged with or applied on a cylindrical mold, is heated, the cylindrical mold is rotated. Preferably, the cylindrical mold is rotated until the surface temperature of the precursor reaches 200°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a tubular molded body containing a polyimide resin.

  An electrophotographic apparatus using an intermediate transfer member is effective as a multicolor image forming apparatus that outputs a formed image obtained by combining and reproducing a multicolor image by sequentially laminating and transferring a plurality of component color images of multicolor image information. It is possible to obtain an image having no color misregistration of each component color image. In addition, it has excellent advantages such as the ability to select from thin paper to thick paper and the ability to transfer images regardless of the size of the paper. Is spreading.

  As the intermediate transfer member, for example, a drum shape, a cylindrical shape, and the like are known, but a thin-walled tubular intermediate transfer member, which is often referred to as a belt, is mainly used due to a demand for downsizing of the apparatus. . Further, as a material for the intermediate transfer member, it is disclosed that polyimide resin is used as an intermediate transfer member material because of demands such as high tensile elastic modulus and high surface smoothness (for example, Patent Documents). 1).

  Conventionally, polyimide tubular molded bodies have been manufactured by the following methods, which are roughly divided into an inner coating method and an outer coating method. In the inner coating method, a polyimide tubular molded body precursor is applied to the inner surface of a cylindrical mold, and then the solvent is volatilized to some extent and / or partial imidization is performed to express self-supporting properties in the coating film. Next, the coating film is peeled off from the mold, and then externally fitted into a cylindrical firing mold for imidization, followed by heating and imidization. On the other hand, the outer coating method is a method in which a precursor of a polyimide tubular molded body is applied to the outer surface of a cylindrical firing mold, and heating and imidization are performed on the same molded tube. In the inner coating method, in a state where a polyimide tubular molded body precursor is applied to the inner surface of a cylindrical mold, solvent evaporation, heating and imidization are performed in one step without external fitting to a cylindrical firing mold for imidization. Is also disclosed (for example, see Patent Document 2). However, as pointed out in Patent Document 2, when heating and imidization are performed without external fitting to a cylindrical firing mold for imidation, the resulting polyimide tubular molded body is likely to have minute irregularities, and There is a problem that the perimeter is likely to be reduced, and therefore, it is preferable to include an outer fitting step to a cylindrical firing mold for imidization.

  The most difficult process in either the inner coating method or the outer coating method is to externally fit or apply the polyimide tubular molded body precursor to the cylindrical firing mold, and then heat the polyimide tubular molded body precursor. This is a step of imidization. When heating to the precursor of the polyimide tubular molded body becomes non-uniform, that is, when the temperature variation becomes large, imidization and accompanying shrinkage stress are generated non-uniformly. As a result, the polyimide tubular molded body finally obtained In some cases, leaning occurs. The polyimide tubular molded body in which the wrinkle is generated cannot be used as a product. Therefore, the wrinkle has been a factor in yield reduction. Even in the case where wrinkles are not generated, the non-uniform shrinkage stress induces variations in the mechanical strength and thickness of the polyimide tubular molded body, and the polyimide tubular molded body deforms during long-term use. The problem that occurred.

The non-uniformity of heating of the precursor of the polyimide tubular molded body described above is noticeably generated particularly in a polyimide tubular molded body having an inner diameter of 200 mm or more, called a large diameter. This is presumably due to the fact that the in-plane temperature variation increases as the diameter of the polyimide tubular molded body increases. As a result, the production yield of large-diameter polyimide tubular molded bodies has been lowered, which has been a factor in raising the production cost of the tubular molded bodies and thus the product unit price.
JP-A-10-171265 JP 2001-47451 A

  It is an object of the present invention to provide a method for producing a polyimide tubular molded body having a good shape with reduced shrinkage stress non-uniformity and no wrinkles.

  As a result of intensive studies, the present inventors have established a method for producing a polyimide cylinder having excellent productivity.

  That is, the present invention is characterized in that after a polyimide tubular molded body precursor is externally fitted or applied to a cylindrical firing mold, the tubular firing mold is rotated in the step of heating the polyimide tubular molded body precursor. And a method for producing a polyimide tubular molded body.

  A preferred embodiment relates to the above-mentioned method for producing a polyimide tubular molded body, wherein the polyimide tubular molded body is rotated at least until the temperature of the precursor surface of the polyimide tubular molded body reaches 200 ° C.

  A further preferred embodiment relates to the method for producing a polyimide tubular molded body according to any one of the above, wherein the inner diameter of the polyimide tubular molded body is 150 mm or more.

  According to the present invention, it is possible to reduce the non-uniformity of the shrinkage stress, and to produce a polyimide tubular molded body having a good shape with no wrinkles.

  The embodiment of the method for producing a polyimide tubular molded body according to the present invention will be described in more detail.

  The method for producing a polyimide tubular molded body according to the present invention includes a step of heating a precursor of a polyimide tubular molded body after the polyimide tubular molded body precursor is externally fitted or applied to a cylindrical firing mold. The baking mold is rotated. By rotating the firing mold, heating to the precursor of the polyimide tubular molded body becomes uniform, and imidization and accompanying shrinkage stress become uniform. As a result, the occurrence of shape defects such as wrinkles can be drastically reduced. With the above rotation, it is important that the entire surface of the precursor of the polyimide tubular molded body is heated substantially uniformly, and the rotation axis, the rotation direction, and the rotation speed are not particularly limited. It can be an intermittent.

  The material of the cylindrical firing mold of the present invention is not particularly limited, and conventionally known materials such as metals, ceramics, and resins can be used. Further, the surface of the cylindrical baking mold may be subjected to coating processing or plating processing. However, in consideration of heat resistance, durability, and workability into a cylindrical shape, it is preferable that a metal is used as at least a part of the material.

  Since the rotation according to the present invention is performed for the purpose of eliminating non-uniformity of imidization of the polyimide tubular molded body, it is preferable to perform the rotation until most of the imidization proceeds. From the above viewpoint, it is particularly preferable to rotate at least until the temperature of the precursor surface of the polyimide tubular molded body reaches 200 ° C., desirably 250 ° C. In addition, when the temperature differs greatly at each position on the surface, it is preferable to adjust the temperature at the position where the accuracy of the surface is required in the product as described above.

  The tubular molded body according to the present invention means a seamless hollow molded body, regardless of the diameter and thickness of the tubular molded body. Therefore, the present invention can be applied to a large-diameter member often called a belt and a small-diameter member often called a tube. However, the method for producing a polyimide tubular molded body of the present invention is more effective as the diameter of the polyimide tubular molded body is increased, in other words, the outer area is increased. From this request, the inner diameter of the polyimide tubular molded body is 150 mm or more, preferably 200 mm or more, and the effects of the present invention can be particularly preferably exhibited. Although there is no restriction | limiting in particular regarding the upper limit of the internal diameter of a polyimide tubular molded object, Considering a manufacturing process and the magnitude | size of the apparatus incorporating the said tubular molded object, a substantial upper limit is 1000 mm.

  The polyimide tubular molded body according to the present invention is characterized in that the main component of the resin is polyimide. Here, the main component of the resin means that polyimide is 50% by weight or more in all resin components, and more preferably 60% by weight or more. Polyimide is obtained by a curing reaction of polyamic acid, and polyamic acid is obtained by polymerizing an acid dianhydride component, preferably an aromatic tetracarboxylic dianhydride component and a diamine component in an organic polar solvent. It is obtained.

  There is no restriction | limiting in particular as a tetracarboxylic dianhydride component, For example, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tri Carboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1, Aliphatic or alicyclic tetracarbo such as 2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Acid dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1 , 4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetra Carboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 2,3,3 ′, 4 '-Biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) ) Dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4 ' -Aromatic tetracarboxylic dianhydrides such as diphenylmethane dianhydride; 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo- And aliphatic tetracarboxylic dianhydride having an aromatic ring such as 3-furanyl) -naphtho [1,2-c] furan-1,3-dione. These tetracarboxylic dianhydrides can be used alone or in combination of two or more. When used alone, pyromellitic dianhydride or biphenyltetracarboxylic acid dianhydride is preferable because it is easy to control the mechanical strength within a suitable range, and even when used in combination of two or more, total acid dianhydride It is preferable to use 50 mol% or more of pyromellitic dianhydride or 50 mol% or more of biphenyltetracarboxylic dianhydrides based on the components. The biphenyltetracarboxylic dianhydride is particularly preferably 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. .

The diamine component used next is not particularly limited as long as it is a diamine. For example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4 ' -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- ( 4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3, 5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluorome Rubenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) ) -Biphenyl, 1,3'-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'- (M-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino- Aromatic diamines such as 2-trifluoromethyl) phenoxy] -octafluorobiphenyl; aromatics having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and heteroatoms other than nitrogen atoms of the amino group Diamine; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentame Tylene diamine, octamethylene diamine, nonamethylene diamine, 4,4-diaminoheptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylene diamine, hexahydro-4,7-methanoin mite diene diamine, tricyclo [6,2,1,0 ^2.7] - undecylenate range methyl diamine, 4,4'-methylenebis can be mentioned aliphatic diamine (cyclohexylamine) and the like and alicyclic diamine. These diamine compounds can be used alone or in combination of two or more. When used alone, 4,4'-diaminodiphenyl ether or phenylenediamine is preferable because it is easy to control the mechanical strength within a suitable range, and even when used in combination of two or more, 50 moles based on the total diamine component. % Or more of 4,4′-diaminodiphenyl ether or 50 mol% or more of phenylenediamines are preferably used. The phenylenediamines are particularly preferably p-phenylenediamine or m-phenylenediamine.

  Examples of the organic polar solvent used for the polymerization reaction of the polyamic acid include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m-, or p -Phenol solvents such as cresol, xylenol, halogenated phenol, catechol, ether solvents such as tetrahydrofuran, dioxane, dioxolane, alcohol solvents such as methanol, ethanol, butanol, cellosolve such as butyl cellosolve or Sa-methyl phosphoramide, .gamma.-butyrolactone, etc. can be mentioned, although it is desirable to use them alone or as a mixture, further xylene, aromatic hydrocarbons such as toluene can be used. The solvent is not particularly limited as long as it dissolves the polyamic acid. Further, it is desirable to remove water as much as possible in order to promote the decomposition of the polyamic acid.

  For the curing reaction of polyamic acid, known methods such as a method using heat, a method of introducing a catalyst and a curing agent into a raw material solution containing polyamic acid, and a method using light can be suitably used. However, it is preferable to introduce a method of introducing a catalyst and a curing agent into a raw material solution containing a polyamic acid into at least a part of the curing reaction because productivity and other physical properties such as elastic modulus can be suitably controlled. . The method for introducing the catalyst and the curing agent into the raw material solution containing the polyamic acid is not particularly limited, and the method of kneading the catalyst and the curing agent in the raw material solution, after kneading only the catalyst in the raw material solution, Examples thereof include a method in which a solution containing a curing agent is brought into contact with a raw material solution by a method such as spraying, coating, and dipping, and a method in which a solution containing a catalyst and a curing agent is brought into contact with the raw material solution.

  As used herein, the curing agent can be used without limitation as long as it is a dehydrating ring-closing agent for polyamic acid. For example, as its main component, aliphatic acid anhydride, aromatic acid anhydride, N, N′-dialkylcarbodiimide is used. , A lower aliphatic halide, a halogenated lower aliphatic acid anhydride, an arylsulfonic acid dihalide, a thionyl halide, or a mixture of two or more thereof can be preferably used. Of these, aliphatic acid anhydrides and aromatic acid anhydrides are particularly preferable because they work well.

  Further, the catalyst herein is a component having an effect of promoting the dehydration ring-closing action of the curing agent on the polyamic acid, and as its main component, an aliphatic tertiary amine, an aromatic tertiary amine, or a heterocyclic tertiary amine. Can be preferably exemplified. Among them, a substituted or unsubstituted nitrogen-containing heterocyclic compound such as imidazole, benzimidazole, isoquinoline, quinoline, or β-picoline is preferable.

  Furthermore, introduction of an organic polar solvent into the solution containing the curing agent and the catalyst may be appropriately selected.

In order to control the resistance value, strength, ultraviolet resistance, moisture resistance and the like, a method generally used for improving resin properties can be applied to the polyimide tubular molded body according to the present invention. For example, in order for the polyimide tubular molded body to exhibit the intermediate transfer capability, the volume resistance value is controlled to be in the range of 1 × 10 ⁶ to 10 ¹³ Ω · cm, preferably 1 × 10 ⁷ to 10 ¹¹ Ω · cm. However, as a concrete method for realizing this, conductive inorganic materials such as carbon black, which are generally used for conducting conductive resin, lowering resistance, and preventing static electricity, are used. It is possible to mix an appropriate amount of powder into the resin. In addition to carbon black, small-diameter metal particles, metal oxide particles, titanium oxide, various inorganic particles, and whiskers formed of a conductive material such as metal oxide can be used in the same manner. Furthermore, it is possible to add an inorganic ion conductive material such as LiCl or an organic ion conductive material such as ethylmethylimidazolium tetrafluoroborate. Further, for example, by introducing a heat conductive inorganic powder into the polyimide tubular molded body, its heat fixing ability can be improved. The heat conductive inorganic powder is not particularly limited as long as it is an inorganic powder having a heat conduction function, and examples thereof include aluminum nitride, boron nitride, alumina, silicon carbide, silicon, silica, and graphite. Among these, boron nitride is more preferable in that it has a high heat conduction function, exhibits a release effect, is chemically stable, and is harmless. The above-mentioned inorganic powder can be used singly or in a mixed system, and can be appropriately selected according to the use of the polyimide tubular molded body.

  Next, the manufacturing method of the polyimide tubular molded body according to the present invention will be described in detail with reference to examples.

(Example 1)
In a vessel equipped with a stirring blade, 1500 g of dimethylformamide (DMF) sufficiently dehydrated with molecular sieves was added, 200 g of 4,4′-diaminodiphenyl ether was added, and the mixture was stirred until completely dissolved. The system was cooled to about 0 ° C. and 218 g of pyromellitic dianhydride was gradually added and stirred well. When the viscosity of the system reached about 3 × 10 ² Pa · s, stirring was stopped to obtain a polyamic acid solution.

  Next, 60 g of filler FT-3000 manufactured by Ishihara Sangyo Co., Ltd. and 300 g of DMF were placed in another container and stirred well, and the mixture was further dispersed in the dispersion by applying an ultrasonic disperser (acicular filler). Dispersion). FT-3000 is a needle-like filler made of titanium oxide whose surface is coated with tin oxide / antimony.

  118 g of the acicular filler dispersion obtained above was collected in a beaker and stirred well. In this beaker, 300 g of the polyamic acid solution obtained above was dissolved and further stirred. Thus, the raw material solution containing the polyamic acid which contains about 30 weight part of acicular fillers with respect to 100 weight part of polyimide resins after hardening was prepared.

  Furthermore, 20 g of isoquinoline as a catalyst and 32 g of acetic anhydride as a curing agent were kneaded in the raw material solution containing the polyamic acid to obtain a precursor of a polyimide tubular molded body.

  The polyimide tubular molded body precursor containing the catalyst and the curing agent obtained above is uniformly injected into a cylindrical space having an inner diameter of 167.7 mm, an outer diameter of 170.0 mm, and a length of 450 mm. It was allowed to stand for 10 minutes in an atmosphere of 23 ° C. and 55% RH until supportability was exhibited. The cylindrical space is formed by inserting a SUS cylindrical firing mold having an outer diameter of 167.7 mm and a length of 450 mm into a SUS outer cylinder having an inner diameter of 170.0 mm and a length of 450 mm. Next, the outer cylinder is removed, and the cylindrical firing mold in which the precursor of the polyimide tubular molded body is externally fitted is placed in the center of the rotary table installed in the oven STPH-201 manufactured by ESPEC, and the long axis is parallel to the vertical direction. It was allowed to stand and sealed. Furthermore, the oven was set at 120 ° C., and the rotary table was rotated at a speed of 0.5 rpm with the force of an external motor with the long axis of the cylindrical baking mold as the rotation center. After maintaining this state for 10 minutes, the temperature was raised from 120 ° C. to 380 ° C. over about 30 minutes while maintaining the rotational motion. Finally, the system was cooled to room temperature to obtain a polyimide tubular molded body.

  About the obtained polyimide tubular molded object, the external appearance test | inspection and the long-term durability test were done.

  The appearance inspection was performed by producing a total of 10 polyimide tubular molded bodies in the same procedure as described above, and visually confirming the presence or absence of wrinkles on all 10 polyimide tubular molded bodies. Those with no wrinkles were marked with ◯, and those with wrinkles were marked with x.

  The long-term durability test was performed according to the following procedure. The obtained polyimide tubular molded body was mounted on a color laser printer ColorLaserWind3310 manufactured by Fuji Xerox Co., Ltd. and used as an intermediate transfer body to form 300,000 A4-sized images in an atmosphere of 23 ° C. and 55% RH. It was. Thereafter, another image was formed, and the long-term durability was observed by evaluating the image. The case where there was no problem in the image was marked with ◯, and the other cases were marked with ×.

  As a result of the above evaluation, it was a good in both the appearance inspection and the long-term durability inspection.

(Example 2)
What was adjusted like the said Example 1 except not adding a catalyst and a hardening | curing agent was made into the precursor of a polyimide tubular molding. The precursor of the polyimide tubular molded body was uniformly cast-applied on the inner wall of a coating mold having an inner diameter of 171.0 mm and a length of 450 mm, and the solvent was volatilized by exposure to hot air at 100 ° C. for 40 minutes. The coating mold is obtained by applying a glass coating to the inner wall of a SUS pipe and then mirror-polishing the inner wall. Next, the coating film was removed from the coating mold, mounted on a SUS cylindrical firing mold having an outer diameter of 167.7 mm, and heated from 100 ° C. to 380 ° C. over about 30 minutes. At this time, rotational motion was performed under the same conditions as in Example 1 (however, the temperature and time were different). Finally, the system was cooled to room temperature to obtain a polyimide molded body.

  Evaluation similar to Example 1 was performed with respect to the obtained polyimide molded body. As a result, both the appearance inspection and the long-term durability inspection were good.

(Example 3)
The same procedure as in Example 1 was performed until the cylindrical firing mold fitted with the precursor of the polyimide tubular molded body was sealed in an oven. Subsequently, the oven was further set to 120 ° C., and the rotary table was rotated at a speed of 0.5 rpm by the force of an external motor with the long axis of the cylindrical baking mold as the rotation center. After maintaining this state for 10 minutes, the temperature was raised from 120 ° C. to 250 ° C. over about 15 minutes while maintaining the rotational motion. Further, the rotational motion was stopped, and the temperature was raised from 250 ° C. to 380 ° C. over about 15 minutes. Finally, the system was cooled to room temperature to obtain a polyimide tubular molded body.

  Evaluation similar to Example 1 was performed with respect to the obtained polyimide molded body. As a result, both the appearance inspection and the long-term durability inspection were good.

(Comparative Example 1)
A polyimide tubular molded body was prepared by the same means as in Example 1 except that the rotary table was not rotated.

  Evaluation similar to Example 1 was performed with respect to the obtained polyimide tubular molding. As a result, 2 out of 10 polyimide tubular molded bodies were wrinkled, and appearance inspection was ×. In long-term durability inspection, image defects due to buckling and partial elongation occurred. Because it was, it was x.

(Comparative Example 2)
A polyimide tubular molded body was prepared by the same means as in Example 2 except that the rotary table was not rotated.

  Evaluation similar to Example 1 was performed with respect to the obtained polyimide tubular molding. As a result, the appearance inspection was “good”, and the long-term durability inspection was “poor” because an image defect occurred due to a wave caused by partial elongation.

  As mentioned above, although the semiconductive resin composition concerning this invention was demonstrated, this invention is not limited to the above-mentioned form.

Claims (3)

  The polyimide tubular molding is characterized by rotating the cylindrical firing mold in the step of heating the polyimide tubular molded body precursor after the polyimide tubular molded body precursor is fitted or applied to the tubular firing mold. Body manufacturing method.   A method for producing a polyimide tubular molded body, characterized in that the polyimide tubular molded body is rotated at least until the temperature of the precursor surface of the polyimide tubular molded body reaches 200 ° C.   A method for producing a polyimide tubular molded body, wherein the inner diameter of the polyimide tubular molded body is 150 mm or more.