JPH08157598A - Polyimide precursor composition for polyimide extrusion, its production, and production of polyimide molding - Google Patents

Abstract

PURPOSE: To obtain a polyimide molding excellent in uniformity in thickness, surface smoothness, and abrasion resistance by producing a polyimide precursor for polyimide extrusion and imidizing the precursor by extrusion. CONSTITUTION: A polyimide precursor soln. is obtd. by reacting an arom. tetracarboxylic dianhydride with an arom. diamine in a good solvent for the precursor. A compd.-mixed precursor soln. is obtd. by adding a function-giving substance to the precursor soln. The compd.-mixed precursor soln. is dispersed in a poor solvent to give a precipitate, which is dried at 0-100 deg.C to give an extrusion compsn. comprising 30-60wt.% compd.-mixed polyimide precursor, 0.1-5wt.% poor solvent, and 35-69.9wt.% good solvent and having a melt index of 10-30g/10min. The compsn. is extruded at 50-100 deg.C and imidized by dehydration by heating at 250-500 deg.C for 0.5-3hr, giving a polyimide molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide precursor composition for polyimide extrusion molding, a method for producing the same, and a method for producing a polyimide molded article.

[0002]

2. Description of the Related Art Since polyimide has excellent performance in mechanical properties and electrical properties in addition to thermal properties, it is indispensable in various fields as a heat resistant material having various usage forms. It has become a material. In addition, in addition to these characteristics, anti-static, surface heat generation, conductivity for the purpose of dielectric, thermal conductivity for the purpose of using thick film, productivity, etc.
Adds functionality such as heat retention and cold retention for thin film use and diaphragms, peelability for offset prevention, sliding, etc., surface roughness for antistatic, sliding, etc., high rigidity, etc. Is being attempted. As a method thereof, a substance having each functionality is mixed alone or in combination with a polyimide, or a polyimide laminate having a function of imidizing after mixing a substance having a function with a polyimide precursor is prepared. There is.

Polyimide allows a wide range of monomer combinations to be selected, but when heat resistance is emphasized, aromatic monomers are used. Aromatic polyimides that use aromatic monomers are not thermoplastic, so the molding method is:
A processing method in which a polyimide precursor is molded while partially imidizing it from a solution of the polyimide precursor and then the molded product obtained is imidized is mainly used. As another processing means, there is a method of molding polyimide powder at high temperature and pressure. As a method of obtaining a polyimide precursor molded article from a polyimide precursor solution, a polyimide precursor solution is applied onto a carrier and the solvent is evaporated by heating while partially imidizing. In order to obtain a desired shape, it is necessary to dry the solution while constantly holding the polyimide precursor solution having a low viscosity on the carrier. Various known processing means can be applied to obtain a molded product having a planar shape, but when manufacturing a molded product other than a planar shape, the processing means is limited. Centrifugal molding, which uses centrifugal force as a constraining force for actually obtaining a target shape, dipping, which utilizes surface tension and adhesive force, and spraying have been proposed. A common drawback of these processing means is that continuous molding is not possible. The centrifugal molding method has a limitation in forming a wide object, a tubular object having a short diameter, or a thin object, and the dipping method or the spray method has a problem in forming a thick object or a tubular object having a long diameter. Further, in the spray method, the thickness of the molded product is not uniform, and there are weak points such as foaming. As a method of solving these problems of the prior art,
The applicant of the present invention discloses a method for producing a polyimide precursor molded article in Japanese Patent Laid-Open No. 5-177689.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to further study the problems of the prior art and to improve the uniformity of thickness and the smoothness of the surface of polyimide molded products, especially tubular molded products. A polyimide precursor composition for use and a method for producing the same. Another object of the present invention is to provide a method for producing a polyimide molded article having excellent thickness uniformity, surface smoothness, and abrasion resistance.

[0005]

The first polyimide precursor composition for polyimide extrusion molding of the present invention comprises an aromatic tetracarboxylic dianhydride or its derivative (a) and an aromatic diamine or its derivative (b). And 30 to 60% by weight of a polyimide precursor (c) obtained by reacting with, a poor solvent of the polyimide precursor of 0.1 to 5% by weight, and a good solvent of the polyimide precursor of 35 to 69.9% by weight. Consists of including.

The second polyimide precursor composition for extrusion molding of the present invention is obtained by reacting an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b). 30% to 60% by weight of a polyimide precursor compound composed of the obtained polyimide precursor (c) and a functional substance, 0.1 to 5% by weight of a poor solvent of the polyimide precursor, and 35 to 69. It comprises 9% by weight.

The method for producing a polyimide precursor composition for polyimide extrusion molding of the present invention is as follows. A poor solvent for a polyimide precursor is put into a mixing vessel equipped with a stirring blade and a stirrer having a disc above it, and the stirring blade and The disk is rotated at a speed of 100 rpm or more to form a high-speed solvent layer of a poor solvent in the vicinity of the inner wall of the container, and then the aromatic tetracarboxylic dianhydride or its derivative (a) and the aromatic diamine or its derivative. A disc is prepared by injecting a polyimide precursor solution obtained by reacting (b) with a good solvent of a polyimide precursor or a polyimide precursor compound mixed solution obtained by adding a function-imparting substance to the solution onto the rotating disc. The polyimide precursor (c) is characterized by being dispersed in a poor solution by centrifugal force. Preferred embodiments include (1) a polyimide precursor or a polyimide precursor compound comprising the polyimide precursor and a functional substance, which is obtained by drying the precipitate at 0 to 100 ° C. and adjusting the good solvent content. 30-60 wt%, the poor solvent 0.1-5 wt% and the good solvent 35-69.
The composition is 9% by weight. (2) The polyimide precursor compound comprises 1 to 80% by weight of the function-imparting substance and 99 to 20% by weight of the polyimide precursor. (3) The good solvent is a solvent containing 30% by weight or more of a component having a boiling point of 170 ° C. or higher. (4) In the reaction of an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent for a polyimide precursor, the reaction between the (a) and (b) The concentration of almost equimolar mixture of
It consists of 0 to 20% by weight.

The first method for producing a polyimide molded article according to the present invention comprises an aromatic tetracarboxylic dianhydride or its derivative (a) and an aromatic diamine or its derivative (b).
And 5 in a good solvent of the polyimide precursor, the obtained polyimide precursor solution is dispersed in a poor solvent of the polyimide precursor, the poor solvent 0.1 to 5 consisting of a precipitate obtained
% Of the good solvent, 35 to 69.9% by weight of the good solvent, and 30 to 60% by weight of the polyimide precursor (c), a polyimide precursor composition for polyimide extrusion molding is extrusion molded at 50 to 100 ° C., and the obtained molding is obtained. The product is then imidized at 250 to 500 ° C.

The second method for producing a molded polyimide article according to the present invention comprises an aromatic tetracarboxylic dianhydride or its derivative (a) and an aromatic diamine or its derivative (b).
Precipitate obtained by dispersing a polyimide precursor compound mixed solution obtained by reacting a polyimide precursor solution obtained by reacting with a polyimide precursor solution with a functionality-imparting substance in a poor solvent of the polyimide precursor 0.1 to 5% by weight of the poor solvent and 35 to 69.9% by weight of the good solvent
And a polyimide precursor composition for polyimide extrusion molding containing 30 to 60% by weight of a polyimide precursor compound consisting of a functionality-imparting substance and a polyimide precursor.
Extruded at 0 ° C., and the obtained molded product is 250 to 500 ° C.
It is characterized in that it is imidized with. As a preferred embodiment, (1) a polyimide precursor composition for polyimide extrusion molding is melted at 50 to 100 ° C., extrusion-molded on a core material which is successively fed, and then heated at 250 to 500 ° C. to imidize. After that, the core material is removed to obtain a polyimide tubular molded article. (2) The good solvent is a solvent containing 30% by weight or more of a component having a boiling point of 170 ° C. or higher. (3) In the reaction of an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent for a polyimide precursor, the reaction between the (a) and (b) The concentration of almost equimolar mixture of
It consists of 0 to 20% by weight. (4) The polyimide extrusion molding composition has a melt index of 10 to 300 (g / 10 min). (5) Extrusion molding is performed using a die formed by coating the die land with a substance having a contact angle of 120 ° or less and a wetting tension of 20 dyne / cm or less. (6) 50 to 100 ° C. of polyimide extrusion molding composition
It is melted and then filtered with a screen pack of 300 mesh or more.

Polyimide precursor (c) according to the present invention
Can be obtained by reacting an aromatic tetracarboxylic dianhydride represented by the following formula or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent.

Embedded image [Here, R ¹ and R ² are aromatic groups, and n is a viscosity of 30 to 4
It is the number of repeating units showing 00 Pascal · second (Pa · s: 25 ° C. rotational viscometer measurement value: 15% by weight dimethylacetamide solution). ]

Specific examples of the aromatic tetracarboxylic dianhydride or its derivative (a) include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,6,7-
Naphthalenetetracarboxylic dianhydride, 1,2,5,6
-Naphthalene tetracarboxylic dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, 2,2'-
Examples thereof include bis (3,4-dicarbonoxyphenyl) propane dianhydride and bis (3,4-dicarboxyphenyl) sulfone dianhydride, and their derivatives, and these can be used alone or as a mixture. Specific examples of the aromatic diamine or its derivative (b) include 4,4′-diaminophenyl ether, 4,4′-diaminophenylmethane, 3,3′-diaminodiphenylmethane, paraphenylenediamine, metaphenylenediamine and benzidine. ,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenyl sulfide, 4,4'-
Diaminodiphenylpropane, 2,2'-bis [4-
(Aminophenoxy) phenyl] propane and the like, and their derivatives, and these can be used alone or as a mixture.

The good solvent according to the present invention is a solvent having a large ability to dissolve the polyimide precursor (c). Specific examples include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, hexamethylenephosphortriamide and the like, and these can be used alone or as a mixture. Further, phenols such as cresol, phenol and xylenol, hexane, benzene and toluene can be mixed with these good solvents. Particularly, a good solvent having a boiling point of 170 ° C. (760 mmHg) or more and 300 ° C. or less is preferable, and a solvent having a boiling point of 190 to 220 ° C. is more preferable.
When the good solvent having a boiling point of 170 ° C. (760 mmHg) or more and 300 ° C. or less is 30% by weight or more in all the good solvents, cracks are few in the imidization stage, and even if they are generated, the cracks are slight and the quality of the molded product is stable. Solvent with a boiling point of 170 ° C or higher is a good solvent 10
It may be 0% by weight. When a good solvent having a low boiling point of less than 170 ° C. is used, cracks occur in the process of evaporation of the solvent. If the sum of the strength resulting from imidization and the affinity of the solute and the solvent exceeds the stress such as volumetric shrinkage that occurs when the solvent evaporates, cracking does not occur, but if the sum is lower, cracking seems to occur. If the solvent evaporates at the stage where the imidization reaction does not create the strength required to maintain the shape of the molded article, cracks are likely to occur.

The polyimide precursor (c) is synthesized by reacting the aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent for the polyimide precursor. By doing things. The reaction is carried out by mixing the aromatic tetracarboxylic dianhydride or its derivative (a) and the aromatic diamine or its derivative (b) in an approximately equimolar mixture at a concentration of 10 to 20% by weight, preferably 11 to 14% by weight. The reaction is completed at a temperature of 80 ° C or lower, preferably 5 to 50 ° C, and a reaction time of 2 to 10 hours. Under such reaction conditions, the reaction can be carried out in a homogeneous system, and a polyimide precursor solution having a viscosity and fluidity suitable for obtaining a precipitate by pouring and dispersing in a poor solvent can be obtained.

The poor solvent according to the present invention is a solvent having a small ability to dissolve the polyimide precursor (c). Specific poor solvents include ethanol, methanol, acetone, benzene, toluene, xylene, ethyl acetate, water,
Alternatively, it is a mixed solvent of two or more of these. The poor solvent is preferably compatible with the good solvent. The poor solvent used for precipitation is 1 to 15 per weight of the polyimide precursor solution.
Double is better. You may use more than this range, but it becomes uneconomical.

The polyimide precursor compound of the present invention has a content of the function-imparting substance in the compound of 1 to
80% by weight, preferably 4 to 60% by weight. The function-imparting substance according to the present invention is a substance added for imparting conductivity, heat conductivity, heat retention and cold retention property, peelability, rough surface property, high rigidity and the like to the molded polyimide. It may be organic or inorganic, and a powdery substance of 100 μm or less is preferable, and 10 μm or less is more preferable. 0.2 to 10 μm is preferable for film forming.

Carbon black as the conductivity-imparting substance,
Graphite, metals and metals such as Al, FeCu, and Ag, and metal compounds such as TiO ₂ , BaTiO ₃ , and K ₂ O.nTiO ₂ as heat conductivity imparting substances such as Ag, Cu,
Metals such as Au, Al, W, Mg, Mo, Zn, Cd and Si, metal compounds such as AlN, Al ₂ O 3, SiC, SiO ₂ and MgO, carbon black, graphite, diamond, BeO, BN and BP, Shirasu micro hollow spheres (hereinafter referred to as balloons) as a substance that imparts heat retention and cold retention,
Silica balloon, aluminosilicate balloon, glass balloon, alumina balloon, zirconia balloon, carbon balloon, perlite, balm culite, etc.
Polytetrafluoroethylene (P
TFE), perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE) and other fluororesin fine powders, surface roughness, Glass beads as high rigidity imparting substance,
Ceramic beads, fine silica powder, Si ₃ N ₄ , TiO
₂ , Ti ₃ N _{4 and the} like can be used, but these may be used alone or in combination according to the purpose.

As a means for dispersing the powder of the function-imparting substance in the polyimide precursor solution, a method of mixing the powder with a good solvent and wetting the surface of the substance with the good solvent,
After the mixing, it is passed through a nip roll or a ball mill to apply shear to the fine powder to improve dispersion, and by attaching stearic acid or the like to the surface of the fine powder, the fine powder is prevented from gelling and dispersed. It is possible to give the way to do.

The method for producing a polyimide precursor composition for polyimide extrusion molding according to the present invention is carried out by placing a poor solvent for a polyimide precursor in a mixing vessel equipped with a stirring blade and a stirrer having a disk above it. And the disk are rotated at a speed of 100 rpm or more, and then the aromatic tetracarboxylic dianhydride or its derivative (a) and the aromatic diamine or its derivative (b) are reacted in a good solvent for the polyimide precursor. The polyimide precursor solution thus obtained is poured onto the rotating disk and dispersed in the poor solution by the disk centrifugal force to precipitate the polyimide precursor (c). The obtained precipitate contains a good solvent and a poor solvent together with the polyimide precursor (c).

This manufacturing method will be described based on the polyimide precursor deposition apparatus shown in FIG. This device is a modification of the Henschel mixer (trade name).
The stirring shaft 10 has a stirring blade 12 and a disc 1 above it.
3 is provided and is connected to the motor 9. The stirring shaft 10 rotates at a high speed of 100 rpm or more. Further, a pressure vessel 15 for injecting the polyimide precursor solution 14 into the disk 13 is provided at the upper part, and an outlet 16 for taking out the solution containing the polyimide precursor deposit is provided. The material of the disk 12 is preferably a material to which the polyimide precursor is hard to adhere, and polyolefin (PP, PE, etc.), polyester resin (PET), and fluororesin are better than metals in terms of dispersibility.
The size of the disk 13 is preferably 30 to 50% of the inner diameter of the mixing container, and if it is too large, precipitates accumulate on the disk and successively form large lumps. When it is small, the disc centrifugal force is small and the dispersibility is insufficient. In order to uniformly inject the polyimide precursor solution 14 in a short time, pressurized air may be added to the pressure vessel 15 having the pore injection port 8 of 5 mmφ or less.

The method of dispersing the polyimide precursor solution in a poor solvent and precipitating it is carried out by mixing a predetermined amount of the poor solvent 17 in the mixing container 11.
And the stirring blade 12 and the disk 13 are rotated at a high speed of 100 rpm or more. At this time, the disk may be submerged in the poor solvent when the disk 13 does not rotate [Fig. 1 (a)].
When rotating at a high speed, the poor solvent surface 18 becomes lower than the upper surface of the disk, and a high speed solvent layer of the poor solvent is formed near the inner wall of the container [see FIG. 1 (b)]. Therefore, it is necessary to determine the amount of the poor solvent to meet such conditions.

A high-speed solvent layer of the poor solvent 17 is formed on the stirring blade 12 and the inner wall of the mixing container 11, and then a narrow stream of the polyimide precursor solution 14 is injected onto the disk 13 and the poor solvent 1 is applied by the disk centrifugal force.
Disperse in 7. Disk rotation speed is 500-1500r
pm is preferred, and the injection of the polyimide precursor solution 14 is
It is injected in a narrow stream of 5 mmφ or less, preferably 2 to 4 mmφ, and further preferably less than that. The deposition temperature is preferably 100 ° C or lower, more preferably 10 to 30 ° C. As a result, it is possible to easily and efficiently obtain the short fibrous flakes and the powdery deposits having a regular shape. The precipitate is separated from the solution phase and then dried to obtain the composition of the present invention. A good solvent may be added to adjust the concentration of the solvent in the composition.

A filter paper, a filter cloth, a net, or a filter is used as the filter material used for separating the precipitate and the solution. The filter medium has a contact angle of 120 ° or less and a wetting tension of 20 dyne /
cm or less, and more preferably net-like one made of monofilament. Examples of the material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer ( ETFE) and the like. When separated by such a filter medium, clogging is less likely to occur, precipitates can be easily removed, the filter medium does not adhere to the filter medium, and the filter medium can be repeatedly used. For separation, it is preferable to put the solution containing the precipitate in a bag using these filter media and perform centrifugal filtration.

The separated precipitate is dried at 0-100 ° C., preferably 40-70 ° C., in air or an inert gas dried at atmospheric pressure or reduced pressure. As a result, the poor solvent containing water in the precipitate can be reduced. If it exceeds 100 ° C, it will be extruded during extrusion (good solvent of polyimide precursor insoluble)
Is frequently generated, which is not preferable. The dry precipitate may be directly extrusion-molded, or a good solvent may be added to the dry precipitate to adjust the concentration and then granulated, followed by extrusion-molding. In this granulation, a good solvent was added to the dried precipitate, and the mixture was uniformly mixed with a roll, a kneader, a mixer, etc.
Cut into 10 mm square to obtain square pellets. This pelletization enables efficient extrusion molding that is less likely to cause blocking, resulting in a more homogeneous molded product. When the composition is stored in a low temperature and low humidity container at room temperature, preferably -10 to 10 ° C until molding, the composition hardly blocks and absorbs moisture.

The content of the polyimide precursor (c) in the polyimide precursor composition for extrusion molding of the present invention is 30% by weight or more and 50% by weight or less, preferably 35 to 45%.
% By weight. If it is less than 30% by weight or more than 50% by weight, the composition cannot have appropriate viscosity and fluidity during extrusion molding. The content of the poor solvent in the composition for extrusion molding of the present invention is 0.1% by weight or more and 5% by weight or less, preferably 2% by weight or less, and more preferably less than that, but it is completely excluded. Difficult and not economical. In particular, by removing the water content of the poor solvent brought in from the good solvent and the poor solvent having hygroscopicity, it is possible to reduce foaming during extrusion molding, film breakage, and poor appearance due to this.

Melt index of polyimide precursor composition for extrusion molding suitable for obtaining the polyimide molded article of the present invention (flowability index, flow test method according to JIS-K7210, 100 ° C., 2 kg load, 2.095 mmφ) × 8m
m-die, unit g / 10 min) is 10 to 300, preferably 50 to 200, more preferably 80 to 1.
50. The amount of the good solvent in the composition is adjusted to fall within this range. Within this range, the self-shape retention property during extrusion molding is good, shear heat generation does not occur in the extruder, and there is no slump over time, which makes continuous extrusion stable for a long time. The extrusion-molded product thus obtained has good moldability in the set shape, there is no surface irregularity due to deterioration of fluidity, there is no appearance defect such as poor smoothness due to uneven extrusion, the occurrence of spots is extremely small, and it is homogeneous and ruptured. Strength, elongation at break,
Excellent elastic modulus. The self-shape retaining property means a viscoelastic state in which a carrier in a vertical state has no self-weight fluidity at room temperature.

Extrusion molding in the method for producing a polyimide molded article of the present invention is uniaxial or biaxial, in the same or different directions of screw rotation, with or without vent, with rapid or slow compression, with or without orifice, with gear pump. Alternatively, it is possible to use a general-purpose resin extruder. Furthermore, it is desirable to have a mechanism that enables accurate adjustment of low-temperature extrusion, has a small dead zone of the extruder, and enables smooth delivery of the molten resin, and has little shear heat generation.
00 ° C or less, preferably 60 to 80 ° C, with a compression ratio (effective area ratio of the feeding part / measuring part) of 1.2 to 3, a bidirectional extruder with vents and a gear pump, fixed or continuous. Filtration with a 300-500 mesh fine screen pack is desirable. As a result, it is possible to greatly reduce the generation of lumps over time, and to obtain a uniform and homogeneous extruded product. As the molding method, film, sheet,
It does not specify irregular shapes, coatings, fibers, hollows, injections, etc.

In the method for producing a polyimide molded article of the present invention, when a tubular molded article is produced, an extrusion device for melting and quantifying the composition for extrusion, a moving device for sequentially feeding out the core material 20, and a molten coating material are used. An apparatus consisting of a coating die for coating the core material is used.

The coating die will be described with reference to FIG.
Reference numeral 20 is a core material that moves downward in the drawing, 21 is a polyimide precursor composition melt inlet, 22 is a spiral flow path, and 23 is
Is a choke (drawing), 24 is a manifold (reservoir), 28 is a thickness adjusting ring, 25 is Gap (die exit gap), and 26 is Land (die exit gap parallel straight line) part. Welding tension 20 dy on inner wall surface and peripheral surface of Land (die exit gap parallel straight line portion) 26 is 120 ° or less
ne / cm or less polytetrafluoroethylene (PTF
E) or the like. A pressure reducing mechanism 29 for reducing the pressure between the core material 20 and the sleeve (melted composition of the composition extruded from the die) 27, and a rubber ring 30 are installed on the upper part of the die.

The core moving device (not shown) has two sets of rolls for supplying the core at a constant speed on the pressure reducing mechanism, and two sets of rolls for continuously feeding the upper part of the core without interruption.
There is a mechanism for holding the core material coated at a constant speed in the lower part of the die and taking it out of the system. With these, the core material 20 is sequentially fed out. When a screen pack of 300 to 500 mesh is attached to an extruder for melting and quantifying the polyimide precursor composition for extrusion, the outflow of lumps can be reduced and the smoothness of the molded article can be obtained. If it is coarse, it is impossible to remove the lump, and if it is fine, the back pressure of extrusion is applied too much.

Land (straight line portion parallel to the die exit gap) 26
Examples of the substance having a contact angle of 120 ° or less and a wetting tension of 20 dyne / cm or less that coats the inner wall and the peripheral portion thereof are polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene. To hexafluoropropylene copolymer (FEP), tetrafluoroethylene to ethylene copolymer (ETFE), and the like.
When coated with a substance having a contact angle of 120 ° or less and a wetting tension of 20 dyne / cm or less, no scale is attached and the surface appearance of the extruded product is good without vertical stripes. Dai Land /
When Gap is 10 to 100, the rectifying function is exhibited, the thickness deviation is ± 20% or less, there is no melt fracture (streamline breakage), and the surface appearance is good. If a pressure reducing mechanism 29 for reducing the pressure between the core material 20 and the sleeve 27 is attached, the surface of the molded product becomes smoother and more uniform without blistering.

As the extrusion conditions, the extrusion temperature is set to 100 ° C. or lower, preferably 60 to 80 ° C., whereby the generation of seeds can be reduced with time. If the number of spots can be reduced, the extrusion back pressure will not increase, stable extrusion can be performed for a long time, and a good appearance can be obtained. Butts (insoluble matter of the polyimide precursor) may be supersaturated precipitates of the polyimide precursor in a good solvent, but it is considered that the polyimide precursor is mainly a low-order imidized and separated from the good solvent. The spots cause devitrification, perforation, film breakage, surface irregularities, screen pack clogging, screw rotation resistance, and the like, and are the biggest impediments to the production of uniform and homogeneous continuous extrusion products. Wall thickness of extruded products,
The outer diameter is set as needed.

In the imidization in the method for producing a molded product of the present invention, the extruded product is heat-treated from room temperature to a temperature of 250 ° C. or higher and 500 ° C. or lower for 0.5 to 3 hours to remove a good solvent by evaporation. Then, dehydration reaction of the polyimide precursor occurs, and imidization is completed. If it is too low, the dehydration reaction takes too much time to obtain sufficiently effective heat resistance and strength, and if it is too high, decomposition begins to turn brown, foaming occurs due to rapid evaporation of the solvent, and cracks occur. . Preferably, the imidization is carried out by raising the temperature from room temperature to 300 to 450 ° C. for 0.8 to 2 hours. Cracks are generated in the process of imidization of the polyimide precursor molded product, and cracks are likely to be generated when the solvent is dried at a stage where the imidization reaction is not progressing.

[0033]

[Examples] Examples and comparative examples will be further described below. -The shape of the precipitates is as follows: there are no large lumps, and there are some. -The polyimide precursor concentration is calculated by the following formula. ((Weight after heat treatment at 425 ° C./k)/weight of composition for extrusion molding) × 100, where k = theoretical value of polyimide molecular weight / theoretical value of polyimide precursor (c) molecular weight. Y (1-Z) /
YK × 100 X: composition weight for extrusion molding Y: weight after heat treatment at 425 ° C. (polyimide + fine powder) Z: weight ratio of fine powder in polyimide compound K: theoretical molecular weight of polyimide after dehydration / polyimide precursor ( c) Theoretical value of molecular weight ・ As for the evaluation of homogeneity, the surface resistance of the carbon-containing polyimide compound 50 μm film was measured by the surface high resistance meter (“Hiresta HT-210” manufactured by Mitsubishi Yuka).
(ASTM D257-61).

The good solvent and poor solvent concentrations are high temperature gas chromatography (1
The peak area ratio belonging to each of the values was obtained.・ MI (100 ° C., 2 kg load) is JIS K-7210 as an index of extrusion fluidity of solid polyimide precursor.
Is applied mutatis mutandis to the test temperature of test condition 2 at 100 ° C. -As for extrusion moldability, the one with good screenability and the one with good screenability, which does not exhibit clogging of screen packs, resistance to screw rotation, etc., and has good productivity, were evaluated as x. -Appearance was rated as ∘ without cracks, surface irregularities, spots, wrinkles, vertical lines, blisters, devitrification, or whitening, and x if not. -The surface smoothness (surface roughness) is (JIS B-0651).
Contact-type surface roughness measurement method: Germany HOMMELWERKE
Manufactured by T1000C, unit: μm).

Example 1 Preparation of Polyimide Precursor Solution Formula (2)

Embedded image 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride represented by the formula (3)

Embedded image 12 parts by weight of an equimolar mixture with para-phenylenediamine represented by are mixed with 88 parts by weight of a good solvent N-methyl-2-pyrrolidone (abbreviated as NMP: boiling point 204 ° C.),
The solution has a viscosity of 17
A polyimide precursor solution (referred to as a PAA solution) having 0 Pascal · second (pa · s) (measured value at 25 ° C. rotational viscometer) was obtained.

(Production of Polyimide Precursor Composition for Polyimide Extrusion Molding) A 20-liter Henschel mixer was remodeled into a mixing vessel 11, a pressure vessel 15 was provided on the upper portion, and a diameter of 130 mmφ (inner diameter of 300 m of the apparatus was provided on the upper portion of the stirring shaft 9.
Approximately 43% of mφ) 5 mm thick polypropylene disc 1
3 and the stirring blade 12 were attached to the lower part (see FIG. 1). Ethanol as a poor solvent in the mixing container 11.
9 kg was put and stirred at a rotation speed of 950 rpm.
Then, 1.8 kg of the above PAA solution 14 is added to the pressure vessel 1
The mixture was placed in a container No. 5 and injected under pressure from a 3 mmφ injection port 8 while hitting a polypropylene disk 13 rotating as a trickle, and after the injection, stirring was continued at 20 ° C. for 30 minutes to precipitate a polyimide precursor. The obtained precipitate was a short fibrous flake with a regular shape.

The solution containing the precipitate was placed in a fluororesin monofilament filter cloth bag and filtered by using a centrifugal separator having a rotation speed of 3000 rpm. It was easy to remove the deposits, and there was little adhesion to the filter bag, allowing repeated use. In order to reduce the poor solvent such as ethanol and water in the filtered precipitate, 600 g of the filtered precipitate is placed in a closed dryer equipped with a biaxial stirring blade to obtain a drying temperature. 4
The temperature was raised stepwise from 0 ° C. to 60 ° C. and dried in nitrogen gas for 40 minutes. The dried product of the obtained precipitate was 330 g. The composition of the dried product was approximately 65% by weight of polyimide precursor, 33% by weight of good solvent NMP, and 2% by weight of poor solvent. To the dried product, 210 g of NMP was added uniformly,
A sheet having a thickness of 2 mm was formed using a pressure roll whose temperature was adjusted to ℃, and a pellet-shaped composition was formed using a square pellet manufacturing machine.
The composition of the pellets is approximately polyimide precursor 40.
%, Good solvent 59%, extraction solvent and poor solvent 1% by weight, and MI was 90 g / 10 min. The work environment after extraction was performed in a moisture-proof and dust-proof system. The composition was stored at a temperature below 10 ° C.

(Production of Polyimide Molded Product) As the extruder, a slow compression type twin-screw extruder with a vent of 20 mm in different directions and a gear pump was used in combination with a fixed 500 mesh screen pack. The coating die is shown in FIG.
A cross head round die having a hole of 46 mmφ is attached to the end of the gear pump, and the round die is composed of a spoiler flow path, a manifold (reservoir), a choke (throttle), and a thickness adjusting ring. Gap 0.5 mm, Land 35 mm, Land The inner surface of the part and the peripheral part of the land part were covered with 30 μm of polytetrafluoroethylene (PTFE). The metal tube 20 having an outer diameter of 45 mmφ is passed through a round die (coating die), while the square pellet composition stored at 10 ° C. is charged into an extruder. The composition is extruded and melted, and is sent to a melt inlet 21 by a gear pump. The melted composition passes through the spiral flow path 22, the choke 23, and the Land 26, becomes a melting sleeve 27 at the Gap 25, and is sequentially fed out. (Core material) 2
Cover 0. As conditions for extrusion coating, the temperature is 80 ° C,
Extrusion rate is 1 kg / hr, metal tube feeding speed is 1.5 m
/ Min, the pressure between the metal tube (core material) 20 and the melting sleeve 27 is 500 mmAq. Is. No foaming, film breakage, devitrification, perforation, surface irregularities, vertical streaks, lumps, or spots, even after continuous extrusion molding for 8 hours, wrinkles, blisters, screen pack clogging, screw rotation Resistance was not exhibited, stable continuous production was possible, and productivity was good. Extruded products coated on metal tubes are
Imidization was carried out for 2 hours while raising the temperature to 5 ° C. It was peeled from the metal tube to obtain a tubular polyimide extruded product having a thickness of 20 μm.

The physical properties of this polyimide extruded product are as follows: breaking strength 31.2 kg / mm ² , breaking elongation 18.8%, elastic modulus 708 kg / mm ² , thickness deviation ± 11%, surface smoothness R
The z was 1.0 μm. The appearance is cracks, surface irregularities, spots,
There were no wrinkles, vertical lines, blisters, devitrification, and whitening.

Comparative Example 1 15 parts by weight of an equimolar mixture of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine was added to a good solvent N, N.
Dimethylacetamide (abbreviated as DMAC: boiling point 165.
5 ° C, 758 mmHg) 85 parts by weight and mixed at a temperature of 10
A polyimide precursor solution having a solution viscosity of 80 Pascal · second (Pa · s) (measured by a rotational viscometer at 25 ° C.) was obtained by synthesizing at 8 ° C. for 8 hours while stirring. 36 parts by weight of ethanol as a poor solvent was put into a Henschel mixer, and 10 parts by weight of the above polyimide precursor solution was injected with stirring.
Stirring was continued for 30 minutes at 0 ° C., and the obtained precipitate was separated by centrifugation. This precipitate was dried under reduced pressure in nitrogen gas at 40 ° C. for 40 minutes. The dry precipitate had a composition of about 55% by weight of polyimide precursor, about 38% by weight of good solvent DMAC and about 7% by weight of poor solvent. The same twin-screw extruder as in Example 1 was used as an extruder for tube coating. 46 mmφ
A cross head round die with a hollow hole is attached, and the round die is composed of a spiral flow path, a manifold (reservoir), a choke (throttle), and a thickness adjusting ring.
0.5 mm, Land 35 mm, the composition was charged into an extruder, the extrusion temperature was 110 ° C., the extrusion rate was 1 kg / Hr,
The metal tube speed was 1.5 m / min. After 8 hours of continuous extrusion molding, foaming, film breakage, vertical lines, devitrification, perforation,
Surface irregularities, wrinkles, blisters due to air traps, and spots often appeared.

The extruded product coated on a metal tube is heated from room temperature to 4
The imidization was carried out to a temperature of 00 ° C. for 2 hours. The physical properties of a polyimide extrusion-molded product having a thickness of 20 μm obtained by peeling from a metal tube have a breaking strength of 18 kg / mm ² and a breaking elongation of 7
%, Elastic modulus 450 kg / mm ² , thickness deviation ± 60%, surface smoothness Rz of 25 μm, cracks, blisters due to air traps, foaming, lines, devitrification, perforation, surface irregularities,
It was a polyimide extrusion molded product that had wrinkles and many spots.

[0042]

[Table 1]

(Example 2) (Preparation of polyimide precursor solution) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride represented by the formula (2) and para represented by the formula (3). 15 parts by weight of an equimolar mixture with phenylenediamine was used as a good solvent N, N-dimethylacetamide (abbreviated as DMAC: boiling point 165.5).
C., 758 mmHg) at 85.degree. C. and mixed at a temperature of 10.degree. C. for 8 hours with stirring to obtain a polyimide precursor solution having a solution viscosity of 50 Pascal.sec (pa.s) (25.degree. C. rotational viscometer measurement value).

(Production of Polyimide Precursor Composition for Polyimide Extrusion Molding) 250 g of carbon black ("Ketjen Black EC-P" manufactured by Lion-Akzo) is DMA
C3045g mixed, ball mill (stainless steel 30m
m spheres) for 6 hours, and then 6000 g of the above polyimide precursor solution was mixed and further dispersed for 6 hours by the above ball mill. Then, pressure filtration was carried out using a 500 mesh screen.

A precipitation apparatus (Fig. 1) obtained by modifying a 20-liter Henschel mixer was used.
Insert 9 kg, and attach a polypropylene disk with a diameter of 130 mmφ (approx. 43% of the apparatus inner diameter of 300 mmφ) and a thickness of 5 mm to the upper part of the stirring shaft and a stirring blade to the lower part 950r.
It was rotated at pm. Then, 1.8 kg of the above-mentioned polyimide precursor compound mixed solution was put in a pressure vessel and injected while being pressed against a polypropylene disc rotating as a stream of 3 mmφ under pressure, and stirring was continued at 20 ° C. for 30 minutes. The deposit was a short fibrous flake with a regular shape.

The solution containing the precipitate was put in a fluororesin monofilament filter cloth bag and filtered by using a centrifugal separator at a rotation speed of 3000 rpm. Precipitates were easily removed, there was little adhesion to the filter bag, and repeated use was possible.
In order to reduce poor solvents such as ethanol and absorbed water, 600 g of the precipitate separated by filtration is started at 40 ° C in a closed dryer equipped with biaxial stirring blades, and gradually added up to a final temperature of 60 ° C. Dried precipitate 3 after drying in nitrogen gas for 40 minutes
20 g was obtained. The dried precipitate is polyimide precursor 5
The composition was 5% by weight, 15% by weight of carbon, 29% by weight of good solvent DMAC, and 1% by weight of poor solvent. 140 g of NMP was evenly added to the dried precipitate, and a sheet having a thickness of 2 mm was formed with a pressure roll whose temperature was adjusted to 10 ° C., and a square pellet composition was obtained with a square pellet manufacturing machine. The composition was about 49% by weight of polyimide precursor compound, about 50% by weight of good solvent (breakdown NMP60, DMAC40), about 1% by weight of poor solvent, and MI was 40. The work environment after extraction was performed in a moisture-proof and dust-proof system. The obtained rectangular pellet-shaped composition was stored at a temperature of 10 ° C or lower.

(Production of Polyimide Molded Product) As an extrusion molding apparatus for coating the core material, an extrusion apparatus for supplying the composition, a die for coating the core material, and a core material moving apparatus were used (see FIG. 2). As an extrusion device, a slow compression type different direction 20 with a compression ratio of 2 is used.
A gear pump is used in combination with the mmφ vented twin-screw extruder.
A fixed 500 mesh screen pack was used. A cross head round die having a hollow hole of 46 mmφ is attached to the tip of the gear pump, and the round die is composed of a spiral flow path, a manifold (reservoir), a choke (throttle), and a thickness adjusting ring, Gap 0.5 mm, Land 35 mm, PTFE30 on the inner surface of the Land part and the peripheral part of the Land part
coated with μm. Further, in order to obtain a close contact coating, coating was performed between the core material and the coating material under a reduced pressure of 500 mmAq. The square pellet composition maintained at 10 ° C. was charged into an extrusion device, and the outer diameter was 45 mm so that it could smoothly pass through the hollow of a round die.
The composition extruded from the die outlet into a φ metal tube has an extrusion temperature of 80 ° C., an extrusion rate of 1 kg / Hr, and a core material speed of 1.5 m / mi.
n. Even after continuous extrusion molding for 8 hours, there is no foaming, film breakage, devitrification, perforation, surface irregularities, vertical streaks, no spots, wrinkles, blisters, screen pack clogging, screw rotation overresistance, etc. It did not develop, and stable continuous production was possible. The productivity was also good.

The extruded product coated on the core material is heated from room temperature to 42
Imidization was carried out at a temperature rise time of 5 ° C. for 3 hours. The core material was peeled off to obtain a carbon compound-containing polyimide compound extrusion molded product having a thickness of 20 μm. The physical properties of this molded product are as follows: breaking strength 20 kg / mm ² , breaking elongation 6%, elastic modulus 630 kg.
/ Mm ² , thickness deviation ± 9%, surface smoothness Rz 1.5 to 2
The surface electrical resistivity was 7 × 10 ³ Ω for both the front and back sides (> 10 ¹⁶ Ω for the same polyimide). In addition, the wear resistance is 17 mg [(1 kg load)-(blank,
13 mg)]. This polyimide carbon compound extrusion molded article has good appearance with no cracks, surface irregularities, spots, wrinkles, vertical lines, blisters, devitrification, whitening, and excellent physical properties such as strength, elongation, elastic modulus, and excellent smoothness, It had little uneven thickness. Further, as a measure of whether or not the functional property-imparting substance is evenly dispersed, the surface electrical resistivities of the front and back surfaces of the film were measured, and the same values were obtained.

(Example 3) A polyimide precursor solution was synthesized according to Example 2, and 15 kg of the solution was mixed with aluminum powder [Mountain Metal K.K. K. Made "VA-2000"] 0.6
15 kg and 3.485 kg of DMAC were mixed and dispersed in a ball mill (stainless steel 30 mmφ ball) for 6 hours, and then pressure filtered through a 500 mesh screen.

According to Example 2, from the above-mentioned polyimide precursor compound mixed solution, 600 g of a substantially fibrous short fiber precipitate was obtained. After drying, 390 g of dried precipitate was obtained. The composition of the dry precipitate is about 5 polyimide precursors.
The content was 4.3% by weight, aluminum was about 14.9% by weight, good solvent DMAC was about 31% by weight, and poor solvent was about 0.5% by weight. 148 g of NMP was added uniformly to the dried precipitate,
It was a rectangular pellet composition. The composition in the form of square pellets is about 50.2% by weight of polyimide precursor compound and about 49.5% by weight of good solvent (breakdown NMP56, DMAC4
4), the composition of the poor solvent is about 0.3% by weight, and the MI is 10
It was 0 g / 10 min.

In accordance with Example 2, the above rectangular pellet composition was coated on a 24 mmφ core material at a coating speed of 1.2 m / min using a crosshead die having hollow holes of 25 mmφ.
And was imidized to obtain an aluminum powder-containing polyimide compound extrusion molded article having a thickness of 50 μm. The physical properties of this molded product are a breaking strength of 24 kg / mm ² and a breaking elongation of 20.
%, Elastic modulus 580 kg / mm ² , thickness deviation ± 9%, surface smoothness Rz 1.0 to 1.5 μm, and wear resistance is 15 mg [(1 kg load)-(blank, 13 m
g)]. This polyimide-aluminum powder compound extruded product had a good appearance as in Example 1,
It was excellent in physical properties and had less uneven thickness.

(Comparative Example 2) 15 parts by weight of an equimolar mixture of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine were mixed with DMA as a good solvent.
C85 parts by weight are mixed, and the mixture is synthesized with stirring at a temperature of 10 ° C. for 8 hours to obtain a solution viscosity of 65 Pascal · sec (pa · s) (2
A polyimide precursor solution of 5 ° C. rotational viscometer measurement value) was obtained. To 15 kg of this polyimide precursor solution, aluminum powder [“VA-2000” manufactured by Yamaishi Metal Co., Ltd.] 0.6
15 kg and DMAC 3.485 kg were mixed and dispersed with a ball mill (stainless steel 30 mmφ ball) for 6 hours,
Then, it was pressurized and filtered through a 500 mesh screen. 36 parts by weight of ethanol as a poor solvent was put in a Henschel mixer, 10 parts by weight of the above-mentioned polyimide precursor compound mixed solution was injected with stirring, and after the injection, stirring was continued for 30 minutes at 30 ° C., and the precipitate was centrifuged to obtain the product. The precipitate was dried at 40 ° C. for 40 minutes in nitrogen gas. The composition of 420 g of the dried precipitate was about 50% by weight of polyimide precursor, about 4% by weight of aluminum, about 29% by weight of good solvent DMAC,
The poor solvent was about 7% by weight.

As an extrusion molding apparatus for coating the core material, an extrusion apparatus for supplying the above composition and a hollow round die for horizontal coating for coating the core material were used. As the extrusion device, a slow compression type extrusion device having a different compression direction of 20 mmφ was used. A crosshead round die with a 46 mmφ hollow hole was attached. The circular die has a spiral flow path, a manifold, a choke, and a thickness adjustment ring (Gap 0.5 mm,
Land 35 mm). The composition was put into an extruder and extruded from a die outlet into a metal tube having an outer diameter of 45 mmφ capable of smoothly passing through the hollow of a round die. Extrusion temperature 110 ° C., extrusion rate 1 kg / Hr, core material coating speed 1 Coated at 0.5 m / min. After continuous extrusion molding for 1 hour, foaming, film breakage, vertical streaks, devitrification, perforation, surface irregularities, wrinkles, blisters due to air traps, and spots often appeared.

The extruded product coated with the core material is heated from room temperature to 40
Imidization was carried out to 0 ° C. with a heating time of 2 hours. It was peeled from the core material to obtain a polyimide extrusion molded product having a thickness of 20 μm.
The physical properties of this molded product are a breaking strength of 15 kg / mm ² , a breaking elongation of 5%, an elastic modulus of 450 kg / mm ² , and a thickness deviation of ± 80.
%, Surface smoothness Rz 25 μm, wear resistance is surface 200 m
g, back side 50 mg [(1 kg load)-(blank, 13
mg)], there are cracks and blisters due to air traps,
Foaming, streaks, devitrification, perforation, surface irregularities, wrinkles,
It was a polyimide extrusion-molded product with many lumps.

(Comparative Example 3) A polyimide precursor compound mixed solution was prepared in the same manner as in Example 2, and a polyimide compound molded product having a diameter of 100 mm and a thickness of 50 μm was prepared.
The film was produced by centrifugal molding. Centrifugal molding method is Japanese Patent No. 318508 (method for manufacturing thin endless belt)
The inner wall of the rotating drum with an inner diameter of 110 mmφ is approximately 2 m in advance.
A silicone rubber layer as a molding layer / release layer of m was formed by reaction curing under centrifugal force, and while heating to 170 to 180 ° C.,
An imide precursor solution having a concentration of about 10% by weight was injected into the drum, and a partial dry imidation was performed under a centrifugal force of a rotation speed of 1000 rpm for about 40 to 50 minutes. After becoming tack-free, it was taken out of the drum, inserted into a core material having an outer diameter of 100 mmφ, and imidization was completed at a temperature rise time of 2.5 hours up to 425 ° C. The physical properties of the obtained polyimide film containing carbon having a diameter of 100 mm and a thickness of 50 μm were as follows. Breaking strength 22 kg / mm ² , breaking elongation 15%,
Elastic modulus 550 kg / mm ² , thickness deviation ± 5%, surface smoothness Rz outer surface 1.5 to 2.5 μm, inner surface 0.5 to 1.0 μm
m, surface electric resistance outer surface 10 ⁰ to ¹ inner surface> 10 ² to ⁵ , wear resistance of surface 103 mg, back surface 11 mg [(1 kg load)-
(Blank, 13 mg)].

Comparative Example 4 A polyimide precursor compound mixed solution was prepared according to Example 3, and a polyimide compound molded product of a film having a diameter of 100 mm and a thickness of 50 μm was prepared by centrifugal molding according to Comparative Example 2. . The physical properties of the obtained polyimide film containing aluminum powder having a diameter of 100 mm and a thickness of 50 μm were as follows. Breaking strength 25 kg / mm ² , breaking elongation 35%, elastic modulus 560 kg / mm ² , thickness deviation ± 5%, surface smoothness Rz outer surface 1.5 to 2.0 μm, inner surface 0.5 to 1.0 μm.
m, wear resistance is 48 mg on the front side, 15 mg on the back side [(1 kg
Load)-(blank, 13 mg)].

[0057]

[Table 2]

[0058]

EFFECT OF THE INVENTION The extrusion molding composition of the present invention is capable of easily molding a polyimide by using a conventional general-purpose thermoplastic resin extrusion molding apparatus, although it is not a thermoplastic resin. Further, it is possible to provide a polyimide precursor precipitate suitable for the method for producing the composition for extrusion molding of the present invention and molding. According to the method for producing a molded article of the present invention, stable extrusion can be performed under the specified conditions by using the above-mentioned composition for extrusion molding, foaming and film breakage do not occur, and the productivity is good. Also, cracks, surface irregularities, spots, wrinkles,
It is possible to provide a molded product having a good appearance without vertical lines, blisters, devitrification, and whitening, excellent physical properties such as strength, elongation, and elastic modulus, and a uniform wall thickness, particularly a tubular molded product.

[Brief description of drawings]

FIG. 1 is a diagram showing a composition depositing apparatus used for producing a polyimide precursor composition for polyimide extrusion molding, in which (a) is stationary and (b) is a stirrer rotating.

FIG. 2 is a schematic view of a coating die of an apparatus for manufacturing a polyimide tubular molded article.

[Explanation of symbols]

8 Polyimide Precursor Solution Injection Port 9 Motor 10 Rotating Shaft 11 Mixer 12 Stirring Blade 13 Disc 14 Polyimide Precursor Solution 15 Pressurizing Container 16 Discharge Port 17 Poor Solvent 18 Poor Solvent Surface 19 Melt Composition 20 Core Material 21 Melt Entrance 22 Spiral flow path 23 Choke 24 Manufacture 25 Gap (die exit gap) 26 Land (die exit gap parallel straight line portion) 27 Melting sleeve (cylindrical melt extruded from round die) 28 Thickness adjusting ring 29 Decompression mechanism 30 Rubber ring 31 Mandrel

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08J 5/00 CFG // B29K 79:00

Claims (16)

[Claims] 1. A polyimide precursor (c), obtained by reacting an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b), in an amount of 30 to 60% by weight, A polyimide precursor composition for polyimide extrusion molding, comprising 0.1 to 5% by weight of a poor solvent of the polyimide precursor and 35 to 69.9% by weight of a good solvent of the polyimide precursor. 2. A polyimide comprising a polyimide precursor (c) obtained by reacting an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) and a functional substance. A polyimide precursor composition for polyimide extrusion molding comprising 30 to 60% by weight of a precursor compound, 0.1 to 5% by weight of a poor solvent for the polyimide precursor, and 35 to 69.9% by weight of a good solvent for the polyimide precursor. 3. A polyimide precursor compound comprising 1 to 80% by weight of a function-imparting substance and a polyimide precursor 99 to 20.
The polyimide precursor composition for polyimide extrusion molding according to claim 2, wherein the polyimide precursor composition comprises 5% by weight. 4. A poor solvent for a polyimide precursor is placed in a mixing container equipped with a stirring blade and a stirrer having a disc above it, and the stirring vane and the disc are rotated at a speed of 100 rpm or more to form an inner wall of the container. A high-speed solvent layer of a poor solvent is formed in the vicinity, and then the aromatic tetracarboxylic dianhydride or its derivative (a) and the aromatic diamine or its derivative (b) are reacted in a good solvent for the polyimide precursor. The resulting polyimide precursor solution or a polyimide precursor compound mixed solution obtained by adding a function-imparting substance to the solution is poured onto the rotating disk and dispersed in a poor solution by disk centrifugal force to thereby produce a polyimide precursor ( A method for producing a polyimide precursor composition for polyimide extrusion molding, which comprises depositing c). 5. A precipitate obtained by dispersing a polyimide precursor solution or a polyimide precursor compound mixed solution obtained by adding a function-imparting substance to the solution in a poor solvent to obtain a precipitate of 0 to 1
By drying at 00 ° C. and adjusting the good solvent content, a polyimide precursor or a polyimide precursor compound 30 to 60 composed of the polyimide precursor and a functional substance is prepared.
The method for producing a polyimide precursor composition for polyimide extrusion molding according to claim 4, wherein the composition is composed of 0.1% by weight of the poor solvent and 0.1 to 5% by weight of the poor solvent and 35 to 69.9% by weight of the good solvent. 6. A polyimide precursor compound comprising 1 to 80% by weight of a functionalizing substance and a polyimide precursor 99 to 20.
The method for producing the polyimide precursor composition for polyimide extrusion molding according to claim 5, wherein the composition is 5% by weight. 7. The component 3 in which the good solvent has a boiling point of 170 ° C. or higher.
6. A solvent containing 0% by weight or more.
Alternatively, the method for producing the polyimide precursor composition for polyimide extrusion molding according to item 6. 8. In the reaction of an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent for a polyimide precursor, said (a) and (b) ) And the concentration of the almost equimolar mixture thereof is 10 to 20% by weight.
Alternatively, the method for producing the polyimide precursor composition for polyimide extrusion molding according to item 7. 9. An aromatic tetracarboxylic dianhydride or its derivative (a) is reacted with an aromatic diamine or its derivative (b) in a good solvent for a polyimide precursor,
0.1-5% by weight of the poor solvent consisting of a precipitate obtained by dispersing the obtained polyimide precursor solution in a poor solvent of the polyimide precursor, 35-56.9% by weight of the good solvent, and a polyimide precursor (C) 50 to 1 of a polyimide precursor composition for polyimide extrusion molding containing 30 to 60% by weight.
Extrusion molding was carried out at 00 ° C.
A method for producing a polyimide molded article, which comprises imidizing at 500 ° C. 10. A polyimide precursor solution obtained by reacting an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent for the polyimide precursor. 0.1 to 5% by weight of the poor solvent consisting of a precipitate obtained by dispersing a polyimide precursor compound mixed solution containing a functional property-imparting substance in a poor solvent of the polyimide precursor, and the good solvents 35 to 6
A polyimide precursor composition for polyimide extrusion molding containing 9.9% by weight and 30 to 60% by weight of a polyimide precursor compound composed of a function-imparting substance and a polyimide precursor is extrusion-molded at 50 to 100 ° C., and the obtained molding is obtained. 25 things
A method for producing a polyimide molded article, which comprises imidizing at 0 to 500 ° C. 11. A polyimide precursor composition for polyimide extrusion molding is melted at 50 to 100 ° C., extrusion coated and molded on a core material which is successively fed, and then heated at 250 to 500 ° C. to imidize, The method for producing a polyimide molded article according to claim 9 or 10, which comprises removing the core material to obtain a polyimide tubular molded article. 12. The good solvent comprises a solvent containing 30% by weight or more of a component having a boiling point of 170 ° C. or higher.
10. The method for producing a polyimide molded article according to 10 or 11. 13. In the reaction of an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) in a good solvent for a polyimide precursor, said (a) and (b) The method for producing a polyimide molded article according to claim 9 or 12, wherein the concentration of the almost equimolar mixture with) is 10 to 20% by weight. 14. A polyimide precursor composition for polyimide extrusion molding having a melt index of 10 to 300 (g / 1).
It is 0 min), The manufacturing method of the polyimide molded article of Claim 9 thru | or 13. 15. A contact angle of 120 ° or less with the die Land,
The method for producing a polyimide molded article according to claim 9, which comprises extruding using a die coated with a substance having a wet tension of 20 dyne / cm or less. 16. A polyimide extrusion molding composition having a composition of 50 to 50.
The method for producing a polyimide molded article according to claim 9, which comprises melting at 100 ° C. and then filtering with a screen pack of 300 mesh or more.