JP2001040108A - Block copolymerized polyimide film and method for molding thereof - Google Patents

Block copolymerized polyimide film and method for molding thereof

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Publication number
JP2001040108A
JP2001040108A JP24602799A JP24602799A JP2001040108A JP 2001040108 A JP2001040108 A JP 2001040108A JP 24602799 A JP24602799 A JP 24602799A JP 24602799 A JP24602799 A JP 24602799A JP 2001040108 A JP2001040108 A JP 2001040108A
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Prior art keywords
polyimide
film
thin film
block copolymer
block
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JP24602799A
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Japanese (ja)
Inventor
Hiroshi Itaya
Shunichi Matsumoto
俊一 松本
博 板谷
Original Assignee
Pi Gijutsu Kenkyusho:Kk
株式会社ピーアイ技術研究所
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Abstract

PROBLEM TO BE SOLVED: To provide a polyimide film and a method for molding thereof. SOLUTION: This method of molding a polyimide film comprise coating a polyimide solution on a surface of a base film, forming the polyimide film by drying the coat, peeling off the formed polyimide film from the base film, and drying and dehydrating the film to have a thickness of 0.5-10 μm. The polyimide solution is prepared by heating a tetracarboxylic acid dianhydride and a diamine in a mole ratio of the dianhydride to the diamine being 1.05-0.95 in the presence of an acid catalyst in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant electrical insulating tape, a heat-resistant thin film capacitor, a heat-resistant electronic device, a laminated circuit board, an electronic circuit, and other insulating materials. The present invention relates to a block copolymerized polyimide thin film having excellent mechanical properties, mechanical properties, and the like, and a molding method.

[0002]

2. Description of the Related Art Hitherto, films made of polyimide such as Kapton and Iupirex have excellent heat resistance, mechanical properties, chemical properties, etc., and are therefore used in various industrial fields, particularly in the electronics industry. It is widely used as heat-resistant electrical insulating tape material, flexible printed circuit board material, and electronic device material.

However, in order to form a polyimide film at the polyamic acid stage, which is a moldable polyimide intermediate, the above-mentioned polyimide film is required to be a polyimide intermediate as a final product. To 350-4
In a heating furnace at 00 ° C., a step of dehydrating and cyclizing the polyamic acid must be provided. During this high-temperature heat treatment, the polyamic acid film molded product has deformation properties such as shrinkage, so that a thin film of 10 μm or less is required. It has been difficult to industrially produce a uniform and thin polyimide film that can be used as a so-called practical electronic material having industrial quality reliability.

[0004] Therefore, most of the commercially available polyimide films currently available on the market are polyimide films which pass through a polyamic acid intermediate, so that the practical polyimide film thickness is 15 µm or more. It is currently limited to

However, in recent years, there has been a demand for smaller, lighter, thinner, and higher-performance electronic devices in electronic devices, and in accordance with those demands, there has been a demand for thinner heat-resistant polyimide films. For example, in the case of heat-resistant capacitors, the capacitance of the capacitor is inversely proportional to the thickness of the insulating film that insulates the conductor. There has been a strong demand for high performance thin film polyimide films.

As described above, in a laminated electronic circuit board as well, as electronic equipment as a whole is required to be smaller, lighter, thinner, and higher in performance, it is industrially practicable and has a higher performance. There has been a demand for a heat-resistant thin-film polyimide film corresponding to the chemical conversion. In addition, insulation-retaining materials for motor winding circuits that require heat resistance, and heat-resistant wiring materials for space rockets and aircraft have also been demanded to be industrially practical, high performance thin films, and light weight.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the conventional polyimide film, and has been made in consideration of the above-mentioned problems. Apply block copolymer polyimide solution directly to base film, especially polyethylene naphthalate film, using heat-resistant thin-film block copolymer polyimide film, which is required as insulating material for laminated printed circuit boards, heat-resistant insulating material for space rockets and aircraft. By forming a block copolymerized polyimide film on the surface of the film, heat resistance, mechanical properties, thin film block copolymerized polyimide film with improved properties such as electrical properties, especially the film thickness is 0.5. -1
It is an object of the present invention to provide a block copolymerized polyimide film having a very small thickness of 0 μm and a method for molding the same.

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventors have studied diligently, are soluble in a solvent, can be applied to a substrate film, and have a temperature below the deformation temperature of the substrate film. The present invention was developed by developing a solvent-soluble block copolymer polyimide capable of forming and drying a film.

According to the present invention, a block copolymerized polyimide thin film is formed by applying a block copolymerized polyimide solution on the surface of a base film and drying the solution, and the formed block copolymerized polyimide thin film is peeled off from the base film. A block copolymer polyimide thin film and a molding method.

According to the present invention, the above block copolymerized polyimide solution is composed of tetracarboxylic dianhydride and diamine, and heated in a solvent in the presence of an acid catalyst produced by lactone and base to form tetracarboxylic acid. A block copolymer characterized by being a solvent-soluble block copolymer polyimide obtained by heating and dehydrating in addition to a molar ratio of acid dianhydride and diamine of 1.05 to 0.95. Polyimide thin film and molding method.

The present invention provides a block copolymer polyimide thin film and a molding method, wherein the base film is a polyethylene terephthalate film.
Further, there is provided a block copolymerized polyimide thin film and a molding method, wherein the polyimide thin film is formed to a thickness of 0.5 to 10 μm.

According to the present invention, the block copolymer polyimide thin film is prepared by applying a block copolymer polyimide solution to the surface of the base film, and then applying the solution at a temperature of 80 to 180 ° C., preferably 90 to 160 ° C. A block copolymerized polyimide thin film formed by drying, and a molding method.

The present invention is characterized in that the block copolymerized polyimide has a weight average molecular weight in terms of polystyrene of 25,000 or more, and preferably 30,000-400,000. And a molding method.

The present invention relates to a method of using as a heat-resistant thin film capacitor comprising forming a conductive thin film on the surface of the above-mentioned block copolymerized polyimide thin film. Further, the present invention is a method of using the above block copolymerized polyimide thin film as a semiconductor passivation film by coating the semiconductor surface.

[0015]

A preferred embodiment of the present invention will be described with reference to a method for molding a solvent-soluble block copolymer polyimide of the present invention. Dirt on the surfaces of the base film and the polyethylene terephthalate film is washed with water or washed with a solvent such as acetone or methanol, and then the solvent is dried and removed to make the polyethylene terephthalate film a clean surface.
If the surface of the base film is clean, this step can be omitted. A block copolymer polyimide solution is applied to the surface of the cleaned polyethylene terephthalate film, and the thickness of the block copolymer polyimide solution on the surface of the polyethylene terephthalate film is made uniform using an applicator or the like.

A polyethylene terephthalate film uniformly coated on the surface with this block copolymerized polyimide solution is placed in a dryer, and the block copolymerized polyimide is uniformly coated at a temperature at which the polyethylene terephthalate film does not deform. The solvent of the solution is dried off. If necessary, the steps of applying and drying the block copolymer polyimide are repeated on both sides of the film surface, whereby a block copolymer polyimide thin film can be formed on both sides of the polyethylene terephthalate film.

As for the method of applying the block copolymerized polyimide solution to the film surface, besides using the above-described applicator, a method of industrially and continuously forming a block copolymerized polyimide solution coated film is generally used. Coating method by screen printing or a method using a gravure coating machine (Jitsuho 2-766)
No. 3), a curtain coat application method, a die coat application method, and a method of spray coating a solution.

Next, the block copolymer polyimide solution used in the present invention will be described. The block copolymerized polyimide used in the present invention is a solvent-soluble block copolymerized polyimide that is polymerized by the following method. Almost equimolar amounts of the acid dianhydride and the diamine are added to the reaction solvent, and the mixture is heated in the presence of a catalyst to produce a block copolymerized polyimide solution by a dehydration imidization reaction. The above reaction catalyst is a two-component composite catalyst. Gamma-valerolactone or crotonic acid is mixed with pyridine or N-methylmorpholine. The mixing ratio is 1: 1-5 (molar equivalent), preferably 1: 1-2. In the presence of water, it acts as an acid-base double salt, catalyzing, completing imidization,
When water goes out of the reaction system, the catalyst loses its catalytic action. The amount of this catalyst to be used is 1 / 100- / mole, preferably 1 / 50-1 ・ 10 mole, based on the acid dianhydride. A general method for producing a solvent-soluble block copolymerized polyimide compound is described in U.S. Pat. No. 5,502,143. The solvent-soluble block copolymerized polyimide used in the present invention is heated to 150 to 220 ° C., preferably 160 to 200 ° C. in a polar solvent in the presence of a composite catalyst to form a tetracarboxylic dianhydride and an aromatic compound. It is synthesized by polycondensation with an aromatic diamine. Water generated during the polycondensation reaction is removed from the reaction system by azeotropic distillation with toluene, xylene and the like.

The tetracarboxylic dianhydride used in the present invention includes pyromellitic dianhydride, 1, 2, 3, and
4-benzenetetracarboxylic dianhydride, 3, 3 ',
4,4′-biphenyltetracarboxylic dianhydride, 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxy) Phenyl) sulfone dianhydride, 4,4 ′-{2,2,2-trifluoro-1- (trifluoromethyl) ethylidene} bis (1,2-benzenedicarboxylic anhydride), 9,9-bis {4 -(3,4-dicarboxyphenoxy) phenyl} fluorene anhydride, 2,3,3 ′, 4′-biphenylethertetracarboxylic dianhydride, 1,2,5,
6-naphthalenetetracarboxylic dianhydride, 2, 3,
6,7-naphthalenetetracarboxylic dianhydride, 1,
4,5,8-naphthalenetetracarboxylic dianhydride,
3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,3 ', 4'-biphenylsulfonetetracarboxylic dianhydride And bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

The diamine component used in the present invention includes, for example, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, benzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'- (or 3,4 '-, 3,3
'-, 2, 4'-) diaminodiphenyl ether, 4,
4 ′-(or 3,3 ′-) diaminodiphenylsulfone, 4,4 ′-(or 3,3 ′-,) diaminodiphenylsulfide, 4,4-′benzophenonediamine,
3,3′-benzophenonediamine, 4,4′-di (4
-Aminophenoxy) phenylsulfone, 4,4'-
Di (3-aminophenoxy) phenylsulfone, 4,
4'-bis (4-aminophenoxy) biphenyl, 1,
4-bis (4-aminophenoxy) benzene, 1,3-
Bis (4-aminophenoxy) benzene, 1,1,1,
3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 3,3′-dimethyl, 4,4 '-Diaminodiphenylmethane, 3, 3',
5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-di (3-aminophenoxy) phenylsulfone, 3,3'-diaminodiphenylsulfone, 2,2'-bis (4- Aminophenyl) propane, 2,2′-trifluoromethyl-4,4′-diaminobiphenyl, 2,2 ′, 6,6′-tetramethyl-
4,4'-diaminobiphenyl, 2,2 ', 6,6'-
Tetratrifluoromethyl-4,4'-diaminobiphenyl, bis {(4-aminophenyl) -2-propyl}
Aromatic diamines such as 1,4-benzene, 9,9-bis (4-aminophenyl) fluorene, and 9,9-bis (4-aminophenoxyphenyl) fluorene, 2,6-diaminopyridine, 2,4-diamino Pyridine, bis (4
-Aminophenyl-2-propyl) -1,4-benzene, and diamines such as diaminopolysiloxane compounds.

The polycondensation reaction between the diamine and the tetracarboxylic dianhydride is usually carried out in an organic solvent. Examples of the organic solvent for this reaction system include N, N-dimethylformamide, N, N-dimethylmethoxyacetamide,
N, N-dimethylethoxyacetamide, N-methyl-
Examples thereof include 2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, dimethylsulfone, and tetramethylurea. These organic solvents can be used alone or in combination of two or more. The concentration of the reaction raw material in the polycondensation reaction is usually 5 to 40% by weight, preferably 10 to 30% by weight.

In the synthesis of polyimide by a conventional method, a polycarboxylic acid is obtained by polycondensing tetracarboxylic dianhydride and an aromatic diamine in a reaction solvent at a temperature of 10 ° C. or less as shown in Kapton. A method is employed in which the polyamic acid is cast, heat-treated at 250 to 350 ° C., and subjected to an imidization reaction to produce a polyimide.
In the method for synthesizing polyimide via the polyamic acid, heat treatment for the imidization reaction causes distortion of the base film, so that a thin-film polyimide film cannot be formed. Also, when trying to synthesize a multi-component polyimide copolymer via this polyamic acid,
Since the exchange reaction between molecules in the reaction solution is fast and a random copolymer is formed, it is extremely difficult to modify the polyimide with the copolymer.

The block copolymer polyimide solution used in the present invention is heated to 150 to 220 ° C., preferably 160 to 200 ° C. in the presence of a composite catalyst in the reaction solution of the present inventors. Utilizes a block copolymerized polyimide solution directly imidized (US Patent: U.S. Pat.
SP5502143). Furthermore, using a sequential reaction,
By using a block copolymerized polyimide, a modified multi-component copolymerized polyimide can be synthesized.

That is, first, an acid dianhydride and a diamine are heated in a polar solvent in the presence of an acid catalyst to form an imide oligomer, and then an acid dianhydride and / or a diamine are added thereto, followed by a second step reaction. To produce a polyimide. In this method, random copolymerizability due to a conversion reaction occurring between amic acids can be prevented. As a result, a wide variety of block copolymerized polyimides are produced, from soft elastomeric polyimides to hard structural polyimides. The block copolymerized polyimide used for the thin film block copolymerized polyimide film of the present invention is required to have excellent chemical resistance, heat resistance, and electrical insulation properties, and to have an appropriate peeling property from the polyethylene naphthalate film.

The polymerization catalyst for the block copolymerized polyimide of the present invention is characterized by using a catalyst system utilizing the following equilibrium reaction of the following lactone, base and water. {Lactone} + {base} + {water} = {acid group} + {base}
- The {acid} + {base} - a system as a catalyst, 150-2
Heat to 20 ° C to obtain a block copolymerized polyimide solution. The generated water is removed from the reaction system by azeotropic distillation with toluene. When the imidization of the reaction system is completed,
+ {Base} - becomes lactone and base are removed from the reaction system together with the simultaneous toluene lose catalysis. The block copolymerized polyimide solution obtained by this method can be industrially used as a high-purity block copolymerized polyimide solution because the catalyst substance is not contained in the polyimide solution after the reaction. Valerolactone is usually used as the above lactone, and pyridine or N-methylmorpholine is used as the base. The lactone is used in an amount of 0.05 to 0.3 mol based on the acid dianhydride (U.S. Pat.
02143).

The block copolymer polyimide solution synthesized in this way has good storage stability. In a closed container,
It can be stably stored at room temperature for several months to several years. The block copolymer polyimide of the present invention has a weight average molecular weight in terms of polystyrene of 20,000 or more, and preferably 30,000 to 400,000, for use as a thin film insulating material exhibiting excellent properties of heat resistance and electrical insulation. .

[0027] The block copolymer polyimide solution synthesized by the above method is uniformly applied to the surface of the substrate film, and the applied substrate film is dried. This drying treatment is desirably performed at a temperature not higher than the deformation temperature of the polyethylene terephthalate film. The drying temperature in the present invention depends on the concentration of the block copolymerized polyimide varnish in the block copolymerized polyimide varnish and the thickness of the coated block copolymerized polyimide varnish, but is generally preferably in the range of 90 to 160 ° C. As a drying method, in addition to the above-described method using a hot air dryer, a method using an infrared dryer is also effectively used.

Next, the characteristics of the block copolymer polyimide thin film obtained as described above will be described. 1) Thermal properties Glass transition temperature: 200-400 ° C Thermal decomposition onset temperature: 450-550 ° C 2) Electrical properties Volume resistivity: 10 (exp17) ohms or more Dielectric constant: 2.5-3.5 3 ) Mechanical properties Tensile strength: 10-20 kgf / mm2 Tensile elongation: 10-100% Tensile elasticity: 100-300 kf / cm2 Water absorption: 1.0-2.0% 4) Chemical properties The polyimide solution is a block. It is a copolymer polyimide. Since the imidation reaction has already been performed on the polyimide solution, the imidation reaction is unnecessary. Therefore, the film forming temperature of the polyimide thin film can be lowered. Good storage stability as a polyimide solution. Does not decompose with water as a polyimide solution.

Next, further industrial uses of the thin film block copolymerized polyimide film of the present invention will be described. The thin-film block copolymerized polyimide film of the present invention is a thermosetting resin excellent in workability, high in heat resistance excellent in adhesion to metals and the like, and excellent in chemical resistance, and excellent in flame retardancy. , And are suitably used for laminated boards and metal-clad laminated boards.
A conductive metal such as metal aluminum, metal copper, metal nickel, metal chromium, gold, and silver is deposited on the surface of the polyethylene terephthalate film described above, which is coated and dried on the surface of the thin film block copolymerized polyimide of the present invention, by a vacuum evaporation method. Then, a conductor thin film is formed on the thin film block copolymerized polyimide film. By peeling the thin film block copolymerized polyimide on which the conductive thin film is formed from the polyethylene terephthalate film, it is possible to obtain a laminated film formed product used for a heat-resistant capacitor.

Further, before peeling the laminated film-formed product from the surface of the polyethylene terephthalate film, the thin film block copolymerized polyimide is uniformly applied on the thin metal surface in the same manner as described above, and the gold decay film is deposited again. As a result, a multilayer laminated film formed product was obtained. This multilayer laminated film-formed product can be used as a heat-resistant capacitor.

Specific examples of the use of the thin film block copolymer polyimide of the present invention as an interlayer insulating film include interlayer insulating films for semiconductor multilayer wiring, interlayer insulating films for rigid boards of multilayer printed boards and flexographic printing plates, and the like. Package or M
Examples include an interlayer insulating film such as a CM substrate. Further, it can be used for other applications, for example, as a passivation film (stress buffer film) of a semiconductor, an alpha ray blocking film, a coverlay film of a flexographic printing plate, an overcoat of a flexographic printing plate, and the like. further,
Other applications of the thin film block copolymerized polyimide film of the present invention include die bonding adhesives, adhesive tapes for lead-on-chip (LOC), tapes for fixing lead frames, adhesive films for multilayer lead frames, and the like. it can.

Next, the method for producing the block copolymerized polyimide solution and the thin film block copolymerized polyimide film used in the present invention will be specifically described with reference to examples. In addition, the combination of various acid dianhydrides and diamines can provide a thin film block copolymer polyimide film having properties such as heat resistance, mechanical properties, electrical properties, adhesive properties, positive photosensitive properties, and low dielectric properties. However, the present invention is not limited to only these examples.

Example 1 A two-liter three-neck flask was equipped with a stainless steel anchor stirrer, a nitrogen inlet tube and a trap equipped with a stopcock, and a reflux condenser equipped with a cooling tube with balls. 38.67 g (120 mmol) of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride
7.33 g (60 mmol) of 4-diaminotoluene,
1.8 g (18 mmol) of gamma-valerolactone;
2.9 g (36 mmol) of pyridine, 300 g of N-methylpyrrolidone and 60 g of toluene were added, and the mixture was heated at 180 ° C. for 1 hour.
Heat for hours.

Then, the mixture is air-cooled to 3, 4, 3 ', 4'-
17.65 g of biphenyltetracarboxylic dianhydride
(60 mmol) 49.26 g of 2,2-bis {4- (4-aminophenoxy) phenyl} propane (120
Mmol), 304 g of N-methylpyrrolidone and 36 g of toluene were added, and the rotation speed of the 180 ° C. stirrer was set to 180 rpm.
Heat at m for 2 hours. Then, at 180 ° C and 100 rpm
For 1 hour. The polyimide solution of the block copolymer obtained by this reaction has a polyimide concentration of 20%.

The weight average molecular weight in terms of polystyrene of the polyimide thus produced is 211,300. The glass transition temperature Tg is 312-314 ° C, and the thermal decomposition onset temperature is 476 ° C. This polyimide solution was diluted with dioxolane to form a varnish with a polyimide concentration of 15%, and a gravure coating machine was used to form a film, thereby forming a polyethylene terephthalate film (a product of Teijin Limited /
A coating film 1 and a coating film 2 having a polyimide thin film of 20 μm and 40 μm formed in a polyimide varnish solution state on the surface of a 75 μm thick: base film) were prepared, and a high temperature was applied at 210 ° C. for 10 minutes. In a thermostat, a non-load heat treatment in the atmosphere was performed and a drying treatment was performed. During this drying treatment, the coating films 1 and 2 of the present invention changed the polyimide film thickness due to the scattering of the solvent of the polyimide varnish, and the final polyimide coating film thickness was 3 μm and 6 μm, respectively. At the time of this drying treatment, phenomena such as peeling between the base film and the base film are not observed.

The coated films 1 and 2 are cooled to room temperature, cut into a required area, and the polyimide thin film is peeled from the cut surface to obtain the desired thin film polyimide film 1 (3 μm) and thin film. Polyimide film 2 (6 microns) could be molded.

Example 2 The same operation as in Example 1 is performed. 16.11 g of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride
(50 mmol) 2,4-diaminotoluene in 3.0
6 g (25 mmol), 1 gamma-valerolactone.
0 g (10 mmol), pyridine 1.6 g (20 mmol), N-methylpyrrolidone 200 g, toluene 30 g
And heat at 180 ° C. for 1 hour.

Then, the mixture is air-cooled to obtain 3, 4, 3 ', 4'-
14.71 g of biphenyltetracarboxylic dianhydride
(50 mmol) 2,53-g (50 mmol) of 2,2-bis {4- (4-aminophenoxy) phenyl} propane 7.31 g (25 mmol) of 1,3-bis (4-aminophenoxy) benzene , N-methylpyrrolidone (189 g) and toluene (20 g) were added, and the mixture was heated at 180 rpm for 2 hours at 180 rpm. Then 1
The mixture was stirred at 80 ° C. and 100 rpm for 1 hour. The polyimide solution of the block copolymer obtained by this reaction has a polyimide concentration of 20%. The weight average molecular weight in terms of polystyrene of the polyimide thus produced is 74,500. The thermal decomposition onset temperature is 496 ° C. Next, the above-mentioned polyimide solution is coated to form an adhesive polyimide thin film 3 (polyimide film thickness 1.
7 μm), and an adhesive polyimide thin film 4 (a polyimide film thickness of 2.9 μm) was obtained.

Example 3 The same operation as in Example 1 is performed. 32.22 g of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride
(100 mmol), 2,4-diaminotoluene.
11 g (50 mmol), 1.5 g (15 mmol) of gamma-valerolactone, 2.4 g (30 mmol) of pyridine, 200 g of N-methylpyrrolidone, toluene 3
Add 0 g and heat at 180 ° C. for 1 hour.

Then, the mixture is air-cooled to obtain 3, 4, 3 ', 4'-
29.42 g of biphenyltetracarboxylic dianhydride
(100 mmol) 3,5-diaminobenzoic acid 7.6
1 g (50 mmol) of 53.55 g of 2,2-bis {4- (4-aminophenoxy) phenyl} propane
00 mmol), 0.70 g of maleic anhydride (7.1
5 mmol), 222 g of N-methylpyrrolidone and 30 g of toluene, and the rotation speed of the 180 ° C. stirrer was set to 180 r.
Heat at pm for 5 hours. The polyimide solution of the block copolymer obtained by this reaction has a polyimide concentration of 20%. The thermal decomposition onset temperatures of the polyimide thus produced are 339 ° C and 500 ° C. Glass transition temperature Tg
Is 310-325 ° C. Next, an adhesive polyimide film 5 (polyimide film thickness of 1.9 microns) and an adhesive polyimide thin film film 6 (polyimide film thickness of 2.8 microns) of the present invention are formed by coating the polyimide solution. I got

Example 4 The same operation as in Example 1 is performed. Bicyclo (2, 2, 2)
19.86 g (80 mmol) of oct-7-ene-2,3,5,6-tetracarboxylic dianhydride
24.02 g of '-diaminodiphenyl ether (12
0 mmol) and 3.0 g of gamma-valerolactone (3
0 mmol), 3.6 g (40 mmol) of pyridine, N
-200 g of methylpyrrolidone and 50 g of toluene were added,
Heat at 180 ° C for 1 hour.

Then, the mixture is air-cooled to obtain 3, 4, 3 ', 4'-
38.67 benzophenone tetracarboxylic dianhydride
g (120 mmol), bis (3-aminophenoxy)
23.38 g (80 mmol) of -1,3-benzene,
196 g of N-methylpyrrolidone and 40 g of toluene are added, and the mixture is heated at 180 ° C. and 180 rpm for 3 hours and 40 minutes. The polyimide solution excluding the reaction reflux has a polyimide concentration of 20%. The weight average molecular weight of the polyimide thus produced in terms of polystyrene is 8800.
0. Glass transition temperature Tg is 215-243 ° C. Next, the above polyimide solution is coated to form an adhesive polyimide thin film 7 of the present invention.
(Polyimide film thickness 2 μm) was obtained.

Example 5 The same operation as in Example 1 is performed. Bicyclo (2, 2, 2)
-Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 24.82 g (100 mmol), 3,4
7.61 g (50 mmol) of '-diaminobenzoic acid,
1.5 g (15 mmol) of gamma-valerolactone,
Pyridine (2.4 g, 30 mmol), N-methylpyrrolidone (120 g), and toluene (30 g) were added.
Heat and stir for 1 hour at 80 rpm.

Then, the mixture is air-cooled to obtain 3, 4, 3 ', 4'-
14.71 g of biphenyltetracarboxylic dianhydride
(50 mmol) 3,1′-diaminodiphenyl ether 10.01 g (50 mmol), 2,2-bis {4
-(4-Aminophenoxy) phenyl} propane in 2
0.53 g, (50 mmol), 169 g of N-methylpyrrolidone and 30 g of toluene were added.
Heat for 2 hours at rpm. The polyimide solution excluding the reaction reflux has a polyimide concentration of 20%. The weight average molecular weight in terms of polystyrene of the polyimide thus produced is 102,600. Next, an adhesive polyimide thin film 8 (polyimide film thickness of 1 micron) of the present invention was obtained by forming a coating film of the above-mentioned polyimide solution.

Example 6 The same operation as in Example 1 is performed. Bicyclo (2, 2, 2)
49.6 g (200 mmol) of oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,5-
15.22 g (100 mmol) of diaminobenzoic acid,
3 g (30 mmol) of gamma-valerolactone, 4.8 g (60 mmol) of pyridine, 300 g of N-methylpyrrolidone, and 60 g of toluene were added, and 180 ° C., 180
Heat and stir for 1 hour at rpm.

Then, the mixture is air-cooled to obtain 3, 4, 3 ', 4'-
29.4 g of biphenyltetracarboxylic dianhydride (1
00 mmol), bis- (3-aminophenoxy)-
58.46 g (200 mmol) of 1,3-benzene,
268 g of N-methylpyrrolidone and 40 g of toluene are added, and the mixture is heated at 180 ° C. and 180 rpm for 4 hours and 30 minutes. The polyimide solution excluding the reaction reflux has a polyimide concentration of 20%. The polystyrene-equivalent weight average molecular weight of the polyimide thus produced is 5460.
0. Next, an adhesive polyimide thin film 9 (polyimide film thickness of 1.7 μm) of the present invention was obtained by forming a coating film of the above polyimide solution.

Example 7 The same operation as in Example 1 is performed. 2,2-bis @ 4- (4
-Aminophenoxy) phenyl @ hexafluoropropane (product of Wakayama Seika Kogyo Co., Ltd.) 44.43 g (10
0 mmol), 9,9-bis (4-aminophenyl) fluorene (product of Wakayama Seika Kogyo Co., Ltd.) 43
g (50 mmol), 1.0 gamma-valerolactone
g (10 mmol), pyridine 1.6 g (20 mmol), N-methylpyrrolidone 200 g, toluene 30 g
And heated and stirred at 180 ° C. and 180 rpm for 1 hour.

Then, the mixture is air-cooled and 2,2-bis @ 4-
25.93 g (50 mmol) of (4-aminophenoxy) phenyl @ hexafluoropropane, 137 g of N-methylpyrrolidone and 10 g of toluene are added, and the mixture is heated at 180 ° C. at 180 rpm for 2 hours and 45 minutes. The polyimide solution excluding the reaction reflux has a polyimide concentration of 20%. The weight average molecular weight in terms of polystyrene of the polyimide thus produced is 51900. next,
The low dielectric constant polyimide thin film 10 (polyimide film thickness of 2.6 μm) of the present invention was obtained by forming a coating film with the above polyimide solution.

Example 7 The same operation as in Example 1 is performed. 11.77 g of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride (4.
0 mmol), 27.88 g (80 mmol) of 9,9-bis (4-aminophenyl) fluorene, 1.0 g (10 mmol) of gamma-valerolactone, 1.
6 g (20 mmol), N-methylpyrrolidone 200
g and 30 g of toluene, and heated at 180 ° C. for 1 hour.

Then, the mixture was air-cooled to obtain 13.09 g (60 mmol) of pyromellitic dianhydride and 2,2-bis {4
10.37 g (20 mmol) of-(4-aminophenoxy) phenyl @ hexafluoropropane, 137 g of N-methylpyrrolidone and 30 g of toluene were added, and the mixture was heated at 180 ° C.
The mixture is heated with stirring at a rotation speed of a stirrer of 180 rpm for 4 hours and 50 minutes. The polyimide solution of the block copolymer obtained by this reaction has a polyimide concentration of 20%. The weight average molecular weight in terms of polystyrene of the polyimide thus produced is 45,900. Next, a low dielectric polyimide thin film 11 (polyimide film thickness of 3.6 μm) of the present invention was obtained by forming a coating film of the above polyimide solution.

[0051]

As described above, since the thin film polyimide film of the present invention can be formed from a solvent-soluble polyimide as a thin film polyimide film, it can be industrially used for small high-performance heat-resistant capacitors. It is possible to provide a thin thin film polyimide film, an adhesive thin film polyimide film required for a small and lightweight electronic device, and a low dielectric thin film polyimide film. Furthermore, the miniaturization, thinning, and heat-resisting thin-film insulating polyimide film, and the motor winding circuit parts that require heat resistance, where the miniaturization, weight reduction, thinning, and high performance of electronic equipment comply with the requirements. Insulation holding materials, heat-resistant wiring materials for space rockets and aircraft can be made thinner and lighter. In addition, the thin film polyimide film has excellent effects, such as easy industrial production and low production cost.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA60 AA75 AA81 AA86 AH12 BA02 BB02 BC01 BC12 4J043 PA09 QC02 SA06 SA43 SA44 SA54 SA72 SA85 SB03 TA14 TA22 TA71 TB03 UA121 UA122 UA131 UA132 UA141 UA151 UA UA UA UA UA UA UA UA UA UA UA UA UB011 UB021 UB022 UB061 UB062 UB121 UB122 UB131 UB132 UB151 UB152 UB281 UB301 UB302 UB401 UB402 XA03 XA16 XA19 XB11 XB17 XB19 XB35 ZA12 ZA31 ZA46 ZB01 ZB11 ZB47 ZB50

Claims (9)

[Claims]
1. A block copolymerized polyimide thin film is formed by applying a block copolymerized polyimide solution on the surface of a base film and drying the same, and the dried block copolymerized polyimide thin film is peeled off from the base film. And a molding method.
2. The block copolymer polyimide solution according to claim 1, wherein
It is composed of a tetracarboxylic dianhydride and a diamine, and is heated in a solvent in the presence of an acid catalyst generated by a lactone and a base, so that the molar ratio of the tetracarboxylic dianhydride to the diamine is 1.05-0. 95, plus heating,
A block copolymerized polyimide thin film and a molding method, which are a solvent-soluble block copolymerized polyimide obtained by dehydration.
3. The block copolymer polyimide thin film according to claim 1, wherein the base film is made of a polyethylene terephthalate film.
4. The block copolymer polyimide thin film according to claim 1, wherein the block copolymer polyimide thin film is formed to a thickness of 0.5 to 10 μm.
5. The block copolymer polyimide thin film according to claim 1,
On the surface of the base film, a block copolymer polyimide solution is applied, and then at 80-180 ° C, preferably 90 ° C.
The block copolymer polyimide thin film according to claim 1, wherein the film is formed by drying at a temperature of −160 ° C., and a molding method.
6. The block copolymer polyimide according to claim 7, wherein the block copolymer polyimide has a weight average molecular weight in terms of polystyrene of 25,000 or more, preferably 30,000 to 400,000, comprising a solution of the block copolymer polyimide composition of claim 1. The block copolymer polyimide thin film according to any one of claims 1 to 5, and a molding method.
7. A method of using as a heat-resistant thin film capacitor, comprising forming a conductive thin film on the surface of the block copolymerized polyimide thin film.
8. The method according to claim 1, wherein the block copolymer polyimide thin film is
A method of using as a semiconductor passivation film comprising coating a semiconductor surface.
9. The method according to claim 9, wherein the block copolymer polyimide thin film is
A method of using as an insulating film for lamination comprising coating the surface of an electronic circuit wiring board.
JP24602799A 1999-07-28 1999-07-28 Block copolymerized polyimide film and method for molding thereof Pending JP2001040108A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035689A1 (en) * 2002-10-16 2004-04-29 Pi R & D Co., Ltd. Solution compositions of block copolyimides comprising pyromellitic dianhydride and process for production thereof
WO2006011513A1 (en) * 2004-07-27 2006-02-02 Kaneka Corporation Polyimide film having high adhesiveness and method for producing same
US8158268B2 (en) 2005-08-04 2012-04-17 Kaneka Corporation Metal-coated polyimide film

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035689A1 (en) * 2002-10-16 2004-04-29 Pi R & D Co., Ltd. Solution compositions of block copolyimides comprising pyromellitic dianhydride and process for production thereof
WO2006011513A1 (en) * 2004-07-27 2006-02-02 Kaneka Corporation Polyimide film having high adhesiveness and method for producing same
US7811660B2 (en) 2004-07-27 2010-10-12 Kaneka Corporation Polyimide film having high adhesiveness and method for producing same
US8158268B2 (en) 2005-08-04 2012-04-17 Kaneka Corporation Metal-coated polyimide film
US8293331B2 (en) 2005-08-04 2012-10-23 Kaneka Corporation Metal-coated polyimide film

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