WO2008050704A1 - Film en polyimide et procédé de production - Google Patents

Film en polyimide et procédé de production Download PDF

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Publication number
WO2008050704A1
WO2008050704A1 PCT/JP2007/070521 JP2007070521W WO2008050704A1 WO 2008050704 A1 WO2008050704 A1 WO 2008050704A1 JP 2007070521 W JP2007070521 W JP 2007070521W WO 2008050704 A1 WO2008050704 A1 WO 2008050704A1
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Prior art keywords
film
particle size
dianhydride
polyimide film
particles
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PCT/JP2007/070521
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English (en)
Japanese (ja)
Inventor
Koichi Sawasaki
Toshihiro Teshiba
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Du Pont-Toray Company, Ltd.
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Publication of WO2008050704A1 publication Critical patent/WO2008050704A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0263—Details about a collection of particles
    • H05K2201/0266—Size distribution

Definitions

  • the present invention relates to a polyimide film and a method for producing the same. More specifically, the added inorganic particles are not exposed, and surface protrusions can be generated in a state of being uniformly dispersed in the film, so that the surface state can be well controlled, and the running property, adhesiveness and dimensional stability of the film are improved.
  • the present invention relates to a polyimide film that can be applied to an AOI and a manufacturing method thereof.
  • Polyimide films are known to have excellent characteristics in heat resistance, cold resistance, chemical resistance, electrical insulation and mechanical strength. Electrical insulation materials for wires, heat insulating materials, flexible printed wiring It is widely used for base films for substrates (FPC), carrier tape films for IC automated tape bonding (TAB), and IC lead frame fixing tapes. Of these, polyimide film and copper foil are usually bonded to each other through various adhesives, especially in applications such as FPC, TAB carrier tape and lead fixing tape.
  • inert inorganic compounds for example, orthophosphoric acid of alkaline earth metal, dicalcium phosphate dibasic, calcium pyrophosphate, silica, talc
  • a method of adding for example, see Patent Document 1
  • a method of performing plasma treatment after forming fine protrusions on the film surface with fine particles for example, see Patent Document 2
  • the inorganic particles shown in these figures have a large particle size, they are not suitable for automatic optical inspection systems! / And! //.
  • inorganic particles having an average particle diameter of 0.01 to 100 m are held in the polyimide surface layer by embedding a part of each particle! / From the partially exposed inorganic particles
  • a method is known in which 1 ⁇ 10 to 5 ⁇ 10 8 pieces / mm 2 are present on the surface layer of the film (for example, see Patent Document 3). This method actively exposes inorganic particles on the surface and reduces the coefficient of friction on the film surface to effectively obtain a slippery effect. As a result, there was a problem in that the surface of the film on the other side of the contact surface was scratched, resulting in poor appearance.
  • Patent Document 1 Japanese Patent Laid-Open No. 62-68852
  • Patent Document 2 JP 2000-191810 A
  • Patent Document 3 Japanese Patent Laid-Open No. 5-25295
  • the object of the present invention is excellent in the runnability, adhesiveness and dimensional stability of the film.
  • the object is to provide a polyimide film applicable to an optical inspection system (AOI) and a method for manufacturing the polyimide film.
  • AOI optical inspection system
  • Inorganic particle force A polyimide film is provided which is dispersed in a film at a ratio of 0.;! To 0.9% by weight per film resin weight.
  • Ratio power S of each component in the polyimide film 4 Parafue two Renjiamin and 50-90 mole 0/0 10-50 mode Honoré percent Jiamin component, 4 'over-diamino diphenyl ether, acid dianhydride component pyromellitic dianhydride as 50-99 mole 0/0, and 3, 3 ', 4, 4
  • the inorganic particles are contained at a ratio of 0.3 to 0.8% by weight per film resin weight;
  • the average particle size of the inorganic particles is 0.;!-0.6 m;
  • the average particle size of the inorganic particles is 0.3 to 0.5 m
  • Protrusions caused by the inorganic particles are present on the film surface, and the number of the protrusions having a height of 2 ⁇ m or more is 5 pieces / 40 cm square or less, and
  • the film thickness is 5 to 75 am
  • the method for producing the polyimide film of the present invention includes a diamine component comprising paraphenylene diamine and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride, and 3, 3 ', 4,
  • the polycarboxylic acid dianhydride component consisting of 4'-biphenyltetracarboxylic dianhydride is reacted in a polar organic solvent to produce polyamic acid, which is imidized. Then, when forming into a film, the particle diameter is within the range of 0 ⁇ 01-1.5 m, the force and the average particle diameter is 0.05-0.7 mm, and the particle diameter is 0.
  • a slurry in which inorganic particles having a particle size distribution in which 15-60.111 inorganic particles occupy 80% by volume or more of all particles is dispersed in the same polar organic solvent as the polar organic solvent is produced by polyimide. It is characterized in that the inorganic particles are added to the polyamic acid solution in the process at a ratio of 0.;! To 0.9% by weight per resin weight.
  • the added inorganic particles are not exposed, and surface protrusions can be generated in a state of being uniformly dispersed in the film, so that the surface state can be controlled well.
  • FPC flexible optical printed circuit boards
  • COF chip-on-film
  • AOI automatic optical inspection systems
  • an aromatic tetracarboxylic dianhydride component and an aromatic diamine component or a chemical substance mainly composed of these components are subjected to addition polymerization in an organic solvent.
  • a varnish-like polyamic acid is obtained.
  • Paraphenylenediamine and 4,4′-diaminodiphenyl ether are used as aromatic diamine components
  • pyromellitic dianhydride and 3 are used as aromatic tetracarboxylic dianhydride components.
  • 3 ', 4, 4'-biphenyltetracarboxylic acid dihydrate are used as main components.
  • four kinds of essential components are paraphenylenediamine, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride, and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. These four types can be obtained by adding only a small amount of other ingredients in addition to these four types.
  • Kunar more preferably preferably 50 to 99 mol% instrument 6 0-90 Monore 0/0, more preferably (or 65 85 Monore 0/0. 3, 3 ,, 4, 4, Bifue two Norete us soft power becomes base when dianhydride is too large, since the hard and too small, 1-50 molar percent preferably fixture further preferably 10 to 40 mole 0/0, more preferably 15 to 35 mole 0/0
  • a small amount of other diamines may be added in addition to 4,2'-diaminodiphenyl ether.
  • a small amount of other acid dianhydride may be added!
  • Specific other diamines and dianhydrides include, but are not limited to, force S, including:
  • organic solvent used in the present invention for forming a polyamic acid solution examples include sulfoxide solvents such as dimethyl sulfoxide and jetyl sulfoxide, N, N Formamide solvents such as dimethylformamide and N, N jetylformamide, N, N dimethylacetamide, and acetateamide solvents such as N, N jetylacetamide, N-methyl 2-pyrrolidone, N-but-2-pyrrolidone Pyrrolidone solvents such as phenolone, phenol, o-, m-, or p Cresol mononole, xylenol, halogenated phenol, catechol, and other phenolic solvents, or hexamethylphosphoramide, ⁇ petit-mouthed ratatones, etc.
  • Protic polar solvents can be mentioned, and these are preferably used alone or as a mixture.
  • Aromatic hydrocarbons such as silene and toluene can also be used.
  • the polymerization method may be any known method, for example, the following method.
  • the aromatic tetracarboxylic acid compound was mixed at a ratio of 95 to 105 mol% with respect to the reaction components for the time required for the reaction. Thereafter, another aromatic diamine compound is added, and then the aromatic tetracarboxylic acid compound is added and polymerized so that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are approximately equal.
  • a polyamic acid solution (A) is prepared by reacting one aromatic diamine component and aromatic tetracarboxylic acid in a solvent so that either one becomes excessive, and the other in another solvent.
  • the polyamic acid solution (B) is prepared by reacting the aromatic diamine component and the aromatic tetracarboxylic acid in an excess amount. A method in which the polyamic acid solutions (A) and (B) thus obtained are mixed to complete the polymerization. At this time, when adjusting the polyamic acid solution (A), if the aromatic diamine component is excessive, in the polyamic acid solution (B), the aromatic tetracarboxylic acid component is excessive, and in the polyamic acid solution (A), the aromatic tetraamine component is excessive.
  • the polyamidic acid solution (B) makes the aromatic diamine component excess, and the polyamic acid solutions (A) and (B) are mixed together with the wholly aromatic diamine component used in these reactions. Adjust so that the aromatic tetracarboxylic acid components are approximately equal.
  • the polymerization method is not limited to these, and other known methods may be used.
  • the polyamic acid solution thus obtained contains 5 to 40% by weight, preferably 10 to 30% by weight of solid content, and its viscosity is 10 to 2000 Pa ′ as measured by a Brookfield viscometer. s, preferably from 100; lOOOPa 's strength is preferably used for stable liquid delivery.
  • the polyamic acid in the organic solvent solution may be partially imidized.
  • the inorganic particles added to the resin in order to form protrusions on the film surface of the present invention must be insoluble in all chemical substances that come into contact in the polyimide film manufacturing process.
  • Inorganic particles that can be used in the present invention include SiO (silica), TiO 2, CaHPO 2, C 3
  • Preferable examples include 2 2 4 a PO. Above all, it was manufactured by the wet grinding method of sol 'gel method
  • Silica is preferably used because it is stable and physically stable in the varnish-like polyamic acid solution and does not affect the properties of the polyimide.
  • the fine silica powder should be used as a silica slurry uniformly dispersed in a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, n-methylpyrrolidone. Therefore, it is preferable because aggregation can be prevented. Since this slurry has a very small particle size, the sedimentation rate is slow and stable. Also, even if it sinks It can be easily redispersed by re-stirring.
  • a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, n-methylpyrrolidone. Therefore, it is preferable because aggregation can be prevented. Since this slurry has a very small particle size, the sedimentation rate is slow and stable. Also, even if it sinks It can be easily redispersed by re-stirring.
  • the inorganic particles added to form protrusions on the surface of the polyimide film have a particle size in the range of 0.01 to 1.5 m and an average particle size of 0.00. 05 ⁇ ⁇ - ⁇ . 7 ⁇ m, more preferably 0.1—0.6 ⁇ m, even more preferably 0.3 to 0.5 m.
  • the average particle size is below these ranges, sufficient slipperiness to the film cannot be obtained, and if it exceeds the average particle size, the automatic inspection system will judge the inorganic particles as foreign matter and cause trouble. Therefore, it is not preferable.
  • the normal film thickness is 5 Hm to 75 [Im], inorganic particles in this particle diameter range are not exposed on the surface of the polyamide film.
  • the addition amount of the inorganic particles is preferably from 0.3 to 0.8% by weight, more preferably from 0.3 to 0.8% by weight per film resin weight. 0.
  • the content is 1% by weight or less, the film surface is insufficient in number of protrusions, so that sufficient slipperiness to the film cannot be obtained, the transportability is deteriorated, and the film winding shape when wound on a roll is also deteriorated. Therefore, it is not preferable.
  • it is 0.9% by weight or more the slipperiness of the film is improved, but coarse protrusions due to abnormal aggregation of inorganic particles increase, and this is judged as foreign matter by the automatic inspection system as a result. It is not preferable because it causes trouble.
  • the particle size distribution of the inorganic particles it is preferable that the particle size distribution is narrow, that is, the proportion of particles of similar size in the total particle is higher. Specifically, the particle size is 0.15 to 0.60. It is preferable that 111 particles occupy 80% by volume or more of all particles. If the proportion of particles below this range and 0.15 m or less increases, the slipperiness of the film decreases, which is not preferable.
  • the force S that can remove coarse particles with a 5 m cut filter or 10 m cut filter, and the proportion of particles over 0.60 m increases, Not only is clogging frequently caused and process stability is deteriorated, but also coarse aggregation of particles tends to occur, which is not preferable.
  • the number of protrusions having a height of 2 m or more is 5 pieces / 40 cm square or less, more preferably 3 pieces / 40 cm square or less, and even more preferably 1 piece / It is desirable that it is 40 cm square or less. If the amount is larger than this, it is not preferable because the inorganic particles are judged as foreign matter by the automatic inspection system and cause trouble.
  • a slurry in which such inorganic particles are dispersed in the same polar solvent as the organic solvent used in the production of the polyimide film is added to the polyamic acid solution in the polyimide production process, and then removed. It is preferable to obtain a polyimide film by cyclization and desolvation. However, after adding the inorganic particle slurry to the organic solvent before polyamic acid polymerization, the polyimide film is subjected to polyamic acid polymerization and decyclization desolvation. It is possible to add the inorganic particle slurry in any step before the decyclization and desolvation, such as obtaining.
  • a polyamic acid solution is cast into a film and thermally decyclized and desolvated to obtain a polyimide film, and a cyclization catalyst and dehydration are added to the polyamic acid solution.
  • Force that includes a method of obtaining a polyimide film by mixing a chemical agent and chemically decyclizing it, and then heating and desolvating the gel film The latter method Keeping the thermal expansion coefficient of the polyimide film low Is preferable.
  • the polyamic acid solution is prepared.
  • the polyamic acid solution can contain a cyclization catalyst (imidization catalyst), a dehydrating agent, a gelation retarder, and the like.
  • cyclization catalyst used in the present invention include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, isoquinoline and pyridine.
  • aliphatic tertiary amines such as trimethylamine and triethylenediamine
  • aromatic tertiary amines such as dimethylaniline
  • isoquinoline and pyridine are examples of the cyclization catalyst used in the present invention.
  • the powers such as heterocyclic tertiary amines such as / 3-picoline, it is preferable to use at least one amine selected from heterocyclic tertiary amines.
  • dehydrating agent used in the present invention include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Of these, acetic anhydride and / or benzoic anhydride are preferred.
  • a method for producing a polyimide film from a polyamic acid solution a polyamic acid solution containing a cyclization catalyst and a dehydrating agent is cast on a support from a die with a slit, and is then formed into a film. The imidization is partially advanced to obtain a gel film having self-supporting property, and then peeled off from the support, heat-dried / imidized, and subjected to heat treatment.
  • the polyamic acid solution is formed into a film shape through a slit-shaped base, cast onto a heated support, undergoes a thermal ring-closing reaction on the support, and has a self-supporting gel film. And peeled off from the support.
  • the support is a metal rotating drum or an endless belt, and its temperature is controlled by radiant heat from a liquid or gas heat medium and / or an electric heater.
  • the gel film is heated to 30 to 200 ° C, preferably 40 to 150 ° C by heat reception from the support and / or heat from a heat source such as hot air or an electric heater, and undergoes a ring-closing reaction.
  • the volatile matter such as the liberated organic solvent is dried to become self-supporting and peeled off from the support.
  • the gel film peeled from the support is usually stretched in the running direction while regulating the running speed with a rotating roll. Stretching is carried out at a temperature of 140 ° C or lower at a magnification of 1.05 ⁇ ; 1. 9 times, preferably 1.;! ⁇ 1.6 times, more preferably 1.;! ⁇ 1.5 times.
  • the gel film stretched in the running direction is introduced into the tenter device, and both ends in the width direction are held by the tenter clip, and stretched in the width method while running with the tenter clip.
  • the film dried in the drying zone is heated for 15 seconds to 10 minutes with hot air, an infrared heater or the like.
  • heat treatment is performed at a temperature of 250 to 500 for 15 seconds to 20 minutes using hot air and / or an electric heater. It is preferable to adjust the film thickness of the resulting polyimide film to 5 to 75,1 m while adjusting the draw ratio in the running direction and the draw ratio in the width direction. If it is thicker or thinner than this range, the film forming property is remarkably deteriorated, which is not preferable.
  • the adhesion evaluation method is based on the method of IPC-FC-241. Bond polyimide film and copper foil with commercially available thermoplastic polyimide adhesive, fix the film on the hard board, and measure. was determined by
  • the base film was inspected using SK-75 manufactured by Onorepo Tech.
  • the case where foreign matter and fine particles can be distinguished is evaluated as ⁇ A '', while the size of foreign matter and fine particles is similar and the two cannot be distinguished! /,
  • the case is evaluated as ⁇ C '', and the middle is ⁇ B '' It was evaluated.
  • the number of protrusions with a height of 2 m or more was counted per 40 cm square area of the film.
  • For height measurement use a scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd., using a Nikon 100x lens (CF Plan ⁇ ⁇ / ⁇ . 95 ⁇ / 0 EPI) in “SURFACE1” mode. This was confirmed by photographing and analyzing the surface.
  • TMA-50 manufactured by Shimadzu Corporation was used, and measurement was performed under the conditions of a measurement temperature range: 50 to 200 ° C. and a heating rate: 10 ° C./min.
  • the total particle size is 0. Ol rn or more and 1.5 m or less, and particles with an average particle size of 0.3 2 ⁇ 111 and a particle size of 0.15—0.60 m are contained in all particles.
  • volume 0/0 of the silica in N, N-dimethyl ⁇ Seto amide slurry, the polyamic acid solution obtained in synthesis example 1 were added the resin weight per 0.3 wt%, sufficiently stirred and dispersed.
  • a conversion agent composed of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight with respect to the polyamic acid solution.
  • acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively.
  • the obtained mixture was cast on a 90 ° C stainless steel drum rotated by a T-shaped slit die to obtain a gel film having a self-supporting property of 55% by weight of residual volatile components and a thickness of about 0.05 mm. .
  • the gel film is peeled off from the drum, and both ends thereof are gripped, and processed at 200 ° CX for 30 seconds, 350 ° CX for 30 seconds, and 550 ° CX for 30 seconds in a Karo heat furnace to obtain a polyimide film with a thickness of 38 ⁇ m. It was.
  • the properties of the obtained polyimide film are shown in Table 1.
  • the particle size of all particles is within the range of 0.01 to 1.5 m, and particles with an average particle size of 0.3 to 7 mm and a particle size of 0.15 to 0.60 m are included in all particles.
  • volume 0/0 of the silica in N, N-dimethyl ⁇ Seto amide slurry, the polyamic acid solution obtained in synthesis example 1 were added the resin weight per 0.35 wt%, sufficiently stirred and dispersed.
  • Acetic anhydride molecule The conversion agent consisting of 102.09
  • isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution.
  • acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively.
  • the obtained mixture was cast on a 90 ° C stainless steel drum rotated by a T-shaped slit die to obtain a self-supporting gel film having a residual volatile component of 55 wt. 0 / o and a thickness of about 0.05 mm. It was.
  • the gel film was peeled off from the drum, and both ends were gripped and treated in a heating furnace at 200 ° CX for 30 seconds, 350 ° CX for 30 seconds, and 550 ° CX for 30 seconds to obtain a polyimide film with a thickness of 25 ⁇ m. .
  • the properties of the resulting polyimide film are shown in Table 2.
  • the rotation speed of the drum was the same as in Example 8, except that the gel film transport speed (film formation speed) after peeling from the drum was twice as fast as in Example 8 to obtain a 12.5 in thick film.
  • the characteristics of the polyimide films obtained in the same manner as in Example 8 were evaluated and are shown in Table 2.
  • the rotation speed of the drum is the same as in Example 8, except that the gel film transport speed (film formation speed) after peeling from the drum is 4 times faster than in Example 8 to obtain a film with a thickness of 7.5 ⁇ 111
  • the characteristics of the polyimide films obtained in the same manner as in Example 8 were evaluated and are shown in Table 2.
  • the rotation speed of the drum is the same as in Example 8, except that the gel film transport speed (film formation speed) after peeling from the drum is half that of Example 8 and a film with a thickness of 50 am is obtained.
  • Table 2 shows the characteristics of the polyimide films obtained in the same manner as in Example 8.
  • the rotating speed of the drum is the same as in Example 8, except that the gel film transport speed (film forming speed) after peeling from the drum is 1/3 of that in Example 8, and a film with a thickness of 7511 m is obtained.
  • Table 2 shows the characteristics of the polyimide films obtained in the same manner as in Example 8. [0073] [Comparative Example 1]
  • a 38-m thick polyimide film was obtained in the same manner as in Example 1 except that silica was not added.
  • the properties of the obtained polyimide film were evaluated and are shown in Table 3.
  • a film with a high coefficient of static friction and poor slip was obtained. Also, the adhesive strength was low.
  • the particle size of all particles is 0.1 l rn or more and 4.5 m or less, and particles with an average particle size of 1. ,, ⁇ m and a particle size of 0.15—0.60 m are included in all particles.
  • a volume% calcium hydrogen phosphate N, N-dimethylacetamide slurry was added to the polyamic acid solution obtained in Synthesis Example 6 in an amount of 0.2% by weight per resin weight, and the mixture was sufficiently stirred and dispersed.
  • an acetic anhydride molecular weight 102.09
  • isoquinoline conversion agent were mixed and stirred at a ratio of 50% by weight to the polyamic acid solution.
  • Table 3 shows the characteristics of a 38-m thick polyimide film obtained in the same manner as in Comparative Example 2 except that 31.4% by volume of silica was used. A film with a high coefficient of static friction and slightly poor sliding properties was obtained. Also, the dimensional change was significant due to the high linear expansion coefficient.
  • Particle size range is 0.01 — 1. ⁇ ⁇ ⁇ average particle size 0.4 ⁇ 111, added amount 0.35 wt%, particle size 0.15-0.
  • a polyimide film having a thickness of 38 111 was obtained in the same manner as in Comparative Example 2 except that the polyamic acid solution obtained in Synthesis Example 1 was used.
  • the properties of the obtained polyimide film were evaluated and are shown in Table 3. In the AOI inspection, there were many abnormal protrusions that could not distinguish between foreign particles and fine particles.
  • a manufactured polyimide film mainly composed of inorganic particles having a particle size in the range of 0.01-1.5 mm and an average particle size of 0.05-0.7 m.
  • the polyimide film of the present invention uniformly distributed in the film at a ratio of 0.;! To 0.9% by weight per film resin weight maintains excellent slipperiness, dimensional stability, and adhesiveness.
  • applications such as flexible printed circuit boards (FPC) and chip-on-film (COF) that form fine wiring It is suitable for.
  • the polyimide film of the present invention can be applied to an academic inspection system (AOI) that has excellent film runnability, adhesiveness, and dimensional stability. It is suitable for applications such as flexible printed wiring boards (FPC) and chip-on-film (COF) that form fine wiring.
  • AOI academic inspection system
  • FPC flexible printed wiring boards
  • COF chip-on-film

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Film en polyimide produit essentiellement par l'imidisation de para-phénylènediamine et de 4,4'-diaminodiphényl éther comme composantes diamine et de dianhydride d'acide pyromellitique et de dianhydride d'acide 3,3'-4,4'-biphényltétracarboxylique comme composantes de dianhydride d'acide, sachant que l'on est en présence de particules inorganiques de diamètre compris entre 0,01 et 1,5 μm, et de diamètre moyen compris entre 0,05 et 0,7 μm, avec une distribution de taille de particule telle que des particules inorganiques ayant un diamètre compris entre 0,15 et 0,60 μm représentent 80 % en volume, ou plus, du volume total de particules, et ces particules sont dispersées dans le film suivant un rapport, en poids, compris entre 0,1 et 0,9 % relativement au poids de la résine de film.
PCT/JP2007/070521 2006-10-25 2007-10-22 Film en polyimide et procédé de production WO2008050704A1 (fr)

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JP4947297B2 (ja) * 2007-05-23 2012-06-06 東レ・デュポン株式会社 銅張り板
JP5524475B2 (ja) * 2008-11-28 2014-06-18 株式会社有沢製作所 ２層両面フレキシブル金属積層板及びその製造方法
KR101404093B1 (ko) * 2009-01-13 2014-06-09 에스케이씨코오롱피아이 주식회사 폴리이미드 필름
JP5458384B2 (ja) * 2010-02-18 2014-04-02 東レ・デュポン株式会社 ポリイミドシート
KR102093696B1 (ko) * 2016-03-31 2020-03-26 코오롱인더스트리 주식회사 마찰특성이 개선된 폴리이미드 수지 조성물 및 이의 필름

Citations (7)

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JPS6395264A (ja) * 1986-10-09 1988-04-26 Ube Ind Ltd 芳香族ポリアミック酸溶液組成物
JPH03170548A (ja) * 1989-11-30 1991-07-24 Mitsui Toatsu Chem Inc ポリイミドフィルム及びその製造方法
JPH09291158A (ja) * 1996-02-27 1997-11-11 Toray Ind Inc 芳香族ポリアミドおよび／または芳香族ポリイミドフィルムおよびそれを用いた磁気記録媒体
JP2001031866A (ja) * 1999-07-21 2001-02-06 Mitsubishi Chemicals Corp ポリイミド組成物及びそれを用いた太陽電池用基板
JP2004217907A (ja) * 2002-12-25 2004-08-05 Du Pont Toray Co Ltd ポリイミドフィルムおよびその製造方法
JP2005314669A (ja) * 2004-03-30 2005-11-10 Du Pont Toray Co Ltd ポリイミドフィルムおよびそれを基材とした銅張積層体
JP2006124685A (ja) * 2004-09-29 2006-05-18 Ube Ind Ltd Ｃｏｆ用ポリイミドフィルムおよび積層体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6395264A (ja) * 1986-10-09 1988-04-26 Ube Ind Ltd 芳香族ポリアミック酸溶液組成物
JPH03170548A (ja) * 1989-11-30 1991-07-24 Mitsui Toatsu Chem Inc ポリイミドフィルム及びその製造方法
JPH09291158A (ja) * 1996-02-27 1997-11-11 Toray Ind Inc 芳香族ポリアミドおよび／または芳香族ポリイミドフィルムおよびそれを用いた磁気記録媒体
JP2001031866A (ja) * 1999-07-21 2001-02-06 Mitsubishi Chemicals Corp ポリイミド組成物及びそれを用いた太陽電池用基板
JP2004217907A (ja) * 2002-12-25 2004-08-05 Du Pont Toray Co Ltd ポリイミドフィルムおよびその製造方法
JP2005314669A (ja) * 2004-03-30 2005-11-10 Du Pont Toray Co Ltd ポリイミドフィルムおよびそれを基材とした銅張積層体
JP2006124685A (ja) * 2004-09-29 2006-05-18 Ube Ind Ltd Ｃｏｆ用ポリイミドフィルムおよび積層体

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