WO2008050703A1 - Film polyimide et procédé de production de ce dernier - Google Patents

Film polyimide et procédé de production de ce dernier Download PDF

Info

Publication number
WO2008050703A1
WO2008050703A1 PCT/JP2007/070520 JP2007070520W WO2008050703A1 WO 2008050703 A1 WO2008050703 A1 WO 2008050703A1 JP 2007070520 W JP2007070520 W JP 2007070520W WO 2008050703 A1 WO2008050703 A1 WO 2008050703A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
particle size
particles
polyimide film
polyimide
Prior art date
Application number
PCT/JP2007/070520
Other languages
English (en)
Japanese (ja)
Inventor
Koichi Sawasaki
Toshihiro Teshiba
Original Assignee
Du Pont-Toray Company, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Du Pont-Toray Company, Ltd. filed Critical Du Pont-Toray Company, Ltd.
Publication of WO2008050703A1 publication Critical patent/WO2008050703A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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.
  • the present invention relates to a polyimide film having adhesiveness and heat resistance that can be applied to an automatic optical inspection system (AOI) of a flexible printed circuit board (FPC) and a chip-on-film (COF), and a manufacturing method thereof.
  • AOI automatic optical inspection system
  • FPC flexible printed circuit board
  • COF chip-on-film
  • Polyimide films are known to have excellent properties such as 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.
  • the adhesiveness to the copper foil is insufficient, and at present, the polyimide is subjected to a surface treatment (alkali treatment, corona treatment, plasma treatment, sandblast treatment, etc.) and bonded.
  • a surface treatment alkali treatment, corona treatment, plasma treatment, sandblast treatment, etc.
  • visual inspection of line widths and foreign materials has been the mainstream.
  • the heat-resistant film manufactured with a conventional formulation that incorporates inorganic powder has been sufficiently satisfactory in terms of running performance! /
  • the AOI is too large, and with the recent narrowing of the pitch of FPC, etc., the particle is judged to be a foreign object, which is a major obstacle to the automatic inspection system!
  • the AOI Automatic Optical Inspection System
  • an inert inorganic compound for example, alkaline earth metal orthophosphate, dicalcium phosphate dibasic, calcium pyrophosphate, silica, talc
  • Patent Document 2 a method of performing plasma treatment after forming fine protrusions on the film surface with fine particles
  • inorganic particles having an average particle diameter of 0.01 to 100 m are held on the polyimide surface layer by embedding a part of each particle, and a plurality of protrusions made of the inorganic particles partially exposed are formed on the film.
  • a method see Patent Document 3 in which 1 ⁇ 10 to 5 ⁇ 10 8 pieces / mm 2 are present in the surface layer. This method effectively obtains a slippery effect by actively exposing inorganic particles on the surface and reducing the coefficient of friction on the film surface, but some inorganic particles are exposed. There is a problem that scratches occur on other film surfaces that come into contact with the film, 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 present invention is to obtain a polyimide film that industrially satisfies running performance (slidability), adhesion, and automatic optical inspection system (AOI) simultaneously. is there.
  • the polyimide film of the present invention has a particle size in the range of 0.0;! To 1.5 ⁇ m and an average particle size of 0.05-0. 7 m and particle size 0 Inorganic particles with a particle size distribution in which 15 to 0.60 particles account for 80% by volume or more of all particles are contained in the film at a rate of 0.;! To 0.9% by weight per film resin weight. It is characterized by being dispersed.
  • the polyimide film of the present invention preferably has the following (i) to (5).
  • 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.
  • Projections caused by inorganic particles are present on the film surface, and the number of projections with a height of 2 ⁇ m or more is 5 pieces / 40 cm square or less.
  • the film thickness is 5 to 175 111.
  • the method for producing a polyimide film of the present invention comprises producing polyamic acid by reacting tetracarboxylic dianhydride and diamine in a polar organic solvent, imidizing it, and then forming into a film.
  • the particle size is within the range of 0.01-1.5 m
  • the average particle size force is 0.05-0.7 mm
  • the particle size is 0.15-0.60 mm.
  • a slurry in which inorganic particles having a particle size distribution accounting for 80% by volume or more in all particles are dispersed in the same polar organic solvent as the polar organic solvent is added to the polyamic acid solution in the polyimide manufacturing process in a resin. It is characterized in that it is added in a proportion of 0 .;
  • the inorganic particles are not exposed on the film surface, and fine surface protrusions are expressed in a state of being uniformly dispersed in the film. Since the runnability and adhesiveness are improved, fine wiring is suitable for the application.
  • the polyamic acid that is a precursor for obtaining the polyimide film of the present invention will be described.
  • an aromatic tetracarboxylic dianhydride component and an aromatic diamine component, or a chemical substance mainly composed of both components is subjected to addition polymerization in an organic solvent to obtain a varnish-like polyamic acid. .
  • aromatic diamine component examples include noraf ⁇ diendamine, metaphenylene diamine, benzidine, paraxylylenediamine, 4, 4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl. Ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3 'dimethyl-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3' -Dimethoxybenzidine, 1,4 bis (3-methyl-5-aminophenyl) benzene and amide-forming derivatives thereof.
  • para-furan diamine, benzidine and 3,4′-diaminodiphenyl ether which are effective in increasing the tensile modulus of the film, are preferred.
  • the amount of these diamines is adjusted so that the finally obtained polyimide film has a tensile elastic modulus of 4. OGPa or more. It is preferable for a fine pitch substrate.
  • aromatic tetracarboxylic dianhydride component examples include pyromellitic acid, 3, 3 ', 4, 4'-biphenyl tetracarboxylic acid, 2, 3', 3, 4'-bifu Enyltetracarboxylic acid, 3, 3 ', 4, 4'-benzophenone tetracarboxylic acid, 2, 3, 6, 7 naphthalene dicarboxylic acid, 2, 2 bis (3,4 dicarboxyphenyl) ether, pyridine
  • 2,3,5,6 tetracarboxylic acids and acid anhydrides such as amide-forming derivatives thereof.
  • organic solvent to be used include, for example, sulfoxide solvents such as dimethyl sulfoxide and jetyl sulfoxide, N, N dimethylformamide, formamide solvents such as N, N dimethylformamide, N, N dimethylamide, and the like.
  • Acetoamide solvents such as cetamide, N, N methylacetoamide, N methyl 2-pyrrolidone, N pyrrolidone solvents such as 2-pyrrolidone, phenol, o-, m-, or p cresol, xylenol, halogenated phenol, Catechol and other phenolic solvents, or aprotic polar solvents such as hexamethylphosphoramide and ⁇ -butyrolataton can be used. These are preferably used alone or as a mixture, but moreover, xylene, toluene Aromatic hydrocarbons such as It is.
  • the polymerization method may be any known method, for example, the following method.
  • [0018] A method in which the total amount of the aromatic diamine component is first put in a solvent, and then the aromatic tetracarboxylic acid component is added so as to be equal to the total amount of the aromatic diamine component.
  • the polyamic acid solution (A) is prepared by reacting one aromatic diamine component and the 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.
  • 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 the solid content, and its viscosity is 10 as measured by a Brookfield viscometer. ⁇ 2000 Pa's, preferably 100 ⁇ ; l
  • the power of OOOPa's is preferably used for stable liquid feeding.
  • 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 usable in the present invention include SiO (silica), TiO, CaHPO, C
  • Preferable examples include 2 2 4 a PO. Above all, it was manufactured by wet pulverization method by sol 'gel method
  • Silica is preferred because it is stable in the varnish-like polyamic acid solution and physically stable and does not affect the physical properties of the polyimide! /.
  • the fine silica powder is a silica slurry that is uniformly dispersed in a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and n-methylpyrrolidone.
  • a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and n-methylpyrrolidone.
  • the particle size of the inorganic particles added to form protrusions on the surface of the polyimide film is in the range of 0.01 to 1.5 m, and the average particle size is 0.05.
  • the film can be used without deteriorating the mechanical properties of the film.
  • the average particle diameter is less than these ranges, it is not preferable if the film is too slippery to obtain sufficient slipperiness because the particles are judged to be foreign by an automatic inspection system.
  • the normal film thickness is 5 to 111 to 175 to 111, particles in this particle size range are not exposed on the surface.
  • the inorganic particles are preferably contained in an amount of 0.3 to 0.8% by weight, more preferably 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. This is not preferable. Also 0.9 times If the amount is more than%, the slipperiness of the film will be improved, but coarse protrusions due to abnormal aggregation of particles will increase, and this will be judged as foreign matter by the automatic inspection system and will cause an obstacle.
  • the surface protrusion by the inorganic particles also increases the film surface area, and the film is sufficiently roughened to show an anchor effect without losing adhesiveness.
  • the particle size distribution of the inorganic particles is narrow, that is, it is better that the proportion of particles of similar size in the total particle is higher.
  • the particle size is 0.15 to 0.60 111. It is preferable that the particles account for 80% by volume or more of the total particles. When the proportion of particles below 0.15 m below this range is increased, the slipperiness of the film is lowered, which is not preferable.
  • force S that can remove coarse particles with a 5 ⁇ m cut filter or 10 ⁇ m cut filter, and the proportion of particles of 0.60 m or more increases. This is not preferable because clogging of the filter frequently occurs and process stability is deteriorated and coarse aggregation of particles is likely to occur.
  • 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, still more preferably 1 piece / It is less than 40cm square. If the amount is larger than this, the particles are judged to be foreign by the automatic inspection system, which is not preferable.
  • a slurry in which such inorganic particles are dispersed in the same polar solvent as the organic solvent used in the production of polyimide is added to the polyamic acid solution in the polyimide production process, followed by decyclization and desolvation. It is preferable to obtain a polyimide film, but after adding inorganic particle slurry to an organic solvent before polyamic acid polymerization, polyamic acid polymerization, decyclization and desolvation, to obtain a polyimide film, etc. In the process before the solvent, it is possible to add the insoluble particle slurry to the process!
  • 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.
  • the polyamic acid solution is prepared, and a cyclization catalyst (imidization catalyst), a dehydrating agent, a gelation retarder, and the like are added.
  • 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. , Force including heterocyclic tertiary amines such as / 3-picoline It is preferable to use at least one amine selected from bicyclic 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.
  • aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride
  • aromatic carboxylic acid anhydrides such as benzoic anhydride.
  • acetic anhydride and / or benzoic anhydride are preferred.
  • 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 die, cast on 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 endless belt, and the temperature thereof is controlled by radiant heat from a liquid or gas heating medium and / or an electric heater.
  • the gel film is heated to 30 to 200 ° C, preferably 40 to 40 ° C by receiving heat from a support and / or heat from a heat source such as hot air or an electric heater; By drying the volatile matter such as the organic solvent, it becomes self-supporting and the support is peeled off.
  • a heat source such as hot air or an electric heater
  • 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 above
  • the film dried in the drying zone is heated for 15 seconds to 10 minutes with hot air or an infrared heater. Next, heat treatment is performed for 15 seconds to 20 minutes at a temperature of 250 to 500 with hot air and / or an electric heater.
  • the film thickness of the polyimide film obtained it is preferable to adjust the film thickness of the polyimide film obtained to 5 to 175 m while adjusting the draw ratio in the running direction and the draw ratio in the width direction. If the thickness is larger or smaller than this range, the film forming property is remarkably deteriorated, which is not preferable.
  • the processed surfaces of the film were overlapped and measured according to JIS K-7125 (1999). That is, using a slip coefficient measuring device Slip Tester (manufactured by Technonez Corporation), the film processing surfaces are overlapped, a 200 g weight is placed on top, one side of the film is fixed, and the other side is fixed at 100 mm / min. And the coefficient of friction was measured.
  • a slip coefficient measuring device Slip Tester manufactured by Technonez Corporation
  • the adhesion evaluation method is based on the method of IPC-FC-241. Bond polyimide polyimide and copper foil with commercially available thermoplastic polyimide adhesive, fix the film on the hard plate, and measure. was determined by
  • the base film was inspected using SK-75 manufactured by Onorepo Tech. If the foreign substance and fine particles are distinguished from each other, “A” is evaluated. On the other hand, if the size of the foreign substance and fine particles is similar, and the distinction between the two is not effective, “C” is evaluated. It was.
  • the number of protrusions with a height of 2 m or more was counted per 40 cm square area of the film. High
  • the film surface was measured in the “SURFACE1” mode using a Nikon 100x lens (CF Plan ⁇ ⁇ / ⁇ . 95 ⁇ / 0 EPI) using a scanning laser microscope “1LM15W” manufactured by Lasertec Corporation. Confirmed by photographing 'analysis.
  • the particle size of all particles is within the range of 0.01 111 to 1.5 m, and particles with an average particle size of 0.3 C ⁇ m and a particle size of 0.15—0.60 m are present in all particles.
  • 87.2 volume 0/0 of the silica one N, N over-dimethyl ⁇ Seto amide slurry was added 0-3 wt% per unit weight of resin in the varnish form polyamic acid solution, sufficiently stirred and dispersed, varnish-like polyamic acid
  • the solution was converted into polyimide using a continuous film forming apparatus, and at the same time dried and solidified to obtain a polyimide film having a thickness of 38 111.
  • Table 1 The obtained characteristics are shown in Table 1.
  • Example 2 It was obtained in the same manner as in Example 1 except that the average particle size of silica, the amount of silica added, and the proportion of particles of 0.15 to 0.60 111 in the total particle were set as shown in Table 1. The properties of the 38,1 m-thick polyimide films were evaluated and are shown in Table 1.
  • the particle size of all particles is within the range of 0.01 Hm to 1.5 m, and all particles with an average particle size of 0.3 to 8 ⁇ m and a particle size of 0.15 to 0.60 ⁇ m.
  • Example 9 Evaluate the characteristics of each polyimide film obtained in the same manner as in Example 8, except that the film-forming speed in the continuous film-forming apparatus was twice as fast as in Example 8, and a 12.5 ⁇ 111-thick film was obtained. These are shown in Table 2.
  • Example 8 Each of the polyimide films obtained in the same manner as in Example 8 was evaluated except that the film-forming speed in the continuous film-forming apparatus was four times faster than in Example 8, and a film of 7.5 ⁇ 111 thickness was obtained. The results are shown in Table 2.
  • 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 range is 0;; ⁇ 4.5 n Average particle size 1. 1 111, addition amount 0.2 wt%, particle size 0.15-0. 60 in. Proportion of all particles 27.
  • Table 3 shows the characteristics of a 38-m-thick polyimide film obtained in the same manner as in Example 1 except that 3% by volume of hydrogen phosphate hydrogen is used. Can AOI inspection distinguish foreign materials from fine particles? Many abnormal protrusions also occurred.
  • Particle size range is 0.01-0.
  • the ratio of the added amount of 0.35% by weight and the particle size of 0.15—0.60 in the total particle 31.4% As in Example 1, except that 4% by volume of calcium hydrogen phosphate was used.
  • the properties of the 38 m thick polyimide film obtained were evaluated and are shown in Table 3. A film with a high coefficient of static friction and slightly slipperiness was obtained.
  • Particle size range is 0.01-1. 111, addition amount 0.35% by weight, particle size 0.15—0.660% of the total particles 72.6% by volume Except for using calcium hydrogen phosphate, Example 1 and The properties of a 38 m thick polyimide film obtained in the same manner were evaluated and are shown in Table 3. In this example, the occupancy ratio of the particle diameter of 0.9 to 1.3 mm accounted for 22.3% by volume of the total, and this increased the number of abnormal projections. In the AOI inspection, it was difficult to distinguish between foreign materials and fine particles, and the result was as follows.
  • a polyimide film uniformly dispersed in the film at a ratio of 0.1 to 0.9% by weight per resin weight maintains excellent slidability and adhesiveness, and the number of projections due to coarse particles is small.
  • the polyimide film of the present invention is suitable for uses such as a flexible printed wiring board (FPC) and a chip-on-film (COF) that form fine wiring without any obstacle that the particles are judged to be foreign matter by AOI inspection.
  • FPC flexible printed wiring board
  • COF chip-on-film

Landscapes

  • 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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film polyimide comprenant une résine de film et des particules inorganiques dispersées dans le film dans une quantité comprise entre 0,1 et 0,9 % en poids relativement à la quantité de la résine de film, les particules inorganiques présentant un diamètre des particules compris entre 0,01 et 0,5 μm, un diamètre des particules moyen compris entre 0,05 et 0,7 μm, et une telle répartition granulométrique que les particules présentant un diamètre des particules compris entre 0,15 et 0,60 μm représentent 80% en volume ou plus du volume des particules total. L'invention concerne également un procédé de production d'un film polyimide, lequel comprend les étapes consistant à faire réagir du dianhydrure d'acide tétracarboxylique avec une diamine dans un solvant organique polaire afin de produire un acide polyamique, à imidiser l'acide polyamique, puis à mouler le produit imidisé sous forme d'un film, une suspension épaisse comprenant des particules inorganiques dispersées dans le même solvant organique polaire que le solvant inorganique polaire utilisé ci-dessus étant ajoutée à une solution de l'acide polyamique produit au cours du procédé de production de polyimide à un taux compris entre 0,1 et 0,9% en poids relativement au poids de la résine, les particules inorganiques présentant un diamètre des particules compris entre 0,01 et 0,15 μm, un diamètre des particules moyen compris entre 0,05 et 0,7 μm et une répartition granulométrique telle que susmentionnée.
PCT/JP2007/070520 2006-10-25 2007-10-22 Film polyimide et procédé de production de ce dernier WO2008050703A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-290149 2006-10-25
JP2006290149A JP2008106138A (ja) 2006-10-25 2006-10-25 ポリイミドフィルムおよびその製造方法

Publications (1)

Publication Number Publication Date
WO2008050703A1 true WO2008050703A1 (fr) 2008-05-02

Family

ID=39324500

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/070520 WO2008050703A1 (fr) 2006-10-25 2007-10-22 Film polyimide et procédé de production de ce dernier

Country Status (4)

Country Link
JP (1) JP2008106138A (fr)
KR (1) KR20090073134A (fr)
TW (1) TW200833786A (fr)
WO (1) WO2008050703A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117358066A (zh) * 2023-12-07 2024-01-09 湖南沁森高科新材料有限公司 一种纳滤膜及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010016244A (ja) * 2008-07-04 2010-01-21 Nitto Denko Corp 配線回路基板の製造方法
TWI800261B (zh) * 2022-02-15 2023-04-21 台虹科技股份有限公司 卷狀層疊體的製造方法

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

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117358066A (zh) * 2023-12-07 2024-01-09 湖南沁森高科新材料有限公司 一种纳滤膜及其制备方法
CN117358066B (zh) * 2023-12-07 2024-03-19 湖南沁森高科新材料有限公司 一种纳滤膜及其制备方法

Also Published As

Publication number Publication date
TW200833786A (en) 2008-08-16
JP2008106138A (ja) 2008-05-08
KR20090073134A (ko) 2009-07-02

Similar Documents

Publication Publication Date Title
JP2005314669A (ja) 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
JP2018145303A (ja) 多層ポリイミドフィルム
JP4392578B2 (ja) 易滑性ポリイミドフィルムおよびその製造方法
WO2008050704A1 (fr) Film en polyimide et procédé de production
JP2010126634A (ja) ポリイミドフィルムおよびその製造方法
JP2008106141A (ja) ポリイミドフィルムおよびその製造方法
WO2008050703A1 (fr) Film polyimide et procédé de production de ce dernier
JP5955603B2 (ja) ポリイミドフィルム及びポリイミドフィルムの製造方法
WO2008050705A1 (fr) Film en polyimide et procédé de production
JP2008201940A (ja) 低熱収縮性ポリイミドフィルムおよびその製造方法
JP2004217907A (ja) ポリイミドフィルムおよびその製造方法
JP5571839B2 (ja) 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
JP4074987B2 (ja) ポリイミドフィルムおよびそれを用いたフレキシブル回路基板用スティフナー
JP5196344B2 (ja) ポリイミドフィルムの接着性を向上させる方法
JP2008222926A (ja) 低熱収縮性高接着性ポリイミドフィルム
JP5285557B2 (ja) 芳香族ポリイミドフィルムおよびその製造方法
JP5329163B2 (ja) ポリイミドフィルムの製造方法およびポリイミドフィルム
JP2006316232A (ja) 接着フィルムおよびその製造方法
JP2009214424A (ja) 多層芳香族ポリイミドフィルム
JP2004107659A (ja) ポリイミドフィルム
JP2005089618A (ja) ポリアミック酸およびそれを用いたポリイミドフィルム
JP2002348388A (ja) ポリイミドフィルム及びその製造方法
JP2008201935A (ja) 低熱収縮性ポリイミドフィルムおよびその製造方法。
JP2008222922A (ja) 低熱収縮性高接着性ポリイミドフィルムおよびその製造方法。
JP2008222925A (ja) 低熱収縮性高接着性ポリイミドフィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07830254

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1020097007054

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07830254

Country of ref document: EP

Kind code of ref document: A1