WO2011093245A1 - ポリイミドフィルムの製造方法及び製造装置 - Google Patents
ポリイミドフィルムの製造方法及び製造装置 Download PDFInfo
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- WO2011093245A1 WO2011093245A1 PCT/JP2011/051232 JP2011051232W WO2011093245A1 WO 2011093245 A1 WO2011093245 A1 WO 2011093245A1 JP 2011051232 W JP2011051232 W JP 2011051232W WO 2011093245 A1 WO2011093245 A1 WO 2011093245A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/52—Measuring, controlling or regulating
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B11/00—Measuring arrangements characterised by the use of optical techniques
- G01B11/02—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
- G01B11/06—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
- G01B11/0691—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of objects while moving
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/86—Investigating moving sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
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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
- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/86—Investigating moving sheets
- G01N2021/869—Plastics or polymeric material, e.g. polymers orientation in plastic, adhesive imprinted band
Definitions
- the present invention relates to a method and apparatus for producing a polyimide film having excellent film properties.
- Polyimide film has high heat resistance and high electrical insulation, and even a thin film satisfies the rigidity, heat resistance and electrical insulation necessary for handling. For this reason, it is widely used in industrial fields, such as an electrical insulation film, a heat insulation film, and a base film of a flexible circuit board.
- Polyimide is generally non-melting and further insoluble in solvents and the like. For this reason, a polyimide precursor solution such as polyamic acid is extruded from the tip of a die and cast onto a metal support surface in the form of a film, which is heat-treated and partially dried to have self-supporting properties. After the film is formed, the solvent is removed by peeling the self-supporting film from the metal support or by further heating the self-supporting film with the self-supporting film laminated on the metal support. And imidation is completed and a polyimide film is manufactured. Since the self-supporting film shrinks during post-heating, the heat treatment is performed while holding both ends of the film with a holder or the like.
- a polyimide precursor solution such as polyamic acid is extruded from the tip of a die and cast onto a metal support surface in the form of a film, which is heat-treated and partially dried to have self-supporting properties. After the film is formed, the solvent is removed by peeling the self
- grasping the solvent content of the self-supporting film is important in producing a polyimide film having uniform physical properties in the plane.
- the thickness of the completed polyimide film is measured, and the measurement result is fed back to adjust the gap at the tip of the die. Has been performed conventionally.
- Patent Document 3 describes that the thickness unevenness of the surface layer of the self-supporting film is measured, and the extrusion amount of the polyimide precursor solution is controlled to be uniform based on the measurement result.
- the self-supporting film is not necessarily uniform in imidation ratio, solvent content, etc., as disclosed in Patent Document 3, the measurement result of the thickness of the self-supporting film is fed back. Even if the extrusion amount of the polyimide precursor solution was adjusted, the thickness unevenness of the polyimide film could not be suppressed.
- an object of the present invention is to provide a polyimide film manufacturing method and a manufacturing apparatus capable of manufacturing a polyimide film having uniform physical properties in a plane with high productivity.
- one aspect of the present invention is to extrude a polyimide precursor solution containing a polyimide precursor and a solvent from the tip of a die and cast it on a metal support surface, thereby casting the polyimide precursor solution.
- the present invention provides a method for producing a polyimide film characterized by controlling one or more selected from post-heating conditions of a self-supporting film and an extrusion amount of a polyimide precursor solution from a die.
- the polyimide film manufacturing method of the present invention is based on the measurement result, and the portion of the self-supporting film in which the solvent content in the width direction is higher than the predetermined solvent content is the flow of the polyimide precursor solution.
- the method for producing a polyimide film of the present invention is based on the measurement result, with respect to a portion where the solvent content over the width direction of the self-supporting film is higher than a predetermined solvent content, the portion in the post-heating step. Increase the temperature and / or supply amount of the heating medium for heating For a portion where the solvent content in the width direction of the self-supporting film is lower than the predetermined solvent content, the temperature and / or supply amount of the heating medium for heating the portion in the post-heating step is lowered. Is preferred.
- the tip of the die has a plurality of extrusion amount adjusting mechanisms in the width direction, Based on the measurement results, for the portion where the solvent content over the width direction of the self-supporting film is higher than the predetermined solvent content, the polyimide precursor solution is extruded from the tip of the die to the relevant portion. Reduce the amount of extrusion from the corresponding die part, For a portion where the solvent content in the width direction of the self-supporting film is lower than a predetermined solvent content, extrusion from the die portion corresponding to the portion in the step of extruding the polyimide precursor solution from the tip of the die. It is preferred to increase the amount.
- the solvent content of the self-supporting film can be measured at a plurality of points over the width direction of the self-supporting film by scanning a measurement mechanism by infrared spectroscopy. It is preferable to measure with a measuring means.
- the method for producing a polyimide film of the present invention comprises a solvent content of the self-supporting film, a wavelength having an absorption peak in the solvent ( ⁇ 2) having no peak in the polyimide film, an absorption peak in the solvent, and a polyimide film Absorbance when a wavelength ( ⁇ 5) having a peak and a wavelength ( ⁇ 1) in which neither a solvent nor a polyimide film has an absorption peak is selected, and the self-supporting film as the object to be measured is irradiated with infrared rays of these wavelengths It is preferable to obtain from the following formulas (1) to (3).
- Polymer amount absorbance at ⁇ 5 / absorbance at ⁇ 1
- Solvent amount absorbance at ⁇ 2 / absorbance at ⁇ 1
- Solvent content solvent amount / (solvent amount + polymer amount) (3)
- the method for producing a polyimide film of the present invention further measures the thickness of the cast product of the polyimide precursor solution before drying, and based on the measurement result, It is preferable to control the extrusion amount of the polyimide precursor solution from the die so that the thickness in the width direction is substantially uniform.
- the thickness of the cast product of the polyimide precursor solution it is preferable to measure the thickness of the cast product of the polyimide precursor solution by a confocal method using a laser beam or a spectral interference method using a superluminescent diode.
- An extrusion apparatus for extruding a polyimide precursor solution from the tip of a die and casting it on a metal support surface to form a cast product of the polyimide precursor solution, and the polyimide precursor solution.
- An apparatus for producing a polyimide film comprising: a drying apparatus for drying a cast of the film to form a self-supporting film having a self-supporting property; and a heating device for post-heating the self-supporting film, Solvent content measuring means for measuring the solvent content of the self-supporting film by infrared spectroscopy, and based on the measurement results, drying conditions of the drying device, heating conditions of the heating device, and extrusion of the extrusion device And a controller for controlling one or more selected from the conditions.
- a polyimide film manufacturing apparatus is provided.
- the control device corresponds to the portion in the drying device for a portion where the solvent content in the width direction of the self-supporting film is higher than a predetermined solvent content. Increasing the temperature and / or supply rate of the drying medium for drying the cast part For a portion where the solvent content in the width direction of the self-supporting film is lower than a predetermined solvent content, the temperature of the drying medium for drying the cast portion corresponding to the portion in the drying device, and It is preferable to control to lower the supply amount.
- the controller heats the part in the heating device for a part where the solvent content in the width direction of the self-supporting film is higher than a predetermined solvent content. Increase the temperature and / or supply amount of the heating medium to For a portion where the solvent content in the width direction of the self-supporting film is lower than a predetermined solvent content, the temperature and / or supply amount of the heating medium for heating the portion in the heating device is lowered. It is preferable to control.
- the control device corresponds to the portion in the extrusion device for a portion where the solvent content in the width direction of the self-supporting film is higher than a predetermined solvent content.
- Reduce the extrusion amount of the polyimide precursor solution from the die part For a portion where the solvent content in the width direction of the self-supporting film is lower than a predetermined solvent content, the extrusion amount of the polyimide precursor solution from the die portion corresponding to the portion in the extrusion apparatus is increased. It is preferable to control.
- the polyimide film manufacturing apparatus of the present invention further comprises a thickness measuring means for measuring the thickness of the cast product of the polyimide precursor solution, and based on the measurement result of the thickness measuring means, the extrusion conditions of the extrusion apparatus It is preferable to control also.
- the solvent content of the self-supporting film is measured by infrared spectroscopy, in-line installation is possible, and the solvent content is accurately measured. can do.
- the measurement result can be fed back almost in real time.
- one kind selected from the drying conditions of the cast product of the polyimide precursor solution, the post-heating conditions of the self-supporting film, and the extrusion amount of the polyimide precursor solution from the die Since the above can be controlled almost in real time, a polyimide film having uniform physical properties within the surface can be produced with high productivity while suppressing the occurrence of defective products.
- the thickness of the cast product of the polyimide precursor solution before being dried is measured, and based on the measurement result, the thickness of the cast product in the width direction is uniform.
- the cause of the thickness nonuniformity of a polyimide film can be discovered at an early stage, and a feedback result can be reflected at an early stage. For this reason, the amount of discarded products can be reduced, and a polyimide film with less thickness unevenness can be manufactured with high productivity.
- 6 is a chart showing spectral characteristics when N, N-dimethylacetamide used as a solvent in one embodiment of the present invention and a polyimide film are each irradiated with infrared rays. It is a flowchart explaining the 1st aspect of the control apparatus in the manufacturing apparatus of the polyimide film of this invention. It is a flowchart explaining the 2nd aspect of the control apparatus in the manufacturing apparatus of the polyimide film of this invention. It is a flowchart explaining the 3rd aspect of the control apparatus in the manufacturing apparatus of the polyimide film of this invention.
- a polyimide precursor solution containing a polyimide precursor and a solvent is extruded from the tip of a die and cast onto a metal support surface to cast a polyimide precursor solution (hereinafter, polyimide).
- FIG. 1 shows a schematic configuration diagram of the polyimide film manufacturing apparatus of the present invention.
- the polyimide film manufacturing apparatus includes an extrusion apparatus that extrudes a polyimide precursor solution 1 from the tip of a die 2 and casts it on a metal belt 3 to form a polyimide precursor casting 1a. That is, in this embodiment, the die 2 constitutes an extrusion apparatus in the present invention.
- a drying furnace 5 is provided on the conveyance path of the metal belt 3, and the polyimide precursor casting is dried in the drying furnace 5 so as to form a self-supporting film 1b having self-supporting properties. It has become.
- the drying furnace 5 constitutes a drying apparatus in the present invention.
- the self-supporting film 1b is peeled off from the metal belt 3 and sent to the heating furnace 6. And in the heating furnace 6, the post-heating process which heats a self-supporting film and completes solvent removal and imidation is performed.
- the said heating furnace 6 comprises the heating apparatus in this invention.
- a winding device 7 for winding the polyimide film 1c after the post-heating step is provided.
- the manufacturing apparatus of the polyimide film of this invention is the drying condition of the drying apparatus 5 based on the solvent content measuring means 4 which measures the solvent content of the self-supporting film 1b by infrared spectroscopy, and this measurement result.
- a control device 8 for controlling at least one selected from heating conditions of the heating device 6 and extrusion conditions of the extrusion device.
- the polyimide film manufacturing method of the present invention is a polyimide that forms a polyimide precursor casting 1a by casting the polyimide precursor solution 1 on a metal belt 3 by an extrusion device using, for example, the manufacturing apparatus as described above.
- a precursor casting forming step, a self-supporting film forming step of drying the polyimide precursor casting 1a by a drying furnace 5 to form a self-supporting film 1b having a self-supporting property, and a self-supporting film 1b Is mainly composed of a post-heating step in which the solvent is removed and the imidization is completed by post-heating in the heating furnace 6.
- each step will be described in detail.
- the polyimide precursor solution 1 is extruded from the tip of the die 2 and cast onto the metal belt 3 to form the polyimide precursor casting 1a.
- the metal belt 3 corresponds to the metal support in the present invention. More specifically, one or a plurality of types of polyimide precursor solutions 1 are discharged from the die 2 discharge port (lip portion) using a film forming apparatus in which a single-layer or multi-layer extrusion forming die is installed. Is extruded onto the metal belt 3 as a single-layer or multi-layer thin film to form a polyimide precursor casting 1a as a thin film of a polyimide precursor solvent solution.
- polyimide precursor solution examples include polyamic acid, polyamic acid salt, polyamic acid alkyl ester, polyamic acid trimethylsilyl ester, a mixed solution of tetracarboxylic acid diester and diamine, and the like containing two or more of these. I can list them.
- the polyamic acid solution which is a polyimide precursor solution can be obtained by reacting a tetracarboxylic acid component and a diamine component by a known method.
- a tetracarboxylic acid component and a diamine component can be produced by polymerizing a tetracarboxylic acid component and a diamine component in an organic solvent usually used for producing polyimide.
- tetracarboxylic acid component examples include aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and the like. Specific examples include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes referred to as “s-BPDA”), pyromellitic dianhydride (hereinafter referred to as “PMDA”).
- s-BPDA 4,4′-biphenyltetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- Aromatic tetracarboxylic dianhydrides such as sulfide dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride It is done.
- diamine component examples include aromatic diamines, aliphatic diamines, and alicyclic diamines. Specific examples include p-phenylenediamine (hereinafter sometimes referred to as “PPD”), 4,4′-diaminodiphenyl ether (hereinafter sometimes referred to as “DADE”), 3,4′-diaminodiphenyl ether, m- Tolidine, p-tolidine, 5-amino-2- (p-aminophenyl) benzoxazole, 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3 -Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4 '-Bis (3-aminophenoxy) biphen
- Examples of the combination of the tetracarboxylic acid component and the diamine component include the following 1) to 3) from the viewpoint of mechanical properties and heat resistance.
- organic solvent known solvents can be used, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like. These organic solvents may be used alone or in combination of two or more. Of these, N, N-dimethylacetamide is preferably used.
- the present invention can also be applied to the case where a polyimide film is formed in any form of thermal imidization performed thermally and chemical imidization performed chemically.
- the present invention can be preferably applied to thermal imidization, which has a slower imidization rate than chemical imidization.
- an imidization catalyst When the imidization is completed by thermal imidization of the polyimide precursor solution, an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyamic acid solution as necessary.
- a cyclization catalyst, a dehydrating agent, inorganic fine particles and the like may be added to the polyamic acid solution as necessary.
- the imidization catalyst examples include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic Heterocyclic compounds are mentioned.
- cyclization catalyst examples include aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines.
- dehydrating agent examples include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides.
- the inorganic fine particles include fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle silicon nitride powder, and titanium nitride.
- examples thereof include inorganic nitride powder such as powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as particulate calcium carbonate powder, calcium sulfate powder, and barium sulfate powder.
- These inorganic fine particles may be used in combination of two or more. In order to uniformly disperse these inorganic fine particles, a means known per se can be applied.
- the solid content concentration (polymer component) of the polyimide precursor solution is not particularly limited as long as it is in a viscosity range suitable for film production by casting. 10% by mass to 30% by mass is preferable, 15% by mass to 27% by mass is more preferable, and 16% by mass to 24% by mass is further preferable.
- the self-supporting film forming step the polyimide precursor cast 1a formed on the metal belt 3 in this way is introduced into the drying furnace 5, heat-treated, dried and self-supporting having self-supporting properties. Film 1b is formed.
- drying refers to an operation of heating the polyimide precursor solution to create a state in which imidization of the polyimide precursor does not proceed completely and a part or most of the organic solvent is removed.
- having self-supporting property means a state having a strength that can be peeled off from the metal belt 3.
- drying conditions (heating conditions) for forming the self-supporting film 1b are not particularly limited, but in the thermal imidization, it can be produced by heating at a temperature of 100 to 180 ° C. for about 2 to 60 minutes.
- a self-supporting film is formed by heating to a temperature at which imidation of the polyimide precursor does not proceed completely and a part or most of the organic solvent can be removed while moving the metal support.
- the thin film on the upper surface of the support is appropriately dried on the support by drying means such as a heater or a hot air blowing device to remove most of the solvent.
- the drying means such as the heater or the hot air blowing device has a plurality of blocks (zones) having different temperatures in the width direction and / or the conveying direction of the casting.
- the drying medium for the drying means include an infrared heater and hot air (a hot gas obtained by heating a gas such as air).
- the self-supporting film 1b is not particularly limited as long as the solvent is removed and / or imidized to such an extent that it can be peeled off from the support.
- the loss on heating is preferably in the range of 20 to 50% by mass. When the loss on heating is in the range of 20 to 50% by mass, the mechanical properties of the self-supporting film are sufficient.
- the loss on heating of the self-supporting film 1b is a value obtained by the following equation from the mass W1 of the self-supporting film and the mass W2 of the cured film.
- Loss on heating (mass%) ⁇ (W1-W2) / W1 ⁇ ⁇ 100
- the self-supporting film 1b is peeled off from the metal belt 3.
- the peeling method is not particularly limited, and examples thereof include a method of cooling the self-supporting film and applying a tension via a roll for peeling.
- the self-supporting film 1b is introduced into the heating furnace 6 and subjected to heat treatment to complete the solvent removal and imidization to obtain the polyimide film 1c.
- this heating method is a stepwise primary heat treatment at a relatively low temperature of about 100 ° C. to about 170 ° C. for about 0.5-30 minutes and then at a temperature of 170 ° C.-220 ° C. for about 0.5 ° C.
- the second heat treatment is performed for ⁇ 30 minutes, and then the third heat treatment is performed at a high temperature of 220 ° C. to 400 ° C. for about 0.5-30 minutes.
- the fourth high-temperature heat treatment may be performed at a high temperature of 400 ° C. to 550 ° C., preferably 450 to 520 ° C.
- pin ends, clips, frames, etc. are used to fix at least the edges in the direction perpendicular to the longitudinal direction of the long solidified film, that is, the width direction of the film. If necessary, the heat treatment may be performed by expanding or contracting in the width direction or the length direction.
- Examples of the heating means for post-heating the self-supporting film include a heater or a hot air blowing device.
- the heating means such as the heater or hot air blowing device has a plurality of blocks (zones) having different temperatures in the width direction and / or the conveying direction of the casting.
- Examples of the heating medium of the heating means include an infrared heater and hot air (a hot gas obtained by heating a gas such as air).
- the thickness of the polyimide film of the present invention is not particularly limited, but is about 3 to 250 ⁇ m, preferably about 4 to 150 ⁇ m, more preferably about 5 to 125 ⁇ m, and still more preferably about 5 to 100 ⁇ m. According to the present invention, a polyimide film having excellent characteristics can be obtained even with a thin film having a thickness of 20 ⁇ m or less, further 15 ⁇ m or less, and further 10 ⁇ m or less. When a thin film is manufactured, the heating time may be short.
- the polyimide film 1c after the post-heating step may be wound up in a roll shape by the winding device 7 or the like.
- a polyimide film is manufactured through these steps.
- the solvent content of the self-supporting film 1b is measured by the solvent content measuring means 4 by infrared spectroscopy.
- the solvent content of the self-supporting film 1b may be measured before the post-heating step. And based on a measurement result, 1 or more types chosen from the drying amount of a polyimide precursor cast, the post-heating conditions of a self-supporting film, and the extrusion amount from the die
- the solvent content of the self-supporting film by infrared spectroscopy is measured by irradiating the self-supporting film, which is the object to be measured, with infrared rays, and converting the intensity of the reflected or transmitted light into the absorbance characteristics, and the obtained absorbance. From the characteristics, the intensity ratio with respect to the reference wavelength is obtained by converting into the solvent content of the self-supporting film according to the Lambert Beer law.
- FIG. 2 shows spectral characteristics when N, N-dimethylacetamide (hereinafter referred to as DMAc) and a polyimide film (Upilex S manufactured by Ube Industries, Ltd.) are irradiated with infrared rays.
- DMAc N, N-dimethylacetamide
- polyimide film Upilex S manufactured by Ube Industries, Ltd.
- the solvent content of the self-supporting film can be measured by infrared spectroscopy using “IM series” (trade name) marketed by Chino Corporation.
- the solvent content can be grasped by the above method, it is preferable to prepare a calibration curve as described below and obtain the solvent content converted by the calibration curve. Thereby, it can be brought closer to the value of the solvent content actually measured by other measurement methods such as a heat loss method.
- heat loss method measurement is performed on the same film as the self-supporting film used for measurement by infrared spectroscopy.
- the film weight after heating is defined as the polymer amount
- the difference between the initial weight of the self-supporting film (weight before heating) and the film weight after heating is defined as the solvent amount.
- a calibration curve can be created by comparing and matching the polymer amount and solvent amount determined by the above formulas (1) and (2) with the polymer amount and solvent amount determined by the heat loss method. By creating such a calibration curve, it is possible to convert the absolute value of the polymer amount, the solvent amount, and the solvent content.
- the drying conditions of the polyimide precursor solution, the post-heating conditions of the self-supporting film, and the control of the extrusion amount of the polyimide precursor solution from the die are the solvent content obtained by infrared spectroscopy, or the calibration prepared as described above. Either of the results of the solvent content converted with a line may be used, but it is preferable to use the solvent content converted with a calibration curve.
- infrared spectroscopy In infrared spectroscopy, infrared light is applied to a specific narrow region of the self-supporting film. Therefore, the solvent content determined by infrared spectroscopy is a pinpoint value.
- the solvent content by the heat loss method is an average value of a film having a certain width and length.
- the measurement of the solvent content by infrared spectroscopy is only necessary to irradiate the self-supporting film with infrared rays, so that the equipment can be inlined and the solvent content of the self-supporting film can be measured with high accuracy. it can.
- the measurement result is fed back almost in real time, after the amount of extrusion of the polyimide precursor solution from the die, the drying conditions of the polyimide precursor casting, and the self-supporting film.
- One or more selected from heating conditions can be controlled.
- the measurement result by infrared spectroscopy is acquired (step S1), and the solvent content of the self-supporting film is determined based on the measurement result (step S2).
- the solvent content of a self-supporting film by infrared spectroscopy is measured by irradiating the self-supporting film, which is the object to be measured, with infrared rays, and converting the reflected light or transmitted light intensity into absorbance characteristics. From the obtained absorbance characteristic, it can be obtained by converting the intensity ratio with the reference wavelength into the solvent content of the self-supporting film according to the Lambert Beer law.
- the solvent content measured by the infrared spectroscopy is compared with a predetermined solvent content (step S3). Specifically, the difference between the measured value of the solvent content and the predetermined value is confirmed. And when solvent content exceeds predetermined value, the temperature and / or supply of the drying medium for drying the cast part corresponding to the part of the self-supporting film which measured the solvent content in the drying furnace 5 The amount is increased (step S4). When the solvent content is less than the predetermined value, the temperature and / or supply amount of the drying medium for drying the cast portion corresponding to the portion of the self-supporting film whose solvent content is measured in the drying furnace 5 is set. Lowered (step S5). If the solvent content is a predetermined value, the drying medium is not controlled. Note that a value having a certain width may be set as the predetermined value (the same applies to the following modes).
- the cast portion corresponding to the portion of the self-supporting film whose solvent content was measured is a self-supporting film whose solvent content was measured when viewed in the width direction as shown in FIG.
- it is represented as an area on a rectangle defined by a vertical dotted line and a horizontal solid line in the self-supporting film forming process.
- the cast portion region may have a certain width in the width direction when viewed from the measurement point of the self-supporting film in which the solvent content is measured.
- the temperature and / or supply amount of the drying medium for drying the cast portion is increased or decreased.
- the drying medium include an infrared heater and hot air (a hot gas obtained by heating a gas such as air).
- an openable / closable damper or the like can be cited.
- the temperature and supply amount of the drying medium are increased, and for the portion having a low solvent content, the temperature and supply amount of the drying medium are decreased.
- the solvent content in the width direction is adjusted to be uniform.
- the shrinkage of the self-supporting film 1b in the post-heating step can be made uniform, and stress is locally applied to the physical properties of the polyimide film. Troubles such as variations and dimensional errors can be solved.
- FIG. 4 shows a case where the heating condition of the self-supporting film in the post-heating step is controlled based on the measurement result of the solvent content of the self-supporting film. It demonstrates based on the flowchart to show. In this case, by varying the heating conditions according to the solvent content in the width direction of the self-supporting film, the characteristic variation in the width direction of the resulting polyimide is reduced.
- step S1 the measurement result by infrared spectroscopy is acquired in the same manner as described above (step S2), and the solvent content of the self-supporting film is determined based on the measurement result (step S2). Then, the solvent content measured by the infrared spectroscopy is compared with a predetermined solvent content (step S3). When the solvent content exceeds a predetermined value, the temperature and / or supply amount of the heating medium for heating the film in the heating furnace 6 portion corresponding to the portion of the self-supporting film whose solvent content is measured is increased. (Step S4).
- Step S5 the temperature and / or supply amount of the heating medium for heating the film in the heating furnace 6 portion corresponding to the portion of the self-supporting film whose solvent content is measured is lowered. If the solvent content is a predetermined value, the heating medium is not controlled.
- the film in the heating furnace 6 portion corresponding to the portion of the self-supporting film whose solvent content was measured is the self whose solvent content was measured when viewed in the width direction, as shown in FIG.
- region in the post-heating process corresponding to the measuring point of a support film is said.
- it is represented as a rectangular region defined by a vertical dotted line and a horizontal solid line in the post-heating step.
- the film partial region may have a certain width in the width direction when viewed from the measurement point of the self-supporting film whose solvent content is measured.
- the temperature and / or supply amount of the heating medium for post-heating the film is increased or decreased.
- the heating medium include an infrared heater and hot air (a hot gas obtained by heating a gas such as air).
- an openable / closable damper or the like can be cited.
- the temperature and supply amount of the heating medium in the initial stage of post-heating are increased, and the part with low solvent content is the ratio of the heating medium in the initial stage of post-heating.
- the solvent content is adjusted to be uniform in the middle stage of post-heating.
- the degree of shrinkage of the self-supporting film can be made substantially uniform, and problems such as variations in physical properties of the polyimide film and dimensional errors caused by local stress can be solved.
- FIG. 5 shows a case where the extrusion amount of the polyimide precursor solution from the die is controlled based on the measurement result of the solvent content of the self-supporting film. This will be described based on a flowchart. In this case, the extrusion amount of the polyimide precursor solution 1 from the die is controlled so that the solvent content in the width direction of the self-supporting film 1b is substantially uniform.
- step S1 the measurement result by infrared spectroscopy is acquired in the same manner as described above (step S2), and the solvent content of the self-supporting film is determined based on the measurement result (step S2). Then, the solvent content measured by the infrared spectroscopy is compared with a predetermined solvent content (step S3). When the solvent content exceeds the predetermined value, the extrusion amount from the die 2 of the cast portion corresponding to the portion of the self-supporting film whose solvent content has been measured is reduced (step S4). When the solvent content is less than the predetermined value, the extrusion amount from the die 2 of the cast portion corresponding to the portion of the self-supporting film whose solvent content has been measured is increased (step S5). If the solvent content is a predetermined value, the amount of extrusion from the die 2 is not controlled.
- the die of the cast part corresponding to the part of the self-supporting film whose solvent content was measured is self-supporting whose solvent content was measured when viewed in the width direction as shown in FIG.
- the die portion corresponding to the measurement point of the conductive film.
- FIG. 9 shows a die portion for supplying a polyimide precursor solution to a casting portion region on a rectangle defined by a vertical dotted line and a horizontal solid line in the polyimide precursor casting forming step. Yes.
- the cast portion region may have a certain width in the width direction when viewed from the measurement point of the self-supporting film in which the solvent content is measured.
- the extrusion amount from the die of the polyimide precursor solution 1 is reduced, and the part with the low solvent content Increases the amount of extrusion of the polyimide precursor solution 1 from the die.
- the following methods (a) and (b) are preferably exemplified as methods for reducing and increasing the amount of extrusion from the die. Also, the methods (a) and (b) may be combined.
- A) A method of adjusting the distance in the height direction of the flow path of the die with a screw, a spring, a heat bolt, or the like.
- B) A method of adjusting the temperature of the polyimide precursor solution discharged from the die tip.
- the thick part of the polyimide precursor casting narrow the gap in the height direction of the flow path at the tip of the die and the vicinity of the part, or lower the temperature of the polyimide precursor solution extruded from the tip of the die.
- the thickness distribution over the width direction of the polyimide precursor casting can be made uniform.
- the measurement by the said infrared spectroscopy at several points over the width direction of the self-supporting film 1b.
- it is selected from the drying conditions of the polyimide precursor cast, the post-heating conditions of the self-supporting film, and the extrusion amount of the polyimide precursor solution from the die.
- One or more types can be controlled more precisely.
- the form provided with the rail for making a measurement mechanism scan substantially parallel to the width direction of the self-supporting film 1b is mentioned.
- the thickness of the polyimide precursor cast 1a before drying is measured by the thickness measuring means 9, and the measurement result is fed back to the control device 8 to provide a thickness over the width direction of the polyimide precursor cast 1a.
- the extrusion of the polyimide precursor solution 1 from the die 2 is controlled so as to be uniform.
- This embodiment may be carried out independently of the polyimide film manufacturing method using the control method shown in any of the first to third aspects, or may be used in combination with these control methods. Can also be implemented.
- the polyimide precursor casting 1a is formed on the metal belt 3, but the metal belt 3 is mirror-finished because the surface shape of the metal belt 3 is transferred to the polyimide precursor casting 1a. There are many. For this reason, the film thickness measurement of the polyimide precursor cast 1a is not affected by the specular reflection from the mirror-finished metal belt 3, and is also accurately measured at a distance from the metal belt 3.
- a measuring means capable of satisfying the above is preferably used. Specifically, measurement means using (1) confocal method using laser light, (2) spectral interference method using super luminescent diode (SLD), etc. are preferably used.
- the measurement principle of the confocal method using laser light is that the laser light L1 emitted from the light source 10 passes through the objective lens 11 moving up and down at high speed, and is focused on the object surface 12.
- the reflected light L2 reflected by the object surface 12 passes through the half mirror 13 and the pinhole 14, and reaches the light receiving element 15.
- the laser light L1 is focused on the object surface 12
- the reflected light L2 is condensed at one point at the position of the pinhole and enters the light receiving element.
- the distance between the objective lens 11 and the object surface 12 can be measured.
- the distance between the objective lens 11 and the object back surface 12 'can can also be measured, so that the thickness of the object can be measured.
- the thickness can be measured without being affected by the change in the surface reflectance of the measurement object.
- LT-9000 series (trade name) marketed by Keyence Corporation can be cited.
- the principle of measurement by spectral interferometry using an SLD is that light L3 in a wide wavelength region emitted from an SLD (light source) 20 is converted into a sensor head 22 and an object surface 23 inside the optical fiber 21. And return to the optical fiber 21.
- the two reflected lights interfere with each other, and the intensity of the interference light at each wavelength is determined by the distance between the sensor head 22 and the object surface 23. Therefore, the distance between the sensor head 22 and the object surface 23 can be measured by separating the interference light for each wavelength by the spectroscope 24 and analyzing it.
- the thickness of the object can be measured.
- the reflected light from the back surface 23 ' is strong with respect to the reflected light from the object surface 23, and measurement is difficult.
- the SLD as a light source, sufficient reflected light from the object surface 23 can be obtained, so that it is difficult to be affected by the reflected light from the back surface 23 '.
- SI-F01 (trade name) marketed by Keyence Corporation can be cited.
- a measurement result by a confocal method using laser light, a spectral interference method using a super luminescent diode (SLD), or the like is acquired (step S1), and based on this measurement result.
- the thickness of the polyimide precursor casting is determined (step S2).
- the laser light emitted from the light source passes through the objective lens that moves up and down at high speed, and is focused on the surface of the object. By raising and lowering, the focal point is focused on the rear surface of the object, and thus the thickness of the object can be calculated by converting from the shift of the focus position.
- the spectral interference method using a super luminescent diode SLD
- light in a wide wavelength region emitted from the SLD is reflected from the two surfaces of the sensor head inside the optical fiber and the surface of the object. Since the reflected light also reflects from the sensor head inside the optical fiber and the back surface of the object, the reflected lights interfere with each other, and the intensity at each wavelength of the interference light is determined by the reflection position.
- the thickness of the object can be determined by analyzing and analyzing each wavelength.
- the above thickness is compared with a predetermined thickness (step S3).
- the extrusion amount from the die 2 is reduced (step S4), and when the thickness is less than the predetermined value, the extrusion amount from the die 2 is increased (step S5).
- the thickness is a predetermined value, the amount of extrusion from the die 2 is not increased or decreased.
- a value having a certain width may be set as the predetermined value.
- the extrusion control of the polyimide precursor solution 1 from the die 2 is performed by using a die having a plurality of extrusion amount adjusting mechanisms capable of adjusting the polyimide precursor solution extruded from the tip of the die in the width direction. Uniform distribution over the width direction of the polyimide precursor casting by adjusting the extrusion amount of the polyimide precursor solution extruded from the tip of the die by a plurality of extrusion amount adjusting mechanisms based on the measured thickness value over the width direction of 1a. A method for achieving the above is preferred.
- the methods (a) and (b) described above are preferably mentioned. Also, the methods (a) and (b) may be combined.
- the thickness of the polyimide precursor cast 1a before being introduced into the drying furnace 5 is measured, and the die 2 is formed so that the thickness of the polyimide precursor cast 1a in the width direction is uniform. Since the feedback result can be reflected at an early stage by controlling the extrusion of the polyimide precursor solution 1 from the product, the amount of discarded products can be reduced, and a polyimide film with less thickness unevenness can be produced with high productivity.
- the thickness is preferably measured at a plurality of points over the width direction of the polyimide precursor casting 1a. Thereby, based on the thickness over the width direction of the polyimide precursor cast before heating, the extrusion amount of the polyimide precursor solution from the die can be controlled more precisely.
- the thickness of the polyimide precursor casting 1a is measured by scanning the measurement mechanism by a confocal method using a laser beam, a spectral interference method using a superluminescent diode, or the like. You may measure by the measurement means which can measure in multiple points over the width direction. Thereby, the thickness can be measured more efficiently and quickly.
- the measurement of the solvent content of the self-supporting film and the polyimide precursor casting In combination with the measurement of the thickness of the feedback of each measurement result, from the drying conditions of the polyimide precursor casting, the post-heating conditions of the self-supporting film and the extrusion amount of the polyimide precursor solution from the die One or more selected may be controlled.
- the polyimide precursor solution 1 is cast on the metal belt 3 to form the polyimide precursor cast 1a, which is heated to form the self-supporting film 1b.
- the polyimide film 1c which peeled from 3 and heated again and completed solvent removal and imidation was manufactured.
- the polyimide precursor solution 1 is cast on a metal foil such as a copper foil to obtain a metal foil having a polyimide precursor cast formed on the surface, and this is heated to self-support the polyimide precursor cast.
- the film may be made into a film, and the self-supporting film may be heated again in a state where the self-supporting film and the metal foil are integrated to complete solvent removal and imidization. By doing in this way, the composite film by which the polyimide film was laminated
- the metal foil corresponds to the metal support in the present invention.
- a metal belt is used as the metal support, a metal drum or the like can be suitably used in addition to the metal belt.
- a polyimide film having a uniform thickness in the width direction and the length direction can be obtained.
- the polyimide film obtained in the present invention can be used as a cover substrate such as a printed wiring board, a flexible printed circuit board, a TAB tape, a COF tape, a chip member such as an IC chip, a liquid crystal display, an organic electroluminescence display, an electronic paper, and a sun. It can be used as a raw material for electronic parts and electronic devices such as base materials such as batteries and cover materials.
- ⁇ Test Example 1> [Measurement of solvent content by infrared spectroscopy (IR)] Using a self-supporting film having a thickness after post-heating of 25 ⁇ m, infrared rays were irradiated in a “perpendicular direction (width direction) to the film transport direction”. IM (manufactured by Chino Corporation) was used as the infrared spectrometer. The fixed self-supporting film was continuously measured in the width direction by operating it with a measuring machine having a measurement area of 50 mm in the width direction and 50 mm in the flow direction and a device having a mechanism for reciprocating the measurement area. The measurement result was set to output an average value during every 50 mm in the width direction.
- the wavelength having the absorption peak in the solvent and having no peak in the polyimide film ( ⁇ 2), the wavelength having no absorption peak in the solvent and having the peak in the polyimide film ( ⁇ 5), and both the solvent and the polyimide film are absorbed.
- a wavelength with no peak ( ⁇ 1) was selected.
- the solvent content was determined from the following formulas (1) to (3) from the ratio of absorbance when the self-supporting film as the object to be measured was irradiated with infrared rays having these wavelengths.
- Polymer amount absorbance at ⁇ 5 / absorbance at ⁇ 1 (1)
- Solvent amount absorbance at ⁇ 2 / absorbance at ⁇ 1
- Solvent content solvent amount / (solvent amount + polymer amount) (3)
- the measurement position in Table 1 refers to the distance from the center in the width direction of the self-supporting film.
- a minus “ ⁇ ” means the left side of the self-supporting film, and a plus “+” means the right side.
- the solvent content shown in Table 1 creates a calibration curve by comparing the polymer amount and solvent amount obtained by the above formulas (1) and (2) with the polymer amount and solvent amount obtained by the heat loss method. It is a numerical value converted by this.
- solvent content [(initial weight of self-supporting film ⁇ weight after heating) / initial weight of self-supporting film ⁇ ⁇ 100
- the measurement position in Table 2 refers to the distance from the center in the width direction of the self-supporting film.
- a minus “ ⁇ ” means the left side of the self-supporting film, and a plus “+” means the right side.
- Example 1 [Production of polyimide film using the infrared spectrometer (control of drying conditions)]
- the infrared spectroscopic device was used in the drying process to produce a polyimide film. Specifically, for a portion where the solvent content in the width direction of the self-supporting film is higher than a predetermined solvent content, a flow corresponding to the portion in the step of drying the cast product of the polyimide precursor solution. The supply amount of the dry hot gas for drying the rolled portion was increased. Moreover, about the part whose solvent content over the width direction of a self-supporting film is lower than predetermined
- the amount of dry hot gas supplied was reduced. As a result, the solvent content in the width direction of the self-supporting film was almost uniform, and the occurrence of defective products was suppressed, and a polyimide film having uniform physical properties within the surface could be produced with high productivity. .
- Example 2 [Production of polyimide film using the infrared spectrometer (control of post-heating conditions)]
- the infrared spectroscopic device was used in the drying process to produce a polyimide film.
- the amount of hot gas supplied for heating to heat the portion in the post-heating step is set. Increased.
- the supply amount of the hot gas for heating the said part in a process by post-heating was lowered
- the solvent content in the width direction of the self-supporting film was almost uniform, and the occurrence of defective products was suppressed, and a polyimide film having uniform physical properties within the surface could be produced with high productivity. .
- Example 3 [Production of polyimide film using the infrared spectrometer (control of the amount of extrusion from a die)]
- the infrared spectroscopic device was used in the drying process to produce a polyimide film.
- the tip of the die for casting the polyimide precursor solution has a plurality of extrusion amount adjusting mechanisms in the width direction. For the portion where the solvent content in the width direction of the self-supporting film is higher than the predetermined solvent content, the extrusion amount from the die portion corresponding to the portion in the step of extruding the polyimide precursor solution from the tip of the die Reduced.
- polyimide precursor solution 1a polyimide precursor casting 1b: self-supporting film 1c: polyimide film 2: die 3: metal belt 4: solvent content measuring means 5: drying furnace 6: heating furnace 7: winding Device 8: Control device 9: Thickness measuring means
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Abstract
Description
溶媒含有量={(自己支持性フィルムの重量-自己支持性フィルムを完全に乾燥させた時の重量(乾燥固形分重量))/自己支持性フィルムの重量}×100 ・・・(A)
前記自己支持性フィルムであって後加熱する前の該自己支持性フィルムの溶媒含有量を赤外分光法により測定し、該測定結果に基づいて、ポリイミド前駆体溶液の流延物の乾燥条件、自己支持性フィルムの後加熱条件及びポリイミド前駆体溶液のダイスからの押出量から選ばれる1種以上を制御することを特徴とするポリイミドフィルムの製造方法を提供するものである。
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記ポリイミド前駆体溶液の流延物を乾燥する工程における当該部分に対応する前記流延物部分を乾燥するための乾燥媒体の温度及び/又は供給量を下げることが好ましい。
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記後加熱工程における当該部分を加熱するための加熱媒体の温度及び/又は供給量を下げることが好ましい。
前記測定結果に基づいて、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記ポリイミド前駆体溶液をダイスの先端から押出す工程における当該部分に対応するダイス部分からの押出量を低減し、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記ポリイミド前駆体溶液をダイスの先端から押出す工程における当該部分に対応するダイス部分からの押出量を増加さることが好ましい。
ポリマー量=λ5の吸光度/λ1の吸光度 ・・・(1)
溶媒量=λ2の吸光度/λ1の吸光度 ・・・(2)
溶媒含有量=溶媒量/(溶媒量+ポリマー量)・・・(3)
前記自己支持性フィルムの溶媒含有量を赤外分光法により測定する溶媒含有量測定手段と、該測定結果に基づいて、前記乾燥装置の乾燥条件、前記加熱装置の加熱条件及び前記押出装置の押出条件から選ばれる1種以上を制御する制御装置とを備えていることを特徴とするポリイミドフィルムの製造装置を提供するものである。
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記乾燥装置における当該部分に対応する前記流延物部分を乾燥するための乾燥媒体の温度及び/又は供給量を下げるように制御することが好ましい。
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記加熱装置における当該部分を加熱するための加熱媒体の温度及び/又は供給量を下げるように制御することが好ましい。
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記押出装置における当該部分に対応するダイス部分からのポリイミド前駆体溶液の押出量を増加させるように制御することが好ましい。
ポリイミド前駆体流延物形成工程では、ポリイミド前駆体溶液1をダイス2の先端から押出し、金属ベルト3上に流延してポリイミド前駆体流延物1aを形成する。この実施形態では、金属ベルト3が、本発明における金属支持体に相当する。より具体的には、単層又は複層の押出形成用ダイスが設置された製膜装置を使用して、1種又は複数の種類のポリイミド前駆体溶液1をダイス2の吐出口(リップ部)から単層又は複層の薄膜状体として金属ベルト3上に押出して、ポリイミド前駆体の溶媒溶液の薄膜としてポリイミド前駆体流延物1aを形成する。
自己支持性フィルム形成工程では、このようにして金属ベルト3上に形成されたポリイミド前駆体流延物1aを乾燥炉5に導入して加熱処理し、乾燥して自己支持性を有する自己支持性フィルム1bを形成する。ここで、乾燥とは、ポリイミド前駆体溶液を加熱することにより、ポリイミド前駆体のイミド化が完全には進まずにかつ有機溶媒の一部又は大部分が除去された状態を作り出す操作をいう。また、自己支持性を有するとは、金属ベルト3から剥離することができる程度の強度を有する状態をいう。
加熱減量(質量%)={(W1-W2)/W1}×100
後加熱工程では、自己支持性フィルム1bを加熱炉6に導入し、加熱処理して溶媒除去とイミド化を完結させて、ポリイミドフィルム1cを得る。
このような工程を経てポリイミドフィルムを製造するが、本発明では自己支持性フィルム1bの溶媒含有量を、赤外分光法による溶媒含有量測定手段4によって測定する。自己支持性フィルム1bの溶媒含有量の測定は後加熱工程前であればよい。そして、測定結果に基づいて、ポリイミド前駆体流延物の乾燥条件、自己支持性フィルムの後加熱条件及びポリイミド前駆体溶液のダイスからの押出量から選ばれる1種以上を制御する。
ポリマー量=λ5の吸光度/λ1の吸光度 ・・・(1)
溶媒量=λ2の吸光度/λ1の吸光度 ・・・(2)
溶媒含有量=溶媒量/(溶媒量+ポリマー量) ・・・(3)
以下、制御装置8における制御方法について説明する。
第1の態様として、自己支持性フィルムの溶媒含有量の測定結果に基づいてポリイミド前駆体流延物の乾燥条件を制御する場合について、図3に示すフローチャートに基づいて説明する。この場合、自己支持性フィルム1bの幅方向にわたる溶媒含有量がほぼ均一になるように、ポリイミド前駆体流延物1aの乾燥条件を制御する。
次に、制御装置8における制御方法の第2の態様として、自己支持性フィルムの溶媒含有量の測定結果に基づいて後加熱工程における自己支持性フィルムの加熱条件を制御する場合について、図4に示すフローチャートに基づいて説明する。この場合、自己支持性フィルムの幅方向にわたる溶媒含有量に応じて、加熱条件を変えることによって、得られるポリイミドの幅方向にわたる特性ばらつきを低減させる。
次に、制御装置8における制御方法の第3の態様として、自己支持性フィルムの溶媒含有量の測定結果に基づいてポリイミド前駆体溶液のダイスからの押出量を制御する場合について、図5に示すフローチャートに基づいて説明する。この場合、自己支持性フィルム1bの幅方向にわたる溶媒含有量がほぼ均一になるように、ポリイミド前駆体溶液1のダイスからの押出量を制御する。
(a)ダイスの流路の高さ方向の間隔をネジやバネ、ヒートボルト等で調整する方法。
(b)ダイス先端から吐出するポリイミド前駆体溶液の温度を調整する方法。
以下、制御装置8における制御方法の第4の態様として、乾燥する前のポリイミド前駆体溶液の流延物の厚みの測定結果に基づいてポリイミド前駆体溶液のダイスからの押出量を制御する場合について、図8に示すフローチャートに基づいて説明する。なお、この制御は、上記図3から図5に示した制御とは独立に、または併用して行うことができる。
後加熱後の厚みが25μm相当の自己支持性フィルムを用いて、フィルムの搬送方向に対して垂直な方向」(幅方向)に赤外線を照射した。赤外分光装置としては、IM(株式会社チノー製)を用いた。幅方向50mm、流れ方向に50mmの測定エリアをもつ測定機と、それを往復運動させる機構を有した装置にて、動作させて、固定した自己支持性フィルムを幅方向に連続的に測定した。測定結果は、幅方向に、50mm進める毎に、その間の平均値を出力するように設定した。
ポリマー量=λ5の吸光度/λ1の吸光度 ・・・(1)
溶媒量=λ2の吸光度/λ1の吸光度 ・・・(2)
溶媒含有量=溶媒量/(溶媒量+ポリマー量) ・・・(3)
赤外分光法による溶媒含有量の測定結果と比較するため、加熱減量法による溶媒含有量の測定を行った。自己支持性フィルムを幅方向に均等な間隔で、幅方向に50mm、流れ方向に100mmの大きさで切り取り、初期重量(乾燥前)と加熱後(乾燥後)の重量変化を測定した。加熱条件は、300℃の電気炉で5℃/分の昇温速度で、400℃まで昇温し、その温度で30分保持させたものである。
溶媒含有量=[(自己支持性フィルムの初期重量-加熱後の重量)/自己支持性フィルムの初期重量}×100
[前記赤外分光装置を用いたポリイミドフィルムの製造(乾燥条件の制御)]
前記赤外分光装置を乾燥工程に使用し、ポリイミドフィルムの製造を行った。具体的には、自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記ポリイミド前駆体溶液の流延物を乾燥する工程における当該部分に対応する流延物部分を乾燥するための乾燥熱ガスの供給量を高めた。また、自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記ポリイミド前駆体溶液を乾燥する工程における当該部分に対応する前記流延物部分を乾燥するための乾燥熱ガスの供給量を下げた。これにより、自己支持性フィルムの幅方向にわたる溶媒含有量がほぼ均一にして、不良品の発生を抑制しつつ、面内で均一な物性を備えたポリイミドフィルムを生産性良く製造することができた。
[前記赤外分光装置を用いたポリイミドフィルムの製造(後加熱条件の制御)]
前記赤外分光装置を乾燥工程に使用し、ポリイミドフィルムの製造を行った。具体的には、自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、後加熱工程における当該部分を加熱するための加熱用の熱ガスの供給量を高めた。また、自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、後加熱して工程における当該部分を加熱するための熱ガスの供給量を下げた。これにより、自己支持性フィルムの幅方向にわたる溶媒含有量がほぼ均一にして、不良品の発生を抑制しつつ、面内で均一な物性を備えたポリイミドフィルムを生産性良く製造することができた。
[前記赤外分光装置を用いたポリイミドフィルムの製造(ダイスからの押出量の制御)]
前記赤外分光装置を乾燥工程に使用し、ポリイミドフィルムの製造を行った。ポリイミド前駆体溶液を流延するためのダイスの先端は幅方向に複数の押出し量調整機構を有している。自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記ポリイミド前駆体溶液をダイスの先端から押出す工程における前記部分に対応するダイス部分からの押出量を低減した。また、自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記ポリイミド前駆体溶液をダイスの先端から押出す工程における前記部分に対応するダイス部分からの押出量を増加させた。これにより、自己支持性フィルムの幅方向にわたる溶媒含有量がほぼ均一にして、不良品の発生を抑制しつつ、面内で均一な物性を備えたポリイミドフィルムを生産性良く製造することができた。
1a:ポリイミド前駆体流延物
1b:自己支持性フィルム
1c:ポリイミドフィルム
2:ダイス
3:金属ベルト
4:溶媒含有量測定手段
5:乾燥炉
6:加熱炉
7:巻き取り装置
8:制御装置
9:厚み測定手段
Claims (13)
- ポリイミド前駆体と溶媒とを含むポリイミド前駆体溶液をダイスの先端から押出し、金属支持体面上に流延してポリイミド前駆体溶液の流延物を形成し、該ポリイミド前駆体溶液の流延物を乾燥し、自己支持性を有する自己支持性フィルムを形成した後、該自己支持性フィルムを後加熱するポリイミドフィルムの製造方法であって、
前記自己支持性フィルムであって後加熱する前の該自己支持性フィルムの溶媒含有量を赤外分光法により測定し、該測定結果に基づいて、ポリイミド前駆体溶液の流延物の乾燥条件、自己支持性フィルムの後加熱条件及びポリイミド前駆体溶液のダイスからの押出量から選ばれる1種以上を制御することを特徴とするポリイミドフィルムの製造方法。 - 前記測定結果に基づいて、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記ポリイミド前駆体溶液の流延物を乾燥する工程における当該部分に対応する前記流延物部分を乾燥するための乾燥媒体の温度及び/又は供給量を高め、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記ポリイミド前駆体溶液の流延物を乾燥する工程における当該部分に対応する前記流延物部分を乾燥するための乾燥媒体の温度及び/又は供給量を下げる、請求項1に記載のポリイミドフィルムの製造方法。 - 前記測定結果に基づいて、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記後加熱工程における当該部分を加熱するための加熱媒体の温度及び/又は供給量を高め、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記後加熱工程における当該部分を加熱するための加熱媒体の温度及び/又は供給量を下げる、請求項1に記載のポリイミドフィルムの製造方法。 - 前記ダイスの先端は幅方向に複数の押出し量調整機構を有し、
前記測定結果に基づいて、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記ポリイミド前駆体溶液をダイスの先端から押出す工程における当該部分に対応するダイス部分からの押出量を低減し、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記ポリイミド前駆体溶液をダイスの先端から押出す工程における当該部分に対応するダイス部分からの押出量を増加さる、請求項1に記載のポリイミドフィルムの製造方法。 - 前記自己支持性フィルムの溶媒含有量を、赤外分光法による測定機構を走査することにより該自己支持性フィルムの幅方向にわたって複数点で測定することができる測定手段で測定する、請求項1~4のいずれか1項に記載のポリイミドフィルムの製造方法。
- 前記自己支持性フィルムの溶媒含有量を、溶媒に吸収ピークを持ち、ポリイミドフィルムでピークの無い波長(λ2)と、溶媒に吸収ピークが無く、ポリイミドフィルムにピークを持つ波長(λ5)と、溶媒、ポリイミドフィルムのいずれも吸収ピークが無い波長(λ1)とを選択し、これらの波長の赤外線を被測定物である自己支持性フィルムに照射したときの吸光度の比から下記式(1)~(3)により求める、請求項1~5のいずれか1項に記載のポリイミドフィルムの製造方法。
ポリマー量=λ5の吸光度/λ1の吸光度 ・・・(1)
溶媒量=λ2の吸光度/λ1の吸光度 ・・・(2)
溶媒含有量=溶媒量/(溶媒量+ポリマー量) ・・・(3) - 更に、前記ポリイミド前駆体溶液の流延物であって乾燥する前の該流延物の厚みを測定し、該測定結果に基づいて、該流延物の幅方向にわたる厚みがほぼ均一になるように前記ダイスからのポリイミド前駆体溶液の押出量を制御する、請求項1~6のいずれか1項に記載のポリイミドフィルムの製造方法。
- 前記ポリイミド前駆体溶液の流延物の厚みを、レーザ光を用いた共焦点法またはスーパールミネッセントダイオードを用いた分光干渉法により測定する、請求項7に記載のポリイミドフィルムの製造方法。
- ポリイミド前駆体溶液をダイスの先端から押出し、金属支持体面上に流延してポリイミド前駆体溶液の流延物を形成する押出装置と、該ポリイミド前駆体溶液の流延物を乾燥し、自己支持性を有する自己支持性フィルムを形成する乾燥装置と、該自己支持性フィルムを後加熱する加熱装置とを備えたポリイミドフィルムの製造装置であって、
前記自己支持性フィルムの溶媒含有量を赤外分光法により測定する溶媒含有量測定手段と、該測定結果に基づいて、前記乾燥装置の乾燥条件、前記加熱装置の加熱条件及び前記押出装置の押出条件から選ばれる1種以上を制御する制御装置とを備えていることを特徴とするポリイミドフィルムの製造装置。 - 前記制御装置は、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記乾燥装置における当該部分に対応する前記流延物部分を乾燥するための乾燥媒体の温度及び/又は供給量を高め、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記乾燥装置における当該部分に対応する前記流延物部分を乾燥するための乾燥媒体の温度及び/又は供給量を下げるように制御する請求項9に記載のポリイミドフィルムの製造装置。 - 前記制御装置は、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記加熱装置における当該部分を加熱するための加熱媒体の温度及び/又は供給量を高め、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記加熱装置における当該部分を加熱するための加熱媒体の温度及び/又は供給量を下げるように制御する請求項9に記載のポリイミドフィルムの製造装置。 - 前記制御装置は、前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも高い部分については、前記押出装置における当該部分に対応するダイス部分からのポリイミド前駆体溶液の押出量を低減し、
前記自己支持性フィルムの幅方向にわたる溶媒含有量が、所定の溶媒含有量よりも低い部分については、前記押出装置における当該部分に対応するダイス部分からのポリイミド前駆体溶液の押出量を増加させるように制御する請求項9に記載のポリイミドフィルムの製造装置。 - 前記ポリイミド前駆体溶液の流延物の厚みを測定する厚み測定手段を更に有し、該厚み測定手段の測定結果に基づいて、前記押出装置の押出条件をも制御する請求項9~12のいずれか1項に記載のポリイミドフィルムの製造装置。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004224994A (ja) * | 2003-01-27 | 2004-08-12 | Teijin Ltd | 二軸配向ポリイミドフィルムおよびその製造方法 |
JP2008292616A (ja) * | 2007-05-23 | 2008-12-04 | Ricoh Co Ltd | 電子写真用シームレスベルトとその製造方法、電子写真装置 |
JP2009067042A (ja) * | 2008-06-02 | 2009-04-02 | Ube Ind Ltd | ポリイミドフィルムの製造法 |
JP2009120772A (ja) * | 2007-11-16 | 2009-06-04 | Ube Ind Ltd | 芳香族ポリイミドフィルムおよびその製造方法 |
JP2009241329A (ja) * | 2008-03-31 | 2009-10-22 | Ube Ind Ltd | 多層ポリイミドフィルムの製法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3673865A (en) * | 1971-04-21 | 1972-07-04 | Westvaco Corp | Method and apparatus for orthogonal variables |
US4844617A (en) * | 1988-01-20 | 1989-07-04 | Tencor Instruments | Confocal measuring microscope with automatic focusing |
JP2612244B2 (ja) * | 1988-12-29 | 1997-05-21 | 王子油化合成紙株式会社 | 延伸樹脂フィルムの肉厚制御方法 |
US5124552A (en) | 1991-01-28 | 1992-06-23 | Measurex Corporation | Sensor and method for measuring web moisture with optimal temperature insensitivity over a wide basis weight range |
JP3305121B2 (ja) * | 1993-07-12 | 2002-07-22 | 株式会社アイ.エス.テイ | ポリイミド管状物の製造方法及び製造装置 |
JP3858101B2 (ja) * | 1997-05-01 | 2006-12-13 | 東セロ株式会社 | 延伸フィルム製造設備、及び製造方法 |
US6734387B2 (en) * | 1999-05-27 | 2004-05-11 | Spectra Physics Lasers, Inc. | Method and apparatus for micro-machining of articles that include polymeric materials |
FI120053B (fi) * | 2000-12-22 | 2009-06-15 | Metso Automation Oy | Menetelmä ja laitteisto liikkuvan paperirainan kosteusprofiilin säätämiseksi |
KR100710099B1 (ko) * | 2002-09-13 | 2007-04-20 | 카네카 코포레이션 | 폴리이미드 필름 및 그의 제조 방법 및 그의 이용 |
CN101080471A (zh) * | 2004-12-17 | 2007-11-28 | 株式会社钟化 | 聚酰亚胺多层粘合膜及其制造方法 |
JP4607779B2 (ja) | 2005-03-25 | 2011-01-05 | 富士フイルム株式会社 | ポリマーフイルムの製造方法 |
-
2011
- 2011-01-24 CN CN201180007140.6A patent/CN102725114B/zh active Active
- 2011-01-24 JP JP2011551842A patent/JP5668694B2/ja active Active
- 2011-01-24 KR KR1020127021802A patent/KR101757498B1/ko active IP Right Grant
- 2011-01-24 WO PCT/JP2011/051232 patent/WO2011093245A1/ja active Application Filing
- 2011-01-24 US US13/575,138 patent/US20120292800A1/en not_active Abandoned
- 2011-01-25 TW TW100102581A patent/TWI524990B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004224994A (ja) * | 2003-01-27 | 2004-08-12 | Teijin Ltd | 二軸配向ポリイミドフィルムおよびその製造方法 |
JP2008292616A (ja) * | 2007-05-23 | 2008-12-04 | Ricoh Co Ltd | 電子写真用シームレスベルトとその製造方法、電子写真装置 |
JP2009120772A (ja) * | 2007-11-16 | 2009-06-04 | Ube Ind Ltd | 芳香族ポリイミドフィルムおよびその製造方法 |
JP2009241329A (ja) * | 2008-03-31 | 2009-10-22 | Ube Ind Ltd | 多層ポリイミドフィルムの製法 |
JP2009067042A (ja) * | 2008-06-02 | 2009-04-02 | Ube Ind Ltd | ポリイミドフィルムの製造法 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102796273A (zh) * | 2012-08-31 | 2012-11-28 | 江苏亚宝绝缘材料股份有限公司 | 一种聚酰亚胺薄膜制备装置及制品 |
KR20160009651A (ko) * | 2013-05-15 | 2016-01-26 | 베른도르프 반트 게엠베하 | 포일 또는 박막 제조 방법 |
JP2016519314A (ja) * | 2013-05-15 | 2016-06-30 | ベルンドルフ バント ゲゼルシャフト ミット ベシュレンクテル ハフツング | フォイル又はフィルムを製造するための方法 |
KR102235658B1 (ko) * | 2013-05-15 | 2021-04-05 | 베른도르프 반트 게엠베하 | 포일 또는 박막 제조 방법 |
JP2015172565A (ja) * | 2014-02-19 | 2015-10-01 | 東レ株式会社 | フィルム検査方法及びそれを用いたフィルム製造方法 |
JPWO2016063993A1 (ja) * | 2014-10-23 | 2017-09-14 | 宇部興産株式会社 | ポリイミドフィルム、ポリイミド前駆体、及びポリイミド |
JP2018503529A (ja) * | 2014-10-24 | 2018-02-08 | ベルンドルフ バント ゲゼルシャフト ミット ベシュレンクテル ハフツング | ベルト鋳造設備用のプロセス最適化 |
JP2018020309A (ja) * | 2016-06-03 | 2018-02-08 | ザ・ボーイング・カンパニーTheBoeing Company | 直接描画システムのためのリアルタイムの検査及び修正技術 |
JP7002221B2 (ja) | 2016-06-03 | 2022-01-20 | ザ・ボーイング・カンパニー | 直接描画システムのためのリアルタイムの検査及び修正技術 |
WO2022163431A1 (ja) * | 2021-01-28 | 2022-08-04 | コニカミノルタ株式会社 | 光学フィルムの製造方法 |
JP7487690B2 (ja) | 2021-03-04 | 2024-05-21 | 株式会社豊田中央研究所 | 材料測定装置および材料測定方法および電極製造装置および電極の製造方法 |
Also Published As
Publication number | Publication date |
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CN102725114B (zh) | 2014-10-08 |
TW201134656A (en) | 2011-10-16 |
JP5668694B2 (ja) | 2015-02-12 |
KR101757498B1 (ko) | 2017-07-12 |
KR20120113273A (ko) | 2012-10-12 |
US20120292800A1 (en) | 2012-11-22 |
CN102725114A (zh) | 2012-10-10 |
TWI524990B (zh) | 2016-03-11 |
JPWO2011093245A1 (ja) | 2013-06-06 |
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