JP2005023235A - Method for packaging polyimide film roll - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for packaging a polyimide film roll in which the influence of moisture absorption and a residual solvent in the polyimide film roll is eliminated and crease is not formed even when stored for a long period. <P>SOLUTION: The method for packaging the polyimide film roll comprises allowing a sheet material to stand without rolling the sheet material for three days of beginning after producing a polyimide film and covering the film with the sheet material since fourth day after production when the outside of the polyimide film roll is covered with the sheet material. A metallic foil, a metallic laminate film or a metallic vapor deposited film is suitably used as the sheet material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a packaging method for covering a polyimide film roll with a sheet material. A roll here is a long film roll obtained by winding up a long film, for example.
[0002]
[Prior art]
It has been conventionally known to provide moisture-proof packaging for the purpose of protecting a roll of a highly hygroscopic film such as a nylon film from moisture absorption during storage until use and during transportation.
[0003]
Further, even a polyester film having a relatively low hygroscopicity may be moisture-proof packaged for uses such as magnetic tape that require high-precision processing.
[0004]
In recent years, polyimide films that have attracted attention due to their heat resistance and high mechanical properties have been utilized as base films for flexible printed boards and base films for semiconductor mounting tapes. However, the polyimide film has moisture absorption characteristics intermediate between nylon and polyester, and moisture absorption during storage cannot be ignored.
[0005]
In order to prevent moisture absorption of polyimide film, moisture-proof packaging has been already proposed as with nylon film and polyester film, but it still cannot prevent slight moisture absorption, and not only the roll surface when stored for a long time. There has been a problem that moisture absorption reaches the film of the inner layer of the roll. In addition to moisture-proof packaging, a silica gel or other desiccant is simultaneously enclosed inside the core cylinder around which the film is wrapped, but this is not sufficient in this case as well, and completely prevents moisture absorption. I couldn't. When the polyimide film roll absorbs moisture, continuous sharp wrinkles (hereinafter referred to as “vertical wrinkles”) along the roll winding direction occur, and these vertical wrinkles remain after processing. It was the cause.
[0006]
In order to solve such a problem, a method of arranging a packaging sheet made of a metal material on the outside of a roll (for example, see Patent Document 1) has been studied. However, when a packaging sheet made of such a metal material is arranged, generation of vertical wrinkles due to moisture absorption can be prevented. However, an organic solvent used at the time of manufacture remains in the polyimide film, and this residual solvent is a metal. Since it becomes the form confined by the packaging sheet which consists of material, it had the problem that wrinkles (horizontal wrinkles, diagonal wrinkles, vertical wrinkles) other than moisture absorption occurred as a result. Although the amount of the residual solvent is extremely small, it is an amount that cannot be ignored when viewed from the whole roll, and there is a problem that not only the wrinkle but also the performance of the film itself deteriorates when stored for a long time.
[0007]
[Patent Document 1]
Japanese Patent Laid-Open No. 2002-370788
[0008]
[Problems to be solved by the invention]
The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.
[0009]
Accordingly, an object of the present invention is to provide a method for packaging a polyimide film roll that eliminates the effects of moisture absorption and residual solvent and does not generate wrinkles even after long-term storage.
[0010]
[Means for Solving the Problems]
In order to achieve the above object, the polyimide film roll packaging method of the present invention is a packaging method in which the outside of a polyimide film roll having a film thickness of 1 to 225 μm is covered with a sheet material. It is characterized in that the sheet material is left unrolled for 3 days and covered with the sheet material after the fourth day after the production.
[0011]
In the packaging method of the polyimide film roll of the present invention,
Covering with a sheet material after 7 days from the formation of the polyimide film,
Covering with a sheet material within 30 days after forming the polyimide film,
The sheet material is a metal foil;
The sheet material is a metal laminate film;
The sheet material is a metal vapor deposition film;
Disposing the sheet material on the surface layer of the polyimide film roll; and
The polyimide film is a film obtained by casting a polyimide precursor solution
Are mentioned as preferable conditions.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The polyimide film roll in the present invention is obtained by winding a polyimide film around a core in a roll shape.
[0013]
Examples of the material for the core include, but are not limited to, paper, plastic, and metal. Specifically, paper cores such as paper, resin-impregnated paper, resin-coated paper, plastic cores such as vinyl chloride, polyethylene, polyester, and epoxy resin, glass fiber and epoxy resin, paper and phenol resin, carbon fiber and epoxy resin, etc. And a fiber reinforced plastic (FRP) core made of a combination of the above and a metal core such as stainless steel, iron, copper, and aluminum.
[0014]
In the polyimide film roll packaged by the packaging method of the present invention, the outside of the polyimide film roll is covered with a sheet material. The sheet material is preferably in close contact with the roll because the shape change of the roll appearance can be suppressed and the moisture absorption preventing effect is improved. In that respect, it is preferable that nothing is present between the sheet material and the polyimide film roll, and the sheet material is directly disposed on the surface layer of the polyimide film roll.
[0015]
The range of covering the polyimide film roll with the sheet material may be determined according to the storage condition of the roll, but it is preferable to cover the entire circumference of the roll. In this case, it is preferable to cover the end surface with the sheet material at the same time for the purpose of improving the moisture absorption preventing effect. When covering the end face, it is preferable to wind the sheet material from the end portion of the core to the inner diameter portion of the core because the moisture absorption preventing effect is improved.
[0016]
As a sheet material used in the present invention, a metal foil such as aluminum, copper or stainless steel, a film obtained by laminating a metal such as aluminum or copper on a polyethylene film, a polypropylene film or a polyester film, or a polyethylene film, a polypropylene film or a polyester A metal vapor deposition film obtained by vapor-depositing a metal such as aluminum, chromium, nickel, copper, gold, silver, or the like can be used. The thickness of these sheet materials is not particularly limited, but if they are too thin, there is a risk of damage during handling and transportation. Conversely, if they are too thick, the rigidity tends to increase and problems in handling are likely to occur, so usually 5 μm to 1 mm, preferably A range of 10 μm to 500 μm is selected. In this case, the thickness of the metal portion of the sheet material is selected in the range of 1 μm to 500 μm, preferably 5 μm to 300 μm.
[0017]
In this invention, it is also preferable to wind a sheet | seat material on the outer side of a polyimide film roll, and to wind a general packaging film further on the outer side. As a general packaging film, polyethylene, polypropylene, polyester, vinyl chloride, or the like is used. Further, for the purpose of enhancing the moisture absorption preventing effect, it is also preferable to use a moisture-proof film having a moisture permeability of 10 g / (m 2 · 24 hr · atm) or less. Examples of such moisture-proof films include polyacrylonitrile-based films, polyvinylidene chloride films, polyvinylidene fluoride films and the like, as well as films in which polyethylene or polypropylene and polyvinylidene chloride are combined by a coextrusion method or a coating method. . The thickness of the general packaging film is not particularly limited, but if the film is too thin, it may be damaged during handling or transportation, or may fall outside the above-described preferable moisture permeability range. Usually, the range of 10 μm to 500 μm is selected because the rigidity increases and problems in handling are likely to occur.
[0018]
About the sealing method of a packaging film, it consists of the method of sticking or sticking the both ends of a film to a core, the method of folding both ends of a film into the inner surface of a core, and pressing and sealing with the pad of a core, and a metal material A method of bonding a sheet material or a packaging film in a bag shape by heating the entrance is used, but not limited thereto.
[0019]
Moreover, in order to protect a film roll, it is also preferable to wrap a buffer material on the outer periphery of the film roll. Furthermore, a pad for preventing end face collapse may be provided on the roll end face or the outermost roll layer. In addition, it is also preferable to store in a container such as a cardboard box after packaging in order to prevent damage during transportation and to improve handling.
[0020]
In the present invention, the outer diameter of the film roll and the dimensions such as the film width are not particularly limited. Further, the dimensions and material of the core are not limited as long as the effects of the present invention are not impaired.
[0021]
The polyimide film of the present invention has a thickness of 1 to 225 μm. When the thickness exceeds 225 μm, the film has high rigidity, so that even when stored for a long period of time, the occurrence of vertical wrinkles is small. The polyimide film of the present invention is not limited to a constant thickness, and may be a film having a thickness variation in the width direction.
[0022]
The polyimide film of the present invention is obtained from various known raw materials, mainly using an organic tetracarboxylic dianhydride and an organic diamine as raw materials, and via a polyimide precursor solution obtained by polymerization in an organic solvent. Is obtained. Examples of the organic tetracarboxylic dianhydride, diamine, and organic solvent include, but are not limited to, the following.
(1) Acid dianhydride
Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 2,3,6,7- Naphthalenedicarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ether, pyridine-2,3,5,6-tetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,4,5,8-decahydronaphthalene tetracarboxylic dianhydride, 4,8-dimethyl-1,2, 5,6-hexahydronaphthalene tet Carboxylic dianhydride, 2,6-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-tetrachloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 2,2-bis (2 , 3-Dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Screw (3,4-Dika Ruboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4 ′ -Benzophenone tetracarboxylic dianhydride and the like.
(2) Diamine
4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, metaphenylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylpropane, 3,4′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, benzidine, 4,4′-diaminodiphenyl sulfide, 3,4′-diamino Diphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 2,6-diaminopyridine, bis- (4 -Aminopheny ) Diethylsilane, 3,3′-dichlorobenzidine, bis- (4-aminophenyl) ethylphosphinoxide, bis- (4-aminophenyl) phenylphosphinoxide, bis- (4-aminophenyl)- N-phenylamine, bis- (4-aminophenyl) -N-methylamine, 1,5-diaminonaphthalene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4′-dimethyl-3 ′ , 4-diaminobiphenyl 3,3′-dimethoxybenzidine, 2,4-bis (p-β-amino-t-butylphenyl) ether, bis (p-β-amino-t-butylphenyl) ether, p- Bis (2-methyl-4-aminopentyl) benzene, p-bis- (1,1-dimethyl-5-aminopentyl) benzene, m-xylylenediamine, p-xylylene Diamine, 1,3-diaminoadamantane, 3,3′-diamino-1,1′-diaminoadamantane, 3,3′-diaminomethyl 1,1′-diadamantane, bis (p-aminocyclohexyl) methane, hexamethylene Diamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 3-methylheptamethylenediamine, 4,4′-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis (3- Aminopropoxy) ethane, 2,2-dimethylpropylenediamine, 3-methoxyhexaethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane 1,12- Diaminooctadecane, 2,5-diamino-1,3,4-oxadiazole, 2,2-bis (4-aminophenyl) hexafluoropropane, N- (3-aminophenyl) -4-aminobenzamide, 4- Such as aminophenyl-3-aminobenzoate.
(3) Organic solvent
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylformamide, dimethylsulfoxide, tetramethylurea, ureas such as N, N-dimethylethylurea, diphenylsulfone, Sulfoxides or sulfones such as tetramethylsulfone, γ-butyllactone, amides such as hexamethylphosphoric triamide, phosphorylamides aprotic solvents, alkyl halides such as chloroform and methylene chloride, benzene, Aromatic hydrocarbons such as toluene, phenols such as phenol and cresol, ethers such as dimethyl ether, diethyl ether and p-cresol methyl ether.
[0023]
A filler such as calcium hydrogen phosphate, silica, mica, titanium oxide, alumina, and glass beads may be added to the polyimide precursor solution.
[0024]
As the polymerization reaction, known methods may be mentioned. For example, one or two diamines are diffused in an organic solvent in a solution or slurry in an inert gas atmosphere such as argon or nitrogen. At least one or more kinds of tetracarboxylic dianhydrides are added to the solution in a solid state, an organic solvent solution state or a slurry state to obtain a polyimide precursor solution. The reaction temperature at this time is −20 ° C. to 50 ° C., preferably 20 ° C. or less. The reaction time is preferably 1 to 6 hours.
[0025]
In this polymerization reaction, contrary to the order of addition, tetracarboxylic dianhydride is first dissolved or diffused in an organic solvent, and a solution or slurry of the diamine solid or organic solvent is added to this solution. May be. Moreover, you may make it react simultaneously, and the addition order of a tetracarboxylic dianhydride component and a diamine component is not limited.
[0026]
The polymerization reaction is generally performed in two stages. Polymerizing low-viscosity polyamic acid called prepolymer in the first stage, and adding high-viscosity polyamic acid while adding an organic solvent in which tetracarboxylic dianhydride or diamine compound is dissolved in the organic solvent in the second stage . When shifting from the first stage to the second stage, a process for removing insoluble raw materials and mixed foreign matters in the prepolymer may be provided by a filter or the like to reduce foreign matters and defects in the film.
[0027]
The concentration of the polyamic acid in the organic solvent is selected such that the polyamic acid is dissolved in the organic solvent in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, and more preferably 13 to 25% by weight.
[0028]
The polyimide is obtained by imidizing the polyimide precursor solution. Examples of the imidization method include a thermal curing method and a chemical curing method. The thermal cure method is a method in which an imidization reaction proceeds by heating alone without using a dehydrating ring-closing agent or the like. The chemical curing method is a method in which a chemical conversion agent and a catalyst are allowed to act on a polyamic acid organic solvent solution. These methods may be used alone, or a chemical curing method and a thermal curing method may be used in combination. The reaction conditions for imidization are appropriately selected depending on the type of polyamic acid, the thickness of the film, the curing method, and the like, but the chemical curing method is preferable from the viewpoint of the toughness, breaking strength, and productivity of the film. In the case of the chemical curing method, as the chemical conversion agent to be added, aliphatic acid anhydride, aromatic acid anhydride, N, N′-dialkylcarbodiimide, lower aliphatic halide, halogenated lower aliphatic halide, halogen Lower fatty acid anhydrides, arylphosphonic acid dihalides, thionyl halides or mixtures of two or more thereof, among which organic carboxylic acid anhydrides are preferred. Here, as the organic carboxylic acid anhydride, acetic anhydride, propionic acid anhydride, butyric acid anhydride, valeric acid anhydride, a mixture in which these are mixed with each other, aromatic monocarboxylic acid such as benzoic acid, naphthoic acid, etc. Mixtures with anhydrides, mixtures of carbonic acid and formic acid and aliphatic ketenes (ketene and dimethylketene) with anhydrides, aliphatic anhydrides such as acetic anhydride, propionic anhydride, and anhydrous lactic acid, or two or more thereof Among them, acetic anhydride can be preferably used. The amount of the chemical conversion agent can be used in a molar ratio of 1.0 to 8.0 times, more preferably 1.2 to 5.0 times with respect to 1 mol of polyamic acid. If the amount of the chemical conversion agent is too small, the imidization rate tends to be smaller than the preferred range. If the amount is too large, decomposition occurs in the process of forming a partially cured and / or partially dried polyamic acid film. It progresses and the target mechanical properties are not expressed.
[0029]
Moreover, in order to perform imidation effectively, it is preferable to use a chemical conversion agent and a catalyst simultaneously. As the catalyst, an aliphatic tertiary amine, an aromatic tertiary amine, a heterocyclic tertiary amine, or the like is used. Among them, those selected from heterocyclic tertiary amines can be particularly preferably used. Specifically, quinoline, isoquinoline, β-picoline, pyridine and the like are preferably used. The amount of the catalyst can be used in a molar ratio of 0.2 to 2.0 times, more preferably 0.3 to 1.5 times with respect to 1 mol of the amic acid of the polyamic acid varnish. If the amount is too small, the imidization rate tends to be smaller than the preferred range, and if the amount is too large, the curing becomes fast and it becomes difficult to cast on the support. Further, an imidization retarder such as acetylacetone may be used in combination as long as the physical properties are not affected.
[0030]
The polyimide precursor solution or the chemical imidizing agent solution added to the polyimide precursor solution may contain an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a heat stabilizer, an ultraviolet absorber, and an inorganic filler as necessary. Or additives such as various reinforcing agents may be added.
[0031]
When producing a polyimide film, the polyamide precursor solution obtained by the above method and a chemical imidizing agent are mixed and then extruded continuously from a slit die as a smooth thin-film curtain on an endless belt or casting drum. And a gel film having self-supporting properties is formed by drying. In this case, it is preferable to use a casting drum, cast on the casting drum, and dry on the casting drum. This gel film is further heat-treated to obtain a polyimide film having the desired mechanical properties.
[0032]
Next, the manufacturing process of the polyimide film concerning this invention is demonstrated.
[0033]
The production method for imidizing the polyamic acid in the polyimide precursor solution to finally form a polyimide film product includes a belt chamber or a drum chamber cast on an endless belt or a casting drum, and a tenter chamber for performing a heat treatment. It is divided into.
[0034]
The specific example of the manufacturing process of the polyimide film concerning this invention is shown. First, in the drum chamber, the polyimide precursor solution mixed by the mixer is extruded by a T-die and formed into a film shape on the casting drum. The polyamic acid formed in a film shape is imidized by heat treatment while being moved to the tenter chamber by rotation of the drum. In the drum chamber and the tenter chamber, reaction products such as water and organic solvents are removed by evaporation. The heat treatment is preferably performed stepwise and continuously, and finally using a high temperature for a short time. Specifically, it is preferable to finally heat at a temperature of 400 to 650 ° C., more preferably at a temperature of 450 to 620 ° C. for 10 to 400 seconds. The polyimide film imidized in the above process is gradually cooled in a slow cooling furnace to obtain a target polyimide film.
[0035]
The obtained polyimide film may be subjected to physical surface treatment such as corona discharge treatment or plasma discharge treatment, chemical surface treatment such as primer treatment, reheating treatment and the like.
[0036]
The polyimide film obtained by the above method is wound on a core to form a film roll. When winding the film into a roll, it is preferable to wind the film while meandering in order to reduce the occurrence of uneven thickness and so-called gauge bands on the roll due to uneven thickness in the width direction of the film. In winding, it is also preferable to cut off the ears of the film and align the end surfaces of the rolls.
[0037]
It is important that the obtained polyimide film roll is not immediately covered with the sheet material, but is left unrolled for at least 3 days and covered with the sheet material after the fourth day after film formation. If the obtained polyimide film roll is immediately covered with a sheet material, the remaining organic solvent remains accumulated in the polyimide film, and when stored for a long period of time, lateral wrinkles, diagonal wrinkles, and vertical wrinkles are not preferable. Usually, since the remaining organic solvent evaporates from the polyimide film in 2 to 3 days, it may be covered with a sheet material after the 4th day, but the evaporation rate of the remaining organic solvent changes depending on the environment in which the roll is left. Therefore, it is preferable that the film is left for 6 days after film formation and covered with a sheet material after the 7th day. Further, if left unattended for a long period of time, a problem of moisture absorption occurs. Therefore, it is important to cover with a sheet material within 30 days after film formation, and it is more preferable to cover with a sheet material within 21 days.
[0038]
The place where the polyimide film roll is left is preferably a place where the humidity is controlled. In the case of a place where the humidity is controlled, the humidity should be managed at 0 to 70%, preferably 10 to 50%. Further, the temperature is preferably controlled at 5 to 45 ° C, preferably 10 to 35 ° C. If the humidity is too high, there is a concern about water absorption during standing, and if the humidity is too low, the film may be deteriorated due to the release of moisture held inside the film, so the above range is preferable. Further, if the temperature is too high, the film may be deteriorated due to softening, and if the temperature is too low, the film may be deteriorated due to freezing of water held inside the film.
[0039]
【Example】
Embodiments and effects of the present invention will be described below with reference to examples, but the present invention is not limited thereto.
[0040]
[Synthesis Example 1]
Acetic anhydride was added to a polyimide precursor solution polymerized with N, N-dimethylacetamide solvent using 202.2 g (1 mol) of 4,4′-diaminodiphenyl ether and 218.1 g (1 mol) of pyromellitic dianhydride. And β-picoline were added in an amount of 0.5% by weight, respectively, based on the polyamic acid, rapidly stirred with a mixer, extruded from a T-die and cast on a casting drum. On this casting drum, it heated at 100 degreeC for 1 minute, and obtained the film which has a self-supporting property. This film was heated at 250 ° C., 350 ° C., and 500 ° C. for 30 seconds each to obtain a polyimide film having a thickness of 12.5 μm.
[0041]
[Synthesis Example 2]
Polyimide polymerized using 294.2 g (1 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 108.1 g (1 mol) of paraphenylenediamine using an N, N-dimethylformamide solvent. To the precursor solution, acetic anhydride and β-picoline were added in an amount of 0.5% by weight with respect to the polyamic acid, respectively, rapidly stirred with a mixer, extruded from a T-die, and cast on a casting drum. The film was heated on this casting drum at 90 ° C. for 1 minute to obtain a self-supporting film. This film was heated at 200 ° C., 350 ° C., and 500 ° C. for 30 seconds each to obtain a polyimide film having a thickness of 9.5 μm.
[0042]
[Synthesis Example 3]
109.1 g (0.5 mol) of pyromellitic dianhydride, 147.1 g (0.5 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether. 1 g (0.5 mol) and 54.1 g (0.5 mol) of paraphenylenediamine were used, and a polyimide precursor solution polymerized using an N, N-dimethylacetamide solvent was mixed with acetic anhydride and β-picoline as a polyamic acid. Each was added in an amount of 0.5% by weight, rapidly stirred with a mixer, extruded from a T-die, and cast on a casting drum. The film was heated on this casting drum at 120 ° C. for 1 minute to obtain a self-supporting film. This film was heated at 270 ° C., 370 ° C., and 470 ° C. for 30 seconds to obtain a polyimide film having a thickness of 25.0 μm.
[0043]
[Synthesis Example 4]
N, N-dimethylacetamide using 218.1 g (1 mol) of pyromellitic dianhydride, 100.1 g (0.5 mol) of 4,4′-diaminodiphenyl ether and 54.1 g (0.5 mol) of paraphenylenediamine Acetic anhydride and β-picoline were added to the polyimide precursor solution polymerized using a solvent in an amount of 0.5% by weight with respect to the polyamic acid, respectively, rapidly stirred with a mixer, extruded from a T-die, and cast onto a casting drum. . The film was heated on this casting drum at 90 ° C. for 90 seconds to obtain a self-supporting film. This film was heated at 220 ° C., 350 ° C. and 480 ° C. for 45 seconds to obtain a polyimide film having a thickness of 50.0 μm.
[0044]
[Example 1]
After the polyimide film of Synthesis Example 1 was formed, it was wound around an epoxy resin-impregnated paper core having an inner diameter of 6 inches and an outer diameter of 7 inches to produce a roll of 1500 m polyimide film. In this state, the film roll was allowed to stand for 8 days under humidity control at a humidity of 40% and a temperature of 30 ° C. On the 9th day after film formation, the film is wrapped with a sheet of 76 μm thick aluminum deposited on a polyester film from the top of the film roll, and the end of the aluminum deposited sheet extends from the end of the paper core to the inner diameter of the paper core It was fixed so as to be involved. The film roll thus packaged was stored in a cardboard box and stored in a constant temperature and humidity chamber at 40 ° C. and 85% RH for one month. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, wrinkles were not generated on the surface layer and the inner layer of the film roll.
[0045]
[Comparative Example 1]
In Example 1, it was the same as Example 1 except that it was packaged with an aluminum vapor deposition sheet immediately after film formation, not on the 9th day after film formation. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, over 20 wrinkles were generated on the entire surface layer and inner layer of the film roll.
[0046]
[Example 2]
The polyimide film of Synthesis Example 2 was wound around a vinyl chloride plastic core having an inner diameter of 6 inches and an outer diameter of 7 inches to produce a roll of 3000 m polyimide film. In this state, the film roll was left to stand for 10 days under humidity control at a humidity of 45% and a temperature of 25 ° C. On the 11th day after film formation, an aluminum laminate sheet having a thickness of 80 μm was wrapped from above the film roll, and the end of the aluminum laminate sheet was fixed so as to be wound from the end of the plastic core to the inner diameter of the plastic core. Furthermore, a polyethylene film sheet having a thickness of 70 μm was packaged from above, and the end of the polyethylene film sheet was fixed so as to be wound around the inner end of the plastic core from the end of the plastic core. The film roll thus packaged was stored in a constant temperature and humidity chamber at 40 ° C. and 85% RH for one month. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, wrinkles were not generated on the surface layer and the inner layer of the film roll.
[0047]
[Comparative Example 2]
In Example 2, it was the same as Example 2 except that it was packaged with an aluminum laminate sheet and a polyethylene film sheet immediately after film formation, not on the 11th day after film formation. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, over 20 wrinkles were generated on the entire surface layer and inner layer of the film roll.
[0048]
[Example 3]
After the polyimide film of Synthesis Example 3 was formed, it was wound around a stainless steel core having an inner diameter of 6 inches and an outer diameter of inches to produce a 3000 m roll polyimide film roll. In this state, the film roll was allowed to stand for 8 days under humidity control at a humidity of 35% and a temperature of 20 ° C. On the 9th day after film formation, the film roll was packaged with a 0.15 mm aluminum sheet. Further, a polypropylene film sheet having a thickness of 70 μm was wrapped from above, and the end of the polypropylene film sheet was fixed so as to be wound from the end of the stainless steel core to the inner diameter of the stainless steel core. The film roll thus packaged was stored in a cardboard box and stored in a constant temperature and humidity chamber at 40 ° C. and 85% RH for one month. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, wrinkles were not generated on the surface layer and the inner layer of the film roll.
[0049]
[Comparative Example 3]
In Example 3, it was the same as Example 3 except that it was packaged with an aluminum sheet immediately after film formation, not on the 9th day after film formation. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, over 20 wrinkles were generated on the entire surface and inner layer of the film and roll.
[0050]
[Example 4]
After the polyimide film of Synthesis Example 4 was formed, it was wound around a paper core having an inner diameter of 6 inches and an outer diameter of inches to produce a roll of 1500 m polyimide film. In this state, the film roll was allowed to stand for 8 days under humidity control at a humidity of 25% and a temperature of 35 ° C. On the 9th day after film formation, the film is wrapped with a sheet of 76 μm thick copper deposited on a polyester film from the top of the film roll, and the end of this copper deposited sheet extends from the end of the paper core to the inner diameter of the paper core. It was fixed so as to be involved. Further, a polyester film sheet having a thickness of 70 μm was packaged from above, and the end of the polyester film sheet was fixed so as to be wound from the end portion of the paper core to the inner diameter portion of the paper core. The film roll thus packaged was stored in a cardboard box and stored in a constant temperature and humidity chamber at 40 ° C. and 85% RH for one month. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, wrinkles were not generated on the surface layer and the inner layer of the film roll.
[Comparative Example 4]
In Example 4, it was the same as Example 4 except that it was packaged with a copper vapor deposited sheet immediately after film formation, not on the 9th day after film formation. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, over 20 wrinkles were generated on the entire surface layer and inner layer of the film roll.
[0051]
[Example 5]
After the polyimide film of Synthesis Example 4 was formed, it was wound around a plastic core having an inner diameter of 6 inches and an outer diameter of inches to produce a roll of 1500 m polyimide film. In this state, the film roll was allowed to stand for 40 days under humidity control at a humidity of 25% and a temperature of 35 ° C. On the 41st day after film formation, the film roll is wrapped with a sheet of 76 μm thick aluminum deposited on a polyester film on the polyester film, and the end of the aluminum vapor deposited sheet extends from the end of the plastic core to the inner diameter of the plastic core. It was fixed so as to be involved. Further, a polyester film sheet having a thickness of 70 μm was packaged from above, and the end of the polyester film sheet was fixed so as to be wound from the end portion of the plastic core to the inner diameter portion of the plastic core. The film roll thus packaged was stored in a cardboard box and stored in a constant temperature and humidity chamber at 40 ° C. and 85% RH for one month. When the film roll after storage was taken out and the state of the roll surface layer and the inner layer was observed, no wrinkles were generated on the inner layer of the film roll, and one or two fine wrinkles were observed on the surface layer.
[0052]
【The invention's effect】
According to the packaging method of the polyimide film roll of the present invention, wrinkles are not generated on the surface layer and the inner layer of the roll stored for a long period of time, so that the occurrence of process troubles due to wrinkles can be effectively eliminated in processing the film. Therefore, it is extremely useful for fields such as a base film for flexible printed circuit boards and a base film for high-density mounting.

Claims (8)

This is a packaging method in which the outer side of a polyimide film roll having a film thickness of 1 to 225 μm is covered with a sheet material. A method for packaging a polyimide film roll, which is covered with a sheet material. The packaging method for a polyimide film roll according to claim 1, wherein the polyimide film is covered with a sheet material on or after the seventh day after the polyimide film is formed. The packaging method for a polyimide film roll according to claim 1, wherein the polyimide film is covered with a sheet material within 30 days after the formation of the polyimide film. The said sheet | seat material is metal foil, The packaging method of the polyimide film roll of any one of Claims 1-3 characterized by the above-mentioned. The method for packaging a polyimide film roll according to claim 1, wherein the sheet material is a metal laminate film. The said sheet | seat material is a metal vapor deposition film, The packaging method of the polyimide film roll of any one of Claims 1-3 characterized by the above-mentioned. The said sheet | seat material is arrange | positioned in the surface layer of a polyimide film roll, The packaging method of the polyimide film roll of any one of Claims 1-6 characterized by the above-mentioned. The said polyimide film is a film obtained by casting a polyimide precursor solution, The packaging method of the polyimide film roll of any one of Claims 1-7 characterized by the above-mentioned.