JP5114668B2 - Heat-resistant polymer film manufacturing apparatus and heat-resistant polymer film manufacturing method - Google Patents

Description

  The present invention relates to an apparatus for producing a heat-resistant polymer film, and in particular, a tenter type (film) when a precursor film is heat-treated at a high temperature to form a heat-resistant polymer film during final heat treatment in producing the heat-resistant polymer film. The present invention relates to an apparatus for producing a heat-resistant polymer film having a feature in a (transport) processing section, and also relates to a method for producing a heat-resistant polymer film using this apparatus in the method.

When a polyimide film is produced, an undried precursor film (green film) is imidized at a high temperature. In this case, the undried precursor film is heat-treated while being transported and dried and heat-treated. The films and precursor films that are retained generally shrink as they are dried. In such film transport / drying / heat treatment, as an apparatus for manufacturing a film by transporting the film in the stretched width direction by holding both ends in the width direction of the film with a large number of pins and clips, A tenter type conveying device for a film (sheet) called a so-called tenter is known (for example, Patent Document 1).
In addition, it is also known to use a tenter type conveying device for manufacturing a polyimide film (for example, Patent Document 2).

By using the film conveying apparatus, it is possible to suppress shrinkage of the film in the width direction due to heat during drying and heat treatment, and to prevent wrinkles due to shrinkage from occurring in the film after drying and heat treatment.
The shrinkage of the film occurs not only in the width direction of the film but in all directions. However, the transporting tension acts in the transport direction of the film and has an effect of suppressing the shrinkage. Thus, the strength and flatness required for the dried and heat-treated film can be ensured by transporting the undried film using the film tenter type transport device when drying and heat-treating.

In particular, a tenter used for producing a polyimide film is subjected to a heat treatment at a temperature exceeding 300 ° C. Therefore, the heat resistance and durability of the tenter itself are essential for industrially stable production. In particular, stainless steel with high heat resistance is used for the drive part that transports the film. However, since the lubricating oil cannot be used only for the sliding part, there is frictional wear between metal parts. Arise. For this reason, there is a limit to the life of the apparatus, and problems such as contamination of the film product by metal fine powder generated due to wear have occurred.
In general, it is known that solid lubricants are used in situations where lubricating oil cannot be used. However, polymer solid lubricants such as fluororesins and silicone resins (for example, Patent Document 3) are used because of high temperatures. I can't. In addition, graphite having relatively high heat resistance (for example, Patent Document 4) is not suitable because it becomes a conductive foreign matter generation source.

Japanese Examined Patent Publication No. 39-029211 JP 09-188863 A JP 2005-325182 A JP 11-166539 A

  The present invention is a polyimide film, a cellulose-based film that has low noise even when operated at a high temperature of 300 ° C. or higher, and is less contaminated with metal dust, conductive foreign matter, etc. An object of the present invention is to provide a heat-resistant polymer film production apparatus excellent in durability suitable for producing a heat-resistant polymer film such as a film, a polyamide film, and a polyamide-imide film.

As a result of intensive investigations, the present inventors have found that in a tenter type transport device used for manufacturing a heat-resistant polymer film such as a polyimide film, the use of a specific solid lubricating compound for the sliding portion reduces surface contamination due to conductive foreign matter. A clean heat-resistant polymer film can be produced, and a production apparatus excellent in durability has been found.
That is, the present invention employs the following configuration.
1. In a film end fixed type tenter that performs heat treatment etc. on heat resistant polymer film or its precursor film, solid on the sliding part of the drive mechanism part for driving the film end gripping mechanism in the film transport direction An apparatus for producing a heat-resistant polymer film, wherein a heat-resistant compound having a lubricating action is allowed to act.
2. 2. The heat-resistant polymer film production apparatus according to claim 1, wherein the heat-resistant compound having a solid lubricating action is any one of a non-metal or metal boride and a metal sulfide.
3. The apparatus for producing a polymer film according to 1 or 2, wherein a fundamental frequency of a frictional sound generated when the film is conveyed after being operated at a temperature of 300 ° C. or more for 3 hours is 3 kHz or less.
4). The heat-resistant polymer film production apparatus according to any one of the first to third aspects, wherein the heat-resistant polymer film is a polyimide film.
5. The heat resistant polymer film manufacturing apparatus according to any one of the first to fourth aspects, wherein the film end gripping mechanism is a pin type or a clip type.
6). A method for producing a heat-resistant polymer film, wherein the heat-resistant polymer film production apparatus according to any one of 1 to 5 is used.
7). The method for producing a heat-resistant polymer film according to claim 6, wherein the heat-resistant polymer film is a polyimide film.

  The heat-resistant polymer film production apparatus of the present invention is compatible with both heat resistance and insulation, and a solid lubricant that maintains a lubricating action even in a high temperature range of 300 ° C. or higher, preferably 380 ° C. or higher, more preferably 460 ° C. or higher. Because it is used for moving parts, the noise during operation is low, and the film can be transported smoothly without giving extra vibration to the film. In addition, it is less contaminated with metal dust and conductive foreign matter. And the distortion of the whole film can be reduced and the film thickness unevenness can be reduced, and even an extremely thin heat-resistant film of 10 μm or less can be produced stably.

In the present invention, the heat resistant polymer film includes a film made of a high melting point or non-melting polymer such as polyamideimide, polyimide, cellulose acetate, and aramid.
The heat-resistant polymer used in the production apparatus of the present invention is usually formed into a film by casting a solution containing these polymers, drying and heat treatment. Examples of the solvent used for the solution containing these polymers include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, methylene chloride, tetrahydrofuran, methanol, and metacresol.
Examples of the polymer solution preferably used in the present invention include N-methyl-2-pyrrolidone solution of polyamideimide, N, N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of polyamide acid which is a polyimide precursor, N , N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of solvent-soluble polyimide, N, N-dimethylacetamide solution, methylene chloride solution of cellulose acetate, methanol solution, methylene chloride solution of polycarbonate, metacresol solution, Examples include a tetrahydrofuran solution of polyvinyl chloride and an N-methyl-2-pyrrolidone solution of aramid.

The polymer film production apparatus and production method of the present invention are particularly suitable for polyamic acid which is a precursor of a polyamic acid which is a polyimide precursor, an N-methyl-2-pyrrolidone solution, an N, N-dimethylacetamide solution or a polyimide benzoxazole. The present invention can be most preferably applied by the casting film forming method using a solution of N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, or the like. Hereinafter, the polyimide film will be described in detail, but is not limited thereto.
The reaction between an aromatic diamine for obtaining a polyimide film, which can be preferably applied to the present invention, and an aromatic tetracarboxylic acid is carried out by reacting an aromatic diamine and an aromatic tetracarboxylic acid (anhydride) in a solvent. (Ring-opening) Polyamide acid solution that is a polyimide precursor is obtained by polyaddition reaction, and then a precursor film (green film) is formed from this polyamic acid solution, followed by drying, heat treatment, dehydration condensation (imide) Manufactured).

Although the polyimide film in this invention is not specifically limited, The combination of the following aromatic diamine and aromatic tetracarboxylic acid (anhydride) is mentioned as a preferable example.
A. A combination of an aromatic diamine having a benzoxazole structure and an aromatic tetracarboxylic acid.
B. A combination of an aromatic diamine having a diaminodiphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid skeleton.
C. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
D. A combination of one or more of the above ABCs.
Examples of aromatic diamines having a benzoxazole structure that can be preferably used in the present invention include the following compounds.

  2,2′-p-phenylenebis (5-aminobenzoxazole), 2,2′-p-phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6- Aminobenzoxazolo) benzene, 2,6- (4,4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (4,4′-diaminodiphenyl) ) Benzo [1,2-d: 4,5-d ′] bisoxazole, 2,6- (3,4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2- d: 5,4-d '] bisoxazole, 2 6- (3,3'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bis-oxazole.

Among these, amino (aminophenyl) benzoxazole isomers are preferable from the viewpoint of ease of synthesis. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.
In the present invention, it is preferable to use 70 mol% or more of the aromatic diamine having the benzoxazole structure.

Examples of the aromatic diamine having a diaminodiphenyl ether skeleton in the present invention include 4,4'-diaminodiphenyl ether (DADE), 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether and derivatives thereof.
Examples of the aromatic diamine having a phenylenediamine skeleton in the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and derivatives thereof.
You may use the following aromatic diamine which is not limited to the above for the polyimide film in this invention.
For example, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3 , 3,3-hexafluoropropane, m-aminobenzylamine, p-aminobenzylamine,

  3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenyl sulfone, 3,4′- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4 -(4-aminophenoxy) phenyl] ethane, 1, -Bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] propane,

1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) Phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- ( 4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphen Le] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,

1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3 Aminophenoxy) benzoyl] benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide,

2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1 -Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4 '-Bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α) , Α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis 4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl Benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene,

3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino5,
5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 4,4′-diamino-5-phenoxybenzophenone, 3,4 '-Diamino-4-phenoxybenzophenone 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'
-Dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′-diamino-4-biphenoxybenzophenone, 3,4′-
Diamino-5′-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4 -Amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4)
-Biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4 -Amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile and part of the hydrogen atoms on the aromatic ring in the above aromatic diamine Or a halogen atom having 1 to 3 carbon atoms in which all or some of the hydrogen atoms of the halogen atom, alkyl group or alkoxyl group having 1 to 3 carbon atoms, cyano group, alkyl group or alkoxyl group are substituted with halogen atoms And aromatic diamines substituted with an alkyl group or an alkoxyl group.
As aromatic tetracarboxylic acids that can be preferably used as the polyimide film in the present invention, aromatic tetracarboxylic acids having a pyromellitic acid skeleton, that is, pyromellitic acid and anhydrides or halides thereof, and aromatic tetracarboxylic acids having a biphenyltetracarboxylic acid skeleton Examples include acids, i.e. biphenyltetracarboxylic acid and anhydrides or halides thereof.
Without being limited thereto, the following aromatic tetracarboxylic acids may be used.

These tetracarboxylic acids may be used alone or in combination of two or more.

  The solvent used when polyamic acid is obtained by polymerizing aromatic diamines and aromatic tetracarboxylic acid anhydrides is particularly limited as long as it dissolves both the raw material monomer and the polyamic acid to be produced. Although not preferred, polar organic solvents are preferred, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide Hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, halogenated phenols and the like, among which N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferably applied. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by mass, The amount is preferably 10 to 20% by mass.

Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for 30 minutes. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited, but it is preferable to add aromatic tetracarboxylic acid anhydrides to the solution of aromatic diamines. The weight of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and the viscosity of the solution is measured with a Brookfield viscometer (25 ° C.). From the viewpoint of the stability of liquid feeding, it is preferably 10 to 2000 Pa · s, and more preferably 100 to 1000 Pa · s.
The reduced viscosity (ηsp / C) of the polyamic acid in the present invention is not particularly limited, but is preferably 3.0 or more, more preferably 4.0 or more, still more preferably 5.0 or more.

Moreover, you may perform superposition | polymerization by adding a small amount of terminal blockers to aromatic diamines before a polymerization reaction. Examples of the end capping agent include compounds having a carbon-carbon double bond such as maleic anhydride. The amount of maleic anhydride used is preferably 0.001 to 1.0 mol per mol of aromatic diamine.
Vacuum degassing during the polymerization reaction is effective in producing a good quality polyamic acid solution.
Furthermore, in order to obtain the polyimide film of the present invention, it is possible to remove bubbles and dissolved gas in the solution in advance by treatment such as decompression when casting and applying a polyamic acid solution described below onto the support. This is an effective process.

  The support on which the polyamic acid solution is applied is only required to have smoothness and rigidity sufficient to form the polyamic acid solution into a film, and a drum or belt whose surface is made of metal, plastic, glass, porcelain, etc. And the like. A method using a polymer film having moderate rigidity and high smoothness is also a preferred embodiment. Among them, the surface of the support is preferably a metal, more preferably stainless steel that does not rust and has excellent corrosion resistance. The surface of the support may be plated with metal such as Cr, Ni, or Sn. The surface of the support can be mirror-finished or processed into a satin finish as required. The air volume and temperature in drying may be appropriately selected and adopted depending on the difference in the support, and the polyamic acid solution can be applied to the support by casting from a nozzle with a slit, extrusion by an extruder, squeegee coating, reverse coating, die Including, but not limited to, coating, applicator coating, wire bar coating and the like, conventionally known solution application means can be used as appropriate.

As imidization / heat treatment, a polyamic acid solution that does not contain a ring-closure (imidization) catalyst or a dehydrating agent is used, and the imidization reaction is advanced by subjecting to a heat treatment (so-called thermal ring-closure method), Examples thereof include a chemical ring closure method in which a catalyst and a dehydrating agent are contained and an imidization reaction is performed by the action of the above ring closing catalyst and the dehydrating agent.
The heat treatment temperature of the thermal ring closure method is preferably 150 to 500 ° C. If the heat treatment temperature is lower than this range, it is difficult to sufficiently close the ring, and if it is higher than this range, the deterioration proceeds and the film tends to become brittle. A more preferable embodiment includes a two-stage heat treatment step having an initial stage heat treatment and a subsequent stage heat treatment in which a heat treatment is performed at 150 to 250 ° C. for 3 to 20 minutes and then heat treatment at 350 to 500 ° C. for 3 to 20 minutes.

The timing for adding the ring-closing catalyst to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. Among them, heterocyclic tertiary amines are mentioned. At least one amine selected from is preferred. Although the usage-amount of a ring-closing catalyst with respect to 1 mol of polyamic acids does not have limitation in particular, Preferably it is 0.5-8 mol.
The timing of adding the dehydrating agent to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Among them, acetic anhydride, benzoic anhydride, etc. Acids or mixtures thereof are preferred. Moreover, the usage-amount of the dehydrating agent with respect to 1 mol of polyamic acids is not particularly limited, but is preferably 0.1 to 4 mol. When a dehydrating agent is used, a gelation retarder such as acetylacetone may be used in combination.

Whether it is a thermal cyclization reaction or a chemical cyclization method, the polyimide film precursor (green sheet, film) formed on the support may be peeled off from the support before it is completely imidized. The film may be peeled after imidization.
Although the thickness of a polyimide film is not specifically limited, Considering using it for the base substrate for printed wiring boards mentioned later, it is 5-150 micrometers, Preferably it is 10-100 micrometers. This thickness can be easily controlled by the amount of the polyamic acid solution applied to the support and the concentration of the polyamic acid solution.
The polyimide film of the present invention is preferably provided with a lubricant in the polyimide to give fine irregularities on the film surface to improve the slipping property of the film.
As the lubricant, inorganic or organic fine particles having an average particle diameter of about 0.03 to 3 μm can be used. Specific examples include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, Examples include magnesium oxide, calcium oxide, and clay minerals.

  When the polymer film of the present invention or a precursor film thereof is processed with a film end fixed tenter, the film end gripping at both side ends in the width direction of the film is a large number of pin sheets and individual pin sheets. Each pin arranged at the innermost side in the film width direction and within the individual pin sheet in the film transport direction. In addition, the pin arrangement in the polymer film manufacturing apparatus, in which all the other pin sheets are arranged at equal intervals, will be described in detail. As shown in the figure, in a processing chamber that receives heat treatment or the like, a large number of pin sheets with a large number of pins are disposed at both ends of the film, and each pin sheet is arranged in series in the conveying direction on the innermost side. A plurality of pins and a plurality of other pins are provided, and the arrangement of the plurality of pins arranged in series in the conveying direction on the innermost side of each individual pin sheet is important. When the plurality of pins arranged in series in the conveying direction are, for example, A1, A2, A3, A4,... An toward the conveying direction, the plurality of pins arranged in series in the conveying direction on the innermost pin sheet adjacent to each other. For example, when B1, B2, B3, B4,... Bn in the transport direction, A1, A2, A3, A4,... An, and B1, B2, B3, B4,. Interval The same is the same, and the interval between An and B1 is also the same as the former, and the above relationship is also true for the plurality of pins arranged in series in the conveying direction on the innermost side of the other pin sheet. The pin sheet travels in parallel with each other at both ends of the film, and at least the film is kept in the processing chamber while the plurality of pin sheets are traveling in parallel with each other at both ends of the film. Gripping and transporting.

    In addition, when the polymer film of the present invention or a precursor film thereof is processed by a film end fixed tenter, film end gripping at both side ends in the width direction of the film is performed with a large number of pin sheets and individual films. It consists of a large number of pins arranged on the pin sheet, and the pins are made by piercing the both side ends of the film, and the individual pins arranged at the innermost side in the film width direction are separated from each other in the film transport direction. In the polymer film manufacturing apparatus characterized in that the pin spacing is 1/10 or less with respect to the width of the gripping film. It is preferable that the film grip uniformity is easily maintained, and the hole expands in the width direction or the conveyance direction of the film at the hole where the pin is bitten. Is prevented from with or breakage occurs, the reduction of distortion in the entire film, reduction of the film thickness unevenness can be achieved.

The heat-resistant compound having a solid lubricating action that acts on the sliding portion of the production apparatus of the present invention is either a non-metal or metal boride or metal sulfide. As the non-metal boride, a hexagonal system is used. Boron nitride (h-BN), CrB, TiB ₂ , MoB, WB, TaB ₂ as metal borides, tungsten disulfide, molybdenum disulfide, niobium sulfide, tungsten disulfide, iron sulfide as metal sulfides Etc.
In addition to these, graphite, fluorinated graphite, cerium fluoride, gold, silver, iridium, barium, and the like may be used supplementarily.

  The method of action of the solid lubricant on the sliding portion is not particularly limited, but a block in which the exemplified heat-resistant compound having a solid lubricant action and a relatively soft metal are sintered in a powder metallurgical manner is prepared, and such a block is used. A film made of a solid lubricant component can be formed by bringing the block into contact with a chain block, a roller, a ball, a bearing or the like.

The method for causing these heat-resistant compounds having a solid lubricating action to act on the sliding portion is not particularly limited.For example, a mechanism for pressing a solid lubricant stick from the lower part of the roller to the roller on which the chain block is placed is added. There is a method in which a solid lubricant component is transferred in advance to a roller rotating body portion and a chain block in contact with the roller.
As the solid lubricant stick, the fixed lubricant exemplified above is used as a relatively soft metal, for example, Ni, Fe, Co, Cu, Sn, Ag, Pb, Mn, Cr, Mo, W, Nb, Ta, Al, Zn. , Ti and the like sintered by powder metallurgy can be used.

  Because of the action of these heat-resistant compounds having a solid lubricating action, the manufacturing apparatus of the present invention can suppress wear of the sliding part even when a high-temperature heat treatment at 300 ° C. or higher is operated for a long time. Friction noise generated during film transport that is considered to be caused by the wear of the film can be made to have a fundamental frequency of 3 kHz or less, the work environment can be improved, and the amount of metal dust on the surface of the manufactured film can be greatly reduced.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows.

1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube. (When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, measurement was performed by dissolving the polymer using N, N-dimethylacetamide.)

2. The thickness of the polyimide film The thickness was measured using a micrometer (Finereuf, Millitron 1245D).

3. Specimen obtained by cutting a polyimide film to be measured into a strip of 100 mm × 10 mm in the flow direction (MD direction) and the width direction (TD direction), respectively. It was. Using a tensile tester (manufactured by Shimadzu Corp., Autograph (R) model name AG-5000A) under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm, the tensile modulus of elasticity and tensile rupture in each of the MD and TD directions. Strength and tensile elongation at break were measured.

4). Quantification of the amount of metal dust 25 squares with a side of 50 mm were randomly cut out from the obtained film, and they were placed in 500 ml of 10% hydrochloric acid aqueous solution at room temperature so that the front and back of each film were in full contact with the aqueous hydrochloric acid After soaking for 24 hours, the film was taken out and the metal component contained in the hydrochloric acid aqueous solution was quantified by atomic absorption analysis.
As metal components, iron, nickel and chromium, which are the main components of stainless steel presumed to be used in the pin tenter sliding portion, were detected. The total was divided by the film area to obtain the amount of metal dust.
Metal dust amount [ng / square cm] = metal component amount [ng] / film area [square cm]

5. Measurement of frictional noise generated during film transport A microphone is installed at a point 1 m from the tenter exit in the film traveling direction and 30 cm above the film surface, and a band analysis is performed using a 2ch small FFT analyzer “SA-78” manufactured by Rion Corporation. The peak frequency of was determined.

[Reference Example 1]
(Preliminary dispersion of inorganic particles)
1.22 parts by mass of amorphous silica spherical particles Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 420 parts by mass of N-methyl-2-pyrrolidone, the wetted part of the container, and the infusion pipe are austenitic stainless steel The mixture was placed in a container of SUS316L and stirred with a homogenizer T-25 basic (manufactured by IKA Labortechnik) at a rotation speed of 1000 rpm for 1 minute to obtain a preliminary dispersion. The average particle size in the preliminary dispersion was 0.11 μm.
(Preparation of polyamic acid solution)
A nitrogen inlet tube, a thermometer, a liquid contact part of a container equipped with a stirring rod, and a pipe for infusion were substituted with nitrogen in the reaction container made of austenitic stainless steel SUS316L, and then 223 parts by mass of 5-amino-2- ( p-Aminophenyl) benzoxazole was added. Next, 4000 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, and then the preliminary dispersion obtained above was added with 420 parts by mass and 217 parts by mass of pyromellitic dianhydride. When the mixture was stirred at ° C. for 24 hours, a brown viscous polyamic acid solution A was obtained. The reduced viscosity (ηsp / C) was 3.8.

[Reference Example 2]
A nitrogen inlet tube, a thermometer, a wetted part of a vessel equipped with a stirring rod, and an infusion pipe were replaced with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 5-amino-2- (p-aminophenyl) ) After adding 223 parts by mass of benzoxazole and 4416 parts by mass of N, N-dimethylacetamide and completely dissolving them, Snowtex DMAC-ST30 (manufactured by Nissan Chemical Industries, Ltd.) 40 in which colloidal silica is dispersed in dimethylacetamide .5 parts by mass (including 8.1 parts by mass of silica) and 217 parts by mass of pyromellitic dianhydride are added and stirred at a reaction temperature of 25 ° C. for 24 hours to obtain a brown and viscous polyamide acid solution B. It was. Ηsp / C of this product was 4.0.

[Reference Example 3]
(Preliminary dispersion of inorganic particles)
7.6 parts by weight of amorphous silica spherical particle Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 390 parts by weight of N-methyl-2-pyrrolidone, the liquid contact part of the container, and the infusion pipe are austenitic stainless steel SUS316L And stirred for 1 minute at a rotation speed of 1000 rpm with a homogenizer T-25 basic (manufactured by IKA Labortechnik) to obtain a preliminary dispersion.
(Preparation of polyamic acid solution)
The liquid contact part of the vessel equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and the pipe for infusion were substituted with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 200 parts by mass of diaminodiphenyl ether was added. Next, after 3800 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, 390 parts by mass and 217 parts by mass of pyromellitic dianhydride were added to the preliminary dispersion obtained above. When the mixture was stirred at 0 ° C. for 5 hours, a brown viscous polyamic acid solution C was obtained. The reduced viscosity (ηsp / C) was 3.7.

[Reference Example 4]
(Preliminary dispersion of inorganic particles)
3.7 parts by mass of amorphous silica spherical particles Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 420 parts by mass of N-methyl-2-pyrrolidone, and the infusion part are austenitic stainless steel SUS316L And stirred for 1 minute at a rotation speed of 1000 rpm with a homogenizer T-25 basic (manufactured by IKA Labortechnik) to obtain a preliminary dispersion.
(Preparation of polyamic acid solution)
The wetted part of the vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and the infusion piping were substituted with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 108 parts by mass of phenylenediamine was added. Next, after 3600 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, 420 parts by mass and 292.5 parts by mass of biphenyltetracarboxylic dianhydride were added to the preliminary dispersion obtained above. When the mixture was stirred at 25 ° C. for 12 hours, a brown viscous polyamic acid solution D was obtained. This reduced viscosity (ηsp / C) was 4.5.

[Comparative Examples 1-4]
The polyamic acid solution obtained in Reference Examples 1 to 4 was coated on a stainless steel endless continuous belt mirror-finished using a die coater (coating width 1240 mm) and dried at 90 to 115 ° C. for 10 minutes. The polyamic acid film which became self-supporting after drying was peeled from the support and cut at both ends to obtain respective green films having a thickness of 17 μm and a width of 1200 mm.
As shown in FIG. 1, the obtained green films are passed through a pin tenter having a pin sheet in which pins are arranged so that the pin interval is constant when the pin sheets are arranged, and the film end is inserted into the pin. The pin sheet spacing is adjusted so that the film does not break and the film does not break, and unnecessary talmi does not occur, and the final pin sheet spacing is 1140 mm. The imidization reaction was allowed to proceed by heating for 2 minutes at 230 ° C. for 2 minutes for the second stage and 6 minutes for the third stage 485 for 6 minutes. Then, it cooled to room temperature in 2 minutes, the part where the flatness of the both ends of a film was bad was cut off with the slitter, it wound up in roll shape, and each polyimide film of Comparative Examples 1-4 which exhibits brown was obtained. The pin sheet is fixed to a stainless steel block connected in a chain shape, and is conveyed on a stainless steel roller as a connecting body. Lubricating oil is not used because the third stage is hot. The length of the pin sheet is 65.0 mm, and the pin interval is 7.0 mm.
Table 1 shows the measurement results such as the characteristics of the obtained polyimide film and the peak frequency of noise generated during film conveyance. During the tenter operation, any polyamic acid film is used, and mechanical sounds, particularly high-pitched sounds, which are sliding sounds between metals, are intermittently generated, and the noise level is high, which hinders conversation near the pin tenter. Came.

[Examples 1 to 4]
The polyamic acid solutions of Reference Examples 1 to 4 were coated and dried on a stainless steel endless continuous belt mirror-finished in the same manner as in Example, and the polyamic acid film that became self-supporting after drying was peeled off from the support. Each green film having a thickness of 21 μm was obtained.
These obtained green films were heat-treated with a pin tenter that differs from the comparative example only in the following points. That is, in the embodiment, a mechanism for pressing the solid lubricant stick from the lower part of the roller is added to the roller on which the chain block is placed (see FIG. 4), and the roller rotating part and the chain block in contact with the roller are solidly lubricated in advance. Heat treatment was performed after sufficiently transferring the agent components.
The others were heat-treated under the same conditions as in the comparative example, and the portions with poor flatness at both ends of the film were cut off with a slitter, rolled up into a roll, and the respective polyimide films of Examples 1 to 4 exhibiting brown color were obtained. . Table 1 shows the results such as the characteristics of the obtained polyimide film and the peak frequency of noise generated during film conveyance. In addition, the mechanical drive sound during the tenter operation was a noise in the mid-low range centered on the drive sound of the motor and the chain, and the noise level was sufficiently lower than that of the comparative example, and there was no particular problem in conversation.
The solid lubricant stick used here is 30% by mass of tungsten disulfide having an average particle size of 2 μm as a solid lubricant, tungsten (64% by mass) of average particle size of 3 μm as a metal component, and an average particle size as a metal boride. After mixing 5 μm of Fe—Ni—B alloy (6 mass%) and mixing and grinding with a ball mill. The product was pressed into pellets at a pressure of about 5 tons / square cm and sintered under conditions of 1150 ° C. × 30 minutes under a low vacuum of 1.0 × 10 ⁻² Pa level.

[Comparative Examples 5 to 8]
The polyamic acid solution obtained in Reference Examples 1 to 4 was coated on a stainless steel endless continuous belt mirror-finished using a die coater (coating width 1240 mm) and dried at 90 to 115 ° C. for 10 minutes. The polyamic acid film which became self-supporting after drying was peeled off from the support and cut at both ends to obtain respective green films having a thickness of 46 μm and a width of 1200 mm.
These obtained green films are passed through a clip tenter equipped with the clips shown in FIGS. 5 to 6, and the film ends are gripped by the clips, so that the film does not break the clip width as appropriate, and an excess film of film is produced. It is adjusted so that the final clip interval is 1140 mm, and the first stage is heated at 170 ° C. for 2 minutes, the second stage is 230 ° C. for 2 minutes, and the third stage 485 is heated for 6 minutes. The imidization reaction was allowed to proceed. Then, it cooled to room temperature in 2 minutes, cut off the part where the flatness of the both ends of a film was bad with a slitter, wound up in roll shape, and obtained each polyimide film of Comparative Examples 5-8 which exhibits brown. The clip is fixed to a stainless steel block connected in a chain shape, and is transported on the rail by a stainless steel roller as a chain-like connection body. Lubricating oil is not used because the third stage is hot.
Table 1 shows the measurement results such as the characteristics of the obtained polyimide film and the peak frequency of noise generated during film conveyance. During the tenter operation, any polyamic acid film is used, and mechanical sounds, particularly high-pitched sounds, which are sliding sounds between metals, are intermittently generated, and the noise level is high, which hinders conversation near the pin tenter. Came.

[Examples 5 to 8]
The polyamic acid solutions of Reference Examples 1 to 4 were coated and dried on a stainless steel endless continuous belt mirror-finished in the same manner as in Example, and the polyamic acid film that became self-supporting after drying was peeled off from the support. Each green film having a thickness of 46 μm was obtained.
These obtained green films were heat-treated under the same conditions in the same clip tenter as Comparative Examples 5-8. However, in the embodiment, a mechanism for pressing the roller solid lubricant stick that transports the chain is added (see FIG. 5), and the solid lubricant component is sufficiently transferred to the roller rotating part and the chain block in contact with the roller in advance. Then, heat treatment was performed.
Others were heat-treated under the same conditions as in the comparative example, and the portions with poor flatness at both ends of the film were cut off with a slitter, rolled up into a roll shape, and the respective polyimide films of Examples 5 to 8 exhibiting brown color were obtained. .
Table 1 shows the characteristics of the obtained polyimide film, the peak frequency of noise generated during film conveyance, and the like. In addition, the mechanical drive sound during the tenter operation was a noise in the mid-low range centered on the drive sound of the motor and the chain, and the noise level was sufficiently lower than that of the comparative example, and there was no particular problem in conversation.
The solid lubricant stick used was 35% by mass of boron nitride having an average particle size of 2.5 μm as a solid lubricant, and silver (20% by mass) and tin (10% by mass) having an average particle size of 2 to 4 μm as metal components. After mixing copper (35% by mass) and mixing and grinding with a ball mill. The product was pressed into pellets at a pressure of about 5 tons / square cm and sintered under conditions of 1000 ° C. for 60 minutes under a low vacuum of 1.0 × 10 ⁻² Pa level.

As shown in Table 1, although the amount of metal dust on the film surface is large in the comparative example, it can be seen that both the noise level and the center frequency of the noise are lowered in the example, and the amount of metal dust is greatly reduced.
As described above, by using the film manufacturing apparatus using the solid lubricant of the present invention, not only the noise during manufacturing can be greatly reduced, but also the amount of metal dust in the product film can be greatly reduced. can do.

  The heat-resistant polymer film manufacturing apparatus of the present invention is low in noise even when operated at a high temperature of 300 ° C. or higher, and can greatly reduce the amount of metal dust in the obtained film. This is industrially very significant as an apparatus for producing a heat-resistant polymer film such as a polyimide film, a cellulose film, a polyamide film, or a polyamideimide film that requires high-temperature heat treatment at 300 ° C. or higher.

It is a schematic side view which shows the example of the pin sheet and chain block in a tenter type film processing machine. It is a schematic top view which shows the example of the pin sheet in a tenter type film processing machine. It is a schematic top view which shows the outline | summary of the whole tenter type film processing machine of this invention. It is a schematic side view which shows the example of the solid lubricant provision part in the pin sheet and chain block part of the tenter type film processing machine of the present invention. It is a schematic side view which shows the example of the solid lubricant provision part in the clip part of the tenter type film processing machine of the present invention. It is a schematic front view which shows the example of the clip part of the tenter type film processing machine of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Pin 2 ... Pin sheet 3 ... Chain block 4 ... Roller 5 ... Cooling part 6 ... Heat processing part 7 ... Chain 8 ... Solid lubricant stick 11 ... Clip movable part 12 ・ ・ Roller 13 ・ ・ Clip gripping part 14 ・ ・ Rotating shaft 15 ・ ・ Solid lubricant

Claims (4)

A film end fixed type tenter that heat-treats a heat resistant polymer film or its precursor film in a high temperature range of 460 ° C. or more , and has a pin type film end holding mechanism, and the film end holding mechanism is a film A method for producing a heat-resistant polymer film , wherein a heat-resistant compound having a solid lubricating action is allowed to act on a sliding portion of a drive mechanism portion for driving in a transport direction. 2. The method for producing a heat-resistant polymer film according to claim 1, wherein the heat-resistant compound having a solid lubricating action is any one of a non-metal or metal boride and a metal sulfide. The method for producing a polymer film according to claim 1 or 2 , wherein the fundamental frequency of frictional sound generated during film conveyance after operating at a temperature of 300 ° C or higher for 3 hours is 3 kHz or less. The method for producing a heat-resistant polymer film according to any one of claims 1 to 3, wherein the heat-resistant polymer film is a polyimide film.