JP5023463B2 - Method and apparatus for producing polymer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing apparatus of a polymeric film capable of suppressing the problem wherein perforations in which pins are bitten of the polymeric film are broken into slots in the lateral direction of the polymeric film when the polymeric film is manufactured by drying or heat treatment using a tenter type feed device, and a manufacturing method of the polymeric film. <P>SOLUTION: The edge grasping mechanism in both side edge parts of the polymeric film is constituted of a large number of pin sheets and a large number of the pins arranged to the individual pin sheets. The pins are thrust in both side edge parts of the film and, in a state that the film is tensioned in its lateral direction or a feed direction, a region, where the film is not brought into contact with the pin planted positions, such as a stand or the like is provided outside the lateral direction of the pin sheets into which the thrusted film is brought into contact with the polymeric film manufacturing apparatus having a film feeding tenter type processing part, is provided and cavity parts are provided to the pin sheets. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  TECHNICAL FIELD The present invention relates to a method and apparatus for producing a polymer film, and in particular, a tenter type (film transport) when a precursor film is subjected to high-temperature heat treatment at the time of final heat treatment when producing a polymer film. ) The present invention relates to a method for producing a polymer film characterized by a processing section and a polymer film production apparatus.

When producing a polyimide film, a precursor film (also referred to as a green film) in which a part of the solvent remains is imidized at a high temperature. In this case, drying and heat treatment are carried out by heating the precursor film while it is being transported, but a film having not less than these solvents generally shrinks as it is 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 (see Patent Document 1).
In addition, it is also known to use a tenter type conveying device for manufacturing a polyimide film (see Patent Document 2).
Japanese Examined Patent Publication No. 39-029211 JP 09-188863 A

The film conveying apparatus has been well known for a long time to be used for drying so as not to cause wrinkles in the drying process after dyeing the cloth. In addition to drying the cloth, it is also used for drying an undried plastic film by a solvent casting method while transporting it in the drying step. 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.

  Among the film tenter type conveying devices, the tenter type conveying device for the film that holds the film stretched in the width direction by biting a large number of pins along both side edges of the film was arranged in parallel A large number of pins are arranged on a pin sheet supported in a row by a pair of moving chains. This film tenter type transport device is simpler in structure than the film transport device such as the clip, or can be structured to reverse the transport conveyor path in the drying chamber. On the other hand, since the fine pieces of the film generate dust when the pins are bitten into the film, it is necessary to reduce the number of pins as much as possible. Moreover, when the shrinkage force of the film becomes large, there are problems such as the holes that have pinned the film surface break into long holes in the width direction of the film.

In order to improve these, there has also been proposed a method in which a film having a high tear strength is additionally stacked for reinforcement at the gripping portion of the film pin (see Patent Document 3).
Furthermore, a tenter type conveying device has also been proposed in which the innermost pin density is increased and the outer pin arrangement density is further reduced in the arrangement of pins that can be placed on both ends of the web when the web is conveyed (patent). Reference 4). Even in these proposals for improvement, there is nothing to consider the arrangement in the conveying direction of the pins, particularly the arrangement of the pins between the pin sheets. There was a problem in the production of films that are likely to occur.
Conventional tenter type transport devices for films tend to cause production loss due to problems such as breakage in the shape of a long hole in the width direction of the film at the hole where the pin is entrapped, and generation of wrinkles. At the same time, the production efficiency was lowered, and it was not satisfactory for users.

Japanese Patent Laid-Open No. 11-254521 JP 09-073315 A

  The present invention uses a polyimide film as a base film which is a polymer film excellent in flatness and homogeneity suitable as a base material for electronic components, and having excellent heat resistance with little warping and curling even when processed at high temperature. A film that is suitable for the production of a polymer film, particularly a polyimide film, for providing a laminated sheet obtained by laminating a metal foil on the adhesive sheet, and a printed wiring board obtained by circuit processing of the laminated metal sheet. Since the portion stabbed with the pin of the pin contacts the pin sheet and directly receives the heat from the pin sheet, the temperature difference between the center and the end of the film becomes large in the tenter, and the strength balance is broken, so it breaks. In addition, since the film is in direct contact with the pin sheet, in some cases, the film is fused to the pin sheet, Film holding portion is easily torn when removing the pin after the treatment, and an object thereof is to provide a solution to the manufacturing device and a manufacturing method that leads to the edge chipping and fracture.

That is, this invention is based on the following structures.
1. When a film made of a polymer or a polymer precursor is processed while being transported by a film end fixed tenter, the film end gripping at both ends in the width direction of the film is caused by a large number of pin sheets and individual films. Consists of a large number of pins arranged on the pin sheet, and the pins push the film with a pressing brush roll to pierce the film at both ends and transport the film in a stretched state in the width and / or transport direction A method for producing a polymer film using a tenter type processing unit, wherein the pin sheet has a portion higher than a pin base installed outside in the width direction, and the pin of the pin sheet is installed The pin pedestal has a cavity so that the film is not in contact with the pin pedestal when the film is pressed down with the pressing brush roll and pierced into the pin. The process for producing a polymer film characterized.
2. 2. The method for producing a polymer film as described in 1 above, wherein a hollow area of the pin pedestal is 10% to 50% of the entire pin pedestal on which the pins are installed.
3. 3. The method for producing a polymer film as described in 1 or 2 above, wherein a cavity in the width direction is installed at a position higher than the pin pedestal installed outside in the width direction of the pin sheet.
4). 80% or more of the entire cross-sectional area of the portion higher than the pin pedestal installed higher in the width direction of the pin sheet than the pin pedestal installed in the width direction outer side of the pin sheet 80 The method for producing a polymer film as described in 3 above, wherein the polymer film has a content of% or less.
5. When a film made of a polymer or polymer precursor is processed with a film end fixed tenter, film end gripping at both ends in the width direction of the film is applied to a large number of pin sheets and individual pin sheets. A tenter that is composed of a number of arranged pins, and the pins push the film with a pressing brush roll to pierce the both side ends of the film and convey the film in a stretched state in the width direction and / or the conveyance direction. A polymer film manufacturing apparatus having a processing unit, wherein the pin sheet has a portion higher than a pin pedestal installed outside in the width direction, and the pin pedestal on which the pin of the pin sheet is installed It has a cavity, and when pressing the film with the pressing brush roll and piercing the pin, the film is not brought into contact with the pedestal of the pin. Apparatus for producing a molecular film.

  The polymer film manufacturing apparatus of the present invention is a tenter type processing unit (conveying device) for a polymer film such as a polyimide film, because it is higher than a pin base provided on the outside in the width direction of the pin sheet (for example, a base). In addition, since the film pierced in the pin gripping part does not come into close contact with the pin base of the pin sheet due to the cavity provided in the pin base, direct heat transfer from the pin sheet to the film gripping part is suppressed. As a result, the temperature difference between the film central portion and the grip portion is reduced, and the difference in breaking strength during film transportation can be reduced, resulting in preventing troubles such as film breakage in the tenter. It becomes possible. Further, since the film is held in a state of being lifted from the pedestal of the pins, there is no fusion at the pin pedestal portion of the pin sheet, and the film can be easily removed after the heat treatment. Further, since the pin sheet itself is not contaminated, it is effective from the viewpoint of maintenance of the apparatus. It is also effective in solving problems such as being unable to obtain a high-quality film for the above reasons, and it is easy to obtain a polymer film such as a high-quality polyimide film, contributing to the productivity of polymer film production, It is extremely effective industrially as a method for producing a polymer film and as a device for producing a polymer film.

In the present invention, the polymer film includes a film made of a high melting point or non-melting polymer such as polyamideimide, polyimide, cellulose acetate, polycarbonate, polyvinyl chloride, and aramid.
The polymer film of the present invention is cast 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 particularly 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, 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′-diamino 5,5′-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′- Amino-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 Some or all of the hydrogen atoms on the aromatic ring in benzonitrile and the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, cyano groups, or some hydrogen atoms of alkyl groups or alkoxyl groups. Or the aromatic diamine etc. which were substituted by the C1-C3 halogenated alkyl group or alkoxyl group by which all were substituted by the halogen atom are mentioned.

As aromatic tetracarboxylic acids that can be preferably used in the polyimide film of 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 are used. Carboxylic 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 mass 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 mass 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 dl / g or more, and more preferably 4.0 dl / g 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 μm 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 film made of a precursor thereof is subjected to a treatment such as a heat treatment with a film end fixing type tenter, the film end gripping at both ends in the width direction of the film is a large number. Consists of a pin sheet and a large number of pins arranged on each pin sheet. The pins are pierced at both ends of the film with a presser brush roll, and the film is transported in a stretched state in the width direction and / or the transport direction. In the polymer film manufacturing method having a tenter type processing section, the shape of the portion higher than the pin pedestal installed outside in the width direction of the pin sheet is not particularly limited, and the pin pedestal is a surface in which the pin is implanted It only needs to have a function that the film is higher in position and the film does not contact the pin base. For example, the outside of the pin sheet in the width direction (pin implantation) It may be a base that is high only in that position and is in contact with the film only at that position, or a pin seat in which the pin base is inclined outward in the width direction. In this case, the shape and size of the table are preferably (1) the height of the table is low in the range of 3 mm or more and 8 mm or less from the tip of the pin, more preferably in the range of 4 mm or more and 6 mm or less. If the height of the base is less than 3 mm below the tip of the pin, the depth of the pin that pierced both ends of the film is shallow, and the frequency of the film coming off from the pin in the subsequent heat treatment step is undesirably high, In addition, if the height of the base is lower than 8 mm from the tip of the pin, it becomes a large resistance when the film is removed from the pin sheet after heat treatment, which leads to tearing of both ends of the worst film. There.

  (2) The height of the base is higher in the range of 1 mm to 5 mm than the pedestal on which the pins are installed, more preferably in the range of 2 mm to 3 mm, and the film on the pin sheet At the time of gripping, the pin insertion depth of the film by the presser brush roll is stably determined, and a direct heat transfer suppression effect from the pin sheet to the film gripping portion is manifested. As a result, the temperature between the film center and the gripping portion is exhibited. The difference is reduced, and the difference in breaking strength during film conveyance is reduced. As a result, troubles such as film breakage during peeling of the film from the pin sheet in the tenter and after the heat treatment in the tenter can be reduced. On the other hand, if the height of the base is less than 1 mm from the pedestal on which the pins are installed, the direct heat transfer suppression effect from the pin sheet to the film gripping portion is reduced. The temperature difference with the gripping part becomes large, and the difference in breaking strength during film conveyance becomes large, resulting in troubles such as film breakage in the tenter, which is not preferable. If it is higher than 5 mm than the pedestal, it is not preferable because it promotes contamination of the pin sheet itself in the heat treatment step. Further, (3) it is preferable that the periphery of the table is chamfered, and if the chamfering is not performed, the film in contact with the periphery of the table is not preferable. (4) Providing a cavity in the pedestal on which the pins are installed has a direct heat transfer suppression effect from the pin sheet to the film, and as a result, the temperature difference between the film center and the grip is small. Thus, the difference in breaking strength during film conveyance is reduced, and as a result, it is effective in preventing troubles such as film breaking in the tenter, which is essential in the present invention. When the pin pedestal has a hollow area of 10% or more and 50% or less of the entire pin pedestal where the pin is installed, the effect is hardly manifested when it is less than 10%, and exceeds 50%. In this case, an undesirable phenomenon is observed in the mechanical stability of the pin sheet itself, that is, in maintaining the flatness.

Moreover, it is a preferable aspect in the manufacturing apparatus and the manufacturing method of the polymer film of the present invention to install a cavity in the width direction at a position higher than the pin pedestal installed on the outer side in the width direction of the pin sheet, than the pin pedestal. It has the effect of suppressing direct heat transfer from a high part to the film. As a result, the temperature difference between the film center and the grip is reduced, and the difference in breaking strength during film transport is reduced, resulting in the tenter. This is effective in preventing troubles such as film breakage. 80% or more of the entire cross-sectional area of the portion higher than the pin pedestal installed higher in the width direction of the pin sheet than the pin pedestal installed in the width direction outer side of the pin sheet 80 % Is less than 20%, and if it is less than 20%, the effect is hardly manifested. If it exceeds 80%, the mechanical stability of the pin base itself installed on the outside in the width direction of the pin sheet, that is, the film An undesirable phenomenon is observed in maintaining the distance between the pin base and the pin base.
Examples of these preferable pin sheets are shown in FIGS. 1 and 3, for example.

When the polymer film of the present invention or a film made of a precursor thereof is subjected to a treatment such as a heat treatment with a film end fixing type tenter, the film end gripping at both ends in the width direction of the film is a large number. Consists of a pin sheet and a large number of pins arranged on each pin sheet. The pins are pierced at both ends of the film with a presser brush roll, and the film is transported in a stretched state in the width direction and / or the transport direction. In a polymer film manufacturing method or manufacturing apparatus having a tenter type processing unit, a hair material made of a material having a melting point or softening point of 150 ° C. or higher and a tensile modulus of elasticity of 4 GPa or higher at the time when the pins pierce both side ends of the film It is also preferable to use a means for piercing the film end into the pin with a member having a brush. A member having a brush made of a bristle material having a melting point or softening point of 150 ° C. or higher and a tensile elastic modulus of 4 GPa or higher is not particularly limited, but a brush roll provided with a brush on a cylindrical plane circumference can be preferably used. .
A brush made of a bristle material having a melting point or softening point of 150 ° C. or more and a tensile modulus of elasticity of 4 GPa or more has the properties so that the film can be pierced uniformly and its function deteriorates even when used for a long time. Is extremely small. When a material having no physical properties is used, the above two points cannot be satisfied at the same time.
A brush made of a bristle material having a melting point or softening point of 150 ° C. or higher and a tensile elastic modulus of 4 GPa or higher is not particularly limited as long as it has this physical property. For example, a high elastic modulus polymer fiber , Carbon fiber, glass fiber, and the like, and polymer materials such as polymer fibers are more preferable, and aromatic polyamides such as Cornex are preferable.

As described above, the pin tenter gripping portion according to the present invention includes a large number of pin sheets and a large number of pins arranged on each pin sheet, as shown in FIG.
In the present invention, as a preferred embodiment, a cooling means is provided at a position immediately before the film heat treatment is finished and the pin or pin sheet turns and returns to the position where film gripping is started. When the film is sufficiently cooled and the film is pierced at both ends by the pins, the film holding uniformity is maintained, and the holes are enlarged or broken in the width direction or the conveying direction of the film at the holes where the pins are entrapped. Is a manufacturing apparatus equipped with cooling means that can suppress the distortion of the entire film and reduce film thickness unevenness, and uses this apparatus. As the cooling means, either air cooling or water cooling may be used, and a refrigerant other than air or water may be used. From the viewpoint of cooling efficiency, it is preferable to use a liquid refrigerant. Further, considering that the tenter itself is heated above the ignition point of a general organic solvent, it is most preferable to use a cooling means based on water cooling specifications.
By providing this cooling means, when the pin and the pin sheet start gripping both ends of the film and start conveyance, the pin etc. is maintained at a high temperature when it is heated to a high temperature such as one end heat treatment temperature such as 450 ° C. and there is no cooling means. In the piercing of both ends of the film with this high-temperature pin, it is difficult to maintain uniformity of film gripping, and the hole expands or breaks in the film width direction or the conveyance direction at the hole where the pin is bitten. Can easily occur, and problems such as an increase in distortion in the entire film and an increase in film thickness unevenness can be solved to some extent.
Furthermore, in the present invention, as a preferred embodiment, in the pin arrangement of the pin tenter, the individual pins arranged on the innermost side in the film width direction during film conveyance are mutually different from each other in the individual pin sheet in the film conveyance direction. It is preferable that the pin sheets are all arranged at equal intervals.

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, the polymer was dissolved using N, N-dimethylacetamide and measured.)

2. The thickness of the polyimide film The thickness was measured using a micrometer (Millitron 1254D manufactured by Fine Reef).

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 (registered trademark), 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, Tensile rupture strength and tensile rupture elongation were measured.

4). Film linear expansion coefficient (CTE)
The expansion / contraction rate was measured under the following conditions, and the range from 30 to 300 ° C. was divided at 15 ° C. intervals and obtained from the average value of the expansion / contraction rate / temperature of each divided range.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

5. Film melting point, glass transition temperature A sample was subjected to DSC measurement under the following conditions, and a melting point (melting peak temperature Tpm) and a glass transition point (Tmg) were determined under the following measurement conditions in accordance with JIS K7121.
Device name: DSC3100S manufactured by MAC Science
Pan ： Aluminum pan (non-airtight)
Sample mass: 4mg
Temperature rising start temperature: 30 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Argon

6). Thermal Decomposition Temperature of Film The thermal decomposition temperature was defined as a 5% mass loss after TGA measurement (thermobalance measurement) of a fully dried sample under the following conditions.
Device name: TG-DTA2000S manufactured by MAC Science
Pan ： Aluminum pan (non-airtight)
Sample mass: 10 mg
Temperature rising start temperature: 30 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Argon

[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 dl / g.

[Reference Example 2]
Nitrogen introduction tube, thermometer, vessel wetted part equipped with stirring rod, and infusion pipe were replaced with nitrogen in the reaction vessel 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 dl / g.

[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 dl / g.

[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 diphenyltetracarboxylic 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. The reduced viscosity (ηsp / C) was 4.5 dl / g.

[Examples 1 to 4]
The polyamic acid solution obtained in Reference Examples 1 to 4 was coated on the non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater (gap: 150 μm, coating width). 1240 mm), and dried at 90 ° C. for 60 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 21 μm and a width of 1200 mm.

These obtained green films were subjected to a heat treatment through a pin tenter having a structure in which pins are implanted in a pin sheet having a table installed outside in the width direction shown in FIG. The pins are arranged so that the pin spacing is constant when the pin sheets are aligned, the pin height from the pin base is 8 mm, and the height of the base installed outside the pin sheet in the width direction is the pin base And 2 mm higher than the tip of the pin and 6 mm lower than the tip of the pin, and the pin sheet spacing is 1140 mm. The length of the pin sheet in the longitudinal direction is 95 mm, the length in the width direction is 35 mm, the length in the longitudinal direction of the table set outside the width direction of the pin sheet is 95 mm, and the length in the width direction is 15 mm. There was chamfering around the base. Further, a cavity corresponding to 25% of the entire pin base was provided between the pins of the pin base.
The heat treatment settings for the tenter are as follows. The first stage was heated at 200 ° C. for 5 minutes and the heating rate was 4 ° C./second, and the second stage was heated at 450 ° C. for 5 minutes under two conditions to proceed the imidization reaction. Then, it cooled to room temperature in 5 minutes, cut off the part with the poor planarity of the both ends of a film with a slitter, wound up in roll shape, and obtained each polyimide film of Examples 1-4 which exhibits brown. Table 1 shows the measurement results such as the conveyance state during the heat treatment and the characteristics of the obtained polyimide film.
The flatness and effective width of the film were defined as follows.
First, the obtained film was spread on a surface plate having a clean surface, and a portion where a space was left between the surface plate due to undulation at the end of the film was regarded as a portion having poor flatness. The ends of the film were not lifted from the surface of the platen, and both ends of the film were cut until the entire film was in close contact with the platen, and the film width at that time was defined as the effective width.
Moreover, the pin tearing measured the film tearing width in a pin part with a ruler in the part about 10m from the head of a film.

[Comparative Examples 1-4]
The polyamic acid solutions of Reference Examples 1 to 4 were applied and dried on a support in the same manner as in Examples, and the polyamic acid film that became self-supporting after drying was peeled off from the support, and each green having a thickness of 21 μm. A film was obtained.
The obtained green film was gripped at both ends by a pin tenter having a needle-like pin implanted in a pin sheet not provided with a base or a cavity as shown in FIG. The polyimide films of Comparative Examples 1 to 4 exhibiting brown color were obtained by cutting off portions having poor flatness at both ends of the film with a slitter, winding up into a roll shape, and giving a brown color. Table 1 shows the results such as the conveyance state during the heat treatment and the characteristics of the obtained polyimide film. The length of the pin sheet in the longitudinal direction is 95 mm, the length in the width direction is 40 mm, and the pin height from the pin base is 8 mm.
As a result, in the comparative example, the width of the portion having poor flatness at the film edge is wide, and as a result, the effective width is narrow. Also, the difference between the left and right film thickness is large, suggesting that the uniformity of the film is not good.

[Examples 5 to 8]
The polyamic acid solution obtained in Reference Examples 1 to 4 was coated on a stainless steel endless belt using a die coater (coating width 1240 mm) and dried at 110 ° C. for 40 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 43 μm and a width of 1200 mm.
These green films thus obtained were passed through a pin tenter having a structure in which pins were planted in a pin sheet having a table installed on the outside in the width direction as shown in FIG. 3, and in the same manner as in Examples 1 to 4 below, The imidization reaction was advanced by heat treatment. Then, it cooled to room temperature in 5 minutes, cut off the part with the poor planarity of the both ends of a film with a slitter, wound up in roll shape, and obtained each polyimide film of Examples 5-8 which exhibits brown. The measurement results such as the properties of the obtained polyimide film are shown in Table 1. The pins are arranged so that the pin spacing is constant when the pin sheets are aligned, the pin height from the pin base is 8 mm, and the height of the base installed outside the pin sheet in the width direction is the pin base 3 mm higher than the tip of the pin and 5 mm lower than the tip of the pin, and the pin sheet spacing is 1140 mm. The length of the pin sheet in the longitudinal direction is 95 mm, the length in the width direction is 35 mm, the length in the longitudinal direction of the table set outside the width direction of the pin sheet is 95 mm, and the length in the width direction is 15 mm. There was chamfering around the base. Further, a cavity corresponding to 29% of the entire pin base was provided between the pins of the pin base. In addition, a cavity corresponding to 38% of the entire cross-sectional area was provided in the base installed outside in the width direction of the pin sheet.

  As described above, in the present invention, the film is less likely to be fused or scorched on the pin sheet, stable transportability is obtained, and a smooth peeling state is obtained even when the film is peeled off from the pin sheet. In addition, since the film can be stably conveyed, it is difficult to tear or break the film, and it is possible to form a film with a wide effective width and less waste. Further, the obtained film has a quality in the width direction and a film thickness. The manufacturing method and the manufacturing apparatus are industrially significant as casting film forming methods for polyimide films, polybenzazole films, cellulose-based films, polyamide films, polyamideimide films, and the like. is there.

The outline of the pin sheet | seat which provided the base in the width direction outer side of the pin which contacts the film in the tenter type film processing machine of this invention, and provided the cavity in the base of the pin is shown.

The whole outline which shows the outline of the pin sheet which touches the film in the conventional tenter type film processing machine is shown.

The outline of the pin sheet | seat which provided the base in the width direction outer side of the pin which contacts the film in the tenter type film processing machine of this invention, and provided the cavity in the site | part higher than a pin base and a pin base is both shown.

Claims (4)

When a film made of a polymer or a polymer precursor is processed while being transported by a film end fixed tenter, the film end gripping at both ends in the width direction of the film is caused by a large number of pin sheets and individual films. Consists of a large number of pins arranged on the pin sheet, and the pins push the film with a pressing brush roll to pierce the film at both ends and transport the film in a stretched state in the width and / or transport direction A method for producing a polymer film using a tenter type processing section, wherein the pin sheet has a portion higher than a pin pedestal installed outside in the width direction, and the portion has a cavity in the width direction. installed will have, and a cavity provided in the pin seating the pin of the pin seat is installed, when piercing the pin holding down the film with the pressing brush roll, pins The process for producing a polymer film which is characterized in that so as not to contact the film to the base.   2. The method for producing a polymer film according to claim 1, wherein a hollow area of the pin pedestal is 10% or more and 50% or less of the entire pin pedestal on which the pins are installed. 80% or more of the entire cross-sectional area of the portion higher than the pin pedestal installed higher in the width direction of the pin sheet than the pin pedestal installed in the width direction outer side of the pin sheet 80 % Or less, The method for producing a polymer film according to claim 1 or 2 . When a film made of a polymer or a polymer precursor is processed while being transported by a film end fixed tenter, the film end gripping at both ends in the width direction of the film is caused by a large number of pin sheets and individual films. Consists of a large number of pins arranged on the pin sheet, and the pins push the film with a pressing brush roll to pierce the film at both ends and transport the film in a stretched state in the width and / or transport direction It is a polymer film manufacturing apparatus having a tenter type processing unit, wherein the pin sheet has a higher part than the pin base installed outside in the width direction, and a cavity in the width direction is installed in the part It is made by, and has a cavity in pin pedestal pins of the pin seat is installed, when piercing the film hold-down to the pin the pressing brush roll, the pin Apparatus for manufacturing a polymer film which is characterized in that so as not to contact the film to the seat.