JP6539655B2 - Porous imide resin film manufacturing system and porous imide resin film manufacturing method - Google Patents

Description

  The present invention relates to a porous imide resin film manufacturing system, a separator, and a porous imide resin film manufacturing method.

  In a lithium ion battery, which is a type of secondary battery, a separator is disposed between a positive electrode and a negative electrode immersed in an electrolytic solution, and the separator is structured to prevent direct electrical contact between the positive electrode and the negative electrode. There is. A lithium transition metal oxide is used for the positive electrode, and lithium or carbon (graphite) is used for the negative electrode. During charge, lithium ions pass from the positive electrode through the separator and move to the negative electrode, and during discharge, lithium ions pass from the negative electrode through the separator and move to the positive electrode. In recent years, it is known to use a separator made of a porous polyimide film having high heat resistance and high safety as such a separator (see, for example, Patent Document 1).

JP, 2011-111470, A

  The porous polyimide film described above is formed, for example, by coating and forming an unbaked film of polyamic acid or polyimide containing fine particles, baking the unbaked film to form a baked film, and removing fine particles from the baked film. Be done. In the past, there was no production system in which the above three steps were carried out in one line, so the production efficiency of the porous polyimide film was not very high. Therefore, a system with higher manufacturing efficiency has been required.

  In view of the above circumstances, according to the present invention, a porous imide resin film manufacturing system, a separator, and a porous imide resin film manufacturing method capable of improving the manufacturing efficiency of a porous imide resin film Intended to provide a method.

A system for producing a porous imide resin film according to an aspect of the present invention is a production system for producing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed. A coating unit for applying a liquid containing polyimide, polyamideimide or polyamide and particles to a substrate to form a non-sintered film, and firing the unsintered film peeled off from the substrate in the coating unit or outside the coating unit Removal is performed to remove particulates from the fired film by immersing the fired film in the included fired film and the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be resolved. And a winding section which winds up a non-sintered film peeled from the substrate, or a non-sintered film including the substrate, to form a roll body.
A system for producing a porous imide resin film according to an aspect of the present invention is a production system for producing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed. A coating unit for applying a liquid containing polyimide, polyamideimide or polyamide and particles to a substrate to form a non-sintered film, and firing the unsintered film peeled off from the substrate in the coating unit or outside the coating unit Removal is performed to remove particulates from the fired film by immersing the fired film in the included fired film and the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be resolved. And a unit for performing an antistatic process on the fired film from which the fine particles have been removed.
A system for producing a porous imide resin film according to an aspect of the present invention is a production system for producing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed. A coating unit for applying a liquid containing polyimide, polyamideimide or polyamide and particles to a substrate to form a non-sintered film, and firing the unsintered film peeled off from the substrate in the coating unit or outside the coating unit Removal is performed to remove particulates from the fired film by immersing the fired film in the included fired film and the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be resolved. A unit and an etching unit which removes a part of calcination film from which particulates were removed.
A system for producing a porous imide resin film according to an aspect of the present invention is a production system for producing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed. A coating unit for applying a liquid containing polyimide, polyamideimide or polyamide and particles to a substrate to form a non-sintered film, and firing the unsintered film peeled off from the substrate in the coating unit or outside the coating unit Removal is performed to remove particulates from the fired film by immersing the fired film in the included fired film and the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be resolved. a unit, only containing, as a liquid, at least fine particles content is different first and second liquids from each other are used, the coating unit, the first liquid And by applying the second liquid to a substrate to form a green film laminated at least fine particles content is different.
The porous imide resin film production system according to the first aspect of the present invention is a production system for producing a porous imide resin film, which comprises a liquid containing polyamic acid, polyimide, polyamidoimide or polyamide and fine particles. A coating unit for coating a substrate to form a non-sintered film, and a firing unit for firing a non-sintered film peeled off from the substrate in or outside the coating unit to form a fired film containing fine particles, firing And a removal unit for removing particulates from the membrane.

  The separator according to the second aspect of the present invention is a separator formed of a porous imide resin film, and the porous imide resin membrane is the porous imide resin according to the first aspect of the present invention Produced by a membrane manufacturing system.

A method for producing a porous imide resin film according to an aspect of the present invention is a method for producing a porous imide resin film in which a large number of continuous pores penetrating in the film thickness direction are formed, which is a polyamic acid or polyimide Applying a liquid containing polyamide imide or polyamide and fine particles to a substrate and then peeling it from the substrate to form an unbaked film, and firing the unbaked film to form a baked film containing fine particles. Removing the particles from the fired film by immersing the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be degraded; A non-sintered film or a non-sintered film containing a base material is wound up to form a roll body.
A method for producing a porous imide resin film according to an aspect of the present invention is a method for producing a porous imide resin film in which a large number of continuous pores penetrating in the film thickness direction are formed, which is a polyamic acid or polyimide Applying a liquid containing polyamide imide or polyamide and fine particles to a substrate and then peeling it from the substrate to form an unbaked film, and firing the unbaked film to form a baked film containing fine particles. Removing the particles from the fired film by immersing the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be degraded; The antistatic film is applied to the fired film.
A method for producing a porous imide resin film according to an aspect of the present invention is a method for producing a porous imide resin film in which a large number of continuous pores penetrating in the film thickness direction are formed, which is a polyamic acid or polyimide Applying a liquid containing polyamide imide or polyamide and fine particles to a substrate and then peeling it from the substrate to form an unbaked film, and firing the unbaked film to form a baked film containing fine particles. Removing the particles from the fired film by immersing the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be degraded; Remove a portion of the fired film.
A method for producing a porous imide resin film according to an aspect of the present invention is a method for producing a porous imide resin film in which a large number of continuous pores penetrating in the film thickness direction are formed, which is a polyamic acid or polyimide Applying a liquid containing polyamide imide or polyamide and fine particles to a substrate and then peeling it from the substrate to form an unbaked film, and firing the unbaked film to form a baked film containing fine particles. Removing the particles from the fired film by immersing the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles are degradable; The first liquid and the second liquid having different contents of each other are used, and by applying the first liquid and the second liquid to the substrate, at least the content of the particles is different and the lamination is performed. Forming an unbaked film.
The method for producing a porous imide resin film according to the third aspect of the present invention is a method for producing a porous imide resin film, which comprises a polyamic acid, a polyimide, a polyamideimide or a liquid containing a polyamide and fine particles. After applying to the material, peeling from the substrate to form an unbaked film, firing the unbaked film to form a fired film containing fine particles, and removing fine particles from the fired film, Including.

  According to the aspect of the present invention, the production efficiency of the porous imide resin film can be improved.

It is a figure showing an example of the manufacturing system concerning an embodiment of the invention. It is a figure which shows an example of the nozzle provided in the application | coating unit which concerns on this embodiment. It is a perspective view which shows an example of the winding-up part which concerns on this embodiment. It is a perspective view showing an example of a baking unit concerning this embodiment. It is a perspective view showing an example of the removal unit concerning this embodiment. It is a figure which shows an example of the manufacturing process of the imide type-resin film which concerns on this embodiment. It is a figure which shows an example of the manufacturing system which concerns on a modification. It is a figure which shows an example of the manufacturing system which concerns on a modification. It is a figure which shows an example of the manufacturing system which concerns on a modification. It is a figure which shows an example of the manufacturing system which concerns on a modification. It is a figure which shows an example of the etching unit which concerns on a modification. It is a figure showing an example of the winding device concerning a modification. It is a figure showing an example of the separator concerning an embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Hereinafter, the directions in the drawing will be described using the XYZ coordinate system. In this XYZ coordinate system, a plane parallel to the horizontal plane is taken as an XY plane. One direction parallel to the XY plane is described as an X direction, and a direction orthogonal to the X direction is described as a Y direction. Also, the direction perpendicular to the XY plane is referred to as the Z direction. In each of the X direction, the Y direction, and the Z direction, the direction of the arrow in the figure is the + direction, and the direction opposite to the direction of the arrow is the − direction.

  FIG. 1 is a diagram illustrating an example of a manufacturing system SYS. The manufacturing system SYS shown in FIG. 1 is for manufacturing a porous resin film F (porous imide resin film). The manufacturing system SYS includes a coating unit 10 for applying a predetermined coating solution to form an unbaked film FA, a firing unit 20 for firing the unfired film FA to form a fired film FB, and fine particles from the fired film FB. It comprises a removal unit 30 for removing and forming the porous resin film F, and a control device (not shown) for controlling the above units in a comprehensive manner.

  The manufacturing system SYS is configured, for example, in the upper and lower two layers, and the coating unit 10 is disposed on the second floor portion, and the baking unit 20 and the removing unit 30 are disposed on the first floor portion. The baking units 20 and the removing units 30 arranged on the same floor are arranged side by side in the Y direction, for example, but it is not limited to this, for example, arranged side by side in the X direction or the composite direction of X direction and Y direction. It may be arranged.

  The hierarchical structure of the manufacturing system SYS and the arrangement of each unit on each floor are not limited to the above. For example, the coating unit 10 and the baking unit 20 are arranged on the second floor, and the removing unit 30 is on the first floor. It may be arranged. Also, all units may be arranged on the same floor. In this case, each unit may be arranged in one row, or may be arranged in a plurality of rows. Also, all units may be arranged in different hierarchies.

  In the manufacturing system SYS, the unfired film FA is formed in a band shape. On the + Y side of the coating unit 10 (forward in the transport direction of the unbaked film FA), a winding unit 40 is provided for winding the belt-shaped unfired film FA in a roll. A delivery unit 50 for delivering the roll-shaped unbaked film FA toward the baking unit 20 is provided on the −Y side of the baking unit 20 (rear of the unbaked film FA in the transport direction). On the + Y side of the removal unit 30 (forward in the transport direction of the fired film FB), a winding unit 60 is provided for winding the porous resin film F in a roll.

  As described above, in a section (first floor portion) from the delivery unit 50 to the winding unit 60 after passing through the baking unit 20 and the removing unit 30, processing according to a so-called roll-to-roll method is performed. Therefore, in this section, the unbaked film FA, the fired film FB, and the porous resin film F are transported in a continuous state.

[Coating solution]
Here, before describing each unit, a coating solution to be a raw material of the porous resin film F will be described. The coating solution contains a predetermined resin material, fine particles, and a solvent. The predetermined resin material includes, for example, polyamic acid, polyimide, polyamide imide, or polyamide. As the solvent, an organic solvent capable of dissolving these resin materials is used.

  In the present embodiment, two types of coating liquids (a first coating liquid and a second coating liquid) having different fine particle content rates are used as the coating liquid. Specifically, the first coating solution is prepared so that the content of fine particles is higher than that of the second coating solution. Thereby, the strength and flexibility of the unbaked film FA, the fired film FB, and the porous resin film F can be ensured. In addition, by providing a layer with a low content of fine particles, the manufacturing cost of the porous resin film F can be reduced.

  For example, the first coating solution contains the resin material and the fine particles in a volume ratio of 19:81 to 45:65. Further, the resin material and the fine particles are contained in the second coating liquid so as to have a volume ratio of 20:80 to 50:50. However, the volume ratio is set such that the content of the particles of the first coating liquid is higher than the content of the particles of the second coating liquid. The volume of each resin material is a value obtained by multiplying the mass of each resin material by its specific gravity.

  In the above case, if the volume of the fine particles is 65 or more when the entire volume of the first coating solution is 100, the particles are uniformly dispersed, and if the volume of the fine particles is within 81, the particles aggregate. It disperses without doing. Therefore, the pores can be uniformly formed in the porous resin film F. In addition, when the volume ratio of the fine particles is within this range, the removability at the time of forming the unbaked film FA can be secured.

  When the volume of the fine particles is 50 or more when the entire volume of the second coating liquid is 100, the fine particles are uniformly dispersed, and if the volume of the fine particles is within 80, the fine particles do not aggregate. In addition, since a crack or the like does not occur on the surface, it is possible to stably form a porous resin film F having good electrical characteristics.

  The above two types of coating solutions are prepared, for example, by mixing a solvent in which fine particles are dispersed in advance and a polyamic acid, a polyimide, a polyamideimide or a polyamide in an arbitrary ratio. Also, it may be prepared by polymerizing polyamic acid, polyimide, polyamidoimide or polyamide in a solvent in which fine particles are dispersed in advance. For example, it can be produced by polymerizing tetracarboxylic acid dianhydride and diamine in an organic solvent in which fine particles are dispersed in advance to form a polyamic acid, or further imidizing to form a polyimide.

  The viscosity of the coating solution is preferably 300 to 2500 cP finally, more preferably in the range of 400 to 1500 cP, and still more preferably in the range of 600 to 1200 cP. If the viscosity of the coating solution is in this range, it is possible to form a film uniformly.

  When the fine particles and the polyamide acid or the polyimide are dried to form the unbaked film FA in the above-mentioned coating solution, the ratio of the fine particles / polyimide is 2 to 6 (mass ratio) when the material of the fine particles is an inorganic material described later. Fine particles and polyamic acid or polyimide may be mixed to obtain It is more preferable to set it as 3-5 (mass ratio). When the material of the fine particles is an organic material described later, the fine particles and the polyamic acid or polyimide may be mixed so that the ratio of fine particles / polyimide is 1 to 3.5 (mass ratio). It is more preferable to set it as 1.2-3 (mass ratio). Further, it is preferable to mix the fine particles and the polyamic acid or the polyimide so that the volume ratio of the fine particles / polyimide becomes 1.5 to 4.5 when forming the unbaked film FA. It is more preferable to set it as 1.8-3 (volume ratio). In the case of the unbaked film FA, if the mass ratio or volume ratio of the fine particles / polyimide is equal to or more than the lower limit value, it is possible to obtain holes of an appropriate density as a separator. The film can be stably formed without causing problems such as internal cracks. Also in the case where the resin material is polyamideimide or polyamide instead of polyamide acid or polyimide, the mass ratio is the same as above.

Each resin material will be specifically described below.
<Polyamic acid>
As the polyamic acid used in the present embodiment, one obtained by polymerizing any tetracarboxylic acid dianhydride and diamine can be used without particular limitation. The use amount of tetracarboxylic acid dianhydride and diamine is not particularly limited, but it is preferable to use 0.50 to 1.50 mol of diamine per 1 mol of tetracarboxylic acid dianhydride, and 0.60 to 1. It is more preferable to use 30 mol, and it is particularly preferable to use 0.70 to 1.20 mol.

  The tetracarboxylic acid dianhydride can be suitably selected from the tetracarboxylic acid dianhydride conventionally used as a synthetic raw material of a polyamic acid. The tetracarboxylic acid dianhydride may be either an aromatic tetracarboxylic acid dianhydride or an aliphatic tetracarboxylic acid dianhydride, but from the viewpoint of the heat resistance of the resulting polyimide resin, an aromatic tetracarboxylic acid dianhydride may be used. It is preferred to use carboxylic dianhydrides. You may use tetracarboxylic dianhydride in combination of 2 or more type.

Preferred specific examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxy) Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic acid dianhydride, 2,2,6,6-biphenyltetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2) , 3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2 -Bis (2,3-dicarboxypheny 1) 1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid dianhydride, 4,4- (p-phenylenedioxy) diphthalic acid Acid dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride Objects 2, 3, 6, 7- Anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, 9,9-bisbisphthalic anhydride fluorene, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid Anhydride etc. are mentioned. Examples of aliphatic tetracarboxylic acid dianhydrides include ethylene tetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexane tetracarboxylic acid dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, etc. are mentioned. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride and pyromellitic acid dianhydride are preferable in terms of cost, availability, and the like. Moreover, these tetracarboxylic dianhydrides can also be used individually or in mixture of 2 or more types.

  The diamine can be suitably selected from the diamine conventionally used as a synthetic raw material of a polyamic acid. The diamine may be an aromatic diamine or an aliphatic diamine, but from the viewpoint of the heat resistance of the resulting polyimide resin, an aromatic diamine is preferred. These diamines may be used in combination of two or more.

  Examples of aromatic diamines include diamino compounds in which one or 2 to 10 phenyl groups are bonded. Specifically, phenylenediamine and derivatives thereof, diaminobiphenyl compounds and derivatives thereof, diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalene and derivatives thereof, aminophenylaminoindane and derivatives thereof, diaminotetraphenyl A compound and a derivative thereof, a diaminohexaphenyl compound and a derivative thereof, and a cardo type fluorenedamine derivative.

  Phenylenediamine is m-phenylenediamine, p-phenylenediamine and the like, and as the phenylenediamine derivative, diamine having an alkyl group such as methyl group and ethyl group bonded thereto, for example, 2,4-diaminotoluene, 2,4-triphenylene And the like.

  The diaminobiphenyl compound is one in which two aminophenyl groups are bound to each other by phenyl groups. For example, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl and the like.

  The diaminodiphenyl compound is one in which two aminophenyl groups are linked to each other via another group. The bond is an ether bond, a sulfonyl bond, a thioether bond, a bond by an alkylene or its derivative group, an imino bond, an azo bond, a phosphine oxide bond, an amide bond, an ureylene bond and the like. The alkylene bond is one having about 1 to 6 carbon atoms, and the derivative group is one in which at least one hydrogen atom of the alkylene group is substituted with a halogen atom or the like.

  Examples of diaminodiphenyl compounds include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone 3,4'-diaminodiphenyl ketone, 2,2-bis (p-aminophenyl) propane, 2,2'-bis (p-aminophenyl) hexafluoropropane, 4-methyl-2,4-bis ( p-Aminophenyl) -1-pentene, 4-methyl-2 4-bis (p-aminophenyl) -2-pentene, iminodianiline, 4-methyl-2,4-bis (p-aminophenyl) pentane, bis (p-aminophenyl) phosphine oxide, 4,4 ' -Diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-diaminodiphenylamide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 3-Bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl Sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophen) ) Phenyl] hexafluoropropane, and the like.

  Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenylether are preferable in terms of cost, availability, and the like.

  The diaminotriphenyl compound is one in which two aminophenyl groups and one phenylene group are both bonded via another group, and the other groups are selected to be the same as the diaminodiphenyl compound. Examples of diaminotriphenyl compounds include 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4-bis (p-aminophenoxy) benzene and the like. be able to.

  As examples of diaminonaphthalene, mention may be made of 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.

  Examples of aminophenylaminoindanes include 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindane.

  Examples of diaminotetraphenyl compounds include 4,4'-bis (p-aminophenoxy) biphenyl, 2,2'-bis [p- (p'-aminophenoxy) phenyl] propane, 2,2'-bis [2 Examples include p- (p'-aminophenoxy) biphenyl] propane, 2,2'-bis [p- (m-aminophenoxy) phenyl] benzophenone and the like.

  9,9-bis aniline fluorene etc. are mentioned to a cardo type flu orange amine derivative.

  The aliphatic diamine preferably has, for example, about 2 to 15 carbon atoms, and specific examples thereof include pentamethylenediamine, hexamethylenediamine, heptamethylenediamine and the like.

  In addition, the compound by which the hydrogen atom of these diamine was substituted by the at least 1 sort (s) of substituent selected from the group of a halogen atom, a methyl group, a methoxy group, a cyano group, a phenyl group etc. may be sufficient.

  There is no restriction | limiting in particular in the means to manufacture the polyamic acid used by this embodiment, For example, well-known methods, such as the method of making an acid and a diamine component react in an organic solvent, can be used.

  The reaction of tetracarboxylic dianhydride with diamine is usually carried out in an organic solvent. The organic solvent used for the reaction of tetracarboxylic acid dianhydride and diamine can dissolve tetracarboxylic acid dianhydride and diamine, in particular, as long as it does not react with tetracarboxylic acid dianhydride and diamine It is not limited. The organic solvents can be used alone or in combination of two or more.

  Examples of the organic solvent used for the reaction of tetracarboxylic acid dianhydride and diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, N-diethylformamide, N-methylcaprolactam, N, N, N ', N'- tetramethylurea; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone Lactone-based polar solvents such as γ-caprolactone and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, Ethers such as cellosolve acetate; include phenolic solvents cresols, and the like. These organic solvents can be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, It is desirable for content of the produced | generated polyamic acid to be 5-50 mass%.

  Among these organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-, in view of the solubility of the formed polyamic acid. Nitrogen-containing polar solvents such as diethylformamide, N-methylcaprolactam, N, N, N ', N'-tetramethylurea are preferred.

  The polymerization temperature is generally −10 to 120 ° C., preferably 5 to 30 ° C. The polymerization time varies depending on the raw material composition used, but is usually 3 to 24 hours (hour). In addition, the intrinsic viscosity of the organic solvent solution of the polyamic acid obtained under such conditions is preferably in the range of 1000 to 100,000 cP (centipoise), and more preferably in the range of 5000 to 70,000 cP.

<Polyimide>
As the polyimide used in the present embodiment, any soluble polyimide that can be dissolved in the organic solvent used in the coating solution is not limited to the structure or molecular weight, and any known polyimide can be used. The polyimide may have a condensable functional group such as a carboxy group in the side chain or a functional group that promotes a crosslinking reaction or the like at the time of firing.

  Use of a monomer for introducing a flexible bending structure into the main chain to obtain a polyimide soluble in an organic solvent, for example, ethylene diamine, hexamethylene diamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, Aliphatic diamines such as 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzanilide, etc. Aromatic diamine; polyoxyalkylene diamine such as polyoxyethylene diamine, polyoxypropylene diamine, polyoxybutylene diamine, etc .; polysiloxane diamine; 2,3,3 ', 4'-oxydiphthalic anhydride, 3,4,3', 4'- oxydiphthalic anhydride, 2, 2-bis (4- Rokishifeniru) propane dibenzoate-3,3 ', use of such 4,4'-tetracarboxylic dianhydride is valid. In addition, use of a monomer having a functional group that improves the solubility in organic solvents, for example, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2-trifluoromethyl-1,4 It is also effective to use fluorinated diamines such as phenylenediamine. Furthermore, in addition to the monomer for improving the solubility of the above-mentioned polyimide, the same monomers as those described in the column of the above-mentioned polyamic acid can be used in combination as long as the solubility is not inhibited.

  There is no particular limitation on the means for producing a polyimide soluble in an organic solvent used in the present invention. For example, known methods such as chemical imidization or heating imidization of polyamic acid and dissolution in organic solvent are used. be able to. As such polyimides, aliphatic polyimides (all aliphatic polyimides), aromatic polyimides and the like can be mentioned, and aromatic polyimides are preferable. As an aromatic polyimide, one obtained by thermally or chemically ring-closing a polyamide acid having a repeating unit represented by the formula (1) or one obtained by dissolving a polyimide having a repeating unit represented by the formula (2) in a solvent Good. In the formula, Ar represents an aryl group.

<Polyamide imide>
As the polyamideimide used in the present embodiment, known polyamideimides can be used without being limited to the structure and molecular weight as long as they are soluble polyamideimides that can be dissolved in the organic solvent used in the coating solution. The polyamide imide may have a functional group capable of condensation such as a carboxy group in the side chain or a functional group that promotes a crosslinking reaction and the like at the time of firing.

  The polyamide imide used in the present embodiment is one obtained by reacting any of trimellitic anhydride and diisocyanate, or a precursor polymer obtained by reacting any reactive derivative of trimellitic anhydride and diamine. It is possible to use those obtained by the reaction without particular limitation.

As the optional anhydrous trimellitic acid or a reactive derivative thereof, for example, trimellitic anhydride, trimellitic anhydride halide such as trimellitic anhydride chloride, and a trimellitic anhydride ester and the like.

  Examples of diisocyanates include metaphenylene diisocyanate, p-phenylene diisocyanate, 4,4′-oxybis (phenylisocyanate), 4,4′-diisocyanatediphenylmethane, bis [4- (4-isocyanatophenoxy) phenyl] sulfone, 2'-bis [4- (4-isocyanate phenoxy) phenyl] propane etc. are mentioned.

  As a diamine, the thing similar to what was illustrated in description of the said polyamic acid is mentioned.

<Polyamide>
The polyamide is preferably a polyamide obtained from a dicarboxylic acid and a diamine, and particularly preferably an aromatic polyamide.

  As dicarboxylic acids, maleic acid, fumaric acid, itaconic acid, methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, phthalic acid, isophthalic acid, terephthalic acid, and diphenic acid Etc.

  As a diamine, the thing similar to what was illustrated in description of the said polyamic acid is mentioned.

<Particles>
Subsequently, fine particles will be described. The fine particles having, for example, a high sphericity and a small particle size distribution index are used. Such fine particles are excellent in dispersibility in a liquid, and do not aggregate each other. The particle size (average diameter) of the fine particles can be set to, for example, about 100 to 2000 nm. By using the fine particles as described above, the pore diameter of the porous resin film F obtained by removing the fine particles in a later step can be made uniform. Therefore, the electric field applied to the separator formed by the porous resin film F can be made uniform.

The material of the fine particles is not particularly limited as long as it is insoluble in the solvent contained in the coating solution and can be removed from the porous resin film F in a later step, and a known material is adopted. can do. For example, inorganic materials include metal oxides such as silica (silicon dioxide), titanium oxide, and alumina (Al ₂ O ₃ ). Further, as the organic material, organic polymer fine particles such as high molecular weight olefin (polypropylene, polyethylene etc.), polystyrene, epoxy resin, cellulose, polyvinyl alcohol, polyvinyl butyral, polyester, polymethyl methacrylate, polyether etc. may be mentioned. Further, examples of the fine particles include colloidal silica such as (monodispersed) spherical silica particles, calcium carbonate and the like. In this case, the pore diameter of the porous resin film F can be made more uniform.

  Further, the fine particles contained in the first coating solution and the fine particles contained in the second coating solution may have the same values of the sphericity, the particle size, the material and the like, or may be different from each other. The fine particles contained in the first coating solution preferably have a particle size distribution index smaller or the same as the fine particles contained in the second coating solution. Alternatively, it is preferable that the fine particles contained in the first coating solution have a sphericity smaller than or the same as the fine particles contained in the second coating solution. The fine particles contained in the first coating solution preferably have a smaller particle size (average diameter) than the fine particles contained in the second coating solution, and in particular, the fine particles contained in the first coating solution are 100 to 1000 nm. The particle diameter is more preferably 100 to 600 nm, and the number of fine particles contained in the second coating solution is preferably 500 to 2000 nm (more preferably 700 to 2000 nm). By using particles smaller than the particle diameter of the fine particles contained in the second coating solution for the particle diameter of the fine particles contained in the first coating film, the ratio of openings of the pores on the surface of the porous resin film F can be made high and uniform. . In addition, the strength of the film can be enhanced as compared to the case where the entire porous resin film F has the particle diameter of the fine particles contained in the first application liquid.

  In addition to the predetermined resin material, the fine particles, and the solvent, the coating solution contains various additives such as a releasing agent, a dispersing agent, a condensing agent, an imidizing agent, and a surfactant, if necessary. It may be

[Coating unit]
The application unit 10 includes a transport unit 11, a first nozzle 12, a second nozzle 13, a drying unit 14, and a peeling unit 15.
The transport unit 11 includes a transport base (base) S, a base delivery roller 11 a, support rollers 11 b to 11 d, a base winding roller 11 e, and a discharge roller 11 f.

  The transport substrate S is formed in a band shape. The transport substrate S is delivered from the substrate delivery roller 11a, spanned by the support rollers 11b to 11d so as to have a tension, and is taken up by the substrate winding roller 11e. As a material of conveyance base material S, although polyethylene terephthalate (PET) etc. are mentioned, for example, it is not limited to this and metal materials, such as stainless steel, may be used.

  Each of the rollers 11 a to 11 f is formed, for example, in a cylindrical shape, and is disposed in parallel to the X direction. In addition, each roller 11a-11f is not restricted to parallel arrangement | positioning to a X direction, At least one may be arrange | positioned inclining with respect to a X direction. For example, the rollers 11a to 11f may be disposed in parallel to the Z direction so that the height positions in the Z direction are the same. In this case, the transport substrate S moves along the horizontal plane in a state of standing with respect to the horizontal plane (XY plane).

  The substrate delivery roller 11a is disposed in a state in which the transport substrate S is wound. The support roller 11 b is disposed on the + Z side of the substrate delivery roller 11 a and is disposed on the −Y side of the substrate delivery roller 11 a. Further, the support roller 11c is disposed on the + Z side of the support roller 11b and is disposed on the + Y side of the support roller 11b. By the arrangement of these three rollers (substrate delivery roller 11a and support rollers 11b and 11c), the transport substrate S is supported on the surface including the -Y side end of the support roller 11b.

  Further, the support roller 11 d is disposed on the + Y side of the support roller 11 c and on the −Z side of the support roller 11 c. In this case, by the arrangement of the three rollers of the support rollers 11b to 11d, the transport substrate S is supported on the surface including the + Z-side end of the support roller 11c.

  The support roller 11d may be disposed at a height position substantially equal to the height position (position in the Z direction) of the support roller 11c. In this case, the transport substrate S is sent from the support roller 11c to the support roller 11d in the + Y direction in a state substantially parallel to the XY plane.

  The substrate winding roller 11 e is disposed on the −Z side of the support roller 11 d. The transport substrate S is fed in the −Z direction from the support roller 11 d toward the substrate winding roller 11 e. The carry-out roller 11 f is disposed on the + Y side and the −Z side of the support roller 11 d. The carry-out roller 11 f sends the unsintered film FA formed by the drying unit 14 in the + Y direction. The unbaked film FA is carried out of the coating unit 10 by the carry-out roller 11 f.

  In addition, said roller 11a-11f is not restricted to a cylindrical shape, A taper-shaped crown may be formed. In this case, it is effective for the deflection correction of the rollers 11a to 11f, and the transport base S or the unsintered film FA described later can uniformly contact the rollers 11a to 11f. In addition, radial type crowns may be formed on the rollers 11a to 11f. In this case, it is effective to prevent the meandering of the transport base S or the unbaked film FA. In addition, a concave of a concave shape (a portion in which a central portion in the X direction is concavely curved) may be formed on the rollers 11 a to 11 f. In this case, it is possible to transport the transport substrate S or the unbaked film FA while applying tension in the X direction, which is effective in preventing the occurrence of wrinkles. Similarly to the above, the following rollers may be configured to have a crown of a tapered type, a radial type, a concave type, or the like.

  FIG. 2A is a perspective view showing an example of the first nozzle 12. As shown in FIGS. 1 and 2A, the first nozzle 12 forms a coating film of the first coating liquid Q1 (hereinafter, referred to as a first coating film F1) on the transport base S. The first nozzle 12 has a discharge port 12a that discharges the first application liquid Q1. The discharge port 12 a is formed, for example, such that the longitudinal direction is substantially the same as the dimension of the transport substrate S in the X direction.

  The first nozzle 12 is disposed at the discharge position P1. The discharge position P1 is a position on the support roller 11b in the -Y direction. The first nozzle 12 is arranged to be inclined such that the discharge port 12 a faces the + Y direction. Therefore, the discharge port 12a is directed to a portion of the transport base S supported by the end of the support roller 11b on the -Y side. The first nozzle 12 discharges the first coating liquid Q1 from the discharge port 12a along the horizontal direction to the transport base S.

  FIG. 2 (b) is a perspective view showing an example of the second nozzle 13. As shown in FIGS. 1 and 2B, the second nozzle 13 overlaps the first coating film F1 on the transport base S to form a coating film of the second coating solution Q2 (hereinafter referred to as a second coating film F2). Form). The second nozzle 13 has a discharge port 13a for discharging the second application liquid Q2. The discharge port 13a is formed, for example, so that the longitudinal direction is substantially the same as the dimension of the transport base S in the X direction.

  The second nozzle 13 is disposed at the discharge position P2. The discharge position P2 is a position on the support roller 11c in the + Z direction. The second nozzle 13 is disposed such that the discharge port 13 a faces in the −Z direction. Therefore, the discharge port 13a is directed to a portion of the transport base S supported by the + Z side end of the support roller 11c. The second nozzle 13 discharges the second coating liquid Q2 from the discharge port 13a along the gravity direction to the transport base S.

  The first nozzle 12 and the second nozzle 13 may be movable in at least one of the X direction, the Y direction, and the Z direction. Also, the first nozzle 12 and the second nozzle 13 may be provided rotatably around an axis parallel to the X direction. Further, the first nozzle 12 and the second nozzle 13 are disposed at the standby position (not shown) when not discharging the application liquid, and move from the standby position to the above-described discharge positions P1 and P2 when discharging the application liquid. You may In addition, a portion that performs the preliminary discharge operation of the first nozzle 12 and the second nozzle 13 may be provided.

  The first nozzle 12 and the second nozzle 13 are connected to a coating liquid supply source (not shown) via connection pipes (not shown) and the like. The first nozzle 12 and the second nozzle 13 are provided with, for example, a holder (not shown) for holding a predetermined amount of coating liquid inside. In this case, the first nozzle 12 and the second nozzle 13 may have a temperature control unit that adjusts the temperature of the liquid material held by the holding unit.

And discharge rate of the coating liquid out paint from the first nozzle 12 or the second nozzle 13, the thickness of the first coating film F1 and the second coating film F2 are each nozzle, each connection pipe (not shown), or The pressure can be adjusted by the pressure of a pump (not shown) connected to a coating liquid supply source (not shown), the transport speed, the position of each nozzle, the distance between the transport substrate S and the nozzle, and the like. The film thickness of the first coating film F1 or the second coating film F2 is, for example, 0.5 μm to 500 μm, respectively.

  When two types of coating solutions (the first coating solution Q1 and the second coating solution Q2) are used as in the present embodiment, the film thickness of the first coating film F1 of the first coating solution Q1 is, for example, 0. It is preferable to adjust in 5 micrometers-10 micrometers, and to adjust the film thickness of 2nd coating film F2 by 2nd coating liquid Q2 in 1 micrometer-50 micrometers, for example.

  A drying unit (not shown) for drying the first coating film F1 may be disposed between the first nozzle 12 and the second nozzle 13. Preferably, the drying unit comprises a heating and drying unit. It is preferable to use a hot air blowing unit or an infrared heater as the heating and drying unit. The heating temperature is, for example, in the range of 50 ° C to 150 ° C, preferably 50 ° C to 100 ° C. By forming the second coating film F2 after drying the first coating film F1, for example, suppressing the particles used in the second coating solution from being mixed with the particles of the first coating film F1 Can.

  As shown in FIG. 1, the drying unit 14 is disposed on the + Y side of the second nozzle 13 and between the support roller 11 c and the support roller 11 d. The drying unit 14 dries the two-layer coating film (the first coating film F1 and the second coating film F2) coated on the transport substrate S to form a non-baked film FA.

  The drying unit 14 has a chamber 14a and a heating unit 14b. The chamber 14a accommodates the transport base S and the heating unit 14b. The heating unit 14 b heats the first coating film F <b> 1 and the second coating film F <b> 2 formed on the transport substrate S. For example, an infrared heater or the like is used as the heating unit 14 b. The heating unit 14 b heats the coating film at a temperature of about 50 ° C. to 100 ° C.

  The peeling part 15 is a part from which the unbaked film FA is peeled from the transport base S. In the present embodiment, the unbaked film FA is peeled off manually by a worker, but the present invention is not limited to this, and may be performed automatically using a manipulator or the like. The unbaked film FA peeled from the transport base S is carried out of the coating unit 10 by the carry-out roller 11 f and sent to the winding unit 40. Further, the transport base S from which the unbaked film FA is peeled off is wound up by the base winding roller 11e.

[Winding unit (1)]
FIG. 3 is a perspective view schematically showing the configuration on the + Y side of the coating unit 10. As shown in FIG.
As shown in FIG. 3, on the + Y side of the coating unit 10, an outlet 10b for unloading the unbaked film FA is provided. The unsintered film FA unloaded from the outlet 10 b is taken up by the winding unit 40.

  The winding portion 40 has a structure in which the shaft member SF is mounted on the bearing 41. The shaft member SF winds up the unsintered film FA unloaded from the outlet 10 b to form a roll body R. The shaft member SF is detachably provided to the bearing 41. When mounted on the bearing 41, the shaft member SF is supported so as to be rotatable around an axis parallel to the X direction. The winding unit 40 has a drive mechanism (not shown) for rotating the shaft member SF mounted on the bearing 41.

  In the winding unit 40, the unbaked film FA is wound so that the surface on the first coated film F1 side of the unbaked film FA is disposed outside. For example, the unsintered film FA is wound up by rotating the shaft member SF counterclockwise in FIG. 1 by the drive mechanism. By removing the shaft member SF from the bearing 41 with the roll body R formed, the roll body R can be moved to another unit.

  In addition, in FIG.1 and FIG.3, although the winding-up part 40 is arrange | positioned independently from the coating unit 10, it does not limit to this. For example, the winding unit 40 may be disposed inside the application unit 10. In this case, the roll body R may be formed by winding the unbaked film FA from the discharge roller 11f (or from the support roller 11d) without arranging the discharge port 10b in the coating unit 10.

[Delivery unit]
FIG. 4 is a perspective view schematically showing the configuration of the baking unit 20 on the -Y side.
As shown in FIG. 4, on the −Y side of the firing unit 20, a loading port 20 a for loading the unfired film FA is provided. The delivery unit 50 delivers the unfired film FA to the loading port 20a.

  The delivery unit 50 is configured such that the shaft member SF can be attached to the bearing 51. The shaft member SF can be used in common with the one mounted on the bearing 41 of the winding unit 40. Therefore, the shaft member SF removed from the winding unit 40 can be attached to the bearing 51 of the delivery unit 50. Thereby, it is possible to arrange the roll body R formed by the winding unit 40 in the delivery unit 50. The bearings 51 and the bearings 41 of the winding unit 40 can be set to have the same height from the floor surface, but may be set at different height positions.

  When mounted on the bearing 51, the shaft member SF is supported so as to be rotatable about an axis parallel to the X direction. The delivery unit 50 has a drive mechanism (not shown) for rotating the shaft member SF attached to the bearing 51. By rotating the shaft member SF clockwise in FIG. 1 by the drive mechanism, the unsintered film FA constituting the roll body R is fed out toward the loading port 20a. Since the unbaked film FA is wound so that the surface of the unbaked film FA on the side of the first applied film F1 is disposed outside in the winding portion 40 described above, the unbaked film FA from the roll body R is In the case where the first coating film F1 is pulled out, the first coating film F1 side is disposed on the upper side.

[Firing unit]
The firing unit 20 is a unit that performs high-temperature treatment on the unfired film FA in the present embodiment. The firing unit 20 fires the unfired film FA to form a fired film FB containing fine particles. The baking unit 20 includes a chamber 21, a heating unit 22, and a transport unit 23. The chamber 21 has a carry-in port 20a for carrying in the unbaked film FA, and a carry-out port 20b for carrying out the baked film FB. The chamber 21 accommodates the heating unit 22 and the transport unit 23.

  The heating unit 22 heats the unsintered film FA carried into the chamber 31. The heating unit 22 has a plurality of heaters 22 a arranged in line in the Y direction. For example, an infrared heater or the like is used as the heater 22a. The heating unit 22 is disposed from the −Y-side end to the + Y-side end inside the chamber 21. The heating unit 22 can heat the unsintered film FA substantially in the entire Y direction. The heating unit 22 can heat, for example, the unbaked film FA to about 120 ° C. to 450 ° C. The heating temperature by the heating unit 22 is appropriately adjusted according to the transport speed of the unbaked film FA, the component of the unbaked film FA, and the like.

  The transport unit 23 includes a transport belt 23a, a drive roller 23b, a driven roller 23c, and tension rollers 23d and 23e. The transport belt 23a is formed in an endless shape and is disposed along the Y direction. The transport belt 23a is formed using a material having durability at the firing temperature of the unfired film FA. The transport belt 23a is bridged between the drive roller 23b and the driven roller 23c so as to be substantially parallel to the XY plane in a state where it has tension. The unsintered film FA and the sintered film FB are transported in the + Y direction while being placed on the transport belt 23a.

  The drive roller 23 b is disposed at the + Y side end inside the chamber 21. The driving roller 23 b is formed, for example, in a cylindrical shape, and is disposed parallel to the X direction. The driving roller 23 b is provided with, for example, a rotational driving device such as a motor. The driving roller 23 b is rotatably provided about an axis parallel to the X direction by the rotation driving device. The transport belt 23a is configured to rotate clockwise in FIG. 1 by the rotation of the drive roller 23b. As the transport belt 23a rotates, the unsintered film FA and the fired film FB placed on the transport belt 23a are transported in the + Y direction.

  The driven roller 23 c is disposed at the −Y side end inside the chamber 21. The driven roller 23c is formed, for example, in a cylindrical shape, and is disposed parallel to the X direction. The driven roller 23c is formed to have the same diameter as the drive roller 23b, and is disposed such that the position (height position) in the Z direction is substantially equal to that of the drive roller 23b. The driven roller 23c is provided rotatably about an axis parallel to the X direction. The driven roller 23c rotates following the rotation of the transport belt 23a.

  The tension roller 23d is disposed on the + Z side of the driven roller 23c. The tension roller 23d is disposed parallel to the X direction, and is provided rotatably about the X axis. The tension roller 23d is provided to be movable up and down in the Z direction. The tension roller 23d can sandwich the unfired film FA with the driven roller 23c. The tension roller 23d is rotatable in a state in which the unfired film FA is sandwiched.

  The tension roller 23e is disposed on the + Z side of the drive roller 23b. The tension roller 23e is disposed in parallel to the X direction, and is provided rotatably around the X axis. The tension roller 23e is provided to be movable up and down in the Z direction. The tension roller 23e can sandwich the fired film FB with the drive roller 23b. The tension roller 23e is rotatable in a state in which the baked film FB is sandwiched.

  When the tension rollers 23d and 23e respectively sandwich the unbaked film FA and the fired film FB between the driven roller 23c and the driving roller 23b, sandwiching of the unbaked film FA and the fired film FB in a series is performed. The tension between the two places will be cut from the outside. Thereby, it is possible to prevent an excessive load from being applied to the unsintered film FA and the sintered film FB. The tension rollers 23 d and 23 e can be adjusted so that tension is not applied to the unsintered film FA and the sintered film FB disposed in the chamber 21.

Removal Unit
The removal unit 30 includes a chamber 31, an etching unit 32, a cleaning unit 33, a drying unit 34, and a transport unit 35. The chamber 31 has a carry-in port 30 a for carrying in the fired film FB, and a carry-out port 30 b for carrying out the porous resin film F. The chamber 31 accommodates the etching unit 32, the cleaning unit 33, the drying unit 34, and the transport unit 35.

  The etching unit 32 performs etching on the fired film FB to remove the fine particles contained in the fired film FB, thereby forming the porous resin film F. The etching unit 32 removes the particulates by immersing the baked film FB in an etchant capable of dissolving or decomposing the particulates. The etching unit 32 is provided with a supply unit (not shown) that supplies such an etching solution, and a storage unit capable of storing the etching solution.

  The cleaning unit 33 cleans the porous resin film F after the etching. The cleaning unit 33 is disposed on the + Y side of the etching unit 32 (forward in the transport direction of the porous resin film F). The cleaning unit 33 has a supply unit (not shown) for supplying a cleaning solution. In addition, it may have a recovery unit (not shown) for recovering the waste liquid after cleaning the porous resin film F, a liquid removing unit (not shown) for removing the porous resin film F, and the like.

  The drying unit 34 dries the porous resin film F after cleaning. The drying unit 34 is disposed on the + Y side of the cleaning unit 33 (forward in the transport direction of the porous resin film F). The drying unit 34 is provided with a heating unit or the like for heating the porous resin film F.

  The transport unit 35 transports the baked film FB and the porous resin film F across the etching unit 32, the cleaning unit 33, and the drying unit 34. The transport unit 35 includes a transport belt 35 a, a drive roller 35 b, and a driven roller 35 c. In addition to the driving roller 35b and the driven roller 35c, a support roller for supporting the transport belt 35a may be disposed inside the etching unit 32, the cleaning unit 33, and the drying unit 34.

  The conveyance belt 35a is formed in an endless shape, and is disposed along the Y direction. The transport belt 35a is formed using a material having durability to the etching solution. The transport belt 35a is stretched between the drive roller 35b and the driven roller 35c so as to be substantially parallel to the XY plane in a state where it has tension. The fired film FB and the porous resin film F are placed on the transport belt 35a.

  The driving roller 35 b is disposed at the + Y side end inside the chamber 31. The driving roller 35 b is formed, for example, in a cylindrical shape, and is disposed parallel to the X direction. The driving roller 35 b is provided with, for example, a rotational driving device such as a motor. The driving roller 35 b is rotatably provided about an axis parallel to the X direction by the rotation driving device. The conveyance belt 35a is configured to rotate clockwise in FIG. 1 by the rotation of the drive roller 35b. By the conveyance belt 35a rotating, the fired film FB and the porous resin film F placed on the conveyance belt 35a are conveyed in the + Y direction.

  The driven roller 35 c is disposed at the −Y side end inside the chamber 31. The driven roller 35c is formed, for example, in a cylindrical shape, and is disposed parallel to the X direction. The driven roller 35c is formed to have the same diameter as the drive roller 35b, and is disposed such that the position in the Z direction (height position) is substantially equal to that of the drive roller 35b. The driven roller 35c is provided rotatably about an axis parallel to the X direction. The driven roller 35c rotates following the rotation of the transport belt 35a.

In addition, in the removal unit 30, it is not limited to when removing microparticles | fine-particles by an etching. For example, when an organic material that decomposes at a temperature lower than that of polyimide is used as the material of the particles, the particles can be decomposed by heating the fired film FB. As such an organic material, any material that decomposes at a lower temperature than polyimide can be used without particular limitation. For example, resin fine particles composed of a linear polymer or a known depolymerizable polymer can be mentioned. A conventional linear polymer is a polymer in which molecular chains of the polymer are randomly cut during thermal decomposition, and a depolymerizable polymer is a polymer which decomposes into a monomer during thermal decomposition. Both of them disappear from the baked film FB by decomposing to low molecular weight substances or CO ₂ . In this case, the decomposition temperature of the fine particles is preferably 200 to 320 ° C., and more preferably 230 to 260 ° C. If the decomposition temperature is 200 ° C. or higher, film formation can be performed even when a high boiling point solvent is used for the coating liquid, and the range of selection of the baking conditions in the baking unit 20 is broadened. Further, if the decomposition temperature is less than 320 ° C., only the fine particles can be eliminated without giving thermal damage to the fired film FB.

[Winding unit (2)]
FIG. 5 is a perspective view schematically showing the configuration on the + Y side of the removing unit 30. As shown in FIG.
As shown in FIG. 5, on the + Y side of the removal unit 30, an outlet 30b for unloading the porous resin film F is provided. The porous resin film F carried out of the outlet 30 b is taken up by the take-up unit 60.

  The winding unit 60 is configured such that the shaft member SF is attached to the bearing 61. The shaft member SF winds up the porous resin film F carried out from the outlet 30b to form a roll body RF. The shaft member SF is provided detachably with respect to the bearing 61. The shaft member SF is supported so as to be rotatable around an axis parallel to the X direction when mounted on the bearing 61. The winding unit 60 has a drive mechanism (not shown) for rotating the shaft member SF mounted on the bearing 61. The porous resin film F is wound up by rotating the shaft member SF by the drive mechanism. By removing the shaft member SF from the bearing 61 in a state in which the roll body RF is formed, the roll body RF can be recovered.

[Production method]
Next, an example of an operation of manufacturing the porous resin film F using the manufacturing system SYS configured as described above will be described. 6 (a) to 6 (f) are diagrams showing an example of the manufacturing process of the porous resin film F. As shown in FIG.

  First, in the coating unit 10, the unbaked film FA is formed. In the coating unit 10, the base material delivery roller 11a is rotated to feed the transport base material S, and after the transport base material S is hung on the support rollers 11b to 11d, the base material take-up roller 11e winds up. Thereafter, the transport substrate S is sequentially delivered from the substrate delivery roller 11a, and wound up by the substrate take-up roller 11e.

  In this state, the first nozzle 12 is disposed at the first position P1, and the discharge port 12a is directed in the + Y direction. As a result, the discharge port 12 a is directed to the portion of the transport substrate S supported by the support roller 11 b. Thereafter, the first application liquid Q1 is discharged from the discharge port 12a. The first coating liquid Q1 is discharged from the discharge port 12a in the + Y direction, and after reaching the transport base S, is applied onto the transport base S as the transport base S moves. Thereby, as shown to Fig.6 (a), the 1st coating film F1 by the 1st coating liquid Q1 is formed on conveyance base material S. As shown in FIG. In the first coating film F1, the fine particles A2 are contained in the resin material A1 at a predetermined volume ratio.

  Subsequently, the second nozzle 12 is disposed at the second position P2, and the discharge port 13a is directed in the -Z direction. As a result, the discharge port 13a is directed to the portion of the transport substrate S supported by the support roller 11c. Thereafter, the second application liquid Q2 is discharged from the discharge port 13a. The second coating liquid Q2 is discharged from the discharge port 13a in the −Z direction, and reaches the first coating film F1 formed on the transport base S, and then the first transport liquid S is moved along with the movement of the transport base S. It apply | coats on the coating film F1. As a result, as shown in FIG. 6B, the second coating film F2 of the second coating liquid is formed on the first coating film F1. In the second coating film F2, the fine particles A2 are contained in the resin material A1 at a predetermined volume ratio. The content ratio of the fine particles is set larger in the first coating film F1 than in the second coating film F2.

  In addition, since the first coating liquid Q1 and the second coating liquid Q2 are applied in a state where the discharge ports 12a and 13a are directed to the portion of the transport base S supported by the support rollers 11b and 11c, the first coating liquid When Q1 and the second application liquid Q2 reach the transport substrate S, the force acting on the transport substrate S is received by the support rollers 11b and 11c. For this reason, generation | occurrence | production of bending of the conveyance base material S, a vibration, etc. is suppressed, and the 1st application film F1 and the 2nd application film F2 are stably formed by uniform thickness on conveyance base material S.

  Subsequently, when the transport base S moves and the stacked portion of the first coating film F1 and the second coating film F2 is carried into the chamber 14a of the drying unit 14, the first coating film F1 and the first coating film F1 are 2 Dry the applied film F2. In the drying unit 14, the first coating film F <b> 1 and the second coating film F <b> 2 are heated, for example, at a temperature of about 50 ° C. to 100 ° C. using the heating unit 14 b. Within this temperature range, the first coating film F1 and the second coating film F2 can be heated without distortion, deformation or the like occurring in the transport substrate S. By drying the laminated body of the first coating film F1 and the second coating film F2, as shown in FIG. 6C, the non-sintered film FA is formed.

  In addition, in this specification, a laminated body means the unbaked film | membrane which consists of said 1st coating film F1 and said 2nd coating film F2. When the porous imide resin film according to the present invention is formed, the same liquid resin is used as the first liquid and the second liquid among polyamic acid, polyimide, polyamide imide, or polyamide. The unbaked film (or porous imide resin film) consisting of the first coating film F1 and the second coating film F2 is substantially a single layer, but the unbaked film (or empty) having different fine particle content Since a porous imide-based resin film having regions with different porosities is formed, in the present specification, it is referred to as a laminate, including the case where the same type of resin is used for the first liquid and the second liquid. .

  Then, when conveyance base material S moves and the tip part of unbaked film FA reaches support roller 11d (peeling part 15), this tip part is conveyed base material S by a manual operation of a worker, for example. Peel from. In the present embodiment, for example, PET is used as the material of the transport base S, so when the unbaked film FA is formed by drying the first coated film F1 and the second coated film F2, from the transport base S Since it becomes easy to peel off, the worker can easily peel off.

  After peeling the tip portion of the unbaked film FA, the transport substrate S continues to move, and the first nozzle 12 forms the first coated film F1. Further, a second coating film F2 is formed by the second nozzle 13 and a non-sintered film FA is formed by the drying unit 14. As a result, the unbaked film FA is formed in a strip shape, and the length of the unbaked film FA unloaded from the drying unit 14 to the + Y side gradually increases. The worker continues to peel off the unbaked film FA at the peeling portion 15. Then, when the tip of the peeled unbaked film FA reaches the shaft member SF of the winding unit 40, the operator manually hangs the unbaked film FA on the unloading roller 11f and is unbaked. The tip portion of the membrane FA is attached to the shaft member SF. Thereafter, the unbaked film FA is sequentially formed, and the shaft member SF is rotated by the winding unit 40 in accordance with the peeling. Thereby, the peeled unbaked film FA is sequentially carried out of the coating unit 10 and taken up by the shaft member SF of the take-up unit 40 to form a roll body R. As shown in FIG. 6D, the unbaked film FA constituting the roll body R is in a state of being peeled off from the transport substrate S, and both the front and back surfaces are exposed.

  The operation of peeling off the front end portion of the unbaked film FA, and the operation of mounting the peeled front end portion on the shaft member SF are not limited to the mode manually performed by the operator, and for example, automatic using a manipulator etc. You may go there. Further, in order to enhance the releasability of the unbaked film FA, a release layer may be formed on the surface of the transport base S.

  After the unbaked film FA of a predetermined length is taken up by the shaft member SF, the unbaked film FA is cut, and the shaft member SF together with the roll body R is removed from the bearing 41. Then, a new shaft member SF is attached to the bearing 41 of the winding portion 40, and the cut end of the unbaked film FA is attached to the shaft member SF and rotated to continuously form the unbaked film FA. Roll body R can be created.

  On the other hand, for example, the worker conveys the shaft member SF removed from the bearing 41 together with the roll body R to the delivery unit 50 and mounts it on the bearing 51. The transport operation and the mounting operation of the shaft member SF may be automatically performed using a manipulator, a transport device, or the like. After the shaft member SF is mounted on the bearing 51, the non-sintered film FA is sequentially pulled out from the roll body R by rotating the shaft member SF, and the non-sintered film FA is carried into the chamber 21 of the baking unit 20. When the tip of the unsintered film FA is carried into the chamber 21, the operator may perform it manually or may automatically perform it using a manipulator or the like.

  The unsintered film FA carried into the chamber 21 is placed on the transport belt 23a, and transported in the + Y direction as the transport belt 23a rotates. The tension may be adjusted using the tension rollers 23d and 23e. Then, the unbaked film FA is fired using the heating unit 22 while transporting the unbaked film FA.

  The temperature at the time of firing varies depending on the structure of the unbaked film FA, but is preferably about 120 ° C. to 375 ° C., and more preferably 150 ° C. to 350 ° C. In addition, when the fine particles contain an organic material, it is necessary to set the temperature lower than the thermal decomposition temperature. In the case where the coating solution contains a polyamic acid, it is preferable to complete the imidization in this baking, but the unbaked film FA is made of polyimide, polyamideimide or polyamide, and the baking unit 20 It is not this limitation when performing high temperature processing.

  In addition, as the baking conditions, for example, when the coating liquid contains a polyamic acid and / or a polyimide, after raising the temperature from room temperature to 375 ° C. for 3 hours, a method of holding at 375 ° C. for 20 minutes or room temperature to 50 ° C. Step-wise heating may be performed such that the temperature is raised stepwise to 375 ° C. (each step is held for 20 minutes) and finally held at 375 ° C. for 20 minutes. Further, the end of the unfired film FA may be fixed to a mold made of SUS or the like to prevent deformation.

  By such baking, as shown in FIG. 6E, the baked film FB is formed. In the fired film FB, the fine particles A2 are contained inside the resin layer A3 that has been imidized or subjected to a high temperature treatment. The film thickness of the fired film FB can be determined, for example, by measuring and averaging the thicknesses of a plurality of portions with a micrometer or the like. As a preferable average film thickness, when used for a separator etc., it is preferable that they are 3 micrometers-500 micrometers, It is more preferable that they are 5 micrometers-100 micrometers, It is still more preferable that they are 10 micrometers-30 micrometers.

  When the fired film FB formed in the firing unit 20 is unloaded from the firing unit 20, the fired film FB is loaded into the removal unit 30 without being wound up. When the tip end portion of the sintered film FB is carried into the removal unit 30, it may be performed manually by an operator or automatically using a manipulator or the like.

  The fired film FB carried into the removing unit 30 is placed on the transport belt 35a, and is transported in the + Y direction as the transport belt 35a rotates. In the removal unit 30, the particulate matter A2 is first removed in the etching unit 32 as the baked film FB is transported. In the case where, for example, silica is used as the material of the fine particles A2, in the etching unit 32, the baked film FB is immersed in an etching solution such as low concentration hydrogen fluoride water. As a result, the fine particles A2 are dissolved in the etching solution and removed, and as shown in FIG. 6F, the porous resin film F in which the porous portion A4 is included in the resin layer A3 is formed.

  Thereafter, the porous resin film F is carried into the cleaning unit 33 and the drying unit 34 in order according to the rotation of the transport belt 35 a. In the cleaning unit 33, the porous resin film F is cleaned by the cleaning solution and the liquid is removed. Further, in the drying unit 34, the porous resin film F after draining is heated, and the cleaning liquid is removed. Then, the porous resin film F is carried out of the removal unit 30 and taken up by the shaft member SF of the take-up unit 60.

  As described above, the manufacturing system SYS according to the present embodiment transports the coating solution (the first coating solution Q1 and the second coating solution Q2) containing the resin material A1 and the fine particles A2 of polyamide acid, polyimide, polyamideimide or polyamide. A coating unit 10 for coating a substrate S to form a non-sintered film FA and a non-sintered film FA peeled off from the transport substrate S in the coating unit 10 are fired to form a fired film FB containing fine particles Since the baking unit 20 and the removal unit 30 for removing the fine particles A2 from the baked film FB are included, the formation of the unbaked film FA, the baking of the unbaked film FA (the formation of the baked film FB), and the removal of the fine particles A2 ( The three steps of formation of the porous resin film F can be performed in a series of flows. Thereby, the manufacturing efficiency of the porous resin film F can be improved.

In addition, the coating unit (10) is applicable to manufacturing processes such as a roll-to-roll method because it forms a band-like unbaked film (FA) on a base material (conveying base material S), and is efficient A porous imide resin film (porous resin film F) can be formed.
In addition, since the removal unit (20) takes in the fired film (FB) fired by the firing unit (10) sequentially without taking up and removes the fine particles (A2), the process from firing to the removal of fine particles is efficiently performed. It can be carried out.
In addition, since the unbaked film (FA) peeled off from the base material (conveying base material S) is wound up to form the roll body (R), the conveyance between units is facilitated. be able to.
In addition, when the roll body (R) is a roll body of a band-like unbaked film (FA) peeled from the base material (conveying base material S), the firing unit (10) sequentially unbaked film from the roll body The drawn film FB can be efficiently formed because it is drawn and baked.
Further, as the liquid, a first liquid (first coating liquid Q1) and a second liquid (second coating liquid Q2) having different contents of at least fine particles (A2) from each other are used, and the coating unit (10) is By applying the first liquid and the second liquid to the base material (conveying base material S), at least the content of the fine particles is different to form a stacked non-baked film (FA), so this non-baked film When a porous imide resin film (porous resin film F) formed based on the above is used as a separator, ions move smoothly and the porous imide resin having the same porosity is obtained. The strength as a film can be secured compared to the case where the film is formed only with the first coating solution Q1.

  Further, in the method of manufacturing the porous resin film F according to the present embodiment, a coating liquid containing a resin material A1 of polyamic acid, polyimide, polyamideimide or polyamide and fine particles A2 (first coating liquid Q1 and second coating liquid Q2) Is applied to the transport substrate S and then peeled off from the transport substrate S to form a non-sintered film FA, and firing the non-sintered film FA to form a fired film FB containing fine particles A2, and firing Since removing the fine particles A2 from the film FB, the formation of the unbaked film FA, the firing of the unbaked film FA (the formation of the fired film FB), and the removal of the fine particles A2 (the formation of the porous resin film F) The three steps can be performed in a series of flows. Thereby, the manufacturing efficiency of the porous resin film F can be improved.

In addition, since the unbaked film (FA) is formed in a belt shape, it can be applied to a manufacturing process such as a roll-to-roll system, and the porous imide resin film (porous resin film F) is efficiently used. Can be formed.
In addition, since the fine particles (A2) are removed from the fired film by sequentially loading the fired film (FB) without winding it up, the steps from firing to the removal of the particles can be performed efficiently.
Moreover, in order to wind up the unbaked film (FA) peeled from the base material (conveyance base material S) and to form a roll body (R), it can be made easy to convey between units.
In addition, when the roll body is a roll body (R) of a band-like unbaked film (FA) peeled from the base material (conveying base material S), the unbaked film is sequentially drawn out from the roll body and fired. Thus, the fired film FB can be formed.
Further, as the liquid, a first liquid (first coating liquid Q1) and a second liquid (second coating liquid Q2) having different contents of at least fine particles (A2) from each other are used, and the first liquid and the second liquid are used. In order to form a non-sintered film (FA) laminated with different contents of at least fine particles (A2) by applying the above liquid to the base material (conveying base material S), the ions are smooth when used as a separator The porous imide resin film (porous resin film F) capable of securing the strength as a film can be manufactured.

[Modification]
In the above embodiment, the configuration in which the winding unit 40 is disposed between the coating unit 10 and the baking unit 20 has been described as an example, but the present invention is not limited to this. FIG. 7 is a diagram showing an example of a part of a manufacturing system SYS2 according to a modification.

  For example, as shown in FIG. 7, the non-sintered film FA carried out of the coating unit 10 may be carried into the baking unit 20 without providing the winding unit 40. In this case, the baking unit 20 sequentially takes out and bakes the unbaked film FA which is carried out of the coating unit 10 and conveyed through the relay roller 70, and forms the baked film FB.

  Thus, the baking unit (20) sequentially takes in and bakes the unbaked film (FA) peeled off from the base material (conveying base material S) without winding it up, so the formation of the unbaked film FA to the baked film FB Can be performed continuously.

  Moreover, in the said embodiment, although the structure which peels unbaked film FA from conveyance base material S is mentioned as an example and demonstrated in the peeling part 15 provided inside the application unit 10, it does not limit to this. For example, in the application unit 10, the unbaked film FA and the transport substrate S are integrally wound without peeling, and the unbaked film FA is peeled from the transport substrate S while being immersed in the liquid outside the application unit 10. It is also good. FIG. 8 is a diagram showing an example of a part of a manufacturing system SYS3 according to a modification.

  For example, as shown in FIG. 8, the coating unit 10 includes a winding unit 73 that integrally rolls the unbaked film FA and the transport base S without peeling. The winding portion 73 includes a bearing 16 and a shaft member SF2. The bearing 16 is disposed on the −Z side of the support roller 11 d. The shaft member SF2 is detachably provided to the bearing 16. When mounted on the bearing 16, the shaft member SF2 is supported so as to be rotatable around an axis parallel to the X direction. The application unit 10 is provided with a drive mechanism (not shown) for rotating the shaft member SF2 attached to the bearing 16. By rotating the shaft member SF2 by this drive mechanism, the unsintered film FA and the transport base S are integrally wound, and the roll body RS is formed.

  A bearing 71 is provided outside the coating unit 10. The immersion portion 72 is provided on the −Z side of the bearing 71. The immersion portion 72 includes a container 72a, a liquid 72b contained in the container 72a, and a roller 72c immersed in the liquid 72b. Examples of the liquid 72b include water.

  When the unbaked film FA and the transport base S are integrally wound by the shaft member SF2 and the roll body RS is formed, the shaft member SF2 is first removed from the bearing 16. Then, the shaft member SF2 is attached to a bearing 71 provided outside the application unit 10.

  After attaching the shaft member SF2 to the bearing 71, the unsintered film FA and the transport base S are pulled out from the roll body RS and immersed in the liquid 72b. For example, the laminate of the unbaked film FA and the transport base S is hung under the roller 72c. In this case, the unbaked film FA and the transport base S drawn out from the roll body RS are sequentially immersed in the liquid 72b. For example, the worker peels the unbaked film FA from the transport substrate S while the unbaked film FA and the transport substrate S are immersed in the liquid 72 b.

  As described above, since the unfired film (FA) containing the base material (the transfer base material S) is taken up to form the roll body (RS), the transfer between units is performed. It can be made easy. When the roll body is a strip (RS) of a non-sintered film (FA) including a base material (conveying base material S), the base material is pulled out from the roll body to be in a predetermined liquid (liquid 72b) Since the immersion part (72) which immerses and peels a non-baked film from this base material is provided, it can peel stably.

  Moreover, as an aspect which immerses unbaked film FA in the liquid 72b, it is not limited when peeling unbaked film FA from conveyance base material S, either. For example, the unbaked film FA peeled off from the transport substrate S may be immersed in a liquid such as water. FIG. 9 is a diagram showing an example of a part of a manufacturing system SYS4 according to a modification.

  As shown in FIG. 9, the second immersion portion 74 is provided on the + Y side of the coating unit 10. The second immersion section 74 includes a container 74a, a liquid 74b contained in the container 74a, and a roller 74c immersed in the liquid 74b. The unbaked film FA carried out of the coating unit 10 is immersed in the liquid 74 b via the roller 74 c. In this case, the unbaked film FA can be immersed in the liquid 74b, for example, for approximately 10 seconds to 5 minutes, preferably for approximately 30 seconds to 40 seconds. This can suppress the formation of wrinkles when firing the unfired film FA.

When immersing the unbaked film FA peeled from the transport base S in a liquid such as water, the unbaked film FA may be wound by the winding unit 40 after immersion, or may be interposed after the immersion. It does not have to be.
Moreover, after immersing unbaked film FA peeled from conveyance base material S in liquids, such as water, you may have the process of forcing the said unbaked film FA. As a means to force, the process of pressing the said unbaked film FA is mentioned. Thereby, formation of wrinkles can be suppressed when drying or baking the unbaked film FA.

  In addition, when not taking up the winding part 40 after immersion of unbaked film FA, unbaked film FA conveyed via a relay roller is sequentially taken in and baked to form fired film FB. Thereby, the baking unit (20) sequentially takes in and bakes the unbaked film (FA) peeled off from the base material (conveying base material S) without winding it up. Up to formation can be performed continuously. Before the unfired film FA to be transported is taken into the baking unit, a step of drying or absorbing water of the liquid attached at the time of immersion may be provided.

  Further, in addition to the configuration of the above-described embodiment, a post-processing unit may be provided to perform post-processing on the porous resin film F formed by the removing unit 30. FIG. 10 is a diagram illustrating an example of a manufacturing system SYS5 according to a modification.

  As shown in FIG. 10, a post-processing unit 80 is disposed between the removing unit 30 and the winding unit 60. As the post-processing unit 80, for example, an electrification preventing unit 81 that performs a static elimination process on the porous resin film F can be used. For example, a static elimination device such as an ionizer is mounted on the antistatic unit 81.

  As described above, since the antistatic unit (81) for performing the antistatic treatment on the fired film (porous resin film F) from which the particles (A2) have been removed, the porous resin film F from which the particles have been removed Can be removed.

  Further, as the post-processing unit 80, for example, an etching unit 82 for removing a part of the porous resin film F can be used. FIG. 11A is a view schematically showing an example of the etching unit 82. As shown in FIG. As shown in FIG. 11A, the etching unit 82 has a storage portion 82a in which the processing liquid 82b is stored. For example, an alkaline solution or the like is used as the treatment liquid 82b. By immersing the porous resin film F in the treatment liquid 82b for a predetermined time, the inside of the porous portion A4 is removed as shown in FIG. 11 (b). In this case, the burrs of the porous portion A4 can be removed and the communication can be maintained.

  When the etching unit 82 is used as the post-processing unit 80, after the post-processing by the etching unit 82, a drying process or a post-baking process may be further performed on the porous resin film F. The temperature of the drying step or the post-baking step may be appropriately set according to the type of the resin of the porous resin film F, and is, for example, 100 to 300 ° C.

  When the etching unit 82 is used as the post-processing unit 80, the drying unit 34 in the removal unit 30 removes the liquid and conveys the porous resin film F to the etching unit 82 without drying or heating. It is also good. In this case, in the liquid removal in the drying unit 34, the liquid attached to the porous resin film F after cleaning is removed. The drying unit 34 is preferably provided with a water absorbing roller or the like, and the porous resin film F adheres to the porous resin film F while being transported by bringing the water absorbing roller into contact with the porous resin film F. Can absorb liquid that is

  Thus, since the etching unit (82) for removing a part of the fired film (porous resin film F) from which the fine particles (A2) are removed is included, the inner surface of the porous portion A4 included in the porous resin film F is In addition to being smooth, communication can be ensured.

  In the above embodiment, as the winding units 40 and 60, the shaft member SF is attached to and detached from the bearings 41 and 61 as an example. However, the present invention is not limited to this. For example, as shown in FIG. A take-up device 90 may be used. Hereinafter, a case where the winding device 90 is used instead of the winding unit 40 will be described as an example.

  As shown in FIG. 12, the winding device 90 includes a frame 91, a shaft member SF, a bearing 92, a drive unit 93, relay rollers 94a to 94e, and a roller support unit 95. The frame 91 supports the shaft member SF, the bearing 92, the drive unit 93, the relay rollers 94a to 94e, and the roller support unit 95.

  The shaft member SF winds up the unbaked film FA unloaded from the coating unit 10 to form a roll body R. The shaft member SF is detachably provided to the bearing 92. When mounted on the bearing 92, the shaft member SF is supported by the bearing 92 so as to be rotatable about an axis parallel to the X direction. By removing the shaft member SF from the bearing 92 in a state in which the roll body R is formed, the roll body R can be moved or recovered to another unit.

  The relay rollers 94a to 94e send the unbaked film FA to the shaft member SF while adjusting the tension of the unbaked film FA. The relay rollers 94a to 94e are formed, for example, in a cylindrical shape, and are disposed parallel to the X direction. In the present embodiment, the unbaked film FA is bridged in the order of the relay rollers 94a, 94b, 94c, 94d, and 94e. However, the present invention is not limited to this, and some relay rollers may not be used. Note that at least one of the relay rollers 94 a to 94 e may be movable by the roller support 95. For example, the roller support 95 may be capable of moving the relay roller 94b in the Z direction or the Y direction. Alternatively, the relay roller 94 b may be rotated by the roller support 95 around an axis AX parallel to the X axis. In this case, the amount of movement (rotation) of the relay roller 94b is fed back to the winding speed of the bearing 92, so that the tension of the unbaked film FA can be kept constant. In addition, the load on the relay roller 94 b may be changed by moving a movable weight (not shown) disposed on the −Y side of the relay roller 94 b via the fulcrum shaft. In this case, it is possible to adjust the tension of the unbaked film FA by adjusting the load applied to the relay roller 94b by the weight.

The relay rollers 94a to 94e are not limited to the arrangement parallel to the X direction, and may be arranged to be inclined with respect to the X direction. Further, the relay rollers 94a to 94e are not limited to the cylindrical shape, and those having a crown of a taper type, a radial type, a concaving type or the like may be used.

  The above-described winding device 90 may be used instead of the winding unit 60. Further, by rotating the shaft member SF in the direction opposite to the direction in which the film such as the unbaked film FA is taken up, it is possible to send out the film such as the unbaked film FA. Therefore, for example, it is also possible to use a winding device 90 in place of the above-described delivery unit 50.

[Separator]
Next, the separator 100 according to the embodiment will be described. FIG. 13 is a schematic view showing an example of the lithium ion battery 200, in which a part is cut open. As shown in FIG. 13, the lithium ion battery 200 has a metal case 201 which doubles as a positive electrode terminal, and a negative electrode terminal 202. Inside the metal case 201, a positive electrode 201a, a negative electrode 202a, and a separator 100 are provided, and are immersed in an electrolyte (not shown). The separator 100 is disposed between the positive electrode 201a and the negative electrode 202a, and prevents electrical contact between the positive electrode 201a and the negative electrode 202a. A lithium transition metal oxide is used as the positive electrode 201a, and, for example, lithium or carbon (graphite) is used as the negative electrode 202a.

  The porous resin film F described in the above embodiment is used as the separator 100 of the lithium ion battery 200. In this case, for example, the battery performance can be improved by setting the surface on which the first coated film F1 is formed to the negative electrode 202a side of the lithium ion battery. In addition, although the separator 100 of the square-shaped lithium ion battery 200 is mentioned as an example and demonstrated in FIG. 13, it does not limit to this. The porous resin film F described above can be used as a separator of any type of lithium ion battery such as a cylindrical type or a laminate type. In addition to the separator of the lithium ion battery, the porous resin film F described above can be used as a fuel cell electrolyte film, a separation film for gas or liquid, and a low dielectric constant material.

As mentioned above, although embodiment was described, this invention is not limited to the description mentioned above, A various change is possible in the range which does not deviate from the summary of this invention.
For example, in the above embodiment and modification, the case where the unbaked film FA is formed using two types of coating liquids having different content rates of fine particles has been described as an example, but the present invention is not limited to this. The unbaked film may be formed of a coating solution of a kind. In this case, either one of the first nozzle 12 and the second nozzle 13 may not be used, or one nozzle may be omitted. When one nozzle is omitted, it is preferable to omit the first nozzle 12 and use the second nozzle 13.

  Further, in the above embodiment and the modified example, although the fired film FB is formed by the firing unit 20 and then carried into the removal unit 30 without winding up the fired film FB as an example, the present invention is limited thereto Instead of the film, the fired film FB may be wound up. In this case, the winding device 90 described in the above modification may be used.

  Moreover, although the said embodiment and modification mentioned as an example the structure by which the application | coating unit 10, the baking unit 20, and the removal unit 30 were arrange | positioned and demonstrated it as an example, it does not limit to this. For example, a plurality of at least one of the units may be provided. In this case, for example, by arranging a large number of units having a small amount (eg, length, etc.) of unbaked film FA, baked film FB, or porous resin film F that can be processed per unit time, the entire manufacturing system SYS Manufacturing efficiency can be improved.

  In the embodiment and the modification, each unit of the coating unit 10, the baking unit 20, the removing unit 30, and the post-processing unit 80 (the antistatic unit 81, the etching unit 82) includes the unbaked film FA and the baked film FB. Or although the case where each film | membrane of the porous resin film F was conveyed along a Y direction was mentioned as an example and demonstrated, it does not limit to this. For example, one of the units may transport the film in the X direction, the Y direction, the Z direction, or a composite direction of these, or the transport direction may be changed as appropriate in one unit.

  Moreover, although the case where the three steps of application in the coating unit 10, baking in the baking unit 20, and removal in the removal unit 30 are performed is described as an example in the embodiment and the modification, the invention is not limited to this. Absent. For example, when a polyimide, a polyamide imide, or a polyamide is used as a material of a coating film, it is not necessary to bake. For this reason, when firing is not performed, for example, by providing a winding device and a delivery device between the firing unit 20 and the removal unit 30, the unbaked film FA formed in the coating unit 10 can It becomes possible to carry in to the removal unit 30 without intervention. Moreover, when not baking, the manufacturing system which manufactures a porous imide type resin film apply | coats the liquid containing a polyamic acid, a polyimide, polyamide imide, or polyamide, and microparticles | fine-particles to a base material, and forms an unbaked film. The manufacturing system may include a unit, and a removal unit configured to remove the fine particles from the unbaked film peeled off from the substrate in the coating unit or outside the coating unit. When the baking is not performed, the above-described post-baking process may be performed after the porous resin film F is unloaded from the removing unit 30 for removing the fine particles. The post-processing unit 80 and / or the etching unit 82 may be interposed before the post-baking process step.

  Moreover, although the said embodiment and modification showed and demonstrated the structure which forms the porous resin film F by the so-called roll-to-roll system as an example, it does not limit to this. For example, when the porous resin film F is carried out of the removal unit 30 after the processing in the removal unit 30 is finished, the film is cut at a predetermined length without being wound by the winding unit 60 and cut. You may collect it.

  SYS, SYS2, SYS3, SYS4, SYS5 ... Production system (porous imide resin production system) F ... Porous resin film (porous imide resin film) FA ... Unbaked film FB ... Fired film S ... Transport group Materials (base material) Q1 First coating solution F1 First coating film Q2 Second coating solution F2 Second coating film A1 Resin material A2 Particulate R, RS, RF Roll body 10 Coating unit 12 First nozzle 13 ... second nozzle 14 ... drying unit 15 ... peeling unit 20 ... firing unit 30 ... removal unit 32 ... etching unit 40, 60, 73 ... winding unit 72 ... immersion unit 80 ... post-processing unit 81 ... antistatic Unit 82: Etching unit 90: Take-up device 100: Separator 200: Lithium ion battery

Claims (12)

A manufacturing system for manufacturing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed ,
An application unit for applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and fine particles to a substrate to form an unbaked film;
A firing unit for firing the unbaked film peeled off from the base material in the coating unit or outside the coating unit to form a fired film containing the fine particles;
The fired film, by immersing the soluble or degradable etchant the fine particles, or by heating the fine particles degradable temperature, see containing and a removal unit for removing the fine particles from the fired film ,
A porous imide-based resin film production system , comprising: a winding section which winds up the unbaked film peeled from the substrate or the unbaked film containing the substrate to form a roll body . When the roll body is a band-like roll body of the unbaked film peeled from the substrate,
The porous imide resin film manufacturing system according to claim 1 , wherein the baking unit sequentially pulls out and bakes the unbaked film from the roll body. When the roll body is a band-like roll body of the unbaked film containing the base material,
The porous imide type-resin film manufacturing system according to claim 1, further comprising: an immersion section which pulls out the base material from the roll body and immerses the base material in a predetermined liquid and peels the unbaked film from the base material. A manufacturing system for manufacturing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed ,
An application unit for applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and fine particles to a substrate to form an unbaked film;
A firing unit for firing the unbaked film peeled off from the base material in the coating unit or outside the coating unit to form a fired film containing the fine particles;
A removal unit for removing the particles from the fired film by immersing the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be degraded ;
And a antistatic unit for performing an antistatic process on the fired film from which the fine particles have been removed . A manufacturing system for manufacturing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed ,
An application unit for applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and fine particles to a substrate to form an unbaked film;
A firing unit for firing the unbaked film peeled off from the base material in the coating unit or outside the coating unit to form a fired film containing the fine particles;
A removal unit for removing the particles from the fired film by immersing the fired film in an etchant capable of dissolving or decomposing the particles, or by heating the particles to a temperature at which the particles can be degraded ;
And an etching unit for removing a part of the fired film from which the fine particles have been removed . A manufacturing system for manufacturing a porous imide resin film in which a large number of continuous pores penetrating in a film thickness direction are formed ,
An application unit for applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and fine particles to a substrate to form an unbaked film;
A firing unit for firing the unbaked film peeled off from the base material in the coating unit or outside the coating unit to form a fired film containing the fine particles;
The fired film, by immersing the soluble or degradable etchant the fine particles, or by heating the fine particles degradable temperature, see containing and a removal unit for removing the fine particles from the fired film ,
As the liquid, a first liquid and a second liquid having different contents of at least the fine particles from each other are used,
The application unit is a porous imide type that forms the unfired film in which at least the fine particles having different contents are laminated by applying the first liquid and the second liquid to the base material. Resin film manufacturing system. A method for producing a porous imide resin film having a large number of continuous pores formed in the film thickness direction ,
After applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and a fine particle to a base material, the base material is peeled off from the base material to form an unbaked film;
Firing the unfired film to form a fired film containing the fine particles;
The fired film, by immersing the soluble or degradable etchant the fine particles, or by heating the fine particles degradable temperature, see contains; and removing the particulates from the fired film,
The porous imide type-resin film manufacturing method which winds up the said unbaked film | membrane which peeled from the said base material, or the said unbaked film | membrane containing the said base material, and forms a roll body . When the roll body is a band-like roll body of the unbaked film peeled from the substrate,
The method for producing a porous imide resin film according to claim 7, wherein the unbaked film is sequentially drawn out from the roll body and baked. When the roll body is a band-like roll body of the unbaked film containing the base material,
The method for producing a porous imide resin film according to claim 7, wherein the base material is pulled out from the roll body and immersed in a predetermined liquid, and the non-sintered film is peeled off from the base material. A method for producing a porous imide resin film having a large number of continuous pores formed in the film thickness direction ,
After applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and a fine particle to a base material, the base material is peeled off from the base material to form an unbaked film;
Firing the unfired film to form a fired film containing the fine particles;
The fired film, by immersing the soluble or degradable etchant the fine particles, or by heating the fine particles degradable temperature, see contains; and removing the particulates from the fired film,
A method for producing a porous imide resin film , wherein an antistatic treatment is performed on the fired film from which the fine particles have been removed . A method for producing a porous imide resin film having a large number of continuous pores formed in the film thickness direction ,
After applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and a fine particle to a base material, the base material is peeled off from the base material to form an unbaked film;
Firing the unfired film to form a fired film containing the fine particles;
The fired film, by immersing the soluble or degradable etchant the fine particles, or by heating the fine particles degradable temperature, see contains; and removing the particulates from the fired film,
The porous imide type-resin film manufacturing method which removes a part of said baked film from which the said microparticles | fine-particles were removed . A method for producing a porous imide resin film having a large number of continuous pores formed in the film thickness direction ,
After applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide and a fine particle to a base material, the base material is peeled off from the base material to form an unbaked film;
Firing the unfired film to form a fired film containing the fine particles;
The fired film, by immersing the soluble or degradable etchant the fine particles, or by heating the fine particles degradable temperature, see contains; and removing the particulates from the fired film,
As the liquid, a first liquid and a second liquid having different contents of at least the fine particles from each other are used,
The porous imide type-resin film manufacturing method which forms the said unbaked film | membrane which the content rate of the said microparticles | fine-particles differed and was laminated | stacked by apply | coating the said 1st liquid and the said 2nd liquid to the said base material .

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