JP6539656B2 - Imide-based resin film production system and imide-based resin film production method - Google Patents

Description

  The present invention relates to an imide resin film production system and a method for producing an imide resin film.

  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

  However, the conventional porous polyimide membrane is not sufficient in terms of the open area ratio of the porous portion, and the movement of lithium ions may be impeded. Therefore, when a porous polyimide film is used as a separator, there is a problem that the internal resistance of the battery is increased. In addition to the polyimide film, in the imide resin film, a high-quality porous film having an excellent porosity is required.

  In view of the above circumstances, the present invention provides an imide resin film manufacturing system and an imide resin film manufacturing method capable of efficiently manufacturing a high quality imide resin film having an excellent porosity. To aim.

An imide resin film production system according to an aspect of the present invention is a production system for producing a porous imide resin film, which comprises dissolving a film containing polyamic acid, polyimide, polyamide imide or polyamide, and particles, particles. Alternatively, by immersing in a degradable etching solution or heating the fine particles to a decomposable temperature, the fine particles are removed to form a porous imide resin having a large number of continuous pores formed in the film thickness direction A film forming unit for forming a film and a chemical etching unit for dissolving a part of an imide resin film are provided. The method for producing an imide resin film according to an aspect of the present invention is a method for producing a porous imide resin film, which is a method comprising producing a film containing polyamic acid, polyimide, polyamide imide or polyamide, and particles. A porous imide system in which fine particles are removed by being immersed in a dissolving or decomposable etching solution or by heating the fine particles to a decomposable temperature to form a large number of continuous pores penetrating in the film thickness direction. Forming a resin film and performing a chemical etching process for dissolving a part of the imide resin film. The 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 fine particles from a film containing polyamic acid, polyimide, polyamide imide or polyamide, and fine particles. It comprises a film forming unit which is removed to form a porous imide resin film, and a chemical etching unit which dissolves a part of the imide resin film.

Imide resin film manufacturing method according to the second aspect of the present invention is a method for producing a porous imide resin film, polyamic acid, polyimide, polyamide-imide or polyamide, and fine particles from the membrane containing a particulate removal Forming a porous imide resin film, and performing a chemical etching process for dissolving a part of the imide resin film.

  According to the aspect of the present invention, it is possible to efficiently manufacture a high quality imide resin film having an excellent porosity.

It is a figure showing an example of the manufacturing system concerning an embodiment of the invention. It is a figure showing an example of the film formation unit concerning this embodiment. 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 chemical etching unit concerning this embodiment. It is a figure which shows typically an example of the chemical etching unit concerning this embodiment. It is a perspective view which shows an example of the winding-up part which concerns on 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 showing an example of a manufacturing system concerning 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. A removal unit 30 for removing and forming the porous resin film F, a chemical etching unit 40 for removing a part of the porous resin film F, and a control device (not shown) for comprehensively controlling the respective units Have. The coating unit 10, the baking unit 20, and the removing unit 30 constitute a film forming unit 70 for forming the porous resin film F.

  The manufacturing system SYS is configured, for example, in two upper and lower layers, and the coating units 10 are disposed on the second floor portion, and the baking unit 20, the removing unit 30, and the chemical etching unit 40 are disposed on the first floor portion. The baking unit 20, the removing unit 30, and the chemical etching unit 40 arranged on the same floor are arranged side by side in the Y direction, for example, but not limited to this, for example, in the X direction or in the X direction and the Y direction. It may be arranged side by side in the synthesis direction.

  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 and the chemical etching unit 40 are provided. May be arranged on the first floor part. 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 50 is provided for winding the unbaked film FA in a band shape in a roll. On the −Y side of the baking unit 20 (at the rear in the conveyance direction of the unbaked film FA), a delivery unit 60 for feeding the roll-shaped unbaked film FA toward the baking unit 20 is provided. On the + Y side of the chemical etching unit 40 (forward in the transport direction of the porous resin film F), a winding unit 80 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 60 to the winding unit 80 after passing through the baking unit 20, the removing unit 30, and the chemical etching unit 40, a so-called roll-to-roll process 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 final viscosity of the coating solution is preferably 300 to 2,000 cP, more preferably 400 to 1,500 cP, and still more preferably 600 to 1,200 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, the generation of streak marks on the first coating film F1 can be suppressed.

  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 50. 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 50.

  The winding unit 50 is configured such that the shaft member SF is attached to the bearing 51. 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 provided detachably with respect to the bearing 51. 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 winding unit 50 has a drive mechanism (not shown) that rotates the shaft member SF attached to the bearing 51.

  In the winding unit 50, 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 51 in a state in which the roll body R is formed, the roll body R can be moved to another unit.

  In addition, in FIG.1 and FIG.3, although the winding-up part 50 is arrange | positioned independently from the coating unit 10, it does not limit to this. For example, the winding unit 50 may be disposed inside the coating 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 60 delivers the unfired film FA to the loading port 20a.

  The delivery portion 60 is configured such that the shaft member SF can be attached to the bearing 61. The shaft member SF can be used in common with the one mounted on the bearing 51 of the winding unit 50. Therefore, the shaft member SF removed from the winding unit 50 can be attached to the bearing 61 of the delivery unit 60. Thus, the roll body R formed by the winding unit 50 can be disposed in the delivery unit 60. The bearings 61 and the bearings 51 of the winding unit 50 can be set to have the same height from the floor surface, but may be set at different height positions.

  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 delivery unit 60 has a drive mechanism (not shown) for rotating the shaft member SF attached to the bearing 61. 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. In the above-described winding portion 50, 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, so 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 removing unit 30 includes a chamber 31, an etching unit 32, a cleaning unit 33, a liquid removing unit 34, and a transfer unit 35. The chamber 31 has a carry-in port 30a for carrying in the fired film FB, and a carry-out port 30b for carrying out the porous resin film F. The chamber 31 accommodates the etching unit 32, the cleaning unit 33, the liquid removing 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. Since the liquid contained in the inside differs in the etching part 32 and the washing | cleaning part 33, you may provide the below-mentioned water absorption roller in the position in front of carrying out from the etching part 32. The water absorbing roller is disposed on at least one of the + Z side and the -Z side of the porous resin film F, preferably on both sides.

  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. Moreover, you may have a collection | recovery part (not shown) etc. which collect | recover the waste liquids after wash | cleaning the porous resin film F.

  The liquid removing section 34 removes the liquid attached to the porous resin film F after cleaning. Pre-drying etc. may be performed. The liquid removing section 34 is disposed on the + Y side of the cleaning section 33 (forward in the transport direction of the porous resin film F). The liquid draining portion 34 is provided with a water absorbing roller and the like. By bringing the water absorbing roller into contact with the porous resin film F, it is possible to absorb the liquid adhering to the porous resin film F while transporting the porous resin film F. The arrangement of the water absorbing roller in the transport direction is not particularly limited as long as it is immediately before being discharged from the liquid removing section 34. In addition, the water absorbing roller is disposed on at least one of the + Z side and the -Z side of the porous resin film F, preferably on both sides.

  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 liquid removal 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 liquid removing 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.

[Chemical etching unit]
The chemical etching unit 40 is disposed on the + Y side of the removal unit 30. FIG. 6 is a view showing an example of the chemical etching unit 40 and the winding unit 80. As shown in FIG. As shown in FIG. 6, the chemical etching unit 40 includes a chamber 41, a transport unit 42, a chemical etching unit 43, a cleaning unit 44, a liquid removal unit 45, and a heating unit 46. The chamber 41 has a carry-in port 40 a for carrying in the porous resin film F, and a carry-out port 40 b for carrying out the porous resin film F. The chamber 41 accommodates the transport unit 42, the chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45.

  The transport unit 42 transports the porous resin film F in the + Y direction across the chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45. The transport unit 42 includes a transport belt 42 a, a drive roller 42 b, and driven rollers 42 c to 42 e. In addition to the driving roller 42b and the driven rollers 42c to 42e, a support roller for supporting the transport belt 42a may be disposed inside the chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45.

  The conveyance belt 42a is formed in an endless shape, and is disposed along the Y direction. The transport belt 42 a is formed using a material having durability to an etching solution (EQ) described later. For example, the entire surface of the transport belt 42a is formed in a mesh shape, and the etching solution can pass through the transport belt 42a. The transport belt 42a is stretched between the driving roller 42b and the driven roller 42c in a tensioned state so as to be substantially parallel to the XY plane. The porous resin film F is placed on the transport belt 42 a and transported.

  The driving roller 42 b is disposed at the + Y side end inside the chamber 41. The driving roller 42 b is formed, for example, in a cylindrical shape and disposed in parallel to the X direction. The driving roller 42b is provided with, for example, a rotational driving device such as a motor. The driving roller 42 b is rotatably provided about an axis parallel to the X direction by the rotation driving device. As the drive roller 42 b rotates, the transport belt 42 a rotates clockwise in FIG. 6. As the transport belt 42a rotates, the porous resin film F placed on the transport belt 42a is transported in the + Y direction.

  The driven roller 42 c is disposed at the −Y side end inside the chamber 41. The driven rollers 42d and 42e are disposed on the -Z side of the driven roller 42c and the drive roller 42b, respectively. The driven rollers 42c to 42e are formed, for example, in a cylindrical shape, and arranged in parallel to the X direction. The driven roller 42c is formed to have the same diameter as the drive roller 42b, and is disposed so that the position (height position) in the Z direction is substantially equal to that of the drive roller 42b. The driven roller 42d is formed to have the same diameter as the drive roller 42e, and is disposed so that the position (height position) in the Z direction is substantially equal to that of the drive roller 42e. The driven rollers 42c to 42e are provided rotatably about an axis parallel to the X direction. The driven rollers 42c to 42e rotate following the rotation of the transport belt 42a.

  The chemical etching unit 43 chemically etches the porous resin film F to dissolve a part of the porous resin film F. FIG. 7 is a view schematically showing an example of the chemical etching unit 43. As shown in FIG. As shown in FIG. 7, the chemical etching unit 43 has an upper nozzle 43a, a lower nozzle 43b, and a roller 43c.

  The upper nozzle 43a is disposed on the + Z side of the transport belt 42a. The upper nozzles 43a are arranged, for example, in the Y direction. Each upper nozzle 43a has a plurality of discharge ports 43d in the X direction. Each discharge port 43 d is directed to the −Z side. A spray-like etching solution EQ is discharged in the -Z direction from each discharge port 43d. A supply source (not shown) of the etching solution EQ is connected to each upper nozzle 43a.

  The lower nozzle 43 b is disposed on the −Z side of the transport belt 42 a. A plurality of lower nozzles 43b are arranged, for example, in the Y direction. Although FIG. 7 shows the upper nozzles 43a and the lower nozzles 43b alternately arranged in the Y direction, the present invention is not limited to this arrangement. Each lower nozzle 43b has a plurality of discharge ports 43e in the X direction. A spray-like etching solution EQ is discharged in the + Z direction from each discharge port 43e. A supply source (not shown) of the etching solution EQ is connected to each lower nozzle 43b.

  For example, one roller 43 c is disposed at each of the + Y side end and the −Y side end of the chemical etching unit 43. The roller 43c can sandwich the porous resin film F with the transport belt 42a. The roller 43c is rotatable along with the rotation of the transport belt 42a.

  The chemical etching unit 43 may have a recovery unit (not shown) for recovering the waste liquid of the etching solution EQ. The chemical etching unit 43 may have an exhaust unit (not shown) for exhausting the inside.

  In the chemical etching unit 43, when the two rollers 43c both contact the porous resin film F, when the etching solution EQ is discharged from the upper nozzle 43a, the etching solution EQ is a section between the two rollers 43c in the Y direction. It becomes easy to accumulate. By continuously discharging the etching solution EQ from the upper nozzle 43a, a reservoir 47 in which the etching solution EQ is stored is formed in this section. The etching solution EQ ejected from the lower nozzle 43b passes through the mesh of the transport belt 42a and reaches the surface on the -Z side of the porous resin film F. The etching solution EQ that has reached the −Z side of the porous resin film F pushes up the porous resin film F in the + Z direction. In this case, the etching solution EQ ejected from the lower nozzle 43 b is disposed between the porous resin film F pushed up and the transport belt 42 a. Therefore, the porous resin film F is immersed in the etching solution EQ stored in the storage section 47 in a state of apparently floating, and the chemical etching process is performed in this state. Thus, the transport unit 42 immerses the porous resin film F in the etching solution EQ in the storage unit 47.

  For example, an inorganic alkali solution or an organic alkali solution is used as the etching solution EQ. As the inorganic alkali solution, for example, a hydrazine solution containing hydrazine hydrate and ethylenediamine, a solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, sodium silicate or sodium metasilicate, an ammonia solution, water The etching solution etc. which have an alkali oxide, a hydrazine, and a 1, 3- dimethyl- 2- imidazolidinone as a main component etc. are mentioned. As the organic alkaline solution, primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyl diethylamine; dimethylethanolamine And alcohol amines such as triethanolamine; quaternary ammonium salts such as tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide; and alkaline solutions such as cyclic amines such as pyrrole and piheridine. In addition, pure water and alcohol can be suitably selected about the solvent of said each solution. It is also possible to use one added with an appropriate amount of surfactant. The alkali concentration is, for example, 0.01 to 20% by mass.

  Moreover, as another aspect of the chemical etching part 43, the structure which has the upper side nozzle 43a, the roller 43c, and a floor member (not shown) may be sufficient. In this aspect, the configurations of the upper nozzle 43a and the parts of the roller 43c are the same as those in the above embodiment, and thus the description thereof will be omitted. The floor member of the chemical etching unit 43 according to this aspect is provided on the -Z side of the mesh of the transport belt 42a, and is formed along the XY plane. The floor member is disposed to face the transport belt 42a. The floor member may or may not be in contact with the transport belt 42a. When the floor member is arranged to be in contact with the transport belt 42a, the storage portion 47 capable of storing the etching solution EQ is formed in the section between the two rollers 43c. Further, even when the floor member is disposed so as not to be in contact with the conveyance belt 42a, the storage portion 47 can be formed. In this case, the transport belt 42a contacts the two rollers 43c and the floor member by, for example, sandwiching the mesh of the transport belt 42a by the lower portions of the two rollers 43c and the floor member. Therefore, the etchant EQ can be stored in the section between the two rollers 43c, and the reservoir 47 is formed. Such a floor member makes it easier to form the reservoir 47 of the etching solution EQ in the section between the two rollers 43c in the Y direction. Therefore, it is easy to maintain the porous resin film F immersed in the etching solution EQ stored in the storage portion 47. As the material of the floor member, a material having durability may be appropriately selected according to the type or concentration of the etching solution EQ as in the case of the transport belt 42a, and is formed using, for example, vinyl chloride or the like. Further, the floor member may be provided with a plurality of holes penetrating in the Z direction. Thereby, the etching solution EQ can be supplied to the storage section 47 from the supply source of the etching solution EQ through the hole of the floor member. When the hole of the floor member is provided, the upper nozzle 43a may not be provided.

Subsequently, as shown in FIG. 6, the cleaning unit 44 cleans the porous resin film F after chemical etching. The cleaning unit 44 is disposed on the + Y side of the chemical etching unit 43 (forward in the transport direction of the porous resin film F). The cleaning unit 44 has a supply unit (not shown) for supplying a cleaning solution. Moreover, you may have a collection | recovery part (not shown) etc. which collect | recover the waste liquids after wash | cleaning the porous resin film F. Since the liquid contained in the inside is different between the chemical etching unit 43 and the cleaning unit 44, the above-described water absorbing roller may be provided at a position before the chemical etching unit 43 is carried out. The water absorbing roller is disposed on at least one of the + Z side and the -Z side of the porous resin film F, preferably on both sides.

  The liquid removal part 45 removes the liquid adhering to the porous resin film F after cleaning. Pre-drying etc. may be performed. The liquid removal part 45 is disposed on the + Y side of the cleaning part 44 (forward in the transport direction of the porous resin film F). The liquid draining portion 45 is provided with a water absorbing roller and the like. By bringing the water absorbing roller into contact with the porous resin film F, it is possible to absorb the liquid adhering to the porous resin film F while transporting the porous resin film F. The arrangement of the water absorbing roller in the transport direction is not particularly limited as long as it is immediately before being discharged from the liquid removing section 34.

  The heating unit 46 is disposed on the + Y side of the chamber 41 (forward in the transport direction of the porous resin film F). The heating unit 46 heats the porous resin film F after liquid removal by the liquid removal unit 45 at about 100 ° C. to 300 ° C., and performs a drying process or a post-baking process. The heating unit 46 is provided with a heating unit and the like for heating the porous resin film F. On the + Y side of the heating unit 46, an outlet 46b for unloading the porous resin film F is provided.

[Winding unit (2)]
FIG. 8 is a perspective view schematically showing the configuration on the + Y side of the chemical etching unit 40. As shown in FIG.
As shown in FIG. 8, on the + Y side of the chemical etching unit 40, an outlet 46b for unloading the porous resin film F is provided. The porous resin film F carried out of the outlet 46 b is taken up by the take-up unit 80.

  The winding unit 80 is configured such that the shaft member SF is attached to the bearing 81. The shaft member SF winds up the porous resin film F carried out from the outlet 40b to form a roll body RF. The shaft member SF is provided detachably with respect to the bearing 81. When mounted on the bearing 81, the shaft member SF is supported so as to be rotatable about an axis parallel to the X direction. The winding unit 80 has a drive mechanism (not shown) for rotating the shaft member SF attached to the bearing 81. 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 81 in a state where 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. 9 (a) to 9 (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. As a result, the first coating film F1 of the first coating liquid Q1 is formed on the transport base S.

  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. Thereby, as shown to Fig.9 (a), 2nd coating film F2 by a 2nd coating liquid is formed on 1st coating film F1. In the first coating film F1 and the second coating film F2, the fine particles A2 are contained in the resin material A1 at different volume ratios. 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 laminate of the first coating film F1 and the second coating film F2, as shown in FIG. 9B, 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 front end of the peeled unbaked film FA reaches the shaft member SF of the take-up unit 50, the operator manually applies the unbaked film FA to the unloading roller 11f by hand and 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 50 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 50 to form the roll body R. As shown in FIG. 9C, the unbaked film FA constituting the roll body R is in a state of being peeled off from the transport base 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 wound around the shaft member SF, the unbaked film FA is cut and the shaft member SF is removed from the bearing 51 together with the roll body R. Then, a new shaft member SF is attached to the bearing 51 of the take-up portion 50, 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 51 together with the roll body R to the delivery unit 60 and mounts the bearing 61 on the bearing 61. 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 attached to the bearing 61, the non-sintered film FA is sequentially drawn 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. 9D, a 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. Thereby, the fine particles A2 are dissolved in the etching solution and removed, and as shown in FIG. 9E, the porous resin film F including the porous portion A4 in the inside of the resin layer A3 is formed.

  Thereafter, the porous resin film F is sequentially carried into the cleaning unit 33 and the liquid removing unit 34 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. Further, in the liquid removal part 34, the porous resin film F is drained, and the cleaning liquid is removed. Then, the porous resin film F is carried out of the removal unit 30 and carried in the chemical etching unit 40.

  The porous resin film F carried into the chemical etching unit 40 is placed on the transport belt 42a, and transported in the + Y direction as the transport belt 42a rotates. In the chemical etching unit 40, along with the transport of the porous resin film F, first, in the chemical etching unit 43, a chemical etching process is performed on the inside of the porous portion A4. In the chemical etching unit 43, the porous resin film F is immersed in the storage unit 47 of the etching solution EQ, and as shown in FIG. 9 (f), the inside of the porous portion A4 is removed. In this case, the burrs of the porous portion A4 can be removed and the communication can be maintained.

  Thereafter, the porous resin film F is sequentially carried into the cleaning unit 44 and the liquid removing unit 45 in accordance with the rotation of the transport belt 42 a. In the cleaning unit 44, the porous resin film F is cleaned by the cleaning solution, and the liquid removing unit 45 performs the liquid removal. Further, in the liquid removing portion 45, the porous resin film F is drained. Then, in the heating unit 46, the porous resin film F after liquid removal is heated to about 100 ° C. to 300 ° C., and the cleaning solution is removed. The porous resin film F is carried out of the chemical etching unit 40 and taken up by the shaft member SF of the take-up unit 80.

  As described above, the manufacturing system SYS according to the present embodiment includes the fine particles A2 from the fired film FB obtained by firing the unbaked film FA including the resin material A1 and the fine particles A2 of polyamide acid, polyimide, polyamideimide or polyamide. Since the film forming unit 70 for removing and forming the porous resin film F and the chemical etching unit 40 for dissolving a part of the porous resin film F are formed, formation of the unbaked film FA, and firing of the unbaked film FA The three steps of (formation of fired film FB) and removal of fine particles A2 (formation of porous resin film F) can be performed in a series of flows. Thereby, the porous resin film F can be manufactured efficiently. Further, since the inside of the porous portion A4 is removed by the chemical etching unit 40, the hole area ratio of the porous portion A4 can be improved, and the communication of the porous portion A4 can be secured. When such a porous resin film F is used as a separator of a lithium ion battery or the like, the ions move smoothly, so that the electrical characteristics of the battery can be improved. Therefore, a high quality porous resin film F excellent in the hole area ratio can be obtained.

In addition, the chemical etching unit (40) stores the etching solution (EQ) in the storage section (47), and the film transport section (transportation) in which the imide resin film (porous resin film F) is immersed in the etching solution in the storage section. And 42), the chemical etching process can be efficiently performed on the imide resin film.
In addition, the imide resin film (porous resin film F) is formed in a band shape, and the chemical etching unit (49) is an imide resin film (porous resin film F) delivered from the film forming unit (70). In order to take in sequentially, it is applicable to the manufacturing process of a roll-to-roll system etc., and can form an imide type-resin film (porous resin film F) efficiently.
In addition, since the winding section (80) is provided for winding the strip-like imide resin film (porous resin film F) discharged from the chemical etching unit (40), the chemical etching process is performed to wind the imide resin film. It can be efficiently recovered.

  Further, in the method of manufacturing the porous resin film F according to the present embodiment, the porous imide is removed by removing the fine particles from the film (the sintered film FB) containing the polyamic acid, the polyimide, the polyamideimide or the polyamide and the fine particles (A2) The formation of the non-sintered film FA, and the formation of the non-sintered film FA, since it includes forming a base resin film (porous resin film F) and performing chemical etching processing for dissolving a part of the imide resin film. The three steps of firing (formation of fired film FB) and removal of fine particles A2 (formation of 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. Further, since the inside of the porous portion A4 is removed by the chemical etching unit 40, the hole area ratio of the porous portion A4 can be improved, and the communication of the porous portion A4 can be secured.

[Modification]
In the above embodiment, the removal unit 30 and the chemical etching unit 40 are described as separate units arranged separately in the Y direction as an example, but the present invention is not limited to this. FIG. 10 is a diagram showing an example of a part of a manufacturing system SYS2 according to a modification. As shown in FIG. 10, the manufacturing system SYS2 has a configuration in which the removing unit 230 and the chemical etching unit 240 are connected in the Y direction.

  The removing unit 230 has an etching unit 32, a cleaning unit 33, and a liquid removing unit 34. The etching unit 32, the cleaning unit 33, and the liquid removing unit 34 are arranged side by side in the Y direction. The configurations of the etching unit 32, the cleaning unit 33, and the liquid removing unit 34 are the same as those in the above embodiment, and thus the description thereof will be omitted.

  The chemical etching unit 240 has a chemical etching unit 43, a cleaning unit 44, and a liquid removal unit 45. The chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45 are arranged side by side in the Y direction. In addition, since the structure of each part of the chemical etching part 43, the washing | cleaning part 44, and the liquid removal part 45 is the same as that of the said embodiment, description is abbreviate | omitted.

  The removal unit 230 and the chemical etching unit 240 have a common chamber 241 and a common transport unit 242. The chamber 241 includes the components (the etching unit 32, the cleaning unit 33, and the liquid removing unit 34) of the removing unit 230, and the components (the chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45) of the chemical etching unit 240. To accommodate. The chamber 241 has a carry-in port 241 a for carrying in the fired film FB, and a carry-out port 241 b for carrying out the porous resin film F.

The transport unit 242 transports the fired film FB and the porous resin film F in the + Y direction across the removal unit 230 and the chemical etching unit 240. Conveying unit 242 includes a conveyor belt 242a, a driving roller 242b, and a driven roller 242c~ 2 42e. In addition to the driving roller 242b and the driven rollers 242c to 242e, a support roller for supporting the transport belt 242a may be disposed inside the removal unit 230 or the chemical etching unit 240.

  The transport belt 242a is formed in an endless shape, and is disposed along the Y direction. The transport belt 242 a is formed using a material having durability to the etching solution used in the etching unit 32 and the chemical etching solution used in the chemical etching unit 43. The transport belt 242a is formed, for example, in a mesh shape. The transport belt 242a is stretched between the driving roller 242b and the driven rollers 242c to 242e so as to be substantially parallel to the XY plane in a state where it has a tension. The porous resin film F is placed on the transport belt 242 a and transported.

  Although the transport belt 242a may be continuous over the removal unit 230 and the chemical etching unit 240, depending on the etching solution and chemical etching solution used in each unit, or the transport distance of each unit Depending on the situation, it may be divided appropriately.

  The driving roller 242 b is disposed at the + Y side end inside the chamber 241. The drive roller 242 b is rotatably provided about an axis parallel to the X direction. The conveyance belt 242a is configured to rotate clockwise in FIG. 10 by the rotation of the drive roller 242b. As the transport belt 242a rotates, the porous resin film F placed on the transport belt 242a is transported in the + Y direction.

  The driven roller 242 c is disposed at the −Y side end inside the chamber 241. The driven rollers 242d and 242e are disposed on the -Z side of the driven roller 242c and the driving roller 242b, respectively. The driven rollers 242c to 242e are provided rotatably about an axis parallel to the X direction. The driven rollers 242c to 242e rotate following the rotation of the transport belt 42a.

  As described above, the film forming unit (70) includes a liquid (first coating liquid Q1, second coating liquid Q2) containing a polyamide acid, a polyimide, a polyamideimide or a polyamide, and fine particles as a substrate (transport substrate S). The application unit (10) for forming an unbaked film (FA) and the unbaked film peeled off from the substrate inside or outside the application unit are fired to form a fired film (FB) containing fine particles A chemical etching unit (40), and a removing unit (30) for removing fine particles from the fired film to form a porous imide resin film (porous resin film F); Since the imide resin film is connected to the removing unit, chemical etching can be efficiently performed.

  In addition, the porous resin film F is transported from the removal unit 230 to the chemical etching unit 240 by the one transport belt 242 a by the transport unit 242. Therefore, it is not necessary to transfer the porous resin film F between the removal unit 230 and the chemical etching unit 240. Thereby, the external force can be prevented from acting on the porous resin film F as much as possible.

In the above embodiment, showing a take-up unit 50, 80 has been described as a structure for attaching and detaching the shaft member SF in bearings 51 and 81 as an example, not limited to this, in FIG. 1 1, for example Such a winding device 90 may be used. Hereinafter, the case where the winding device 90 is used instead of the winding unit 50 will be described as an example.

  As shown in FIG. 11, 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 R21 to R25 are not limited to the cylindrical shape, and may be formed into a crown of a taper type, a radial type, a concaving type or the like.

  The above-described winding device 90 may be used instead of the winding unit 80. 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 possible to use a winding device 90 in place of the above-described delivery unit 60.

[Separator]
Next, the separator 100 according to the embodiment will be described. FIG. 12 is a schematic view showing an example of the lithium ion battery 200, showing a state in which a part is cut open. As shown in FIG. 12, the lithium ion battery 200 has a metal case 201 which also serves 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. 12, 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, when removing a part of the porous resin film F, the case of performing only the chemical etching method has been described as an example, but the present invention is not limited to this. For example, a part of the porous resin film F may be removed by a method combining the chemical etching method and the physical removal method. As a physical method, for example, dry etching by plasma (oxygen, argon, etc.), corona discharge, etc., an abrasive (eg, alumina (hardness 9), etc.) is dispersed in liquid, and this is the surface of aromatic polyimide film The method of processing the polyimide film surface etc. can be used by irradiating at a speed | rate of 30 m / s-100 m / s. These techniques can be applied either before or after removal of the particles from the fired film FB in the removal unit 30. In addition, as a physical method applicable only when the removal is performed after removing the fine particles, the target surface is pressure-bonded to a base film (for example, a polyester film such as a PET film) wetted with a liquid, and then dried or dried. It is also possible to adopt a method of peeling the resin film F from the backing film. The porous resin film F is peeled from the backing film in a state where only the surface layer of the porous resin film F is left on the backing film due to surface tension or electrostatic adhesion of the liquid.

  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.

  Moreover, although the said embodiment and modification showed and mentioned as an example the structure by which the coating unit 10, the baking unit 20, the removal unit 30, and the chemical etching unit 40 were arrange | positioned to 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 chemical etching unit 40 is each film of the unbaked film FA, the baked film FB, or the porous resin film F. Although the case of conveying along the Y direction has been described as an example, the present invention is not limited 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.

  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 partially removed by the chemical etching unit 40. As this post-processing unit, for example, an antistatic unit that performs a static elimination process on the porous resin film F can be mentioned. For example, a static elimination device such as an ionizer is mounted on the antistatic 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. Also, the chemical etching unit 40 may be interposed before the post-baking process step. In this case, the post-baking process may be performed by the heating unit 46.

  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 chemical etching unit 40 after the processing in the chemical etching unit 40 is completed, the film is cut at a predetermined length without being wound by the winding unit 80. You may collect things.

  SYS, SYS2: Manufacturing system F: Porous resin film (imide resin film) FA: Unbaked film FB: Fired film S: Transport base material (substrate) Q1: First coating liquid (liquid) Q2: Second coating Liquid (liquid) EQ: Etching solution A1: Resin material A2: Fine particles A4: Porous portion 10: Coating unit 20: Firing unit 30, 230: Removal unit 40, 240: Chemical etching unit 42: Conveying portion 43: Chemical etching portion 47 ... Reservoir 70 ... film formation unit 100 ... separator 200 ... lithium ion battery

Claims (6)

A production system for producing a porous imide resin film, comprising:
Removing the particles by immersing the film containing the polyamic acid, polyimide, polyamide imide or polyamide, and the particles in an etchant capable of dissolving or decomposing the particles, or heating the particles to a temperature at which the particles are decomposable A film forming unit for forming the porous imide resin film, in which a large number of continuous holes penetrating in the film thickness direction are formed ;
An imide resin film manufacturing system comprising a chemical etching unit that dissolves a part of the imide resin film.   The imide-based resin film manufacturing system according to claim 1, wherein the chemical etching unit comprises a storage unit for storing an etching solution, and a film transport unit for immersing the imide-based resin film in the etching solution in the storage unit. The imide resin film is formed in a band shape,
The imide system resin film manufacturing system according to claim 1 or 2 in which said chemical etching unit takes in said imide system resin film sent out from said film formation unit one by one.   The imide type-resin film manufacturing system of any one of Claims 1-3 provided with the winding-up part which rolls up the said strip | belt-shaped imide type-resin film | membrane discharged | emitted from the said chemical etching unit. The film forming unit comprises a coating unit for applying a liquid containing a polyamic acid, a polyimide, a polyamideimide or a polyamide, and fine particles to a substrate to form a non-sintered film, and the group inside or outside the coating unit. A firing unit for firing the unbaked film peeled from the material to form a fired film containing the fine particles, and a removing unit for removing the fine particles from the fired film to form the porous imide resin film , Including
The imide resin film manufacturing system according to any one of claims 1 to 4, wherein the chemical etching unit is connected to the removing unit. A method for producing a porous imide resin film, comprising:
Removing the particles by immersing the film containing the polyamic acid, polyimide, polyamide imide or polyamide, and the particles in an etchant capable of dissolving or decomposing the particles, or heating the particles to a temperature at which the particles are decomposable Forming the porous imide resin film in which a large number of continuous pores penetrating in the film thickness direction are formed ;
Performing the chemical etching process which melt | dissolves a part of said imide type-resin film, The imide type-resin film manufacturing method containing these.

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