TW201603897A - Coating apparatus and system for producing porous imide resin film - Google Patents

Abstract

Provided are: a coating apparatus which is capable of producing a high-quality porous imide resin film; and a system for producing a porous imide resin film. A coating apparatus which is provided with: a band-like base (S1) which moves in a predetermined direction; a first nozzle (12) which forms a first coating film (F1) by applying a first coating liquid (Q1) over the band-like base (S1), said first coating liquid (Q1) containing a polyamide acid, a polyimide, a polyamide-imide or polyamide, and fine particles; and a second nozzle (13) which forms a second coating film (F2) by applying a second coating liquid (Q2) over the first coating film (F1), said second coating liquid (Q2) containing a polyamide acid, a polyimide, a polyamide-imide or polyamide, and fine particles such that at least the content ratio of the fine particles is different from that of the first coating liquid (Q1). A system for producing a porous imide resin film.

Description

Coating device and porous yttrium-based resin film manufacturing system

The present invention relates to a coating apparatus and a porous yttrium-based resin film production system.

A lithium ion battery of one type of secondary battery is a structure in which a separator film is disposed between a positive electrode and a negative electrode of an electrolytic solution, and a direct contact between the positive electrode and the negative electrode is prevented by a separator. A lithium transition metal oxide is used for the positive electrode, and for example, lithium or carbon (graphite) or the like is used for the negative electrode. During charging, lithium ions pass through the separator from the positive electrode and move toward the negative electrode. When discharging, lithium ions pass through the separator from the negative electrode and move toward the positive electrode.

This lithium ion battery has doubts such as a negative electrode, a lithium metal precipitated in a dendritic shape, and a decrease in electrical characteristics of the battery due to repeated charging and discharging. For this reason, for example, it is proposed to use a porous separator to improve the electrical characteristics of the lithium ion battery. In the porous separator film, a separator film composed of a porous polyimide film having high heat resistance and high safety has been tried in recent years (see, for example, Patent Document 1).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-111470

[Summary of the Invention]

The porous polyimide film is, for example, coated with an unfired film of polyamic acid or polyimine containing microparticles, and the unfired film is fired to form a fired film, and is self-fired. The film is removed by removing fine particles. However, when the unfired film formed by the conventional coating step is used, the porous polyimide film produced is still insufficient in terms of uniformity, density, and the like of the pores. Therefore, there is a need for a coating apparatus that can produce a higher quality porous polyimide film. Further, it is not limited to a polyimide film, and a coating device capable of forming a high-quality porous film is also required.

In view of the above, an object of the present invention is to provide a coating apparatus for producing a high-quality porous quinone-imide resin film and a porous yttrium-based resin film production system.

A coating apparatus according to a first aspect of the present invention is a coating apparatus for forming a porous yttrium-based resin film, comprising: a substrate that moves in a specific direction; and a poly-proline醯imine, polyamidimide or polyfluorene The first liquid of the amine and the fine particles is applied onto the substrate to form a first coating portion of the first layer; and the polyamine, polyimine, polyamidimide or polyamine may be contained. And the fine particles, and at least the second liquid having a different content rate of the fine particles is applied to the first layer to form the second coating portion of the second layer.

The porous yttrium imide resin film production system according to the second aspect of the present invention is a production system for producing a porous bismuth amide resin film, and includes a coating device according to the first aspect.

According to the aspect of the invention, it is possible to provide a coating apparatus for producing a high-quality porous quinone-imide resin film and a porous yttrium-based resin film production system.

SYS‧‧‧ Manufacturing System

F‧‧‧Porous resin film

FA‧‧‧Unfired film

S1, S2‧‧‧ ribbon substrate

S1b‧‧‧ below

Q1‧‧‧1st coating solution

F1‧‧‧1st coating film

Q2‧‧‧2nd coating solution

F2‧‧‧2nd coating film

F3‧‧‧Layer

R‧‧‧Roll body

A1‧‧‧Resin materials

A2‧‧‧Microparticles

A3‧‧‧ resin layer

A4‧‧‧Porous Department

S3‧‧‧Transporting components

10, 10A, 10B, 210, 310, 310A, 410‧‧‧ coating unit

11‧‧‧Transportation Department

11b‧‧‧Support roller (1st roller)

11c‧‧‧Support roller (2nd roller)

11e‧‧‧Substrate winding roller (winding section)

12‧‧‧1st nozzle (1st coating part)

13‧‧‧2nd nozzle (2nd coating part)

14‧‧‧Drying Department

15‧‧‧Main heating section (heating section)

16‧‧‧Sub heating section (heating section)

17‧‧‧ peeling department

Fig. 1 is a view showing an example of a manufacturing system according to a first embodiment of the present invention.

Fig. 2 is a view showing an example of a nozzle provided in the coating unit of the embodiment.

Fig. 3 is a view showing an example of a drying unit provided in the coating unit of the embodiment.

Fig. 4 is a perspective view showing an example of a winding portion of the embodiment.

Fig. 5 is a perspective view showing an example of a firing unit of the embodiment.

Fig. 6 is a perspective view showing an example of a removing unit of the embodiment.

Fig. 7 is a view showing an example of a manufacturing process of the quinone-based resin film of the present embodiment.

Fig. 8 is a view showing an example of a coating unit of a modification.

Fig. 9 is a view showing an example of a coating unit according to a second embodiment of the present invention.

Fig. 10 is a view showing an example of a coating unit according to a third embodiment of the present invention.

Fig. 11 is a view showing an example of a coating unit of a modification.

Fig. 12 is a view showing an example of a coating unit according to a fourth embodiment of the present invention.

Fig. 13 is a view showing an example of a winding device according to a modification.

Fig. 14 is a view showing an example of a separator film of the embodiment.

In the present invention or the present specification, the layered system refers to an unfired film composed of the first layer and the second layer. When the porous bismuth imide resin film of the present invention is formed, among the first liquid and the second liquid, the same species is used for polyamine, polyimine, polyamidimide or polyamine. In the case of the resin, the unfired film (or the porous yttrium-based resin film) formed of the first layer and the second layer is substantially one layer, but the content of the fine particles is not burned. The film (or a bismuth imine resin film having a porosity in a region having a different porosity) is also included in the first liquid and the second liquid, and is referred to in the present invention or in the present specification. Laminated body.

Embodiments of the present invention will be described below with reference to the drawings. The following uses the XYZ coordinate system to illustrate the direction in the figure. In this XYZ coordinate system, a plane parallel to the horizontal plane serves as an XY plane. One direction parallel to the XY plane is marked in the X direction, and the direction orthogonal to the X direction is marked in the Y direction. Further, the direction perpendicular to the XY plane is marked as the Z direction. The direction of the arrow in the X direction, the Y direction, and the Z direction in the figure is the + direction, and the direction opposite to the arrow direction is described as the - direction.

Fig. 1 is a view showing an example of a manufacturing system SYS. The manufacturing system SYS shown in FIG. 1 is a porous resin film F (porous yttrium-based resin film). The manufacturing system SYS includes a coating unit (coating apparatus) 10 that forms a specific coating liquid, forms an unfired film FA, and a firing unit 20 that fires the unfired film FA to form a fired film FB. The removing unit 30 is formed by removing the fine particles from the fired film FB, and the removing unit 30 for forming the porous resin film F and the control device (not shown) for controlling the respective units described above are integrated.

The manufacturing system SYS is configured, for example, in the upper and lower layers, the coating unit 10 is disposed in the second-order portion, and the firing unit 20 and the removing unit 30 are disposed in the first-order portion. The firing unit 20 and the removing unit 30 disposed in the same order are arranged in the Y direction, for example. However, the firing unit 20 and the removing unit 30 are arranged in the Y direction, for example, in the X direction or the Y direction and the Y direction.

The hierarchical structure of the manufacturing system SYS or the arrangement of each unit of each step is not limited to the above. For example, the coating unit 10 and the firing unit 20 may be disposed in the second-order portion, and the removing unit 30 may be placed in the first-order portion. Also, all units can be configured in the same order. At this time, each unit can be configured in one column or in multiple columns. Also, all units can be configured at different levels.

In the manufacturing system SYS, the unfired film FA is formed into a strip shape. The +Y side of the coating unit 10 (the front side in the conveyance direction of the unfired film FA) is provided with the winding portion 40 in which the strip-shaped unfired film FA is wound into a roll shape. The -Y side of the firing unit 20 (the rear side in the transport direction of the unfired film FA) is provided with the delivery portion 50 that feeds the unfired film FA of the roll shape to the firing unit 20. The +Y side of the removal unit 30 (the front side in the conveyance direction of the fired film FB) is provided with the winding portion 60 in which the porous resin film F is wound into a roll shape.

In this manner, the section (first-order portion) from the delivery unit 50 to the winding unit 60 via the firing unit 20 and the removal unit 30 is processed by a so-called roll-to-roll method. Therefore, in this section, each film of the unfired film FA, the fired film FB, and the porous resin film F is conveyed in a continuous state.

[coating liquid]

Here, the coating liquid which becomes a raw material of the porous resin film F is demonstrated before each unit. The coating liquid contains specific resin materials, fine particles, and a solvent. Specific resin materials include, for example, polyaminic acid, polyimine, polyamidimide, or polyamine. As the solvent, an organic solvent which can dissolve the resin materials can be used.

In the present embodiment, two types of coating liquids (first coating liquid and second coating liquid) having different microparticle content ratios can be used as the coating liquid. With In the first embodiment, the first coating liquid is prepared such that the content ratio of the fine particles is higher than that of the second coating liquid. Thereby, the strength and flexibility of the unfired film FA, the fired film FB, and the porous resin film F can be secured. Moreover, by providing a layer having a low content of fine particles, it is possible to reduce the manufacturing cost of the porous resin film F.

For example, in the first coating liquid, a resin material and fine particles are contained in a volume ratio of 19:81 to 45:65. Further, in the second coating liquid, a resin material and fine particles are contained in a volume ratio of 20:80 to 50:50. However, the content ratio of the fine particles in the first coating liquid is higher than the content ratio of the fine particles in the second coating liquid, and the volume ratio is set. 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, when the volume of the first coating liquid is set to 100, the particles are uniformly dispersed when the volume of the fine particles is 65 or more, and when the volume of the fine particles is 81 or less, the particles are not aggregated and dispersed. Therefore, the porous resin film F can uniformly form pores. Further, when the volume ratio of the fine particles is within this range, the peeling property at the time of film formation of the unfired film FA can be ensured.

When the volume of the second coating liquid is 100, the volume of the fine particles is 50 or more, and the fine particles are uniformly dispersed. When the volume of the fine particles is 80 or less, the fine particles do not aggregate with each other, and the surface does not. Since cracks or the like are generated, the porous resin film F having good electrical characteristics can be stably formed.

The above two types of coating liquids are prepared by, for example, mixing a solvent in which fine particles are dispersed in advance with polyamine, polyimine, polyamidimide or polyamine at an arbitrary ratio. Also, it can be dispersed in advance The solvent of the microparticles is prepared by polymerizing polylysine, polyimine, polyamidamine or polyamine. For example, it can be produced by polymerizing a tetracarboxylic dianhydride and a diamine into a polyphthalic acid in an organic solvent in which fine particles are dispersed in advance, or by further performing ruthenium imidization.

The viscosity of the coating liquid is preferably from 300 to 2500 cP, more preferably from 400 to 1500 cP, and even more preferably from 600 to 1200 cP. When the viscosity of the coating liquid is within this range, the film can be uniformly formed.

In the coating liquid, when the fine particles are dried with polyacrylic acid or polyimine as the unfired film FA, when the material of the fine particles is an inorganic material to be described later, the ratio of the fine particles/polyimine is 2 to 6 ( Mass ratio), it is sufficient to mix the fine particles with polyamic acid or polyimine. More preferably 3 to 5 (mass ratio). When the material of the fine particles is an organic material to be described later, the ratio of the fine particles/polyimine is 1 to 3.5 (mass ratio), and the fine particles may be mixed with polyamic acid or polyimine. More preferably 1.2 to 3 (mass ratio). Further, in the case of the unfired film FA, the volume ratio of the fine particles/polyimine is 1.5 to 4.5, and the fine particles may be mixed with polyamic acid or polyimine. More preferably, it is 1.8 to 3 (volume ratio). When the mass ratio or the volume ratio of the fine particles/polyimine is less than or equal to the lower limit value, the separator can obtain pores having an appropriate density, and when the amount is less than the upper limit, the viscosity does not increase or the film is formed. The problem of cracking in the middle can be stabilized into a film. When the polyacetamide or the polyimine is substituted, and the resin material is polyamidamine or polyamine, the mass ratio is also the same as described above.

Each resin material will be specifically described below.

<polylysine>

The polyamic acid used in the present embodiment is not particularly limited as long as it is obtained by polymerizing any of the tetracarboxylic dianhydride and the diamine. The amount of the tetracarboxylic dianhydride and the diamine to be used is not particularly limited, and is preferably from 0.50 to 1.50 moles, more preferably from 0.60 to 1.30 moles, per mole of the tetracarboxylic dianhydride. Jia uses 0.70~1.20 moules.

As the tetracarboxylic dianhydride, a tetracarboxylic dianhydride which has been conventionally used as a synthetic raw material of polyamic acid can be suitably selected. The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride, but from the viewpoint of heat resistance of the obtained polyamidene resin, aromatic four is preferably used. Carboxylic dianhydride. The tetracarboxylic dianhydride may be used in combination of two or more kinds.

Preferred specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, and bis(2,3-di). Carboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic 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-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3',4,4'-benzophenone tetracarboxylate Acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, 2,2',3,3'-benzophenone tetracarboxylate Acid dianhydride, 4,4-(p-phenylenedioxy)diphthalic dianhydride, 4,4-(m-phenylenedioxy)diphthalic dianhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-double Bismuth phthalate, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, and the like. Examples of the aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and the like. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable in terms of price, availability, and the like. Further, these tetracarboxylic dianhydrides may be used singly or in combination of two or more.

As the diamine, a diamine which has been conventionally used as a synthetic raw material of polylysine can be suitably selected. The diamine may be an aromatic diamine or an aliphatic diamine, but from the viewpoint of heat resistance of the obtained polyimine resin, an aromatic diamine is preferred. These diamines can also be used in combination of 2 or more types.

The aromatic diamine may, for example, be a diamine compound having one or two to ten phenyl groups bonded thereto. Specifically, it is phenylenediamine and its derivatives, diaminobiphenyl compounds and derivatives thereof, diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalenes and Its derivatives, aminophenylaminoindoline (Indane) and its derivatives, diaminotetraphenyl compounds and their derivatives, diaminohexabenzene compounds and their derivatives, cardo type quinone diamine derivatives .

The phenylenediamine is m-phenylenediamine, p-phenylenediamine or the like, and the phenylenediamine derivative is a diamine to which an alkyl group such as a methyl group or an ethyl group is bonded, for example, 2,4-diaminotoluene, 2 , 4-triphenyldiamine, and the like.

The diaminobiphenyl compound is a group in which two aminophenyl groups are bonded to each other with a phenyl group. 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 bonded to each other via a phenyl group. The bond is an ether bond, a sulfonyl bond, a thioether bond, a bond of an alkyl group or a derivative thereof, an imine bond, an azo bond, a phosphine oxide bond, a guanamine bond, a ureido bond, or the like. . When the alkyl group has a carbon number of about 1 to 6, the hydrogen atom of one or more of the alkyl groups of the derivative group is substituted by a halogen atom or the like.

Examples of the diaminodiphenyl compound include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether. 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diamine Diphenyl 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, sub Aminodiphenylamine, 4-methyl-2,4-bis(p-aminophenyl)pentane, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-diaminodiphenylguanamine, 1,4-bis(4-aminophenoxy)benzene, 1,3-double (4 -aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4- Aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-amine Phenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane.

Among these, in terms of price, ease of access, etc. Preferred are p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene and 4,4'-diaminodiphenyl ether.

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

Examples of the diaminonaphthalenes include 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.

Examples of the aminophenylaminoindoline are 5 or 6-amino-1-(p-aminophenyl)-1,3,3-trimethylindoline.

Examples of the diaminotetraphenyl compound include 4,4'-bis(p-aminophenoxy)biphenyl and 2,2'-bis[p-(p'-aminophenoxy)phenyl group. Propane, 2,2'-bis[p-(p'-aminophenoxy)biphenyl]propane, 2,2'-bis[p-(m-aminophenoxy)phenyl]di Benzophenone and the like.

The cardo type quinone diamine derivative may, for example, be 9,9-bisaniline oxime or the like.

The aliphatic diamine has a carbon number of, for example, about 2 to 15, and specific examples thereof include pentaethylenediamine, hexamethylenediamine, and heptylenediamine.

Further, a compound in which a hydrogen atom of the diamine is substituted with at least one substituent selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a cyano group, and a phenyl group may also be used.

The means for producing the poly-proline used in the present embodiment is not particularly limited, and for example, it can be used in an organic solvent to reverse the acid and diamine components. The method of the application, such as the method.

The reaction of the tetracarboxylic dianhydride with the diamine is usually carried out in an organic solvent. The organic solvent used for the reaction between the tetracarboxylic dianhydride and the diamine is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and the diamine and does not react with the tetracarboxylic dianhydride or the diamine. The organic solvent may be used singly or in combination of two or more.

Examples of the organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-diethylacetamidine. Amine, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, N,N,N',N'-tetramethylurea, etc. Nitrogen polar solvent; lactone-based polar solvent such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone; dimethyl Acetone; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cyproterone acetate An ether such as ethyl acetaminophen; a phenolic solvent such as cresol. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but it is preferably such that the content of the produced polyamine is 5 to 50% by mass.

Among these organic solvents, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-di are preferable in terms of solubility of the produced polylysine. Ethyl acetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, N,N,N',N'-tetramethyl A nitrogen-containing polar solvent such as urea.

The polymerization temperature is usually -10 to 120 ° C, preferably 5 to 30 ° C. The polymerization time varies depending on the composition of the raw materials used, and is usually from 3 to 24 hours (hours). Further, the organic solvent solution of the polyamic acid obtained under such conditions preferably has an intrinsic viscosity of from 1,000 to 100,000 cP (percentage of poise) and more preferably from 5,000 to 70,000 cp.

<polyimine]

The polyimine used in the present embodiment is not limited as long as it can dissolve the soluble polyimine of the organic solvent used in the coating liquid, and a conventional one can be used. The polyimine may have a condensable functional group such as a carboxyl group in the side chain or a functional group which promotes a crosslinking reaction or the like at the time of firing.

In order to be a polyimine soluble in an organic solvent, a monomer for introducing a main chain into a soft curved structure can be used, for example, ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane can be used. An aliphatic diamine such as 1,3-diaminocyclohexane or 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-tolidine; An aromatic diamine such as m-tolidine, 3,3'-dimethoxybenzidine or 4,4'-diaminobenzimidamide; polyoxyethylene diamine, polyoxypropylene diamine, poly Polyoxyalkylene diamine such as oxybutylene diamine; polyoxyalkylene diamine; 2,3,3',4'-oxydiphthalic anhydride, 3,4,3',4'-oxygen Phthalic anhydride, 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride, and the like. Further, a monomer having a functional group for improving solubility in an organic solvent is used, and for example, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2-trifluoromethyl can be used. A fluorinated diamine such as 1,4-phenylenediamine. In addition, in addition to the monomer for improving the solubility of the above polyimine, The same monomers as those described in the above column of polyamic acid can be used in combination within the range in which the solubility is inhibited.

The means for producing the polyimine which can be dissolved in the organic solvent used in the present invention is not particularly limited, and for example, polyacrylic acid can be chemically imidized or heated by imidization to dissolve in an organic solvent. Methods such as methods. Examples of the polyimine are aliphatic polyimine (all aliphatic polyimine), aromatic polyimine, and the like, and aromatic polyimine is preferred. The aromatic polyimine may be obtained by a thermal or chemical ring closure reaction of a polylysine having a repeating unit represented by the formula (1), or may have a repeating unit as shown in the formula (2). Polyimine dissolved in solvent. Wherein Ar represents an aryl group.

<polyamidoquinone imine>

The polyamidoximine used in the present embodiment is not limited to its structure or molecular weight as long as it is a soluble polyamidoquinone which can be dissolved in an organic solvent used in the coating liquid, and a conventional one can be used. The polyamidoquinone may have a side chain having a condensable functional group such as a carboxyl group or a functional group which promotes a crosslinking reaction upon firing.

The polyamidoximine used in the present embodiment can be obtained by reacting any trimellitic anhydride with a diisocyanate or by using a reactive derivative of any trimellitic anhydride and a diamine, without particular limitation. The precursor polymer obtained by the reaction is obtained by ruthenium imidization.

Examples of the above-mentioned trimellitic anhydride or a reactive derivative thereof include trimellitic anhydride halides such as trimellitic anhydride and trimellitic anhydride chloride, and trimellitic anhydride.

The diisocyanate may, for example, be an exophenylene diisocyanate, p-phenylene diisocyanate, 4,4'-oxybis(phenyl isocyanate), 4,4'-diisocyanate diphenylmethane, or a double [4- (4-Isocyanate phenoxy)phenyl]anthracene, 2,2'-bis[4-(4-isocyanatephenoxy)phenyl]propane, and the like.

The diamine can be exemplified by the same as exemplified in the description of the aforementioned polyamic acid.

<polyamide>

The polyamine is preferably a polyamine obtained from a dicarboxylic acid and a diamine, and particularly preferably an aromatic polyamine.

Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and A. Kamalyx, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, phthalic acid, isophthalic acid, terephthalic acid and biphenyl Diphenic acid and the like.

The diamine may be the same as the illustrative example of the above polyamic acid.

<microparticle>

Next, the fine particles will be described. The microparticles can be used, for example, in which the true spherical ratio is high and the particle size distribution index is small. Such fine particles are excellent in dispersibility in a liquid, and are in a state in which they do not aggregate. The particle diameter (average diameter) of the fine particles can be set, for example, to about 100 to 2000 nm. By using the fine particles as described above and removing the fine particles in the subsequent steps, the pore diameter of the obtained porous resin film F can be made uniform. The electric field applied to the separator film 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 liquid, and the subsequent step can be removed from the porous resin film F, and a conventional one can be used. For example, examples of the inorganic material include metal oxides such as silica, titanium oxide, and aluminum oxide (Al ₂ O ₃ ). Examples of the organic material include high molecular weight olefins (polypropylene, polyethylene, etc.), polystyrene, epoxy resin, cellulose, polyvinyl alcohol, polyvinyl butyral, polyester, polymethyl methacrylate, Organic polymer microparticles such as polyether. Examples of the fine particles include a ruthenium sol such as (monodisperse) spherical cerium oxide particles, calcium carbonate, and the like. At this time, the pore diameter of the porous resin film F can be made more uniform.

Further, the fine particles contained in the first coating liquid and the fine particles contained in the second coating liquid may be the same or different from each other in terms of true spherical ratio, particle diameter, material, and the like. The fine particles contained in the first coating liquid preferably have a smaller particle size distribution index than the fine particles contained in the second coating liquid. The fine particles contained in the first coating liquid preferably have a lower true spherical ratio than the fine particles contained in the second coating liquid. Further, the fine particles contained in the first coating liquid have a smaller particle diameter (average diameter) than the fine particles contained in the second coating liquid, and particularly, the fine particles contained in the first coating liquid are 100 to 1000 nm. (more preferably, it is 100 to 600 nm), and the fine particles contained in the second coating liquid are preferably 500 to 2000 nm (more preferably 700 to 2000 nm). When the particle diameter of the fine particles contained in the first coating film is smaller than the particle diameter of the fine particles contained in the second coating liquid, the opening ratio of the pores on the surface of the porous resin film F can be made high and uniform. Moreover, the strength of the film can be further improved as compared with the case where the entire porous resin film F is the particle diameter of the fine particles contained in the first coating liquid.

Further, the coating liquid may contain various additives such as a release agent, a dispersant, a condensing agent, a ruthenium imidating agent, and a surfactant, in addition to a specific resin material, fine particles, and a solvent.

[Coating unit]

The coating unit 10 of the present embodiment includes a conveying unit 11, a first nozzle (first coating unit) 12, a second nozzle (second coating unit) 13, a drying unit 14, and a main heating unit (heating unit) 15, The sub heating unit (heating unit) 16 and the peeling unit 17 are provided.

The conveyance unit 11 has a belt-shaped base material (base material) S1, a base material delivery roller 11a, a support roller (first roller) 11b, a support roller (second roller) 11c, The support roller 11d, the substrate winding roller 11e, and the carry-out roller 11f.

The belt-shaped base material S1 is formed into a belt shape. The belt-shaped base material S1 is fed by the base material feed roller 11a, and has a tension across the support rollers 11b to 11d, and is wound by the base material winding roller 11e. Therefore, the lower surface S1b of the strip-shaped substrate S1 is guided by the support rollers 11b to 11d. The material of the belt-shaped base material S1 may, for example, be polyethylene terephthalate (PET), but is not limited thereto, and may be a metal material such as stainless steel.

Each of the rollers 11a to 11f is formed, for example, in a cylindrical shape, and is disposed in parallel with the X direction. Further, each of the rollers 11a to 11f is not limited to the arrangement parallel to the X direction, and at least one of them may be disposed obliquely with respect to the X direction. For example, the rollers 11a to 11f are arranged in parallel with the Z direction, and the height positions in the Z direction can be arranged in the same manner. At this time, the strip-shaped substrate S1 moves in the erect state along the horizontal plane with respect to the horizontal plane (XY plane).

The substrate feeding roller 11a is disposed in a state in which the belt-shaped base material S1 is wound. The support roller 11b is disposed on the +Z side of the substrate feed roller 11a, and is disposed closer to the -Y side than the substrate feed roller 11a. Further, the support roller 11c is disposed on the +Z side of the support roller 11b, and is disposed closer to the +Y side than the support roller 11b. By the arrangement of the three rollers (the substrate feeding roller 11a and the supporting rollers 11b and 11c), the belt-shaped base material S1 is supported by a surface including the end portion on the -Y side of the supporting roller 11b.

Further, the support roller 11d is disposed on the +Y side of the support roller 11c, and is disposed on the -Z side of the support roller 11c. At this time, the belt-shaped base material S1 is supported by the surface including the +Z-side end portion of the support roller 11c by the arrangement of the three rollers supporting the rollers 11b to 11d.

Further, the support roller 11d can be placed at substantially the same height position as the height position (position in the Z direction) of the support roller 11c. At this time, the belt-shaped base material S1 is fed to the support roller 11d by the support roller 11c, and is sent to the +Y direction in a state substantially parallel to the XY plane.

The substrate winding roller 11e is disposed on the -Z side of the support roller 11d. The support roller 12d is wound toward the base material winding roller 11e, and the belt-shaped base material S1 is sent to the -Z direction. The carry-out roller 11f is disposed on the +Y side of the support roller 11d and on the -Z side. The unloading roller 11f sends the unfired film FA formed by the main heating unit 15 to the +Y direction. This unfired film FA is carried out to the outside of the coating unit 10 by carrying out the roller 11f.

The rollers 11a to 11f are not limited to a cylindrical shape, and a tapered crown portion (CROWN) may be formed. At this time, it is useful for the relaxation correction of the rollers 11a to 11f, and the belt-shaped base material S1 or the unfired film FA described later can be brought into uniform contact with the rollers 11a to 11f. Further, the rollers 11a to 11f can also form a crown portion of a radiation type. At this time, it is possible to effectively prevent the meandering of the belt-shaped base material S1 or the unfired film FA. Further, the rollers 11a to 11f may be formed in a crown portion of a CONCAVE type (a portion in which the central portion in the X direction is concavely curved). At this time, the tension is imparted to the X direction, and the belt-shaped base material S1 or the unfired film FA can be conveyed, so that the occurrence of wrinkles can be effectively prevented. The following roller may have a configuration of a crown portion such as a tapered shape, a radiation type, or a concave shape, as described above.

Fig. 2(a) is a perspective view showing an example of the first nozzle 12. As shown in FIG. 1 and FIG. 2( a ), the first nozzle 12 is a coating film (hereinafter referred to as a first coating film F1 ) in which the first coating liquid Q1 is formed on the upper surface S1 a of the belt-shaped base material S1 . The first nozzle 12 has a discharge port for discharging the first coating liquid Q1. 12a. For example, the discharge port 12a is formed in the longitudinal direction substantially the same as the dimension of the strip-shaped base material S1 in the X direction.

The first nozzle 12 is disposed at the discharge position P1. The discharge position P1 is a position in the -Y direction with respect to the support roller 11b. The first nozzle 12 is disposed such that the discharge port 12a faces the +Y direction and is inclined. Therefore, the discharge port 12a faces the belt-shaped base material S1 to support the portion supported by the -Y side end portion of the roller 11b. The first nozzle 12 discharges the first coating liquid Q1 in the horizontal direction (Y direction) from the discharge port 12a with respect to the upper surface S1a of the belt-shaped base material S1.

The first nozzle 12 can be formed, for example, by moving in the Y direction. Therefore, the first nozzle 12 moves in the direction (+Y direction) and the alienation direction (-Y direction) in which the belt-shaped base material S1 can approach. Further, the first nozzle 12 can also move in the X direction or the Z direction. Further, the first nozzle 12 may be provided to be rotatable about an axis parallel to the X direction.

Fig. 2(b) is a perspective view showing an example of the second nozzle 13. As shown in FIG. 1 and FIG. 2(b), the second nozzle 13 is formed on the belt-shaped base material S1 and overlaps with the first coating film F1 to form a coating film of the second coating liquid Q2 (hereinafter referred to as the second Coating film F2). The second nozzle 13 has a discharge port 13a for discharging the second coating liquid Q2. For example, the longitudinal direction is substantially the same as the dimension of the strip-shaped substrate S1 in the X direction to form the discharge port 13a.

The second nozzle 13 is disposed at the discharge position P2. The discharge position P2 is a position corresponding to the support roller 11c, and is located in the +Z direction with respect to the support roller 11c. The second nozzle 13 is disposed such that the discharge port 13a faces the -Z direction. Therefore, the discharge port 13a faces the strip-shaped substrate S1. The portion supported by the +Z side end portion of the support roller 11c. The second nozzle 13 discharges the second coating liquid Q2 in the gravity direction (Z direction) from the discharge port 13a in the belt-shaped base material S1. Therefore, the discharge directions (horizontal direction and gravity direction: application direction) of the first nozzle 12 and the second nozzle 13 are arranged to intersect each other.

The second nozzle 13 can be formed, for example, by moving in the Z direction. Therefore, the second nozzle 13 moves in the direction (-Z direction) in which the belt-shaped base material S1 can be moved and the direction (+Z direction) in the distance. Further, the second nozzle 13 can also move in the X direction or the Y direction. Further, the second nozzle 13 may be provided to be rotatable about an axis parallel to the X direction.

When the first nozzle 12 and the second nozzle 13 do not discharge the coating liquid, they are placed at a standby position (not shown), and when the coating liquid is discharged, the standby position can be moved to the discharge positions P1 and P2, respectively. Further, a portion where the first nozzle 12 and the second nozzle 13 perform a preliminary discharge operation can be provided.

Each of the first nozzle 12 and the second nozzle 13 is connected to a coating liquid supply source (not shown) via a connection pipe (not shown) or the like. For example, the first nozzle 12 and the second nozzle 13 are provided with a holding portion (not shown) that holds a specific amount of the coating liquid. At this time, the first nozzle 12 and the second nozzle 13 may have a temperature adjustment unit that adjusts the temperature of the liquid body held by the holding unit.

The discharge amount of each coating liquid discharged from the first nozzle 12 or the second nozzle 13 or the thickness of the first coating film F1 or the second coating film F2 can be set by each nozzle and each connecting pipe (not shown). The pressure of the pump (not shown) to which the coating liquid supply source (not shown) is connected, the conveyance speed, the position of each nozzle, or the distance between the strip-shaped base material S1 and the nozzle, etc. are adjusted. First coating film F1 or The film thickness of the second coating film F2 is, for example, 0.5 μm to 500 μm.

In the present embodiment, when two types of coating liquids (first coating liquid Q1 and second coating liquid Q2) are used, the film thickness of the first coating film F1 obtained by the first coating liquid Q1 is For example, it is preferable to adjust the film thickness of the second coating film F2 obtained by the second coating liquid Q2 in the range of from 1 μm to 50 μm, in the range of from 0.5 μm to 10 μm.

Further, the drying unit 14 is disposed between the first nozzle 12 and the second nozzle 13 . The drying unit 14 dries the first coating film F1 formed on the belt-shaped base material S1. By drying the first coating film F1 and forming the second coating film F2, for example, it is possible to prevent the fine particles used for the second coating liquid from being mixed with the fine particles of the first coating film F1.

3(a) and 3(b) are views showing an example of the drying unit 14. As shown in FIGS. 3(a) and 3(b), the drying unit 14 includes a gas supply unit 14a, a gas discharge nozzle 14b, an exhaust frame 14c, and a mounting portion 14d.

The gas supply unit 14a heats the gas to a specific temperature as necessary, and supplies it to the gas discharge nozzle 14b. The gas supply unit 14a includes, for example, an infrared heater that heats the gas and a gas delivery unit that transports the heated gas. Further, the heating temperature of the gas is, for example, in the range of 50 ° C to 150 ° C, preferably 50 ° C to 100 ° C. Further, the gas may be ejected from the gas ejection nozzle 14b without heating. In addition, the flow rate of the gas supplied from the gas supply unit 14a may be appropriately adjusted in accordance with the conveyance speed of the belt-shaped base material S1 or the width of the belt-shaped base material S1.

The gas discharge nozzle 14b discharges the gas supplied from the gas supply unit 14a toward the first coating film F1. Gas ejection nozzle 14b It is formed in a long strip shape in the X direction. The gas ejection nozzle 14b has a connection portion 14e. The connecting portion 14e is provided on the end surface of the gas discharge nozzle 14b on the +Z side. The gas discharge nozzle 14b is connected to the gas supply unit 14a via the connection portion 14e.

Further, the gas discharge nozzle 14b has a discharge port 14f for discharging a gas. The discharge port 14f is formed in a slit shape. The longitudinal direction of the discharge port 14f is the X direction. The gas ejection nozzle 14b is a hollow portion having an elongated shape in the X direction. In the gas discharge nozzle 14b, the gas in the gas supply portion 14a is diffused in the X direction, and is formed by ejecting the entire X direction of the discharge port 14f.

The size of the discharge port 14f in the longitudinal direction (X direction) is substantially equal to the width of the strip-shaped base material S1 (the dimension in the X direction). The size of the discharge port 14f in the longitudinal direction may be formed to be larger than the width of the belt-shaped base material S1, or may be formed smaller than the width of the belt-shaped base material S1. The gas discharge nozzle 14b is provided with a discharge adjustment plate 14g. The discharge adjustment plate 14g can adjust the opening width of the discharge port 14f.

The exhaust frame 14c is disposed around the gas discharge nozzle 14b as shown in Fig. 3(b). The exhaust frame 14c is disposed between the gas discharge nozzle 14b and the gap 14h. The exhaust frame 14c is integrally fixed to the gas discharge nozzle 14b in a state where a gap 14h is formed between the gas discharge nozzle 14b and the gas discharge nozzle 14b.

The exhaust frame 14c has a suction port 14i and an exhaust port 14j. The suction port 14i faces the first coating film F1 side (the strip-shaped substrate S1 side). The suction port 14i and the exhaust port 14j communicate with each other via the gap 14h. Again, row The port 14j is formed on the end face of the exhaust frame 14c on the +Z side. The exhaust port 14j is arranged in a plurality of rows in the X direction. In the present embodiment, the exhaust port 14j is provided at two locations. The exhaust port 14j has an exhaust pipe connection. This exhaust pipe is connected to attract a suction source such as a pump. By driving this suction source, the exhaust pipe becomes a negative pressure. Thereby, the gas on the surface of the first coating film F1 is sucked by the suction port 14i by the gap 14h. Further, the gas sucked by the gap 14h is exhausted through the exhaust port 14j via the exhaust pipe. Therefore, it is possible to prevent the gas discharged from the discharge port 14f from leaking on the first nozzle 12 side or the second nozzle 13 side, and it is possible to prevent the discharge ports 12a and 13a from drying.

The mounting portion 14d is attached to a frame (not shown) and fixed. As shown in FIG. 3(a), the mounting portion 14d is disposed such that the strip-shaped base material S1 is placed in the X direction. Therefore, the gas ejected from the discharge port 14f can be prevented from leaking in the X direction.

Next, as shown in FIG. 1, the main heating unit 15 is the +Y side of the second nozzle 13, and is disposed between the support roller 11c and the support roller 11d. In the main heating unit 15, the laminate F3 of the first coating film F1 and the second coating film F2 applied to the belt-shaped base material S1 is heated and dried to form an unfired film FA.

The main heating portion 15 has a chamber 15a and a heater 15b. The cavity 15a accommodates the strip substrate S1 and the heater 15b. The cavity 15a is arranged along the transport direction of the strip-shaped substrate S1, and the end on the +Y side is arranged obliquely on the -Z side. An exhaust duct 15c is provided in the chamber 15a. The exhaust pipe 15c is connected to an exhaust pipe (not shown). The gas in the chamber 15a is exhausted to the outside via the exhaust pipe 15c and the exhaust pipe.

The heater 15b heats the first coating film F1 and the second coating film F2. As the heater 15b, for example, an infrared heater or the like can be used. The heater 15b heats the coating film at a temperature of about 30 ° C to 100 ° C. Further, the heater 15b may be provided to be heated in a plurality of regions in the Y direction.

The sub-heating unit 16 heats the unfired film FA, and the unfired film FA formed by the main heating unit 15 is easily peeled off from the belt-shaped base material S1. The sub heating unit 16 heats the gas to a specific temperature and blows it to the unfired film FA. The heating temperature of the gas of the sub-heating unit 16 is set to a temperature at which the unfired film FA is easily peeled off by the belt-shaped base material S1. In FIG. 1, the sub heating unit 16 is provided separately from the main heating unit 15, but may be provided inside the main heating unit 15.

The peeling portion 17 is a portion where the unfired film FA is peeled off by the belt-shaped base material S1. In the present embodiment, the unfired film FA is peeled off by the operator's hand. However, the present invention is not limited thereto, and automatic peeling by a robot or the like may be used. Moreover, at the time of automatic peeling, the peeling member etc. which can isolate the blade of the unfired film FA from the tape-form base material S1 can be arrange|positioned. The unfired film FA peeled off from the belt-shaped base material S1 is carried out to the outside of the coating unit 10 by the carry-out roller 11f, and is sent to the winding unit 40. Moreover, the strip-shaped base material S1 after the unfired film FA is peeled off is wound by the base material winding roller 11e.

[Winding section (1)]

Fig. 4 is a schematic perspective view showing the configuration of the +Y side of the coating unit 10.

As shown in FIG. 4, the +Y side of the coating unit 10 is provided to carry out the unfired film. FA's export 10b. The unfired film FA carried out by the carry-out port 10b is wound by the winding portion 40.

The winding portion 40 is configured such that the bearing 41 is attached to the shaft member SF. The shaft member SF winds the unfired film FA carried out by the carry-out port 10b to form the roll body R. The shaft member SF is detachably attached to the bearing 41. When the shaft member SF is attached to the bearing 41, it can be supported by being rotated about an axis parallel to the X direction. The winding portion 40 has a drive mechanism (not shown) that can rotate the shaft member SF attached to the bearing 41.

In the unwound film FA, the surface of the uncoated film FA is disposed on the outer side of the first coating film F1, and the unfired film FA is wound. For example, the shaft member SF is rotated counterclockwise about FIG. 1 by a drive mechanism to wind the unfired film FA. In a state in which the reel body R is formed, the shaft member SF is removed by the bearing 41, and the reel body R can be moved to another unit.

[Send out]

Fig. 5 is a perspective view schematically showing a configuration of the -Y side of the firing unit 20.

As shown in Fig. 5, the inlet side 20a of the unfired film FA is placed on the -Y side of the firing unit 20. The delivery unit 50 sends the unfired film FA to the carry-in port 20a.

The delivery portion 50 is a structure in which the shaft member SF can be attached to the bearing 51. The shaft member SF can be used together with the bearing 41 attached to the winding portion 40. Therefore, the shaft member SF taken out from the winding portion 40 can be attached to the bearing 51 of the delivery portion 50. Thereby, the roll body R formed by the winding portion 40 can be formed It is disposed in the delivery unit 50. Further, the bearings 51 of the bearing 51 and the winding portion 40 may be set to have the same height from the ground or may be set to different height positions.

When the shaft member SF is attached to the bearing 51, it can be supported by being rotated about an axis parallel to the X direction. The delivery unit 50 has a drive mechanism (not shown) that rotates the shaft member SF attached to the bearing 51. The shaft member SF is rotated clockwise around FIG. 1 by the drive mechanism, and the unfired film FA constituting the roll body R is sent toward the transfer port 20a. In the wound portion 40, the unfired film FA is disposed on the outer side of the first coating film F1 side to wind the unfired film FA, so that the unfired film FA is pulled by the roll body R When it is out, the 1st coating film F1 side is arrange|positioned on the upper side.

[burning unit]

In the present embodiment, the firing unit 20 performs a high temperature treatment on the unfired film FA. In the firing unit 20, the unfired film FA is fired to form a fired film FB containing fine particles. The firing unit 20 has a cavity 21, a heating unit 22, and a conveying unit 23. The chamber 21 has a transfer inlet 20a into which the unfired film FA is carried, and a transfer port 20b into which the fired film FB is carried out. The cavity 21 houses the heating unit 22 and the conveying unit 23.

The heating unit 22 heats the unfired film FA carried into the cavity 31. The heating unit 22 has a plurality of heaters 22a arranged in the Y direction. As the heater 22a, for example, an infrared heater or the like can be used. The heating portion 22 is disposed so that the end portion on the -Y side of the inside of the cavity 21 crosses the +Y side end portion. The heating unit 22 is substantially the entire Y direction, and the unfired film FA can be used. heating. The heating unit 22 can heat the unfired film FA to, for example, about 120 to 450 ° C. The heating temperature of the heating unit 22 can be appropriately adjusted in accordance with the conveying speed of the unfired film FA or the constituent components of the unfired film FA.

The conveyance unit 23 has a conveyance belt 23a, a drive roller 23b, a passive roller 23c, and tension rollers 23d and 23e. The conveyor belt 23a is formed in an endless shape and arranged along the Y direction. The conveyor belt 23a is formed using a material having durability against the firing temperature of the unfired film FA. The conveyor belt 23a is substantially parallel to the XY plane in a state of being tensioned, and is bridged between the drive roller 23b and the driven roller 23c. The unfired film FA and the fired film FB are conveyed to the +Y direction while being placed on the conveyor belt 23a.

The drive roller 23b is disposed at the +Y side end of the inside of the cavity 21. The drive roller 23b is formed, for example, in a cylindrical shape, and is disposed in parallel with the X direction. The drive roller 23b is provided with a rotary drive such as a motor. The drive roller 23b is arranged to be rotatable about an axis parallel to the X direction by means of the rotary drive. By the rotation of the drive roller 23b, the conveyor belt 23a rotates clockwise around FIG. By the rotation of the conveyor belt 23a, the unfired film FA and the fired film FB placed on the conveyor belt 23a are conveyed to the +Y direction.

The passive roller 23c is disposed at the -Y side end of the inside of the cavity 21. The driven roller 23c is formed, for example, in a cylindrical shape, and is disposed in parallel with the X direction. The driven roller 23c has the same diameter as the driving roller 23b, and the position (height position) in the Z direction is substantially equal to the driving roller 23b. The passive roller 23c is arranged to be rotatable about an axis parallel to the X direction. The passive roller 23c rotates by tracking the rotation of the conveyance belt 23a.

The tension roller 23d is disposed on the +Z side of the driven roller 23c. The tension roller 23d is disposed in parallel with the X direction and is set to be rotatable about the X axis. The tension roller 23d is provided to be movable up and down in the Z direction. The tension roller 23d is placed between the passive roller 23c and the unfired film FA. The tension roller 23d is rotatable in a state in which the film FA is not burned.

The tension roller 23e is disposed on the +Z side of the drive roller 23b. The tension roller 23e is disposed in parallel with the X direction and is provided to be rotatable about the X axis. The tension roller 23e is provided to be movable up and down in the Z direction. The tension roller 23e is adjacent to the drive roller 23b so as to be adjacent to the unfired film FB. The tension roller 23e is rotatable in a state in which the film FB is not fired.

Each of the tension rollers 23d and 23e is in the state of the unfired film FA and the fired film FB, and the unfired film FA and the fired film FB are placed between the passive roller 23c and the drive roller 23b. The part between the two places, blocking the tension from the outside. Thereby, it is possible to prevent an excessive load from being applied to the unfired film FA and the fired film FB. The tension rollers 23d and 23e can be adjusted to prevent tension from being applied to the unfired film FA and the fired film FB disposed in the cavity 21.

[removal unit]

The removal unit 30 has a cavity 31, an etching unit 32, a cleaning unit 33, a drying unit 34, and a conveying unit 35. The chamber 31 has a transfer inlet 30a into which the fired film FB is carried, and a transfer port 30b through which the porous resin film F is carried out. The cavity 31 houses the etching unit 32, the cleaning unit 33, the drying unit 34, and the conveying unit 35.

The etching unit 32 etches the fired film FB to remove the burn The fine particles contained in the film formation FB form a porous resin film F. In the etching portion 32, the sintered film FB is immersed in an etching liquid capable of dissolving or decomposing the fine particles to remove the fine particles. The etching unit 32 is provided with a supply unit (not shown) that supplies such an etching liquid or a storage unit that can store the etching liquid.

The cleaning unit 33 is a porous resin film F after the etching. The cleaning portion 33 is disposed on the +Y side of the etching portion 32 (before the conveyance direction of the porous resin film F). The cleaning unit 33 has a supply unit (not shown) that supplies the cleaning liquid. In addition, a recovery unit (not shown) that collects the waste liquid after washing the porous resin film F, and a liquid removal unit (not shown) that removes the liquid of the porous resin film F may be provided.

The drying unit 34 dries the washed porous resin film F. The drying unit 34 is disposed on the +Y side of the cleaning unit 33 (before the conveyance direction of the porous resin film F). The drying unit 34 is provided with a heating unit or the like that heats the porous resin film F.

The conveyance unit 35 traverses the etching unit 32, the cleaning unit 33, and the drying unit 34, and conveys the fired film FB and the porous resin film F. The conveyance unit 35 has a conveyance belt 35a, a drive roller 35b, and a passive roller 35c. Further, in addition to the driving roller 35b and the driven roller 35c, a supporting roller that supports the conveying belt 35a may be disposed inside the etching portion 32, the cleaning portion 33, and the drying portion 34.

The conveyor belt 35a is formed in an endless shape and arranged along the Y direction. The conveyor belt 35a is formed using a material having durability to the above etching liquid. The conveyance belt 35a is bridged between the drive roller 35b and the passive roller 35c in a state of being in tension with the XY plane. The fired film FB and the porous resin film F are placed on the conveyor belt 35a.

The drive roller 35b is disposed at the +Y side end of the inside of the cavity 31. The drive roller 35b is formed, for example, in a cylindrical shape, and is disposed in parallel with the X direction. The drive roller 35b is provided with a rotary drive such as a motor. The drive roller 35b is arranged to be rotatable about an axis parallel to the X direction by means of the rotary drive. By the rotation of the drive roller 35b, the conveyor belt 35a rotates clockwise around FIG. By the rotation of the conveyance belt 35a, the fired film FB and the porous resin film F placed on the conveyance belt 35a are conveyed to the +Y direction.

The passive roller 35c is disposed at the -Y side end of the inside of the cavity 31. The passive roller 35c is formed, for example, in a cylindrical shape and arranged in parallel with the X direction. The driven roller 35c has the same diameter as the driving roller 35b, and the position (height position) in the Z direction is substantially equal to the driving roller 35b. The passive roller 35c is arranged to be rotatable about an axis parallel to the X direction. The passive roller 35c rotates while tracking the rotation of the conveyor belt 35a.

Further, the removing unit 30 is not limited to the case where the fine particles are removed by etching. For example, when the material of the fine particles is an organic material which decomposes at a lower temperature than the polyimide, the fine particles are decomposed by heating the fired film FB. The organic material is not particularly limited as long as it is an organic material which decomposes at a lower temperature than the polyimide. For example, resin fine particles composed of a linear polymer or a conventional depolymerizable polymer may be mentioned. When a linear polymer is thermally decomposed, the molecular chain of the polymer is irregularly cut, and the depolymerizable polymer is decomposed into a monomeric polymer upon thermal decomposition. Both are decomposed into a low molecular weight body or CO ₂ and disappear from the fired film FB. The decomposition temperature of the fine particles at this time is preferably 200 to 320 ° C, more preferably 230 to 260 ° C. When the decomposition temperature is 200° C. or higher, when the coating liquid is a high boiling point solvent, film formation can be performed, and the selection of the firing conditions in the firing unit 20 can be widened. Further, when the decomposition temperature is less than 320 ° C, no thermal damage is applied to the fired film FB, and only the fine particles can be eliminated.

[Winding section (2)]

Fig. 6 is a schematic perspective view showing the configuration of the +Y side of the removal unit 30.

As shown in FIG. 6, the +Y side of the coating unit 30 is provided with the carry-out port 30b which carries out the porous resin film F. The porous resin film F carried out by the outlet 30b is wound by the winding portion 60.

The winding portion 60 is configured such that the bearing 61 is attached to the shaft member SF. The shaft member SF winds the porous resin film F carried out from the delivery port 30b to form a roll body RF. The shaft member SF is detachably attached to the bearing 61. When the shaft member SF is attached to the bearing 61, it can be supported by being rotated about an axis parallel to the X direction. The winding portion 60 has a drive mechanism (not shown) that can rotate the shaft member SF attached to the bearing 61. The shaft member SF is rotated by a drive mechanism to wind the porous resin film F. In a state in which the reel body RF is formed, the shaft member SF is removed from the bearing 61, and the reel 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 having the above configuration will be described. Figures 7(a) to (f) show porous resins A diagram of an example of the manufacturing process of the film F.

First, in the coating unit 10, an unfired film FA is formed. In the coating unit 10, the substrate feeding roller 11a is rotated to feed the belt-shaped base material S1, and the belt-shaped base material S1 is placed on the supporting rollers 11b to 11d, and then wound by the substrate winding roller 11e. Then, the tape-like substrate S1 is sequentially fed out from the substrate feeding roller 11a, and the substrate winding roller 11e is wound. The belt-shaped base material S1 is conveyed by the support rollers 11b to 11d and the lower surface S1b is guided.

In this state, the first nozzle 12 is placed at the first position P1, and the discharge port 12a is oriented in the +Y direction. Thereby, the discharge port 12a is directed toward the belt-shaped base material S1 by the portion supported by the support roller 11b. Then, the first coating 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 reaches the belt-shaped base material S1, and is applied to the upper surface S1a of the belt-shaped base material S1 as the belt-shaped base material S1 moves. Thereby, as shown in FIG. 7(a), the first coating film F1 obtained by the first coating liquid Q1 is formed on the upper surface S1a of the belt-shaped base material S1. In the first coating film F1, the resin material A1 contains fine particles A2 having a specific volume ratio.

The first coating film F1 moves in the +Z direction as the belt-shaped substrate S1 moves. When the first coating film F1 reaches the drying unit 14, the heating gas is discharged from the discharge port 14f of the gas discharge nozzle 14b, and the surface of the first coating film F1 is dried. Further, the exhaust gas (not shown) connected to the exhaust port 14j is actuated, and the heated gas injected into the first coating film F1 is exhausted through the suction port 14i, the gap 14h, and the exhaust port 14j. Thereby, it is possible to prevent the heating gas from leaking on the side of the first nozzle 12 or the side of the second nozzle 13 The drying of the discharge ports 12a and 13a can be suppressed.

Next, the second nozzle 12 is placed at the second position P2, and the discharge port 13a is oriented in the -Z direction. Thereby, the discharge port 13a is directed toward the belt-shaped base material S1 by the portion supported by the support roller 11c. When the first coating film F1 reaches the -Z side of the discharge port 13a as the belt-shaped base material S1 moves, the second coating 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 belt-shaped base material S1, and is then applied to the belt-shaped base material S1. On the first coating film F1. Thereby, as shown in FIG. 7(b), the second coating film F2 obtained by the second coating liquid is formed on the first coating film F1. In the second coating film F2, the resin material A1 contains fine particles A2 having a specific volume ratio. The content ratio of the fine particles is set such that the first coating film F1 is larger than the second coating film F2. Since the surface of the first coating film F1 is in a dry state by the drying unit 14, the first coating film F1 and the second coating film F2 are hardly mixed with the fine particles A2 and the like, and the first one is maintained. The content ratio of the fine particles of the coating film F1 and the second coating film F2.

In addition, the first coating liquid Q1 and the second coating liquid Q2 are applied to the strip-shaped base material S1, and the first coating liquid Q1 and the second coating liquid Q2 are applied in a state where the portions of the belt-shaped base material S1 are supported by the support rollers 11b and 11c. When the coating liquid Q1 and the second coating liquid Q2 reach the belt-shaped base material S1, the force acting on the belt-shaped base material S1 is received by the support rollers 11b and 11c. Therefore, the occurrence of flexibility, vibration, and the like of the belt-shaped base material S1 is suppressed, and the first coating film F1 and the second coating film F2 are formed in a uniform thickness on the belt-shaped base material S1.

Next, the strip substrate S1 moves, and the first coating film F1 When the laminated portion of the second coating film F2 is carried into the cavity 15a of the main heating portion 15, the first coating film F1 and the second coating film F2 are dried in the main heating portion 15. The main heating unit 15 uses the heater 15b to heat the first coating film F1 and the second coating film F2 at a temperature of, for example, about 50° C. to 100° C. In the temperature range, the strip-shaped substrate S1 is not strained or deformed, and the first coating film F1 and the second coating film F2 can be heated. By drying the laminate of the first coating film F1 and the second coating film F2, an unfired film FA is formed as shown in Fig. 7(c).

When the unfired film FA is formed, when the unfired film FA reaches the sub-heating unit 16 by the movement of the strip-shaped substrate S1, the gas heated to a specific temperature is ejected from the sub-heating unit 16 to the unfired film FA. The unfired film FA is heated. Thereby, the unfired film FA is easily peeled off from the belt-shaped base material S1.

Then, the strip-shaped base material S1 moves, and when the end portion of the unfired film FA reaches the peeling portion 17, the tip end portion is peeled off from the strip-shaped base material S1 by, for example, an operator's hand. In the present embodiment, the material of the belt-shaped base material S1 is, for example, PET. When the first coating film F1 and the second coating film F2 are dried to form the unfired film FA, the strip substrate S1 is easily peeled off. Therefore, the operator is easy to peel off.

After the front end portion of the unfired film FA is peeled off, the belt-shaped base material S1 is moved, and the first coating film F1 is formed by the first nozzle 12 . Then, the second coating film F2 is formed by the second nozzle 13, and the unfired film FA is formed by the main heating portion 15. Thereby, the unfired film FA is formed into a strip shape, and the length of the unfired film FA carried out from the main heating unit 15 to the +Y side is gradually increased. The gradient is long. The operator continues to peel off the unfired film FA at the peeling portion 17. Then, when the unfired film FA after being peeled off reaches the length of the shaft member SF of the winding portion 40, the operator sets the unfired film FA on the carry-out roller 11f by hand, and the unfired film FA The front end portion is mounted to the shaft member SF. Then, the unfired film FA is sequentially formed, and the shaft member SF is rotated in the winding portion 40 in order to fit the peeling. Thereby, the unfired film FA which has been peeled off is sequentially carried out by the coating unit 10, and is wound by the shaft member SF of the winding portion 40 to form the roll body R. As shown in Fig. 7(d), the unfired film FA constituting the roll body R is in a state of being peeled off by the tape-shaped base material S1, and the surface and the inside are exposed.

The work of peeling off the front end portion of the unfired film FA and the work of attaching the front end portion to the shaft member SF after peeling are not limited to the case where the operator performs the work by hand, and for example, an automatic hand or a member for peeling can be used. get on. Further, in order to improve the releasability of the unfired film FA, a release layer may be formed on the surface of the belt-shaped base material S1.

After the unfired film FA of a specific length is wound around the shaft member SF, the unfired film FA is cut, and the shaft member SF is continuously removed from the roll body R by the bearing 41. Then, the new shaft member SF is attached to the bearing 41 of the winding portion 40, and the cut end portion of the unfired film FA is attached to the shaft member SF, and the unfired film FA is formed by the rotation to make a new one. Roll reel R.

Further, for example, the operator transports the shaft member SF that has been removed by the winding body R of the bearing 41 to the delivery unit 50, and is attached to the bearing 51. The transfer operation and mounting operation of the shaft member SF can also be performed by using a robot or transporting The device or the like is automatically performed. After the shaft member SF is attached to the bearing 51, the unfired film FA is sequentially pulled out from the roll body R by rotating the shaft member SF, and the unfired film FA is carried into the cavity 21 of the firing unit 20. Further, when the front end of the unfired film FA is carried into the chamber 21, the operator can also work by hand or automatically using a robot or the like.

The unfired film FA carried into the cavity 21 is placed on the conveyor belt 23a, and is conveyed to the +Y direction in accordance with the rotation of the conveyor belt 23a. Further, the tension can be adjusted using the tension rollers 23d and 23e. Then, the unfired film FA is transferred, and the heating portion 22 is used to perform baking of the unfired film FA.

The temperature at the time of firing varies depending on the structure of the unfired film FA, and is preferably from about 120 ° C to about 375 ° C, more preferably from 150 ° C to 350 ° C. Further, when the organic material is contained in the fine particles, it is necessary to set a temperature lower than the thermal decomposition temperature. When the coating liquid contains polylysine, it is preferable to carry out the ruthenium imidation at the time of baking, but it is not limited to the unfired film. The FA is composed of polyimine, polyamidimide or polyamine. The case where the unfired film FA is subjected to high temperature treatment by the firing unit 20 is used.

Further, for the firing conditions, for example, when the coating liquid contains polyamic acid and/or polyimine, the temperature may be raised to 375 ° C from room temperature for 3 hours, and then held at 375 ° C for 20 minutes or 50 ° C. The scale was gradually increased from room temperature to 375 ° C (each stage was maintained for 20 minutes), and finally, the stage heating was carried out by holding at 375 ° C for 20 minutes or the like. Further, the end portion of the unfired film FA can be fixed to a model made of SUS or the like to prevent deformation.

By this baking, as shown in FIG. 7(e), a fired film is formed. FB. The fired film FB contains fine particles A2 inside the resin layer A3 which is subjected to hydrazine imidization or high temperature treatment. The film thickness of the fired film FB can be measured by measuring the thickness at a plurality of places such as a micrometer to obtain an average value. The preferred average film thickness is preferably from 3 μm to 500 μm, more preferably from 5 μm to 100 μm, still more preferably from 10 μm to 30 μm, when used in a separator film or the like.

When the fired film FB formed by the firing unit 20 is carried out by the firing unit 20, it is unwound and loaded into the removal unit 30. When the front end portion of the fired film FB is carried into the removal unit 30, the operator can perform the work by hand or automatically using a robot or the like.

The fired film FB of the loading and unloading unit 30 is placed on the conveyance belt 35a, and is conveyed to the +Y direction in accordance with the rotation of the conveyance belt 35a. The removal unit 30 is transported along with the fired film FB. First, the fine particles A2 are removed in the etching unit 32. When the material of the fine particles A2 is, for example, cerium oxide, in the etching portion 32, the fired film FB is immersed in an etching liquid such as hydrogen fluoride having a low concentration. By this, the fine particles A2 are dissolved in the etching liquid and removed, and as shown in FIG. 7(f), the porous resin film F containing the porous portion A4 inside the resin layer A3 is formed.

Thereafter, the porous resin film F is sequentially carried into the cleaning unit 33 and the drying unit 34 in accordance with the rotation of the conveyor belt 35a. The cleaning unit 33 cleans the porous resin film F by the cleaning liquid, and then removes the liquid. Further, the dry portion 34 is heated by the porous resin film F after the liquid is removed, and the cleaning liquid is removed. Then, the porous resin film F is carried out from the removal unit 30, and the shaft member SF of the winding portion 60 is wound.

As described above, the coating unit 10 of the present embodiment includes: a strip-shaped substrate S1 that moves in a specific direction; and a first coating liquid Q1 that contains a resin material A1 of polylysine, polyimine, polyamidamine or polyamine, and fine particles A2 is applied to the belt The first nozzle 12 of the first coating film F1 is formed on the substrate S1; and the resin material A1 and the fine particles A2 are contained, and at least the content of the fine particles A2 is different from the first coating liquid Q1. (2) The coating liquid Q2 is applied to the first coating film F1 to form the second nozzle 13 of the second coating film F2. Therefore, two layers having different contents of the fine particles A2 can be formed on the unfired film FA.

Therefore, when the unfired film FA is fired to form the fired film FB, and the fine particles A2 are removed from the fired film FB to form the porous resin film F, the first resin film F and the first coating film F1 are formed. The corresponding layer can form a pore of the porous portion uniformly and densely with respect to the layer corresponding to the second coating film F2. When the porous resin film F is used as a separator film such as a lithium ion battery, the ions are smoothly moved by being disposed on the negative electrode surface side of the first coating film F1 side, so that the electrical characteristics of the battery can be improved. In addition, in the case of forming a porous yttrium imide resin film having the same porosity only in the first coating liquid Q1, the strength of the film can be secured. By using the coating unit 10 of the present embodiment, the porous resin film F is produced based on the unfired film FA formed, and a high-quality porous resin film F can be obtained.

Further, since the manufacturing system SYS of the present embodiment includes the coating unit 10, the formation of the unfired film FA, the firing of the unfired film FA (formation of the fired film FB), and the like can be performed in a series of steps. Three steps of removing the fine particles A2 (formation of the porous resin film F). Thereby, the manufacturing efficiency of the porous resin film F can be improved.

Further, since the base material is formed into a strip-shaped base material (S1), a strip-shaped unfired film (FA) can be formed. Therefore, it can be applied to a manufacturing step such as a roll-to-roll method, and a porous bismuth imide resin film (porous resin film F) can be efficiently formed.

Further, the first roller (support roller 11b) and the second roller (support roller 11c) for guiding the lower surface (S1b) of the strip-shaped base material (S1) are provided, and the second coating portion (second nozzle 13) and the second coating portion are provided. When the second liquid (the second coating liquid Q2) reaches the belt-shaped base material, the force acting on the belt-shaped base material is received by the second roller. Therefore, the occurrence of entanglement or vibration of the belt-shaped base material can be suppressed, and the second layer (second coating film F2) can be formed stably on the belt-shaped base material with a uniform thickness.

In addition, the first roller (support roller 11b) and the second roller (support roller 11c) are disposed in different positions in the vertical direction, and the first application portion (first nozzle 12) and the second application portion (second nozzle 13) Since the respective coating directions are arranged so as to intersect each other, the first layer (first coating film F1) and the second layer (second coating film F2) can be formed at different height positions. Thereby, the first application portion and the second application portion can be disposed by effectively utilizing the space.

In addition, each of the first application portion (first nozzle 12) and the second application portion (second nozzle 13) can move in the direction of approaching and escaping to the base material (the belt-shaped base material S1), so that the first adjustment portion can be adjusted. 1 The distance between the coating portion and the second coating portion and the substrate.

Further, between the first application portion (first nozzle 12) and the second application portion (second nozzle 13), a drying portion for drying at least the surface of the first layer (first coating film F1) is provided ( 14), so in the first coating film F1 and the second coating The resin film, the fine particles, and the like are prevented from being mixed between the film films F2.

Further, a heating unit (15) for heating the laminate (F3) composed of the first layer (first nozzle 12) and the second layer (second nozzle 13) on the base material (the belt-shaped base material S1) is provided. 16), it is possible to form the unfired film FA having two layers having different contents of fine particles.

Further, the heating unit (15, 16) includes a main heating unit (15) that heats the laminate (F3) and a sub heating unit that heats the laminate (unfired film FA) conveyed by the main heating unit to a specific temperature (16). Therefore, the unfired film FA can be formed efficiently, and the unfired film FA can be easily peeled off from the substrate (the belt-shaped substrate S1).

In addition, a laminate (unfired film FA) composed of a first layer (first coating film F1) and a second layer (second coating film F2) on a substrate (ribbon substrate S1) is provided. Since the peeling part (17) peeled off from the base material, the unfired film FA is effectively peeled off.

[Modification 1]

In the above-described first embodiment, the case where the first coating liquid Q1 is applied to the first nozzle 12 in a state where the discharge port 12a is supported by the support roller 11b is used as an example. To illustrate, but not limited to this.

(a) and (b) of FIG. 8 are views showing a configuration example of portions of the coating units 10A and 10B according to the modification.

As shown in Fig. 8(a), the coating unit 10A sets the discharge position P1A at a position deviated from the +Z side by the support roller 11b. At this time, the first nozzle 12 The first coating liquid Q1 is applied in a state where the discharge port 12a faces the belt-shaped base material S1 and deviates from the portion of the support roller 11b (for example, a portion deviated from the +Z side). When a foreign matter is caught between the lower surface S1b of the belt-shaped base material S1 and the support roller 11b, the belt-shaped base material S1 may be bulged to form a projection. When the first coating liquid Q1 is applied to the portion where the projections are formed, the first coating film F1 has a problem that pinholes or the like are formed. On the other hand, in the present modification, the first coating liquid Q1 is caused to reach the portion of the belt-shaped base material S1 and deviated from the support of the support roller 11b, and the first coating film F1 can be prevented from forming a pinhole or the like.

Further, as shown in Fig. 8(b), the coating unit 10B is disposed between the support roller 11b and the support roller 11c, and another support roller 11g is disposed, and the belt-shaped substrate S1 is supported by the roller 11b and the support roller 11g. The state in which the support roller 11c is guided. Moreover, the coating unit 10B sets the discharge position P1B at the position deviated from the +Z side by the support roller 11b. At this time, the first nozzle 12 is applied with the first coating liquid Q1 in a state where the discharge port 12a faces the belt-shaped base material S1 and supports the portion between the roller 11b and the support roller 11g. Thereby, similarly to the above, it is possible to prevent the first coating film F1 from forming a pinhole or the like.

[Second Embodiment]

Next, a second embodiment will be described. Fig. 9 is a view showing an example of the coating unit 210 of the second embodiment. In the above embodiment, the configuration of the belt-shaped base material S1 formed of a resin material such as PET is used as an example. However, in the present embodiment, the material of the belt-shaped base material or the like is different from that of the first embodiment. Hereinafter, the main points are different from the first embodiment. Bright.

As shown in Fig. 9, in the conveying unit 211 of the coating unit 210 of the present embodiment, a belt-shaped base material S2 formed of a metal material such as stainless steel is used as the base material. Since the belt-shaped base material S2 is formed of a metal material, it becomes difficult to form wrinkles or the like. The belt-shaped base material S2 is formed in an endless shape and has tension, and is bridged between the support roller 211a, the support rollers 11b, 11c, and 11d, and the support roller 211e. Therefore, the lower surface S2b of the strip-shaped substrate S2 is guided by the support rollers 211a, 11b, 11c, 11d, and 211e. Each of the strip-shaped base materials S2 is, for example, looped in the clockwise direction of FIG. 9 between the support rollers 211a, 11b, 11c, 11d, and 211e.

Further, the first nozzle 12 forms the first coating film F1 on the upper surface S2a of the strip-shaped substrate S2. Moreover, the second nozzle 13 is placed on the upper surface S2a of the strip-shaped base material S2, and is superposed on the first coating film F1 to form the second coating film F2.

In the main heating unit 15, the laminate F3 formed on the belt-shaped base material S2 is heated. Since the belt-shaped base material S2 is formed of a metal material, the heating temperature in the main heating portion 15 can be set higher than when a base material formed of a resin material is used. Therefore, heating can be performed at a high temperature and for a short period of time, so that the unfired film FA can be efficiently formed. Moreover, the upper surface S2a of the strip-shaped base material S2 is formed, for example, to form a mirror surface in order to easily peel off the formed unfired film FA. Further, in the upper surface S2a, a release layer may be formed in advance by a release agent or the like.

A cleaning portion 212 is disposed between the support roller 211e and the support roller 211a. The cleaning unit 212 cleans the strip-shaped substrate S2 from which the unfired film FA is peeled off. The cleaning portion 212 has the upper surface of the strip substrate S2 removed The removal portion of the foreign matter of S2a. Moreover, the cleaning unit 212 may have a static eliminating portion such as an electrostatic remover, and the strip-shaped substrate S2 may be electrostatically removed.

As described above, in the present embodiment, the belt-shaped base material (S2) is circulated in an endless shape, and the material for forming the belt-shaped base material can be saved, and the cost can be reduced. In addition, since the strip-shaped base material (S2) is formed of a metal material, it is less likely to form wrinkles or the like as compared with the case where the strip-shaped base material is formed of a resin material, and has a structure excellent in durability. Thereby, the unfired film FA can be formed stably.

[Third embodiment]

Next, a third embodiment will be described. Fig. 10 is a view showing an example of the coating unit 310 of the third embodiment. In the present embodiment, the configuration of the conveying unit 311 for conveying the belt-shaped base material S1 is different from that of the first embodiment. Hereinafter, differences from the first embodiment will be mainly described.

As shown in FIG. 10, the conveyance unit 311 has a belt-shaped base material (base material) S1, a base material delivery roller 11a, a support roller (first roller) 11b, and a support roller (second roller) as in the first embodiment. 11c, a support roller 11d, a substrate winding roller 11e, and a carry-out roller 11f.

Moreover, the conveyance part 311 has the conveyance member S3 and the support rollers 311a and 311e. The conveying member S3 is formed in a belt shape, and is formed in an endless shape by using a metal material such as stainless steel. The conveying member S3 has a tension and is bridged between the support supporting roller 311a, the supporting rollers 11b, 11c, 11d and the supporting roller 311e. Therefore, the lower surface of the conveying member S3 is guided by the support rollers 311a, 11b, 11c, 11d, and 311e. The conveying member S3 is between the supporting rollers 311a, 11b, 11c, 11d, and 311e, for example, as shown in the figure. Loop 10 in a clockwise direction.

The belt-shaped base material S1 is formed into a belt shape. The belt-shaped base material S1 is sent out by the base material feeding roller 11a, has a tension across the conveying member S3, and is wound by the base material winding roller 11e. Therefore, the lower surface S1b of the strip-shaped base material S1 is guided by the conveying member S3.

In addition, the first nozzle 12 forms the first coating film F1 on the upper surface S1a of the belt-shaped base material S1 supported by the conveying member S3. In addition, the second nozzle 13 is placed on the upper surface S1a of the belt-shaped base material S1 supported by the conveying member S3, and overlaps with the first coating film F1 to form the second coating film F2. Therefore, the first coating film F1 and the second coating film F2 can be formed stably.

In the main heating unit 15, the laminate F3 formed on the belt-shaped base material S1 is heated. Since the strip-shaped base material S1 is disposed so as to overlap the transporting member S3, it is less likely to form wrinkles or the like than the strip-shaped base material S1 alone, and has a structure excellent in durability. Moreover, since the strip-shaped base material S1 formed using the resin material is disposed on the surface side, it has a structure excellent in peelability. Therefore, it is not necessary to form the surface of the conveying member S3 into a mirror surface. Therefore, the unfired film FA can be formed efficiently and stably.

The peeling portion 17 is formed by peeling off the unfired film FA formed on the belt-shaped base material S1. Therefore, it is easier to peel off than the case where the unfired film FA formed on the strip-shaped base material of the metal material is peeled off.

Further, a cleaning portion 312 is disposed between the support roller 311e and the support roller 311a. The washing unit 312 is a washing and conveying member S3. The cleaning unit 312 has a removal portion that removes foreign matter on the upper surface S3a of the conveying member S3. Thereby, it is possible to prevent between the conveying member S3 and the belt-shaped base material S1. Since the foreign matter is formed, it is possible to suppress the formation of pinholes or the like in the unfired film FA. Further, the cleaning unit 312 may be a static eliminating unit having an electrostatic discharge device or the like, and may be configured to remove static electricity from the conveying member S3.

As described above, according to the present embodiment, the strip-shaped base material (S1) is formed in the base material, and at least the first coating portion (first nozzle 12) and the second coating portion (second nozzle 13) are used. In the range, the conveying member (S3) for conveying the belt-shaped base material is provided, and the conveying member is belt-shaped and is formed in an endless shape, so that the first layer (first coating film F1) and the second layer (second) can be stably formed. Coating film F2). In addition, since the conveyance member (S3) is formed of a metal material, the belt-shaped base material S1 is less likely to form wrinkles or the like, and has a structure excellent in durability.

[Modification 2]

In the third embodiment, the support roller 11b is supported by the support roller 11c, and the belt-shaped base material S1 is transported while being supported by the transport member S3. However, the present invention is not limited thereto.

Fig. 11 is a view showing a configuration example of a part of the coating unit 310A of the modification.

As shown in FIG. 11, between the support roller 11b and the support roller 11c, the auxiliary roller 11h is provided. The auxiliary roller 11h is disposed between the belt-shaped base material S1 and the conveying member S3, and is supported while applying tension to the belt-shaped base material S1. The auxiliary roller 11h is set so as not to be in contact with the conveying member S3. Therefore, between the support roller 11b and the support roller 11c, the belt-shaped base material S1 is conveyed in a state of being separated from the conveyance member S3.

In addition, the first coating liquid 12 is applied to the strip-shaped base material S1, and the first coating liquid Q1 is applied in a state of being displaced from the support portion of the support roller 11b (for example, a portion deviated from the +Z side). Thereby, even when a foreign matter is caught between the lower surface of the belt-shaped base material S1 and the conveying member S3, it is possible to prevent the first coating film F1 from forming a pinhole or the like.

Further, the drying unit 14 is disposed between, for example, the support roller 11b and the auxiliary roller 11h. However, the present invention is not limited thereto, and may be disposed corresponding to the auxiliary roller 11h or may be disposed between the auxiliary roller 11h and the support roller 11c.

[Fourth embodiment]

Next, a fourth embodiment will be described. Fig. 12 is a view showing an example of the coating unit 410 of the fourth embodiment. In the present embodiment, the winding device for winding the unfired film FA is provided in the coating unit 410, which is different from the first embodiment. Hereinafter, the differences from the first embodiment will be mainly described.

As shown in FIG. 12, the coating unit 410 is provided with a winding portion (a roll holding portion) 440. The winding portion 440 is wound by the belt-shaped base material S1 to be supported to support the unfired film FA conveyed by the roller 11i. The configuration of the winding portion 440 is substantially the same as the configuration of the winding portion 40 of the first embodiment. For example, the winding portion 440 is configured to be attached to the shaft member SF of the bearing 441. The shaft member SF is wound to support the unfired film FA conveyed by the roller 11i to form a roll body R. The shaft member SF is detachably attached to the bearing 441. The winding portion 440 has a shaft member that is mounted to the bearing 441 The drive mechanism of the SF rotation without illustration. Further, the winding portion 440 is an unfired film FA, and the surface on the first coating film F1 side is disposed on the outer side to wind the unfired film FA. For example, the shaft member SF is rotated counterclockwise about FIG. 18 by the drive mechanism to wind the unfired film FA. In a state in which the roll body R is formed, the shaft member SF is removed by the bearing 441, and the roll body R can be moved to another unit. Moreover, the strip-shaped base material S1 after the unfired film FA is peeled off is wound by the base material winding roller (winding portion) 11e.

As described above, according to the present embodiment, the roll holding portion (winding portion 440) for holding the roll body (R) of the belt-shaped base material (S1) and the tape-shaped base drawn by the roll body are wound. Since the winding portion (the substrate winding roller 11e) of the material is suitable for the production process such as the roll-to-roll method, the porous yttrium-based resin film (porous resin film F) can be efficiently formed. ). Moreover, the tape-shaped base material after peeling off the unfired film FA is wound by the winding part, and the tape-shaped base material can be collect|recovered efficiently.

[Modification 3]

In the above-described embodiment, the winding portions 40, 60, and 440 are described as an example in which the shaft member SF is detached from the bearings 41, 61, and 441. However, the present invention is not limited thereto. For example, the winding shown in FIG. 13 can be used. Device 90. Hereinafter, a case where the winding unit 40 is used instead of the winding unit 40 will be described as an example.

As shown in FIG. 13, the winding device 90 has a frame body 91, a shaft member SF, a bearing 92, a driving portion 93, relay rollers 94a to 94e, and a roller supporting portion 95. The frame 91 supports each of the shaft member SF, the bearing 92, the drive unit 93, the relay rollers 94a to 94e, and the roller support portion 95.

The shaft member SF winds the unfired film FA carried out by the coating unit 10 to form a roll body R. The shaft member SF is detachably attached to the bearing 92. When the shaft member SF is attached to the bearing 92, it can be rotated about an axis parallel to the X direction and supported by the bearing 92. In a state in which the roll body R is formed, the shaft member SF is removed by the bearing 92, and the roll body R can be moved to another unit or collected.

The relay rollers 94a to 94e adjust the tension of the unfired film FA, and send the unfired film FA to the shaft member SF. The relay rollers 94a to 94e are formed, for example, in a cylindrical shape, and are arranged in parallel with the X direction. In the present embodiment, the unfired film FA is bridged in the order of the relay rollers 94a, 94b, 94c, 94d, and 94e. However, the present invention is not limited thereto, and a part of the relay roller may not be used. Further, at least one of the relay rollers 94a to 94e may be moved by the roller support portion 95. For example, the roller support portion 95 may move the relay roller 94b in the Z direction or the Y direction. Further, the relay roller 94b may be configured to be rotated around the axis AX parallel to the X-axis by the roller support portion 95. At this time, the amount (distance) of the relay roller 94b is moved (rotated) to feed back the winding speed of the bearing 92, and the tension of the unfired film FA can be kept constant. Further, a configuration in which the movable overlap (not shown) disposed via the fulcrum shaft is moved on the -Y side of the relay roller 94b, and the load on the relay roller 94b is changed. At this time, the tension applied to the relay roller 94b by the overlap adjustment can adjust the tension of the unfired film FA.

The relay rollers 94a to 94e are not limited to being arranged in parallel with the X direction, and may be arranged obliquely in the X direction. Further, the relay rollers R21 to R25 are not limited to a cylindrical shape, and may be formed into a tapered type or a radiation type. The crown of the concave type, etc.

Further, the winding device 90 may be used instead of the winding portion 60. In addition, the film of the unfired film FA or the like can be rotated by rotating the film of the unfired film FA or the like in the opposite direction to the winding, and the film of the unfired film FA or the like can be sent out. Therefore, for example, the winding device 90 may be used instead of the above-described delivery portion 50.

[separator film]

Next, the separator film 100 of the embodiment will be described. Fig. 14 is a schematic view showing an example of a lithium ion battery 200 in which a portion is cut. As shown in FIG. 14, the lithium ion battery 200 has a metal case 201 and a negative electrode terminal 202 which are also positive electrode terminals. The positive electrode 201a, the negative electrode 202a, and the separator film 100 are provided inside the metal shell 201, and are immersed in an electrolytic solution (not shown). The separator 100 is disposed between the positive electrode 201a and the negative electrode 202a to prevent electrical contact between the positive electrode 201a and the negative electrode 202a. A lithium transition metal oxide can be used for the positive electrode 201a, and lithium, carbon (graphite) or the like can be used for the negative electrode 202a.

The porous resin film F described in the above embodiment is used as the separator film 100 of the lithium ion battery 200. At this time, for example, the surface on which the first coating film F1 is formed is used as the negative electrode 202a side of the lithium ion battery, and battery performance can be improved. Further, FIG. 14 is an example in which the separator film 100 of the prismatic lithium ion battery 200 is taken as an example, but is not limited thereto. As the porous resin film F, a separator film of a lithium ion battery of any form such as a cylindrical type or a laminated type can be used. Further, the porous resin film F can be used as a fuel cell electrolyte membrane, a gas or liquid separation membrane, or a low dielectric material, in addition to the separator film of the lithium ion battery.

The present invention has been described above with respect to the embodiments, but the present invention is not limited to the above description, and various modifications can be made without departing from the spirit and scope of the invention.

For example, the above-described embodiment is described as an example in which the unfired film FA is peeled off from the strip-shaped base material S1 in the peeling portion 17 provided inside the coating unit 10, but the present invention is not limited thereto. For example, in the coating unit 10, the unfired film FA is not peeled off from the belt-shaped base material S1, and is integrally wound, and is immersed in a liquid such as water outside the coating unit 10 while the film FA is not fired. It can also be peeled off from the strip substrate S1.

Moreover, the aspect in which the unfired film FA is immersed in the liquid is not limited to the case where the unfired film FA is peeled off from the belt-shaped base material S1. For example, the unfired film FA which has been peeled off from the belt-shaped base material S1 may be immersed in a liquid such as water. Thereby, when the unfired film FA is fired, wrinkle formation can be suppressed. In addition, the unfired film FA which is peeled off by the strip-shaped base material S1 may be immersed in a liquid such as water, and the unfired film FA may be forced. Forcible means, for example, a step of pressing the unfired film FA. Thereby, when the unfired film FA is dried or fired, wrinkle formation can be suppressed.

In addition, in the above-described embodiment and modification, the coating unit 10 includes a conveying unit 11, a first nozzle (first coating unit) 12, a second nozzle (second coating unit) 13, a drying unit 14, and a main heating unit. The configuration of the (heating unit) 15, the sub heating unit (heating unit) 16, and the peeling unit 17, but among these, the sub heating unit (heating unit) 16 may be removed.

Further, the above-described embodiments and modifications are three steps of applying the coating unit 10, firing the firing unit 20, and removing the removing unit 30. The case of the case is described as an example, but is not limited thereto. For example, when the material of the coating film is polyimine, polyamidimide or polyamine, the firing may not be performed. Therefore, when the firing is not performed, for example, by providing a winding device, a feeding device, and the like between the firing unit 20 and the removing unit 30, the unfired film FA formed by the coating unit 10 can be prevented from firing. The unit 20 is carried into the removal unit 30. Further, in the case where the firing is not performed, the production system for producing the porous bismuth imide resin film may include: containing polylysine, polyimine, polyamidimide or polyamine and fine particles. a coating unit in which a liquid is applied to a substrate to form an unfired film; and a removal unit in which the fine particles are removed from the unfired film after the substrate is peeled off from the substrate or in the coating unit system.

In the above-described embodiments and modifications, the configuration in which the porous resin film F is formed by a so-called roll-to-roll method is described as an example, but the invention is not limited thereto. For example, when the processing of the removal unit 30 is completed, the porous resin film F is unwound by the winding unit 60, and is cut by a specific length, and the cut person can be recovered.

10, 10B‧‧‧ coating unit

11, 23, 35‧‧‧Transportation Department

11a‧‧‧Substrate feed roller

11b‧‧‧Support roller (1st roller)

11c‧‧‧Support roller (2nd roller)

11d‧‧‧Support roller

11e‧‧‧Substrate winding roller (winding section)

11f‧‧‧ moving out of the wheel

12‧‧‧1st nozzle (1st coating part)

12a, 13a‧‧‧ spitting

13‧‧‧2nd nozzle (2nd coating part)

14, 34‧‧‧Drying Department

15‧‧‧Main heating section (heating section)

15a, 21, 31‧‧‧ cavity

15, 22a‧‧‧ heater

15c‧‧‧Exhaust pipe

16‧‧‧Sub heating section (heating section)

17‧‧‧ peeling department

20‧‧‧burning unit

20a, 30a‧‧‧

20b, 30b‧‧‧ moving out

22‧‧‧ Containment heating department

23a, 35a‧‧‧Transport belt

23b, 35b‧‧‧ drive roller

23c, 35c‧‧‧passive roller

23d, 23e‧‧‧ tension roller

30‧‧‧Removal unit

32‧‧‧Erosion Department

33‧‧‧Decoration Department

40, 60‧‧‧ Winding Department

41, 51, 61‧ ‧ bearings

50‧‧‧Send out

F‧‧‧Porous resin film

F1‧‧‧1st coating film

F2‧‧‧2nd coating film

FA‧‧‧Unfired film

FB‧‧‧Boiled film

P1, P2‧‧‧ spitting position

R, RF‧‧ ‧ roll body

S1‧‧‧Striped substrate

S1a‧‧‧above

S1b‧‧‧ below

SF‧‧‧shaft components

SYS‧‧‧ Manufacturing System

Claims (14)

A coating device for forming a porous bismuth imide resin film, comprising: a substrate that moves in a specific direction; and containing polylysine, polyimine, and polyamine The first liquid of sulfimine, polyamine, and fine particles is applied onto the substrate to form a first coating portion of the first layer; and the polyamine, polyimine, and polyamide An imine, a polyamine, and a fine particle, and at least a second liquid having a different content rate of fine particles is applied to the first layer to form a second coating portion of the second layer. . The coating apparatus of claim 1, wherein the substrate is a strip-shaped substrate formed into a strip shape. The coating device according to claim 2, further comprising a first roller and a second roller that guide the lower surface of the strip-shaped substrate, wherein the second coating portion is disposed corresponding to the second roller. The coating device according to claim 3, wherein the first roller and the second roller are disposed in different positions in the vertical direction, and the coating directions of the first coating portion and the second coating portion are respectively Cross each other to configure. The coating device according to any one of claims 1 to 4, wherein each of the first coating portion and the second coating portion is movable toward and away from the substrate. And formed. The coating device according to any one of claims 1 to 5, wherein the first coating portion and the second coating portion are provided at least in front of each other A drying section for drying the surface of the first layer. The coating apparatus according to any one of claims 1 to 6, further comprising a heating unit that heats the laminate of the first layer and the second layer on the substrate. The coating apparatus according to claim 7, wherein the heating unit includes a main heating unit that heats the laminate, and a sub heating unit that heats the laminate conveyed by the main heating unit to a specific temperature. The coating device according to any one of claims 1 to 8, further comprising a laminate in which the laminate of the first layer and the second layer on the substrate is peeled off from the substrate . The coating device according to the second aspect of the invention, further comprising: a roll holding portion for holding the roll body of the strip-shaped base material; and a roll for winding the strip-shaped base material drawn by the roll body Winding around. The coating apparatus of claim 2, wherein the strip-shaped substrate is formed into an endless shape for circulation. The coating device according to any one of claims 2 to 12, wherein the substrate is a strip-shaped substrate formed into a strip shape, and corresponds to at least the first coating portion and the second coating portion. In the range, the conveying member that conveys the belt-shaped base material is provided, and the conveying member has a belt shape and is formed in an endless shape to circulate. The coating device of claim 12, wherein the conveying member is formed of a metal material. A porous bismuth imide resin film production system for producing a porous bismuth imide resin film manufacturing system, It is a coating apparatus according to any one of claims 1 to 13.