TWI673154B - Porous bismuth imide resin film production system, separator film, and porous bismuth imide resin film production method - Google Patents

Abstract

The present invention provides a porous fluorene-imide-based resin film manufacturing system, a separator, and a method for manufacturing a porous fluorene-imide-based resin film that can improve the production efficiency of a porous fluorene-imide-based resin film.

It is a coating liquid (first coating liquid (Q1)) containing a resin material (A1) and fine particles (A2) containing polyamic acid, polyimide, polyimide, or polyimide And the second coating liquid (Q2) is applied to the transfer substrate (S) to form an unfired coating (FA) coating unit (10), and in this coating unit (10), the transfer substrate (10) S) firing the unfired film (FA) after peeling to form a firing unit (20) of a fired film (FB) containing fine particles and removal of fine particles (A2) from the fired film (FB) Unit (30).

Description

Porous perylene imine-based resin film manufacturing system, separator film, and porous perylene imine-based resin film manufacturing method

The present invention relates to a porous fluorene imine-based resin film manufacturing system, a separation film, and a porous fluorene-imide resin film manufacturing method.

A lithium-ion battery, which is a type of secondary battery, has a structure in which a separator is arranged between a positive electrode and a negative electrode which are immersed in an electrolytic solution. The separator prevents direct electrical contact between the positive electrode and the negative electrode. The positive electrode uses a lithium transition metal oxide, and the negative electrode uses, for example, lithium or carbon (graphite). During charging, lithium ions move from the positive electrode through the separator to the negative electrode, and during discharge, lithium ions move from the negative electrode through the separator to the positive electrode. Such a separator has been known in recent years as a separator composed of a porous polyimide film having high heat resistance and high safety (see, for example, Patent Document 1).

[Prior technical literature] [Patent Literature]

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

The porous polyimide film is, for example, applied to form an unfired film of polyamic acid or polyimide containing fine particles, and the unfired film is fired to form a fired film, and self-fired It is formed by removing fine particles from the film. Conventionally, there has not been a manufacturing system in which the above three steps are performed in one line. Therefore, the production efficiency of a porous polyimide film is not high. Therefore, a more efficient system needs to be manufactured.

In view of the above circumstances, an object of the present invention is to provide a porous ammonium resin film manufacturing system, a separator, and a porous ammonium resin that can improve the production efficiency of a porous ammonium resin film Film manufacturing method.

According to the first aspect of the present invention, a porous amidine resin film production system is a production system for producing a porous amidine resin film, and the system includes: polyamine, polyimide, Polyamide, imine, or liquid of polyamine and fine particles are applied to the substrate to form an unfired coating unit; unfired after peeling from the substrate in or outside the coating unit The film is fired to form a firing unit for a fired film containing fine particles and a removing unit for removing the fine particles from the fired film.

The separator film according to the second aspect of the present invention is a separator formed by using a porous sulfonium-based resin film, and the porous resin film according to the first aspect of the pore is based on a porous Made of fluorene imide resin film Build system.

The third aspect of the present invention is a porous osmium resin. A method for producing a film, which is a method for producing a porous sulfonium-based resin film, comprising: coating a liquid containing polyamic acid, polyimide, polyimide, polyimide, or polyimide and fine particles After the cloth is applied to the substrate, the substrate is peeled to form an unfired film; the unfired film is fired to form a fired film containing fine particles; and the fine particles are removed from the fired film.

According to the aspect of the present invention, it is possible to improve the production efficiency of a porous fluorene-imide-based resin film.

SYS, SYS2, SYS3, SYS4, SYS5 ‧‧‧ manufacturing system (Porous hydrazine resin manufacturing system)

F‧‧‧Porous Resin Film (Porous Polyimide-based Resin Film)

FA‧‧‧Unfired

FB‧‧‧fired film

S‧‧‧ Conveying substrate (substrate)

Q1‧‧‧The first coating liquid

F1‧‧‧The first coating film

Q2‧‧‧Second coating solution

F2‧‧‧The second coating film

A1‧‧‧Resin material

A2‧‧‧ Particle

R, RS, RF‧‧‧ roll

10‧‧‧ Coating Unit

12‧‧‧The first nozzle

13‧‧‧ Nozzle 2

14‧‧‧ Drying section

15‧‧‧ stripping department

20‧‧‧ firing unit

30‧‧‧ Remove unit

32‧‧‧Etching Department

40, 60, 73‧‧‧ Winding section

72‧‧‧ Dip

80‧‧‧ post-processing unit

81‧‧‧static prevention unit

82‧‧‧etching unit

90‧‧‧ Winding device

100‧‧‧ separator

200‧‧‧lithium-ion battery

[FIG. 1] A diagram showing an example of a manufacturing system according to an embodiment of the present invention.

[Fig. 2] A diagram showing an example of a nozzle provided in a coating unit of this embodiment.

Fig. 3 is a perspective view showing an example of a winding portion according to this embodiment.

Fig. 4 is a perspective view showing an example of a firing unit according to this embodiment.

Fig. 5 is a perspective view showing an example of a removal unit according to this embodiment.

FIG. 6 is a diagram showing an example of a manufacturing process of a fluorene imine-based resin film according to this embodiment.

FIG. 7 is a diagram showing an example of a manufacturing system according to a modification.

FIG. 8 is a diagram showing an example of a manufacturing system according to a modification.

FIG. 9 is a diagram showing an example of a manufacturing system according to a modification.

FIG. 10 is a diagram showing an example of a manufacturing system according to a modification.

11 is a diagram showing an example of an etching unit according to a modification.

[Fig. 12] A diagram showing an example of a winding device according to a modification.

FIG. 13 is a diagram showing an example of a separation film according to the embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. the following Use the XYZ coordinate system to explain the orientation in the figure. In this XYZ coordinate system, a plane parallel to the horizontal plane is taken as the XY plane. A direction parallel to the XY plane is marked as the X direction, and a direction orthogonal to the X direction is marked as the Y direction. A direction perpendicular to the XY plane is referred to as a Z direction. Each of the X direction, the Y direction, and the Z direction in the drawing is a + direction, and a direction opposite to the arrow direction is described as a-direction.

FIG. 1 is a diagram showing an example of a manufacturing system SYS. Figure 1 The manufacturing system SYS shown below is one that manufactures a porous resin film F (a porous imine resin film). The manufacturing system SYS includes a coating unit 10 that applies a specific coating liquid to form an unfired film FA, a firing unit 20 that fires the unfired film FA to form a fired film FB, and a self-fired film FB The removal unit 30 for removing fine particles to form a porous resin film F, and a control device (not shown) that integrally controls the above units.

The manufacturing system SYS is composed of two layers, for example, The cloth unit 10 is arranged in the second-stage part, the firing unit 20 and the removing unit 30 is arranged in the first-order section. The firing units 20 and the removing units 30 arranged at the same stage are arranged in the Y direction, for example, but are not limited thereto. For example, they may be arranged in the X direction or a combined direction of the X direction and the Y direction.

Hierarchical structure of manufacturing system SYS or each unit of each stage The arrangement and the like are not limited to those described above. For example, the coating unit 10 and the firing unit 20 may be arranged in a second-stage portion, and the removal unit 30 may be arranged in a first-stage portion. In addition, all the units may be arranged at the same stage. At this time, each unit may be arranged in one row or in plural rows. In addition, all units can be arranged in different levels.

In the manufacturing system SYS, the unfired film FA is formed into a band shape. The + Y side of the coating unit 10 (front of the unfired film FA in the conveying direction) is provided with a winding portion 40 for winding the tape-shaped unfired film FA into a roll shape. The -Y side of the firing unit 20 (behind the conveyance direction of the unfired film FA) is provided with a delivery unit 50 that sends the roll-shaped unfired film FA to the firing unit 20. The + Y side of the removal unit 30 (forward of the conveyance direction of the fired film FB) is provided with a winding portion 60 for winding the porous resin film F into a roll shape.

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

[Coating liquid]

Here, before explaining each unit, the coating liquid used as a raw material of the porous resin film F is demonstrated. The coating liquid contains a specific resin material, fine particles, and a solvent. Specific resin materials include, for example, polyamic acid, polyimide, polyimide, or polyimide. As the solvent, an organic solvent that can dissolve these resin materials can be used.

In the present embodiment, the coating liquid may contain fine particles. Two types of coating liquids (a first coating liquid and a second coating liquid) having different ratios. Specifically, the first coating liquid is prepared so that the content of fine particles is higher than that of the second coating liquid. This ensures the strength and flexibility of the unfired film FA, the fired film FB, and the porous resin film F. In addition, by providing a layer having a low content rate of fine particles, it is possible to reduce the manufacturing cost of the porous resin film F.

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

In the above case, the entire volume of the first coating liquid is set. When it is 100, when the volume of the fine particles is 65 or more, the particles are uniformly dispersed, and when the volume of the fine particles is less than 81, the particles are not aggregated and dispersed. Therefore, the porous resin film F can form pores uniformly. In addition, when the volume ratio of the fine particles is within this range, peelability during film formation of the unfired film FA can be secured.

When the entire volume of the second coating liquid is set to 100, fine particles When the volume of the particles is 50 or more, the fine particles are uniformly dispersed, and when the volume of the particles is less than 80, the particles will not agglomerate with each other, and the surface will not crack, so it can form stable electrical properties. A porous resin film F.

The two types of coating liquids are dispersed in advance by, for example, The fine particle-containing solvent is prepared by mixing polyamic acid, polyimide, polyimide, or polyimide at an arbitrary ratio. Moreover, it can also be prepared by polymerizing polyamic acid, polyimide, polyimide, or polyimide in a solvent in which fine particles are dispersed in advance. For example, it can be produced by polymerizing tetracarboxylic dianhydride and diamine into a polyfluorinated acid in an organic solvent in which fine particles are dispersed in advance, or by further carrying out imidization to form polyimide.

The viscosity of the coating liquid is finally preferably 300 ~ 2500cP, more It is preferably in the range of 400 to 1500 cP, and more preferably in the range of 600 to 1200 cP. When the viscosity of the coating liquid is within this range, a uniform film can be formed.

In the coating solution, fine particles are mixed with polyamic acid or polyfluorene When imine is dried as unfired film FA, when the material of the fine particles is an inorganic material described later, the ratio of fine particles / polyimide becomes 2 to 6 (mass ratio), and the fine particles are mixed with polyamic acid or polyimide Amine is sufficient. More preferably, it is 3 to 5 (mass ratio). When the material of the fine particles is an organic material described later, the ratio of the fine particles / polyimide is 1 to 3.5 (mass ratio), and the fine particles and the polyamic acid or polyimide may be mixed. More preferably, it is 1.2 to 3 (mass ratio). In the case of unfired film FA, the volume ratio of the fine particles / polyimide is 1.5 to 4.5, and the fine particles may be mixed with the polyamic acid or polyimide. More preferably, it is 1.8 to 3 (volume ratio). When used as unfired film FA, fine particles / polyimide When the mass ratio or volume ratio is above the lower limit value, pores of an appropriate density can be obtained for the separation film. When it is below the upper limit value, no increase in viscosity or cracks in the film can be caused, and the film can be formed stably. When the polyamic acid or polyimide is substituted and the resin material is polyimide or polyimide, the mass ratio is also the same as described above.

Each resin material will be specifically described below.

<Polyamic acid>

The polyamino acid used in this embodiment is obtained by polymerizing any tetracarboxylic dianhydride and diamine, and it can be used without particular limitation. The amount of tetracarboxylic dianhydride and diamine used is not particularly limited. Compared to 1 mol of tetracarboxylic dianhydride, 0.50 to 1.50 mol of diamine is preferred, and 0.60 to 1.30 mol is more preferred. It is best to use 0.70 ~ 1.20 moles.

Tetracarboxylic dianhydride can be appropriately selected as a polyamine Tetracarboxylic dianhydride used as a synthetic raw material. The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride, but from the viewpoint of the heat resistance of the obtained polyimide resin, it is preferable to use an aromatic tetracarboxylic dianhydride. Carboxylic dianhydride. 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, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyl Phenyl) 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-double (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 tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-di Carboxyphenyl) ether dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylene dioxy) diphthalic dianhydride, 4 , 4- (m-phenylene dioxy) diphthalic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, 2,3,6 , 7-Anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bisphthalic anhydride hydrazone, 3,3 ', 4,4'-diphenyl碸 tetracarboxylic dianhydride and so on. 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 preferred in terms of price and availability. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Diamine can be used as a suitable synthetic source of polyamines Material used in the diamine. The diamine may be an aromatic diamine or an aliphatic diamine, but in terms of the heat resistance of the obtained polyimide resin, an aromatic diamine is preferred. These diamines may be used in combination of two or more kinds.

Aromatic diamines, including one or two to ten left bonds Diamino compound of right phenyl. Specifically, phenylenediamine and its derivatives, diamino biphenyl compounds and its derivatives, diamino diphenyl compounds and its derivatives, diamino triphenyl compounds and its derivatives, diamino naphthalene and Derivatives thereof, aminophenylaminoindane (Indane) and derivatives thereof, diamines Tetraphenyl compounds and their derivatives, diaminohexabenzene compounds and their derivatives, and cardo-type fluorene diamine derivatives.

Phenylenediamine is m-phenylenediamine, p-phenylenediamine, etc. Organisms are diamines bonded to alkyl groups such as methyl and ethyl, such as 2,4-diaminotoluene and 2,4-triphenyldiamine.

Diamino biphenyl compounds are two amino phenyl groups Bonding here. For example, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl and the like.

Diamine diphenyl compounds are two aminophenyl via other And phenyl groups are bonded to each other. The bond is an ether bond, a sulfonyl bond, a thioether bond, a bond with an alkylene group or a derivative thereof, an imine bond, an azo bond, a phosphine oxide bond, a fluorenyl bond, a ureido bond, etc. . An alkylene bond has a carbon number of about 1 to 6, and its derivative group is one in which more than one hydrogen atom of an alkylene group is replaced by a halogen atom or the like.

Examples of diaminodiphenyl compounds include 3,3'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylphosphonium, 3,4'-di Aminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2 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, iminodiphenylamine, 4-methyl-2,4-bis (p-amine Phenyl) pentane, bis (p-aminophenyl) phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodi Phenylurea, 4,4'-diaminodiphenylphosphoniumamine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] Hydrazone, bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like.

Among these, in terms of price, availability, etc., P-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferred.

Diamine triphenyl compounds are two amine phenyl and one extension The phenyl groups are all bonded through other groups, and the other groups are the same as those of the diaminodiphenyl compound. Examples of the diamino triphenyl 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 diaminonaphthalene include 1,5-diaminonaphthalene and 2,6- Diaminonaphthalene.

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

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

Cardo-type fluorene diamine derivatives include 9,9-bisaniline fluorene Wait.

The aliphatic diamine is, for example, one having 2 to 15 carbon atoms, specifically, Examples include pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and the like.

Furthermore, the hydrogen atom of these diamines may be replaced by a halogen atom. A compound substituted with at least one kind of substituent selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, a cyano group, and a phenyl group.

There is no means for producing the polyamic acid used in this embodiment There is a special limitation, for example, a conventional method such as a method for reacting an acid and a diamine component in an organic solvent can be used.

The reaction of tetracarboxylic dianhydride with diamine, usually in organic solvents In progress. The organic solvent used for the reaction of tetracarboxylic dianhydride and diamine is not particularly limited as long as it can dissolve tetracarboxylic dianhydride and diamine and does not react with tetracarboxylic dianhydride and diamine. The organic solvents can be used alone or in combination of two or more.

Organic solvents used in the reaction of tetracarboxylic dianhydride and diamine Examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, Nitrogen-containing polar solvents such as N-diethylformamide, N-methylcaprolactam, N, N, N ', N'-tetramethylurea; β-propiolactone, γ-butyrolactone , Γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone and other lactone-based polar solvents; dimethyl sulfene; acetonitrile; fatty acids such as ethyl lactate and butyl lactate Esters; ethers of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cyperidine acetate, ethyl cyperidine acetate; etc. Phenolic solvents such as phenols. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but it is preferred that The content is 5 to 50% by mass.

Among these organic solvents, In terms of solubility, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, and N, N-dimethylformamidine are preferred. Nitrogen-containing polar solvents such as amines, N, N-diethylformamide, N-methylcaprolactam, N, N, N ', N'-tetramethylurea and the like.

The polymerization temperature is generally -10 to 120 ° C, preferably 5 to 30 ° C. Although the polymerization time varies depending on the composition of the raw materials used, it is usually 3 to 24 Hr (hours). In addition, the inherent viscosity of the organic solvent solution of the polyamic acid obtained under such conditions is preferably in the range of 1,000 to 100,000 cP (percent poise), and more preferably in the range of 5,000 to 70,000 cP.

<Polyimide>

The polyimide used in this embodiment is not limited in structure or molecular weight as long as it is a soluble polyimide that can dissolve the organic solvent used in the coating solution, and it can be used by a conventional one. The polyfluorene imine may have a condensable functional group such as a carboxyl group in a side chain, or a functional group that promotes a crosslinking reaction or the like during firing.

In order to be polyimide soluble in organic solvents, Monomers for introducing a flexible, curved structure into the main chain, for example, ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4, Aliphatic diamines such as 4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-dimethyltoluidine, m-dimethyltoluidine, 3,3'-dimethoxy Aromatic diamines such as benzidine, 4,4'-diaminobenzidine aniline; polyoxyethylene Diamine, polyoxypropylene diamine, polyoxybutylene diamine, etc .; polyoxyalkylene diamine; polysiloxane diamine; 2, 3, 3 ', 4'-oxydiphthalic anhydride, 3, 4,3 ', 4'-oxydiphthalic anhydride, 2,2-bis (4-hydroxyphenyl) propane dibenzoate-3,3', 4,4'-tetracarboxylic dianhydride Wait. Moreover, a monomer having a functional group that improves the solubility in an organic solvent is used, and for example, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2-trifluoromethyl Fluorinated diamines such as 1,4-phenylenediamine. In addition to the monomers for improving the solubility of the polyimide, as long as the solubility is not inhibited, the same monomers as those described in the column of the polyamidic acid can be used in combination.

Polymers soluble in organic solvents used in the present invention The method of hydrazone is not particularly limited, and for example, a conventional method such as a method of chemically hydrazone of a polyamic acid or heating hydrazone to dissolve it in an organic solvent can be used. Examples of such polyimide include aliphatic polyimide (full aliphatic polyimide), aromatic polyimide, and the like, and aromatic polyimide is preferred. The aromatic polyimide may be obtained by a polyamic acid having a repeating unit represented by the formula (1) by a thermal or chemical ring closure reaction, or an aromatic polyimide having a repeating unit represented by the formula (2) Polyimide is dissolved in a solvent. In the formula, Ar represents an aryl group.

<Polyamide and imine>

As long as the polyamidoamine imine used in this embodiment is a soluble polyamidoamine imine that is soluble in the organic solvent used in the coating liquid, the structure or molecular weight is not limited, and a known one can be used. The polyamidamine / imine may have a condensable functional group such as a carboxyl group at its side chain, or a functional group that promotes a crosslinking reaction during firing.

The polyamidoamine imine used in this embodiment can be used without any particular limitation, obtained by reacting any trimellitic anhydride with a diisocyanate, or a reactive derivative of any trimellitic anhydride with a diamine. The precursor polymer obtained by the reaction is obtained by amidation.

Examples of the arbitrary trimellitic anhydride or a reactive derivative thereof include trimellitic anhydride halides, trimellitic anhydride esters, and the like, such as trimellitic anhydride, trimellitic anhydride chloride, and the like.

Examples of diisocyanates include m-phenylene diisocyanate Ester, p-phenylene diisocyanate, 4,4'-oxybis (phenyl isocyanate), 4,4'-diisocyanate diphenylmethane, bis [4- (4-isocyanatephenoxy) phenyl ] 碸, 2,2'-bis [4- (4-isocyanatephenoxy) phenyl] propane and the like.

Examples of the diamine include those described in the foregoing description of the polyamidic acid. Show the same.

<Polyamine>

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 formic acid. Maleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, phthalic acid, isophthalic acid, terephthalic acid and biphenyl Formic acid (Diphenic acid) and the like.

Examples of the diamines are the same as those described above for the polyamidic acid. Kind of person.

<Fine particles>

Next, fine particles are described. As the fine particles, for example, those having a high true sphere ratio and a small particle size distribution index can be used. Such fine particles have excellent dispersibility in a liquid and are in a state where they do not aggregate with each other. The particle diameter (average diameter) of the fine particles can be set to, for example, about 100 to 2000 nm. By using the fine particles as described above 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 partition 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 solution and can be removed from the porous resin film F in the subsequent steps, and it can be a known one. 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 particles such as polyether. Examples of the fine particles include (monodisperse) silica sols such as spherical silica particles, calcium carbonate, and the like. In this case, the pore diameter of the porous resin film F can be made more uniform.

The fine particles contained in the first coating liquid and the second coating The fine particles contained in the liquid may be the same or different from each other in terms of sphericity, particle size, and materials. The particle size distribution index of the fine particles contained in the first coating liquid is smaller or the same as that of the fine particles contained in the second coating liquid. Or, the fine particles contained in the first coating liquid have a true sphere ratio smaller than or the same as the fine particles contained in the second coating liquid. The particle size (average diameter) of the fine particles contained in the first coating liquid is preferably smaller than the fine particles contained in the second coating liquid. In particular, the fine particles contained in the first coating liquid are 100 to 1000 nm. (More preferably 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). The particle diameter of the fine particles contained in the first coating film is made smaller than that of the fine particles contained in the second coating liquid, so that the opening ratio of the pores on the surface of the porous resin film F can be made high and uniform. Moreover, compared with the case where the whole porous resin film F is the particle diameter of the microparticles | fine-particles contained in a 1st coating liquid, the strength of a film can also be improved.

In addition, the coating liquid is not limited to a specific resin material or fine particles. Various additives such as a release agent, a dispersant, a condensing agent, an imidizing agent, and a surfactant may be contained in addition to the solvent and the solvent, if necessary.

[Coating unit]

The coating unit 10 includes a conveying section 11, a first nozzle 12, a second nozzle 13, a drying section 14, and a peeling section 15.

The transfer unit 11 includes a transfer substrate (base material) S, a substrate delivery roller 11a, support rollers 11b to 11d, a substrate winding roller 11e, and a delivery roller 11f.

The transport substrate S is formed in a belt shape. Conveying substrate S The material sending roller 11a sends out, has tension bridged over the supporting rollers 11b to 11d, and is wound by the substrate winding roller 11e. Examples of the material of the transport substrate S include polyethylene terephthalate (PET). However, the material is not limited to this and may be a metal material such as stainless steel.

Each of the rollers 11a to 11f is formed into a cylindrical shape, for example, The directions are arranged in parallel. In addition, each of the rollers 11a to 11f is not limited to an arrangement parallel to the X direction, and at least one of the rollers 11a to 11f may be arranged obliquely 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 may be the same. At this time, the conveying substrate S is moved along the horizontal plane in an upright state with respect to the horizontal plane (XY plane).

The substrate delivery roller 11a is a state in which the substrate S is wound. State to configure. The support roller 11b is arranged on the + Z side of the substrate sending-out roller 11a, and is also arranged closer to the -Y side than the substrate sending-out roller 11a. 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. With the arrangement of the three rollers (the substrate delivery roller 11a, the support rollers 11b, 11c), the conveyance substrate S is supported by a surface including the -Y side end portion of the support roller 11b.

The support roller 11d is disposed on the support roller 11c. The + Y side is simultaneously arranged on the -Z side of the support roller 11c. At this time, by arranging the three rollers of the support rollers 11b to 11d, the conveyance substrate S is supported by a surface including the + Z side end portion of the support roller 11c.

In addition, the support roller 11d may be placed in contact with the support roller 11c. The height position (position in the Z direction) is approximately the same height position. At this time, the transport substrate S is moved from the support roller 11c toward the support roller 11d, and is transported to the + Y direction in a state substantially parallel to the XY plane.

The substrate winding roller 11e is arranged on the support roller 11d. -Z side. The support roller 11d is wound toward the base material by the support roller 11e, and the conveyance base material S is sent to the -Z direction. The carry-out roller 11f is located on the + Y side of the support roller 11d and is arranged on the -Z side. The unloading roller 11f sends the unfired film FA formed in the drying section 14 to the + Y direction. This unfired film FA is carried out to the outside of the coating unit 10 by a carrying-out roller 11f.

The rollers 11a to 11f are not limited to a cylindrical shape, and may be formed. CROWN. At this time, it is useful for slack correction of the rollers 11a to 11f, and the conveyance substrate S or the unfired film FA described later can be brought into uniform contact with the rollers 11a to 11f. The rollers 11a to 11f may form a radial crown. In this case, the meandering of the substrate S or the unfired film FA can be effectively prevented. In addition, the rollers 11a to 11f can also form a CONCAVE crown (X The central part of the direction is a concavely curved portion). At this time, by applying tension to the X direction, the substrate S or the unfired film FA can be transported, and thus the occurrence of wrinkles can be effectively prevented. The following rollers may also have a crown, such as a tapered shape, a radial shape, or a concave shape, as described above.

FIG. 2 (a) is a perspective view showing an example of the first nozzle 12. Such as As shown in FIG. 1 and FIG. 2 (a), the first nozzle 12 is a coating film (hereinafter, the first coating film F1) that forms the first coating liquid Q1 on the transport substrate S. The first nozzle 12 has a discharge port 12a that discharges the first coating liquid Q1. For example, the discharge port 12a is formed with a dimension substantially the same as the X-direction dimension of the transport substrate S.

The first nozzle 12 is arranged at the discharge position P1. Spit position P1 is a position in the -Y direction with respect to the support roller 11b. The first nozzle 12 is arranged so that the discharge port 12a is inclined in the + Y direction. Therefore, the discharge port 12a is directed toward the portion of the conveyance substrate S and is supported by the end portion on the -Y side of the support roller 11b. The first nozzle 12 discharges the first coating liquid Q1 from the discharge port 12a in the horizontal direction with respect to the conveyed substrate S.

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 a coating film of the second coating liquid Q2 formed on the conveying substrate S by overlapping with the first coating film F1 (hereinafter referred to as the second coating) Film F2). The second nozzle 13 has a discharge port 13a that discharges the second coating liquid Q2. For example, the dimension of the length direction and the X direction of the conveyance base material S are substantially the same, and the discharge opening 13a is formed.

The second nozzle 13 is arranged at the discharge position P2. Spit position P2 is a position in the + Z direction with respect to the support roller 11c. 2nd nozzle The 13-system discharge port 13a is arranged toward the -Z direction. Therefore, the discharge opening 13a is a portion which is supported by the end portion on the + Z side of the support roller 11c toward the conveying substrate S. The second nozzle 13 discharges the second coating liquid Q2 from the discharge port 13a in the direction of gravity with respect to the conveyed substrate S.

The first nozzle 12 and the second nozzle 13 may be Move in at least one of the X direction, the Y direction, and the Z direction. The first nozzle 12 and the second nozzle 13 may be provided so as 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 arranged in a standby position (not shown), and when the coating liquid is discharged, they can be moved from the standby position to the above-mentioned discharge positions P1 and P2, respectively. Further, the first nozzle 12 and the second nozzle 13 may be provided with a portion for performing a preliminary discharge operation.

Each of the first nozzle 12 and the second nozzle 13 is connected via a connection. A tube (not shown) and the like are connected to a coating liquid supply source (not shown). The first nozzle 12 and the second nozzle 13 are provided with a holding portion (not shown) for holding a predetermined amount of the coating liquid, for example. At this time, the first nozzle 12 and the second nozzle 13 may have a temperature adjustment section that adjusts the temperature of the liquid body held by the holding section.

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

As in this embodiment, two types of coating liquids (the first coating Cloth liquid Q1 and second coating liquid Q2) The film thickness of the first coating film F1 is adjusted, for example, in a range of 0.5 μm to 10 μm, and the film thickness of the second coating film F2 obtained by the second coating solution Q2 is, for example, in a range of 1 μm to 50 μm. Better.

In addition, between the first nozzle 12 and the second nozzle 13, A drying section (not shown) for drying the first coating film F1 was set. It is preferable that the drying section includes a heating drying section. It is preferable to use a warm air supply section or an infrared heater for the heating and drying section. The heating temperature is, for example, in a range of 50 ° C to 150 ° C, and preferably in a range of 50 ° C to 100 ° C. By drying the first coating film F1 and forming the second coating film F2, for example, it is possible to suppress the fine particles used in the second coating liquid from being mixed with the fine particles of the first coating film F1.

As shown in FIG. 1, the drying section 14 is connected to the second nozzle 13. The + Y side is disposed between the support roller 11c and the support roller 11d. The drying section 14 dries the two coating films (the first coating film F1 and the second coating film F2) applied to the transport substrate S to form an unfired film FA.

The drying section 14 has a chamber 14a and a heating section 14b. The cavity 14a contains the conveyance substrate S and the heating part 14b. The heating section 14b heats the first coating film F1 and the second coating film F2 formed on the transfer substrate S. As the heating unit 14b, for example, an infrared heater can be used. The heating portion 14b heats the coating film at a temperature of about 50 ° C to 100 ° C.

The peeling portion 15 is a portion where the unfired film FA is peeled from the transport substrate S. In the present embodiment, the unfired film FA is peeled off by the operator's hand, but it is not limited to this, and it can be peeled off automatically using a robot or the like. The unfired film FA peeled off from the transport substrate S is picked up by the unloading roller 11f. It is carried out to the outside of the coating unit 10 and sent to the winding unit 40. In addition, the transported substrate S after the unfired film FA is peeled off is wound by the substrate winding roller 11e.

[Winding section (1)]

FIG. 3 is a perspective view schematically showing the configuration of the + Y side of the coating unit 10.

As shown in FIG. 3, the + Y side of the coating unit 10 is provided with a carrying-out port 10b for carrying out the unfired film FA. The unfired film FA carried out from the carrying-out port 10b is wound by the winding part 40.

The winding portion 40 is a structure of the bearing 41 to which the shaft member SF is mounted. to make. The shaft member SF is a roll R formed by winding the unfired film FA carried out from the carrying-out port 10b. The shaft member SF is detachably provided to the bearing 41. When the shaft member SF is attached to the bearing 41, it is supported by being rotatable about an axis parallel to the X direction. The winding portion 40 includes a driving mechanism (not shown) that can rotate the shaft member SF mounted on the bearing 41.

In the wound portion 40, among the unfired films FA, the first The surface on the coating film F1 side is arranged on the outside, and the unfired film FA is wound. For example, the shaft member SF is rotated counterclockwise in FIG. 1 by a driving mechanism to wind the unfired film FA. In a state where the roll body R is formed, the shaft member SF is removed from the bearing 41, and the roll body R can be moved to another unit.

In FIGS. 1 and 3, the winding unit 40 is separated from the coating unit 10. Independent configuration, but not limited to this. For example, the winding portion 40 may be disposed inside the coating unit 10. At this time, the carrying-out port 10b is not arranged in the coating unit 10, and the unfired film can be wound by the carrying-out roller 11f (or the supporting roller 11d). FA, forming the roll body R.

[Submission Department]

FIG. 4 is a perspective view schematically showing the configuration of the -Y side of the firing unit 20.

As shown in FIG. 4, the -Y side of the firing unit 20 is provided with a carrying port 20a for carrying in the unfired film FA. The sending-out part 50 sends out the unfired film FA with respect to the carrying port 20a.

The delivery unit 50 is a structure in which the shaft member SF can be attached to the bearing 51. to make. The shaft member SF can be used in common with a bearing 41 mounted on the winding portion 40. Therefore, the shaft member SF removed from the winding portion 40 can be attached to the bearing 51 of the sending-out portion 50. Thereby, the roll body R formed by the winding part 40 can be arrange | positioned at the sending-out part 50. In addition, each of the bearing 51 and the bearing 41 of 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 mounted on the bearing 51, An axis parallel to the direction is rotated and supported. The sending-out portion 50 includes a driving mechanism (not shown) that rotates the shaft member SF attached to the bearing 51. By the drive mechanism, the shaft member SF is rotated clockwise in FIG. 1, and the unfired film FA constituting the roll body R is sent out toward the loading port 20 a. In the winding section 40, the unfired film FA has the surface on the side of the first coating film F1 disposed outside to wind the unfired film FA. Therefore, the unfired film FA is pulled by the roll body R. At the time of exit, the first coating film F1 side is arranged above.

[Baking unit]

The firing unit 20 is a unit that performs high-temperature processing on the unfired film FA in this embodiment. The firing unit 20 fires the unfired film FA to form a fired film FB containing fine particles. The firing unit 20 includes a cavity 21, a heating unit 22, and a transport unit 23. The cavity 21 has a carry-in port 20a for carrying in the unfired film FA and a carry-out port 20b for carrying out the fired film FB. The cavity 21 contains a heating unit 22 and a transport unit 23.

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

The transport unit 23 includes a transport belt 23a, a driving roller 23b, The passive roller 23c and the tension rollers 23d and 23e. The conveying belt 23a is endless and is arranged along the Y direction. The transfer belt 23a is formed using a material having durability against the firing temperature of the unfired film FA. The conveying belt 23a is substantially parallel to the XY plane in a state of tension, and bridges between the driving roller 23b and the passive roller 23c. The unfired film FA and the fired film FB are conveyed in the + Y direction while being placed on the conveying belt 23 a.

The driving roller 23b is arranged at the + Y inside the cavity 21. Side end. The driving roller 23b is formed in a cylindrical shape, for example, and is parallel to the X direction. Configuration. The driving roller 23b is provided with a rotary driving device such as a motor. The driving roller 23b is provided to rotate around the axis parallel to the X direction by rotating the driving device. By the rotation of the driving roller 23b, the conveying belt 23a rotates clockwise around FIG. As the conveyance belt 23 a rotates, the unfired film FA and the fired film FB placed on the conveyance belt 23 a are conveyed to the + Y direction.

The passive roller 23c is arranged on the -Y side of the interior of the cavity 21. Ends. The passive roller 23c is formed in a cylindrical shape, for example, and is arranged parallel to the X direction. The passive roller 23c is formed to have 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 provided so as to be rotatable about an axis parallel to the X direction. The passive roller 23c rotates following the rotation of the conveyance belt 23a.

The tension roller 23d is arranged on the + Z side of the passive roller 23c. The tension roller 23d is arranged parallel to the X direction and is provided 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 and the passive roller 23c can hold the unfired film FA. The tension roller 23d can be rotated while holding the unfired film FA.

The tension roller 23e is arranged on the + Z side of the driving roller 23b. The tension roller 23e is arranged parallel to the X direction and is provided so as to be rotatable about the X axis. The tension roller 23e is provided so that it can move up and down in a Z direction. Between the tension roller 23e and the driving roller 23b, the fired film FB can be held. The tension roller 23e can be rotated while holding the fired film FB.

The tension rollers 23d and 23e are respectively held between the passive roller 23c and the driving roller 23b, and the unfired film FA and the fired film FB are held respectively. Of the continuous unfired film FA and fired film FB, the tension between the two places is blocked from the outside. This prevents an excessive load from being applied to the unfired film FA and the fired film FB. The tension rollers 23 d and 23 e can be adjusted to avoid applying tension to the unfired film FA and the fired film FB disposed in the cavity 21.

[Remove unit]

The removing unit 30 includes a cavity 31, an etching portion 32, a washing portion 33, a drying portion 34, and a transfer portion 35. The cavity 31 has a carrying inlet 30a for carrying in the fired film FB and a carrying outlet 30b for carrying out the porous resin film F. The cavity 31 contains an etching section 32, a cleaning section 33, a drying section 34, and a transfer section 35.

The etching section 32 etches the firing film FB to remove the firing. The fine particles contained in the FB are formed into a porous resin film F. In the etching section 32, the fired film FB is immersed in an etching solution capable of dissolving or decomposing the fine particles to remove the fine particles. The etching section 32 is provided with a supply section (not shown) that supplies such an etching solution or a storage section that can store the etching solution.

The cleaning portion 33 is a porous resin film F after the etching. The cleaning section 33 is disposed on the + Y side of the etching section 32 (front of the porous resin film F in the conveying direction). The cleaning section 33 includes a supply section (not shown) that supplies a cleaning solution. The porous resin film F may include a recovery unit (not shown) for recovering the waste liquid after washing the porous resin film F, and a liquid discharge unit (not shown) for removing liquid from the porous resin film F.

The drying section 34 performs washing of the porous resin film F dry. The drying section 34 is disposed on the + Y side of the washing section 33 (a porous resin film F forward of the transport direction). The drying section 34 is provided with a heating section or the like that heats the porous resin film F.

The transport section 35 straddles the etching section 32, the cleaning section 33, and the drying section. The section 34 conveys the fired film FB and the porous resin film F. The transport unit 35 includes a transport belt 35a, a driving roller 35b, and a passive roller 35c. Further, in addition to the drive roller 35b and the passive roller 35c, a support roller that supports the transport belt 35a may be disposed inside the etching section 32, the cleaning section 33, and the drying section 34.

The conveying belt 35a is endless, and is arranged along the Y direction. Home. The conveying belt 35a is formed using a material having durability against the etching solution. The conveying belt 35a is in a state of being substantially parallel to the XY plane under a tension state, and bridges between the driving roller 35b and the passive roller 35c. The fired film FB and the porous resin film F are placed on the transfer belt 35a.

The driving roller 35b is arranged at the + Y side end inside the cavity 31 unit. The drive roller 35b is formed in a cylindrical shape, for example, and is arranged parallel to the X direction. The drive roller 35b is provided with a rotary drive device such as a motor. The driving roller 35b is provided to rotate around the axis parallel to the X direction by rotating the driving device. By the rotation of the driving roller 35b, the conveying belt 35a rotates clockwise around FIG. When the conveyance belt 35a is rotated, 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 arranged at the -Y side end of the inside of the cavity 31 unit. The passive roller 35c is formed in a cylindrical shape, for example, and is arranged parallel to the X direction. The passive roller 35c is formed with the same diameter as the driving roller 35b, Z The position in the direction (height position) is arranged substantially equal to the driving roller 35b. The passive roller 35c is provided to be rotatable about an axis parallel to the X direction. The passive roller 35c rotates following the rotation of the conveyance belt 35a.

The removing unit 30 is not limited to the case of removing fine particles by etching. For example, when the material of the fine particles is an organic material that decomposes at a lower temperature than polyimide, the fine particles can be decomposed by heating the fired film FB. As long as this organic material is an organic material which decomposes at a lower temperature than polyimide, it can be used without particular limitation. Examples thereof include resin fine particles composed of a linear polymer or a conventional depolymerizable polymer. When a normal linear polymer is thermally decomposed, the molecular chain of the polymer is irregularly cut, and a depolymerizable polymer is a polymer that is decomposed into monomers during thermal decomposition. Both decompose into low molecular weight bodies 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, and more preferably 230 to 260 ° C. When the decomposition temperature is 200 ° C. or higher, when a high-boiling-point solvent is used as the coating liquid, a film can also be formed, and the selection of the firing conditions in the firing unit 20 becomes wider. When the decomposition temperature is less than 320 ° C, thermal damage is not applied to the fired film FB, and only fine particles can be eliminated.

[Winding section (2)]

FIG. 5 is a perspective view schematically showing the configuration of the + Y side of the removal unit 30.

As shown in FIG. 5, the + Y side of the coating unit 30 is provided with the carrying-out port 30b which carries out the porous resin film F. The porous resin film F carried out from the carrying-out port 30b is wound by the winding part 60.

The winding portion 60 is connected to the structure of the bearing 61 to which the shaft member SF is mounted. to make. The shaft member SF is a roll RF formed by winding the porous resin film F carried out from the carrying-out port 30b. The shaft member SF is detachably provided to the bearing 61. When the shaft member SF is attached to the bearing 61, it is supported by being rotatable about an axis parallel to the X direction. The winding unit 60 includes a driving mechanism (not shown) that can rotate the shaft member SF mounted on the bearing 61. The shaft member SF is rotated by the driving mechanism to wind the porous resin film F. In a state where the roll body RF is formed, the shaft member SF is removed from the bearing 61, and the roll body RF can be recovered.

[Production method]

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

First, in the coating unit 10, an unfired film FA is formed. The coating unit 10 rotates the substrate sending-out roller 11a, sends out the transfer substrate S, sets the transfer substrate S on the support rollers 11b to 11d, and winds it with the substrate winding roller 11e. Then, the substrate S is sequentially delivered by the substrate delivery roller 11a, and is wound by the substrate winding roller 11e.

In this state, the first nozzle 12 is arranged at the first position. P1 makes the discharge port 12a face the + Y direction. Thereby, the discharge opening 12a is oriented toward the portion of the conveyance substrate S that is 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 after reaching the transfer substrate S, it is applied to the transfer substrate S as the transfer substrate S moves. Take this as As shown in FIG. 6 (a), the first coating film F1 obtained by the first coating liquid Q1 is formed on the transport substrate S. In the first coating film F1, the resin material A1 contains fine particles A2 in a specific volume ratio.

Next, the second nozzle 12 is arranged at the second position P2, and the discharge port 13a is oriented in the -Z direction. Thereby, the ejection opening 13a is oriented toward the portion of the conveyance substrate S that is supported by the support roller 11c. Then, the second coating liquid Q2 is discharged from the discharge port 13a. The second coating liquid Q2 is discharged toward the -Z direction from the discharge port 13a, and after reaching the first coating film F1 formed on the conveying substrate S, it is applied to the first coating film S as it moves. On the coating film F1. Thereby, as shown in FIG.6 (b), the 2nd coating film F2 obtained by the 2nd coating liquid is formed on the 1st coating film F1. In the second coating film F2, the resin material A1 contains fine particles A2 in a specific volume ratio. The content of the fine particles is set such that the first coating film F1 is larger than the second coating film F2.

In addition, the first and second coating liquids Q1 and Q2 are applied in a state where the discharge ports 12a and 13a face the portions supported by the support rollers 11b and 11c in the conveyance substrate S. Therefore, the first When the 1 coating liquid Q1 and the 2nd coating liquid Q2 reach the conveyance base material S, the force which acts on the conveyance base material S is received by the support rollers 11b and 11c. Therefore, occurrence of flexibility, vibration, and the like of the transport substrate S is suppressed, and the first coating film F1 and the second coating film F2 are formed stably with uniform thickness on the transport substrate S.

Next, when the conveying substrate S moves, and the laminated portion of the first coating film F1 and the second coating film F2 is carried into the cavity 14a of the drying section 14, the first coating film F1 and Drying of the second coating film F2. The drying section 14 uses a heating section 14b, for example, at 50 ° C ~ The first coating film F1 and the second coating film F2 are heated at a temperature of about 100 ° C. In this temperature range, the first base film F1 and the second base film F2 can be heated without strain or deformation of the transported substrate S. By drying the laminated body of the first coating film F1 and the second coating film F2, as shown in FIG. 6 (c), an unfired film FA is formed.

In the present specification, the laminated system refers to an unfired film composed of the first coating film F1 and the second coating film F2. When forming the porous fluorene-based imide resin film of the present invention, among the first liquid and the second liquid, the same kind is used among polyamic acid, polyfluorene, polyfluorene, or polyfluorene, respectively. In the case of a resin, an unfired film (or a porous fluorene imine-based resin film) composed of the first coating film F1 and the second coating film F2 formed is substantially a single layer. Unfired films with different microparticle content ratios (or porous imine-based resin films with regions with different porosity), so the case of using the same resin in the first liquid and the second liquid is also included. This manual It is also called a laminate.

Next, when the conveyance substrate S moves and the front end portion of the unfired film FA reaches the support roller 11d (the peeling portion 15), the front end portion is peeled from the conveyance substrate S, for example, by the operator's hand. In this embodiment, for example, PET is used as the material of the transport substrate S. Therefore, when the first coating film F1 and the second coating film F2 are dried to form the unfired film FA, peeling from the transport substrate S becomes easy. It is easy for a worker to peel.

After the front end portion of the unfired film FA is peeled off, the conveyance substrate S is moved to form the first coating film F1 by the first nozzle 12. Then, a second coating film F2 is formed by the second nozzle 13 and dried. The portion 14 forms an unfired film FA. Thereby, the unfired film FA is formed into a band shape, and the length of the unfired film FA carried out from the drying section 14 to the + Y side is gradually increased. The worker continues peeling the unfired film FA in the peeling part 15. Then, when the front end of the peeled unfired film FA reaches the length of the shaft member SF of the winding section 40, the operator sets the unfired film FA on the take-out roller 11f by hand, and at the same time, the unfired film FA The front end portion is attached to the shaft member SF. Then, the unfired film FA is sequentially formed, and the shaft member SF is rotated at the winding portion 40 in order to accommodate peeling. Thereby, the peeled unfired film FA is sequentially carried out from the coating unit 10, and is wound by the shaft member SF of the winding section 40 to form a roll body R. As shown in FIG. 6 (d), the unfired film FA constituting the roll body R is in a state after being peeled from the transport substrate S, and both the surface and the inside are exposed.

Work for peeling unfired film FA front end part, and peeling The work of attaching the rear front end portion to the shaft member SF is not limited to a situation in which the operator performs the work by hand, for example, it can be performed automatically using a robot or the like. In addition, in order to improve the releasability of the unfired film FA, a release layer may be formed on the surface of the transport substrate S.

An unfired film FA of a specific length is wound around the shaft member SF After that, the unfired film FA is cut, and the shaft member SF and the roll body R are removed from the bearing 41 at the same time. Then, a new shaft member SF is mounted on the bearing 41 of the winding portion 40, and the cut end of the unfired film FA is mounted on the shaft member SF, and the unfired film FA is formed by rotation, and a new The roll body R.

In addition, for example, the operator will roll the roller R- The removed shaft member SF is transported to the sending-out portion 50 and is attached to the bearing 51. The movement and installation of the shaft member SF can also be performed automatically using a robot or a transfer device. After the shaft member SF is mounted on the bearing 51, the shaft member SF is rotated to sequentially pull out the unfired film FA from the roll body R, and the unfired film FA is carried into the cavity 21 of the firing unit 20. In addition, when the front end of the unfired film FA is carried into the cavity 21, the operator may perform the operation manually, or may perform the operation automatically using a robot or the like.

The unfired film FA carried into the cavity 21 is placed on the carrying belt 23a, and is rotated to the + Y direction in accordance with the rotation of the carrying belt 23a. The tension can also be adjusted using the tension rollers 23d and 23e. Then, the unfired film FA is conveyed, and the unfired film FA is fired using the heating unit 22 at the same time.

The temperature during firing varies depending on the structure of the unfired film FA, and is preferably about 120 ° C to 375 ° C, and more preferably 150 ° C to 350 ° C. When the fine particles contain organic materials, it is necessary to set a temperature lower than the thermal decomposition temperature. When the coating liquid contains polyamic acid, it is better to complete the fluorination at this firing, but the unfired film FA is not limited to polyfluorine, polyfluorene, imine, or polyamine In the case where the unfired film FA is subjected to a high temperature treatment by the firing unit 20.

The firing conditions include, for example, a method in which the coating solution contains polyamic acid and / or polyimide, the temperature can be raised from room temperature to 375 ° C for 3 hours, and the method can be maintained at 375 ° C for 20 minutes or 50 ° C. Graduation, stepwise heating from room temperature to 375 ° C (20 minutes at each stage), and finally, stepwise heating at 375 ° C for 20 minutes. In addition, unfired film FA can be formed. The end is fixed to a model made of SUS, etc. to prevent deformation.

By this firing, as shown in FIG. 6 (e), a firing film is formed. FB. The fired film FB contains fine particles A2 in the inside of the resin layer A3 that has been imidized or high-temperature treated. The film thickness of the fired film FB can be determined by measuring the thickness at a plurality of places, for example, using a micrometer, to obtain an average value. The preferred average film thickness is 3 μm to 500 μm, more preferably 5 μm to 100 μm, and even more preferably 10 μm to 30 μm when used in a separator film or the like.

The firing film FB formed in the firing unit 20 is fired by When the unit 20 is carried out, it is carried into the removal unit 30 without being wound. When the front end portion of the fired film FB is carried into the removal unit 30, the operator may perform the operation manually, or may perform the operation automatically using a robot or the like.

The fired film FB carried into the removal unit 30 is placed in the carrying The conveyance belt 35a follows the rotation of the conveyance belt 35a and is conveyed to the + Y direction. The removal unit 30 removes the fine particles A2 in the etching section 32 as the fired film FB is transported. For the material of the fine particles A2, for example, when silicon dioxide is used, the fired film FB in the etching section 32 is immersed in an etching solution such as a low concentration of hydrogen fluoride. Thereby, the fine particles A2 are dissolved in the etching solution and removed, and as shown in FIG. 6 (f), a porous resin film F containing a porous portion A4 is formed inside the resin layer A3.

Thereafter, following the rotation of the conveyance belt 35 a, the porous resin film F is sequentially carried into the washing section 33 and the drying section 34. The washing section 33 is configured to wash the porous resin film F with a washing solution, and then remove the liquid. The porous resin film F after the liquid in the drying section 34 is removed is heated, and the washing liquid is removed. Then, the porous resin film F is removed from the removing unit 30. When unloaded, the shaft member SF is wound by the winding unit 60.

As described above, the manufacturing system SYS of this embodiment is a package Containing: A coating liquid (a first coating liquid Q1 and a second coating liquid Q2) containing a resin material A1 and fine particles A2 containing polyamic acid, polyimide, polyamidine, or polyimide. A coating unit 10 that is applied to the transfer substrate S to form an unfired film FA. In this coating unit 10, the unfired film FA peeled from the transfer substrate S is fired to form a fired film containing fine particles. The firing unit 20 of the FB is a removing unit 30 for removing the fine particles A2 from the fired film FB. Therefore, a series of processes can be performed to form the unfired film FA and the firing of the unfired film FA (the formation of the fired film FB). ), And three steps of removing fine particles A2 (formation of porous resin film F). Thereby, the manufacturing efficiency of the porous resin film F can be improved.

The coating unit (10) is formed on a substrate (conveying substrate S). It is a strip-shaped unfired film (FA), so it can be applied to manufacturing steps such as a roll-to-roll method, and can efficiently form a porous sulfonium-imide-based resin film (porous resin film F).

In addition, the removal unit (20) removes fine particles (A2) by sequentially taking in the fired film (FB) fired by the firing unit (10) without winding in order to remove the fine particles (A2). The steps from firing to removal of fine particles are performed.

In addition, since the unfired film (FA) peeled from the base material (conveying base material S) is wound and a winding portion (40) is formed to form a roll body (R), it can be easily transported between units.

When the roll body (R) is a roll body of a strip-shaped unfired film (FA) peeled off from the base material (conveying base material S), the firing unit (10) sequentially pulls out the Since the film is formed and fired, the fired film FB can be efficiently formed.

In addition, as the liquid, at least the first liquid (the first coating liquid Q1) and the second liquid (the second coating liquid Q2) whose content rates of the fine particles (A2) are different from each other, and the coating unit (10) The first liquid and the second liquid are applied to a substrate (conveying substrate S) to form at least a fine particle content, and a laminated unfired film (FA) is formed based on the unfired film. When used as a separator, the porous imine resin film (porous resin film F) can smoothly move ions, and at the same time, it can form a porous material with the same porosity compared with the first coating liquid Q1. In the case of an amine resin film, the strength as a film can be more ensured.

The manufacturing method of the porous resin film F of this embodiment The law system includes a coating liquid (a first coating liquid Q1 and a second coating liquid) containing a resin material A1 and fine particles A2 containing polyamic acid, polyimide, polyimide, or polyimide Q2) After being coated on the transfer substrate S, it is peeled off from the transfer substrate S to form an unfired film FA; the unfired film FA is fired to form a fired film FB containing fine particles A2; and the fired film FB The fine particles A2 are removed in the process, so the unfired film FA can be formed in a series of processes, the unfired film FA can be fired (the fired film FB is formed), and the fine particles A2 can be removed (the porous resin film F is formed). 3 steps. Thereby, the manufacturing efficiency of the porous resin film F can be improved.

In addition, the unfired film (FA) is formed in a band shape, so it can be applied to Production steps such as a roll-to-roll method can efficiently form a porous fluorene-imide-based resin film (porous resin film F).

In addition, by storing the fired film (FB) in sequence without winding, and removing the fine particles (A2) from the fired film, the firing to the fine particles can be efficiently performed. Steps to remove.

In addition, since the unfired film (FA) peeled from the substrate (transport substrate S) is wound to form a roll (R), it can be easily transported between units.

In addition, when the roll body is a roll-shaped unfired film (FA) stripped from the base material (conveying base material S), the unfired film is sequentially pulled out from the roll body to perform The firing is performed, so that the firing film FB can be formed efficiently.

As the liquid, at least the first liquid (the first coating liquid Q1) and the second liquid (the second coating liquid Q2) having different contents of the fine particles (A2) were used, and the first liquid and the second liquid were applied. On the substrate (conveying substrate S), at least fine particles (A2) are formed, and the laminated unfired film (FA) is formed. Therefore, when used as a separation film, ions move smoothly and can be manufactured to ensure the The strength of the film is a porous imine resin film (porous resin film F).

[Modification]

The above embodiment is described by taking the configuration in which the winding unit 40 is arranged between the coating unit 10 and the firing unit 20 as an example, but it is not limited thereto. FIG. 7 is a diagram showing an example of a part of a manufacturing system SYS2 according to a modification.

For example, as shown in FIG. The unfired film FA carried out from the cloth unit 10 is configured to be carried into the firing unit 20. At this time, the firing unit 20 is an unfired film FA which is carried out by the coating unit 10 and conveyed via the relay roller 70, and is sequentially stored and fired to form a fired film FB.

As described above, the firing unit (20) S) The peeled unfired film (FA) is unrolled and stored in sequence for firing, so The formation from the unfired film FA to the firing film FB is continuously performed.

In addition, the above-mentioned embodiment is provided in the coating unit 10 Although the internal peeling part 15 has demonstrated the structure which peeled the unfired film FA from the conveyance base material S as an example, it is not limited to this. For example, in the coating unit 10, the unfired film FA and the conveyance substrate S are not peeled off, and they are wound integrally. They are immersed in a liquid outside the coating unit 10, and the unfired film FA can be transferred from the conveyance substrate at the same time. S peeled. FIG. 8 is a diagram showing an example of a part of a manufacturing system SYS3 according to a modification.

For example, as shown in FIG. 8, the coating unit 10 has an unfired film. The FA and the transfer substrate S are not peeled, and the winding portion 73 is integrally wound. The winding portion 73 includes a bearing 16 and a shaft member SF2. The bearing 16 is arranged on the -Z side of the support roller 11d. The shaft member SF2 is detachable from the bearing 16. When the shaft member SF2 is mounted on the bearing 16, it can be rotatably supported around an axis parallel to the X direction. The coating unit 10 is provided with a driving mechanism (not shown) capable of rotating the shaft member SF2 mounted on the bearing 16. By this drive mechanism, the shaft member SF2 is rotated, and the unfired film FA and the conveyance base material S are integrally wound, and the roll body RS is formed.

A bearing 71 is provided outside the coating unit 10. This bearing 71 A dipping portion 72 is provided on the -Z side. The immersion section 72 includes a container 72a, a liquid 72b stored in the container 72a, and a roller 72c immersed in the liquid 72b. The liquid 72b is, for example, water.

By the shaft member SF2, the unfired film FA and the transport substrate S When it is wound up integrally to form the roll body RS, first, the shaft member SF2 is formed by The bearing 16 is removed. The shaft member SF2 is mounted on a bearing 71 provided outside the coating unit 10.

After the shaft member SF2 is installed in the bearing 71, the roll body RS The unfired film FA and the transport substrate S are pulled out, and immersed in the liquid 72b. For example, a laminate of the unfired film FA and the transport substrate S is provided below the roller 72c. At this time, the unfired film FA drawn out from the roll RS and the transport substrate S are sequentially immersed in the liquid 72b. For example, the operator peels the unfired film FA from the transport substrate S in a state where the unfired film FA and the transport substrate S are immersed in the liquid 72b.

In this manner, it is possible to provide unfired materials including a substrate (conveying substrate S). The film (FA) is wound to form a winding portion (73) of the roll body (RS), so that it can be easily transported between units. In addition, when the roll body is a roll body (RS) of a strip-shaped unfired film (FA) containing a base material (conveying base material S), the roll body is provided with the base material being pulled out from the roll body and immersed in a specific liquid ( In the liquid 72b), the unfired immersion part (72) is peeled off from the base material, so that the substrate can be peeled off stably.

In the state where the unfired film FA is immersed in the liquid 72b, It is not limited to the case where the unfired film FA is peeled from the conveyance base material S. For example, the unfired film FA peeled from the transport substrate S can be immersed in a liquid such as water. FIG. 9 is a diagram showing an example of a part of a manufacturing system SYS4 according to a modification.

As shown in FIG. 9, the + Y side of the coating unit 10 is provided with a second Visitors 74. The second immersion section 74 includes a container 74a, a liquid 74b stored in the container 74a, and a roller 74c immersed in the liquid 74b. The unfired film FA carried out from the coating unit 10 is immersed in the liquid through the roller 74c. Body 74b. At this time, the unfired film FA may be immersed in the liquid 74b for, for example, about 10 seconds to 5 minutes, preferably about 30 seconds to 40 seconds. This makes it possible to suppress the formation of wrinkles when the unfired film FA is fired.

The unfired film FA peeled from the transport substrate S is immersed in water In the case of a liquid such as this, the unfired film FA may be wound by the winding portion 40 after immersion, or may not pass through the winding portion 40 after immersion.

Moreover, you may have the process of forcibly immersing the unfired film FA peeled from the conveyance base material S with liquid, such as water, and forcing it. The compulsory means includes a step of pressing the unfired film FA. Accordingly, when the unfired film FA is dried or fired, the formation of wrinkles can be suppressed.

After impregnation of unfired film FA, the winding section 40 At this time, the unfired film FA conveyed via the relay roller is sequentially stored and fired to form a fired film FB. This allows the firing unit (20) to unwind the unfired film (FA) peeled from the substrate (conveying substrate S), and sequentially store and fire it. Therefore, continuous firing of the unfired film FA can be performed. Formation to the formation of the fired film FB. Before the transferred unfired film FA is stored in the firing unit, a step of drying or absorbing the liquid adhered during the immersion may be provided.

In addition to the configuration of the above embodiment, a countermeasure may be provided. The porous resin film F formed by the removal unit 30 is subjected to a post-treatment and then the unit is processed. FIG. 10 is a diagram showing an example of a manufacturing system SYS5 according to a modification.

As shown in FIG. 10, between the removal unit 30 and the winding section 60, 间 Configure a post-processing unit 80. Thereafter, the processing unit 80 may use, for example, In the porous resin film F, an antistatic unit 81 is subjected to antistatic treatment. The static electricity prevention unit 81 is equipped with a static elimination device such as a static eliminator.

In this way, it is possible to provide a fired film for removing fine particles (A2). (Porous resin film F) is an antistatic unit (81) that performs an antistatic treatment. Therefore, static electricity can be removed from the porous resin film F after fine particles have been removed.

The post-processing unit 80 can be used for removing porous trees, for example. An etching unit 82 of a part of the lipid film F. FIG. 11 (a) is a diagram schematically showing an example of the etching unit 82. As shown in FIG. 11 (a), the etching unit 82 includes a storage portion 82a that stores a processing liquid 82b. As the treatment liquid 82b, for example, an alkali solution or the like can be used. The porous resin film F is immersed in the treatment liquid 82b for a predetermined time, and as shown in FIG. 11 (b), the inside of the porous portion A4 can be removed. At this time, the burrs of the porous portion A4 can be removed while ensuring connectivity.

When the post-processing unit 80 uses the etching unit 82, After the etching unit 82 is processed, the porous resin film F may be dried or post-baked. The temperature of the drying step or the post-baking treatment step can be set according to the type of the resin of the porous resin film F, and is suitably set, for example, 100 to 300 ° C.

When the post-processing unit 80 uses the etching unit 82, In the drying unit 34 in the removing unit 30, the liquid is removed, and the porous resin film F can be transferred to the etching unit 82 without drying or heating. At this time, when the liquid in the drying section 34 is removed, the liquid adhered to the washed porous resin film F is removed. The drying section 34 is preferably provided with a water-absorbing roller or the like. The porous portion is conveyed by bringing the water-absorbing roller into contact with the porous resin film F. The resin film F can absorb the liquid to which the porous resin film F is attached.

In this way, since the etching unit (82) which partially removes a part of the fired film (porous resin film F) from which the fine particles (A2) have been removed, the inner surface of the porous portion A4 contained in the porous resin film F is included. Will become smooth and ensure connectivity.

In the above embodiment, the winding portions 40 and 60 are described as examples of the structure in which the shaft member SF is detached from the bearings 41 and 61, but the invention is not limited to this. For example, the winding device 90 shown in FIG. . Hereinafter, a case where the winding device 90 is used instead of the winding portion 40 will be described as an example.

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

The shaft member SF is formed by winding an unfired film FA carried out from the coating unit 10 to form a roll body R. The shaft member SF is detachable from the bearing 92. When the shaft member SF is attached to the bearing 92, it can rotate around an axis parallel to the X direction and is supported by the bearing 92. In a state where the roll body R is formed, the shaft member SF is removed from the bearing 92, and the roll body R can be moved to another unit or recovered.

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 in a cylindrical shape, for example, and are arranged in parallel to the X direction. In this embodiment, the unfired film FA passes in the order of the relay rollers 94a, 94b, 94c, 94d, and 94e, but it is not limited to this, and a part of the relay rollers may not be used wheel. In addition, at least one of the relay rollers 94 a to 94 e can be moved by the roller support portion 95. For example, the roller support portion 95 can move the relay roller 94b to the Z direction or the Y direction. A configuration may also be adopted in which the relay roller 94b is rotated around an axis AX parallel to the X axis by the roller support portion 95. At this time, the amount (distance) of moving (revolving) the relay roller 94b to feed the winding speed of the bearing 92 can keep the tension of the unfired film FA constant. Further, a configuration in which a movable overlap (not shown) arranged via a fulcrum axis is moved on the -Y side of the relay roller 94b, and the load on the relay roller 94b may be changed. At this time, the tension applied to the unfired film FA can be adjusted by the aforementioned overlapping adjustment of the load applied to the relay roller 94b.

The relay rollers 94a to 94e are not limited to the arrangement parallel to the X direction, but may be arranged obliquely to the X direction. Further, the relay rollers 94a to 94e are not limited to a cylindrical shape, and crowns having a tapered shape, a radial shape, a concave shape, or the like may be used.

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 shaft member SF in the opposite direction to that at the time of winding, so that the film of the unfired film FA or the like can be sent out. Therefore, for example, the winding unit 90 may be used in place of the above-mentioned delivery unit 50.

[Separator]

Next, the separation film 100 according to the embodiment will be described. FIG. 13 is a schematic diagram showing an example of the lithium-ion battery 200, and a part of the lithium-ion battery 200 is cut away. As shown in FIG. 13, the lithium-ion battery 200 includes a metal case 201 and a negative terminal 202 that also serve as a positive terminal. Inside the metal case 201 are provided a positive electrode 201a and a negative electrode 202a and the separator 100 are immersed in an electrolytic solution (not shown). The separator 100 is disposed between the positive electrode 201a and the negative electrode 202a, and prevents electrical contact between the positive electrode 201a and the negative electrode 202a. As the positive electrode 201a, a lithium transition metal oxide can be used, and as the negative electrode 202a, lithium, carbon (graphite), or the like can be used.

The porous resin film F described in the above embodiment is made of For this purpose, the separator 100 of the lithium ion battery 200 is used. In this case, for example, using the surface on which the first coating film F1 is formed as the negative electrode 202a side of the lithium ion battery can improve battery performance. 13 illustrates the separation film 100 of the angular lithium ion battery 200 as an example, but it is not limited thereto. The porous resin film F may be a separator of a lithium ion battery in any form such as a cylindrical type or a laminated type. In addition to the separator film of a lithium ion battery, the porous resin film F can be used as a fuel cell electrolyte film, a gas or liquid separation film, or a low-dielectric-constant material.

The embodiment has been described above, but the present invention is not limited to this. The above description can be modified in various ways without departing from the technical characteristics of the present invention.

For example, the above-mentioned embodiment and modified example are described using the case where two types of coating liquids having different contents of fine particles are used to form an unfired film FA. However, the invention is not limited to this, and may be a type of coating. The cloth liquid forms unfired film. In this case, either the first nozzle 12 or the second nozzle 13 may not be used, and one of the nozzles may be omitted. When one of the nozzles is omitted, the first nozzle 12 is preferably omitted and the second nozzle 13 is used.

It should be noted that the above embodiments and modifications are based on the firing unit 20 After the fired film FB is formed, the fired film FB is not wound, but is moved into a removal unit The structure of 30 is described as an example, but it is not limited to this, and the fired film FB may be wound. In this case, the winding device 90 described in the above modification may be used.

It should be noted that the above-mentioned embodiment and modified examples are based on a coating unit. 10. The configuration in which each of the firing unit 20 and the removing unit 30 is arranged is described as an example, but it is not limited to this. For example, at least one of the above units may be provided with a plurality of units. At this time, for example, by increasing the number of units (e.g., length, etc.) of unfired film FA, fired film FB, or porous resin film F that can be processed per unit time, the manufacturing system SYS can be improved. Overall manufacturing efficiency.

In addition, the above-mentioned embodiment and modification are described with the coating unit. 10. Each unit of the firing unit 20, the removing unit 30, and the post-processing unit 80 (the antistatic unit 81, the etching unit 82) transports the unfired film FA, the fired film FB, or the porous resin film F along the Y direction. The case of each film is described as an example, but it is not limited to this. For example, the film can be transported to the X direction, the Y direction, the Z direction, or a composite direction thereof in any unit, or the transport direction can be appropriately changed in one unit.

In addition, the above-mentioned embodiments and modifications are performed by coating The case of the three steps of applying, firing in the element 10, and removing in the removing unit 30 is described as an example, but it is not limited to this. For example, when polyimide, polyimide, or polyimide is used as the material of the coating film, firing may not be performed. Therefore, when firing is not performed, for example, by providing a winding device and a feeding device between the firing unit 20 and the removing unit 30, the unfired film FA formed by the coating unit 10 can be passed through without firing. The unit 20 is carried into a removal unit 30. When firing is not performed, manufacturing The production system of a porous fluorene-based imide resin film may include: coating a substrate with a liquid containing polyamic acid, polyfluorene, polyfluorene, imine, or polyamine and fine particles to form a non-fluorine A coating unit for a fired film; a manufacturing system for a removal unit for removing the fine particles in the unfired film after the substrate is peeled from the substrate, or outside the coating unit. When the firing is not performed, the porous resin film F is removed from the fine particle removing unit 30, and then the aforementioned post-baking treatment step may be performed. Before the post-baking process step, the post-processing unit 80 and / or the etching unit 82 may be used.

It should be noted that the above-mentioned embodiments and modification examples are so-called In the roll-to-roll method, the configuration for forming the porous resin film F is described as an example, but it is not limited to this. For example, after the processing in the removal unit 30 is completed, when the porous resin film F is carried out from the removal unit 30, the porous resin film F is not wound by the winding portion 60, but is cut by a specific length, and the cut person may be recovered.

Claims (21)

A porous fluorene imine-based resin film manufacturing system is a system for manufacturing a porous fluorene-imide resin film, which contains: polyimide, polyimide, and polyimide A liquid of amine, polyamine, and fine particles is applied to a conveying substrate to form an unfired coating unit. The unfired material is peeled from the conveying substrate in the coating unit or outside the coating unit. The film is fired to form a firing unit including a fired film containing the fine particles and a removing unit for removing the fine particles from the fired film. The porous imine-based resin film manufacturing system according to claim 1, wherein the coating unit is a strip-shaped unfired film formed on the substrate. For example, the porous fluorene-imide-based resin film manufacturing system according to claim 1 or 2, wherein the removal unit is to sequentially store and remove the fired film fired by the fired unit without winding it. The aforementioned fine particles. The porous sulfonimide-based resin film manufacturing system according to claim 1 or 2, which is formed by winding the unfired film peeled from the base material or the unfired film containing the base material to form a roll. The winding part of the roll body. For example, if the porous imine-based resin film manufacturing system of claim 4 is used, the roll body is a strip-shaped unfired roll body peeled from the substrate, and the firing unit is configured to pass the The fired film is formed by the aforementioned roll body. Sequentially pulled out for firing. The porous imine-based resin film manufacturing system according to claim 4, wherein when the roll body is a roll-shaped unfired roll body containing the base material, the method includes the step of removing the base material from the roll. The body is pulled out, immersed in a specific liquid, and the impregnated portion of the base material is peeled off from the unfired film. For example, the porous fluorene-imide resin film manufacturing system according to claim 1 or 2, wherein the firing unit is an unfired film peeled from the base material without being wound, and is sequentially stored for firing. The porous imidene resin film manufacturing system according to claim 1 or 2, further comprising an antistatic unit that performs antistatic treatment on the fired film from which the fine particles have been removed. The porous fluorene-imide-based resin film manufacturing system according to claim 1 or 2, further comprising an etching unit for removing a part of the fired film from which the fine particles have been removed. For example, the porous imidene resin film manufacturing system according to claim 1 or 2, wherein the liquid is a first liquid and a second liquid whose content ratios of at least fine particles are different from each other, and the coating unit is configured by applying the first The liquid and the second liquid are applied to the base material to form the unfired film laminated with at least fine particles having different content rates. A separator film is a separator film formed by a porous polyimide film, and the porous polyimide film is made of a porous imine system according to any one of claims 1 to 10. Produced by a resin film manufacturing system. A method for producing a porous fluorene imine-based resin film, which is a method for producing a porous fluorene-imide resin film, comprising: containing polyamic acid, a polyimide, and a polyimide After the liquid of polyamine and fine particles is applied to the conveying substrate, the unfired film is peeled off from the conveying substrate, and the unfired film is fired to form a fired film containing the fine particles, and The fine particles are removed from the fired film. The method for producing a porous fluorene imine-based resin film according to claim 12, wherein the unfired film system is formed into a band shape. According to claim 12 or 13, the method for producing a porous sulfonyl imide-based resin film is a method in which the fired film is not wound, but is sequentially stored, and the fine particles are removed from the fired film. The method for producing a porous imine-based resin film according to claim 12 or 13, comprising winding the unfired film peeled from the substrate or the unfired film containing the substrate to form a roll. body. For example, the method for producing a porous imine-based resin film according to claim 15, wherein when the roll is a strip-shaped unfired roll that is peeled from the substrate, the roll is sequentially pulled by the roll. The aforementioned unfired film was fired. The method for producing a porous imine-based resin film according to claim 15, wherein when the roll body is a roll-shaped unfired roll body containing the base material, the base material is removed from the roll body. It is pulled out, immersed in a specific liquid, and the said unfired film peels off a base material. Made of porous imine resin film as claimed in item 12 or 13 The manufacturing method is that the unfired film peeled from the substrate is unrolled and sequentially stored for firing. The method for producing a porous fluorene-imide-based resin film according to claim 12 or 13, wherein the fired film from which the fine particles have been removed is subjected to an antistatic treatment. A method for producing a porous fluorene-imide-based resin film according to claim 12 or 13, which comprises removing a part of the fired film from which the fine particles have been removed. For example, the method for producing a porous fluorene-imide-based resin film according to claim 12 or 13, wherein the first liquid and the second liquid whose content ratios of at least fine particles are different from each other are obtained by combining the first liquid and the second liquid The liquid is applied to the substrate to form the unfired film laminated with at least fine particles having different contents.