TW201600563A - Imide resin film production system and imide resin film production method - Google Patents

Abstract

The present invention efficiently produces a high-quality imide resin film with outstanding porosity. This imide resin film production system comprises: a film-forming unit (70) which fires an unfired film (FA) containing polyamic acid, polyimide, polyamide-imide, or polyamide resin material (A1) and microparticles (A2), and removes the microparticles (A2) from the fired film (FB) to form a porous resin film (F); and a chemical etching unit (40) which dissolves part of the porous resin film (F).

Description

Bismuth amide resin film production system and yttrium amide resin film production method

The present invention relates to a ruthenium-based resin film production system and a method for producing a ruthenium-based resin film.

A lithium ion battery of one type of secondary battery is provided between a positive electrode and a negative electrode which are immersed in an electrolytic solution, and a separator film is disposed to prevent direct electrical contact between the positive electrode and the negative electrode by a separator. A lithium transition metal oxide is used for the positive electrode, and for example, lithium or carbon (graphite) or the like is used for the negative electrode. During charging, lithium ions pass through the separator from the positive electrode and move toward the negative electrode. When discharging, lithium ions pass through the separator from the negative electrode and move toward the positive electrode. In the separator film, a separator film composed of a porous polyimide film having high heat resistance and high safety has been known in recent years (see, for example, Patent Document 1).

[Previous Technical Literature] [Patent Document]

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

[Summary of the Invention]

However, in the conventional porous polyimide film, the opening ratio in the porous portion is still insufficient, which may hinder the movement of lithium ions. Therefore, when a porous polyimide film is used as a separator, there is a problem that the internal resistance of the battery becomes high. Further, the polyimide film is not limited to a polyimide film, and a high-quality porous film having an excellent open cell ratio is also required.

In view of the above, an object of the present invention is to provide a ruthenium-based resin film production system and a method for producing a ruthenium-based resin film which can efficiently produce a high-quality quinone-based resin film having an excellent open cell ratio.

A system for producing a bismuth imine resin film according to a first aspect of the present invention, which is a system for producing a porous bismuth amide resin film, comprising: a polyamid acid, a polyimine, and a polyamine A film forming unit that removes fine particles to form a porous bismuth imide resin film, and a chemical etching unit that partially dissolves the quinone imide resin film in the film of ruthenium, polyamine, and fine particles.

A method for producing a ruthenium-based resin film according to a second aspect of the present invention, which is a method for producing a porous bismuth amide-based resin film, comprising: comprising polyamidamine, polyimine, and polyamine In the film of ruthenium, polyamine, and fine particles, the fine particles are removed to form a porous bismuth imide resin film; and a chemical etching treatment for partially dissolving one of the quinoneimide resin films is performed.

According to the aspect of the invention, it is possible to efficiently produce a high-quality quinone imide resin film having an excellent open cell ratio.

SYS, SYS2‧‧‧ Manufacturing System

F‧‧‧Porous resin film (醯iamine resin film)

FA‧‧‧Unfired film

FB‧‧‧Boiled film

S‧‧‧Transporting substrate (substrate)

Q1‧‧‧1st coating liquid (liquid)

Q2‧‧‧Second coating liquid (liquid)

EQ‧‧‧etching solution

A1‧‧‧Resin materials

A2‧‧‧Microparticles

A4‧‧‧Porous Department

10‧‧‧ Coating unit

20‧‧‧burning unit

30, 230‧‧‧ removal unit

40, 240‧‧‧ chemical etching unit

42‧‧‧Transportation Department

43‧‧‧Chemical Etching Department

47‧‧‧ Storage Department

70‧‧‧film forming unit

100‧‧‧Separate film

200‧‧‧Lithium-ion battery

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

Fig. 2 is a view showing an example of a film forming unit of the embodiment.

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

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

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

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

Fig. 7 is a view showing an example of a chemical etching unit of the present embodiment in a mode.

Fig. 8 is a perspective view showing an example of a winding portion of the embodiment.

Fig. 9 is a view showing an example of a manufacturing process of the quinone-based resin film of the present embodiment.

Fig. 10 is a view showing an example of a manufacturing system of a modification.

Fig. 11 is a view showing an example of a winding device according to a modification.

Fig. 12 is a view showing an example of a separator film of the embodiment.

[Formation of the Invention]

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

Fig. 1 is a view showing an example of a manufacturing system SYS. The manufacturing system SYS shown in FIG. 1 is a porous resin film F (porous yttrium-based resin film). The manufacturing system SYS includes a coating unit 10 that applies a specific coating liquid to form an unfired film FA, and 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 the fine particles, the chemical etching unit 40 for removing the porous resin film F, and the control device (not shown) for controlling the respective units described above are integrated. Further, the coating unit 10, the firing unit 20, and the removing unit 30 constitute a film forming unit 70 that forms the porous resin film F.

The manufacturing system SYS is configured, for example, in the upper and lower layers, the coating unit 10 is disposed in the second-order portion, and the firing unit 20, the removing unit 30, and the chemical etching unit 40 are disposed in the first-order portion. The firing unit 20, the removing unit 30, and the chemical etching unit 40 disposed in the same first step, for example, Although they are arranged in the Y direction, they are not limited thereto. For example, they may be arranged in the X direction or in the combined direction of the X direction and the Y direction.

The hierarchical structure of the manufacturing system SYS or the arrangement of each unit of each step is not limited to the above. For example, the coating unit 10 and the firing unit 20 may be disposed in the second-order portion, and the removing unit 30 and the chemical etching unit 40 may be placed. 1st order part. Also, all units can be configured in the same order. At this time, each unit can be configured in one column or in multiple columns. Also, all units can be configured at different levels.

In the manufacturing system SYS, the unfired film FA is formed into a strip shape. The +Y side of the coating unit 10 (the front side in the conveyance direction of the unfired film FA) is provided with the winding portion 50 in which the strip-shaped unfired film FA is wound into a roll shape. The -Y side of the firing unit 20 (the rear side in the conveyance direction of the unfired film FA) is provided with the delivery part 60 which sent the roll-form unfired film FA to the baking unit 20. The +Y side of the chemical etching unit 40 (in front of the transport direction of the porous resin film F) is provided with a wound portion 80 in which the porous resin film F is wound into a roll shape.

In this way, the section (first-order part) from the delivery unit 60 to the winding unit 80 via the firing unit 20, the removal unit 30, and the chemical etching unit 40 is by a so-called roll-to-roll. Way to handle. Therefore, in this section, each film of the unfired film FA, the fired film FB, and the porous resin film F is conveyed in a continuous state.

[coating liquid]

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

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

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

In the above case, when the volume of the first coating liquid is set to 100, the particles are uniformly dispersed when the volume of the fine particles is 65 or more, and when the volume of the fine particles is 81 or less, the particles are not aggregated and dispersed. Therefore, the porous resin film F can uniformly form pores. Further, when the volume ratio of the fine particles is within this range, the peeling property at the time of film formation of the unfired film FA can be ensured.

When the entire volume of the second coating liquid is set to 100, when the volume of the fine particles is 50 or more, the fine particles are uniformly dispersed, and When the volume of the fine particles is within 80, the fine particles do not aggregate with each other, and cracks or the like are not formed on the surface. Therefore, the porous resin film F having good electrical properties can be stably formed.

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

The viscosity of the coating liquid is preferably from 300 to 2000 cP, more preferably from 400 to 1500 cP, and even more preferably from 600 to 1200 cP. When the viscosity of the coating liquid is within this range, the film can be uniformly formed.

In the coating liquid, when the fine particles are dried with polyacrylic acid or polyimine as the unfired film FA, when the material of the fine particles is an inorganic material to be described later, the ratio of the fine particles/polyimine is 2 to 6 (mass ratio), it is sufficient to mix the fine particles with polyamic acid or polyimine. More preferably 3 to 5 (mass ratio). When the material of the microparticles is an organic material to be described later, the ratio of the fine particles to the polyimide may be 1 to 3.5 (mass ratio), and the fine particles may be mixed with polyacrylic acid or polyimine. More preferably 1.2 to 3 (mass ratio). In addition, when the FA is not fired, the volume ratio of the fine particles/polyimine is 1.5 to 4.5, and the fine particles may be mixed with polyamic acid or polyimine. More preferably, it is 1.8 to 3 (volume ratio). When the FA is not fired, the mass ratio or volume ratio of the fine particles/polyimine is above the lower limit value. In the case of the separator, a pore having an appropriate density can be obtained. When it is at most the upper limit value, there is no problem such as an increase in viscosity or cracking in the film, and the film formation can be stabilized. When the polyacetamide or the polyimine is substituted, and the resin material is polyamidamine or polyamine, the mass ratio is also the same as described above.

Each resin material will be specifically described below.

<polylysine>

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

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

Preferred specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, and bis(2,3-di). Carboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 - bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane II Anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)ether Anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4-(p-phenylenedioxy)diphthalic dianhydride, 4,4-(m- Phenyldioxy)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-decanetetracarboxylic dianhydride, 2,3,6,7-decanetetracarboxylic acid Acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-diphthalic anhydride oxime, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride Wait. Examples of the aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and the like. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable in terms of price, availability, and the like. Further, these tetracarboxylic dianhydrides may be used singly or in combination of two or more.

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

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

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

The diaminobiphenyl compound is a group in which two aminophenyl groups are bonded to each other with a phenyl group. For example, it is 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl or the like.

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

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

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

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

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

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

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

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

The aliphatic diamine may be, for example, a carbon number of 2 to 15 or so. Examples of the body include pentaethylenediamine, hexamethylenediamine, and heptylenediamine.

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

The means for producing the polyamic acid used in the present embodiment is not particularly limited, and for example, a conventional method such as a method of allowing an acid or a diamine component to be used in an organic solvent can be used.

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

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

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

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

<polyimine]

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

In order to be a polyimine soluble in an organic solvent, a monomer for introducing a main chain into a soft curved structure can be used, for example, ethylenediamine, hexamethylenediamine, or 1,4-diaminocyclohexane can be used. An aliphatic diamine such as an alkane, a 1,3-diaminocyclohexane or a 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-tolidine An aromatic diamine such as m-tolidine, 3,3'-dimethoxybenzidine or 4,4'-diaminobenzimidamide; polyoxyethylene diamine, polyoxypropylene diamine, a polyoxyalkylene diamine such as polyoxybutylene diamine; Polyoxyalkylene diamine; 2,3,3',4'-oxydiphthalic anhydride, 3,4,3',4'-oxydiphthalic anhydride, 2,2-double (4 -Hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride or the like. Further, a monomer having a functional group for improving solubility in an organic solvent can also be used, and for example, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2-three can be used. A fluorinated diamine such as fluoromethyl-1,4-phenylenediamine. Further, in addition to the monomer for improving the solubility of the above polyimine, the same monomer as described in the above column of polyamic acid may be used in combination insofar as the solubility is not inhibited.

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

<polyamidoquinone imine>

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

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

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

Examples of the diisocyanate include meta-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-oxybis(phenyl isocyanate), 4,4'-diisocyanate diphenylmethane, and bis[4- (4-Isocyanate phenoxy)phenyl]anthracene, 2,2'-bis[4-(4-isocyanatephenoxy)phenyl]propane, and the like.

The diamine may be the same as those exemplified in the description of the above polyamic acid.

<polyamide>

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

Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, and fluoromalay. Acid, phthalic acid, isophthalic acid, terephthalic acid, and diphenic acid.

The diamine may be the same as those exemplified in the description of the polyamic acid.

<microparticle>

Next, the fine particles will be described. The microparticles can be used, for example, in which the true spherical ratio is high and the particle size distribution index is small. Such fine particles are excellent in dispersibility in a liquid, and are in a state in which they do not aggregate. The particle diameter (average diameter) of the fine particles can be set, for example, to about 100 to 2000 nm. By using the fine particles as described above and removing the fine particles in the subsequent steps, the pore diameter of the obtained porous resin film F can be made uniform. The electric field applied to the separator film formed by the porous resin film F can be made uniform.

The material of the fine particles is not particularly limited as long as it is insoluble in the solvent contained in the coating liquid and can be removed from the porous resin film F in the subsequent step, and a conventional one can be used. For example, examples of the inorganic material include metal oxides such as silica, titanium oxide, and aluminum oxide (Al ₂ O ₃ ). Examples of the organic material include high molecular weight olefins (polypropylene, polyethylene, etc.), polystyrene, epoxy resin, cellulose, polyvinyl alcohol, polyvinyl butyral, polyester, polymethyl methacrylate, Organic polymer microparticles such as polyether. Examples of the fine particles include a ruthenium sol such as (monodisperse) spherical cerium oxide particles, calcium carbonate, and the like. At this time, the pore diameter of the porous resin film F can be made more uniform.

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

Further, the coating liquid may contain a releasing agent, a dispersing agent, a condensing agent, and the like, in addition to a specific resin material, fine particles, and a solvent. Various additives such as ruthenium iodide and surfactant.

[coating unit]

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

The conveyance unit 11 has a conveyance base material (base material) S, a base material delivery roller 11a, support rollers 11b to 11d, a base material winding roller 11e, and a carry-out roller 11f.

The transport substrate S is formed into a strip shape. The conveyance base material S is sent out by the base material delivery roller 11a, and is stretched across the support rollers 11b to 11d with tension, and is wound by the base material winding roller 11e. The material of the substrate S to be transported is, for example, polyethylene terephthalate (PET), but is not limited thereto, and may be a metal material such as stainless steel.

Each of the rollers 11a to 11f is formed, for example, in a cylindrical shape, and is disposed in parallel with the X direction. Further, each of the rollers 11a to 11f is not limited to the arrangement parallel to the X direction, and at least one of them may be disposed obliquely with respect to the X direction. For example, each of the rollers 11a to 11f may be arranged in parallel with the Z direction, and the height positions in the Z direction may be the same. At this time, the conveyance base material S moves along the horizontal plane in an upright state with respect to a horizontal plane (XY plane).

The substrate feeding roller 11a is disposed in a state in which the conveying substrate S is wound. The support roller 11b is disposed on the +Z side of the substrate feed roller 11a, and is disposed closer to the -Y side than the substrate feed roller 11a. Further, the support roller 11c is disposed on the +Z side of the support roller 11b, and is disposed closer to the +Y side than the support roller 11b. With this 3 wheels The arrangement of the substrate feeding roller 11a and the supporting rollers 11b and 11c is such that the conveying substrate S is supported by a surface including the end portion on the -Y side of the supporting roller 11b.

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

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

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

The rollers 11a to 11f are not limited to a cylindrical shape, and a tapered crown portion (CROWN) may be formed. At this time, it is useful for the deflection 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. Further, the rollers 11a to 11f can also form a crown portion of a radiation type. At this time, it is possible to effectively prevent the meandering of the substrate S or the unfired film FA. Further, the rollers 11a to 11f may be formed in a crown portion of a CONCAVE type (a portion in which the central portion in the X direction is concavely curved). At this time, the tension can be imparted to the X direction, and at the same time, the substrate S or the unfired film FA is carried out. It can be effectively transported to prevent wrinkles. The following roller may have a configuration of a crown portion such as a tapered shape, a radiation type, or a concave shape, similarly to the above.

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

The first nozzle 12 is disposed at the discharge position P1. The discharge position P1 is a position in the -Y direction with respect to the support roller 11b. The first nozzle 12 is disposed such that the discharge port 12a faces the +Y direction and is inclined. Therefore, the discharge port 12a faces the conveyance base material S, and supports the portion supported by the -Y side end portion of the roller 11b. In the first nozzle 12, the first coating liquid Q1 is discharged from the discharge port 12a in the horizontal direction with respect to the conveyance 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 formed on the transport substrate S, and a coating film of the second coating liquid Q2 is formed on the first coating film F1 (hereinafter, the second coating is applied). Film F2). The second nozzle 13 has a discharge port 13a for discharging the second coating liquid Q2. For example, the discharge port 13a is formed in the longitudinal direction substantially the same as the dimension of the transport substrate S in the X direction.

The second nozzle 13 is disposed at the discharge position P2. The discharge position P2 is at a position in the +Z direction with respect to the support roller 11c. The second nozzle 13 is disposed such that the discharge port 13a faces the -Z direction. Therefore, spitting The 13a is directed toward the conveyance base material S to support the portion supported by the +Z side end portion of the roller 11c. In the second nozzle 13 , the second coating liquid Q2 is discharged from the discharge port 13 a in the direction of gravity with respect to the conveyance substrate S.

Further, the first nozzle 12 and the second nozzle 13 may be movable in at least one of the X direction, the Y direction, and the Z direction. Further, the first nozzle 12 and the second nozzle 13 may be provided to be rotatable about an axis parallel to the X direction. When the first nozzle 12 and the second nozzle 13 do not discharge the coating liquid, they are placed at a standby position (not shown), and when the coating liquid is discharged, the standby position can be moved to the discharge positions P1 and P2, respectively. Further, a portion where the first nozzle 12 and the second nozzle 13 perform a preliminary discharge operation can be provided.

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

The discharge amount of each coating liquid discharged from the first nozzle 12 or the second nozzle 13 or the thickness of the first coating film F1 or the second coating film F2 can be set by each nozzle and each connecting pipe (not shown). The pressure of the pump (not shown) connected to the coating liquid supply source (not shown), the conveyance speed, the position of each nozzle, the distance between the conveyance substrate S and the nozzle, and the like 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.

As in the present embodiment, two types of coating liquids are used (first In the case of the coating liquid Q1 and the second coating liquid Q2), the film thickness of the first coating film F1 obtained by the first coating liquid Q1 is adjusted, for example, in the range of 0.5 μm to 10 μm, and the second coating layer is used. The film thickness of the second coating film F2 obtained by the coating liquid Q2 is preferably adjusted in the range of, for example, 1 μm to 50 μm.

Further, between the first nozzle 12 and the second nozzle 13, a drying portion (not shown) for drying the first coating film F1 can be disposed. It is preferable that the drying section has a heating and drying section. It is preferable to use a warm air blowing unit or an infrared heater in the heating and drying unit. The heating temperature is, for example, in the range of 50 ° C to 150 ° C, preferably 50 ° C to 100 ° C. By drying the first coating film F1 and forming the second coating film F2, the occurrence of a stripe trace of the first coating film F1 can be suppressed.

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

The drying unit 14 has a chamber 14a and a heating portion 14b. The chamber 14a accommodates the transport substrate S and the heating unit 14b. The heating unit 14b heats the first coating film F1 and the second coating film F2 formed on the conveying substrate S. For example, an infrared heater or the like can be used for the heating portion 14b. 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 off by the conveyance substrate S. In this embodiment, the operator does not burn by the hand of the operator. The FA is formed, but is not limited thereto, and may be automatically peeled off using a robot or the like. The unfired film FA which has been peeled off by the conveyance substrate S is carried out to the outside of the coating unit 10 by the carry-out roller 11f, and is sent to the winding unit 50. Moreover, the conveyed base material S after peeling of the unfired film FA is wound by the base material winding roller 11e.

[Winding section (1)]

Fig. 3 is a schematic perspective view 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 carry-out port 10b for carrying out the unfired film FA. The unfired film FA carried out by the carry-out port 10b is wound by the winding portion 50.

The winding portion 50 is configured such that the bearing 51 is attached to the shaft member SF. The shaft member SF winds the unfired film FA carried out by the carry-out port 10b to form the roll body R. The shaft member SF is provided to be detachable with respect to the bearing 51. When the shaft member SF is attached to the bearing 51, it can be supported by being rotated about an axis parallel to the X direction. The winding portion 50 has a drive mechanism (not shown) that can rotate the shaft member SF attached to the bearing 51.

In the unwound film FA, the surface of the unfired film FA is disposed on the outer side of the first coating film F1 side, and the unfired film FA is wound. For example, the shaft member SF is rotated counterclockwise about FIG. 1 by a drive mechanism to wind the unfired film FA. By removing the shaft member SF from the bearing 51 in a state in which the roll body R is formed, the roll body R can be moved to another unit.

In FIGS. 1 and 3, the winding portion 50 is separated from the coating unit 10 Independent configuration, but not limited to this. For example, the winding portion 50 may be disposed inside the coating unit 10. At this time, the unloading port 10 is not disposed in the coating unit 10, and the unfired film FA can be wound by the unloading roller 11f (or the supporting roller 11d) to form the roll body R.

[sending department]

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

As shown in FIG. 4, the inlet side 20a in which the unfired film FA is carried in the -Y side of the baking unit 20 is provided. The delivery unit 60 sends the unfired film FA to the carry-in port 20a.

The delivery portion 60 is a structure in which the shaft member SF can be attached to the bearing 61. The shaft member SF can be used together with the bearing 51 attached to the winding portion 50. Therefore, the shaft member SF taken out from the winding portion 50 can be attached to the bearing 61 of the delivery portion 60. Thereby, the roll body R formed by the winding part 50 can be arrange|positioned in the delivery part 60. Further, the bearings 51 of the bearing 61 and the winding portion 50 may be set to have the same height from the ground or may be set to different height positions.

When the shaft member SF is attached to the bearing 61, it can be supported by being rotated about an axis parallel to the X direction. The delivery unit 60 has a drive mechanism (not shown) that rotates the shaft member SF attached to the bearing 61. The shaft member SF is rotated clockwise in FIG. 1 by the drive mechanism, and the unfired film FA constituting the roll body R is sent toward the transfer port 20a. In the wound portion 50, the uncoated film FA is disposed on the surface of the first coating film F1 side. When the unfired film FA is wound on the outside, when the unfired film FA is pulled out by the roll body R, the first coat film F1 side is placed above.

[burning unit]

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

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

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

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

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

The tension roller 23d is disposed on the +Z side of the driven roller 23c. The tension roller 23d is disposed in parallel with the X direction and is 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 is placed between the passive roller 23c and the unfired film FA. The tension roller 23d is rotatable in a state in which the unfired film FA is next to it.

The tension roller 23e is disposed on the +Z side of the drive roller 23b. The tension roller 23e is disposed in parallel with the X direction and is provided to be rotatable about the X axis. The tension roller 23e is provided to be movable up and down in the Z direction. tension The roller 23e is placed between the passive roller 23b and the fired film FB. The tension roller 23e is rotatable in a state in which the unfired film FB is next to it.

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

[removal unit]

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

The etched portion 32 etches the fired film FB to remove the fine particles contained in the fired film FB to form the porous resin film F. In the etching portion 32, the sintered film FB is immersed in an etching liquid capable of dissolving or decomposing the fine particles to remove the fine particles. The etching unit 32 is provided with a supply unit (not shown) that supplies such an etching liquid or a storage unit that can store the etching liquid. Since the etching unit 32 and the cleaning unit 33 have different liquids contained therein, the etching unit 32 can carry out the front surface position, and a water absorbing roller to be described later can be provided. The water absorbing roller is disposed on at least one of the +Z side and the -Z side with respect to the porous resin film F. It is preferably arranged on both sides.

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

The liquid removing portion 34 removes the liquid adhering to the washed porous resin film F. Pre-drying, etc. can be performed. The liquid draining portion 34 is disposed on the +Y side of the cleaning portion 33 (before the transport direction of the porous resin film F). The liquid discharge portion 34 is provided with a water suction roller or the like. By bringing the water absorbing roller into contact with the porous resin film F, the porous resin film F is conveyed, and the liquid adhering to the porous resin film F can be absorbed. The arrangement of the water suction roller in the conveyance direction is not particularly limited as long as it is carried out by the liquid discharge unit 34. In addition, the water absorbing roller is disposed on at least one of the +Z side and the -Z side with respect to the porous resin film F, and is preferably disposed on both sides.

The conveyance unit 35 carries the fired film FB and the porous resin film F across the etching unit 32, the cleaning unit 33, and the liquid discharge unit 34. The conveyance unit 35 has a conveyance belt 35a, a drive 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 conveyance belt 35a may be disposed inside the etching portion 32, the cleaning portion 33, and the liquid discharge portion 34.

The conveyor belt 35a is formed in an endless shape and arranged along the Y direction. The conveyor belt 35a is formed using a material having durability to the above etching liquid. The conveyor belt 35a has a tension and is larger than the XY plane. In parallel, it is bridged between the drive roller 35b and the passive roller 35c. The fired film FB and the porous resin film F are placed on the conveyor belt 35a.

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

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

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

[Chemical etching unit]

The chemical etching unit 40 is disposed on the +Y side of the removing unit 30. FIG. 6 is a view showing an example of the chemical etching unit 40 and the winding unit 80. As shown in FIG. 6, the chemical etching unit 40 has a cavity 41, a conveying portion 42, a chemical etching portion 43, a cleaning portion 44, a liquid removing portion 45, and a heating portion 46. The cavity 41 has a transfer inlet 40a into which the porous resin film F is carried, and a transfer port 40b through which the porous resin film F is carried out. The chamber 41 houses the transport unit 42, the chemical etching unit 43, the cleaning unit 44, and the liquid drain unit 45.

The conveyance unit 42 conveys the porous resin film F to the +Y direction across the chemical etching unit 43, the cleaning unit 44, and the liquid removal unit 45. The conveyance unit 42 has a conveyance belt 42a, a drive roller 42b, and passive rollers 42c to 42e. Further, in addition to the drive roller 42b and the passive rollers 42c to 42e, a support roller that supports the conveyance belt 42a may be disposed inside the chemical etching portion 43, the cleaning portion 44, and the liquid discharge portion 45.

The conveyor belt 42a is formed in an endless shape and arranged along the Y direction. The conveyor belt 42a is formed using a material having durability against an etching liquid (EQ) to be described later. The conveyor belt 42a, for example, completely forms a mesh In the form of a mesh, the etching liquid can pass through the conveying belt 42a. The conveyor belt 42a is substantially parallel to the XY plane and has a tension state, and is bridged between the drive roller 42b and the driven roller 42c. The porous resin film F is placed on the conveyance belt 42a and conveyed.

The drive roller 42b is disposed at the +Y side end of the inside of the cavity 41. The drive roller 42b is formed, for example, in a cylindrical shape and arranged in parallel with the X direction. The drive roller 42b is provided with a rotary drive such as a motor. The drive roller 42b is arranged to be rotatable about an axis parallel to the X direction by means of the rotary drive. By rotating the drive roller 42b, the conveyor belt 42a rotates clockwise as shown in FIG. The porous resin film F placed on the conveyor belt 42a is conveyed to the +Y direction by the rotation of the conveyor belt 42a.

The passive roller 42c is disposed at the -Y side end of the inside of the cavity 41. The passive rollers 42d and 42e are disposed on the -Z side of the driven roller 42c and the driving roller 42b, respectively. The passive rollers 42c to 42e are formed, for example, in a cylindrical shape and arranged in parallel with the X direction. The driven roller 42c has the same diameter as the driving roller 42b, and the position (height position) in the Z direction is substantially equal to the driving roller 42b. The passive roller 42d has the same diameter as the passive roller 42e, and the position (height position) in the Z direction is substantially equal to the passive roller 42e. The passive rollers 42c to 42e are arranged to be rotatable about an axis parallel to the X direction. The passive rollers 42c to 42e rotate by tracking the rotation of the conveyor belt 42a.

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

The upper nozzle 43a is disposed on the +Z side of the conveyor belt 42a. The upper nozzles 43a are arranged in plural numbers, for example, in the Y direction. Each of the upper nozzles 43a has a plurality of discharge ports 43d in the X direction. Each of the discharge ports 43d faces the -Z side. The sprayed etching liquid EQ is discharged to the -Z direction by the respective discharge ports 43d. Each of the upper nozzles 43a is connected to a supply source (not shown) of the etching liquid EQ.

The lower nozzle 43b is disposed on the -Z side of the conveyor belt 42a. The lower nozzles 43b are arranged in plural numbers, for example, in the Y direction. FIG. 7 shows a state in which the upper nozzle 43a and the lower nozzle 43b are alternately arranged in the Y direction, but the configuration is not limited thereto. Each of the lower nozzles 43b has a plurality of discharge ports 43e in the X direction. The sprayed etching liquid EQ is discharged to the +Z direction from each of the discharge ports 43e. Each of the lower nozzles 43b is connected to a supply source (not shown) of the etching liquid EQ.

The roller 43c is disposed, for example, at each of the +Y side end portion and the -Y side end portion of the chemical etching portion 43. The roller 43c is interposed between the conveyor belt 42a and the porous resin film F. The roller 43c is rotatable in accordance with the rotation of the conveyor belt 42a.

The chemical etching unit 43 may have a recovery unit (not shown) or the like that collects the waste liquid of the etching liquid EQ. Further, the chemical etching unit 43 may have an exhaust unit (not shown) that exhausts the inside.

In the chemical etching portion 43, when the two rollers 43c are in contact with the porous resin film F, when the etching liquid EQ is discharged from the upper nozzle 43a, the etching liquid EQ is likely to remain in the Y direction between the two rollers 43c. between. The etching liquid EQ is continuously discharged from the upper nozzle 43a, whereby the storage portion 47 storing the etching liquid EQ is formed in this section. Moreover, the etching liquid EQ discharged from the lower nozzle 43b passes through the mesh of the conveyance belt 42a, and reaches the surface on the -Z side of the porous resin film F. The etching liquid EQ that has reached the -Z side of the porous resin film F causes the porous resin film F to protrude in the +Z direction. At this time, the etching liquid EQ discharged from the lower nozzle 43b is disposed between the protruding porous resin film F and the conveyance belt 42a. Therefore, the porous resin film F is immersed in the etching liquid EQ stored in the storage portion 47 in a state of apparently floating, and is subjected to a chemical etching treatment in this state. In this manner, the conveying unit 42 immerses the porous resin film F in the etching liquid EQ in the storage unit 47.

Further, as the etching solution EQ, for example, an inorganic alkali solution or an organic alkali solution can be used. The inorganic alkali solution may, for example, be a solution containing an alkali metal hydroxide such as hydrazine hydrate and ethylenediamine, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium citrate or sodium metasilicate. An ammonia solution, an etching solution containing hydrazine hydroxide, hydrazine and 1,3-dimethyl-2-imidazolidinone as main components. The organic alkali solution is, for example, a first-grade amine such as ethylamine or n-propylamine; a second-order amine such as diethylamine or di-n-butylamine; and a third amine such as triethylamine or methyldiethylamine. Alkamines; alkanolamines such as dimethylethanolamine and triethanolamine; fourth-order ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; cyclic amines such as pyrrole and piperidine; Alkaline solution. Further, as the solvent of each of the above solutions, pure water or an alcohol can be appropriately selected. Further, a surfactant to which an appropriate amount of a surfactant is added may also be used. The alkali concentration is, for example, 0.01 to 20% by mass.

Moreover, the other aspect of the chemical etching unit 43 may also be There are a configuration of the upper nozzle 43a, the roller 43c, and the bed member (not shown). In this aspect, the configuration of each of the upper nozzle 43a and the roller 43c is the same as that of the above embodiment, and thus the description thereof will be omitted. The bed member of the chemical etching portion 43 of this aspect is formed on the -Z side of the mesh of the conveyor belt 42a, and is formed along the XY plane. This bed member is disposed opposite to the conveyor belt 42a. The bed member may or may not be in contact with the conveyor belt 42a. When the bed member contact conveyance belt 42a is disposed, the storage portion 47 in which the etching liquid EQ can be stored is formed in the interval between the two rollers 43c. Further, when the bed member is not in contact with the conveyance belt 42a, the storage portion 47 may be formed. At this time, for example, the conveyance belt 42a is in contact with the two rollers 43c and the bed member in a state in which the lower portion of the two rollers 43c and the bed member are next to the mesh of the conveyance belt 42a. Therefore, the interval between the two rollers 43c is such that the etching liquid EQ can be stored to form the storage portion 47. With such a bed member, in the Y direction, the interval between the two rollers 43c becomes easier to form the storage portion 47 of the etching liquid EQ. Therefore, it is easy to maintain the state in which the porous resin film F is immersed in the etching liquid EQ stored in the storage portion 47. Similarly to the conveyor belt 42a, the material of the bed member may be selected from materials having a durability, such as vinyl chloride or the like, in accordance with the type or concentration of the etching liquid EQ. Further, the bed member may be provided with a plurality of holes that are penetrated in the Z direction. Thereby, the etching liquid EQ can be supplied to the storage portion 47 through the hole of the bed member from the supply source of the etching liquid EQ. When the hole of the bed member is provided, the upper nozzle 43a may not be provided.

Next, as shown in FIG. 6, the cleaning part 44 washes the porous resin film F after the purification etching. The cleaning unit 44 is disposed on the +Y side of the chemical etching unit 43 (before the conveyance direction of the porous resin film F). Wash The portion 44 has a supply unit (not shown) that supplies the cleaning liquid. In addition, a recovery unit (not shown) or the like for recovering the waste liquid after washing the porous resin film F may be provided. Since the chemical etching unit 43 and the cleaning unit 44 have different liquids contained therein, the water absorbing roller can be provided at the position before the chemical etching unit 43 is carried out. The water absorbing roller is disposed on at least one of the +Z side and the -Z side with respect to the porous resin film F, and is preferably disposed on both sides.

The liquid removal unit 45 removes the liquid adhering to the washed porous resin film F. Pre-drying is possible. The liquid draining portion 45 is disposed on the +Y side of the cleaning portion 44 (before the transport direction of the porous resin film F). The liquid discharge portion 45 is provided with a water suction roller or the like. By bringing the water absorbing roller into contact with the porous resin film F, the porous resin film F is conveyed, and the liquid adhering to the porous resin film F can be absorbed. The arrangement of the water suction roller in the conveyance direction is not particularly limited as long as it is carried out by the liquid discharge unit 45.

The heating unit 46 is disposed on the +Y side of the chamber 41 (before the conveyance direction of the porous resin film F). The heating unit 46 heats the porous resin film F after the liquid is removed by the liquid removing unit 45 at a temperature of about 100° C. to 300° C. to perform a drying step or a post-baking treatment step. The heating unit 46 is provided with a heating unit or the like that heats the porous resin film F. The +Y side of the heating unit 46 is provided with a discharge port 46b for carrying out the porous resin film F.

[Winding section (2)]

FIG. 8 is a perspective view schematically showing a configuration of the +Y side of the chemical etching unit 40.

As shown in FIG. 8, the +Y side of the chemical etching unit 40 is provided with a carry-out port 46b for carrying out the porous resin film F. The porous resin film F carried out from the carry-out port 46b is wound around the winding portion 80.

The winding portion 80 is configured such that the bearing 81 is attached to the shaft member SF. The shaft member SF winds the porous resin film F carried out from the delivery port 40b to form a roll body RF. The shaft member SF is provided to be detachable with respect to the bearing 81. When the shaft member SF is attached to the bearing 81, it can be supported by being rotated about an axis parallel to the X direction. The winding portion 80 has a drive mechanism (not shown) that can rotate the shaft member SF attached to the bearing 81. The shaft member SF is rotated by a drive mechanism to wind the porous resin film F. In a state in which the reel body RF is formed, the shaft member SF is removed by the bearing 81, and the reel body RF can be recovered.

〔Production method〕

Next, an example of an operation of manufacturing the porous resin film F using the manufacturing system SYS having the above configuration will be described. (a) to (f) of FIG. 9 are views 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. In the coating unit 10, the substrate feeding roller 11a is rotated, the conveying substrate S is fed out, and the conveying substrate S is placed on the supporting rollers 11b to 11d, and then wound by the substrate winding roller 11e. Then, the roller 11a is fed from the substrate, and the conveyance substrate S is sequentially fed, and the substrate winding roller 11e is wound.

In this state, the first nozzle 12 is disposed at the discharge position P1, and the discharge port 12a is oriented in the +Y direction. Thereby, the discharge port 12a is oriented Among the conveyance base materials S, the portion supported by the support roller 11b. Then, the first coating liquid Q1 is discharged from the discharge port 12a. The first coating liquid Q1 is discharged from the discharge port 12a in the +Y direction, and reaches the conveyance base material S, and is applied to the conveyance base material S in association with the movement of the conveyance substrate S. Thereby, the first coating film F1 obtained by the first coating liquid Q1 is formed on the conveyance substrate S.

Next, the second nozzle 13 is disposed at the discharge position P2, and the discharge port 13a faces the -Z direction. Thereby, the discharge port 13a is directed toward the conveyance base material S, and supports the portion supported by the roller 11c. Then, the second coating liquid Q2 is discharged from the discharge port 13a. The second coating liquid Q2 is discharged from the discharge port 13a in the -Z direction, reaches the first coating film F1 formed on the conveyance substrate S, and is applied to the first coating in association with the movement of the conveyance substrate S. On film F1. Thereby, as shown in FIG. 9(a), the second coating film F2 obtained from the second coating liquid is formed on the first coating film F1. Further, in the first coating film F1 and the second coating film F2, the fine particles A2 are contained in the resin material A1 at a different volume ratio from each other. Further, the content ratio of the fine particles is set such that the first coating film F1 is larger than the second coating film F2.

In the state in which the discharge rollers 11a and 13a are supported by the support rollers 11b and 11c, the first coating liquid Q1 and the second coating liquid Q2 are applied to the conveyance base material S, so that the first coating liquid Q1 and the second coating liquid Q2 are applied. When the coating liquid Q1 and the second coating liquid Q2 reach the conveying substrate S, the force acting on the conveying substrate S is received by the supporting rollers 11b and 11c. Therefore, the occurrence of deflection, vibration, and the like of the conveyance substrate S is suppressed, and the first coating film F1 and the second coating film F2 are formed in a uniform thickness on the conveyance substrate S.

Next, the transfer substrate S moves, and the first coating film F1 and When the laminated portion of the second coating film F2 is carried into the cavity 14a of the drying unit 14, the drying of the first coating film F1 and the second coating film F2 is performed in the drying unit 14. The drying unit 14 heats the first coating film F1 and the second coating film F2 at a temperature of, for example, about 50° C. to 100° C., using the heating unit 14 b. In this temperature range, the conveyance substrate S does not undergo strain or deformation, and the first coating film F1 and the second coating film F2 can be heated. By drying the laminate of the first coating film F1 and the second coating film F2, as shown in FIG. 9(b), the unfired film FA is formed.

In the present specification, the lamination system refers to an unfired film composed of the first coating film F1 and the second coating film F2. When the porous bismuth imide resin film of the present invention is formed, among the first liquid and the second liquid, the same species is used for polyamine, polyimine, polyamidimide or polyamine. In the case of the resin, the unfired film (or the porous yttrium-based resin film) composed of the first coating film F1 and the second coating film F2 formed is substantially one layer, but forms fine particles. In the case of an unfired film (or a bismuth imino resin film having a porosity in a region having a different porosity), the same liquid is used in the first liquid and the second liquid, and is referred to in the present specification. It is a laminate.

Then, the conveyance substrate S moves, and when the end portion of the unfired film FA reaches the support roller 11d (peeling portion 15), the tip end portion is peeled off from the conveyance substrate S by, for example, an operator's hand. In the present embodiment, the material for transporting the substrate S is, for example, PET. When the first coating film F1 and the second coating film F2 are dried to form the unfired film FA, the separation of the substrate S is facilitated. The operator can easily peel off.

After the front end portion of the unfired film FA is peeled off, the conveyance substrate S moves, and the first coating film F1 is formed by the first nozzle 12 . Then, the second coating film F2 is formed by the second nozzle 13, and the unfired film FA is formed in the drying portion 14. Thereby, the unfired film FA is formed into a strip shape, and the length of the unfired film FA carried out by the drying section 14 to the +Y side gradually becomes longer. The operator continues to peel off the unfired film FA at the peeling portion 15. Then, when the front end of the unfired film FA which has been peeled off reaches the length of the shaft member SF of the winding portion 50, the operator hangs the unfired film FA on the carry-out roller 11f by hand, and at the same time, the unfired film The front end portion of the FA is mounted on the shaft member SF. Then, in order to form the unfired film FA in order to be sequentially peeled off, the shaft member SF is rotated in the winding portion 50. Thereby, the unfired film FA which has been peeled off is sequentially carried out by the coating unit 10, and is wound by the shaft member SF of the winding portion 50 to form the roll body R. As shown in Fig. 9(c), the unfired film FA constituting the roll body R is in a state of being peeled off by the transfer substrate S, and both the surface and the inside are exposed.

The work of peeling off the front end portion of the unfired film FA and the work of attaching the front end portion to the shaft member SF after peeling are not limited to the case where the operator performs the work by hand, and can be automatically performed, for example, using a robot or the like. Further, in order to improve the releasability of the unfired film FA, a release layer may be formed on the surface of the conveyance substrate S.

After the unfired film FA of a specific length is wound around the shaft member SF, the unfired film FA is cut, and the shaft member SF is continuously removed from the roll body R by the bearing 51. Then, the new shaft member SF is attached to the bearing 51 of the winding portion 50, and the cut end portion of the unfired film FA is attached to the shaft structure. The SF is rotated to form an unfired film FA, and a new roll body R can be produced.

Further, for example, the operator transports the shaft member SF that has been removed by the bearing 51 continuous rolling cylinder R to the delivery portion 60, and is attached to the bearing 61. The conveying operation and the mounting operation of the shaft member SF can also be automatically performed using a robot or a conveying device. After the shaft member SF is attached to the bearing 61, the unfired film FA is sequentially pulled out from the roll body R by rotating the shaft member SF, and the unfired film FA is carried into the cavity 21 of the firing unit 20. Further, when the front end of the unfired film FA is carried into the chamber 21, the operator can also work by hand or automatically using a robot or the like.

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

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

Further, when the baking conditions include polyamic acid and/or polyimide, the temperature can be raised from room temperature to 375 ° C for 3 hours. The method of holding at 375 ° C for 20 minutes or 50 ° C scale, the temperature is raised from room temperature to 375 ° C (each stage is maintained for 20 minutes), and finally, the stage heating is carried out by holding at 375 ° C for 20 minutes or the like. Further, the end portion of the unfired film FA can be fixed to a model made of SUS or the like to prevent deformation.

By this baking, as shown in FIG. 9(d), the fired film FB is formed. The fired film FB contains fine particles A2 inside the resin layer A3 which is subjected to hydrazine imidization or high temperature treatment. The film thickness of the fired film FB can be obtained by measuring the thickness at a plurality of points, for example, by a micrometer or the like, and obtaining an average value. The preferred average film thickness is preferably from 3 μm to 500 μm, more preferably from 5 μm to 100 μm, still more preferably from 10 μm to 30 μm, when used in a separator film or the like.

When the fired film FB formed by the firing unit 20 is carried out by the firing unit 20, it is carried into the removing unit 30 without being wound. When the front end portion of the fired film FB is carried into the removal unit 30, the operator can perform the work by hand or automatically using a robot or the like.

The fired film FB of the loading and unloading unit 30 is placed on the conveyance belt 35a, and is conveyed to the +Y direction in accordance with the rotation of the conveyance belt 35a. The removal unit 30 is transported along with the fired film FB. First, the fine particles A2 are removed in the etching unit 32. When the material of the fine particles A2 is, for example, cerium oxide, in the etching portion 32, the fired film FB is immersed in an etching liquid such as hydrogen fluoride having a low concentration. Thereby, the fine particles A2 are dissolved in the etching liquid and removed, and as shown in FIG. 9(e), the porous resin film F containing the porous portion A4 inside the resin layer A3 is formed.

Thereafter, following the rotation of the conveyor belt 35a, the porous resin The film F is sequentially carried into the cleaning unit 33 and the liquid removing unit 34. The cleaning unit 33 cleans the porous resin film F by the cleaning liquid. Moreover, the liquid discharge part 34 removes the liquid of the porous resin film F, and removes a washing liquid. Then, the porous resin film F is carried out by the removing unit 30 and carried into the chemical etching unit 40.

The porous resin film F carried into the chemical etching unit 40 is placed on the conveyor belt 42a, and is conveyed to the +Y direction in accordance with the rotation of the conveyor belt 42a. The chemical etching unit 40 carries out the chemical etching treatment on the inside of the porous portion A4 in the chemical etching portion 43 as the porous resin film F is transported. The chemical etching portion 43 is a porous resin film F immersed in the storage portion 47 of the etching liquid EQ, and as shown in FIG. 9(f), the inside of the porous portion A4 is removed. At this time, the burrs of the porous portion A4 are removed while ensuring connectivity.

Thereafter, the porous resin film F is sequentially carried into the cleaning portion 44 and the liquid discharge portion 45 in accordance with the rotation of the conveyor belt 42a. The cleaning unit 44 cleans the porous resin film F by the cleaning liquid, and the liquid removing unit 45 removes the liquid. Further, the liquid removing portion 45 performs liquid removal of the porous resin film F. Then, in the heating unit 46, the porous resin film F after the liquid is removed is heated to about 100 to 300 ° C to remove the cleaning liquid. The porous resin film F is carried out by the chemical etching unit 40 and wound by the shaft member SF of the winding portion 80.

As described above, the manufacturing system SYS of the present embodiment includes the unfired film FA including the resin material A1 and the fine particles A2 containing polyglycine, polyimine, polyamidamine or polyamine. Burning In the obtained fired film FB, the fine particle A2 is removed, the film forming unit 70 which forms the porous resin film F, and the chemical etching unit 40 which partially dissolves the porous resin film F are formed, so that the unfired film FA can be carried out in a series of processes. Three steps of formation of the unfired film FA (formation of the fired film FB) and removal of the fine particles A2 (formation of the porous resin film F) are carried out. Thereby, the porous resin film F can be efficiently produced. Further, since the inside of the porous portion A4 is removed by the chemical etching unit 40, the opening ratio of the porous portion A4 can be increased, and the connectivity of the porous portion A4 can be ensured. When such a porous resin film F is used as a separator film of a lithium ion battery or the like, ions are smoothly moved, so that electrical characteristics of the battery can be improved. Therefore, a high-quality porous resin film F having an excellent opening ratio can be obtained.

In addition, the chemical etching unit (40) includes a storage unit (47) for storing an etching solution (EQ), and a film conveying unit for immersing the yttrium imide resin film (porous resin film F) in the storage portion (transporting) Since the portion 42) is used, the chemical etching treatment can be efficiently performed on the quinone imine resin film.

Further, the quinone imine resin film (porous resin film F) is formed into a strip shape, and the chemical etching unit (49) sequentially transports the quinone imine resin film (porous resin film F) sent from the film forming unit (70). Since it can be applied to a manufacturing process such as a roll-to-roll method, the quinone-imide resin film (porous resin film F) can be efficiently formed.

In addition, the winding portion (80) for winding a strip-shaped yttrium-based resin film (porous resin film F) discharged from the chemical etching unit (40) is provided, so that it can be subjected to chemical etching treatment. Amine resin film roll Wrap around and recycle efficiently.

Moreover, the method for producing the porous resin film F of the present embodiment includes a film containing a polyaminic acid, a polyimine, a polyamidimide or a polyamide and a fine particle (A2) (a fired film). In FB), the porous bismuth imide resin film (porous resin film F) is removed, and the chemical etching process for partially dissolving one of the quinone imide resin films is performed, so that the process can be carried out in a series of processes. The formation of the fired film FA, the firing of the unfired film FA (formation of the fired film FB), and the removal of the fine particles A2 (formation of the porous resin film F) are three steps. Thereby, the manufacturing efficiency of the porous resin film F can be improved. Further, since the inside of the porous portion A4 is removed by the chemical etching unit 40, the opening ratio of the porous portion A4 can be increased, and the connectivity of the porous portion A4 can be ensured.

[Modification]

In the above-described embodiment, the configuration in which the removing unit 30 and the chemical etching unit 40 are arranged in a separate unit form and arranged in the Y direction is described as an example, but the present invention is not limited thereto. Fig. 10 is a view showing an example of a part of a manufacturing system SYS2 of a modification. As shown in FIG. 10, the manufacturing system SYS2 is configured such that the removing unit 230 and the chemical etching unit 240 are connected in the Y direction.

The removing unit 230 has an etching portion 32, a cleaning portion 33, and a liquid removing portion 34. The etching unit 32, the cleaning unit 33, and the liquid removal unit 34 are arranged side by side in the Y direction. The configuration of each of the etching portion 32, the cleaning portion 33, and the liquid discharge portion 34 is the same as that of the above-described embodiment, and thus the description thereof is omitted.

The chemical etching unit 240 has a chemical etching portion 43 and is cleaned. The portion 44 and the liquid removing portion 45. The chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45 are arranged side by side in the Y direction. The configuration of each of the chemical etching unit 43, the cleaning unit 44, and the liquid removing unit 45 is the same as that of the above embodiment, and thus the description thereof is omitted.

The removal unit 230 and the chemical etching unit 240 have a common cavity 241 and a common transfer portion 242. The cavity 241 houses the respective configurations (the etching portion 32, the cleaning portion 33, and the liquid removing portion 34) of the removing unit 230 and the chemical etching unit 240 (the chemical etching portion 43, the cleaning portion 44, and the liquid removing portion 45). The cavity 241 has a transfer inlet 241a into which the fired film FB is carried, and a transfer port 241b through which the porous resin film F is carried out.

The conveyance unit 242 bridges the removal unit 230 and the chemical etching unit 240, and conveys the fired film FB and the porous resin film F to the +Y direction. The conveyance unit 242 has a conveyance belt 242a, a drive roller 242b, and passive rollers 242c to 42e. Further, in addition to the driving roller 242b and the passive rollers 242c to 242e, a supporting roller that supports the conveying belt 242a may be provided inside the removing unit 230 or the chemical etching unit 240.

The conveyor belt 242a is formed in an endless shape and arranged along the Y direction. The conveyor belt 242a is formed using a material having durability for each of the etching liquid used in the etching portion 32 and the chemical etching liquid used in the chemical etching portion 43. The conveyor belt 242a is formed, for example, in a mesh shape. The conveyance belt 242a is in a state of being tensioned, and is substantially parallel to the XY plane, and is bridged between the drive roller 242b and the passive rollers 242c to 242e. The porous resin film F is placed on the conveyance belt 242a and conveyed.

Also, the conveyor belt 242a can bridge the removal unit 230 and chemistry Although the etching unit 240 is continuous, it can be formed by mixing the etching liquid and the chemical etching liquid used for each unit, or the conveyance distance of each unit.

The drive roller 242b is disposed at the +Y side end of the inside of the cavity 241. The drive roller 242b is arranged to be rotatable about an axis parallel to the X direction. By rotating the drive roller 242b, the conveyor belt 242a is rotated clockwise as shown in FIG. The porous resin film F placed on the conveyance belt 242a is conveyed to the +Y direction by the rotation of the conveyance belt 242a.

The passive roller 242c is disposed at the -Y side end of the interior of the cavity 241. The passive rollers 242d and 242e are respectively disposed on the -Z side of the driven roller 242c and the driving roller 242b. The passive rollers 242c-242e are arranged to rotate about an axis parallel to the X direction. The passive rollers 242c to 242e rotate by tracking the rotation of the conveyor belt 42a.

In this manner, the film forming unit (70) includes a liquid containing a poly-proline, a polyimine, a polyamidamine or a polyamide, and fine particles (the first coating liquid Q1, the second coating liquid) Q2) coating unit (10) coated on a substrate (transporting substrate S) to form an unfired film (FA); unfired after being peeled off from the substrate in the coating unit or outside the coating unit The film is fired to form a firing unit (20) containing a sintered film (FB) of fine particles; and the yttrium imide resin film (porous resin film F) is formed by removing fine particles from the fired film to form a porous yttrium-based resin film (porous resin film F). Since the unit (30) and the chemical etching unit (40) are connected to the removing unit, chemical etching can be efficiently performed on the quinone-based resin film.

Moreover, the porous resin film F is the transport unit 242 The transfer unit 230 is transported from the removal unit 230 to the chemical etching unit 240 by one transfer belt 242a. Therefore, between the removal unit 230 and the chemical etching unit 240, the porous resin film F does not have to be delivered. Thereby, the porous resin film F can suppress the external force generating action as much as possible.

Further, in the above embodiment, the winding portions 50 and 80 are exemplified as a configuration in which the shaft member SF is detached from the bearings 51 and 81. However, the present invention is not limited thereto, and for example, the winding device 90 shown in Fig. 12 may be used. . Hereinafter, a case where the winding device 90 is used instead of the winding portion 50 will be described as an example.

As shown in FIG. 11, the winding device 90 has a frame body 91, a shaft member SF, a bearing 92, a drive unit 93, relay rollers 94a to 94e, and a roller support portion 95. The frame 91 supports each of the shaft member SF, the bearing 92, the drive unit 93, the relay rollers 94a to 94e, and the roller support portion 95.

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

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

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

Further, the winding device 90 may be used instead of the winding portion 80. In addition, by rotating the shaft member SF in a direction opposite to the case where the film of the unfired film FA or the like is wound, the film of the unfired film FA or the like can be sent out. Therefore, for example, the winding device 90 may be used instead of the above-described delivery portion 60.

[separator film]

Next, the separator film 100 of the embodiment will be described. Fig. 12 is a schematic view showing an example of a lithium ion battery 200, in a state in which a part is cut. As shown in FIG. 12, the lithium ion battery 200 has a metal case 201 and a negative electrode terminal 202 which are also positive electrode terminals. The inside of the metal shell 201 is provided with a positive electrode 201a and a negative electrode. 202a and the separator film 100 are immersed in an electrolyte solution (not shown). The separator 100 is disposed between the positive electrode 201a and the negative electrode 202a to prevent electrical contact between the positive electrode 201a and the negative electrode 202a. A lithium transition metal oxide can be used for the positive electrode 201a, and lithium, carbon (graphite) or the like can be used for the negative electrode 202a.

The porous resin film F described in the above embodiment is used as the separator film 100 of the lithium ion battery 200. At this time, for example, the surface on which the first coating film F1 is formed is used as the negative electrode 202a side of the lithium ion battery, and battery performance can be improved. Further, FIG. 12 is an example in which the separator film 100 of the prismatic lithium ion battery 200 is taken as an example, but is not limited thereto. As the porous resin film F, a separator film of a lithium ion battery of any form such as a cylindrical type or a laminate type can be used. Further, the porous resin film F can be used as a fuel cell electrolyte membrane, a gas or liquid separation membrane, or a low dielectric material, in addition to the separator film of the lithium ion battery.

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

For example, in the above-described embodiment and the modification, when one portion of the porous resin film F is removed, the case where only the chemical etching method is performed will be described as an example, but the invention is not limited thereto. For example, a part of the porous resin film F may be removed by a combination of a chemical etching method and a physical removal method. The physical method can be, for example, dry etching using a plasma (oxygen, argon, or the like), corona discharge, or the like, and dispersing an abrasive (for example, alumina (hardness 9) or the like) in a liquid, thereby imparting aroma to the liquid. The surface of the polyimide film is irradiated at a speed of 30 m/s to 100 m/s to treat the surface of the polyimide film. Such The method can be applied to any of the removal unit 30 before the removal of the fine particles from the fired film FB and after the removal of the fine particles. Further, the physical method which can be applied only to the case after the removal of the fine particles can be carried out by press-bonding a pasteboard film (for example, a polyester film such as a PET film) which is wetted with a liquid on the surface of the object. After drying or drying, the porous resin film F is peeled off from the paperboard film. The porous resin film F is pulled and peeled off from the cardboard film in a state where only the surface layer of the porous resin film F remains on the cardboard film due to the surface tension of the liquid or the electrostatic adhesion.

For example, in the above-described embodiments and modifications, the case where the unfired film FA is formed by using two types of coating liquids having different contents of fine particles is described as an example. However, the present invention is not limited thereto, and may be applied in one type. The cloth liquid forms an unfired film. In this case, one of the first nozzle 12 and 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 omitted and the second nozzle 13 is preferably used.

Further, in the above-described embodiments and modifications, the configuration in which the coating unit 10, the firing unit 20, the removing unit 30, and the chemical etching unit 40 are disposed one by one is described as an example, but the invention is not limited thereto. For example, at least one of the above units may be provided with a plurality of units. In this case, for example, a unit having a small amount (for example, length) of the unfired film FA, the fired film FB, or the porous resin film F which can be processed per unit time can be disposed, and the manufacturing system SYS can be manufactured as a whole. effectiveness.

Further, the above embodiments and modifications are coating units 10. Each of the firing unit 20, the removing unit 30, and the chemical etching unit 40 is an example in which each of the unfired film FA, the fired film FB, or the porous resin film F is transported in the Y direction. Description, but not limited to this. For example, any of the units may transport the film to the X direction, the Y direction, the Z direction, or the like, or the transfer direction may be appropriately changed in one unit.

Further, in addition to the configuration of the above embodiment, a post-processing unit that performs post-treatment on the partially removed porous resin film F in the chemical etching unit 40 may be provided. After that, the processing unit performs a static electricity prevention unit or the like for removing the static electricity, for example, the porous resin film F. The static electricity prevention unit is mounted with a static elimination device such as an electrostatic discharge device.

Further, the above-described embodiments and modifications are described by taking three steps of applying the coating unit 10, firing the firing unit 20, and removing the removing unit 30 as an example, but are not limited thereto. For example, when the material of the coating film is polyimine, polyamidimide or polyamine, the firing may not be performed. Therefore, when the firing is not performed, for example, by providing a winding device, a feeding device, and the like between the firing unit 20 and the removing unit 30, the unfired film FA formed by the coating unit 10 can be prevented from firing. The unit 20 is carried into the removal unit 30. Further, in the case where the firing is not performed, the production system for producing the porous bismuth imide resin film may include: containing polylysine, polyimine, polyamidimide or polyamine and fine particles. a coating unit in which a liquid is applied to a substrate to form an unfired film; and a removal unit in which the fine particles are removed from the unfired film after the substrate is peeled off from the substrate or in the coating unit system. When the firing is not performed, the porous resin film F is removed by the removing unit 30 for removing fine particles. After the release, the aforementioned post-baking treatment step can also be performed. Also, the chemical etching unit 40 may be passed before the post-baking treatment step. At this time, the post-baking treatment step can be performed by the heating portion 46.

Further, in the above-described embodiments and modifications, the configuration in which the porous resin film F is formed by the so-called roll-to-roll method is described as an example, but the invention is not limited thereto. For example, when the porous resin film F is carried out by the chemical etching unit 40 after the completion of the treatment in the chemical etching unit 40, it is not necessary to be wound by the winding portion 80, and it can be cut at a specific length, and can be recovered by the cut.

SYS‧‧‧ Manufacturing System

F‧‧‧Porous resin film (醯iamine resin film)

FA‧‧‧Unfired film

FB‧‧‧Boiled film

10‧‧‧ Coating unit

20‧‧‧burning unit

30‧‧‧Removal unit

40‧‧‧Chemical etching unit

50‧‧‧Winding Department

60‧‧‧Send out

70‧‧‧film forming unit

80‧‧‧Winding Department

Claims (6)

A system for producing a quinone imine resin film, which is a system for producing a porous bismuth imide resin film, comprising: a polyamido acid, a polyamidiamine, a polyamidimide or a polyamine And a film forming unit that forms the porous bismuth imide resin film and a chemical etching unit that partially dissolves the quinone imide resin film in the film of the fine particles. The imine-based resin film production system according to the first aspect of the invention, wherein the chemical etching unit includes: a storage portion for storing the etching liquid; and a film transfer of the etching liquid in which the quinone-based resin film is immersed in the storage portion unit. The imine-based resin film production system according to claim 1 or 2, wherein the quinone imine resin film is formed into a strip shape, and the chemical etching unit is the quinone imide resin sent from the film forming unit. The film is stored in order. The yttrium-imide-based resin film production system according to any one of the first to third aspects of the present invention, further comprising a winding portion that winds the strip-shaped bismuth imide resin film discharged by the chemical etching unit . The quinone imine resin film manufacturing system according to any one of claims 1 to 4, wherein the film forming unit comprises: polyglycine, polyimine, polyamidimide or poly a coating unit in which a liquid of guanamine and fine particles is applied to a substrate to form an unfired film; and the unfired film after peeling off the substrate in the coating unit or outside the coating unit a firing unit that forms a fired film containing the fine particles, and a removal unit that removes the fine particles from the fired film to form a porous bismuth imide resin film; the chemical etching unit and the removal Unit connection. A method for producing a quinone imine resin film, which is a method for producing a porous bismuth imide resin film, comprising: comprising a polyaminic acid, a polyimine, a polyamidimide or a polyamine In the film of the fine particles, the microparticles are removed to form the porous quinone imine resin film, and one of the quinoneimide resin films is partially dissolved and chemically etched.