KR20170012341A - Porous imide resin film production system, separator, and porous imide resin film production method - Google Patents

Abstract

The present invention provides a porous imide resin film production system, a separator, and a porous imide resin film production method capable of improving the production efficiency of a porous imide resin film. A coating unit (10) for applying a coating liquid (a first coating liquid and a second coating liquid) containing a resin material of polyamide acid, polyimide, polyamideimide or polyamide and fine particles to a transportation substrate to form a microcapsule, And a removal unit (30) for removing the fine particles from the fired film and a firing unit (20) for firing the microfilm peeled off from the transport substrate in the coating unit (10) to form a fired film containing fine particles.

Description

TECHNICAL FIELD [0001] The present invention relates to a porous imide resin film production system, a separator, and a porous imide resin film production method.

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

A lithium ion battery, which is a type of secondary battery, has a structure in which a separator is disposed between a positive electrode and a negative electrode immersed in an electrolytic solution to prevent direct electrical contact between the positive electrode and the negative electrode by a separator. Lithium transition metal oxide is used for the positive electrode, and lithium or carbon (graphite) is used for the negative electrode. During charging, lithium ions move from the positive electrode to the negative electrode through the separator, and at the time of discharging, lithium ions move from the negative electrode to the positive electrode through the separator. As such a separator, it is known to use a separator made of a porous polyimide film having high heat resistance and high safety (see, for example, Patent Document 1, etc.).

Japanese Patent Laid-Open No. 2011-111470

The porous polyimide film is formed by coating a microfabricated film of polyamic acid or polyimide containing fine particles, firing the microfilm to form a fired film, and removing fine particles from the fired film . In the past, the production efficiency of the porous polyimide film was not so high because there was no manufacturing system for carrying out the above three processes in one line. Therefore, a system with higher production efficiency has been required.

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a porous imide resin film production system, a separator, and a porous imide resin film production method capable of improving the production efficiency of a porous imide resin film do.

A porous imidic resin film production system according to the first aspect of the present invention is a production system for producing a porous imidic resin film, comprising a liquid containing polyamic acid, polyimide, polyamideimide or polyamide and fine particles, And a removing unit for removing the fine particles from the firing film. The firing unit removes fine particles from the firing film. The firing unit removes fine particles from the firing film. .

The separator according to the second aspect of the present invention is a separator formed by a porous imide resin film, and a porous imide resin film is produced by the porous imide resin film production system according to the first embodiment of the present invention.

A porous imidic resin film production method according to a third aspect of the present invention is a method for producing a porous imidic resin film, comprising the steps of: preparing a liquid containing a polyamic acid, a polyimide, a polyamideimide or polyamide and fine particles, Forming a microfilm by removing the microfilm from the substrate after the application, firing the microfilm to form a fired film containing fine particles, and removing fine particles from the fired film.

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

1 is a diagram showing an example of a manufacturing system according to an embodiment of the present invention.
2 is a view showing an example of a nozzle provided in the coating unit according to the embodiment.
3 is a perspective view showing an example of a winding section according to the present embodiment.
4 is a perspective view showing an example of the baking unit according to the present embodiment.
5 is a perspective view showing an example of a removal unit according to the present embodiment.
6 is a view showing an example of a process of manufacturing the imide resin film according to this embodiment.
7 is a view showing an example of a manufacturing system according to a modification.
8 is a view showing an example of a manufacturing system according to a modification.
9 is a view showing an example of a manufacturing system according to a modification.
10 is a view showing an example of a manufacturing system according to a modification.
11 is a view showing an example of an etching unit according to a modified example.
12 is a view showing an example of a winding device according to a modification.
13 is a view showing an example of a separator according to the embodiment.

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

1 is a diagram showing an example of a manufacturing system (SYS). The production system SYS shown in Fig. 1 is to produce a porous resin film (porous imide resin film). The manufacturing system SYS includes a coating unit 10 for applying a predetermined coating liquid to form an unfired film FA, a firing unit 20 for firing the unfired film FA to form a fired film FB, A removal unit 30 for removing fine particles from the firing film FB to form a porous resin film F, and a control device (not shown) for controlling the respective units collectively.

The manufacturing system SYS is composed of, for example, upper and lower two layers, in which the coating unit 10 is disposed in the two-layer portion, and the firing unit 20 and the removal unit 30 are disposed in the first layer portion. The firing unit 20 and the removal unit 30 disposed on the same layer are arranged in the Y direction, for example, but are not limited thereto. For example, the firing unit 20 and the removal unit 30 may be arranged in the X direction or the composite direction in the X direction and the Y direction They may be arranged side by side.

For example, the coating unit 10 and the firing unit 20 are disposed in the two-layer portion and the removal unit (not shown) 30 may be disposed in the first floor portion. All the units may be arranged on the same layer. In this case, each unit may be arranged in a line or in a plurality of lines. Further, all the units may be arranged in different layers.

In the manufacturing system SYS, the microfilm FA is formed in a band shape. On the + Y side (in front of the direction of conveyance of the microfilm (FA)) of the application unit 10, a winding unit 40 for winding the band-shaped microfilm FA in a roll form is provided. A delivery section 50 is provided on the -Y side of the firing unit 20 (behind the transport direction of the microfilm FA) for delivering the microfilm FA in the roll toward the firing unit 20. A winding portion 60 for winding the porous resin film F in a roll form is provided on the + Y side (in front of the firing film FB transport direction) of the removal unit 30.

As described above, in the section from the delivery section 50 to the winding section 60 via the firing unit 20 and the removal unit 30, the so-called roll-to-roll process is performed do. Accordingly, in this section, the films of the micro-film (FA), the fired film (FB) and the porous resin film (F) are transported in a series of states.

[Application liquid]

Before describing each unit, the coating liquid to be a raw material of the porous resin film (F) will be described. The coating liquid includes a predetermined resin material, fine particles, and a solvent. Examples of the predetermined resin material include polyamide acid, polyimide, polyamideimide, and polyamide. As the solvent, an organic solvent capable of dissolving these resin materials is used.

In the present embodiment, two kinds of coating liquids (first coating liquid and second coating liquid) having different contents of fine particles are used as the coating liquid. Specifically, the first coating liquid is prepared so that the content of the fine particles is higher than that of the second coating liquid. Thus, the strength and flexibility of the micro-film (FA), the fired film (FB), and the porous resin film (F) can be secured. In addition, by providing a layer having a low content of fine particles, the production cost of the porous resin film (F) can be reduced.

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

In this case, when the volume of the first coating liquid is 100, the particles are uniformly dispersed if the volume of the particles is 65 or more. If the volume of the particles is 81 or less, the particles disperse without aggregation. Therefore, it is possible to uniformly form holes in the porous resin film (F). If the volume fraction of the fine particles is within this range, the peeling property at the time of forming the micro-film (FA) can be ensured.

When the total volume of the second coating liquid is 100, if the volume of the fine particles is 50 or more, the fine particles are uniformly dispersed and if the volume of the fine particles is 80 or less, the fine particles do not aggregate, It is possible to form the porous resin film (F) stably with good electrical characteristics.

The two kinds of coating liquids are prepared by mixing, for example, a solvent in which fine particles are preliminarily dispersed and a polyamic acid, a polyimide, a polyamideimide or a polyamide at an arbitrary ratio. In addition, it may be prepared by polymerizing a polyamic acid, a polyimide, a polyamideimide, or a polyamide in a solvent in which fine particles are dispersed in advance. For example, it can be produced by polymerizing a tetracarboxylic acid dianhydride and a diamine in an organic solvent in which fine particles are preliminarily dispersed to obtain a polyamic acid, or further converting the imide into a polyimide.

The viscosity of the coating liquid is preferably 300 to 2500 cP, more preferably 400 to 1500 cP, and still more preferably 600 to 1200 cP. When the viscosity of the coating liquid is within this range, it is possible to form the film uniformly.

When the particulate material and the polyamic acid or polyimide are dried to form an unfired film (FA) in the coating liquid, when the material of the particulate material is an inorganic material to be described later, the ratio of particulates / polyimide is 2 to 6 (mass ratio) It is sufficient that the fine particles and the polyamic acid or polyimide are mixed. More preferably 3 to 5 (mass ratio). When the material of the fine particles is an organic material to be described later, the fine particles and the polyamic acid or the polyimide may be mixed so that the ratio of the fine particles / polyimide is 1 to 3.5 (mass ratio). More preferably 1.2 to 3 (mass ratio). In addition, fine particles and a polyamic acid or polyimide may be mixed so that the volume ratio of the fine particles / polyimide becomes 1.5 to 4.5 in the case of the unfilled film (FA). More preferably 1.8 to 3 (volume ratio). When the mass ratio or the volume ratio of the fine particles / polyimide is not less than the lower limit value, it is possible to obtain a hole with an appropriate density as the separator. When the mass ratio is less than the upper limit value, there is no case such as an increase in viscosity, The film can be stably formed. Even when the resin material is polyamideimide or polyamide instead of polyamide acid or polyimide, the mass ratio is the same as above.

Hereinafter, each resin material will be described in detail.

<Polyamide acid>

The polyamic acid used in the present embodiment can be obtained by polymerizing any of tetracarboxylic dianhydride and diamine without particular limitation. The amount of the tetracarboxylic acid dianhydride and the diamine to be used is not particularly limited, but the diamine is preferably used in an amount of 0.50 to 1.50 moles, more preferably 0.60 to 1.30 moles, and more preferably 0.70 to 1.20 moles per mole of the tetracarboxylic acid dianhydride Particularly preferred.

The tetracarboxylic acid dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as a starting material for synthesis of polyamic acid. The tetracarboxylic acid dianhydride may be an aromatic tetracarboxylic acid dianhydride or an aliphatic tetracarboxylic dianhydride, but from the viewpoint of the heat resistance of the obtained polyimide resin, it is preferable to use an aromatic tetracarboxylic dianhydride. The tetracarboxylic acid dianhydride may be used in combination of two or more.

Suitable examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis , 4-dicarboxyphenyl) methane dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2,6 Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) , 3,3,3-hexafluoropropane dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis -Dicarboxyphenyl) ether dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylenedioxy) diphthalic acid 2-anhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3 , 6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetra Carboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, 9,9-bis phthalic anhydride fluorene, and 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride. have. Examples of the aliphatic tetracarboxylic acid dianhydride include ethylene tetracarboxylic acid dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride , 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and the like. Of these, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoint of cost, availability and the like. These tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

The diamine can be appropriately selected from diamines conventionally used as starting materials for the synthesis of polyamic acid. The diamine may be an aromatic diamine or an aliphatic diamine, but from the viewpoint of the heat resistance of the obtained polyimide resin, an aromatic diamine is preferable. These diamines may be used in combination of two or more.

As the aromatic diamine, there can be mentioned a diamino compound in which one or two to ten or more phenyl groups are bonded. Specific examples thereof include phenylenediamine and derivatives thereof, diaminobiphenyl compounds and derivatives thereof, diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalenes and derivatives thereof, Derivatives thereof, diaminotetraphenyl compounds and derivatives thereof, diaminohexaphenyl compounds and derivatives thereof, and cardo-type fluorenediamine derivatives.

Phenylenediamine is m-phenylenediamine, p-phenylenediamine and the like. Examples of the phenylenediamine derivative include diamines to which alkyl groups such as methyl and ethyl are bonded, for example, 2,4-diaminotoluene, 2,4-triphenyl Lt; / RTI &gt;

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

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

Examples of the diaminodiphenyl compound include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone , 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2-bis (p-aminophenyl ) Propane, 2,2'-bis (p-aminophenyl) hexafluoropropane, 4-methyl- (p-aminophenyl) phosphine oxide, 4,4'-diamino azobenzene (p-aminophenyl) , 4,4'-diaminodiphenyl urea, 4,4'-diaminodiphenylamide, 1,4-bis (4-aminophenoxy) benzene, 1,3- , 1,3-bis (3-aminophenoxy) benzene Bis (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, and the like.

Of these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price and availability.

The diaminotriphenyl compound is a compound in which two aminophenyl groups and one phenylene group are bonded through different groups, and the other groups are the same as the diaminodiphenyl compound. Examples of the diaminotriphenyl compound include 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4- .

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

An example of the aminophenylamino indane is 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindan.

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

The carrageenan fluorenediamine derivatives include 9,9-bisaniline fluorene and the like.

The aliphatic diamine preferably has, for example, 2 to 15 carbon atoms, and specifically includes pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and the like.

And the hydrogen atoms of these diamines may be 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.

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

The reaction of the tetracarboxylic dianhydride and the diamine is usually carried out in an organic solvent. The organic solvent used for the reaction of the tetracarboxylic acid dianhydride and the diamine is not particularly limited as long as it can dissolve the tetracarboxylic acid dianhydride and the diamine and does not react with the tetracarboxylic acid dianhydride and the diamine. The organic solvent may be used alone 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, N, N-diethylacetamide, N, , N-diethylformamide, N-methylcaprolactam, N, N, N ', N'-tetramethylurea and the like; lactone-based polar solvents such as? -propiolactone,? -butyrolactone,? -valerolactone,? -valerolactone,? -caprolactone and? -caprolactone; Dimethyl sulfoxide; Acetonitrile; Fatty acid esters such as ethyl lactate and butyl lactate; Ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate and ethyl cellosolve acetate; And phenol-based solvents such as cresol and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent to be used is not particularly limited, but the content of the produced polyamic acid is preferably 5 to 50% by mass.

Among these organic solvents, from the solubility of the produced polyamic acid, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, , N-diethylformamide, N-methylcaprolactam, N, N, N ', N'-tetramethylurea and the like are preferable.

The polymerization temperature is generally -10 to 120 占 폚, preferably 5 to 30 占 폚. The polymerization time varies depending on the raw material composition used, but is usually 3 to 24 Hr (hour). The intrinsic viscosity of the organic solvent solution of polyamic acid obtained under such conditions is preferably in the range of 1,000 to 100,000 cP (centipoise), and still more preferably in the range of 5,000 to 70,000 cP.

<Polyimide>

The polyimide used in the present embodiment may be a soluble polyimide surface soluble in an organic solvent used in a coating liquid, and any known polyimide may be used without being limited by its structure or molecular weight. The polyimide may have a functional group capable of condensing a carboxyl group or the like on the side chain or a functional group for promoting a crosslinking reaction during firing.

In order to obtain a polyimide soluble in an organic solvent, use of a monomer for introducing a flexible bending structure into the main chain, for example, use of a monomer such as ethylideneamine, hexamethylenediamine, 1,4-diaminocyclohexane, Aliphatic diamines such as cyclohexane and 4,4'-diaminodicyclohexylmethane; Aromatic diamines such as 2-methyl-1,4-phenylenediamine, o-triazine, m-triazine, 3,3'-dimethoxybenzidine and 4,4'-diaminobenzanilide; Polyoxyalkylene diamines such as polyoxyethylene diamine, polyoxypropylene diamine, and polyoxybutylene diamine; Polysiloxane diamines; Oxydiphthalic anhydride, 2,3,3 ', 4'-oxydiphthalic anhydride, 3,4,3', 4'-oxydiphthalic anhydride, 2,2-bis (4-hydroxyphenyl) propane dibenzoate- ', 4,4'-tetracarboxylic dianhydride and the like are effective. The use of a monomer having a functional group for improving the solubility in an organic solvent, for example, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2-trifluoromethyl- It is also effective to use a fluorinated diamine such as 1,4-phenylenediamine. In addition to the monomers for improving the solubility of the polyimide, monomers such as those listed in the columns of the polyamic acid may be used in combination as long as the solubility is not impaired.

No particular limitation is imposed on the means for producing the polyimide soluble in the organic solvent used in the present invention. For example, a known method such as a method in which a polyamic acid is chemically imidized or heat-imidized and dissolved in an organic solvent Can be used. Examples of such polyimides include aliphatic polyimides (all aliphatic polyimides) and aromatic polyimides, and aromatic polyimides are preferred. As the aromatic polyimide, a polyamic acid having a repeating unit represented by the formula (1) may be obtained by thermal or chemical ring-closure reaction, or a polyimide having a repeating unit represented by the formula (2) may be dissolved in a solvent. Ar represents an aryl group.

However,

[Figure 2]

<Polyamideimide>

The polyamide imide used in the present embodiment may be any known polyamide imide soluble in an organic solvent used for the coating liquid, without limitation to its structure or molecular weight. The polyamideimide may have a functional group capable of condensing a carboxyl group or the like on the side chain or a functional group for promoting a crosslinking reaction during firing.

The polyamideimide used in the present embodiment is obtained by reacting an arbitrary anhydride trimellitic acid with a diisocyanate or a polyimide imide obtained by imidizing a precursor polymer obtained by reacting a reactive derivative of any trimellitic anhydride with a diamine, Can be used without a case.

Examples of the optional anhydride trimec and an acid or a reactive derivative thereof include anhydrous trimellitic acid halide such as trimellitic anhydride and trimellitic anhydride chloride, trimellitic anhydride, and the like.

Examples of the diisocyanate include diisocyanates such as m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-oxybis (phenylisocyanate), 4,4'-diisocyanate diphenylmethane, bis [4- Phenyl] sulfone, 2,2'-bis [4- (4-isocyanatophenoxy) phenyl] propane, and the like.

Examples of the diamine include the same ones as those exemplified in the description of the polyamic acid.

<Polyamide>

As polyamides, polyamides obtained from dicarboxylic acids and diamines are preferable, and aromatic polyamides are particularly preferable.

Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, phthalic acid, isophthalic acid, terephthalic acid, have.

Examples of the diamine include the same ones as those exemplified in the description of the polyamic acid.

&Lt; Particles &gt;

Next, the fine particles will be described. The fine particles are, for example, those having a high sphericity and a small particle size distribution index. Such fine particles are excellent in dispersibility in a liquid, and are in a state in which they do not aggregate with each other. The particle diameter (average diameter) of the fine particles can be set to, for example, about 100 to 2000 nm. By using the above-mentioned fine particles, the pores of the porous resin film (F) obtained by removing the fine particles in the subsequent step can be made equal. Therefore, the electric field applied to the separator formed by the porous resin film (F) can be made uniform.

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

The fine particles contained in the first coating liquid and the fine particles contained in the second coating liquid may be the same in size, material, and material, or they may be different from each other. It is preferable that the particle size distribution index of the fine particles contained in the first coating liquid is smaller than or equal to that of the fine particles contained in the second coating liquid. Or the fine particles contained in the first coating liquid are preferably smaller or equal to those of the fine particles contained in the second coating liquid. The fine particles contained in the first coating liquid are preferably smaller in particle diameter (average diameter) than the fine particles contained in the second coating liquid, and more preferably, the fine particles contained in the first coating liquid have a particle diameter of 100 to 1000 nm , And the fine particles contained in the second coating liquid are preferably 500 to 2000 nm (more preferably 700 to 2000 nm). It is possible to make the opening ratio of the holes on the surface of the porous resin film (F) high and uniform by using the particle diameter of the fine particles contained in the first coating film smaller than the particle diameter of the fine particles contained in the second coating liquid. Further, the strength of the film can be increased more than when the entirety of the porous resin film (F) is made to have a particle diameter of the fine particles contained in the first coating liquid.

The coating liquid may contain various additives such as a releasing agent, a dispersing agent, a condensing agent, an imidizing agent, a surfactant and the like in addition to a predetermined resin material, fine particles and solvent.

[Application unit]

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

The transport section 11 has a transport substrate (substrate) S, a substrate delivery roller 11a, support rollers 11b to 11d, a substrate take-up roller 11e and a take-out roller 11f.

The conveying substrate S is formed in a band shape. The conveying substrate S is fed from the substrate feeding roller 11a and is stretched over the supporting rollers 11b to 11d so as to have a tension and is wound by the substrate winding roller 11e. The material of the conveying substrate S may be, for example, polyethylene terephthalate (PET) or the like, but the material is not limited thereto and may be a metallic material such as stainless steel.

Each of the rollers 11a to 11f is formed in a cylindrical shape, for example, and arranged in parallel to the X direction. The rollers 11a to 11f are not limited to the arrangement parallel to the X direction, and at least one of the rollers 11a to 11f may be arranged to be inclined with respect to the X direction. For example, the rollers 11a to 11f may be arranged so as to be parallel to the Z direction and to have the same height position in the Z direction. In this case, the transporting substrate S moves along the horizontal plane in a line state with respect to the horizontal plane (XY plane).

The substrate feed roller 11a is disposed in a state in which the transport substrate S is wound. The support roller 11b is disposed on the + Z side of the substrate feed roller 11a and on the -Y side of the substrate feed roller 11a. The support roller 11c is disposed on the + Z side of the support roller 11b and on the + Y side of the support roller 11b. By the arrangement of the three rollers (the substrate feeding roller 11a and the supporting rollers 11b and 11c), the conveying base S is supported by the surface including the -Y side end portion of the supporting roller 11b.

The support roller 11d is arranged on the + Y side of the support roller 11c and on the -Z side of the support roller 11c. In this case, by the arrangement of the three rollers of the support rollers 11b to 11d, the conveying base S is supported by the surface including the + Z side end portion of the support roller 11c.

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

The substrate take-up roller 11e is disposed on the -Z side of the support roller 11d. The transporting substrate S is fed in the -Z direction from the support roller 11d toward the substrate take-up roller 11e. The unloading roller 11f is disposed on the + Y side and the -Z side of the support roller 11d. The unloading roller 11f sends the microfilm FA formed in the drying section 14 in the + Y direction. This untreated film FA is carried out of the coating unit 10 by the take-out roller 11f.

Further, the rollers 11a to 11f are not limited to a cylindrical shape, and a tapered crown may be formed. In this case, it is effective for correcting the bending of the rollers 11a to 11f, and the conveying base S or the later-described minute film FA can be evenly contacted to the rollers 11a to 11f. A radial crown may be formed on the rollers 11a to 11f. In this case, it is effective to prevent meandering of the conveying substrate S or the micro-film FA. In addition, a cone-shaped crown (a concave curved portion in the central portion in the X direction) may be formed on the rollers 11a to 11f. In this case, since the conveying substrate S or the micro-film FA can be conveyed while giving a tensile force in the X direction, it is effective for preventing the occurrence of wrinkles. The following rollers may also have a crown having a tapered shape, a radial shape, a cone shape or the like as described above.

2 (a) is a perspective view showing an example of the first nozzle 12. 1 and 2 (a), the first nozzle 12 is a coating film (hereinafter referred to as a first coating film F1) of the first coating liquid Q1 on the transporting substrate S, . The first nozzle 12 has a discharge port 12a through which the first coating liquid Q1 is discharged. The discharge port 12a is formed, for example, such that the lengthwise direction thereof is substantially equal to the dimension of the carrying 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 arranged so as to be inclined so that the discharge port 12a faces the + Y direction. Therefore, the discharge port 12a is directed to a portion of the conveying base S supported by the -Y side end portion of the support roller 11b. The first nozzle 12 discharges the first coating liquid Q1 from the discharge port 12a to the carrying substrate S along the horizontal direction.

Fig. 2 (b) is a perspective view showing an example of the second nozzle 13. Fig. As shown in Figs. 1 and 2B, the second nozzle 13 is formed by stacking a first coating film F1 on a transporting substrate S to form a coating film (hereinafter referred to as &quot; 2 coating film F2) is formed. The second nozzle 13 has a discharge port 13a for discharging the second coating liquid Q2. The discharge port 13a is formed, for example, such that the lengthwise direction thereof is substantially equal to the dimension of the carrying substrate S in the X direction.

And the second nozzle 13 is disposed at the discharge position P2. The discharge position P2 is a position in the + Z direction with respect to the support roller 11c. The second nozzle 13 is arranged so that the discharge port 13a faces the -Z direction. Therefore, the discharge port 13a is directed to a portion of the conveying base S supported by the + Z side end portion of the support roller 11c. The second nozzle 13 discharges the second coating liquid Q2 to the carrying substrate S from the discharge port 13a along the gravity direction.

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. The first nozzle 12 and the second nozzle 13 may be provided so as to be rotatable around an axis parallel to the X direction. The first nozzle 12 and the second nozzle 13 are disposed at a standby position (not shown) when the coating liquid is not discharged. When the coating liquid is discharged, the discharging positions P1, Respectively. It is also possible to provide a portion for performing the preliminary ejection operation of the first nozzle 12 and the second nozzle 13.

The first nozzle 12 and the second nozzle 13 are connected to a coating liquid supply source (not shown) through a connection pipe (not shown) or the like, respectively. The first nozzle 12 and the second nozzle 13 are provided with a holding portion (not shown) for holding a predetermined amount of coating liquid, for example. In this case, the first nozzle 12 and the second nozzle 13 may have a temperature control unit for adjusting the temperature of the liquid body held by the holding unit.

The amount of each coating liquid to be led out from the first nozzle 12 or the second nozzle 13 and the film thickness of the first coating film F1 or the second coating film F2 are determined by the respective nozzles, (Not shown) connected to a supply source (not shown) of the coating liquid, a conveying speed, a position of each nozzle, or a distance between the conveying base S and the nozzle. The film thicknesses of the first coating film F1 or the second coating film F2 are, for example, 0.5 μm to 500 μm, respectively.

When two kinds of coating liquids (the first coating liquid Q1 and the second coating liquid Q2) are used as in the present embodiment, the film of the first coating film F1 by the first coating liquid Q1 It is preferable to adjust the thickness of the second coating film F2 in the range of 0.5 to 10 mu m and adjust the thickness of the second coating film F2 in the second coating liquid Q2 to be in the range of 1 to 50 mu m, Do.

A drying unit (not shown) for drying the first coating film F1 may be disposed between the first nozzle 12 and the second nozzle 13. [ It is preferable that the drying section includes a heating and drying section. As the heat drying unit, it is preferable to use a hot air blowing unit or an infrared heater. The heating temperature is, for example, in the range of 50 占 폚 to 150 占 폚, preferably 50 占 폚 to 100 占 폚. By forming the second coating film F2 after the first coating film F1 is dried, it is possible to suppress, for example, mixing of the fine particles used for the second coating solution with the fine particles of the first coating film F1 have.

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

The drying section 14 has a chamber 14a and a heating section 14b. The chamber 14a accommodates the conveying substrate S and the heating portion 14b. The heating section 14b heats the first coating film F1 and the second coating film F2 formed on the transporting substrate S. [ As the heating section 14b, for example, an infrared heater or the like is used. The heating section 14b heats the coating film at a temperature of about 50 deg. C to about 100 deg.

The peeling section 15 is a part where the micro-film FA is peeled from the conveying substrate S. In the present embodiment, peeling of the microfilm (FA) is performed manually by an operator, but the present invention is not limited to this, and the microfilm may be automatically performed using a manipulator or the like. The unfilled film (FA) peeled off from the conveying substrate (S) is taken out to the outside of the coating unit (10) by the take-out roller (11f) and sent to the winding part (40). In addition, the conveying base S on which the untreated film FA has been peeled off is wound up by the substrate take-up roller 11e.

[Winding part (1)]

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

As shown in Fig. 3, on the + Y side of the coating unit 10, there is provided a discharge port 10b for discharging the microfilm (FA). The unfired film (FA) taken out from the semi-discharge port (10b) is wound by the winding section (40).

The winding portion 40 is configured such that the shaft member SF is mounted on the bearing 41. [ The shaft member SF forms a roll body R by winding up the microfilm FA discharged from the exit port 10b. The shaft member (SF) is detachably provided to the bearing (41). When the shaft member (SF) is mounted on the bearing (41), it is supported so as to be rotatable about an axis parallel to the X direction. The winding section 40 has a driving mechanism (not shown) for rotating the shaft member SF mounted on the bearing 41. [

In addition, in the winding section 40, the microfilm FA is wound so that the side of the microfilm FA on the side of the first coated film F1 is located on the outer side. For example, the shaft member SF is rotated counterclockwise in Fig. 1 by a drive mechanism so that the micro-film FA is wound. It is possible to move the roll body R to another unit by separating the shaft member SF from the bearing 41 in a state where the roll body R is formed.

1 and 3, the winding unit 40 is disposed independently of the coating unit 10, but the present invention is not limited thereto. For example, the winding unit 40 may be disposed inside the coating unit 10. [ In this case, even if the roll body R is formed by winding the micro-film FA from the take-out roller 11f (or from the support roller 11d) without arranging the exit port 10b in the coating unit 10 do.

[Feeder]

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

As shown in Fig. 4, on the -Y side of the firing unit 20, there is provided an inlet port 20a for feeding the microfilm (FA). The dispensing section 50 sends a microfilm (FA) to the inlet 20a.

The feeding portion 50 is configured such that the shaft member SF can be mounted on the bearing 51. [ The shaft member SF can be used in common with that mounted on the bearing 41 of the winding section 40. Therefore, the shaft member SF removed from the winding section 40 can be mounted on the bearing 51 of the sending section 50. [ This makes it possible to dispose the roll body R formed by the winding section 40 in the delivery section 50. [ The bearings 51 of the winder 51 and the bearings 41 of the winder 40 may be set to have the same height from the bottom surface, but they may be set at different height positions.

When the shaft member (SF) is mounted on the bearing (51), it is supported so as to be rotatable about an axis parallel to the X direction. The dispensing section 50 has a driving mechanism (not shown) for rotating the shaft member SF mounted on the bearing 51. The shaft member SF is rotated by the clockwise rotation shown in Fig. 1 by the driving mechanism so that the minute film FA constituting the roll body R is fed toward the inlet 20a. Since the unfired film FA is wound around the wound portion 40 so that the side of the first coated film F1 side of the uncured film FA is located on the outer side, The first coating film F1 side is disposed on the upper side.

[Firing unit]

The firing unit 20 is a unit that performs high temperature processing for the microfilm (FA) in the present embodiment. The firing unit 20 fires the microfilm FA to form a fired film FB containing microparticles. The firing unit 20 has a chamber 21, a heating section 22, and a carry section 23. The chamber 21 has an inlet 20a for feeding the microfilm FA and an outlet 20b for discharging the fired film FB. The chamber 21 accommodates the heating section 22 and the carry section 23.

The heating section 22 heats the microfilm FA loaded into the chamber 31. The heating section 22 has a plurality of heaters 22a arranged side by side in the Y direction. As this heater 22a, for example, an infrared heater or the like is used. The heating portion 22 is disposed from the -Y side end portion to the + Y side end portion inside the chamber 21. [ The heating section 22 is capable of heating the microfilm FA almost in the entire Y-direction. The heating section 22 can heat, for example, the microfilm (FA) at about 120 ° C to 450 ° C. The heating temperature by the heating unit 22 is appropriately adjusted according to the transport speed of the microfilm (FA), the constituents of the microfilm (FA), and the like.

The transport section 23 has a transport belt 23a, a drive roller 23b, a follower roller 23c and tension rollers 23d and 23e. The conveyor belt 23a is formed endlessly and arranged in the Y direction. The transport belt 23a is formed using a material having durability at the firing temperature of the micro-film FA. The conveyor belt 23a is stretched between the drive roller 23b and the driven roller 23c so as to be substantially parallel to the XY plane in a state of having a tension. The micro-film (FA) and the firing film (FB) are transported in the + Y direction while being placed on the transport belt (23a).

The drive roller 23b is disposed at the + Y side end of the chamber 21. The drive roller 23b is formed, for example, in a cylindrical shape and is arranged in parallel to the X direction. The drive roller 23b is provided with a rotation drive device such as a motor. The drive roller 23b is rotatably provided around the axis parallel to the X direction by the rotation drive device. As the drive roller 23b rotates, the conveyor belt 23a rotates clockwise in Fig. The transport belt 23a rotates to transport the microfilm FA and the plastic film FB placed on the transport belt 23a in the + Y direction.

The driven roller 23c is disposed at the -Y side end of the chamber 21. The driven roller 23c is formed, for example, in a cylindrical shape and is arranged in parallel to the X direction. The follower roller 23c is formed to have the same diameter as the drive roller 23b and is arranged so that the position (height position) in the Z direction becomes substantially the same as the drive roller 23b. The driven roller 23c is rotatably provided around an axis parallel to the X direction. The driven roller 23c rotates following the rotation of the conveyor belt 23a.

The tension roller 23d is disposed on the + Z side of the driven roller 23c. The tension roller 23d is arranged parallel to the X direction and is rotatable around the X axis. The tension roller 23d is provided so as to be movable up and down in the Z direction. The tension roller 23d is capable of sandwiching the micro-film FA between the driven roller 23c and the driven roller 23c. The tension roller 23d is rotatable with the microfilm FA interposed therebetween.

The tension roller 23e is disposed on the + Z side of the drive roller 23b. The tension roller 23e is arranged parallel to the X-direction and is rotatable around the X-axis. The tension roller 23e is provided so as to be movable up and down in the Z direction. The tension roller 23e can sandwich the firing film FB between the tension roller 23e and the drive roller 23b. The tension roller 23e is rotatable with the firing film FB sandwiched therebetween.

The tension roller 23d and the tension roller 23e are sandwiched between the driven roller 23c and the drive roller 23b so as to sandwich the FA and the fired film FB, The tension between the two portions sandwiched in the FB is cut off from the outside. As a result, it is possible to prevent an excessive load from being applied to the micro-film (FA) and the fired film (FB). The tension rollers 23d and 23e can be adjusted so that tension is not applied to the microfilm FA and the fired film FB disposed in the chamber 21. [

[Removal Unit]

The removal unit 30 has a chamber 31, an etching section 32, a cleaning section 33, a drying section 34, and a transport section 35. The chamber 31 has an inlet port 30a for feeding the firing film FB and an outlet port 30b for discharging the porous resin film F. [ The chamber 31 accommodates the etching section 32, the cleaning section 33, the drying section 34, and the transport section 35.

The etching section 32 etches the firing film FB to remove the fine particles contained in the firing film FB to form the porous resin film F. [ In the etching section 32, the fining film FB is immersed in an etching solution capable of dissolving or decomposing the fine particles to remove fine particles. The etching part 32 is provided with a supply part (not shown) for supplying such an etching solution and a storage part capable of storing the etching solution.

The cleaning section 33 cleans the porous resin film F after etching. The cleaning portion 33 is disposed on the + Y side of the etching portion 32 (in front of the transport direction of the porous resin film F). The cleaning section 33 has a supply section (not shown) for supplying the cleaning liquid. A recovery unit (not shown) for recovering the wastewater after cleaning the porous resin film (F), a liquid removal unit (not shown) for removing the liquid of the porous resin film (F), and the like may also be used.

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

The transport section 35 transports the fired film FB and the porous resin film F over the etching section 32, the cleaning section 33, and the drying section 34. The conveying section 35 has a conveying belt 35a, a driving roller 35b and a driven roller 35c. In addition to the driving roller 35b and the driven roller 35c, a supporting roller for supporting the conveyor belt 35a may be disposed inside the etching section 32, the cleaning section 33, and the drying section 34. [

The conveyor belt 35a is formed in an endless manner and arranged along the Y direction. The conveyor belt 35a is formed using a material having durability in the etchant. The conveyor belt 35a is stretched between the drive roller 35b and the driven roller 35c so as to be substantially parallel to the XY plane in a state of having a tension. The firing film FB and the porous resin film F are placed on the conveying belt 35a.

The driving roller 35b is disposed at the + Y side end inside the chamber 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 rotation drive device such as a motor. The drive roller 35b is rotatably provided around the axis parallel to the X direction by the rotation drive device. As the drive roller 35b rotates, the conveyor belt 35a rotates clockwise in Fig. The transport belt 35a rotates to transport the fired film FB and the porous resin film F placed on the transport belt 35a in the + Y direction.

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

Further, the removal unit 30 is not limited to the case where the fine particles are removed by etching. For example, when an organic material that is decomposed at a lower temperature than polyimide is used as the material of the fine particles, the fine particles can be decomposed by heating the firing film FB. Such an organic material can be used without any particular limitation as long as it is decomposed at a lower temperature than polyimide. Examples thereof include resin fine particles comprising a linear polymer or a known solution polymerizable polymer. Conventional linear polymers are polymers in which the molecular chains of the polymer are randomly cleaved at the time of thermal decomposition and the depolymerization polymers are polymers in which the polymer decomposes into monomers upon thermal decomposition. All of them are decomposed to a low molecular weight or CO ₂ , thereby disappearing from the fired film FB. In this case, the decomposition temperature of the fine particles is preferably 200 to 320 ° C, more preferably 230 to 260 ° C. When the decomposition temperature is 200 DEG C or more, the film can be formed even when a high boiling solvent is used in the coating liquid, and the firing condition in the firing unit 20 can be selected in a wider range. If the decomposition temperature is lower than 320 DEG C, only fine particles can be lost without giving thermal damage to the fired film FB.

[Winding Part (2)]

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

As shown in Fig. 5, on the + Y side of the removal unit 30, there is provided a recovery port 30b for discharging the porous resin film (F). The porous resin film (F) taken out from the semi-outlet (30b) is wound by the winding part (60).

The winding portion 60 has a structure in which the shaft member SF is mounted on the bearing 61. [ The shaft member SF forms a roll body RF by winding the porous resin film F taken out from the exit port 30b. The shaft member (SF) is detachably provided to the bearing (61). When mounted on the bearing 61, the shaft member SF is supported so as to be rotatable about an axis parallel to the X direction. The winding portion 60 has a driving mechanism (not shown) for rotating the shaft member SF mounted on the bearing 61. [ By rotating the shaft member SF by the driving mechanism, the porous resin film F is wound. The roll body RF can be recovered by separating the shaft member SF from the bearing 61 in a state in which the roll body RF is formed.

[Manufacturing method]

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

First, in the coating unit 10, a microfilm (FA) is formed. In the coating unit 10, the substrate conveying roller 11a is rotated to convey the conveying substrate S, and the conveying substrate S is guided to the supporting rollers 11b to 11d and wound around the substrate winding roller 11e . Thereafter, the substrate S is wound on the substrate take-up roller 11e while sequentially conveying the substrate S from the substrate feed roller 11a.

In this state, the first nozzle 12 is disposed at the first position P1, and the discharge port 12a is directed in the + Y direction. As a result, the discharge port 12a is directed to the portion of the conveying base S supported by the support roller 11b. Thereafter, the first coating liquid Q1 is discharged from the discharge port 12a. The first coating liquid Q1 is dispensed toward the + Y direction from the discharge port 12a and reaches the transportation substrate S, and then is coated on the transportation substrate S in accordance with the movement of the transportation substrate S. As a result, as shown in Fig. 6A, the first coating film F1 is formed on the transporting substrate S by the first coating liquid Q1. The first coating film F1 contains the resin material A1 and the fine particles A2 at a predetermined volume ratio.

Then, the second nozzle 12 is arranged at the second position P2 so that the discharge port 13a is directed in the -Z direction. As a result, the discharge port 13a is directed to the portion of the conveying base S supported by the support roller 11c. Thereafter, the second coating liquid Q2 is discharged from the discharge port 13a. The second coating liquid Q2 is discharged from the discharge port 13a in the -Z direction and reaches the first coating film F1 formed on the conveying substrate S, Is applied on the coating film F1. Thus, as shown in Fig. 6 (b), the second coating film F2 formed by the second coating liquid is formed on the first coating film F1. The second coating film (F2) contains the resin material (A1) and the fine particles (A2) at a predetermined volume ratio. The content rate of the fine particles is set so that the first coating film F1 is larger than the second coating film F2.

Since the first coating liquid Q1 and the second coating liquid Q2 are applied in such a state that the discharge ports 12a and 13a are directed to the portion of the conveying substrate S supported by the supporting rollers 11b and 11c When the first coating liquid Q1 and the second coating liquid Q2 reach the carrying substrate S, the force acting on the carrying substrate S is received by the supporting rollers 11b and 11c. Therefore, the occurrence of warpage or vibration of the conveying substrate S is suppressed, and the first coated film F1 and the second coated film F2 are stably formed on the conveying substrate S with a uniform thickness.

Subsequently, when the conveying substrate S moves and the laminated portion of the first coated film F1 and the second coated film F2 is carried into the chamber 14a of the drying unit 14, the drying unit 14 The first coating film F1 and the second coating film F2 are dried. In the drying section 14, the heating section 14b is used to heat the first coating film F1 and the second coating film F2 at a temperature of, for example, about 50 ° C to 100 ° C. With this temperature range, the first coated film F1 and the second coated film F2 can be heated without occurrence of warping or deformation in the conveying substrate S. By drying the laminated body of the first coated film F1 and the second coated film F2, a microfilm FA is formed as shown in Fig. 6C.

In the present specification, the laminate refers to a micro-film composed of the first coating film F1 and the second coating film F2. When the porous imide resin film according to the present invention is formed by using a resin of the same kind among polyamide acid, polyimide, polyamideimide or polyamide in the first liquid and the second liquid, (Or a porous imide-based resin film) composed of the coating film F1 and the second coating film F2 becomes substantially one layer. However, in the case of a microfilm film having different contents of fine particles (or a film having a different porosity A porous imide resin film) is formed. Therefore, the case where a resin of the same kind is used for the first liquid and the second liquid is also referred to as a laminate in this specification.

Subsequently, when the conveying substrate S moves and the leading end portion of the microfilm FA reaches the supporting roller 11d (peeling section 15), for example, by manual operation of the operator, And the leading end portion is peeled off from the conveying substrate (S). In the present embodiment, for example, PET is used as the material of the transporting substrate S, when the first coated film F1 and the second coated film F2 are dried to form the microfilm FA , It is easy to peel off the transfer substrate S, so that the operator can easily peel off.

After the leading end portion of the untreated film FA is peeled off, the transporting substrate S continues to move, and the first coated film F1 is formed by the first nozzle 12. Further, the second coating film F2 is continuously formed by the second nozzle 13, and the microfilm FA is formed by the drying unit 14. As a result, the microfilm FA is formed in a band shape, and the length of the microfilm FA discharged from the drying section 14 to the + Y side is gradually increased. The worker continuously peels the microfilm (FA) from the peeling section (15). When the leading end of the peeled microfilm FA reaches a length reaching the shaft member SF of the take-up portion 40, the operator manually hands the microfilm FA to the take-out roller 11f , The leading end portion of the micro-film (FA) is mounted on the shaft member (SF). Thereafter, as the unfired films FA are sequentially formed and peeled off, the winding member 40 rotates the shaft member SF. The peeled untreated film FA is sequentially taken out from the coating unit 10 and wound up by the shaft member SF of the winding unit 40 to form the roll body R. [ As shown in Fig. 6 (d), the unfilled film FA formed by the roll body R is in a state of being peeled from the conveying substrate S, and the front side and the back side thereof are exposed together.

The operation of peeling the tip portion of the microfilm (FA) and the operation of attaching the peeled tip portion to the shaft member (SF) are not limited to the manual operation by the operator. For example, a manipulator And may be performed automatically. Further, in order to improve the peeling property of the micro-film FA, a release layer may be formed on the surface of the transport substrate S.

The shaft member SF is separated from the bearing 41 for each roll body R while cutting the microfilm FA after the microfilm FA having a predetermined length is wound around the shaft member SF. The new shaft member SF is mounted on the bearing 41 of the winding unit 40 and the cut end of the micro film unit FA is mounted on the shaft member SF and rotated to rotate the micro film unit FA By continuing formation, a new roll (R) can be produced.

On the other hand, for example, the operator transports the shaft member SF separated for each roll R from the bearing 41 to the delivery portion 50, and mounts the shaft member SF on the bearing 51. The carrying operation and the mounting operation of the shaft member SF may be automatically carried out using a manipulator, a carrying device, or the like. After the shaft member SF is mounted on the bearing 51, the shaft member SF is rotated to sequentially take out the microfilm FA from the roll R and the microfilm FA is transferred to the chamber of the firing unit 20 (21). In addition, when the tip of the microfilm (FA) is brought into the chamber 21, it may be manually performed by an operator or automatically by using a manipulator or the like.

The microfilm FA transferred into the chamber 21 is placed on the transport belt 23a and transported in the + Y direction in accordance with the rotation of the transport belt 23a. Further, the tension may be adjusted by using tension rollers 23d and 23e. Then, the baking of the microcapsule FA is carried out using the heating unit 22 while conveying the microcapsule film FA.

The temperature at the time of baking is preferably 120 占 폚 to 375 占 폚, and more preferably 150 占 폚 to 350 占 폚, though it differs depending on the structure of the microfilm (FA). When an organic material is contained in the fine particles, it is necessary to set the temperature to a temperature lower than the thermal decomposition temperature. When the coating liquid contains a polyamic acid, it is preferable to complete the imidization in this firing. However, it is preferable that the micro-film (FA) is composed of polyimide, polyamideimide or polyamide, This is not the case when high temperature treatment is applied to the film formation (FA).

The firing conditions include, for example, a method of raising the temperature from room temperature to 375 DEG C over 3 hours and then maintaining the temperature at 375 DEG C for 20 minutes when the coating liquid contains polyamic acid and / or polyimide, Stepwise heating may be performed such that the temperature is raised stepwise at 50 DEG C to 375 DEG C (each step is held for 20 minutes), and finally, the temperature is maintained at 375 DEG C for 20 minutes. Further, the end of the microfilm (FA) may be fixed to a die made of SUS to prevent deformation.

By this firing, as shown in Fig. 6E, the fired film FB is formed. In the firing film FB, fine particles A2 are contained in the interior of the resin layer A3 imidized or subjected to high temperature treatment. The film thickness of the fired film FB can be obtained by measuring the thickness of a plurality of portions with a micrometer, for example, and averaging them. When the separator is used for a separator or the like, the average film thickness is preferably from 3 탆 to 500 탆, more preferably from 5 탆 to 100 탆, and further preferably from 10 탆 to 30 탆.

The fired film FB formed in the firing unit 20 is carried into the removal unit 30 without being wound if it is taken out of the firing unit 20. Further, in the case of bringing the leading end portion of the fired film FB into the removal unit 30, it may be carried out manually by an operator or automatically by using a manipulator or the like.

The fired film FB carried into the removal unit 30 is placed on the transport belt 35a and transported in the + Y direction in accordance with the rotation of the transport belt 35a. In the removal unit 30, the fine particles A2 are first removed by the etching unit 32 in accordance with the transfer of the firing film FB. In the case where silica is used as the material of the fine particles A2, for example, in the etching portion 32, the fired film FB is immersed in an etching solution such as hydrogen fluoride water at a low concentration. As a result, the fine particles A2 are dissolved and removed in the etchant and the porous resin film F containing the pores A4 in the resin layer A3 is formed as shown in Fig. 6 (f) do.

Thereafter, in accordance with the rotation of the conveying belt 35a, the porous resin film F is conveyed in order to the cleaning section 33 and the drying section 34 in order. In the cleaning section 33, the porous resin film F is cleaned by the cleaning liquid to remove the liquid. In the drying section 34, the porous resin film F after the liquid removal is heated to remove the cleaning liquid. The porous resin film F is taken out from the removal unit 30 and wound by the shaft member SF of the winding unit 60. [

As described above, the production system SYS according to the present embodiment is characterized in that a coating liquid (a first coating liquid (liquid composition) containing a resin material A1 of polyamide acid, polyimide, polyamideimide or polyamide and fine particles A2 A coating unit 10 for coating the transfer substrate S with a first coating liquid Q1 and a second coating liquid Q2 to form an untreated film FA; A firing unit 20 for firing an unfired film FA to form a fired film FB containing fine particles and a removal unit 30 for removing the fines particles A2 from the fired film FB , The formation of the microfilm (FA), the firing of the microfilm (FA) (formation of the fired film FB), and the removal of the microfine particles A2 (formation of the porous resin film F) Flow. Thus, the production efficiency of the porous resin film (F) can be improved.

In addition, since the coating unit 10 forms a strip-shaped micro-film FA on the substrate (transfer substrate S), it can be applied to a manufacturing process such as a roll-to-roll process, A resin film (porous resin film (F)) can be formed.

Since the removal unit 20 removes the fine particles A2 by introducing the firing film FB fired by the firing unit 10 in succession without being wound up, the steps from firing to removal of fine particles are efficiently carried out can do.

In addition, since the winding unit 40 for winding the roll of film R by winding the peeling film T from the base material (conveying substrate S) is provided, it is easy to carry the toner between the units.

In the case where the roll body R is a roll of strip-shaped microfilm (FA) stripped from the base material (transport substrate S), the firing unit 10 takes out the microfibers sequentially from the roll and fires, The fired film FB can be efficiently formed.

The first liquid (the first coating liquid Q1) and the second liquid (the second coating liquid Q2) having different contents of at least the fine particles A2 are used as the liquid, (FA) formed by laminating the first liquid and the second liquid on the base material (transport substrate (S)) so that the content ratio of at least the fine particles is different from that of the first base material In the case where the resin film (porous resin film (F)) is used as a separator, the intensity of the film is higher than that in the case where the imide resin film having the same porosity and having the same porosity is formed of only the first coating liquid Q1 .

In the method for producing a porous resin film (F) according to the present embodiment, a coating liquid (a first coating liquid) containing a resin material (A1) of polyamide acid, polyimide, polyamideimide or polyamide and fine particles (FA) is peeled off from the conveying substrate (S) after coating the substrate (S) with the fine particles (Q1 and the second coating liquid (Q2) Since the formation of the fired film FB including the fired film A2 and the removal of the fine particles A2 from the fired film FB, the formation of the microfiltration film FA and the firing of the microfiltration film FA (Formation of the fired film FB) and removal of the fine particles A2 (formation of the porous resin film F) can be performed in a series of flows. Thus, the production efficiency of the porous resin film (F) can be improved.

In addition, since the microcapsule film FA is formed in a band shape, it can be applied to a manufacturing process such as a roll-to-roll system and can efficiently form a porous imide resin film (porous resin film (F)) have.

Since the fine particles A2 are removed from the fired film by introducing the fired films FB in turn without being taken up, the steps from firing to removal of fine particles can be performed efficiently.

In addition, since the rolled body R is formed by winding up the minute film (FA) peeled off from the base material (the conveying substrate S), it is easy to carry out transportation between the units.

When the roll body is a roll body R of a strip-shaped microfilm (FA) peeled from the base material (transport substrate S), the microfibers are successively taken out from the roll body and fired, Can be formed.

The first liquid (the first coating liquid Q1) and the second liquid (the second coating liquid Q2) having different contents of at least the fine particles A2 are used as the liquid, and the first liquid and the second liquid (FA) having a different content ratio of at least the fine particles (A2) is formed by applying the fine particles (A) to the base material (transport substrate (S)). Therefore, when used as a separator, ions move smoothly, (Porous resin film (F)) capable of securing a porous imide resin film can be produced.

[Modifications]

In the above embodiment, the winding unit 40 is disposed between the coating unit 10 and the firing unit 20, but the present invention is not limited to this. Fig. 7 is a view showing an example of a part of the manufacturing system SYS2 according to the modified example.

The microfilm FA discharged from the coating unit 10 may be brought into the firing unit 20 without providing the winding unit 40 as shown in Fig. In this case, the firing unit 20 introduces the micro-film FA which is carried out from the coating unit 10 and fed through the relay rollers 70 in order and fired to form the fired film FB .

As described above, the firing unit 20 introduces the fired films FA from the substrate (the carrier substrate S) in succession without taking up the fired films FA, Can be continuously carried out.

In the above embodiment, the peeling portion 15 provided inside the coating unit 10 has been described as peeling the micro-film FA from the transporting substrate S. However, the present invention is not limited to this. For example, in the coating unit 10, the microfilm (FA) and the transporting substrate (S) are integrally wound without peeling, and the microfilm (FA) is immersed in the liquid outside the coating unit (10) (S). Fig. 8 is a diagram showing an example of a part of the manufacturing system SYS3 according to the modified example.

For example, as shown in Fig. 8, the coating unit 10 has a winding unit 73 for winding up the unfused film FA and the transporting substrate S in an integrated manner without peeling. The winding portion 73 has a bearing 16 and a shaft member SF2. The bearing 16 is disposed on the -Z side of the support roller 11d. The shaft member SF2 is detachably provided with respect to the bearing 16. When the shaft member SF2 is mounted on the bearing 16, it is supported so as to be rotatable about an axis parallel to the X direction. The coating unit 10 is provided with a driving mechanism (not shown) for rotating the shaft member SF2 mounted on the bearing 16. By rotating the shaft member SF2 by this driving mechanism, the roll of the roll Rs is formed by integrally winding the microfilm FA and the conveying base S together.

A bearing 71 is provided outside the coating unit 10. On the -Z side of the bearing 71, a dipping portion 72 is provided. The dipping section 72 has a container 72a, a liquid 72b contained in the container 72a and a roller 72c immersed in the liquid 72b. As the liquid 72b, for example, water and the like can be mentioned.

The shaft member SF2 is separated from the bearing 16 in the case where the free roll film FA and the transporting substrate S are integrally wound by the shaft member SF2 and the roll body RS is formed. The shaft member SF2 is mounted on the bearing 71 provided outside the coating unit 10. [

After the shaft member SF2 is mounted on the bearing 71, the small film FA and the transport substrate S are taken out from the roll body RS and dipped in the liquid 72b. For example, a laminate of the film substrate FA and the conveying substrate S is placed under the roller 72c. In this case, the unfilled film (FA) taken out from the roll body (RS) and the transporting substrate (S) are immersed in the liquid (72b) in order. For example, the operator separates the microfilm (FA) from the conveying substrate (S) while the microfilm (FA) and the conveying substrate (S) are immersed in the liquid (72b).

As described above, since the winding rollers 73 for winding the rolls RS are provided by winding up the minute film FA including the base material (conveying substrate S), the conveyance between the units can be facilitated. When the roll body is a roll body RS of a band-like unfired film FA including a base material (conveying substrate S), the base material is taken out from the roll body and dipped in a predetermined liquid (liquid 72b) And the dipping portion 72 for peeling off the micro-film from the film-forming portion 72 can be stably peeled off.

The embodiment in which the microfilm (FA) is immersed in the liquid (72b) is not limited to the case of peeling the microfilm (FA) from the transport substrate (S). For example, the microfilm (FA) peeled off from the conveying substrate (S) may be immersed in a liquid such as water. Fig. 9 is a view showing an example of a part of the manufacturing system SYS4 according to the modified example.

As shown in Fig. 9, on the + Y side of the coating unit 10, a second dipping section 74 is provided. The second dipping section 74 has a container 74a, a liquid 74b contained in the container 74a, and a roller 74c immersed in the liquid 74b. The microfilm FA discharged from the application unit 10 is immersed in the liquid 74b through the roller 74c. In this case, the micro-film FA can be immersed in the liquid 74b for about 10 seconds to 5 minutes, preferably about 30 seconds to 40 seconds. As a result, it is possible to suppress the formation of wrinkles when the micro-film FA is fired.

When immersing the microfilm (FA) peeled from the conveying substrate (S) in a liquid such as water, the microfilm (FA) may be taken up by the winding unit (40) after immersion, ).

In addition, a step of forcing the microfilm (FA) after immersing the microfilm (FA) peeled off from the transport substrate (S) in a liquid such as water may be employed. As a means for forcing, there is a step of pressing the micro-film (FA). As a result, it is possible to suppress formation of wrinkles when drying or firing the micro-film (FA).

In the case of not passing through the take-up unit 40 after the immersion of the micro-film FA, the micro-film FA conveyed through the relay roller is introduced in sequence and fired to form the fired film FB. As a result, the firing unit 20 introduces the fired film FA from the base material (transfer substrate S) in turn, without taking up the fired film FA, Can be continuously carried out. A step of drying or absorbing the liquid adhered at the time of immersion may be provided before introducing the transferred microfilm (FA) into the firing unit.

Further, in addition to the configuration of the above-described embodiment, a post-treatment unit for post-treating the porous resin film (F) formed in the removal unit (30) may be provided. 10 is a diagram showing an example of a manufacturing system SYS5 according to a modified example.

10, a post-processing unit 80 is disposed between the removal unit 30 and the take-up unit 60. The post- As the post-processing unit 80, for example, an antistatic unit 81 for performing a de-electrification process on the porous resin film F can be used. The antistatic unit 81 is provided with a static eliminator such as, for example, an ionizer.

As described above, since the antistatic unit 81 for carrying out the antistatic treatment on the fired film (porous resin film F) from which the fine particles A2 have been removed is provided, the static electricity is removed from the porous resin film F after the particulate removal Can be removed.

As the post-treatment unit 80, for example, an etching unit 82 for removing a part of the porous resin film F may be used. Fig. 11A is a diagram schematically showing an example of the etching unit 82. Fig. As shown in Fig. 11 (a), the etching unit 82 has a containing portion 82a containing the process liquid 82b. As the treatment liquid 82b, for example, an alkali solution or the like is used. By immersing the porous resin film F in the treatment liquid 82b for a predetermined time, the inside of the porous portion A4 is removed as shown in Fig. 11 (b). In this case, the burr of the porous member A4 falls, and the communicability is ensured.

When the etching unit 82 is used as the post-processing unit 80, the post-processing by the etching unit 82 may be further followed by a post-baking process or a drying process of the porous resin film (F). The temperature of the drying step or the post-baking treatment step may be suitably set in accordance with the type of the resin of the porous resin film (F), for example, 100 to 300 占 폚.

When the etching unit 82 is used as the post-treatment unit 80, liquid is removed from the drying unit 34 in the removal unit 30, and the porous resin film F is removed without drying or heating, May be returned to the etching unit 82. In this case, in the liquid removal in the drying section 34, the liquid attached to the porous resin film F after cleaning is removed. It is preferable that the drying section 34 is provided with an absorbing roller or the like and the absorbing roller is brought into contact with the porous resin film F so that the liquid attached to the porous resin film F .

As described above, since the etching unit 82 for removing a part of the fired film (porous resin film F) from which the fine particles A2 have been removed is included in the porous resin film F, The inner surface becomes smooth and the communication property can be ensured.

In the above-described embodiment, the shaft member SF is attached to and detached from the bearings 41 and 61 as the winding portions 40 and 60. However, the present invention is not limited thereto. For example, A winding device 90 such as a bar may be used. Hereinafter, a case where the winding device 90 is used instead of the winding portion 40 will be described as an example.

12, the winding device 90 includes a frame 91, a shaft member SF, a bearing 92, a driving portion 93, relay rollers 94a to 94e, a roller support portion 95). The frame 91 supports the shaft member SF, the bearing 92, the driving portion 93, the relaying rollers 94a to 94e, and the roller supporting portion 95, respectively.

The shaft member SF forms the roll body R by winding up the unfired film FA taken out from the coating unit 10. The shaft member (SF) is detachably provided to the bearing (92). When the shaft member SF is mounted on the bearing 92, it is supported by the bearing 92 so as to be rotatable about an axis parallel to the X direction. The roll body R can be moved or collected to another unit by separating the shaft member SF from the bearing 92 in a state in which the roll body R is formed.

The relay rollers 94a to 94e transmit the microfilm (FA) to the shaft member (SF) while adjusting the tension of the microfilm (FA). The relaying rollers 94a to 94e are formed, for example, in a cylindrical shape, and are arranged parallel to the X direction. In the present embodiment, the microfilm FA extends in the order of the relay rollers 94a, 94b, 94c, 94d, and 94e, but the present invention is not limited to this, and some relay rollers may not be used. At least one of the relay rollers 94a to 94e may be movable by the roller supporting portion 95. For example, the roller support portion 95 may move the relay roller 94b in the Z direction or the Y direction. The relay roller 94b may be rotated around the axis AX parallel to the X axis by the roller supporting portion 95. In this case, it is possible to maintain the tension of the microfilm (FA) constant by feeding back the amount (distance) to which the relay roller 94b moves (rotates) to the winding speed of the bearing 92. The load on the relay roller 94b may be changed by moving a movable weight (not shown) disposed on the -Y side of the relay roller 94b and disposed through the fulcrum axis. In this case, by adjusting the load applied to the relay roller 94b by the weight, it is possible to adjust the tension of the micro-formed film FA.

The relaying rollers 94a to 94e are not limited to the arrangement parallel to the X direction but may be arranged to be inclined with respect to the X direction. The relaying rollers R21 to R25 are not limited to the cylindrical shape, and may be formed with a crown such as a tapered shape, a radial shape, a cone shape, or the like.

Further, the winding device 90 may be used in place of the winding portion 60. In addition, by rotating the shaft member SF in a direction opposite to the case of winding a film such as a micro-film (FA), a film such as a micro-film (FA) can be fed out. For this reason, for example, the winding unit 90 may be used instead of the feeding unit 50 described above.

[Separator]

Next, the separator 100 according to the embodiment will be described. 13 is a schematic view showing an example of the lithium ion battery 200, and shows a state in which a part of the lithium ion battery 200 is cut. As shown in Fig. 13, the lithium ion battery 200 has a metal case 201 serving also as a positive electrode terminal and a negative electrode terminal 202. A positive electrode 201a, a negative electrode 202a and a separator 100 are provided in the metal case 201 and 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. As the positive electrode 201a, a lithium transition metal oxide is used, and as the negative electrode 202a, for example, lithium or carbon (graphite) is used.

The porous resin film (F) described in the above embodiment is used as a separator (100) of the lithium ion battery (200). In this case, for example, the surface on which the first coating film F1 is formed is made toward the negative electrode 202a of the lithium ion battery, thereby improving battery performance. In Fig. 13, the separator 100 of the rectangular lithium ion battery 200 is described as an example, but the present invention is not limited thereto. The porous resin film (F) can also be used as a separator of any type of lithium ion battery, such as a cylindrical or laminate type. In addition to the separator of the lithium ion battery, the porous resin film (F) can be used as a fuel cell electrolyte membrane, a separating membrane for gas or liquid, and a low dielectric constant material.

Although the embodiment has been described above, the present invention is not limited to the above description, and various modifications are possible without departing from the gist of the present invention.

For example, in the above-described embodiment and modified examples, the case of forming the microcavities FA by using two kinds of coating liquids having different microparticle content rates has been described as an example. However, the present invention is not limited to this, To form an untreated film. In this case, either the first nozzle 12 or the second nozzle 13 may not be used, and one of the nozzles may be omitted. In the case of omitting one of the nozzles, it is preferable that the first nozzle 12 is omitted and the second nozzle 13 is used.

In the above-described embodiment and modified examples, a configuration is described in which, after the firing film FB is formed in the firing unit 20, the firing film FB is carried into the removal unit 30 without being wound, But it is also possible to wind the bake film FB. In this case, the winding device 90 described in the modification may be used.

In the above-described embodiment and modified examples, the configuration in which one coating unit 10, the firing unit 20, and the removal unit 30 are arranged is described as an example, but the present invention is not limited thereto. For example, at least one of the units may be provided. In this case, a large number of units having a small amount (for example, length, etc.) of the microfilm FA, the firing film FB or the porous resin film F that can be processed per unit time are arranged, The overall manufacturing efficiency can be increased.

In the above embodiment and modified examples, the coating unit 10, the firing unit 20, the removal unit 30, and the post-processing unit 80 (the antistatic unit 81 and the etching unit 82) The unit transports each film of the micro-film (FA), the fired film (FB), or the porous resin film (F) along the Y direction. However, the present invention is not limited to this. For example, several units may transport the film in the X direction, the Y direction, the Z direction, or the combination direction thereof, or the transport direction may be appropriately changed in one unit.

In the above-described embodiment and modified examples, the case where the three steps of coating in the coating unit 10, firing in the firing unit 20, and removal in the removal unit 30 has been described as an example, The present invention is not limited thereto. For example, when polyimide, polyamideimide, or polyamide is used as the material of the coating film, firing may not be performed. Therefore, when the firing is not performed, for example, by providing a winding device and a delivery device between the firing unit 20 and the removal unit 30, the microfilm (FA) formed in the application unit 10, It is possible to carry it into the removal unit 30 without involving the firing unit 20. In the case of not carrying out firing, the production system for producing a porous imide resin film is a system in which a liquid containing polyamic acid, polyimide, polyamideimide or polyamide and fine particles is applied to a substrate to form a microfilm And a removing unit for removing the fine particles from the microfilm film peeled from the substrate in the coating unit or outside the coating unit. If the firing is not performed, the post-baking process described above may be performed after the porous resin film (F) is taken out from the removal unit (30) for removing fine particles. Processing unit 80 and / or the etching unit 82 before the post-baking process.

In the above-described embodiment and the modified example, the configuration in which the porous resin film (F) is formed by the roll-to-roll method has been described as an example, but the present invention is not limited thereto. For example, when the porous resin film F is taken out from the removal unit 30 after the treatment in the removal unit 30 is completed, the porous resin film F is cut into a predetermined length without being wound by the winding unit 60 And the cut may be recovered.

SYS, SYS2, SYS3, SYS4, SYS5 ... Manufacturing system (porous imide resin manufacturing system) F ... Porous resin film (porous imide resin film) FA ... Smiling Tabernacle FB ... Blown film S ... Return equipment (substrate) Q1 ... The first coating liquid F1 ... The first coating film Q2 ... The second coating liquid F2 ... The second coating film A1 ... Resin material A2 ... Particle R, RS, RF ... Roll body 10 ... The coating unit 12 ... The first nozzle 13 ... The second nozzle 14 ... Drying section 15 ... Peeling section 20 ... The sintering unit 30 ... Removal unit 32 ... Etching portions 40, 60, 73 ... The winding part 72 ... Dipping section 80 ... The post-processing unit 81 ... The antistatic unit 82 ... Etching unit 90 ... The winding device 100 ... Separator 200 ... Lithium ion battery

Claims (21)

As a manufacturing system for manufacturing a porous imide resin film,
A coating unit for applying a liquid containing polyamic acid, polyimide, polyamideimide or polyamide and fine particles to a substrate to form a microcapsule,
A firing unit for firing the microfilm film peeled from the base material in the coating unit or outside the coating unit to form a fired film containing the fine particles;
And a removing unit for removing the fine particles from the firing film. The method according to claim 1,
Wherein the coating unit forms the strip-shaped micro-film on the substrate. The method according to claim 1 or 2,
Wherein the removal unit removes the fine particles by introducing the fired film fired by the firing unit in turn without winding the porous fired film. The method according to any one of claims 1 to 3,
And a winding section for winding the microfilm film peeled from the base material or the microfilm film including the base material to form a rolled body. The method of claim 4,
When the roll body is a roll of the strip-shaped micro-film peeled off from the substrate,
And the firing unit sequentially takes out the microfilm from the roll and fires the microfilm. The method of claim 4,
When the roll body is a roll of the strip-shaped micro-film including the substrate,
And a dipping section for taking out the substrate from the roll and immersing the substrate in a predetermined liquid, and peeling the microfilm from the substrate. The method according to any one of claims 1 to 3,
Wherein the baking unit introduces and fires the microfilm peeled off from the substrate in turn without winding, and firing the microfilm. The method according to any one of claims 1 to 7,
And an antistatic unit that performs antistatic treatment on the fired film from which the fine particles have been removed. The method according to any one of claims 1 to 8,
And an etching unit for removing a part of the fired film from which the fine particles have been removed. The method according to any one of claims 1 to 9,
The first liquid and the second liquid having different contents of at least the fine particles are used as the liquid,
Wherein the coating unit forms the microfilm film in which the content ratio of at least the microfine particles is different by applying the first liquid and the second liquid to the substrate. As a separator formed by a porous polyimide film,
The porous polyimide film is produced by the porous imide-based resin film production system according to any one of claims 1 to 10. As a method for producing a porous imide resin film,
A method in which a liquid containing polyamic acid, polyimide, polyamideimide or polyamide and fine particles is applied to a substrate and then peeled from the substrate to form a microcapsule,
Firing said microfilm film to form a fired film containing said microfilm,
And removing the fine particles from the firing film. The method of claim 12,
Wherein the micro-film is formed in a band-like shape. The method according to claim 12 or 13,
And removing the fine particles from the firing film by introducing the firing film in turn without winding. The method according to any one of claims 12 to 14,
Based resin film is formed by winding the microfilm film peeled from the base material or the microfilm film including the base material to form a roll. 16. The method of claim 15,
When the roll body is a roll of the strip-shaped micro-film peeled off from the substrate,
And the microfilm is sequentially taken out from the roll and fired. 16. The method of claim 15,
When the roll body is a roll of the strip-shaped micro-film including the substrate,
And removing the substrate from the roll, immersing the substrate in a predetermined liquid, and peeling the micro-film from the substrate. The method according to any one of claims 12 to 14,
Wherein the microfilm film peeled off from the substrate is introduced in turn without being wound and fired. The method according to any one of claims 12 to 18,
Wherein the antireflection treatment is performed on the fired film from which the fine particles have been removed. The method according to any one of claims 12 to 19,
And removing a part of the fired film from which the fine particles have been removed. The method of claim 12,
The first liquid and the second liquid having different contents of at least the fine particles are used as the liquid,
And the first liquid and the second liquid are applied to the base material to form the microcapsule in which the content of at least the microparticles is differently stacked.

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