KR20170085445A - Method for producing laminate, and laminate - Google Patents

Abstract

A method for producing a laminated body comprising a flat film as a resin thin film and a porous support film, characterized by comprising the steps of: filling the pores of the flat film with the material of the flat film without damaging or wrinkling the flat film; A laminated body having a permeable flat film which is suitably produced by the above method and which is excellent in strength without being easily broken even when a pressure is applied, and a laminated body having the laminated body as a separator And a separation method using the filter.
A supporting film having a cover film on one main surface is laminated so that the supporting film and the flat film are in contact with each other, and then the flat film and the supporting film , The cover film laminate including the cover film is peeled from the substrate, and the laminate composed of the flat film and the support film is peeled off from the resulting laminate with the cover film.

Description

METHOD FOR PRODUCING LAMINATE, AND LAMINATE [0002]

TECHNICAL FIELD The present invention relates to a method for producing a laminate composed of a flat film as a resin thin film and a support film as a porous film, and a laminate suitably produced by the above-mentioned production method.

Recently, a self-supporting thin film having a large surface area and having a thickness of nanometer order and permeability for transmitting a minute substance has been attracting attention as a selective permeable membrane, a microsensor, a film for drug delivery, and the like. Therefore, various methods for producing a self-supporting thin film having permeability have been studied, and a surface casting method, an interface reaction method using a silane coupling agent, and the like are known. However, the thin films obtained by these methods usually suffer from problems such as insufficient mechanical strength, difficulty in increasing the area of the thin film, and limitations in the precision of the resulting thin film.

As the self-supporting thin film, a polymer thin film having self-supporting property even when the thickness is 100 nm or less and the polymer thin film are known (Patent Document 1). In the method described in Patent Document 1, a sacrificial layer is provided on the surface of a support, the polymerizable compound in the composition is subjected to chain polymerization on the surface of the sacrificial layer, and then the sacrificial layer is removed to separate the composition polymerized with the support, do.

Further, for the purpose of supplementing the strength of the thin film without losing the permeability of the thin film, there has been proposed a laminate in which a porous film having a certain thickness and a transparent thin film are laminated. As such a laminate, a laminate in which a gas separation membrane (thin film) comprising polyimide and a thick porous film are laminated is known (Patent Document 2).

Japanese Patent Application Laid-Open No. 2008-285617 Japanese Patent Laid-Open Publication No. 2015-83296

Clearly, the thin film produced by the method described in Patent Document 1 has an autonomous property as an extremely thin film of 100 nm or less. However, since it is a thin film of nanometer order, the problem of strength still can not be solved.

Further, even if the thin film described in Patent Document 1 is used for gas separation, if the pressure difference is generated on both sides of the membrane at the time of separation, the membrane tends to break.

On the other hand, the laminate described in Patent Document 2 is prepared by applying a coating liquid containing a polyimide compound onto a porous film, and then removing the solvent. However, in the production method described in Patent Document 1, the coating liquid containing the polyimide compound is contained in the pores of the porous film due to capillary phenomenon or the like. For this reason, in the laminate described in Patent Document 1, the thickness of the polyimide filled in the pores of the porous film is smaller than the thickness of the gas separation membrane made of polyimide, and the permeation distance of the gas becomes longer.

For this reason, in the method described in Patent Document 2, it is difficult to obtain a laminate having a desired gas separation performance particularly when the thickness of the gas separation membrane is designed to be thin.

On the other hand, when the porous membrane is directly laminated with the extremely thin gas separation membrane from which the solvent has already been removed, there is no problem that the polyimide is filled in the pores of the porous membrane.

However, it is very difficult to laminate an extremely thin gas separation membrane and a porous membrane without causing breakage or wrinkling on the membrane.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing a laminate comprising a flat film as a resin thin film and a support film as a porous film, A method capable of laminating a flat film and a supporting film without generating wrinkles and wrinkles and a method of producing a laminated body having a flat film capable of transmitting a gas suitably produced by the above method and having excellent strength not easily broken even when pressure is applied And a gas filter provided with the laminate as a separator, and a separation method using the filter.

The present inventors have found that, after bringing a peeling liquid containing water into contact with a thin flat film formed on a substrate, a supporting film having a cover film on one main surface is laminated so that the supporting film and the flat film are in contact with each other, The laminate comprising the flat film, the support film, and the cover film is peeled off from the substrate, and the laminate comprising the flat film and the support film is peeled off from the obtained laminate with the cover film, The above problems can be solved.

The inventors of the present invention have found that a laminate comprising a flat film and a support film has a flat film having a thickness of 1000 nm or less, a through hole having an opening diameter of 1 nm or more, and a porous film having a surface roughness of 100 nm or less, It has been found that the above problems can be solved by using a support film having an average diameter of the plurality of openings of less than 1000 nm and an aperture ratio of the main surface of 40% or less by area.

Thus, the present inventors have completed the present invention.

That is, in the first aspect of the present invention,

A method for producing a laminate comprising a planar film and a porous support film,

A step of applying a resin solution onto a substrate to form a coating film,

Removing the solvent from the coating film to form a flat film,

A step of bringing the flat film into contact with a peeling liquid containing water,

A step of laminating a support film having a cover film on one main surface so that the support film and the planar film are in contact with each other,

A step of peeling the cover film laminate including the flat film, the support film and the cover film from the substrate,

And peeling the laminate from the laminate with the cover film.

A second aspect of the present invention is a laminate comprising a flat film and a support film,

The flat film has a film thickness of 1000 nm or less, does not have a through hole having an opening diameter of 1 nm or more,

The support film is a porous film having a surface roughness of 100 nm or less,

The average diameter of the plurality of openings on the main surface of the support film is less than 1000 nm,

And the opening ratio of the main surface of the support film is not more than 40% by area.

A third aspect of the present invention relates to a filter for gas comprising a laminate as a separation membrane related to the second aspect.

A fourth aspect of the present invention uses a filter associated with the third aspect,

Separation of gases from a mixture comprising solids and gases,

Separation of gas from a mixture comprising liquid and gas, or

The present invention relates to a separation method for separating at least one gas from a mixed gas containing two or more gases.

According to the present invention, there is provided a method for producing a laminated body comprising a flat film as a resin thin film and a supporting film as a porous film, without filling the pores of the flat film with the material of the flat film and without damaging or wrinkling the flat film , A method capable of stacking a flat film and a supporting film, a laminate having a permeable flat film suitably produced by the above method and excellent in strength not easily broken even under application of pressure, It is possible to provide a gas filter provided as a separation membrane and a separation method using the filter.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram schematically showing a suitable example of a method for producing a laminate according to the present invention. Fig.

≪ Method of producing laminate >

A manufacturing method of a laminated body composed of a flat film made of a resin and a supporting film made of a porous material,

A step of applying a resin solution on a substrate to form a coating film (hereinafter also referred to as a " coating step "),

A step of removing the solvent from the coated film to form a flat film (hereinafter also referred to as a " flat film forming step "),

(Hereinafter also referred to as a " contact step ") in which a flat film is brought into contact with a peeling liquid containing water,

(Hereinafter also referred to as a " lamination process ") in which a support film having a cover film on one main surface is laminated so that the support film and the flat film are in contact with each other,

(Hereinafter also referred to as a " peeling step ") of peeling a laminate with a cover film including a flat film, a support film, and a cover film from the substrate,

And a step of peeling the laminate from the laminate with the cover film (hereinafter also referred to as a laminate obtaining process).

Hereinafter, the above process will be described with reference to Fig. 1 (Figs. 1A to 1H). Fig. 1 is a diagram for explaining each step relating to the method for producing a laminate by a cross section observed in the cross-sectional direction of the substrate 10. Fig.

<Coating Step>

As shown in Figs. 1A and 1B, in the coating step, a resin solution is applied onto the substrate 10 to form a coating film 11. [ Examples of the method of applying the resin solution on the substrate 10 include a contact transfer type application device such as a roll coater, a reverse coater, and a bar coater, a spinner (rotary application device), a curtain flow coater, an ink jet device, A non-contact type coating apparatus may be used.

Even in the case of forming a large-area coating film 11 among the coating methods, a slit coating apparatus is preferable because it is easy to form the coating film 11 having a uniform thickness.

The film thickness of the coating film 11 is not particularly limited and is appropriately determined depending on the film thickness of the flat film 12 formed by removing the solvent from the coating film.

The material on the substrate 10 is not particularly limited as long as it is a resin solution, a material which dissolves in a releasing solution to be described later, a resin solution, or a material which does not swell by a releasing solution to be described later.

Examples of the material on the substrate 10 include inorganic materials such as glass and metals such as stainless steel, iron, copper and aluminum, and inorganic materials such as polyamide (nylon), polyester (PET, PBT and the like), polystyrene, epoxy resin, polyimide resin, Polyimide-imide resin, and the like.

The resin contained in the resin solution is not particularly limited as long as it is soluble in a solvent and can be formed into a film by removing the solvent from the coating film (11).

However, a water-soluble resin can not be used. When a water-soluble resin is used, a water-soluble flat film 12 is formed. If the flat film 12 is water-soluble, the flat film 12 is dissolved in the peeling liquid 13 in the contact step to be described later, and the laminate 17 of the desired structure can not be formed.

When an aqueous solution containing alcohol is used as the peeling liquid 13 and the flat film 12 is not dissolved in the peeling liquid excessively, a resin soluble in the alcohol can be used as the material of the flat film 12 have.

The dissolution rate of the flat film 12 and the support film 14 to be described below is preferably 1 nm / sec or less in terms of resistance to the exfoliation liquid 13.

The resin is appropriately selected depending on the kind of the solvent or the type of the gas permeable to the layered product 17 when the layered product 17 is separated.

Suitable resins include, for example, polyamic acid, polyimide, polybenzoxazole, epoxy resin, and acrylic resin.

The hydrogenated products of isoprene-butadiene-styrene copolymer, hydrogenated products of isoprene-butadiene-styrene copolymer, butadiene-styrene copolymer, hydrogenated products of butadiene-styrene copolymer, isoprene-styrene copolymer, , Styrene polymers such as ethylene-propylene-styrene copolymer, propylene-styrene copolymer, ethylene-styrene copolymer ethylene-propylene-1-butene styrene copolymer and polystyrene are also preferable.

In addition, a cyclic olefin such as an ethylene norbornene copolymer, a propylene norbornene copolymer, an ethylene tetracyclodecene copolymer, a propylene tetracyclodecene copolymer, an ethylene propylene norbornene copolymer, and an ethylene propylene tetracyclodecene copolymer An olefin-based copolymer is also preferable.

When the resin is a copolymer, it may be a random copolymer or a block copolymer. When the resin is a block copolymer containing units derived from styrene, a block copolymer having blocks of units derived from styrene at both ends of the molecular chain is preferable. In addition, the above-mentioned preferable resin may have a hydroxyl group at both ends or at one end of the molecular chain.

The solvent contained in the resin solution is appropriately selected depending on the type of resin.

Suitable examples of the solvent include aliphatic monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol and 2-ethylhexyl alcohol; Polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and glycerin; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Cellosolve such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate and isobutyl propionate; Other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as? -butyrolactone; And the like.

The area of the main surface of the layered product 17 produced by the embodiment of the present invention is preferably 10 cm ² or more. According to the embodiment of the present invention described here, the layered product 17 having the main surface area of 10 cm ² or more can be easily manufactured.

Therefore, the flat area of the major surface of the film 12 and Figure 10cm ² or more is preferable, and preferably at least 20cm ² than this, 30cm ² or more is particularly preferable.

It is preferable that the area of the major surface of the flat film 12 and the area of the major surface of the laminate 17 match with each other, And the area of the main surface of the layered product 17 may be different.

When removing the solvent at the time of forming the flat film 12, the area of the flat film 12 may be smaller than the area of the coated film 11 in some cases. In this case, the area of the coating film 11 is determined in consideration of the amount of shrinkage due to removal of the solvent.

&Lt; Flat film formation step &

1B and 1C, in the flat film forming step, the solvent is removed from the coating film 11 to form the flat film 12. As shown in Fig.

The method of removing the solvent is not particularly limited as long as it is a method in which the flat film 12 is wrinkled or the flat film 12 is not thermally deteriorated.

Examples of the method for removing the solvent include a method in which the coating film 11 on the substrate 10 is heated at atmospheric pressure or under reduced pressure or a method in which the coating film 11 is subjected to air flow or air flow of an inert gas such as nitrogen And a method of placing the coating film 11 in a reduced-pressure atmosphere at a temperature near the room temperature.

When the coating film 11 is heated to remove the solvent, the heating temperature is appropriately determined in consideration of the boiling point of the solvent, the material of the flat film 12, and the like. If the heating temperature is too high or the heating rate is too high, bubbles may be contained in the flat film 12 or wrinkles may occur.

The thickness of the flat film 12 is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less.

When the layered product 17 produced by the embodiment of the present invention is used as a filter, a gas which satisfactorily permeates the flat film 12 and a gas, a liquid or the like which is difficult to permeate or permeable to the flat film 12 The solid is separated.

In this case, since the desired kind of gas permeates the flat film 12 more favorably, the efficiency of separation by the layered product 17 is improved, so that the film thickness of the flat film 12 is preferably as thin as possible.

The flat film 12 preferably has no opening with an opening diameter of 1 nm or more. As described above, the layered product 17 produced by the embodiment of the present invention can be used for gas separation. If an opening having an opening diameter of 1 nm or more is present in the flat film 12, undesired components may easily permeate through the layered product 17.

The tensile strength of the flat film 12 is not particularly limited. The tensile strength of the flat film 12 is preferably 1 GPa to 5 GPa in view of ease of suppressing the breakage of the flat film 12 when the laminate 17 is used as a filter.

<Contact Process>

As shown in Fig. 1D, in the contact step, the flat film 12 is brought into contact with the peeling liquid 13 containing water. The peeling liquid 13 is a liquid containing water and is not particularly limited as long as it is a solution that does not dissolve or swell the flat film 12 or the supporting film 14. [

The surface tension of the peeling liquid 13 is preferably 10 to 75 mN / m, more preferably 10 to 50 mN / m, because the flattening film 12 is easily wetted by the peeling liquid 13.

The method of preparing the surface tension of the peeling liquid 13 is not particularly limited. Adjustment of the surface tension of the peeling liquid 13 is typically carried out by adding various additives to water.

Suitable examples of such an additive include a water-soluble organic solvent and a surfactant.

Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and glycerin; Propylene glycol monomethyl ether acetate, and the like.

As the surfactant, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used.

As the additive used for adjusting the surface tension, a water-soluble organic solvent is preferable in that no deposits are generated in the layered product 17 after the peeling solution 13 is dried. Among the water-soluble organic solvents, alcohols are preferable, and methanol, ethanol, n-propanol, and isopropanol are more preferable, and methanol and ethanol are particularly preferable because of adjustment of the surface tension of the peeling liquid 13 and ease of drying. desirable.

The flat film 12 on the substrate 10 is wetted with the peeling liquid 13 so that the cover film laminated body 16 can be prevented from being damaged without causing destruction of the flat film 12 in a peeling step The substrate 10 can be easily peeled off.

It is considered that the adhesion force between the substrate 10 and the flat film 12 is lowered by the penetration of the peeling liquid 13 into the minute gap between the substrate 10 and the flat film 12. [

The method of bringing the flat film 12 into contact with the peeling liquid 13 is not particularly limited. Examples of the contacting method include a method of applying or spraying the peeling liquid 13 on the flat film 12, a method of flowing the peeling liquid 13 on the flat film 12, a method of immersing the flat film 12 in the peeling liquid, etc. .

The temperature of the peeling liquid 13 to be brought into contact with the flat film 12 is not particularly limited as long as it is a temperature at which the flat film 12 is not swollen or melted. The temperature of the peeling liquid 13 should not be a temperature far from the room temperature. Typically, it is about 0 to 50 ° C, preferably 5 to 45 ° C, and more preferably 10 to 40 ° C.

<Lamination Process>

1E and 1F, in the laminating step, the supporting film 14 having the cover film 15 on one main surface is laminated so that the supporting film 14 and the flat film 12 are in contact with each other.

The support film 14 will be described later in detail.

The lamination method is not particularly limited, and a well-known method can be employed. As a suitable method, for example, a roll or the like may be used at a pressure such that the support film 14 or the flat film 12 is not broken, and the support film 14 including the cover film 15 may be formed as a flat film 12).

In this case, the pressure of the roller is preferably 0.1 to 10 kgf / cm ² , and more preferably 0.2 to 5 kgf / cm ² . The temperature of the roller is preferably 20 to 120 占 폚, more preferably 25 to 100 占 폚.

The material of the cover film 15 is not particularly limited as long as it can be laminated with the support film 14. [ The cover film 15 may be made of an organic material or an inorganic material, preferably an organic material. As the organic material, a resin is generally used.

Examples of the resin include polyacetal, polyamide, polycarbonate, polyester (polybutylene terephthalate, polyethylene terephthalate, polyarylate and the like), FR-AS resin, FR-ABS resin, AS resin, ABS resin, (Polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyimide, polyamideimide, polyamide bismaleimide, polyimide, polyimide, polyimide, , Polyetherimide, polybenzoxazole, polybenzothiazole, polybenzimidazole, silicone resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth) acrylic resin (polymethyl methacrylate Etc.), polystyrene, and the like.

Of these resins, polyester, polycarbonate, (meth) acrylic resin, polystyrene, polyimide, polyethylene, polypropylene and the like are preferable from the viewpoint of obtaining a cover film easily.

The thickness of the cover film 15 is not particularly limited. The thickness of the cover film is preferably, for example, 10 to 100 mu m, more preferably 10 to 50 mu m.

The method of adjusting the support film 14 having the cover film 15 on one main surface is not particularly limited. The cover film 15 and the support film 14 are laminated and the support film 14 having the cover film 15 is prepared in a known manner.

As a suitable method, for example, a method of thermally pressing the cover film 15 and the support film 14 using a roll or the like at a pressure not breaking the support film 14 can be mentioned.

The cover film 15 is preferably pasted on one side of the main surface of the supporting film 14 through an adhesive layer (not shown). That is, it is preferable that an adhesive layer is present between the cover film 15 and the support film 14.

When the adhesive layer is present, the cover film laminated body 16 including the flat film 12, the supporting film 14 and the cover film 15 is peeled off from the substrate 10 in the peeling step to be described later Only the cover film 15 is apt to be peeled off from the substrate.

The method of providing the adhesive layer is not particularly limited. As a preferable method, it is preferable to apply the solution of the adhesive layer material on the cover film 15 or the support film 14, and then remove the solvent.

It is preferable that the adhesive layer is provided on the cover film 15 since the surface of the support film 14 is not clogged by the material of the adhesive layer at the time of forming the adhesive layer.

The material of the adhesive layer is not particularly limited as long as it can adhere the cover film 15 and the support film 14. [

Suitable examples of the material of the adhesive layer include amorphous polyester, styrene-based resin, and olefin-based resin.

When the material of the adhesive layer is an organic material, the glass transition point of the organic material is preferably 80 DEG C or less, more preferably 50 DEG C or less.

When the glass transition point of the material of the adhesive layer is within this range, the cover film 15 is provided while being heated to such a low temperature as not to adversely affect the flat film 12, the support film 14, the cover film 15, The support film 14 can be laminated to the flat film 12. [

In this case, the adhesive layer is softened, and the cover film 15 and the supporting film 14 are adhered well.

The support film 14 including the cover film 15 may be heated to a temperature equal to or higher than the softening point of the adhesive layer before the support film 14 having the cover film 15 is laminated. And the support film 14 are adhered well.

The wetting flat film 12 covered with the peeling liquid 13 is covered with the cover film 15 to suppress the volatilization of the peeling liquid 13. The cover film laminated body 16 including the flat film 12, the supporting film 14 and the cover film 15 is preferably peeled off from the substrate 10 in the following peeling step .

<Peeling process>

1F and 1G, in the peeling step, the cover film laminated body 16 including the flat film 12, the support film 14 and the cover film 15 is removed from the substrate 10 Peel off.

The peeling method is not particularly limited. For example, the edge of the cover film 15 is gripped by a finger, a tweezers, or the like, and the cover film laminated body 16 is peeled from the substrate 10. [

At this time, since the flat film 12 in direct contact with the substrate 10 is wetted by the peeling liquid 13, the laminated body 16 with the cover film can be prevented from peeling off the substrate (10).

<Stacked body obtaining step>

1 H, in the laminate obtaining step, the flat film 12, the support film 14 and the cover film 15 are laminated from the laminate 16 with a cover film, The laminate 17 made of the support film 14 is peeled off.

The method for peeling the laminate 17 from the cover film-attached laminate 16 is not particularly limited. As a suitable method, for example, after the edge of the cover film laminate is curved and a gap is generated between the cover film 15 and the laminate 17, at least the laminate 17 and the cover film 15 And then grasping one side to peel off the two.

The laminate 17 thus obtained has excellent strength because the thin flat film 12 is favorably permeable to the gas while the support film 14 is provided. Therefore, the stacked body 17 can be formed by separating a specific gas from the mixed gas by selective permeation of the gas, gas-liquid separation for the liquid containing the gas, ) Is used suitably for separation.

&Lt; Supporting film &

The support film 14 is a porous film made of a porous material. The use of the porous film as the supporting film 14 allows the gas to be separated to reach the flat film 12 while the flat film 12 is supported by the supporting film 14 without breaking the very thin flat film 12 So that various fluids can be circulated in the stacked body 17.

Hereinafter, the porous film used as the support film 14 will be described.

The material of the porous film is not particularly limited, and it may be an organic material or an inorganic material. An organic material is preferable as the material of the porous film because it is easy to form a porous film having a desired pore size and porosity. Such an organic material is typically a resin.

As the resin, the resin exemplified as the material of the cover film 15 is preferably used.

Of the resins, polyvinylidene fluoride, polyethersulfone, polyimide, and polyamideimide are preferable from the viewpoint of obtaining a porous film that is thermally or chemically stable and has excellent mechanical strength.

As the material of the porous film, two or more kinds of resins may be mixed and used.

The surface roughness (Ra) of the porous film is preferably 100 nm or less, more preferably 90 nm or less.

The surface roughness of the porous film is defined as an average value of the surface roughness of any three points in the data of the porous film having the size of 5 cm x 5 cm.

When the surface roughness Ra of the porous film used as the support film 14 is 100 nm or less, peeling of the flat film 12 and the support film 14 at the time of producing the layered product 17 is unlikely to occur.

The porous film has a plurality of openings on its main surface. The average diameter of the plurality of openings on the main surface of the porous film is preferably less than 1000 nm, more preferably 900 nm or less, particularly preferably 700 nm or less, most preferably 500 nm or less.

The average diameter of the plurality of openings on the main surface of the porous membrane can be obtained by observing the surface of the porous membrane with a scanning electron microscope (SEM) at a magnification of 1000 times and measuring the area of the openings by means of image analysis software (ImageJ).

The average diameter is calculated as an average value of diameters of 10 or more openings. The diameter of the opening is the diameter per circle calculated from the area of the opening.

When the edge of the hole on the surface is unclear due to the reason such as the hole in the film being visible at the time of image analysis, the third to the third contrast peak at the color contrast peak is selected and the opening of the porous film surface is specified did.

When the average diameter of the opening of the porous film used as the supporting film 14 is excessively large, peeling of the flat film 12 and the supporting film 14 tends to occur at the time of producing the laminated body 17, It is difficult to obtain the layered product 17.

The opening ratio of the main surface of the porous film is preferably 40% by area or less with respect to the area of the main surface.

The opening ratio of the main surface of the porous film is obtained by measuring the area of the opening by image analysis by the same method as that of measuring the average diameter of the plurality of openings on the main surface of the porous film.

If the opening ratio of the main surface of the porous film is more than 40% by area, peeling of the flat film 12 and the supporting film 14 easily occurs or it is difficult to obtain the layered product 17 having excellent pressure resistance.

The shape of the vacancies present in the porous film is such that when the layered body 17 having the porous film as the supporting film 14 is used, the opening from the surface of the supporting film 14 to the surface of the flat film 12 So long as the fluid can flow.

For example, the porous film may be a porous film having a plurality of through holes penetrating the film in the thickness direction, or may be a porous film having a structure in which a plurality of holes communicate with each other (hereinafter, referred to as a communication hole).

Such a porous membrane is advantageous in that the porous membrane can be easily produced. However, even if the average opening diameter and the opening ratio of the main surface of the porous membrane are low, it is easy to flow the fluid in the porous body. Hereinafter, abbreviated as a communicating hole).

The idea of the shape of the hole is a concept involving a genuine concept, but it is not necessarily limited to a sphere. The spherical shape means a substantially spherical shape, and the spherical shape includes a shape that can be recognized as an approximate spherical shape when the magnified image of the hole (hole) is visually confirmed.

Concretely, in the upper air hole, the surface defining the study is a curved surface.

When the porous film includes a spherical shape, the average diameter of the spherical shape is preferably less than 1000 nm.

The individual spheres are typically holes formed by the removal of individual fine particles present in the resin-particulate composite membrane described below in a subsequent process. Further, the communication hole is formed by removing a plurality of fine particles which are in contact with the resin-fine particle composite film in a subsequent step in a production method of a porous film to be described later. The portion where the spherical balls communicate with each other in the communication hole comes from a portion where a plurality of fine particles before being removed come into contact with each other.

The permeability of the porous membrane is appropriately set so that the support membrane 14 has a desired permeability. The permeability (gluing degree) of the support film 14 is preferably 1 to 300 sec / 100 cc, more preferably 5 to 200 sec / 100 cc. The air permeability is adjusted by adjusting the average diameter of the openings of the porous film and the opening ratio.

The production method of the porous film is not particularly limited. As a preferable production method of a porous film having a communicating hole made of a spherical work, which is a suitable porous film, for example, there can be mentioned the methods described in International Publication Nos. 2014/175011 and 2014-214767.

«Laminate»

Hereinafter, a suitable laminate that can be produced by the above-described method for producing a laminate will be described.

The laminate described below may be produced by a manufacturing method other than the above-described method for producing a laminate.

The layered body 17 is composed of a thin flat film 12 having a film thickness of 1000 nm or less and a supporting film 14 for supporting the flat film.

Hereinafter, the flat film 12 and the supporting film 14 will be described.

<Flat film>

The flat film 12 has a film thickness of 1000 nm or less and does not have a through hole having an opening diameter of 1 nm or more.

The thickness of the flat film 12 is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less.

When the laminate 17 having the flat film 12 is used as a filter, a gas which satisfactorily permeates the flat film 12 and a gas, a liquid or the like which is difficult to permeate or permeable to the flat film 12 The solid is separated.

In this case, since the desired type of gas permeates the flat film 12 more favorably, the efficiency of separation by the layered product 17 is improved, so that the thinner the film thickness of the flat film is, the better.

The flat film 12 does not have an opening with an opening diameter of 1 nm or more. The laminate 17 having the flat film 12 can be used for gas separation. If an opening having an opening diameter of 1 nm or more is present in the flat film 12, undesired components may easily permeate through the layered product 17.

The tensile strength of the flat film 12 is not particularly limited. The tensile strength of the flat film 12 is preferably 1 GPa to 5 GPa in view of ease of suppressing the breakage of the flat film 12 when the laminate 17 is used as a filter.

As described above, the above-described method using a peeling solution containing water is preferable as a method for producing the layered product 17 composed of the flat film 12 and the support film 14. For this reason, from the viewpoint of resistance to the peeling liquid 13, the dissolution rate with respect to water for the flat film 12 and the support film 14 described later is preferably 1 nm / sec or less.

The material of the flat film is not particularly limited. From the standpoint of ease of processing and the like, the material of the flat film is preferably a resin. The resin is appropriately selected depending on the kind of gas to be passed through the laminate when the laminate is subjected to the separation.

A suitable example of the resin is the same as a suitable example of the resin used for preparing the resin solution used for forming the flat film 12, which is listed in the description of the production method of the above-described laminate.

The area of the main surface of the layered product 17 is preferably 3 cm ² or more. Therefore, the flat area is more than ² degrees 3cm of the major surface of film 12 and preferably, at least 10cm ^2, more preferred, 30cm ² or more is particularly preferable.

It is preferable that the area of the main surface of the flat film 12 coincides with the area of the main surface of the layered product 17. However, And the area of the main surface of the layered product 17 may be different from each other.

&Lt; Supporting film &

The support film 14 is a porous film made of a porous material. The porous film 12 is supported by the supporting film 14 so that the gas to be separated reaches the flat film 12 while the porous film 12 is used as the supporting film so that the very thin flat film 12 is not broken, The fluid of the branches can be circulated inside the laminate.

Hereinafter, the porous film used as the support film 14 will be described.

The material of the porous film is not particularly limited, and it may be an organic material or an inorganic material. An organic material is preferable as the material of the porous film because it is easy to form a porous film having a desired pore size and porosity. Such an organic material is typically a resin.

A suitable example of the resin is the same as a suitable example of the resin exemplified as the material of the cover film 15, which is listed in the description of the method for producing the above-described laminate.

Of the resins, polyvinylidene fluoride, polyethersulfone, polyimide, and polyamideimide are preferable from the viewpoint of obtaining a porous film that is thermally or chemically stable and has excellent mechanical strength.

As the material of the porous film, two or more kinds of resins may be mixed and used.

The surface roughness (Ra) of the porous film is 100 nm or less, preferably 90 nm or less.

The surface roughness of the porous film is defined as an average value of the surface roughness of any three points in the data of the porous film having the size of 5 cm x 5 cm.

When the surface roughness (Ra) of the porous film used as the support film 14 is 100 nm or less, peeling of the planarized film 12 and the porous film at the time of producing the laminated body is unlikely to occur.

The porous film has a plurality of openings on its main surface. The preferable range of the average diameter of the plurality of openings on the main surface of the porous film and the average diameter of the plurality of openings on the main surface of the porous film are the ranges described in the above- .

When the average diameter of the openings on the surface of the porous film used as the support film is excessively large, the layered product 17, which is easily peeled off from the flat film and the porous film at the time of producing the layered product 17, It is difficult to obtain.

In addition, when the average diameter of the openings on the surface of the porous film is excessively large, the selectivity of the transmittance of a plurality of kinds of gases may be lowered when the laminate 17 is used for separating a plurality of gases.

The defects that can be generated when a suitable range of the opening ratio of the main surface of the porous film and an opening ratio of the main surface of the porous film are too high are the same as the range and the defect described in the above-described production method of the layered product 17.

The shape of the pores present in the porous film is the same as that described in the above-described method for producing the layered product (17).

As described above, it is easy to manufacture a porous membrane as the porous membrane. However, even if the average opening diameter and the aperture ratio of the main surface of the porous membrane are low, it is easy to flow the fluid in the porous body. (Hereinafter, abbreviated as a communication hole).

The definition of the spherical shape and the preferable range of the average diameter of the spherical shape study are the same as those described in the above-described method of producing the layered product 17. [

In the case where the porous film includes a communicating hole communicating with the spherical hole, a typical method of forming the air hole and the communicating hole is the same as that described in the above-described method of producing the stacked body.

The preferable ranges of the permeability of the porous film and the method of adjusting the air permeability of the porous film are the same as those described in the above-described production method of the layered product (17).

The production method of the porous film is not particularly limited. As a preferable production method of the porous film having the communicating hole formed by the spherical study, which is a suitable porous film, there can be mentioned, for example, the methods described in International Publication Nos. 2014/175011 and 2014-214767 have.

The laminate 17 composed of the thin flat film 12 having a film thickness of 1000 nm or less and the supporting film 14 for supporting the flat film 12 described above can be manufactured preferably by the above- do.

«Gas filter»

The above-described laminate can be suitably used as a separator in a gas filter. As the separation performed by the gas filter,

Separation of gases from a mixture comprising solids and gases,

Separation of gas from a mixture comprising liquid and gas, or

The separation of at least one gas from a mixed gas containing two or more gases is preferably used.

When the laminate is mounted on the separator, for example, it may be folded in a serpentine form or rolled in a roll form unless the laminate is broken.

By performing separation using the above-described laminate, minute solid droplets and minute droplets can be satisfactorily separated from the gas. Alternatively, a small gas having a molecular size such as hydrogen or helium may be selectively transmitted using the difference in molecular size. Here, the selective transmission means not only transmitting a gas having a low molecular weight but also preferentially transmitting a gas having a low molecular weight.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

[Example 1]

An N-methylpyrrolidone solution of polyamic acid having a solid concentration of 2% by mass was applied to a glass substrate using a slit coating apparatus to form a coating film. The formed coating film was heated at 80 DEG C for 2 minutes to form a flat film having a size of 370 cm in length x 470 cm in width and a film thickness of 100 nm.

As polyamic acid, polyamic acid derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether was used.

Separately, a polyethylene terephthalate film (cover film) having a size of 25 cm x 15 cm and a thickness of 50 mu m and a polyimide porous film (supporting film) having a size of 20 cm x 10 cm and a film thickness of 20 mu m were laminated on the surface of an amorphous polyester Temperature: 50 占 폚) to prepare a laminate.

As the material of the support film, a polyimide resin derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether was used.

As the supporting film, a porous film having a communicating hole made of spherical working was used.

The average diameter of the opening on the surface of the support film measured by the above-described method was 216 nm, the opening ratio of the surface of the support film was 20.3 area%, and the surface roughness was 86 nm.

Then, an aqueous solution of ethanol (surface tension: 28 mN / m) with a concentration of 50 mass% was applied to the flat film on the substrate. After the application of the aqueous ethanol solution, the support film was laminated on the flat film at a roller pressure of 3 kgf / cm ² , a roller temperature of 60 캜, and a roller speed of 0.4 m / min.

After lamination, the end portion of the cover film was held, and the laminate including the flat film, the support film, and the cover film was peeled from the substrate. Then, in the laminate including the obtained flat film, the support film, and the cover film, the laminate composed of the flat film and the support film was peeled off so that the adhesive layer remained on the cover film.

With the above-described method of Example 1, it was possible to produce a laminate comprising a flat film as a resin thin film and a support film as a porous film without causing breakage or wrinkling on the flat film.

[Comparative Example 1]

A laminate composed of a flat film and a support film was formed in the same manner as in Example 1, except that the application of the aqueous ethanol solution was not performed. However, in this case, when the laminate including the flat film, the support film, and the cover film is attempted to be peeled off, the laminate including the cover film and the support film is flat It was stripped from the membrane.

[Comparative Example 2]

Ethanol aqueous solution, and a layered body composed of a flat film and a support film was formed in the same manner as in Example 1 except that ethanol was sprayed. However, in this case, when the laminate including the flat film, the support film, and the cover film is attempted to be peeled off, the flat film is strongly adhered firmly to the substrate, .

[Example 2]

A laminate composed of a flat film and a support film was formed in the same manner as in Example 1, except that the film thickness of the flat film was changed to 800 nm.

Also in the method of Example 2, a laminate composed of a flat film as a resin thin film and a supporting film as a porous film could be produced without causing breakage or wrinkles in the flat film.

[Example 3]

A polyimide porous film was formed in the same manner as in Example 1, except that the polyimide porous film was changed to a polycarbonate porous film having a film thickness of 25 占 퐉, an average opening diameter of the surface of 441 nm, an aperture ratio of the surface of 26.5% Thereby forming a laminate composed of a support film.

The polycarbonate porous film was also a porous film having a plurality of through holes penetrating the film in the thickness direction.

Also in the method of Example 3, a laminate composed of a flat film as a resin thin film and a support film as a porous film could be produced without causing breakage or wrinkles in the flat film.

[Example 4]

Except that the material of the flat film was changed from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether to polyimide resin. Thereby forming a laminate comprising a film and a support film.

Also in the method of Example 4, a laminate composed of a flat film as a resin thin film and a support film as a porous film could be produced without causing breakage or wrinkling on the flat film.

[Example 5]

Except that the material of the flat film is changed to a hydrogenated product of a styrene-isoprene-butadiene-styrene block copolymer containing a terminal hydroxyl group and the solvent used for preparing a resin solution for forming a flat film is changed to decahydronaphthalene (decalin) A laminate composed of a planar film and a support film was formed in the same manner as in Example 1.

Also in the method of Example 5, a laminate composed of a flat film as a resin thin film and a support film as a porous film could be produced without causing breakage or wrinkling in the flat film.

[Example 6]

The procedure of Example 1 was repeated except that the material of the flat film was changed to a hydrogenated product of styrene-isoprene-styrene block copolymer and the solvent used for preparing the resin solution for forming a flat film was changed to decahydronaphthalene (decalin) A laminate composed of a flat film and a support film was formed.

Also in the method of Example 6, a laminate composed of a flat film as a resin thin film and a support film as a porous film could be produced without causing breakage or wrinkles in the flat film.

[Example 7]

The procedure of Example 1 was repeated except that the material of the flat film was changed to ethylene tetracyclododecene copolymer and the solvent used to prepare the resin solution for flat film formation was changed to decahydronaphthalene (decalin) To form a laminate.

Also in the method of Example 7, a laminate composed of a flat film as a resin thin film and a support film as a porous film could be produced without causing breakage or wrinkling in the flat film.

[Example 8]

Except that the material of the flat film was changed to polystyrene and the solvent used for preparing the resin solution for forming a flat film was changed to propylene glycol 1-monomethyl ether 2-acetate (PGMEA) Thereby forming a laminate composed of a support film.

Also in the method of Example 8, a laminate composed of a flat film as a resin thin film and a support film as a porous film could be produced without causing breakage or wrinkles in the flat film.

[Example 9]

A N-methylpyrrolidone solution of polyamic acid having a solid concentration of 2% by mass was applied to a glass substrate using a spin coater to form a coating film. The formed coating film was heated at 80 占 폚 for 1 minute to form a flat film having a size of 10 cm × 10 cm and a film thickness of 100 nm.

As polyamic acid, polyamic acid derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether was used.

Separately, a polyethylene terephthalate film (cover film) having a size of 15 cm x 15 cm and a thickness of 50 m and a polyimide porous film (support film) having a size of 5 cm x 5 cm and a film thickness of 20 m were immersed in an amorphous polyester Temperature: 50 占 폚) to prepare a laminate.

As the material of the support film, a polyimide resin derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether was used.

As the supporting film, a porous film having a communicating hole made of spherical working was used.

The average diameter of the opening on the surface of the support film measured by the above-described method was 216 nm, the opening ratio of the surface of the support film was 20.3 area%, and the surface roughness was 86 nm.

Then, an aqueous solution of ethanol (surface tension: 28 mN / m) with a concentration of 50 mass% was applied to the flat film on the substrate. After the application of the aqueous ethanol solution, the support film was laminated on the flat film at a roller pressure of 3 kgf / cm ² , a roller temperature of 60 캜, and a roller speed of 0.4 m / min.

After lamination, the end portion of the cover film was held, and the laminate including the flat film, the support film, and the cover film was peeled from the substrate. Then, in the laminate including the obtained flat film, the support film, and the cover film, the laminate composed of the flat film and the support film was peeled off so that the adhesive layer remained on the cover film.

With the above-described method, it was possible to produce a laminate composed of a flat film as a resin thin film and a supporting film as a porous film without causing breakage or wrinkling on the flat film.

With respect to the obtained laminate, the pressure resistance and the He / N ₂ selectivity were evaluated according to the following methods. The evaluation results are shown in Table 1.

&Lt; Pressure resistance and He / N ₂ selection ratio evaluation method &gt;

First, a sample of the laminate was mounted on the gas holder portion of the gas line including the gas holder. A gas bomb, an area flow meter, a regulator, a pressure sensor, a flow sensor, an exhaust gas line, and an exhaust gas line end valve were provided on the supply side with respect to the gas holder. A pressure sensor and a precise membrane flow meter were provided on the permeation side with respect to the gas holder.

N ₂ gas was supplied from the gas cylinder to the sample, and the flow rate of the feed gas was adjusted to 100 ml / min and the pressure was set to 200 kPa with the area type flow meter and the regulator.

At this time, when the pressure on the supply side reached 200 kPa with the pressure sensor, the pressure resistance was determined as O, and when the pressure did not reach 200 kPa, the pressure resistance was evaluated as X.

Then, the flow rate of the N ₂ gas was measured by a precision film flow meter on the transmission side under these conditions. The permeation flow rate of the He gas was measured in the same procedure, and the He / N ₂ selection ratio? Was calculated from the permeation flow rate obtained.

The case where the He / N ₂ selection ratio? Was 10 or more was judged as?, And the case where the He / N ₂ selection ratio was less than 10 was judged as?

[Examples 10 to 16 and Comparative Examples 3 to 11]

Except that the material and the film thickness of the flat film were changed as shown in Table 1 and the opening ratio (area%) and the surface roughness of the support film were changed as shown in Table 1 A laminate was prepared in the same manner as in Example 9.

With respect to Examples 10 to 12, the pressure resistance and the He / N ₂ selectivity were evaluated in the same manner as in Example 9. The evaluation results are shown in Tables 1 and 2.

Further, when film peeling between the flat film and the support film occurred in the production of the laminate, the pressure resistance and the He / N ₂ selectivity ratio were not evaluated.

Resin 1 is a polyamic acid derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether with respect to the material of the flat film.

Resin 2 is a polyimide resin derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether.

Resin 3 is a hydrogenated product of a terminal hydroxyl group-containing styrene-isoprene-butadiene-styrene block copolymer. Resin 4 is a hydrogenated product of a styrene-isoprene-styrene block copolymer. Resin 5 is an ethylene tetracyclododecene copolymer.

In the case of using Resins 3 to 5, decahydronaphthalene (decalin) was used as a solvent for the preparation of the resin solution for forming a flat film.

Resin 6 is polystyrene. In the case of using Resin 6, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) was used as a solvent for preparing a resin solution for forming a flat film.

As for the material of the support film, PI is the same polyimide resin as that of Resin 2, PC is polycarbonate, PES is polyethersulfone, and PTFE is polytetrafluoroethylene.

As for the support film, the PI porous film is a porous film having a communicating hole made of a spherical shape. The PC porous film is a porous film having a plurality of through holes penetrating the film in the thickness direction.

Flat membrane Support membrane evaluation material Film thickness
(Nm) material surface
Aperture ratio
(%) Surface roughness
Ra
(Nm) The laminate
Manufacturing situation Pressure resistance
(200 kPa) Example 9 Resin 1 100 PI 20.3 86 Good ○ Example 10 Resin 1 800 PC 20.3 86 Good ○ Example 11 Resin 1 100 PI 26.5 24 Good ○ Example 12 Resin 2 100 PI 20.3 86 Good ○ Example 13 Resin 3 100 PI 20.3 86 Good ○ Example 14 Resin 4 100 PI 20.3 86 Good ○ Example 15 Resin 5 100 PI 20.3 86 Good ○ Example 16 Resin 6 100 PI 20.3 86 Good ○ Comparative Example 3 Resin 1 10000 PI 20.3 86 Peeling in the interme - Comparative Example 4 Resin 2 10000 PI 20.3 86 Peeling in the interme - Comparative Example 5 Resin 1 100 PES 46.4 147 Peeling in the interme - Comparative Example 6 Resin 1 800 PES 46.4 147 Peeling in the interme - Comparative Example 7 Resin 1 100 PES 36.6 239 Peeling in the interme - Comparative Example 8 Resin 1 800 PES 36.6 239 Peeling in the interme - Comparative Example 9 Resin 1 100 PC 12.9 17 Good ○ Comparative Example 10 Resin 1 100 PTFE 45.1 1451 Peeling in the interme - Comparative Example 11 Resin 1 800 PTFE 45.1 1451 Peeling in the interme -

Flat membrane Support membrane evaluation material Film thickness
(Nm) material Opening
Average diameter
(Nm) He / N ₂
Selection ratio? Example 9 Resin 1 100 PI 216 ◎ Example 10 Resin 1 800 PC 216 ◎ Example 11 Resin 1 100 PI 441 ○ Example 12 Resin 2 100 PI 216 ○ Comparative Example 9 Resin 1 100 PC 6050 ×

It was confirmed from Examples 9 to 16 and Comparative Examples 3 to 11 that a planarizing film having a film thickness of 1000 nm or less and no through hole having an opening diameter of 1 nm or more and a planarizing film having a surface roughness Ra of 100 nm or less the average diameter of the aperture is less than 1000nm, if the aperture ratio of the major surface consisting of 40 area% or less, the support film laminate, to prepare a laminate without support in case of the interval separation, and pressure resistance and He / N _2, select the non-seen that excellent .

10 substrate
11 Coating film
12 flat membrane
13 Release liquid
14 Support membrane
15 Cover film
16 Cover film laminate
17 laminate

Claims (18)

A method for producing a laminate comprising a planar film and a porous support film,
A step of applying a resin solution onto a substrate to form a coating film,
Removing the solvent from the coating film to form a flat film,
A step of bringing the flat film into contact with a peeling liquid containing water,
A step of laminating a support film having a cover film on one main surface so that the support film and the planar film are in contact with each other;
A step of peeling the cover film laminated body including the flat film, the support film and the cover film from the substrate,
And peeling off the laminate from the cover film-attached laminate. The method according to claim 1,
Wherein the cover film is pasted to one surface of the main surface of the support film through an adhesive layer. The method of claim 2,
Wherein the adhesive layer is made of an organic material having a glass transition point of 50 占 폚 or less. The method according to claim 1 or 2,
Wherein the planarizing film has a thickness of 1000 nm or less. The method according to claim 1 or 2,
Wherein an area of a main surface of the laminate is 10 cm ² or more. The method according to claim 1 or 2,
And the surface tension of the peeling liquid is 10 to 75 mN / m or less. The method according to claim 1 or 2,
Wherein the peeling liquid is an alcohol aqueous solution. The method according to claim 1 or 2,
Wherein the peeling liquid has a boiling point of 100 占 폚 or less. The method according to claim 1 or 2,
Wherein the application of the resin solution is carried out using a slit coating apparatus. A laminate comprising a flat film and a support film,
The flat film has a film thickness of 1000 nm or less and does not have a through hole having an opening diameter of 1 nm or more,
The support film is a porous film having a surface roughness of 100 nm or less,
The average diameter of the plurality of openings on the main surface of the support film is less than 1000 nm,
Wherein an opening ratio of the main surface of the support film is 40% or less. The method of claim 10,
Wherein the support film has a communicating hole communicating with a spherical or substantially spherical hole portion. The method of claim 11,
Wherein an average diameter of said work is less than 1000 nm. The method according to claim 10 or 11,
Wherein the dissolution rate of the flat film in water and the dissolution rate of the support film in water are 1 nm / second or less, respectively. The method according to claim 10 or 11,
Wherein the support film has an air permeability of 10 to 300 sec / 100 cc. The method according to claim 10 or 11,
Wherein the flat film has a tensile strength of 1 to 5 GPa. The method according to claim 10 or 11,
Wherein the support film comprises at least one resin selected from the group consisting of polyimide, polyamideimide, polyethersulfone, and polyvinylidene fluoride. A filter for a gas comprising a laminate according to claim 10 or claim 11 as a separator. Using the filter of claim 17,
Separation of gases from a mixture comprising solids and gases,
Separation of gas from a mixture comprising liquid and gas, or
A separation method for separating at least one gas from a mixed gas containing two or more gases.

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