JP6126324B1 - Method for producing composite membrane - Google Patents

Abstract

A porous substrate and a porous layer formed by applying a coating liquid containing a resin and a solvent on one or both surfaces of the porous substrate, and a method for producing a composite film comprising: (1) A step of applying a liquid compatible with a solvent of a coating solution to one or both sides of a porous substrate, and using a roll-like rotating member having an outer peripheral layer having a porous structure, Applying a liquid that oozes from the inside of the rotating member to the outer peripheral surface to the porous substrate, and (2) applying the coating liquid on one or both surfaces of the porous substrate coated with the liquid. A step of forming a working liquid layer; and (3) a step of solidifying a resin contained in the coating liquid layer to obtain a composite film having a porous layer containing the resin on one side or both sides of the porous substrate. (4) removing the solvent and liquid from the composite membrane, and a method for producing the composite membrane.

Description

  The present invention relates to a method for producing a composite membrane.

  Conventionally, composite membranes having a porous layer on a porous substrate are known as battery separators, gas filters, liquid filters, and the like. As a method for producing this composite film, a coating liquid containing a resin and a solvent is applied onto a porous substrate to form a coating liquid layer, and then the resin contained in the coating liquid layer is solidified to be porous. Manufacturing methods for forming layers are known.

  In the above production method, a part of the coating liquid applied on the porous substrate soaks into the porous substrate, or the solvent of the coating liquid soaks into the porous substrate. Sometimes. Due to this phenomenon, a part of the resin in the coating liquid layer solidifies at an unintended time, and the uniformity of the surface direction of the coating liquid layer is lowered, and as a result, various physical properties of the composite film are in the surface direction. May become uneven.

  As means for solving the above-described problems, for example, as disclosed in Patent Documents 1 and 2, a manufacturing method is known in which a coating liquid is applied onto a porous substrate impregnated with a liquid. With this manufacturing method, the coating liquid and the solvent of the coating liquid are less likely to penetrate into the porous substrate, and therefore the porous layer is easily formed uniformly in the surface direction.

Japanese Patent Laid-Open No. 2001-23602 Special table 2013-533370 gazette

  From the viewpoint of the production efficiency of the composite membrane, it is desirable to apply a coating liquid by transporting a long porous base material having a wide width at a high speed. However, as the width of the porous substrate becomes wider and the conveyance speed of the porous substrate becomes faster, the porous layer formed on the porous substrate tends to be non-uniform in the surface direction. Even when a wide porous substrate is conveyed at high speed, a production method capable of producing a composite film having excellent uniformity in the surface direction is required.

The embodiment of the present disclosure has been made under the above circumstances.
An object of the embodiment of the present disclosure is to provide a method for producing a composite film, which can produce a composite film having excellent uniformity in the surface direction even when a wide porous substrate is conveyed at high speed. .

  Specific means for solving the above-described problems include the following modes.

[1] A porous substrate, and a porous layer formed by applying a coating liquid containing a resin and a solvent for dissolving or dispersing the resin on one or both surfaces of the porous substrate. A method of manufacturing a composite membrane comprising:
(1) A step of applying a liquid compatible with the solvent to one or both sides of the porous base material, and using the roll-shaped rotating member having an outer peripheral layer having a porous structure, the roll shape Applying the liquid that oozes from the inside of the rotating member to the outer peripheral surface to the porous substrate;
(2) A step of coating the coating liquid on one or both sides of the porous substrate on which the liquid is applied to form a coating liquid layer;
(3) solidifying the resin contained in the coating liquid layer to obtain a composite film having a porous layer containing the resin on one or both surfaces of the porous substrate;
(4) removing the solvent and the liquid from the composite membrane;
A method for producing a composite membrane.
[2] The method for manufacturing a composite film according to [1], wherein the outer peripheral layer of the roll-shaped rotating member is a porous ceramic layer.
[3] The method for producing a composite film according to [1] or [2], wherein the outer peripheral layer of the roll-shaped rotating member is a porous layer having an average pore diameter of 2 μm or more and 20 μm or less.
[4] In the step (2), a first coating means for coating one surface and a second surface for coating the other surface are arranged apart from each other in the transport direction of the porous substrate. The production of the composite film according to any one of [1] to [3], wherein the coating liquid is a step of sequentially coating the coating liquid on both sides of the porous substrate one by one using a second coating means. Method.
[5] The step (2) is a step of applying the coating liquid using a coating unit in which a pressing unit that presses the porous substrate against the coating unit is not disposed. ] The manufacturing method of the composite film in any one of [4].
[6] The method for producing a composite film according to any one of [1] to [5], wherein in the step (2), the conveyance speed of the porous substrate is 20 m / min or more.
[7] The composite according to any one of [1] to [6], wherein the step (1) is a step of applying the liquid to the porous base material in an amount of 1 g / m ^{2 to} 30 g / m ^2. A method for producing a membrane.
[8] The method for producing a composite membrane according to any one of [1] to [7], wherein the porous substrate is a polyolefin microporous membrane.

  According to the embodiment of the present disclosure, there is provided a method for manufacturing a composite film that can manufacture a composite film having excellent uniformity in the surface direction even when a wide porous substrate is conveyed at high speed.

It is a conceptual diagram which shows one Embodiment of the manufacturing method of this indication. It is a conceptual diagram which shows one Embodiment of the manufacturing method of this indication. It is the schematic which shows one Embodiment of a roll-shaped rotation member. 2 is a schematic view of a shaft 14. FIG. 2 is a schematic view of a shaft 14. FIG. It is the schematic which shows one Embodiment of a coating process. It is the schematic which shows one Embodiment of a coating process.

  Embodiments will be described below. These descriptions and examples illustrate the embodiments and do not limit the scope of the embodiments.

  In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

  In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .

  In this specification, the “machine direction” means the long direction in the porous base material and composite membrane produced in a long shape, and the “width direction” means the direction orthogonal to the “machine direction”. means. The “machine direction” is also referred to as “MD direction”, and the “width direction” is also referred to as “TD direction”.

  In the present disclosure, “compatible” with respect to a liquid means that they can be dissolved into each other to form a uniform solution.

<Production method of composite membrane>
The production method of the present disclosure is a method of producing a composite film including a porous substrate and a porous layer provided on one or both surfaces of the porous substrate. The manufacturing method of the present disclosure includes coating a coating liquid containing a resin and a solvent for dissolving or dispersing the resin to form a porous layer. Specifically, the following steps (1) to ( 4) is a production method in which a porous layer is provided on one or both sides of a porous substrate.

Step (1): A step of applying a liquid (also referred to as “pretreatment liquid”) that is compatible with the solvent of the coating liquid to one or both sides of the porous substrate, and having an outer peripheral layer having a porous structure The process of apply | coating the pretreatment liquid which oozes out to the outer peripheral surface from the inside of this roll-shaped rotation member using the roll-shaped rotation member provided with (it is also called a "pretreatment process").
Step (2): A step of coating the coating liquid on one or both sides of the porous substrate on which the pretreatment liquid has been applied to form a coating liquid layer (also referred to as “coating process”).
Step (3): a step of solidifying the resin contained in the coating liquid layer to obtain a composite film having a porous layer containing the resin on one or both sides of the porous substrate (also referred to as “coagulation step”) .)
Step (4): A step of removing the solvent of the coating liquid and the pretreatment liquid from the composite film (also referred to as “solvent removal step”).

  Step (3) may be a wet process or a dry process. Details of the wet process and the dry process will be described later.

  Examples of the step (4) include a step of washing the composite membrane with water and / or a step of drying the composite membrane.

  The manufacturing method of the present disclosure may further include a coating liquid preparation step for preparing a coating liquid used in step (2).

  FIG. 1 is a conceptual diagram illustrating an embodiment of a manufacturing method of the present disclosure. In FIG. 1, on the left side of the figure, a porous base material roll (roll obtained by winding a long porous base material) for production of the composite film is placed, and on the right side of the figure, the composite film is placed. A wound roll is placed. The embodiment shown in FIG. 1 includes a coating liquid preparation process, a pretreatment process, a coating process, a coagulation process, a water washing process, and a drying process. In this embodiment, the coagulation step is performed in a wet manner, and the water washing step corresponds to a solvent removal step (note that the drying step may also correspond to the solvent removal step). In the present embodiment, a pretreatment process, a coating process, a coagulation process, a water washing process, and a drying process are sequentially performed sequentially, and a coating liquid preparation process is performed in accordance with the execution timing of the coating process. Details of each step will be described later.

  FIG. 2 is a conceptual diagram illustrating another embodiment of the manufacturing method of the present disclosure. In FIG. 2, a porous base material roll (roll obtained by winding a long porous base material) used for manufacturing the composite film is placed on the left side of the figure, and the composite film is shown on the right side of the figure. A wound roll is placed. The embodiment shown in FIG. 2 has a coating liquid preparation process, a pretreatment process, a coating process, and a coagulation process. In this embodiment, the coagulation process is performed in a dry manner, and the coagulation process is also a solvent removal process. In the present embodiment, a pretreatment process, a coating process, and a coagulation process (also a solvent removal process) are sequentially performed sequentially, and a coating liquid preparation process is performed in accordance with the execution timing of the coating process. Details of each step will be described later.

  In the production method of the present disclosure, the pretreatment step is performed by applying a liquid (pretreatment solution) that is compatible with the solvent of the coating solution to be applied to the porous substrate, on one side of the porous substrate or before the coating step. It is a process of applying to both sides. Since the pretreatment liquid is a liquid that is compatible with the solvent of the coating liquid, it does not prevent the coating liquid from adhering to the surface of the porous substrate, and therefore, adhesion between the porous substrate and the porous layer is prevented. I do not disturb. Then, by performing the pretreatment step, the coating liquid is applied to the porous base material containing the liquid, so that the coating liquid and the solvent of the coating liquid soak into the porous base material. It is suppressed that a part of the resin in the coating liquid layer is solidified before the solidification step. Thereby, the porous layer is easily formed uniformly in the plane direction, and as a result, a composite film excellent in the uniformity in the plane direction can be manufactured.

  In the manufacturing method of the present disclosure, the pretreatment step uses a roll-shaped rotating member having an outer peripheral layer having a porous structure, and a pretreatment liquid that oozes out from the inside of the roll-shaped rotating member to the outer peripheral surface It is the process of apply | coating. By using the roll-shaped rotating member, even when a wide porous substrate is conveyed at high speed, the pretreatment liquid can be applied to the porous substrate with high uniformity, resulting in uniform surface direction. A composite film having excellent properties can be manufactured at a large area and at high speed. Therefore, the manufacturing method of this indication is excellent in productivity of a composite membrane. The roll-like rotating member is also advantageous from the viewpoint of less scattering of the pretreatment liquid when applying the pretreatment liquid.

  The excellent uniformity of the composite film in the plane direction means that, for example, the film thickness of the composite film and / or the force (peel strength) when peeling the porous layer from the porous substrate is the plane direction (particularly the width direction). ) Means less variation.

  Hereinafter, each process of the manufacturing method of this indication is explained in detail.

[Coating liquid preparation process]
The manufacturing method of this indication may have a coating liquid preparation process which prepares a coating liquid used for a coating process. The manufacturing method of this indication does not need to have a coating liquid preparation process, and may provide the coating liquid already manufactured and stored for the coating process.

  A coating liquid preparation process is a process of preparing the coating liquid containing resin and its solvent. The coating solution is prepared by dissolving or dispersing the resin in a solvent. The coating liquid may contain components other than the resin and the solvent, for example, a filler. The resin and filler used for the preparation of the coating liquid, that is, the resin and filler contained in the porous layer will be described in detail in the section of [Porous layer] described later.

  Examples of the solvent for dissolving the resin (also referred to as “good solvent”) used for preparing the coating liquid include polar amide solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethylformamide. From the viewpoint of forming a porous layer having a good porous structure, it is preferable to mix a phase separation agent that induces phase separation in a good solvent. Examples of the phase separation agent include water, methanol, ethanol, propyl alcohol, butyl alcohol, butanediol, ethylene glycol, propylene glycol, and tripropylene glycol. The phase separation agent is preferably mixed with the good solvent in an amount ratio within a range that can ensure the viscosity of the coating liquid suitable for coating.

  As a solvent used for the preparation of the coating liquid, from the viewpoint of forming a good porous structure, it contains 50% by mass or more (more preferably 60% by mass or more) of a good solvent and 10% by mass to 50% by mass of a phase separation agent. A mixed solvent containing (more preferably 10% by mass to 40% by mass) is preferable. From the viewpoint of forming a good porous structure, the coating liquid contains a resin at a concentration of 3% by mass to 10% by mass and a filler at a concentration of 10% by mass to 90% by mass. preferable.

  For the preparation of the coating solution, a homogenizer, a glass bead mill, a ceramic bead mill, or the like can be used in order to enhance the solubility and dispersibility of the resin and filler in a solvent. In order to further increase the dispersion efficiency, pre-dispersion in a dispersant may be performed before the resin or filler is mixed with the solvent.

  The viscosity of the coating liquid is preferably from 0.1 Pa · s to 5.0 Pa · s from the viewpoint of the suitability for application to the porous substrate. The viscosity of the coating liquid can be controlled by the composition ratio of the solvent, the resin and the filler.

[Pretreatment process]
A pretreatment process is a process of apply | coating the liquid (pretreatment liquid) which is compatible with the solvent of a coating liquid to the single side | surface or both surfaces of a porous base material. The pretreatment step is a step of applying a pretreatment liquid that oozes out from the inside of the roll-shaped rotating member to the outer peripheral surface using a roll-shaped rotating member having an outer peripheral layer having a porous structure. It is.

-Pretreatment liquid-
The pretreatment liquid is a liquid that is applied to the porous substrate before the coating step for the purpose of preventing the coating liquid and the solvent of the coating liquid from entering the porous substrate.

Examples of the pretreatment liquid include the following (i) to (iv).
(I) The same type of liquid as the good solvent contained in the coating liquid.
(Ii) The same type of liquid as the phase separation agent contained in the coating liquid.
(Iii) A good solvent different from the good solvent contained in the coating liquid, which is compatible with the good solvent contained in the coating liquid.
(Iv) A liquid in which at least two selected from (i) to (iii) are mixed.

  Examples of (i) and (iii) include polar amide solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethylformamide. Examples of (ii) include water, methanol, ethanol, propyl alcohol, butyl alcohol, butanediol, ethylene glycol, propylene glycol, and tripropylene glycol.

  The pretreatment liquid is preferably a liquid containing at least the above (i) or (iii) from the viewpoint of suppressing the solidification of the resin before the solidification step at the interface between the pretreatment liquid and the coating liquid, A liquid containing at least the above (i) is more preferable, and a liquid having the same composition as the solvent of the coating liquid is particularly preferable. Specifically, the (i) is contained in an amount of 50% by mass or more (more preferably 60% by mass or more), and the (ii) is contained in an amount of 10% by mass to 50% by mass (more preferably 10% by mass to 40% by mass). Mixed solvents are preferred.

The coating amount of the pretreatment liquid to the porous ^{substrate, 1g / m 2 ~30g / m} 2 is preferred. When the application amount of the pretreatment liquid is 1 g / m ² or more, it is possible to sufficiently suppress the coating liquid and the solvent of the coating liquid from penetrating into the porous substrate. From the above viewpoint, the coating amount of the pretreatment liquid is more preferably 3 g / m ² or more, and further preferably 5 g / m ² or more. On the other hand, when the coating amount of the pretreatment liquid is 30 g / m ² or less, uneven coating of the coating liquid is unlikely to occur. From the above viewpoint, the coating amount of the pretreatment liquid is more preferably 20 g / m ² or less, and still more preferably 15 g / m ² or less.

  The temperature of the pretreatment liquid when applied to the porous substrate is, for example, 10 ° C to 50 ° C.

  When application of the coating liquid is performed only on one side of the porous substrate, in the pretreatment step, the pretreatment liquid may be applied only to that side, and the pretreatment liquid is applied only to the opposite side. Application of the pretreatment liquid may be performed on both sides.

  When application of the coating liquid is performed on both surfaces of the porous substrate, in the pretreatment step, the pretreatment liquid may be applied only to one surface of the porous substrate, Alternatively, the pretreatment liquid may be applied.

-Roll-shaped rotating member-
In the manufacturing method of the present disclosure, the roll-shaped rotating member used for application of the pretreatment liquid includes an outer peripheral layer having a porous structure, and the member from which the pretreatment liquid oozes from the inside to the outer peripheral surface through the porous structure It is.

  Examples of the material of the outer peripheral layer of the roll-shaped rotating member include inorganic materials such as ceramics, metal, and glass; organic materials such as synthetic resins (for example, urethane, polypropylene, polyester, fluorine resin, nylon), and cellulose. The material of the outer peripheral layer of the roll-shaped rotating member is preferably a material that is durable to the pretreatment liquid. For example, an organic material such as synthetic resin or cellulose may be dissolved in an organic solvent such as N-methylpyrrolidone or dimethylacetamide. Therefore, when an organic solvent is used as the pretreatment liquid, an organic layer is formed on the outer peripheral layer of the roll-shaped rotating member. When the material is applied, the outer peripheral layer may be dissolved or damaged. On the other hand, since organic materials such as synthetic resin and cellulose are difficult to dissolve in an aqueous solvent, when an aqueous solvent is used as the pretreatment liquid, the organic material can be applied to the outer peripheral layer of the roll-shaped rotating member. That is, it is necessary to select the material of the outer peripheral layer of the roll-shaped rotating member in consideration of dissolution resistance with respect to the pretreatment liquid.

  As the outer peripheral layer of the roll-shaped rotating member, specifically, porous ceramics, urethane foam, resin fiber nonwoven fabric, glass fiber nonwoven fabric, metal fiber nonwoven fabric, paper, natural fiber woven fabric, natural fiber nonwoven fabric, Examples thereof include porous synthetic rubber.

  The outer peripheral layer of the roll-shaped rotating member is preferably a porous ceramic. Porous ceramics have high resistance to dissolution in both organic solvents and aqueous solvents, and the porous structure is not easily damaged by the pretreatment liquid. Therefore, when porous ceramics are applied to the outer peripheral layer of the roll-shaped rotating member, the types of solvents that can be used as the pretreatment liquid can be expanded, and various types of coating layers can be formed. Moreover, since the porous ceramic has high surface smoothness, it is difficult to damage the porous substrate. Further, since the porous ceramic has a porous structure with a high curvature, the pretreatment liquid slowly oozes out on the outer peripheral surface and is thinly placed on the outer peripheral surface, so that it is easy to control the application amount of the pretreatment liquid.

  The outer peripheral layer of the roll-shaped rotating member is preferably a porous layer having an average pore diameter of 2 μm to 20 μm. When the average pore diameter of the outer peripheral layer is within the above range, it is easy to control the amount of the pretreatment liquid that oozes out to the outer peripheral surface. From the above viewpoint, the average pore diameter of the outer peripheral layer is preferably 2 μm or more, more preferably 5 μm or more, preferably 20 μm or less, more preferably 10 μm or less. The average pore diameter of the outer peripheral layer of the roll-shaped rotating member is a value measured using a palm porometer based on a mercury intrusion method.

  The outer peripheral layer of the roll-shaped rotating member may be a single porous layer or a multilayer porous layer in which the same kind of materials or different kinds of materials are laminated. When the outer peripheral layer of the roll-shaped rotating member is a multilayer, it is preferable that at least the outermost peripheral layer is a porous ceramic.

  The outer peripheral layer of the roll-shaped rotating member has a layer thickness of 5 mm to 10 mm, for example. The axial length of the outer peripheral layer of the roll-shaped rotating member is not particularly limited as long as it is equal to or larger than the width of the porous substrate, and is, for example, a length of +0 cm to +50 cm with respect to the width of the porous substrate. The outer diameter of the roll-shaped rotating member is, for example, 50 mm to 200 mm.

  The roll-like rotating member may be a driving roll that is rotated by a motor, or a driven roll that is rotated according to the conveyance of the porous substrate.

  Hereinafter, exemplary embodiments of the roll-shaped rotating member will be described with reference to the drawings, but it is a matter of course that the manufacturing method of the present disclosure is not limited to these examples.

  FIG. 3 is a schematic view illustrating an example of a roll-shaped rotating member. A roll-shaped rotating member 10 shown in FIG. 3 includes an outer peripheral layer 12 and a shaft 14.

  The outer peripheral layer 12 is a layer having a porous structure. The outer peripheral layer 12 is disposed on the outer peripheral surface of the shaft 14 and constitutes the outer peripheral surface of the roll-shaped rotating member 10. The outer peripheral layer 12 is, for example, a porous ceramic. The pretreatment liquid oozes out from the inner peripheral surface side of the outer peripheral layer 12 to the outer peripheral surface through the porous structure.

  The shaft 14 is a hollow member made of metal (stainless steel, aluminum, iron, brass, copper, etc.), for example. Both axial ends of the shaft 14 are held by bearings (not shown) so that the shaft 14 is rotatable. The pretreatment liquid flows through the hollow portion of the shaft 14.

  The shaft 14 has a through-hole in the area | region where the outer peripheral layer 12 is arrange | positioned of the outer peripheral surface. 4A and 4B are schematic views of the shaft 14 in a state where the outer peripheral layer 12 is removed from the roll-shaped rotating member 10, and an example of a through hole that the shaft 14 has on the outer peripheral surface is shown. The through hole 16a shown in FIG. 4A has a circular opening, and a plurality of the through holes 16a are provided periodically. The through holes 16b shown in FIG. 4B are slits that are orthogonal to the axial direction of the shaft 14, and a plurality of the through holes 16b are provided at predetermined intervals. The pretreatment liquid moves from the hollow portion of the shaft 14 to the outer peripheral layer 12 through the through hole 16a (or the through hole 16b).

  One embodiment of the shaft 14 is a hollow member having both axial ends open. In this embodiment, the pretreatment liquid flows through the hollow portion of the shaft 14 in one direction in the axial direction, and a part of the pretreatment liquid passes through the through hole 16a (or the through hole 16b) to the outer peripheral layer 12 in the meantime. Transition. Then, the pretreatment liquid oozes out to the outer peripheral surface through the porous structure of the outer peripheral layer 12. The pretreatment liquid that has flowed out of the shaft 14 without moving to the outer peripheral layer 12 is preferably circulated into the hollow portion of the shaft 14.

  In another embodiment of the shaft 14, one end is an open end, the other end is a closed end, the hollow portion is divided into two chambers that are long in the axial direction by a partition member, and the two chambers are closed. It is a hollow member connected on the end side. In this embodiment, the pretreatment liquid flows into one chamber from the open end of the shaft 14 and flows into the other chamber on the closed end side. A part of the pretreatment liquid moves to the outer peripheral layer 12 through the through hole 16a (or the through hole 16b) while flowing through the two chambers. Then, the pretreatment liquid oozes out to the outer peripheral surface through the porous structure of the outer peripheral layer 12. The pretreatment liquid that has flowed out of the shaft 14 without moving to the outer peripheral layer 12 is preferably circulated into the hollow portion of the shaft 14.

[Coating process]
The coating process is a process of forming a coating liquid layer by coating a coating liquid containing a resin and its solvent on one or both surfaces of a porous substrate.

  The coating process is performed after the pretreatment process and before the pretreatment liquid is lost from the porous substrate by drying. The time from the application of the pretreatment liquid to the porous substrate to the application of the coating liquid is preferably within 5 minutes, for example.

  Examples of the coating method of the coating liquid on the porous substrate include die coating, roll coating, gravure coating, bar coating, and knife coating.

  One embodiment of the coating step is a step of applying the coating liquid using a coating unit that does not include a pressing unit that presses the porous substrate against the coating unit. In this embodiment, the coating means does not make surface contact with the porous base material, and the coating means makes a coating in contact with the porous base material linearly in the width direction. Although this embodiment is preferable from the viewpoint of increasing the conveyance speed of the porous substrate, the higher the conveyance speed of the porous substrate, the more easily the non-uniformity of the porous layer becomes apparent. According to the manufacturing method of the present disclosure, even when the coating process adopts the present embodiment to increase the transport speed of the porous substrate, it is possible to manufacture a composite film having excellent uniformity in the surface direction. it can. Examples of the coating method that employs the present embodiment include die coating, roll coating, and gravure coating.

  One embodiment of the coating process includes a first coating means for coating one surface and a second coating for coating the other surface, which are arranged to face each other with a porous substrate interposed therebetween. In this step, the coating liquid is simultaneously coated on both surfaces of the porous substrate using the means.

  One embodiment of the coating process includes a first coating means for coating one surface and a second coating for coating the other surface, which are arranged apart in the transport direction of the porous substrate. In this step, the coating solution is sequentially applied to both surfaces of the porous base material one by one using a processing means. The present embodiment will be described with reference to FIGS. 5A and 5B. FIG. 5A and FIG. 5B are schematic views each showing an embodiment of a coating process.

  In the embodiment shown in FIG. 5A, the coating method is die coating, and the support roll 51, the die coater 21 (first coating means), the die coater 22 ( The second coating means) and the support roll 52 are arranged in order. The die coater 21 and the die coater 22 are spaced apart in the transport direction of the porous substrate 71. In the embodiment shown in FIG. 5A, the die coater 21 and the die coater 22 are not provided with a backup roll (a pressing means for pressing the porous substrate against the coating means). Does not come into surface contact with the porous base material 71 but comes into contact with the porous base material 71 linearly in the width direction. Although the backup roll may be arrange | positioned at the die-coater 21 and the die-coater 22, it is preferable that the backup roll is not arrange | positioned from a viewpoint which can speed up the conveyance speed of a porous base material.

  In the embodiment shown in FIG. 5A, first, the coating liquid is applied to one surface of the porous substrate 71 by the die coater 21, and subsequently, the coating is applied to the other surface of the porous substrate 71 by the die coater 22. Apply liquid.

  In the embodiment shown in FIG. 5B, the coating method is gravure coating, and from the upstream side in the transport direction of the porous substrate 71, the support roll 51, the gravure coater 41 (first coating means), and the gravure coater 42 ( The second coating means) and the support roll 52 are arranged in order. The gravure coater 41 and the gravure coater 42 are spaced apart from each other in the transport direction of the porous substrate 71. Since the gravure coater 41 and the gravure coater 42 are not provided with a backup roll (pressing means for pressing the porous base material against the coating means), the gravure coater 41 and the gravure coater 42 face the porous base material 71. It does not contact, but contacts the porous substrate 71 linearly in the width direction. Although the backup roll may be arrange | positioned at the gravure coater 41 and the gravure coater 42, it is preferable that the backup roll is not arrange | positioned from a viewpoint which can speed up the conveyance speed of a porous base material.

  In the embodiment shown in FIG. 5B, first, a coating liquid is applied to one surface of the porous substrate 71 by the gravure coater 41, and then applied to the other surface of the porous substrate 71 by the gravure coater 42. Apply liquid.

  As shown in FIG. 5A and FIG. 5B, in the embodiment in which two coating units are arranged apart from each other in the conveying direction of the porous substrate and coating is performed one side at a time, the two coating units are interposed via the porous substrate. The porous substrate is less likely to be scratched and the thickness of the coating liquid layer can be easily controlled on a surface-by-surface basis, compared to the embodiment in which coating is performed on both sides simultaneously. The conveyance speed can be increased. According to the manufacturing method of the present disclosure, even when the embodiment in which coating is performed on each side is employed to increase the transport speed of the porous substrate, a composite film having excellent surface direction uniformity is manufactured. be able to.

  From the viewpoint of production efficiency, the conveyance speed of the porous substrate in the coating process is preferably 20 m / min or more, more preferably 30 m / min or more, and further preferably 40 m / min or more. According to the production method of the present disclosure, even when a wide porous substrate is conveyed at a high speed (for example, 20 m / min or more), a composite film having excellent uniformity in the plane direction can be produced. The transport speed is preferably faster to some extent from the viewpoint of producing a composite film that is more excellent in uniformity in the plane direction, and the above range is preferable. The upper limit of the conveyance speed is preferably 150 m / min or less, more preferably 100 m / min or less, from the viewpoint of suppressing the occurrence of coating unevenness.

The coating amount of the coating liquid, the sum of both sides, such as ^{10g / m 2 ~60g / m 2} .

[Coagulation process]
The coagulation process is a wet process in which the coating liquid layer is brought into contact with the coagulation liquid to solidify the resin contained in the coating liquid layer to obtain a porous layer; the solvent contained in the coating liquid layer is removed and the coating liquid is removed. Any of the dry process of solidifying the resin contained in the layer to obtain a porous layer may be used. Since the porous layer tends to be denser in the dry process than in the wet process, the wet process is preferable from the viewpoint of obtaining a good porous structure.

  In the wet process, it is preferable to immerse the porous substrate having the coating liquid layer in the coagulation liquid, and specifically, it is preferable to pass through a tank (coagulation tank) containing the coagulation liquid.

  The coagulating liquid used in the wet process is generally a mixed solution of a good solvent and a phase separation agent used for preparing the coating liquid and water. It is preferable in production that the mixing ratio of the good solvent and the phase separation agent is matched to the mixing ratio of the mixed solvent used for preparing the coating liquid. The concentration of water is appropriately 40% by mass to 80% by mass with respect to the total amount of the coagulating liquid, from the viewpoint of formation of the porous structure and productivity. The temperature of the coagulation liquid is, for example, 20 ° C to 50 ° C.

  When the coagulation process is a dry process, the coagulation process is also a solvent removal process. By this step, the liquid component (the pretreatment liquid applied to the porous substrate and the solvent of the coating liquid) contained in the composite film is removed. The method for removing the liquid component from the composite film is not limited, for example, a method in which the composite film is brought into contact with the heating member; a method in which the composite film is transported into a chamber adjusted in temperature and humidity; a method in which hot air is applied to the composite film And so on. When heat is applied to the composite membrane, the temperature is, for example, 50 ° C. or higher and below the melting point of the porous substrate.

[Washing process]
One embodiment of the manufacturing method of the present disclosure employs a wet process for the coagulation process, and includes a water washing process for washing the composite membrane after the coagulation process. The water washing step is a step performed for the purpose of removing liquid components other than water (pretreatment liquid applied to the porous substrate, solvent for the coating liquid, and solvent for the coagulation liquid) contained in the composite membrane. is there. When the coagulation process is a wet process, the water washing process corresponds to the solvent removal process. Specifically, the water washing step is preferably performed by transporting the composite membrane through a water bath. The temperature of the water for washing is, for example, 0 ° C to 70 ° C.

[Drying process]
One embodiment of the manufacturing method of the present disclosure includes a drying step of removing water from the composite membrane after the water washing step. The drying process may also correspond to a solvent removal process. The method for removing water from the composite membrane is not limited, for example, a method in which the composite membrane is brought into contact with a heating member; a method in which the composite membrane is transported into a chamber adjusted in temperature and humidity; a method in which hot air is applied to the composite membrane; Etc. When heat is applied to the composite membrane, the temperature is, for example, 50 ° C. or higher and below the melting point of the porous substrate.

The manufacturing method of the present disclosure may adopt the following embodiment from the viewpoint of improving coating quality or productivity.
As a part of the coating liquid preparation step, for the purpose of removing foreign substances from the solvent for preparing the coating liquid, a process of passing the solvent through a filter is performed before mixing with the resin. The retained particle diameter of the filter used for this treatment is, for example, 0.1 μm to 100 μm.
-A stirrer is installed in the tank for carrying out the coating liquid preparation step, and the coating liquid is constantly stirred with the stirrer to suppress sedimentation of solid components (for example, filler) in the coating liquid.
-The piping that transports the coating liquid from the coating liquid preparation process to the coating process is circulated, and the coating liquid is circulated in the pipe to suppress aggregation of solid components in the coating liquid. In this case, it is preferable to control the temperature of the coating liquid in the pipe to be constant. The length of the pipe is 20 m, for example.
-A filter is installed in the middle of the pipe that transports the coating liquid from the coating liquid preparation process to the coating process, and aggregates and / or foreign matters in the coating liquid are removed.
-As a pump for supplying the coating liquid from the coating liquid preparation process to the coating process, for example, a non-pulsation metering pump is installed.
-A static eliminating device is arranged upstream of the pretreatment process and / or between the pretreatment process and the coating process to neutralize the surface of the porous substrate.
A housing is provided around the coating means to keep the environment of the coating process clean and to control the temperature and humidity of the atmosphere of the coating process.
・ A sensor for detecting the coating amount is arranged downstream of the coating means to correct the coating amount in the coating process.

  Hereinafter, the porous base material and the porous layer of the composite membrane will be described in detail.

[Porous substrate]
In the present disclosure, the porous substrate means a substrate having pores or voids therein. Examples of such a substrate include a microporous film; a porous sheet made of a fibrous material such as a nonwoven fabric and paper; a composite porous material in which one or more other porous layers are laminated on the microporous film or the porous sheet. Quality sheet; and the like. In the present disclosure, a microporous membrane is preferable from the viewpoint of thinning and strength of the composite membrane. A microporous membrane means a membrane that has a large number of micropores inside and has a structure in which these micropores are connected, allowing gas or liquid to pass from one surface to the other. To do.

  The material for the porous substrate is preferably an electrically insulating material, and may be either an organic material or an inorganic material.

  As a material for the porous substrate, a thermoplastic resin is preferable from the viewpoint of providing a shutdown function to the porous substrate. The shutdown function means that when the composite membrane is applied to the battery separator, when the battery temperature rises, the constituent materials dissolve and block the pores of the porous substrate, thereby blocking the movement of ions. A function that prevents thermal runaway. As the thermoplastic resin, a thermoplastic resin having a melting point of less than 200 ° C. is suitable, and polyolefin is particularly preferable.

  As the porous substrate, a microporous membrane containing polyolefin (referred to as “polyolefin microporous membrane”) is preferable. Examples of the polyolefin microporous membrane include polyolefin microporous membranes that are applied to conventional battery separators, and it is preferable to select one having sufficient mechanical properties and material permeability.

  The polyolefin microporous membrane preferably contains polyethylene from the viewpoint of exhibiting a shutdown function, and the polyethylene content is preferably 95% by mass or more based on the total mass of the polyolefin microporous membrane.

  The polyolefin microporous membrane is preferably a polyolefin microporous membrane containing polyethylene and polypropylene from the viewpoint of heat resistance that does not easily break when exposed to high temperatures. Examples of such a polyolefin microporous membrane include a microporous membrane in which polyethylene and polypropylene are mixed in one layer. Such a microporous membrane preferably contains 95% by mass or more of polyethylene and 5% by mass or less of polypropylene from the viewpoint of achieving both a shutdown function and heat resistance. Further, from the viewpoint of achieving both a shutdown function and heat resistance, the polyolefin microporous membrane has a laminated structure of two or more layers, and at least one layer contains polyethylene and at least one layer contains polypropylene. A membrane is also preferred.

  The polyolefin contained in the polyolefin microporous membrane is preferably a polyolefin having a weight average molecular weight of 100,000 to 5,000,000. When the weight average molecular weight of the polyolefin is 100,000 or more, sufficient mechanical properties can be secured. On the other hand, when the weight average molecular weight of the polyolefin is 5 million or less, the shutdown characteristics are good and the film can be easily formed.

  As a method for producing a polyolefin microporous membrane, a melted polyolefin resin is extruded from a T-die to form a sheet, which is crystallized and then stretched, and then heat-treated to form a microporous membrane: liquid paraffin, etc. Examples include a method in which a polyolefin resin melted together with a plasticizer is extruded from a T-die, cooled, formed into a sheet, and stretched, and then the plasticizer is extracted and heat-treated to form a microporous film.

  Examples of porous sheets made of fibrous materials include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; heat-resistant resins such as aromatic polyamide, polyimide, polyethersulfone, polysulfone, polyetherketone, and polyetherimide; cellulose And a porous sheet made of a fibrous material such as non-woven fabric and paper. The heat resistant resin refers to a resin having a melting point of 200 ° C. or higher, or a resin having no melting point and a decomposition temperature of 200 ° C. or higher.

  Examples of the composite porous sheet include a sheet in which a functional layer is laminated on a porous sheet made of a microporous film or a fibrous material. Such a composite porous sheet is preferable from the viewpoint of further function addition by the functional layer. Examples of the functional layer include a porous layer made of a heat resistant resin and a porous layer made of a heat resistant resin and an inorganic filler from the viewpoint of imparting heat resistance. Examples of the heat resistant resin include one or more heat resistant resins selected from aromatic polyamide, polyimide, polyethersulfone, polysulfone, polyetherketone and polyetherimide. Examples of the inorganic filler include metal oxides such as alumina; metal hydroxides such as magnesium hydroxide. As a composite method, a method of applying a functional layer to a microporous film or a porous sheet; a method of bonding a microporous film or a porous sheet and a functional layer with an adhesive; a microporous film or a porous sheet; The method of thermocompression bonding with a functional layer; etc. are mentioned.

  The width of the porous substrate is preferably 0.3 m to 3.0 m from the viewpoint of compatibility with the manufacturing method of the present disclosure. According to the manufacturing method of the present disclosure, even when a wide porous substrate (for example, a width of 0.5 m or more) is transported at a high speed, a composite film excellent in surface direction uniformity can be manufactured. .

  The length of the porous substrate is preferably 50 m or more from the viewpoint of suitability for the production method of the present disclosure.

  The thickness of the porous substrate is preferably 5 μm to 50 μm from the viewpoint of mechanical strength.

  From the viewpoint of mechanical strength, the breaking elongation of the porous substrate is preferably 10% or more in the MD direction, more preferably 20% or more, more preferably 5% or more in the TD direction, and more preferably 10% or more. The breaking elongation of the porous substrate is determined by conducting a tensile test at a tensile rate of 100 mm / min using a tensile tester in an atmosphere at a temperature of 20 ° C.

  The Gurley value (JIS P8117: 2009) of the porous substrate is preferably 50 seconds / 100 cc to 800 seconds / 100 cc from the viewpoint of mechanical strength and material permeability.

  The porosity of the porous substrate is preferably 20% to 60% from the viewpoints of mechanical strength, handling properties, and material permeability.

  The average pore diameter of the porous substrate is preferably 20 nm to 100 nm from the viewpoint of substance permeability. The average pore diameter of the porous substrate is a value measured using a palm porometer according to ASTM E1294-89.

[Porous layer]
In the present disclosure, the porous layer has a structure in which a large number of micropores are formed in the inside and these micropores are connected to each other, and a gas or liquid can pass from one surface to the other surface. It is.

  When the composite membrane is applied to a battery separator, the porous layer is preferably an adhesive porous layer that can adhere to an electrode. The adhesive porous layer is preferably on both sides rather than on only one side of the porous substrate.

  The thickness of the porous layer is preferably 0.5 μm to 5 μm on one side of the porous substrate from the viewpoint of mechanical strength.

  The porosity of the porous layer is preferably 30% to 80% from the viewpoints of mechanical strength, handling properties, and material permeability.

  The average pore diameter of the porous layer is preferably 20 nm to 100 nm from the viewpoint of substance permeability. The average pore diameter of the porous layer is a value measured using a palm porometer according to ASTM E1294-89.

  The porous layer is formed by applying a coating liquid containing at least a resin and its solvent. Therefore, the porous layer contains at least a resin. The porous layer may further contain a filler and the like. Hereinafter, components such as a resin contained in the coating liquid and the porous layer will be described.

[resin]
The type of resin contained in the porous layer is not limited. As resin contained in a porous layer, what has a function which fixes a filler (what is called binder resin) is preferable. The resin contained in the porous layer is preferably a hydrophobic resin from the viewpoint of production compatibility when the composite membrane is produced by a wet process. When the composite membrane is applied to a battery separator, the resin contained in the porous layer is stable in an electrolytic solution, electrochemically stable, has a function of immobilizing inorganic particles, and adheres to an electrode. What is obtained is preferred. The porous layer may contain one kind of resin or two or more kinds.

  Examples of the resin include polyvinylidene fluoride, polyvinylidene fluoride copolymer, styrene-butadiene copolymer, homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile, polyethylene oxide, polypropylene oxide, and the like. Polyethers are preferred. Among these, polyvinylidene fluoride and a polyvinylidene fluoride copolymer (these are referred to as “polyvinylidene fluoride resins”) are particularly preferable.

  As the polyvinylidene fluoride resin, a homopolymer of vinylidene fluoride (that is, polyvinylidene fluoride); a copolymer of vinylidene fluoride and another copolymerizable monomer (polyvinylidene fluoride copolymer); a mixture thereof ; Examples of the monomer copolymerizable with vinylidene fluoride include tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, trichloroethylene, vinyl fluoride and the like, and one kind or two or more kinds can be used. The polyvinylidene fluoride resin can be produced by emulsion polymerization or suspension polymerization.

  The resin contained in the porous layer is preferably a heat-resistant resin (a resin having a melting point of 200 ° C. or higher, or a resin having no melting point and a decomposition temperature of 200 ° C. or higher) from the viewpoint of heat resistance. Examples of the heat resistant resin include polyamide (nylon), wholly aromatic polyamide (aramid), polyimide, polyamideimide, polysulfone, polyketone, polyetherketone, polyethersulfone, polyetherimide, cellulose, and a mixture thereof. It is done. Among them, wholly aromatic polyamides are preferable from the viewpoints of easy formation of a porous structure, binding properties with inorganic particles, oxidation resistance, and the like. Among wholly aromatic polyamides, meta-type wholly aromatic polyamides are preferable from the viewpoint of easy molding, and polymetaphenylene isophthalamide is particularly preferable.

  In the present disclosure, a particulate resin or a water-soluble resin may be used as the resin. Examples of the particulate resin include particles containing a resin such as polyvinylidene fluoride resin, fluorine rubber, and styrene-butadiene rubber. The particulate resin can be dispersed in a dispersion medium such as water and used for preparing a coating liquid. Examples of the water-soluble resin include cellulose resins and polyvinyl alcohol. The water-soluble resin can be dissolved in water, for example, and used for preparing a coating solution. The particulate resin and the water-soluble resin are suitable when the coagulation step is carried out by a dry method.

[Filler]
The filler may be either an inorganic filler or an organic filler. The filler preferably has a volume average particle size of primary particles of 0.01 μm to 10 μm, more preferably 0.1 μm to 10 μm, and still more preferably 0.1 μm to 3.0 μm.

  The porous layer preferably contains inorganic particles as a filler. The inorganic particles contained in the porous layer are preferably those that are stable to the electrolytic solution and electrochemically stable. The porous layer may contain one kind of inorganic particles or two or more kinds.

  Examples of the inorganic particles include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, cerium hydroxide, nickel hydroxide, boron hydroxide; silica, alumina, zirconia And metal oxides such as magnesium oxide; carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and calcium sulfate; clay minerals such as calcium silicate and talc; Among these, metal hydroxides and metal oxides are preferable from the viewpoints of imparting flame retardancy and neutralizing effect. The inorganic particles may be surface-modified with a silane coupling agent or the like.

  The particle shape of the inorganic particles is arbitrary, and may be spherical, elliptical, plate-like, needle-like, or indefinite. The volume average particle size of the primary particles of the inorganic particles is preferably 0.01 μm to 10 μm, and preferably 0.1 μm to 10 μm from the viewpoints of the moldability of the porous layer, the material permeability of the composite membrane, and the slipperiness of the composite membrane. More preferably, 0.1 μm to 3.0 μm is even more preferable.

  When the porous layer contains inorganic particles, the proportion of the inorganic particles in the total amount of the resin and the inorganic particles is, for example, 30% by volume to 90% by volume.

  The porous layer may contain an organic filler as a filler. Examples of the organic filler include cross-linked poly (meth) acrylic acid, cross-linked poly (meth) acrylic acid ester, cross-linked polysilicon, cross-linked polystyrene, cross-linked polydivinylbenzene, styrene-divinylbenzene copolymer cross-linked product, polyimide, and melamine resin. And particles made of a crosslinked polymer such as a phenol resin and a benzoguanamine-formaldehyde condensate; particles made of a heat-resistant resin such as polysulfone, polyacrylonitrile, aramid, polyacetal, and thermoplastic polyimide.

[Characteristics of composite membrane]
The thickness of the composite film is, for example, 5 μm to 100 μm, and in the case of a battery separator, for example, 5 μm to 50 μm.

  The Gurley value (JIS P8117: 2009) of the composite membrane is preferably 50 seconds / 100 cc to 800 seconds / 100 cc from the viewpoint of mechanical strength and material permeability.

  The porosity of the composite membrane is preferably 30% to 60% from the viewpoints of mechanical strength, handling properties, and material permeability.

  In the present disclosure, the porosity of the composite membrane is determined by the following equation. The same applies to the porosity of the porous substrate and the porosity of the porous layer.

  Porosity (%) = {1− (Wa / da + Wb / db + Wc / dc +... + Wn / dn) / t} × 100

Wa, Wb, Wc, ..., Wn are the masses (g / cm ² ) of the constituent materials a, b, c, ..., n, and da, db, dc, ..., dn are constituent materials a, b, c,..., n is the true density (g / cm ³ ), and t is the film thickness (cm).

[Use of composite membrane]
Applications of the composite membrane include, for example, battery separators, capacitor films, gas filters, liquid filters, and the like, and particularly preferable applications include non-aqueous secondary battery separators.

  The production method of the present disclosure will be described more specifically with reference to examples. However, the manufacturing method of this indication is not limited to a following example.

<Quality evaluation method for composite membrane>
The composite films produced in the following examples and comparative examples were evaluated by the following quality evaluation method.

[Thickness uniformity]
The thickness (μm) of the composite film was measured at 20 points at intervals of 4 cm in the width direction with a contact-type thickness gauge (Mitutoyo Corporation LITEMASIC, measuring terminal: cylindrical terminal with a diameter of 5 mm, applied load: 7 g), The average of 20 points was calculated and classified as follows.

A: The film thickness difference at each measurement point with respect to the average film thickness is less than 0.2 μm.
B: There is one measurement point having a film thickness difference of 0.2 μm or more and less than 0.5 μm with respect to the average film thickness, and the other measurement points have a film thickness difference of less than 0.2 μm with respect to the average film thickness.
C: There are 2 to 4 measurement points having a film thickness difference of 0.2 μm or more and less than 0.5 μm with respect to the average film thickness, and other measurement points have a film thickness difference of less than 0.2 μm with respect to the average film thickness. It is.
D: There are 5 or more measurement points with a film thickness difference of 0.2 μm or more and less than 0.5 μm with respect to the average film thickness, and other measurement points have a film thickness difference of less than 0.2 μm with respect to the average film thickness. .
E: There are 5 or more measurement points with a film thickness difference of 0.2 μm or more and less than 0.5 μm with respect to the average film thickness, and 1 or more measurement points with a film thickness difference of 0.5 μm or more with respect to the average film thickness. is there.

[Uniformity of peel strength]
The composite membrane was cut out from a total of 5 locations, 1 cm inside and 20 cm inside from one end, 1 cm inside and 20 cm inside from the other end, 1 cm in TD direction, 10 cm in MD direction, and 3M company on one side. A mending tape was applied as a test piece. The mending tape is peeled off together with the porous layer directly below from one end in the length direction of the test piece (that is, MD direction of the composite membrane), and the two separated ends are turned into Tensilon (Orientec RTC-1210A). A T-peeling test was performed by gripping. The tensile rate of the T-peel test is 20 mm / min, the load (N) when the porous layer is peeled from the porous substrate is measured, and the load from 10 mm to 40 mm is sampled at intervals of 0.4 mm after the measurement is started. The average was calculated. Furthermore, the average of the measured values of 5 test pieces was calculated and classified as follows.

A: The strength difference of each test piece is less than 0.02N with respect to the average strength of 5 test pieces.
B: There is a test piece having a strength difference of 0.02N or more and less than 0.04N with respect to the average strength of five test pieces.
C: There is a test piece having a strength difference of 0.04 N or more and less than 0.06 N with respect to the average strength of five test pieces.
D: There is a test piece having a strength difference of 0.06 N or more and less than 0.08 N with respect to the average strength of five test pieces.
E: There is a test piece having a strength difference of 0.08 N or more with respect to the average strength of five test pieces.

<Manufacture of composite membrane>
[Example 1]
-Coating liquid preparation process-
Polymetaphenylene isophthalamide (PMIA) is dissolved in a mixed solvent (mass ratio 1: 1) of dimethylacetamide (DMAc) and tripropylene glycol (TPG), and further aluminum hydroxide particles (Al (OH) ₃ , primary particles). The volume average particle size of 0.8 μm) was dispersed to prepare a coating solution. The composition (mass ratio) of the coating solution was PMIA: Al (OH) ₃ : DMAc: TPG = 4: 16: 40: 40.

-Pretreatment process-
A long polyethylene microporous film having a width of 0.8 m (film thickness: 10 μm) was prepared as a porous substrate. DMAc and TPG were mixed at a mass ratio of 1: 1 to prepare a pretreatment liquid. As a means for applying the pretreatment liquid, a ceramic roll having a shape shown in FIG. 3 (a roll having a stainless steel hollow shaft having a shape shown in FIG. 4A and a porous ceramic outer peripheral layer. An axial length of 1.2 m, an outer peripheral layer thickness of 5 mm, and an outer peripheral layer average pore diameter of 10 μm were prepared.

  The outer peripheral surface of the ceramic roll in which the pretreatment liquid was circulated and supplied to the hollow shaft was brought into contact with the porous substrate being conveyed, and the pretreatment liquid was applied to one side of the porous substrate.

-Coating process-
As shown in FIG. 5A, the coating solution was applied to both sides of the porous substrate on which the pretreatment liquid was applied, by two die coaters that were arranged apart from each other in the conveyance direction of the porous substrate. The two die coaters were not provided with backup rolls, and the coating liquid was applied by bringing the die coater into linear contact with the porous substrate in the width direction.

-Solidification process-
The porous substrate after coating the coating liquid on both sides is conveyed to a coagulation tank and immersed in a coagulation liquid (water: DMAc: TPG = 43: 40: 17 [mass ratio], liquid temperature 30 ° C.). The resin contained in the coating liquid layer was solidified to obtain a composite film.

-Washing process, drying process-
The composite membrane was transported to a water bath controlled at a water temperature of 30 ° C. and washed with water, and the composite membrane after washing was passed through a drying apparatus equipped with a heating roll and dried.

  Said each process was implemented continuously and the composite film provided with the porous layer on both surfaces of the polyethylene microporous film was manufactured.

[Examples 2-3]
A composite membrane was produced in the same manner as in Example 1 except that the conveying speed of the porous substrate in the coating process was changed as shown in Table 1.

[Examples 4 to 5]
A composite membrane was produced in the same manner as in Example 1 except that the coating amount of the pretreatment liquid was changed as shown in Table 1.

[Example 6]
Example 1 except that polymetaphenylene isophthalamide was changed to polyvinylidene fluoride (PVDF) and aluminum hydroxide particles were changed to alumina particles (Al ₂ O ₃ , volume average particle diameter of primary particles 0.1 μm). A composite membrane was produced in the same manner.

[Example 7]
A composite membrane was produced in the same manner as in Example 1 except that polymetaphenylene isophthalamide was changed to polyvinylidene fluoride (PVDF) and aluminum hydroxide particles were not used.

[Comparative Example 1]
A composite membrane was produced in the same manner as in Example 1 except that the pretreatment step was not performed.

[Comparative Example 2]
The means for applying the pretreatment liquid was changed to a towel cloth (width 1.3 m) hung at a height to be in contact with the porous substrate being conveyed. The composite membrane was supplied in the same manner as in Example 1 except that the porous substrate was conveyed while being in contact with the towel fabric while the pretreatment solution was being supplied to the towel fabric, and the pretreatment solution was applied to one side of the porous substrate. Manufactured.

[Comparative Example 3]
A composite membrane was produced in the same manner as in Example 1 except that the means for applying the pretreatment liquid was changed to the slot die coater.

  Table 1 shows the results of quality evaluation of the composite films of Examples 1 to 7 and Comparative Examples 1 to 3.

  The disclosure of Japanese Patent Application No. 2015-233612 filed on November 30, 2015 is incorporated herein by reference in its entirety.

  All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Roll-shaped rotating member 12 Porous layer 14 Shaft 16a Through-hole 16b Through-hole 21, 22 Die coater 41, 42 Gravure coater 51, 52 Support roll 71 Porous base material

Claims (8)

A composite membrane comprising: a porous substrate; and a porous layer formed by applying a coating liquid containing a resin and a solvent for dissolving or dispersing the resin on one or both surfaces of the porous substrate. A method of manufacturing
(1) A step of applying a liquid compatible with the solvent to one or both sides of the porous base material, and using the roll-shaped rotating member having an outer peripheral layer having a porous structure, the roll shape Applying the liquid that oozes from the inside of the rotating member to the outer peripheral surface to the porous substrate;
(2) A step of coating the coating liquid on one or both sides of the porous substrate on which the liquid is applied to form a coating liquid layer;
(3) solidifying the resin contained in the coating liquid layer to obtain a composite film having a porous layer containing the resin on one or both surfaces of the porous substrate;
(4) removing the solvent and the liquid from the composite membrane;
A method for producing a composite membrane.   The manufacturing method of the composite film of Claim 1 whose said outer peripheral layer of the said roll-shaped rotation member is a porous layer of ceramics.   The method for producing a composite membrane according to claim 1 or 2, wherein the outer peripheral layer of the roll-shaped rotating member is a porous layer having an average pore diameter of 2 µm or more and 20 µm or less.   In the step (2), the first coating means for coating one surface and the second coating for coating the other surface, which are spaced apart in the transport direction of the porous substrate, The manufacturing method of the composite film as described in any one of Claims 1-3 which is the process of applying the said coating liquid to the both surfaces of the said porous base material one by one using a construction means. .   The said (2) process is a process of applying the said coating liquid using the application means in which the press means which presses the said porous base material to an application means is not arrange | positioned. Item 5. The method for producing a composite membrane according to any one of Items 4 to 5.   The method for producing a composite film according to any one of claims 1 to 5, wherein, in the step (2), the conveyance speed of the porous substrate is 20 m / min or more. The composite film according to any one of claims 1 to 6, wherein the step (1) is a step of applying the liquid to the porous base material in an amount of 1 g / m ² or more and 30 g / m ² or less. Manufacturing method.   The manufacturing method of the composite film as described in any one of Claims 1-7 whose said porous base material is a polyolefin microporous film.