JP2014028326A - Laminate having porus layer and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem of loss caused by separation of a base material and a porus layer during an immersion process in a method of manufacturing a laminate having the porus layer on at least one surface of the base material by casting a polymer solution in a film shape on the base material, and then immersing it in a congealed liquid, and drying.SOLUTION: A method of manufacturing a laminate prevents loss during manufacturing caused by separation of a base material and a porus layer in a manufacturing process of the laminate including the base material and the porus layer structured of a polymer on at least one surface of the base material. The porus layer is obtained by the method. As a solution, adhesiveness of the base material and the porus layer is improved by carrying out surface treatment appropriate for a surface of the base material to dissolve generation of the separation during the manufacturing.

Description

  The present invention relates to a method for producing a laminate having a porous layer in which a large number of independent micropores made of a polymer and having low connectivity are formed on at least one surface of a substrate with high yield. The laminated body having this porous layer, by utilizing the pore characteristics of the porous layer and the porous film as they are, circuit board, electromagnetic wave control material such as electromagnetic wave shield and electromagnetic wave absorber, low dielectric constant material, It can be used as a wide range of substrate materials such as antennas, separators, cushion materials, ink image-receiving sheets, insulating materials, heat insulating materials, cell culture substrates and the like.

  As a method for producing a laminate composed of a substrate and a porous layer, JP 2009-73124 A discloses a method for forming a porous layer on forming a porous layer on the surface of the substrate. A polymer solution containing molecular components is cast into a film on a substrate, and then immersed in a coagulation liquid, followed by drying. It is disclosed that a laminate having a porous layer formed with can be obtained.

JP 2009-73124 A

  Porous material disclosed in the above Japanese Patent Application Laid-Open No. 2009-73124 by “casting a polymer solution on a substrate in the form of a film, and then immersing it in a coagulation liquid and then subjecting it to drying” In the method for producing the layer, there is a case where the interface and the porous film are peeled off in the dipping step in the coagulating liquid, and there is a problem in stable production.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor has improved the adhesion between the base material and the porous layer by performing an appropriate surface treatment on the surface of the base material, and the immersion process in the coagulation liquid. Solved the peeling problem.

  The present invention includes the following inventions.

  (1) A polymer solution containing a polymer component that constitutes the porous layer is cast into a film on a substrate, and then immersed in a coagulation liquid, followed by drying. A method for producing a laminate comprising a substrate and a porous layer laminated on at least one side of the substrate, wherein the substrate is adhered to the porous layer on the surface on which the porous layer is laminated. The manufacturing method of the laminated body which uses what performed the surface treatment to improve.

  (2) The method for producing a laminate according to (1), wherein the surface treatment performed on the substrate is any one of a scratch treatment, a sand blast treatment (sand mat treatment), and a polishing sheet processing treatment.

  (3) After casting the polymer solution in the form of a film on the substrate, the polymer solution is kept for 0.2 to 15 minutes in an atmosphere having a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C. The manufacturing method of the laminated body as described in (1) or (2) immersed in.

  (4) The polymer solution is composed of 8 to 25% by weight of the polymer component to constitute the porous layer, 0 to 10% by weight of the water-soluble polymer, 0 to 10% by weight of water, and 30 to 82% by weight of the water-soluble polar solvent. The method for producing a laminate according to any one of (1) to (3), wherein the laminate is a mixed solution.

  (5) The polymer component constituting the porous membrane is a polyimide resin, polyamideimide resin, polyethersulfone resin, polyetherimide resin, polycarbonate resin, polyphenylene sulfide resin, polyester resin, liquid crystal Selected from the group consisting of polyester resins, aromatic polyamide resins, polyamide resins, polybenzoxazole resins, polybenzimidazole resins, polybenzothiazole resins, polysulfone resins, cellulose resins, and acrylic resins. The method for producing a laminate according to any one of (1) to (4), wherein the laminate is at least one kind.

  (6) Base material is polyimide resin, polyamideimide resin, polyethersulfone resin, polyetherimide resin, polycarbonate resin, polyphenylene sulfide resin, polyester resin, liquid crystalline polyester resin, aromatic polyamide Resin, polyamide resin, polybenzoxazole resin, polybenzimidazole resin, polybenzothiazole resin, polysulfone resin, cellulose resin, acrylic resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene (1) to (5) are resin films made of at least one resin material selected from the group consisting of terephthalate resins, polyetheretherketone resins, fluorine resins, olefin resins, and polyarylate resins. ) The method for producing a laminate according.

  (7) The average pore diameter of the micropores in the porous layer is 0.01 to 10 μm, the porosity is 30 to 80%, and the micropores are independent micropores having low communication properties. The manufacturing method of the laminated body as described in (6).

  (8) The average pore diameter of the micropores in the porous membrane is 0.01 to 10 μm, the porosity is 30 to 80%, the thickness of the porous membrane is 5 to 200 μm, and the Gurley value is used. The method for producing a laminate according to any one of (1) to (7), wherein the air permeability is 30 seconds / 100 cc or more.

(9) Tape peeling test based on the following method:
On the surface of the porous layer of the laminate, a masking tape [film masking tape No. 603 (# 25)] is applied for a length of 50 mm from one end of the tape, and the attached tape is pressed with a roller having a diameter of 30 mm and a load of 200 gf, and then the other end of the tape is peeled off using a tensile tester. Pulling at a speed of 50 mm / min to perform T-type peeling: The method for producing a laminate according to any one of (1) to (8), wherein interfacial peeling does not occur between the base material and the porous layer.

  (10) The method for producing a laminate according to (1) to (9), wherein the porous layer has a thickness of 0.1 to 100 μm.

  (11) The manufacturing method of the laminated body as described in (1)-(10) whose thickness of a base material is 1-1000 micrometers.

  (12) The method for producing a laminate according to any one of (1) to (11), wherein a conductor is further formed on the surface of the porous layer by printing.

  (13) The method for producing a laminate according to any one of (1) to (12), wherein the surface of the porous layer is further coated with a chemical resistant polymer.

  According to the method for producing a porous film laminate of the present invention, the interfacial peeling between the substrate and the porous film does not occur in the production process, and the porous film laminate can be produced stably.

  First, the porous layer laminate of the present invention will be described.

  The porous layer laminate of the present invention is a laminate comprising a base material and a porous layer composed of a polymer on at least one side of the base material, and an average of micropores in the porous layer The pore diameter is preferably 0.01 to 10 μm, the porosity is preferably 30 to 80%, and the micropore is a laminate that is an independent micropore with low communication.

  In the porous layer laminate of the present invention, peeling between the substrate and the porous layer does not occur during production, and after production, a tape peeling test based on the following method: 24 mm wide Teraoka Seisakusho on the porous layer surface of the laminate Masking tape [film masking tape No. 603 (# 25)] is applied for a length of 50 mm from one end of the tape. ), And then pulling the other end of the tape at a peeling speed of 50 mm / min using a tensile tester to perform T-type peeling: interfacial peeling between the substrate and the porous layer It does not cause That is, it means that the base material and the porous layer are directly laminated with an interlayer adhesion strength that does not cause interface peeling in the tape peeling test.

  As described above, the porous membrane laminate of the present invention has a structure in which the base material and the porous layer are directly laminated with a specific interlayer adhesion strength, so that while having flexibility and excellent pore characteristics, Easy to handle due to its high rigidity. In addition, since the polymer component constituting the porous layer can be widely selected, there is an advantage that it can be applied as a material in various fields. The interlayer adhesion strength between the substrate and the porous layer can be adjusted by appropriately setting the type of material constituting each layer and the physical characteristics of the interface.

  The material constituting the substrate is not particularly limited as long as it does not cause interfacial peeling from the porous layer by the tape peeling test, and can be appropriately selected according to the material constituting the porous layer. Examples of the material constituting the substrate include polyimide resins, polyamideimide resins, polyethersulfone resins, polyetherimide resins, polycarbonate resins, polyphenylene sulfide resins, polyester resins, and liquid crystalline polyester resins. , Aromatic polyamide resins, polyamide resins, polybenzoxazole resins, polybenzimidazole resins, polybenzothiazole resins, polysulfone resins, cellulose resins, acrylic resins, polyethylene terephthalate resins, polyethylene naphthalate resins Examples thereof include plastics such as resins, polybutylene terephthalate resins, polyether ether ketone resins, fluorine resins, olefin resins (including cyclic olefin resins), polyarylate resins, and the like.These materials may be used alone or in admixture of two or more, and the above-mentioned resin copolymer (graft polymer, block copolymer, random copolymer, etc.) is used alone or in combination. It is also possible. Furthermore, it is also possible to use a polymer containing the resin skeleton (polymer chain) in the main chain or side chain. Specific examples of such a polymer include polysiloxane-containing polyimide containing a polysiloxane and polyimide skeleton in the main chain.

  The substrate may be a single layer or a composite film composed of a plurality of layers made of the same or different materials. The composite film may be a laminated film obtained by laminating a plurality of films using an adhesive or the like as necessary, or may be obtained by performing a treatment such as coating, vapor deposition, or sputtering.

  The substrate in the present invention is preferably a substrate in which a change in film quality such as dissolution or severe deformation of the film does not occur when a polymer solution (coating solution) used for forming a porous layer is applied.

  As the base material in the present invention, commercially available films and the like exemplified below can also be used. As the polyimide resin film, “Kapton” manufactured by Toray DuPont Co., Ltd., “Apical” manufactured by Kaneka Co., Ltd., “Upilex” manufactured by Ube Industries, Ltd., and the like are commercially available. As the polyethylene terephthalate resin film, “Teijin Tetron Film”, “Melinex”, “Mylar” manufactured by Teijin DuPont Films Ltd., “Lumirror” manufactured by Toray Industries, Inc., etc. are commercially available. As the polyethylene naphthalate resin film, “Teonex” manufactured by Teijin DuPont Films Ltd. is commercially available.

  As a liquid crystalline polyester resin, use a film of a commercially available resin such as “Vectra” manufactured by Polyplastics Co., Ltd., “Siberus” manufactured by Toray Industries, Inc., or “Sumika Super LCP” manufactured by Sumitomo Chemical Co., Ltd. Is possible.

  Examples of the most widely used film as the olefin resin film include a polypropylene film, and a commercially available film can be easily obtained. In addition, a film made of a cyclic olefin resin having a cyclic structure can be used. For example, “TPX” manufactured by Mitsui Chemicals, Inc. “Zeonor” manufactured by Nippon Zeon Co., Ltd., “ Commercially available resins such as “TOPAS” can be used as a film.

  The base material is subjected to any one of a scratch treatment, a sand blast treatment (sand mat treatment), and an abrasive sheet processing treatment in order to improve adhesion with the porous layer and prevent peeling during production. A commercially available product that has been subjected to any of scratching, sandblasting (sand matting), and polishing sheet processing can also be used.

  The thickness of a base material is 1-300 micrometers, for example, Preferably it is 5-200 micrometers, More preferably, it is 5-100 micrometers. If the thickness is too thin, handling becomes difficult, while if it is too thick, the flexibility may decrease. The commercially available base materials exemplified above include those having a thickness of 12 μm, 12.5 μm, 25 μm, 50 μm, 75 μm, 125 μm and the like, and any of them can be used.

  The main component of the porous layer is composed of, for example, a polymer component. As the polymer component that constitutes the porous layer, it is possible to form a substrate that does not cause separation between the substrate and the porous layer at the time of manufacture, and does not cause interface separation from the porous layer by the tape peeling test after production. There is no particular limitation as long as it is present, and it can be appropriately selected according to the material constituting the substrate. Examples of the polymer component include polyimide resins, polyamideimide resins, polyethersulfone resins, polyetherimide resins, polycarbonate resins, polyphenylene sulfide resins, polyester resins, liquid crystalline polyester resins, and aromatics. Group polyamide resins, polyamide resins, polybenzoxazole resins, polybenzimidazole resins, polybenzothiazole resins, polysulfone resins, cellulose resins, acrylic resins, and the like. These polymer components may be used alone or in admixture of two or more, and copolymers of the above resins (graft polymers, block copolymers, random copolymers, etc.) alone or in combination. Can also be used. Furthermore, it is also possible to use a polymer containing the resin skeleton (polymer chain) in the main chain or side chain. Specific examples of such a polymer include polysiloxane-containing polyimide containing a polysiloxane and polyimide skeleton in the main chain.

  Among them, as a preferred example of the polymer component constituting the porous layer, polyamideimide resin or polyimide resin having heat resistance, thermoforming, excellent mechanical strength, chemical resistance, and electrical properties Is the main component. The polyamide-imide resin can be usually produced by polymerization by reaction of trimellitic anhydride and diisocyanate or reaction of trimellitic anhydride chloride and diamine, followed by imidization. The polyimide resin can be produced, for example, by obtaining a polyamic acid by a reaction between a tetracarboxylic acid component and a diamine component and further imidizing it. When the porous layer is composed of a polyimide resin, the solubility becomes worse when imidized, so first form a porous film at the polyamic acid stage and then imidize (thermal imidization, chemical imidization, etc.) Often done.

  When the substrate is a resin film or a metal foil, the thickness of the porous layer is, for example, 0.1 to 100 μm, preferably 0.5 to 70 μm, and more preferably 1 to 50 μm. If the thickness is too thin, it is difficult to produce stably, whereas if it is too thick, it is difficult to uniformly control the pore size distribution.

  The thickness of the porous layer is, for example, 0.1 to 1000 μm, preferably 0.5 to 500 μm, and more preferably 1 to 200 μm when the substrate has a large number of through holes. If the thickness is too thin, it is difficult to produce stably, whereas if it is too thick, it is difficult to uniformly control the pore size distribution.

  In the porous film laminate of the present invention, the substrate and the porous layer are laminated with an interlayer adhesion strength that does not cause interfacial peeling in the tape peeling test directly without passing through another layer. In general, when another layer is laminated on the surface of the base material, as a means of improving the adhesion between the base material and the other layer, a sandblast treatment (sand mat treatment) is performed on the surface of the base material on the side where the other layer is laminated. ) Methods for applying appropriate surface treatments such as corona discharge treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, plasma treatment, chemical etching treatment, water mat treatment, flame treatment, silane coupling agent treatment, etc. As a component constituting the other layer, there may be mentioned a method of using a combination of materials capable of exhibiting good adhesion (affinity, compatibility). However, in the porous membrane laminate of the present invention, it was effective as a surface treatment method of the substrate to improve the interlayer adhesion strength between the substrate and the porous layer, scratch treatment, sand blast treatment (sand mat treatment), Any of the above-mentioned surface treatment methods is not necessary as long as it is one of polishing sheet processing. In addition, it was also investigated to combine the base material and the porous layer with materials capable of exhibiting good adhesion (affinity, compatibility), but no such material combination was found.

  From the viewpoint of adhesion between the base material and the porous layer, the porous membrane laminate of the present invention has, for example, a polymer component constituting the porous layer, a polyimide resin, a polyamideimide resin, a polyetherimide resin. And at least one selected from the group consisting of aromatic polyamide and polyamide resin, and the material constituting the base material is polyimide resin, polyamideimide resin, polyetherimide resin, polyester resin, liquid crystalline polyester It is preferably composed of at least one selected from resins, aromatic polyamide resins, polyethylene terephthalate resins, and polyethylene naphthalate resins. From the same viewpoint, as a preferred embodiment of the porous membrane laminate, a part or all of each component constituting the substrate and the porous layer is the same, for example, at least a part of the monomer unit of the polymer compound constituting both layers The structure which is common is mentioned. In such a porous film laminate, for example, the material constituting the substrate / porous layer is polyimide / polyimide, polyamideimide / polyimide, polyimide / polyamideimide, polyetherimide / polyimide, polyimide / polyetherimide, A laminate comprising a combination of polyamideimide / polyetherimide, polyetherimide / polyamideimide and the like is included.

  The porous layer in the present invention has a large number of independent micropores with low communication properties, and the average pore size of the micropores (= average pore size inside the film) is 0.01 to 10 μm. The average pore diameter of the micropores is preferably 0.05 to 5 μm. If the average pore diameter is out of the above range, the pore characteristics are inferior in that it is difficult to obtain the desired effect according to the application.For example, when the size is too small, the cushion performance is lowered, the heat insulation is lowered, etc. If it is too large, the relative dielectric constant may be inhomogeneous depending on the location.

  The average open area ratio (porosity) inside the porous layer is, for example, 30 to 80%, preferably 40 to 80%, more preferably 45 to 80%, and particularly preferably 50 to 80%. When the porosity is out of the above range, it is difficult to obtain desired porosity characteristics corresponding to the application.For example, if the porosity is too low, the dielectric constant increases, the cushion performance decreases, the heat insulating property If the porosity is too high, the strength and folding resistance may be inferior. Moreover, as a surface area porosity (surface area ratio) of a porous layer, it is 48% or less (for example, 0 to 48%), for example, Preferably it is about 0 to 30%. If the surface porosity is too high, the strength and folding resistance are likely to be reduced, the adhesive penetrates into the copper foil when adhering to it and the relative permittivity is lowered, or the etching solution is porous during etching There is a possibility that undesired etching from the inside may occur by penetrating the inside of the layer. A low porosity on the surface of the porous layer is basically preferable, but it is appropriate to sufficiently wash the water-soluble polar solvent and water-soluble polymer used when forming the porous layer. A small opening may be preferred. In addition, when plating or printing is performed on the surface of the porous layer, an appropriate opening may be preferable in order to exert an anchor effect and ensure adhesion with plating or ink.

  The porous layer should just be formed in the at least single side | surface of a base material, and can also be formed in both surfaces. By forming a porous layer on both surfaces of the substrate, a porous film laminate having low dielectric constant properties, cushioning properties, heat insulating properties, etc. on both surfaces can be obtained by taking advantage of its pore characteristics. Furthermore, by functionalizing the surface, circuit boards, heat radiation materials (heat sinks, radiation plates), electromagnetic wave control materials such as electromagnetic wave shields and electromagnetic wave absorbers, low dielectric constant materials, antennas, separators, cushion materials, insulation materials, It can be used as a wide range of substrate materials such as heat insulating materials and cell culture substrates.

  In the porous film laminate of the present invention, the porous layer may be subjected to chemical resistance imparting treatment. By imparting chemical resistance to the porous membrane laminate, it avoids problems such as delamination, swelling, dissolution, and alteration when it comes in contact with solvents, acids, alkalis, etc. in various forms of use of the porous membrane laminate This is advantageous in that it can. Examples of the chemical resistance imparting treatment include physical treatment with heat, ultraviolet light, visible light, electron beam, radiation, etc .; chemical treatment for coating the porous layer with a chemical resistant polymer or the like.

  In the porous membrane laminate of the present invention, for example, the porous layer may be coated with a chemical resistant polymer. Such a porous membrane laminate can constitute a laminate having chemical resistance, for example, by forming a chemical-resistant film on the surface of the porous layer. Here, the chemical is known as a substance that dissolves, swells, shrinks, and decomposes a resin that constitutes a conventional porous film, thereby reducing the function as the porous film. However, specific examples of such chemicals are dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc). A strong polar solvent such as N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone, cyclohexanone, acetone, methyl acetate, ethyl acetate, ethyl lactate, acetonitrile, methylene chloride, chloroform, tetrachloroethane, tetrahydrofuran (THF); Sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, charcoal Inorganic salts such as potassium; amines such as triethylamine; alkaline solutions such as aqueous solutions and organic solvents in which alkalis such as ammonia are dissolved; inorganic acids such as hydrogen chloride, sulfuric acid and nitric acid; organics having carboxylic acids such as acetic acid and phthalic acid Examples thereof include an aqueous solution in which an acid such as an acid is dissolved, an acidic solution such as an organic solvent, and a mixture thereof.

  The chemical resistant polymer compound is not particularly limited as long as it has excellent resistance to chemicals such as strong polar solvents, alkalis, acids, etc. For example, phenolic resin, xylene resin, urea resin, melamine Thermosetting resin such as resin, benzoguanamine resin, benzoxazine resin, alkyd resin, triazine resin, furan resin, unsaturated polyester, epoxy resin, silicon resin, polyurethane resin, polyimide resin, or light Curable resin: Thermoplastic resins such as polyvinyl alcohol, cellulose acetate resin, polypropylene resin, fluorine resin, phthalic acid resin, maleic acid resin, saturated polyester, ethylene-vinyl alcohol copolymer, chitin, chitosan, etc. Is mentioned. These polymer compounds can be used alone or in combination. The polymer compound may be a copolymer or a graft polymer.

  A porous film laminate composed of a porous layer coated with such a chemical-resistant polymer dissolves the porous layer even when it comes into contact with the strong polar solvent, alkali, acid or other chemicals. Or can be suppressed to such an extent that it does not affect the use purpose or application. For example, in an application where the porous layer and the chemical are in contact with each other for a short time, it is only necessary to provide chemical resistance that does not change within that time.

  In addition, since the said chemical resistant polymer compound often has heat resistance at the same time, there is little possibility that the heat resistance is lowered as compared with before the porous layer is coated with the chemical resistant polymer compound.

  Since the porous membrane laminate of the present invention has a structure in which a flexible porous membrane is laminated on a substrate having sufficient strength, it has excellent pore characteristics as described above and at the same time has sufficient folding resistance. I have. The folding resistance is evaluated by repeatedly performing a bending test based on the following conditions and having folding resistance when the number of times until the test material is cut is 10 times or more. In addition, it is judged that the higher the number of folds until cutting, the better the folding resistance. For example, in applications where repeated bending is required for electronic materials, etc., the number of folds is about 100 or more. It is preferable. The bending test uses an MIT fatigue resistance tester MIT-D manufactured by Toyo Seiki Seisakusho, sample shape 15 × 110 mm, bending angle 135 °, bending radius of curvature (R) 0.38 mm, bending speed 175 cpm, tension It is performed according to the fold resistance test of JIS C 5016 under the condition of 4.9N.

  According to the porous membrane laminate of the present invention, the porous film laminate includes those that are not cut even when the number of bendings is 20000 and that have extremely excellent folding resistance. For this reason, excellent workability and moldability can be exhibited, and it can be used in a wide variety of applications in various forms.

  In a preferred embodiment of the present invention, one or both surfaces of a substrate are covered with a porous layer, have independent micropores with low communication, and the micropores have an average pore diameter of 0.01 to 10 μm. The porous layered product has a porous layer, the thickness of the porous layer is 0.1 to 100 μm, the porosity is 30 to 80%, and the thickness of the substrate is 1 to 300 μm. Such a porous membrane laminate can be produced by appropriately setting the material and thickness constituting the porous layer and the substrate, production conditions (for example, humidification conditions), and the like.

  The porous membrane laminate of the present invention is obtained by casting a polymer solution in the form of a film on a base material, bringing it into contact with a coagulation liquid and subjecting it to a porous treatment, followed by drying as it is, It can manufacture by the method of obtaining the laminated body which the porous film laminated | stacked on the support body by the method of obtaining this laminated body.

  In the method for producing a porous membrane laminate of the present invention, a polymer solution is cast onto a substrate in the form of a film, guided to a coagulation liquid, and then dried to laminate a porous layer on at least one side of the substrate. Thus, a porous film laminate is obtained. According to this method, a porous layer is formed on a substrate using a wet phase conversion method, and then subjected to drying as it is, so that it can be laminated in close contact with the substrate surface simultaneously with the formation of the porous layer. Therefore, manufacturing efficiency can be improved. In addition, since the porous layer having a large number of micropores is flexible, the film constituting the porous layer is difficult to handle and the laminating process is difficult, but according to the manufacturing method of the present invention for laminating simultaneously with film formation, Such a problem can be avoided, and a porous film laminate in which a porous layer having excellent pore characteristics and a substrate are directly laminated can be easily obtained.

  The temperature of the coagulation liquid is not particularly limited, but may be 0 to 100 ° C., for example. When the temperature of the coagulation liquid is less than 0 ° C., the cleaning effect of a solvent or the like tends to be lowered. When the temperature of the coagulating liquid exceeds 100 ° C., the solvent and the coagulating liquid are volatilized and the working environment is impaired. As the coagulation liquid, water is preferably used from the viewpoints of cost, safety, toxicity and the like. When water is used as the coagulation liquid, a water temperature of about 5 to 60 ° C. is appropriate. The immersion time in the coagulation liquid is not particularly limited, but a time for sufficiently washing the solvent and the water-soluble polymer may be appropriately selected. If the washing time is too short, the porous structure may be broken in the drying process due to the remaining solvent. If the cleaning time is too long, the production efficiency is lowered, leading to an increase in product cost. The cleaning time cannot be unconditionally because it depends on the thickness of the porous material, but about 0.5 to 30 minutes is appropriate.

  After casting the polymer solution on a substrate in the form of a film, the polymer solution is kept in an atmosphere of a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C. for 0.2 to 15 minutes. It is preferable to immerse.

  As the base material, those which do not easily deteriorate when contacted with the coagulation liquid are preferably used, and examples thereof include those exemplified above as materials for forming the base material constituting the porous film laminate.

  Examples of the polymer solution to be cast include, for example, a polymer component that is a material constituting the porous layer, a water-soluble polar solvent, a water-soluble polymer as necessary, a mixed solution containing water as necessary, and the like. Can be used.

  As the polymer component constituting the material constituting the porous layer, those having solubility in a water-soluble polar solvent and capable of forming a film by a phase inversion method are preferred, and one or two or more of those exemplified above are mixed Can be used. Instead of the polymer component constituting the porous layer, a monomer component (raw material) of the polymer component, an oligomer thereof, a precursor before imidization or cyclization, or the like may be used.

  Addition of a water-soluble polymer or water to the polymer solution to be cast is effective for making the membrane structure porous like a sponge. Examples of the water-soluble polymer include polyethylene glycol, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polysaccharides, derivatives thereof, and mixtures thereof. Among these, polyvinylpyrrolidone is preferable in that it can suppress the formation of voids inside the film and improve the mechanical strength of the film. These water-soluble polymers can be used alone or in combination of two or more. From the viewpoint of porosity, the molecular weight of the water-soluble polymer is preferably 200 or more, preferably 300 or more, particularly preferably 400 or more (for example, about 400 to 200,000), and particularly a molecular weight of 1000 or more. It may be. The void diameter can be adjusted by adding water. For example, when the amount of water added to the polymer solution is increased, the void diameter can be increased.

  The water-soluble polymer is very effective for making the membrane structure into a sponge, and various structures can be obtained by changing the type and amount of the water-soluble polymer. For this reason, the water-soluble polymer is very suitably used as an additive for forming a porous layer for the purpose of imparting desired pore characteristics. On the other hand, the water-soluble polymer is an unnecessary component to be removed that does not ultimately constitute a porous layer. In the method of the present invention using the wet phase conversion method, the water-soluble polymer is removed by washing in a step of phase conversion by dipping in a coagulating liquid such as water. On the other hand, in the dry phase conversion method, components that do not constitute the porous layer (unnecessary components) are removed by heating, and water-soluble polymers are usually unsuitable for removal by heating, making it extremely difficult to use as an additive. It is. Thus, while it is difficult to form various pore structures depending on the dry layer conversion method, the production method of the present invention easily produces a porous film laminate having desired pore characteristics. This is advantageous in that it is possible.

  However, when the amount of the water-soluble polymer is increased, the hole communication tends to be increased. Therefore, when it is preferable that the connectivity is low as in the present invention, the amount of the water-soluble polymer is preferably the minimum amount. If not necessary, it is possible not to use a water-soluble polymer.

  Examples of the water-soluble polar solvent include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone, and mixtures thereof. In addition, those having solubility (good solvent for the polymer component) can be used according to the chemical skeleton of the resin used as the polymer component.

  As the polymer solution to be cast, the polymer component 8-25% by weight, the water-soluble polymer 0-10% by weight, the water 0-10% by weight, the water-soluble polar solvent 30-82 as the material constituting the porous film. A mixed solution consisting of% by weight is preferred. At this time, if the concentration of the polymer component is too low, the thickness of the porous layer becomes insufficient, desired pore characteristics are difficult to obtain, and if it is too high, the porosity tends to decrease. The water-soluble polymer is added to make the inside of the film into a uniform sponge-like porous structure, but if the concentration is too high at this time, the pores in the film will be highly connected. The added amount of water can be used to adjust the void diameter, and the diameter can be increased by increasing the added amount.

  When casting the polymer solution in the form of a film, the film is kept in an atmosphere consisting of a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C. for 0.2 to 15 minutes, and then the non-solvent of the polymer component It is desirable to lead to a coagulating liquid. By placing the film-like material after casting under the above conditions, the porous layer can be made homogeneous and highly communicable. The reason for this is considered to be that moisture enters from the surface of the film into the interior by placing it under humidification, and effectively promotes phase separation of the polymer solution. Particularly preferable conditions are a relative humidity of 90 to 100%, a temperature of 30 to 80 ° C, a relative humidity of about 100% (for example, 95 to 100%), and a temperature of 40 to 70 ° C. When the amount of moisture in the air is less than this, there may be a problem that the porosity is not sufficient.

  According to the above method, for example, a porous layer having a large number of independent micropores with low communication and an average pore diameter of 0.01 to 10 μm can be easily formed. As described above, the micropore diameter, porosity, and porosity of the porous layer constituting the porous membrane laminate in the present invention are the types and amounts of the constituent components of the polymer solution, the amount of water used, the flow rate. It can be adjusted to a desired value by appropriately selecting the humidity, temperature, time, and the like at the time of delay.

  The coagulation liquid used in the phase conversion method may be any solvent that coagulates the polymer component, and is appropriately selected depending on the type of polymer used as the polymer component. For example, the polyamideimide resin or polyamic acid is coagulated. Solvents that can be used include, for example, water; alcohols such as monohydric alcohols such as methanol and ethanol; polyhydric alcohols such as glycerin; water-soluble polymers such as polyethylene glycol; water-soluble coagulating liquids such as mixtures thereof Can be used.

  In the production method of the present invention, a porous film having a structure in which the porous layer is directly laminated on the surface of the base material by directing it to the coagulation liquid and forming a porous layer on the surface of the base material, followed by drying as it is A laminate is produced. The drying is not particularly limited as long as it is a method capable of removing a solvent component such as a coagulation liquid, and may be under heating or natural drying at room temperature. The method for the heat treatment is not particularly limited, and may be a hot air treatment, a hot roll treatment, or a method of putting it in a thermostatic bath, an oven or the like, as long as it can control the porous film laminate to a predetermined temperature. The heating temperature can be selected from a wide range of room temperature to about 600 ° C., for example. The atmosphere during the heat treatment may be air, nitrogen or an inert gas. The use of air is the least expensive but may involve an oxidation reaction. In order to avoid this, nitrogen or an inert gas is preferably used, and nitrogen is preferable from the viewpoint of cost. The heating conditions are appropriately set in consideration of productivity, physical properties of the porous layer and the substrate, and the like. By subjecting to drying, a porous membrane laminate in which a porous layer is directly formed on the surface of the substrate can be obtained.

  The porous film laminate thus obtained may be further subjected to a crosslinking treatment using heat, visible light, ultraviolet light, electron beam, radiation or the like. By the above treatment, polymerization, crosslinking, curing, etc. of the precursor constituting the porous layer proceed to form a polymer compound. When the polymer porous layer is composed of a polymer compound, crosslinking or curing is performed. And the like, and a porous membrane laminate having a porous layer with improved properties such as rigidity and chemical resistance can be obtained. For example, a polyimide porous layer can be obtained by subjecting a porous layer formed using a polyimide precursor to thermal imidization or chemical imidization. The porous layer formed using the polyamideimide resin can be subjected to thermal crosslinking. The thermal crosslinking can also be performed simultaneously with the heat treatment for drying after being led to the coagulation liquid.

  In some cases, the crosslinking treatment may cause a crosslinking reaction between the polymer porous layer and the substrate film. Thereby, the adhesiveness of a base film and a porous layer improves. For example, when a polyimide film on which a porous layer of a polyimide-based precursor is formed is heat-treated, the precursor becomes a polyimide and simultaneously adheres to the polyimide film. In addition, when the polyimide film on which the polyamideimide resin porous layer is formed is heat-treated, the porous layer adheres to the polyimide film.

  According to the production method of the present invention, one surface or both surfaces of the base film are covered with the polymer porous layer, and the polymer porous layer has a large number of independent micropores with low communication, A film having a porous layer having an average pore diameter of 0.01 to 10 μm can be easily obtained.

  The porous film laminated body of this invention should just have the porous layer laminated | stacked on the at least single side | surface of a base material, and may have a porous layer on both surfaces of a base material. Further, the porous film laminate may be subjected to heat treatment or film formation treatment as necessary in order to impart desired characteristics.

  Since the porous membrane laminate of the present invention has the above-described configuration, it can be applied to various uses in a wide range of fields. Specifically, it can be used as, for example, a low dielectric constant material, a separator, a cushion material, an ink image receiving sheet, a test paper, an insulating material, a heat insulating material, etc. by utilizing the pore characteristics of the porous layer as it is. Furthermore, as a composite material in which other layers (metal plating layer, magnetic plating layer, etc.) are laminated on the porous membrane laminate, electromagnetic wave control such as circuit boards, heat dissipation materials (heat dissipation plates, etc.), electromagnetic wave shields and electromagnetic wave absorbers, etc. It can be used as a material, cell culture substrate and the like.

  Moreover, the laminated body of this invention may have a metal plating layer and / or a magnetic plating layer laminated | stacked on the surface of the at least 1 porous layer which comprises the porous film laminated body of the said invention. Such a laminate may be referred to as a composite material in this specification.

  For example, the metal plating layer may be formed as a thin metal coating on the surface of the porous layer. Examples of the metal constituting the metal plating layer include copper, nickel, silver, gold, tin, bismuth, zinc, aluminum, lead, chromium, iron, indium, cobalt, rhodium, platinum, palladium, and alloys thereof. be able to. In addition, nickel-phosphorus, nickel-copper-phosphorus, nickel-iron-phosphorus, nickel-tungsten-phosphorus, nickel-molybdenum-phosphorus, nickel-chromium-phosphorus, nickel-boron-phosphorus, etc. An alloy film can also be mentioned. The metal plating layer may be used alone or in combination of the above metals, may be a single layer, or a plurality of layers may be laminated.

  The material constituting the magnetic plating layer is not particularly limited as long as it is a compound having magnetism, and may be either a ferromagnetic material or a paramagnetic material. For example, nickel-cobalt, cobalt-iron-phosphorus, cobalt- Alloys such as tungsten-phosphorus, cobalt-nickel-manganese; compounds having a site capable of generating radicals such as methoxyacetonitrile polymer, metal complex compounds such as charge transfer complexes of decamethylferrocene, and carbonized carbon materials An organic magnetic material composed of a compound such as polyacrylonitrile can be exemplified.

  Such a composite material can be manufactured using a known method as a method of forming a layer using a metal or an organic compound on the surface of the porous layer of the porous membrane laminate of the present invention.

  For the formation of the metal plating layer, a known method such as electroless plating or electrolytic plating can be used. In the porous membrane laminate of the present invention, electroless plating described later is preferably used in that the porous layer is composed of a polymer component, and a combination of electroless plating and electrolytic plating can also be used.

  The plating solutions used for forming the metal plating layer are known in various compositions, and those sold by manufacturers can also be obtained. The composition of the plating solution is not particularly limited, and various requests (aesthetics, hardness, abrasion resistance, discoloration resistance, corrosion resistance, electrical conductivity, thermal conductivity, heat resistance, sliding property, water repellency, wettability) The soldering wettability, sealing properties, electromagnetic wave shielding characteristics, reflection characteristics, etc. may be selected.

  In the method for producing a composite material of the present invention, a photosensitive composition comprising a compound that generates a reactive group by light is applied to the surface of at least one porous layer constituting the porous film laminate of the present invention. A step of exposing the photosensitive layer through a mask to form a reactive group in the exposed portion, and a step of forming a conductive pattern by combining the reactive group generated in the exposed portion with a metal, Alternatively, in the method for producing a composite material of the present invention, a step of eliminating a reactive group by light instead of a compound that generates a reactive group by light, and a step of eliminating the reactive group in an exposed area, a reaction remaining in an unexposed area This is performed by a method including a step of forming a conductor pattern by bonding a group to a metal.

  The compound that generates a reactive group by light is not particularly limited as long as it is a compound that generates a reactive group in a molecule that can form a bond with a metal (including a metal ion). For example, an onium salt derivative or a sulfonium ester And photosensitive compounds containing at least one derivative selected from derivatives, carboxylic acid derivatives and naphthoquinonediazide derivatives. These photosensitive compounds are versatile and can easily generate a reactive group capable of binding to a metal by light irradiation, so that a conductive portion having a fine pattern can be accurately formed.

  As a compound that loses a reactive group by light, for example, a compound having a reactive group capable of forming a bond with a metal (including a metal ion), and the reactive group generates a hydrophobic functional group by irradiation with light. And compounds that are difficult to dissolve or swell in water.

  The reactive group generated or disappeared by the light is not particularly limited as long as it is a reactive group capable of forming a bond with the metal (including a metal ion), and examples thereof include a functional group capable of ion exchange with a metal ion. Preferably, a cation exchange group is used. The cation exchange group includes, for example, an acidic group such as -COOX group, -SO3 X group or -PO3 X2 group (where X is a hydrogen atom, an alkali metal or an alkaline earth metal, and periodic groups I and II). Typical metals to which it belongs, ammonium groups) and the like. Among them, a cation exchange group having a pKa value of 7.2 or less is preferable because it can form a bond with a sufficient metal per unit area, and can easily obtain desired conductivity. Such a reactive group is subjected to metal ion exchange in the next step, and can exhibit a stable adsorption ability by a metal reductant or metal fine particles.

  The irradiation light is not particularly limited as long as the generation or disappearance of the reactive group can be promoted. For example, light having a wavelength of 280 nm or more can be used. However, in order to avoid deterioration due to exposure of the porous film laminate, the wavelength is preferably 300 nm. More than the above (about 300 to 600 nm), particularly 350 nm or more is preferably used.

  By irradiating with light through a mask and then washing as necessary, a pattern composed of reactive groups can be formed in the exposed or unexposed areas. In this way, the reactive group provided on the surface of the porous layer is bonded to a metal by the method described below to form a conductor pattern.

  In the present invention, an electroless plating method is preferably used as a method for bonding the reactive group to the metal. Electroless plating is known to be useful as a method of laminating a metal on a resin layer generally formed of plastic or the like. The porous membrane surface of the porous membrane laminate may be subjected to treatments such as degreasing, washing, neutralization, and catalyst treatment in advance for the purpose of improving the adhesion with the metal. As the catalyst treatment, for example, a catalyst metal nucleation method in which a catalyst metal capable of promoting metal deposition is attached to the surface to be treated can be used. The catalytic metal nucleation method is a method of promoting chemical plating by contacting a colloidal solution containing a catalytic metal (salt) and then contacting an acid or alkali solution or a reducing agent (catalyzer (catalyst) -accelerator). Method): A method of forming a catalytic metal nucleus by contacting a colloidal solution containing fine particles of catalytic metal and then removing the solvent and additives by heating or the like (metal fine particle method); An acid or alkali solution containing a reducing agent And then contacting the catalyst metal with an acid or alkali solution and bringing the catalyst into contact with an activating liquid (sensitizing)-activating (activating) ) Method).

  As the catalyst metal (salt) -containing solution in the catalyzer-accelerator method, for example, a metal (salt) -containing solution such as a tin-palladium mixed solution or copper sulfate can be used. The catalyzer-accelerator method is, for example, by immersing the porous membrane laminate in an aqueous copper sulfate solution, washing and removing excess copper sulfate as necessary, and then immersing it in an aqueous solution of sodium borohydride to thereby laminate the porous membrane. A catalyst nucleus composed of copper fine particles can be formed on the surface of the porous layer of the body. In the metal fine particle method, for example, a colloidal solution in which silver nanoparticles are dispersed is brought into contact with the surface of the porous layer, and then heated to remove additives such as a surfactant and a binder, whereby the surface of the porous layer is removed. Catalyst nuclei made of silver particles can be deposited. In the sensitizing-activating method, for example, after contacting with a hydrochloric acid solution of tin chloride, a catalyst nucleus made of palladium can be precipitated by contacting with a hydrochloric acid solution of palladium chloride. As a method of bringing the porous film laminate into contact with these treatment liquids, a method of applying the metal plating layer on the porous layer surface, a method of immersing the porous film laminate in the treatment liquid, or the like can be used.

  In the above catalytic metal nucleation method, when a porous membrane laminate in which one surface is composed of a substrate and the other surface is composed of a porous layer is immersed in the treatment liquid, the substrate is formed as a homogeneous layer. It is preferable. When a porous membrane laminate having a homogeneous substrate on one side is immersed in the treatment liquid, catalyst nuclei are formed not only on the porous layer surface of the porous membrane laminate but also on the substrate surface, but the porous surface has a large surface area. A large amount of catalyst nuclei adhere to and are easily retained on the surface of the material layer. On the other hand, on a homogeneous substrate, the substrate film surface is smooth, so that the catalyst nuclei are not easily deposited and easily fall off. In this way, a metal plating layer can be selectively formed on the surface of the porous layer in which a sufficient amount of catalyst nuclei are formed by subsequent electroless plating.

  Examples of main metals used for electroless plating include copper, nickel, silver, gold, nickel-phosphorus, and the like. The plating solution used for electroless plating contains, for example, the above metals or salts thereof, reducing agents such as formaldehyde, hydrazine, sodium hypophosphite, sodium borohydride, ascorbic acid, glyoxylic acid, acetic acid It contains complexing agents and precipitation control agents such as sodium, EDTA, tartaric acid, malic acid, citric acid and glycine, and many of these are commercially available and can be easily obtained. Electroless plating is performed by immersing the porous film laminate subjected to the above treatment in the above plating solution. In addition, since electroless plating is performed only on the other surface by applying electroless plating in a state where a protective sheet is pasted on one side of the porous film laminate, for example, metal deposition on a base material or the like is prevented. be able to.

  The thickness of the metal plating layer is not particularly limited and can be appropriately selected depending on the application, and is, for example, about 0.01 to 20 μm, preferably about 0.1 to 10 μm. In order to efficiently increase the thickness of the metal plating layer, for example, a method of forming a metal plating layer by combining electroless plating and electrolytic plating may be performed. In other words, since the surface of the porous layer on which the metal film is formed by electroless plating is imparted with conductivity, it is possible to obtain a thick metal plating layer in a short time by applying more efficient electrolytic plating. Become.

  The above method is particularly suitable as a method for obtaining a composite material used for a circuit board, a heat dissipation material, or an electromagnetic wave control material.

  A circuit board is generally manufactured by a method in which a copper foil is bonded to a substrate surface made of glass, epoxy resin, polyimide, or the like, and an unnecessary portion of the copper foil is removed by etching to form wiring. However, according to such a conventional method, it has become difficult to form fine wiring that can be used for a circuit board with a high density. In order to advance the miniaturization of wiring, it is necessary to attach a very thin copper foil strongly to a substrate made of glass, epoxy resin, polyimide, etc., but the thin copper foil is extremely inferior in handleability, The lamination process was very difficult. In addition, the manufacture of thin copper foils is difficult and expensive per se, and the glass / epoxy resin and polyimide used for the base material and the copper foil do not have a large adhesive force, so miniaturization is promoted. There was a problem that the wiring peeled off from the substrate.

  In such a background, according to the composite material of the present invention, it is also possible to form fine openings on the surface of the porous layer of the porous membrane laminate, and in that case, sufficient adhesion with the metal plating layer is ensured. This is suitable for a circuit board material having fine wiring. When constituting the circuit board material, the metal plating layer is preferably made of copper, nickel, silver or the like.

  The porous film laminate of the present invention is extremely useful as a circuit board produced by a method of forming fine wiring directly on the surface of the porous layer. As a method for producing such a circuit board, the method described as the method for producing a composite material of the present invention can be used. According to this method, since the porous film laminate of the present invention is used, it is possible to form fine wiring firmly entangled with the porous layer, and to form wiring accurately and easily using an exposure technique. it can. Single-sided wiring can be formed with a film having a porous layer on one side, and double-sided wiring can be formed with a film having a porous layer on both sides. When via wiring connecting both surfaces is required, a hole can be formed by a conventionally used drill or laser and filled by conductive paste or plating. Up to now, a method of forming a wiring by using an electroless plating method on a porous body has been known. However, the conventional porous body has poor strength and has a problem in that it is inferior in handleability and damaged during the manufacturing process. It was. On the other hand, when the porous membrane laminate of the present invention is used, since the porous layer is molded in close contact with the base material, a sufficient strength can be ensured, and a circuit board excellent in handleability can be obtained. Can be provided.

  The electromagnetic wave control material is used as a material that blocks (shields) or absorbs electromagnetic waves in order to reduce or suppress the influence on the surrounding electromagnetic environment and the influence of the device itself from the surrounding electromagnetic environment. There are many electromagnetic sources such as electrical / electronic devices, wireless devices, systems, etc. that are close to us, such as the spread of digital electronic devices, personal computers and mobile phones, and they emit various electromagnetic waves. Electromagnetic waves radiated from these devices may affect the surrounding electromagnetic environment, and the device itself is also affected by the surrounding electromagnetic environment. As countermeasures against these problems, electromagnetic wave control materials such as electromagnetic wave shielding materials and electromagnetic wave absorber materials have become important year after year. The composite material of the present invention can provide an electromagnetic wave shielding property by blocking electromagnetic waves by, for example, imparting conductivity by a metal plating layer, and can absorb electromagnetic waves by filling the pores constituting the porous layer with an electromagnetic wave absorbing material. Therefore, it is extremely useful as an excellent electromagnetic wave control material.

  The metal plating layer constituting the electromagnetic wave control material is preferably one that can impart conductivity, and for example, it is effective to be formed of nickel, copper, silver, or the like. Further, when the composite material has a layer structure in which a magnetic plating layer is formed on the surface of the porous layer by electroless plating, it is useful as an electromagnetic wave absorber material. Examples of the material used for forming the magnetic plating layer by electroless plating include magnetic materials such as alloys of nickel, nickel-cobalt, cobalt-iron-phosphorus, cobalt-tungsten-phosphorus, cobalt-nickel-manganese, and the like. Can be mentioned. The composite material of the present invention is very thin and highly flexible, and since the metal or magnetic material formed by plating is entangled with the porous layer, the plating layer is difficult to peel off and bending resistance (fold resistance) Sex) can be improved. Such a composite material can be used by being installed or affixed in any place of an electronic device.

  The porous film laminate and porous film of the present invention are also useful as a low dielectric constant material. With the advent of the broadband era, it is necessary to transmit a large amount of information at high speed. For this reason, the frequency used in electronic devices is also increasing, and the electronic components used therein must also support high-frequency signals. When conventional wiring boards (mainly glass epoxy resin) are used in high frequency circuits, (1) transmission signal delay due to high dielectric constant, (2) signal interference / attenuation due to high dielectric loss, power consumption Increase, and heat generation in the circuit occurs. A porous material is considered useful as a high-frequency wiring board material for solving these problems. This is because the relative dielectric constant of air is as low as 1, whereas a porous material can achieve a low relative dielectric constant. For this reason, a porous substrate material has been conventionally required. However, in order to achieve a low dielectric constant, it is necessary to increase the porosity, resulting in a problem that the strength as a substrate is reduced. It was. The porous film laminate of the present invention has a porous layer laminated on a base material and has low dielectric constant characteristics, and is sufficient for handling because the porous layer is in close contact with the base material. It is a medium that can secure strength and is preferable as a low dielectric constant material.

  When using the porous film laminate or porous film of the present invention as a low dielectric constant circuit board material, as described above, a copper foil is bonded to the surface of the porous film laminate or porous film, and the copper foil is etched by etching. It is conceivable to manufacture by a method of forming wiring by removing unnecessary portions. Although miniaturization and high density wiring are becoming difficult, most circuit boards are still made by this conventional method, and the porous film laminate and porous film of the present invention should also be used in this method. Can do. It can be said that this is a useful material that can cope with the reduction of the dielectric constant of the substrate, which has become very demanding. Due to the low connectivity of the porous layer, when etching the copper foil, it is difficult for the etchant to enter the porous layer, it is difficult to etch from the back side of the undesirable copper foil, and an independent porous with low connectivity It is possible to take advantage of the characteristics of the layer.

  Ink image-receiving sheets, also called print media, are often used in printing technology. On the other hand, many printing methods are currently put into practical use and used. For example, inkjet printing, screen printing, dispenser printing, letterpress printing (flexographic printing), sublimation printing, offset printing, laser, etc. Examples include printer printing (toner printing), intaglio printing (gravure printing), contact printing, and microcontact printing. The constituent components of the ink used are not particularly limited, and examples thereof include conductors, dielectrics, semiconductors, insulators, resistors, dyes, and the like.

  Advantages of creating electronic materials by printing methods are: (1) can be manufactured with a simple process, (2) is a low environmental impact process with little waste, (3) can be manufactured in a short time with low energy consumption, ( 4) Although the initial investment amount can be greatly reduced, it is also true that high-definition printing that has never been required is required and is technically difficult. Therefore, especially for printing used for manufacturing electronic materials, not only the performance of the printing machine but also the characteristics of the ink and the ink image-receiving sheet have a great influence on the printing result. In the porous membrane laminate of the present invention, the porous layer is in close contact with the substrate, and the fine porous structure of the porous layer can absorb ink and fix the ink precisely, so that it has never been so far High-definition printing can be achieved and it is very preferably used. In addition, since the porous layer is in close contact with the base material, it is possible to ensure sufficient strength for handling, for example, it is possible to print continuously by roll-to-roll, which significantly improves production efficiency. Can do.

  When the electronic material is manufactured by printing, the above-described method can be used as a printing method. Specific examples of electronic materials produced by printing include liquid crystal displays, organic EL displays, field emission displays (FEDs), IC cards, IC tags, solar cells, LED elements, organic transistors, capacitors (capacitors), electronic paper, Examples include a flexible battery, a flexible sensor, a membrane switch, a touch panel, and an EMI shield.

  The method for producing the electronic material includes a step of printing an ink containing an electronic material such as a conductor, a dielectric, a semiconductor, an insulator and a resistor on the surface of the porous layer (substrate). For example, a capacitor (capacitor) can be formed by printing on the surface of the porous layer (substrate) with ink containing a dielectric. Examples of such a dielectric material include barium titanate and strontium titanate. A transistor or the like can be formed by printing with an ink containing a semiconductor. As the semiconductor, pentacene, liquid silicon, fluorene-bithiophene copolymer (F8T2), poly (3-hexylthiophene) (P3HT), and the like can be given.

  Since wiring can be formed by printing with ink containing a conductor, a flexible substrate, a TAB substrate, an antenna, or the like can be manufactured. Examples of the conductor include conductive inorganic particles such as silver, gold, copper, nickel, ITO, carbon, and carbon nanotube; and particles made of conductive organic polymers such as polyaniline, polythiophene, polyacetylene, and polypyrrole. Can do. Examples of the polythiophene include poly (ethylenedioxythiophene) (PEDOT). These can be used as a solution or a colloidal ink. Among these, conductor particles made of inorganic particles are preferable, and silver particles and copper particles are particularly preferably used from the viewpoint of balance of electrical characteristics and cost. Examples of the shape of the particles include a spherical shape and a scale shape (flakes). The particle size is not particularly limited, but so-called nanoparticles having an average particle diameter of about several μm to several nanometers can also be used. These particles can be used by mixing a plurality of types. As a conductive ink, a silver ink (silver paste) that can be easily obtained will be described as an example. However, the present invention is not limited to this, and other types of ink can also be applied.

  Silver ink generally contains silver particles, a surfactant, a binder, a solvent, and the like as components. As another example, utilizing the property that silver oxide is reduced by heating, an ink containing silver oxide particles is printed and then heated and reduced to form a silver wiring. As yet another example, there is an ink that contains an organic silver compound and is then thermally decomposed to form a silver wiring. Organic silver compounds that can be dissolved in a solvent can also be used. As particles constituting the silver ink, silver particles, silver oxide, organic silver compounds and the like may be used singly or in combination, and those having different particle diameters may be used in combination. The temperature (baking temperature) at which the ink is cured after printing with the silver ink can be appropriately selected according to the composition of the ink, the particle diameter, etc., but is usually in the range of about 100 to 300 ° C. Many. Since the porous film laminate of the present invention is an organic material, the firing temperature is preferably relatively low in order to avoid deterioration, but in general, it is preferably fired at a high temperature in order to reduce the electrical resistance of the wiring. Therefore, it is necessary to select and use an ink having an appropriate curing temperature. As commercial products of such silver ink, trade name “CA-2503” manufactured by Daiken Chemical Industry Co., Ltd., trade name “Nano-Dotite XA9053” manufactured by Fujikura Kasei Co., Ltd., manufactured by Harima Kasei Co., Ltd. Trade names “NPS”, “NPS-J” (average particle diameter of about 5 nm), and trade names “Finesphere SVW102” (average particle diameter of about 30 nm) manufactured by Nippon Paint Co., Ltd. are known. In consideration of the balance between the electrical resistance required for the wiring board and the wiring adhesion, it is preferable to select the particle size, particle size distribution, and mixing ratio of the conductor added to the ink.

  In the case of screen printing, if the viscosity is too low, it is difficult to retain the ink on the screen, so it is preferable that the viscosity is rather high, and there is no particular problem even if the particle size of the particles contained in the ink is large. When is small, it is preferable to reduce the amount of solvent. Therefore, the particle diameter is preferably about 0.01 to 10 μm.

  The wiring may be formed only on one side of the porous layer, or may be formed on both sides. When wiring is formed on both sides, a via that connects the wirings on both sides can be formed as necessary. The via hole may be formed by a drill or a laser. The conductor in the via hole may be formed by a conductive paste or may be formed by plating.

  Further, the surface of the wiring formed of conductive ink can be used by being coated with plating or an insulator. In particular, it has been pointed out that silver wiring tends to cause electromigration and ion migration when compared with copper wiring (Nikkei Electronics, 2002.2.67, page 75). Therefore, for the purpose of improving the reliability of the wiring, it is effective to cover the wiring surface formed of silver ink with plating. Examples of plating include copper plating, gold plating, and nickel plating. Plating can be performed by a known method.

  Furthermore, the surface of the wiring formed of conductive ink can be covered with a resin. The above configuration can be suitably used for purposes such as wiring protection, wiring insulation, wiring oxidation and migration prevention, and flexibility improvement. For example, there is a possibility that the silver wiring becomes silver oxide by oxidation and the copper wiring becomes copper oxide, and the conductivity may decrease. However, by covering the wiring surface with the resin, the wiring comes into contact with oxygen or moisture. Can be avoided, and a decrease in conductivity can be suppressed. Examples of the method for selectively coating the surface of the wiring with a resin include methods such as dropper, dispenser, screen printing, and inkjet using a curable resin or a soluble resin described later as the resin to be coated.

  When the porous portion after the wiring is formed remains a void, the porous portion has a low dielectric constant, and is therefore preferably used as a high-frequency wiring board.

  As a use of the porous laminate of the present invention, in addition to the case of using the porous layer with pores remaining as it is, the porous structure of the present invention is subjected to a solvent treatment for the porous structure of the porous layer. It is also conceivable to use it by losing it.

  Although it does not specifically limit as resin which coat | covers wiring, For example, the curable resin used without a solvent, the soluble resin utilized by melt | dissolving in a solvent, etc. are mentioned. When using a soluble resin, it is necessary to coat in consideration of the volume reduction when the solvent volatilizes.

  Examples of the curable resin include an epoxy resin, an oxetane resin, an acrylic resin, and a vinyl ether resin.

  Epoxy resins include bisphenol A type and bisphenol F type bisphenol type, novolak type glycidyl ether type epoxy resins such as phenol novolak type and cresol novolak type; alicyclic epoxy resins and their modified resins Resin is included. Commercially available epoxy resins include “Araldite” from Huntsman Advanced Materials, “Denacol” from Nagase ChemteX, “Celoxide” from Daicel Chemical Industries, “Epototo” from Toto Kasei Co., Ltd., etc. The cured epoxy resin can be obtained, for example, by a method in which a curing reaction is started by a curable resin composition obtained by mixing a curing agent with an epoxy resin and the reaction is accelerated by heating. As the curing agent for the epoxy resin, for example, organic polyamine, organic acid, organic acid anhydride, phenols, polyamide resin, isocyanate, dicyandiamide and the like can be used.

  The cured epoxy resin is obtained by a method in which a curing reaction is initiated by heating or irradiation with light such as ultraviolet rays to a curable resin composition obtained by mixing a curing catalyst called a latent curing agent with an epoxy resin. You can also. As the latent curing agent, commercially available products such as “Sun-Aid SI” manufactured by Sanshin Chemical Industry Co., Ltd. can be used.

  If a highly flexible thing is used as a cured epoxy resin, it can be made flexible like a flexible substrate. Moreover, when heat resistance and high dimensional stability are requested | required, it can also be used as a rigid board | substrate (hard board | substrate) by using the composition which becomes hard after hardening as a curable resin composition.

  When an epoxy resin is used for coating, the curable resin composition is easy to handle if it has a low viscosity. Examples of such a characteristic include a bisphenol F-based composition and an aliphatic polyglycidyl ether-based composition.

  Examples of the oxetane resin include “Aron Oxetane” manufactured by Toagosei Co., Ltd. The cured oxetane resin can be obtained by mixing the oxetane resin with, for example, a cationic photopolymerization initiator “IRGACURE 250” manufactured by Ciba Specialty Chemicals, and starting the curing reaction by irradiating with ultraviolet rays. it can.

  Soluble resins include low dielectric resin “Oligo phenylene ether” manufactured by Mitsubishi Gas Chemical Company, polyamideimide resin “Vilomax” manufactured by Toyobo Co., Ltd., polyimide ink “Iupicoat” manufactured by Ube Industries, Ltd. Polyimide ink “Everrec” manufactured by NI Material, polyimide ink “ULIN COAT” manufactured by NI Material Co., Ltd., polyimide ink “Q-PILON” manufactured by PI Engineering Laboratory, saturated polyester resin “Nichigo Polyester” manufactured by Nippon Synthetic Chemical Co., Ltd. Commercially available products such as an acrylic solvent-type pressure-sensitive adhesive “Coponil” and an ultraviolet / electron beam curable resin “Shikou” can be used.

  As a solvent for dissolving the soluble resin used at the time of filling, it can be appropriately selected from known organic solvents according to the kind of the resin. A typical example of a resin solution (soluble resin solution) in which a soluble resin is dissolved in a solvent is, for example, a resin solution in which “oligo-phenylene ether” is dissolved in a general-purpose solvent such as methyl ethyl ketone or toluene; A resin solution (trade name “HR15ET”) dissolved in an ethanol / toluene mixed solvent; a resin solution in which “Iupicoat” is dissolved in triglyme can be used.

  The method of coating the wiring with the resin is not particularly limited, but the curable resin composition or the soluble resin solution is developed on the surface of the porous layer by using means such as a dropper, a spoon, a dispenser, screen printing, and an ink jet. (Applying) and, if necessary, a method of removing excess resin with a spatula or the like can be used. Examples of the spatula include fluorine resins such as polypropylene and Teflon (registered trademark), rubbers such as silicone rubber, resins such as polyphenylene sulfide, and metals such as stainless steel. Among these, a plastic spatula is preferably used because it hardly damages the wiring and the porous layer. In addition, a method of dropping an appropriate amount onto the surface of the porous layer using a means capable of controlling the discharge amount such as a dropper, a dispenser, screen printing, and ink jet without using a spatula is also possible.

  In order to smoothly develop the resin on the surface of the porous layer, an uncured resin having a low viscosity is preferably used. In addition, it is possible to improve the handleability of a resin having a high viscosity by lowering the viscosity using means such as heating at an appropriate temperature. However, when a curable resin is used, the curing reaction rate is increased by heating, so that heating more than necessary is not preferable because workability deteriorates.

  After the resin component is spread on the surface of the porous layer, heat treatment is preferably performed for the purpose of accelerating the curing of the resin or volatilizing the solvent. The heating method is not particularly limited, but rapid heating is preferably a method in which the temperature is gently raised because there is a possibility that unevenness may occur due to volatilization of the resin or curing agent or volatilization of the solvent. The temperature increase may be either continuous or sequential. It is preferable to appropriately adjust the temperature and time for curing and drying depending on the type of resin and solvent.

  The composite material of the present invention may have a structure in which the pore structure of the porous layer is lost due to the solvent treatment as a structure other than the above. Specifically, after forming a wiring pattern on the porous layer, the porous layer can be lost by wetting the porous layer with a solvent, swelling and softening, and drying.

  When the porosity of the porous layer of the present invention increases the porosity of the porous layer or the pore diameter is reduced, the strength of the porous layer portion is weakened due to the porous structure, and the adhesion strength with the substrate is reduced. It may decrease. By eliminating the porous structure by the above method, it may be possible to increase the strength of this layer or to increase the adhesion strength with the substrate. Further, by eliminating the porous structure, the irregular reflection of visible light can be suppressed and the transparent structure can be made transparent.

  In general, the porous layer before the solvent treatment has a configuration in which visible light is irregularly reflected in the pores in the layer and becomes opaque, and since the transparency is low, the opposite side cannot be seen through from one side. In contrast, a solvent-treated porous layer often becomes transparent because it does not cause irregular reflection. A transparent porous layer, for example, can be easily inspected when used on a wiring board, and it is easy to recognize the positional relationship of components when the wiring board is assembled to a device. This is advantageous. Furthermore, when the porous film laminate is composed of a colorless and transparent base material such as PET or PEN, the transparency of the region other than the wiring portion is very high. According to such a porous film laminate, wiring and circuits can be formed on the display screen itself, so that the circuit board can be omitted and the display itself can be thinned, and the cost can be reduced by simplifying the structure. Is possible.

  By making the pores of the porous layer in the porous membrane laminate transparent with a solvent treatment, there is a possibility of expanding to the above applications. In order to obtain a porous film laminate excellent in transparency, a porous layer having a thin resin color or a thin layer is preferably used.

  On the other hand, an electromagnetic wave is generated from a display such as a PDP, causing an adverse effect (noise) on peripheral devices. In order to prevent (shield) such electromagnetic waves, it is necessary to provide an electromagnetic wave shielding function to the filter disposed on the front surface of the PDP, and a grid-like wiring is provided as such a filter. A film is used.

  The electromagnetic wave shielding film for the above uses generally has a configuration in which a metal layer is laminated on a highly transparent film (highly transparent film). Such a film can be formed by, for example, a method of providing a metal layer on a highly transparent film by sputtering; a method of providing a metal mesh by etching after attaching a copper foil or the like to the highly transparent film. As an example of such an electromagnetic wave shielding film, a film having a lattice pattern having a line width of 20 to 30 μm and a pitch (repetition interval) of about 300 μm can be mentioned.

  According to the present invention, the electromagnetic wave shielding film having the above-described configuration can be provided by forming a lattice-like wiring on the porous film laminate and then performing solvent treatment. At this time, it is considered that the cost can be reduced by simply creating the wiring by using a printing method such as screen printing.

  Furthermore, it is possible to further increase the transparency of the wiring portion by printing using ITO (indium tin oxide) ink which is a transparent (transmittance of visible light of about 90%). An ITO ink manufactured by CI Kasei Co., Ltd. or an ITO ink “Nano Metal Ink” manufactured by ULVAC MATERIAL CO., LTD. Can be used. By using a transparent conductor, there is a possibility that it can be used for flat panel displays such as liquid crystal panels and organic EL, solar cells, resistive touch panels, and the like. Another example is a method of forming wiring using zinc oxide ink as another transparent conductor.

  The composite material of the present invention may have a configuration in which the pores of the porous layer are left as they are. The composite material in which the pores of the porous layer are left as it is means that the porous layer has characteristics as a porous body. Specifically, for example, the composite material is a printing technology. This means that the same pore structure as that of the porous layer at the time when the conductor is formed is retained. Such a composite material may have a configuration in which other layers are laminated or various treatments are performed as long as the porous layer can maintain the characteristics as a porous body. Further, such a composite material does not include a composite material in which the pore structure of the porous layer is lost by solvent treatment or the like.

  For example, when leaving the pores of the porous layer as they are for reducing the dielectric constant, the solvent treatment is not performed. However, in order to protect the wiring, insulate the wiring, prevent the wiring from being oxidized, and improve the flexibility, only the wiring portion may be covered with a resin by the above-described method.

  The porous layer can be made transparent by, for example, wetting and softening the porous layer laminate by wetting the porous film laminate on which the wiring is formed, and then drying the porous layer to eliminate the pore structure of the porous portion. Is realized. As a method of wetting the porous film stack with the solvent, dipping, spraying, or a sponge roller may be used. Drying after wetting with the solvent may be natural drying or by heating. What is necessary is just to select in consideration of the boiling point etc. of a solvent. In order to make it transparent uniformly, it is preferable to dry slowly.

  A suitable solvent for eliminating the porous structure varies depending on the resin of the porous layer and cannot be generally specified, but is not limited as long as it can swell and soften the resin of the porous layer. However, a resin that completely dissolves and fluidizes the resin of the porous layer is not preferable and must be avoided. This is because the wiring pattern formed on the porous material collapses. The solvent is not necessarily a single solvent, and a mixture of two or more solvents may be used. Rather, it is possible to swell and soften at an appropriate level by mixing the solvent.

  As a specific example, for example, polyamideimide that can be used in a porous layer is hardly soluble in many solvents, but is soluble in some polar solvents (NMP, DMF, DMSO, DMAc, etc.). is there. When the porous membrane laminate is wetted with these polar solvents themselves, the porous layer dissolves and the wiring pattern collapses, but the solvent that can be mixed with these polar solvents and does not dissolve the porous layer (water, acetone, THF) , Methanol, ethanol, IPA, methyl ethyl ketone, etc.), the porous layer can be swollen and softened.

  Such a mixed solvent system can be dried in two stages. For example, a low boiling point solvent (water, acetone, THF, methanol, ethanol, IPA, methyl ethyl ketone, etc.) is naturally dried or dried at a relatively low temperature, and then a high boiling point solvent (NMP, DMF, DMSO, DMAc, etc.) ) May be dried at a high temperature with a dryer or the like. The final drying temperature and time may be selected so that the high boiling point solvent is sufficiently volatilized. As another method, a method of slowly raising the temperature from room temperature can be mentioned. When high transparency is required for display applications or the like, it is preferable to select a colorless and highly transparent resin for the porous layer, and it is preferable to select a porous layer with a thin thickness as much as possible. Further, it is preferable to select a substrate having a high transparency such as PET or PEN.

  When the porous layer is swollen and softened with a solvent and the porous structure is lost, the substrate of the porous film laminate is preferably insoluble or hardly soluble in the solvent used. This is because if the base material swells and softens like the porous layer, the base material is deformed and the dimensional stability as a wiring board is lowered. Inappropriate solvents differ depending on the substrate and cannot be generally described. However, PET, PEN, and polyimide are preferable because they are insoluble or hardly soluble in many solvents.

  As described in the section on filling the resin into the porous layer, it is possible to further increase the transparency by forming the wiring using ITO or zinc oxide ink, which is a transparent conductor, and such characteristics are required. Can be used for future applications. Although the porous structure can be made transparent by the above method, the wiring may remain bare in this case. It is preferable to properly insulate by covering with resin as described above or forming a coverlay.

  The wiring board is usually joined to other components or a board with solder, a connector or the like in order to pass electricity. Therefore, the contact portion must be filled with a resin in a masked state or coated with a resin while avoiding the contact portion. As such a resin, the above-described curable resin or soluble resin can be used as a resin for covering the wiring.

  In addition, the wiring board is not only formed by wiring, but a semiconductor chip, a capacitor, a resistor, etc. can be bonded onto the wiring board by soldering, wire bonding, or the like, such as TAB or COF. Furthermore, wiring formation and component mounting can be performed not only on one side of the porous film laminate but also on both sides, and a plurality of substrates can be laminated to be multilayered.

  In the composite material of the present invention, a coverlay may be laminated on the porous layer. For example, in the case of a flexible substrate, the wiring is generally covered with a cover lay made of a resin film such as a polyimide film or a PET film for the purpose of protecting the wiring, insulating the wiring, preventing the oxidation of the wiring, and improving the flexibility. There are many cases. Examples of such a coverlay film include “Nikaflex” manufactured by Nikkan Kogyo Co., Ltd. and products manufactured by Arisawa Seisakusho.

  Examples of the method of laminating the coverlay include a method of thermocompression bonding a coverlay film in which an adhesive is applied to one side of a coverlay such as a polyimide film or a PET film after the solvent treatment to the porous layer. It is done. As the adhesive for the coverlay film, a known one can be used, and it is often in a semi-cured (B stage) state so as to be easy to handle.

  A cover lay is not always necessary and can be omitted if sufficient wiring protection, wiring insulation, wiring oxidation prevention, and bendability can be achieved with a resin coating on the porous layer. is there.

  The porous film laminate and the porous film of the present invention can be used for an antenna having higher frequency characteristics.

  Recently, many wireless devices are used, and an antenna is required for transmitting and receiving signals. The spread of mobile phones, wireless LANs, IC cards, etc. is remarkable. Use of a low dielectric constant material for the antenna is preferable because it can increase the antenna gain. For example, a loop-shaped RFID antenna is used for an IC card or the like, and these are currently made by a subtractive method (etching method).

  By replacing a conventionally used PET substrate or the like with the porous film laminate or the porous film of the present invention, an antenna having higher frequency characteristics can be manufactured. As a manufacturing method, a subtractive method can be used. Specifically, in the same manner as shown in the method for producing a low dielectric constant circuit board, a copper film is bonded to a porous film laminate or a porous film surface based on a resin film, and after forming a resist pattern, This can be done by removing unnecessary portions of the copper foil by etching. Moreover, as another method, after forming a resist pattern in the porous film laminated body which used metal foils, such as copper, as a base material, it can etch and remove by removing an unnecessary part of copper foil. And the conventional subtractive method is a method which requires a long process and requires labor and cost. As described in the ink image-receiving sheet, when an antenna is formed by printing with ink containing a conductor, it can be manufactured more easily and at low cost.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The tape peeling test, average pore diameter, porosity, and surface roughness were measured by the following methods.

1. Tape peel test:
(i) 24 mm wide masking tape manufactured by Teraoka Seisakusho [film masking tape no. 603 (# 25)] is applied for a length of 50 mm from one end of the tape, and the attached tape is a roller having a diameter of 30 mm and a load of 200 gf (Holbein Art Materials Inc., oil resistant hard rubber roller No. 10). ).
(ii) The other end of the tape is pulled at a peeling speed of 50 mm / min using a universal tensile testing machine [trade name “TENSILON RTA-500” manufactured by Orientec Co., Ltd.] to perform T-type peeling.
(iii) The presence or absence of interface peeling between the porous layer and the substrate is observed.

  The average pore diameter and porosity of the porous layer were calculated by the following method. These average pore diameter and porosity are obtained only for the micropores visible in the electron micrograph.

2. Average pore diameter From the electron micrograph, the area of any 30 or more holes on the surface or cross section of the laminate was measured, and the average value was defined as the average pore area Save. Assuming that the hole is a perfect circle, the value converted from the average hole area to the hole diameter using the following formula was defined as the average hole diameter. Here, π represents a circumference ratio.
Surface or internal average pore diameter [μm] = 2 × (Save / π) 1/2

3. Porosity The porosity in the porous layer was calculated from the following formula. V represents the volume [cm 3] of the film, W represents the weight [g] of the porous layer, and ρ represents the density [g / cm 3] of the porous layer material. The density of polyamideimide was 1.45 [g / cm3], and the density of polyimide was 1.42 [g / cm3]. Further, in the case of a laminate in which a porous layer was laminated on a substrate, the porosity inside the porous layer was calculated by subtracting the volume and weight of the substrate.
Porosity [%] = 100-100 × W / (ρ · V)

4). Surface Roughness The surface of the base material (treated surface) was manufactured by Tokyo Seimitsu Co., Ltd. under the conditions of distance 0.1 [mm] and speed 0.06 [mm / s] using the product name “surfcom HRC-0098”. It was measured.

[Example 1]
As a base material, a film having a surface roughness Ra = 0.14 μm prepared by scratching the surface of a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) was used. Polyamideimide resin solution (trade name “Vilomax HR11NN” manufactured by Toyobo Co., Ltd .; solid concentration 15% by weight, solvent NMP (N-methyl-2-pyrrolidone), solution viscosity 20 dPa · s / 25 ° C.) 100 parts by weight In addition, 25 parts by weight of polyvinylpyrrolidone (molecular weight: 50,000) was added as a water-soluble polymer to prepare a porous layer stock solution. The substrate was fixed on a glass plate with a tape, and a stock solution of a porous layer at 25 ° C. was cast using a film applicator under the condition of a gap of 51 μm between the film applicator and the substrate. Immediately after casting, it was kept in a container having a humidity of about 100% and a temperature of 50 ° C. for 4 minutes. Then, it was immersed in water to be solidified, then pulled up from water and naturally dried at room temperature to obtain a laminate in which a porous layer was laminated on a substrate. The thickness of the porous layer was about 15 μm, and the total thickness of the laminate was about 65 μm. When immersed in water and solidified, the porous layer did not peel from the substrate.

  When the tape peeling test was performed on the obtained laminate, the substrate and the porous layer did not cause interface peeling. When this laminate was observed with an electron microscope, the porous layer was in close contact with the polyimide film, the inside of the porous layer was almost homogeneous, and there were micropores having an average pore diameter of about 1.0 μm over the entire area. Existed. The porosity inside the porous layer was 70%.

[Example 2]
Example except that a polyimide film having a surface roughness of Ra = 0.46 μm (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) prepared by sand plasting the surface was used as a base material. Operation similar to 1 was performed and the laminated body by which the porous layer was laminated | stacked on the base material was obtained. The thickness of the obtained porous layer was about 17 μm, and the total thickness of the laminate was about 67 μm. When immersed in water and solidified, the porous layer did not peel from the substrate.

  When the tape peeling test was performed on the obtained laminate, the substrate and the porous layer did not cause interface peeling. When this laminate was observed with an electron microscope, the porous layer was in close contact with the polyimide film, the inside of the porous layer was almost homogeneous, and there were micropores having an average pore diameter of about 1.0 μm over the entire area. Existed. The porosity inside the porous layer was 70%.

[Example 3]
As the base material, the surface roughness was Ra = 0.15 μm, which was prepared by polishing the surface three times each in the vertical and horizontal directions with an abrasive sheet (trade name “Uniwool GRADE # 1500” manufactured by Nihon Kenshi Co., Ltd.). The same operation as in Example 1 was performed except that a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) was used to obtain a laminate in which a porous layer was laminated on a substrate. It was. The thickness of the obtained porous layer was about 16 μm, and the total thickness of the laminate was about 66 μm. When immersed in water and solidified, the porous layer did not peel from the substrate.

  When the tape peeling test was performed on the obtained laminate, the substrate and the porous layer did not cause interface peeling. When this laminate was observed with an electron microscope, the porous layer was in close contact with the polyimide film, the inside of the porous layer was almost homogeneous, and there were micropores having an average pore diameter of about 1.0 μm over the entire area. Existed. The porosity inside the porous layer was 70%.

[Comparative Example 1]
The same operation as in Example 1 was performed except that a polyimide film having an untreated surface (trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 μm, surface roughness Ra = 0.03 μm) was used as the substrate. It performed and the laminated body by which the porous layer was laminated | stacked on the base material was obtained. In some cases, the porous layer was peeled off from the base material naturally when immersed in water and solidified. When peeled, a sheet consisting only of a porous layer was obtained by natural drying at room temperature. The thickness of the sheet | seat which consists only of the obtained porous layer was about 18 micrometers.

[Comparative Example 2]
A polyimide film with a surface roughness of Ra = 0.06 μm (trade name manufactured by Toray DuPont Co., Ltd.) whose surface was corona-treated with a “A3SW-FNLW-A type” corona discharge surface treatment apparatus for A3size manufactured by Wedge. The same operation as in Example 1 was performed except that “Kapton 200H”, thickness 50 μm) was used. The porous layer peeled off from the base material when solidified by immersion in water. The peeled porous layer had a thickness of about 17 μm.

[Comparative Example 3]
Example 1 except that a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 μm, surface roughness Ra = 0.05 μm), which is a manufacturer-treated product whose surface was plasma-treated, was used as the substrate. The same operation was performed. The porous layer peeled off from the base material when solidified by immersion in water. The peeled porous layer had a thickness of about 18 μm.

  As is clear from the results in Table 1, by performing an appropriate surface treatment on the surface of the base material, loss due to peeling between the base material and the porous layer during the dipping process was eliminated.

  The laminate including the porous layer produced by the production method of the present invention includes a circuit board, an electromagnetic wave control material such as an electromagnetic wave shield and an electromagnetic wave absorber, a low dielectric constant material, an antenna, a separator, a cushion material, an ink image receiving sheet, It can be used as a wide range of substrate materials such as insulating materials, heat insulating materials and cell culture substrates.

Claims (13)

  A polymer solution containing a polymer component that constitutes the porous layer is cast into a film on a substrate, and then immersed in a coagulation liquid, and then dried to form a substrate. And a porous layer that is laminated on at least one side of the substrate, and as a substrate, improves adhesion to the porous layer on the surface on which the porous layer is laminated The manufacturing method of the laminated body which uses what surface-treated.   The manufacturing method of the laminated body of Claim 1 whose surface treatment performed to a base material is any one of a scratch process, a sand blast process (sand mat process), and an abrasive sheet processing process.   After casting the polymer solution in the form of a film on the base material, it is kept for 0.2 to 15 minutes in an atmosphere having a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C., and then immersed in the coagulation liquid. The manufacturing method of the laminated body of Claim 1 or 2.   The polymer solution contains 8 to 25% by weight of the polymer component to constitute the porous layer, 0 to 10% by weight of the water-soluble polymer, 0 to 10% by weight of water, and 30 to 82% by weight of the water-soluble polar solvent. The manufacturing method of the laminated body of Claims 1-3 which is a mixed solution.   The polymer component constituting the porous membrane is polyimide resin, polyamideimide resin, polyethersulfone resin, polyetherimide resin, polycarbonate resin, polyphenylene sulfide resin, polyester resin, liquid crystalline polyester resin. At least one selected from the group consisting of aromatic polyamide resins, polyamide resins, polybenzoxazole resins, polybenzimidazole resins, polybenzothiazole resins, polysulfone resins, cellulose resins, and acrylic resins. The manufacturing method of the laminated body of Claims 1-4 which is a seed | species.   The base material is polyimide resin, polyamideimide resin, polyethersulfone resin, polyetherimide resin, polycarbonate resin, polyphenylene sulfide resin, polyester resin, liquid crystalline polyester resin, aromatic polyamide resin, Polyamide resin, polybenzoxazole resin, polybenzimidazole resin, polybenzothiazole resin, polysulfone resin, cellulose resin, acrylic resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin A resin film comprising at least one resin material selected from the group consisting of a polyether ether ketone resin, a fluorine resin, an olefin resin, and a polyarylate resin. The method for producing a laminate according to.   The average pore diameter of the micropores in the porous layer is 0.01 to 10 μm, the porosity is 30 to 80%, and the micropores are independent micropores with low communication. The manufacturing method of the laminated body of description.   The average pore diameter of the micropores in the porous membrane is 0.01 to 10 μm, the porosity is 30 to 80%, the thickness of the porous membrane is 5 to 200 μm, and the Gurley value is 30 seconds. The manufacturing method of the laminated body of Claims 1-7 which has air permeability of / 100cc or more. Tape peeling test based on the following method:
On the surface of the porous layer of the laminate, a masking tape [film masking tape No. 603 (# 25)] is applied for a length of 50 mm from one end of the tape, and the attached tape is pressed with a roller having a diameter of 30 mm and a load of 200 gf, and then the other end of the tape is peeled off using a tensile tester. Pulling at a speed of 50 mm / min to perform T-type peeling: The method for producing a laminate according to claim 1, wherein interfacial peeling is not caused between the substrate and the porous layer.   The manufacturing method of the laminated body of Claims 1-9 whose thickness of a porous layer is 0.1-100 micrometers.   The manufacturing method of the laminated body of Claims 1-10 whose thickness of a base material is 1-1000 micrometers.   The method for producing a laminate according to claim 1, wherein a conductor is further formed on the surface of the porous layer by printing.   The method for producing a laminate according to claim 1, wherein the surface of the porous layer is further coated with a chemical resistant polymer.