WO2011074418A1 - 多孔質層を有する積層体、及びそれを用いた機能性積層体 - Google Patents
多孔質層を有する積層体、及びそれを用いた機能性積層体 Download PDFInfo
- Publication number
- WO2011074418A1 WO2011074418A1 PCT/JP2010/071492 JP2010071492W WO2011074418A1 WO 2011074418 A1 WO2011074418 A1 WO 2011074418A1 JP 2010071492 W JP2010071492 W JP 2010071492W WO 2011074418 A1 WO2011074418 A1 WO 2011074418A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- porous layer
- layer
- laminate
- resin
- substrate
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249988—Of about the same composition as, and adjacent to, the void-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/24999—Inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
Definitions
- the present invention relates to a laminate having a porous layer mainly composed of a polymer on a substrate and a method for producing the same, and a functional laminate using the laminate having the porous layer and a method for producing the same.
- the laminate having the porous layer of the present invention can utilize a wide range of substrate materials such as a low dielectric constant material, a separator, a cushioning material, an ink image receiving sheet, an insulating material, and a heat insulating material by utilizing the pore characteristics of the porous layer. Furthermore, by functionalizing the surface of the porous layer, circuit boards, heat dissipation materials (heat sinks, heat dissipation plates), electromagnetic wave control materials such as electromagnetic wave shields and electromagnetic wave absorbers, antennas, cells It can be used as a culture substrate.
- the laminate having the porous layer of the present invention exhibits excellent printing characteristics due to the micropores of the porous layer, fine printing of the functional material on the porous layer is possible. It is useful as a substrate material for electromagnetic wave control materials, circuit boards, antennas, heat sinks and the like.
- Japanese Laid-Open Patent Publication No. 2000-143848 and Japanese Laid-Open Patent Publication No. 2000-158798 include a resin that constitutes a porous layer and this resin.
- An ink image-receiving sheet produced by subjecting a coating film containing a good solvent and a poor solvent to dry phase conversion to form a porous layer is disclosed.
- the dry phase inversion method disclosed in both of the above publications is a method in which the solvent contained in the coating film is volatilized to cause microphase separation, so that the resin (polymer compound) constituting the porous layer has a low boiling point. There is a problem that it is limited to those which can be dissolved in a good solvent, and a high molecular weight and essentially insoluble polymer compound cannot be used.
- a low-viscosity coating solution is preferably used, but as a result, it is difficult to obtain a coating film having a sufficient thickness, Among the components of the coating film, the components that are not removed during solvent volatilization remain in the porous layer, making it difficult to use non-volatile additives, and the porous layer obtained by heating conditions and manufacturing environment conditions during the manufacturing process.
- the film quality such as pore diameter, hole area ratio, porosity, and thickness tends to vary.
- a copper foil is bonded to the laminate to form a copper-clad laminate, and then etched.
- the strength of the porous layer is weak, there is a possibility that the copper foil and the laminate cannot exhibit sufficient adhesive strength.
- Japanese Unexamined Patent Application Publication No. 2004-175104 discloses a porous membrane composed only of a porous layer by a wet phase conversion method.
- Japanese Unexamined Patent Publication No. 2009-73124 discloses a laminate composed of a substrate and a porous layer by a wet phase conversion method, and discloses a porous film consisting only of a porous layer by a wet phase conversion method. Has been.
- Japanese Unexamined Patent Publication No. 2000-143848 Japanese Unexamined Patent Publication No. 2000-158798 International Publication WO98 / 25997 Pamphlet International Publication WO2007 / 097249 Pamphlet Japanese Unexamined Patent Publication No. 2004-175104 Japanese Unexamined Patent Publication No. 2009-73124 Japanese Unexamined Patent Publication No. 2006-237322
- a high molecular weight and essentially insoluble polymer compound can be used, non-volatile additives effective in forming a porous structure can be used, and the production environment conditions can be stabilized, so that the quality can be stabilized and the porous layer produced by the dry phase inversion method.
- the porous layer can be made thicker than the porous layer manufactured by the dry phase inversion method, and the thickness of the porous layer can be increased. There are many advantages that performance can be improved.
- the porous layer is formed of a polymer compound that is soluble in a water-soluble polar solvent, the porous layer may be dissolved or swelled in the water-soluble polar solvent. It becomes difficult.
- the laminate disclosed in International Publication WO2007 / 097249 and JP-A-2009-73124 can be used as a wiring board or the like, and a general manufacturing process for incorporating the laminate into a target product, In the use of the laminate, the substrate and the porous layer are not peeled off. Moreover, it is also possible to improve the adhesiveness of a base material and a porous layer more by post-processing.
- the adhesion at the interface between the substrate and the porous layer depends on the adhesive property of the polymer forming the porous layer, in applications where high adhesion is required at the interface between the substrate and the porous layer. May have insufficient adhesion. Moreover, since it is a porous structure, the strength of the porous layer itself is inferior to that of a general non-porous resin.
- An object of the present invention is a laminate having a porous layer on a base material, which has excellent pore characteristics, flexibility, excellent handleability and molding processability, and is porous with a substrate by forming a crosslinked structure.
- An object of the present invention is to provide a laminate having excellent adhesion with a porous layer, film strength of the porous layer itself, heat resistance, chemical resistance and durability, and a method for producing the same.
- Another object of the present invention is to provide a functional laminate using the laminate having the porous layer and a method for producing the functional laminate. More specifically, the object of the present invention is to use a functional material such as a conductive material on the surface of the porous layer or the polymer layer derived from the porous layer, using the laminate having the porous layer. It is providing the functional laminated body in which the functional layer was formed, and its manufacturing method.
- the present invention includes the following inventions.
- a laminate comprising a substrate and a porous layer on at least one side of the substrate,
- the substrate is a resin film made of at least one resin material selected from the group consisting of a polyimide resin, a polyamideimide resin, a polyamide resin, and a polyetherimide resin, or a metal foil.
- the porous layer comprises, as main components, at least one polymer selected from the group consisting of polyimide resins, polyamideimide resins, polyamide resins, and polyetherimide resins, and a crosslinking agent. Consisting of The laminate having an average pore diameter of 0.01 to 10 ⁇ m and a porosity of 30 to 85% in the porous layer.
- Each of the above polymers constituting the porous layer has a crosslinkable functional group.
- the crosslinking agent is capable of crosslinking with a functional group in each polymer. Therefore, according to the said crosslinking agent, a crosslinked structure is formed in the said porous layer by performing a heat processing and / or an active energy ray irradiation process, and making a crosslinking agent react.
- crosslinking agent is at least one selected from the group consisting of a compound containing two or more epoxy groups, a polyisocyanate compound, and a silane coupling agent.
- the porous layer is formed by casting a solution of a material for forming a porous layer containing the polymer and the cross-linking agent that constitute the porous layer onto the substrate, and then The laminate according to any one of (1) to (3) above, which is formed by immersing this in a coagulation liquid and then subjecting it to drying.
- a method for producing the laminate according to any one of (1) to (6) above A solution of a porous layer forming material containing the polymer to form the porous layer and the cross-linking agent is cast into a film on the substrate, and then immersed in a coagulation liquid. Then, the manufacturing method of a laminated body including giving to drying.
- a conductor layer, a dielectric layer, a semiconductor On the surface of the porous layer or the polymer layer derived from the porous layer of the laminate according to any one of (1) to (4) above, a conductor layer, a dielectric layer, a semiconductor
- the porous layer or the polymer layer derived from the porous layer is a functional laminate in which a crosslinked structure is formed by the crosslinking agent.
- the polymer layer derived from the porous layer is used to express a crosslinking treatment (heating treatment, active energy ray irradiation treatment) for forming a crosslinked structure and / or the functionality of the functional layer.
- a crosslinking treatment heat treatment, active energy ray irradiation treatment
- the polymer layer derived from the porous layer may be transparent due to the disappearance of micropores.
- a conductor layer, a dielectric layer, a semiconductor On the surface of the porous layer or the polymer layer derived from the porous layer of the laminate according to any one of (1) to (4) above, a conductor layer, a dielectric layer, a semiconductor A method for producing a functional laminate having a functional layer selected from the group consisting of a layer, an insulator layer, and a resistor layer, On the surface of the porous layer of the laminate according to any one of (1) to (4) above, a conductor layer, a dielectric layer, a semiconductor layer, an insulator layer, a resistor layer, and the layer Forming a layer selected from the group consisting of precursor layers of A method for producing a functional laminate, comprising performing a heat treatment and / or an active energy ray irradiation treatment to form a crosslinked structure with the crosslinking agent in the porous layer.
- the average pore diameter and the porosity of the micropores in the porous layer are in a specific range, and the flexibility of the porous layer is excellent. Therefore, it has sufficient strength, and has excellent folding resistance and handleability.
- the porous layer includes a polymer having a crosslinkable functional group selected from the group consisting of a polyimide resin, a polyamideimide resin, a polyamide resin, and a polyetherimide resin, and the functional group.
- a crosslinking agent that can crosslink the porous material is subjected to a crosslinking treatment such as heat treatment and / or active energy ray irradiation treatment according to the type of the crosslinking agent.
- a crosslinked structure is formed in the layer.
- the base material is a heat-resistant resin film made of a resin material selected from the group consisting of a polyimide resin, a polyamideimide resin, a polyamide resin, and a polyetherimide resin, or a metal foil. Adhesion between the substrate and the porous layer is improved. It is presumed that cross-linking is also formed at the interface between the substrate and the porous layer. Therefore, a laminate having excellent adhesion, rigidity, heat resistance, chemical resistance and durability between the substrate and the porous layer can be obtained.
- the laminate having the porous layer of the present invention can utilize a wide range of substrate materials such as a low dielectric constant material, a separator, a cushioning material, an ink image receiving sheet, an insulating material, and a heat insulating material by utilizing the pore characteristics of the porous layer. Furthermore, by functionalizing the surface of the porous layer, circuit boards, heat dissipation materials (heat sinks, heat dissipation plates), electromagnetic wave control materials such as electromagnetic wave shields and electromagnetic wave absorbers, antennas, cell culture It can be widely used as a base material.
- the laminate having the porous layer of the present invention exhibits excellent printing characteristics due to the micropores of the porous layer, fine printing of the functional material on the porous layer is possible. It is useful as a substrate material for electromagnetic wave control materials, circuit boards, antennas, heat sinks and the like.
- the functional laminate of the present invention is a functional laminate having various functional layers on the surface of the porous layer of the laminate having the porous layer of the present invention or the polymer layer derived from the porous layer.
- a crosslinked structure is formed by the crosslinking agent.
- FIG. 4 is an electron micrograph (x5000 magnification) of the porous layer surface of the laminate obtained in Example 5.
- FIG. 6 is an electron micrograph (x2000 magnification) of a cross section of the laminate obtained in Example 5.
- FIG. 2 is an electron micrograph (x5000 magnification) of the porous layer surface of the laminate obtained in Example 16. It is an electron micrograph (x4000 times) of the cross section of the laminate obtained in Example 16. It is an electron micrograph (x5000 times) of the porous layer surface of what heat-processed the laminated body obtained in Example 5.
- FIG. It is an electron micrograph (x2000 times) of the cross section of what heat-processed the laminated body obtained in Example 5.
- porous layer laminate a laminate having a porous layer of the present invention
- the laminate having the porous layer of the present invention is a laminate comprising a base material and a porous layer on at least one side of the base material, and the base material includes a polyimide resin, a polyamideimide resin, It is a resin film made of at least one resin material selected from the group consisting of a polyamide-based resin and a polyetherimide-based resin, or a metal foil, and the porous layer contains, as a main component, a polyimide-based resin, a polyamide-imide-based resin It is comprised from the composition containing at least 1 sort (s) of polymer chosen from the group which consists of resin, a polyamide-type resin, and a polyetherimide type resin, and a crosslinking agent,
- the average hole diameter of the micropore in the said porous layer is 0.00. It is 01 to 10 ⁇ m, and the porosity is 30 to 85%.
- the many micropores of the porous layer may be independent micropores with low communication or may be micropores with communication.
- the average pore diameter of the micropores in the porous layer is 0.01 to 10 ⁇ m.
- a porous layer having an average pore size of less than 0.01 ⁇ m is difficult to produce by the phase separation method of the present invention, and when the average pore size exceeds 10 ⁇ m, it is difficult to uniformly control the pore size distribution in the porous layer. Become.
- the porous layer has a large number of micropores can be judged by observation with an electron microscope.
- the presence of spherical chambers, circular / elliptical holes, or fibrous components can be determined by observation from the surface of the porous layer, and spherical walls can be determined by observing the cross section of the porous layer. It is possible to confirm the existence of a small chamber surrounded by a fibrous structure.
- a thin skin layer may be formed on the surface of the porous layer, or a hole may be opened.
- the porosity (average porosity) inside the porous layer is 30 to 85%.
- 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, cushion performance may be deteriorated or printing characteristics may be degraded. If the porosity is too high, the strength and folding resistance may be inferior.
- the porous layer laminate of the present invention has an appropriate interlayer adhesion strength between the substrate and the porous layer even when the crosslinking agent contained in the porous layer is in an unreacted state. is doing.
- the porous layer laminate of the present invention is a 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 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).
- the porous layer laminate of the present invention has a specific interlayer adhesion strength between the substrate and the porous layer even when the cross-linking agent contained in the porous layer is unreacted. Since it has a laminated structure, it has flexibility and excellent pore characteristics, while it has an appropriate rigidity, so that handleability is improved.
- 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 substrate is a resin film made of at least one resin material selected from the group consisting of a polyimide resin, a polyamideimide resin, a polyamide resin, and a polyetherimide resin, or a metal foil. These are all excellent in heat resistance and can be appropriately selected according to the material constituting the porous layer described later.
- resin materials may be used alone or in admixture of two or more, and the above-mentioned resin copolymer (graft polymer, block copolymer, random copolymer) 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.
- a transparent resin film for the purpose of use described later. That is, when the porous layer is converted to a transparent polymer layer by heat treatment or the like to obtain a transparent functional laminate as a whole, it is preferable to use a transparent resin film substrate.
- the transparent resin film substrate includes not only a completely transparent one but also a so-called translucent one that allows the opposite side of the film substrate to be visually recognized through the film substrate.
- a film substrate having a total light transmittance of 30 to 100% may be used.
- a colored transparent substrate such as a polyimide film absorbs light of some wavelengths, and therefore has a lower total light transmittance than a completely colorless transparent substrate. Further, the total light transmittance decreases as the thickness of the substrate increases.
- 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.
- an adhesive layer may be formed on the other side of the base material, and a protective film (separated on the adhesive layer for easier handling). Type film) may be affixed.
- the resin base material in the present invention when a solution (coating liquid) of a material for forming a porous layer containing a polymer that constitutes the porous layer is applied on the surface of the base material, the resin film dissolves or vigorously dissolves. It is preferable that the film quality change such as deformation does not occur or is extremely small.
- the resin base material in the present invention commercially available films and the like exemplified below can be used.
- polyimide resin films “Kapton” manufactured by Toray DuPont Co., Ltd., “Apical” manufactured by Kaneka Co., Ltd., “Upilex” manufactured by Ube Industries, Ltd., and “Neoprim” manufactured by Mitsubishi Gas Chemical Co., Ltd. are commercially available. ing.
- “HDN-20” manufactured by Shin Nippon Rika Co., Ltd. has been announced.
- Toyobo Co., Ltd. has developed a transparent heat-resistant film of polyamide-imide resin, Gunze Co., Ltd.
- the substrate is first subjected to any treatment such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, and then a silane coupling agent treatment. Etc. can be used.
- the above method may be strengthened compared to the single treatment of the silane coupling agent, and a high effect can be expected particularly with a polyimide-based substrate.
- the silane coupling agent include products manufactured by Shin-Etsu Chemical Co., Ltd. and Japan Energy.
- the thickness of the resin base material is, for example, 1 to 1000 ⁇ m, usually 1 to 300 ⁇ m, preferably 5 to 200 ⁇ m, and more preferably 5 to 100 ⁇ m. If the thickness is too thin, it becomes difficult to handle, whereas if it is too thick, the flexibility of the resin substrate may be lowered.
- the commercially available base materials exemplified above include those having a thickness of 12 ⁇ m, 12.5 ⁇ m, 25 ⁇ m, 50 ⁇ m, 75 ⁇ m, 125 ⁇ m and the like, and any of them can be used.
- the material constituting the metal foil base material is not particularly limited as long as it does not cause interface peeling with 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 metal foil substrate include copper foil, aluminum foil, iron foil, nickel foil, gold foil, silver foil, tin foil, zinc foil, and stainless steel foil.
- the metal foil substrate may be a single layer or a composite metal foil composed of a plurality of layers made of the same or different materials.
- the composite metal foil may be a laminated film obtained by laminating a plurality of metal foils using an adhesive or the like, if necessary, or may be obtained by a treatment such as coating, vapor deposition, or sputtering.
- an adhesive layer may be formed on the other side of the base material, and a protective film on the adhesive layer for easier handling. (Release film) may be affixed.
- the film quality does not change or the film quality changes such as the film dissolves or deforms severely.
- metal foil substrate in the present invention commercially available film-like metal foils exemplified below can be used.
- electrolytic copper foil type: HTE, VP, HS, SV
- rolled copper foil type: RCF, RCF-AN
- electrolytic manufactured by Mitsui Metal Mining Co., Ltd. Copper foil (variety: HTE, VLP), rolled copper foil manufactured by Nippon Foil Co., Ltd., etc. are commercially available.
- metal foil adhesive tape aluminum foil adhesive tape
- stainless foil adhesive tape of Teraoka Manufacturing Co., Ltd. Conductive copper foil adhesive tape, conductive aluminum foil adhesive tape, shield adhesive tape (conductive cloth adhesive tape), etc. are available.
- commercially available products such as stainless steel tape manufactured by Nitoms Corporation can also be used.
- metal foil base materials roughening treatment, easy adhesion treatment, antistatic treatment, sand blast treatment (sand mat treatment), corona discharge treatment, plasma treatment, chemical etching treatment, water mat treatment, flame treatment, acid treatment, alkali treatment
- surface treatment such as oxidation treatment may be performed, and a commercially available product subjected to such surface treatment can also be used.
- a metal foil base material for example, a copper foil subjected to a roughening treatment and the like can be mentioned.
- the thickness of the metal foil base material is, for example, 1 to 1000 ⁇ m, usually 1 to 300 ⁇ m, preferably 5 to 200 ⁇ m, and more preferably 5 to 100 ⁇ m. If the thickness is too thin, it becomes difficult to handle, while if it is too thick, the flexibility of the metal foil substrate may be reduced.
- the commercially available base materials exemplified above include those having a thickness of 9 ⁇ m, 12 ⁇ m, 18 ⁇ m, 35 ⁇ m, 70 ⁇ m, and any of them can be used.
- the resin film base material and the metal foil base material may have through holes formed therein.
- the “base material in which through holes are formed” means a base material having pores penetrating in a direction substantially perpendicular to the base material plane.
- the base material having a large number of through holes is not particularly limited as long as a large number of through holes are formed and interface peeling with the porous layer is not caused by the tape peeling test.
- Punching film; Metal foil or sheet such as punching metal, expanded metal, etching metal, etc. can be mentioned, and can be appropriately selected and used according to characteristics such as water resistance, heat resistance and chemical resistance.
- the punching film a film made of a hole such as a circle, a square, a rectangle or an ellipse by punching a film of polyimide or the like can be used.
- the punching metal includes a punched metal foil or sheet that has holes such as a circle, a square, a rectangle, and an ellipse.
- Examples of the material include iron, aluminum, stainless steel, copper, and titanium.
- cocoon expanded metal examples include JIS standard shapes. For example, there are XS63 and XS42 flats. Examples of the material include iron, aluminum, and stainless steel.
- a base material having a large number of through holes can be manufactured by a conventional method corresponding to a material such as a processing method such as etching, punching, or laser irradiation.
- a polymer solution (a solution of a porous layer forming material) is applied to the surface and a porous layer is laminated, so that the above-mentioned high Since the molecular solution enters, there is an advantage that lamination can be performed with excellent interlayer adhesion strength.
- it since it has a softness
- the surface area ratio is about 20 to 80%, preferably about 30 to 70%.
- the numerical value of the surface open area ratio is too low, the permeability of gas or liquid tends to deteriorate, and when the numerical value is too high, the strength tends to decrease and the handling property tends to be inferior.
- the surface porosity is about 20 to 80%, preferably about 25 to 70%.
- the numerical value of the surface open area ratio is too low, the permeability of gas or liquid tends to deteriorate, and when the numerical value is too high, the strength tends to decrease and the handling property tends to be inferior.
- the porous layer has, as a main component, at least one functional group capable of cross-linking selected from the group consisting of a polyimide resin, a polyamideimide resin, a polyamide resin, and a polyetherimide resin. It is comprised from the composition containing the seed
- These polymer components have excellent heat resistance, can be thermoformed, and have excellent mechanical strength, chemical resistance, and electrical characteristics.
- crosslinkable functional group contained in the polymer examples include an amide group, a carboxy group, an amino group, an isocyanate group, a hydroxyl group, an epoxy group, an aldehyde group, and an acid anhydride group. Any number of these functional groups may be contained in the polymer.
- the polyamide-imide resin can be usually produced by imidization after polymerization by reaction of trimellitic anhydride and diisocyanate or reaction of trimellitic anhydride chloride and diamine. Since it has many amide groups in the molecule, it can be preferably used as a crosslinkable functional group. In addition, some imides remain reactive as unreacted precursors (amic acids), and the amide groups and carboxyl groups that make up the amic acids can be used as crosslinkable functional groups. Can do.
- polyamideimide resin is produced by polymerization by reaction of trimellitic anhydride and diisocyanate or reaction of trimellitic anhydride chloride and diamine as described above, a carboxyl group, isocyanate group, amino In many cases, groups and the like remain, and these can also be used as crosslinkable functional groups.
- the polyimide resin can be produced, for example, by obtaining a polyamic acid (polyimide precursor) by a reaction between a tetracarboxylic acid component and a diamine component, and further imidizing it.
- a polyamic acid polyimide precursor
- 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.) Good.
- the precursor molecule has a large number of carboxyl groups and amide groups, it can be preferably used as a crosslinkable functional group.
- a carboxyl group, an amino group, or the like often remains at the terminal, and these can also be used as crosslinkable functional groups.
- the polyamide-based resin can be produced by polycondensation of diamine and dicarboxylic acid, ring-opening polymerization of lactam, polycondensation of aminocarboxylic acid, or the like.
- Aromatic polyamide resins are also included. Since it has many amide groups in the molecule, it can be preferably used as a crosslinkable functional group. As in the case of the polyamideimide resin, a carboxyl group, an amino group or the like often remains at the terminal, and these can be used as a crosslinkable functional group.
- the polyetherimide resin can be produced, for example, by obtaining a polyamic acid by a reaction between an aromatic tetracarboxylic acid component having an ether bond and a diamine component, and further imidizing it.
- the amide group and carboxyl group constituting this amic acid can be used as a crosslinkable functional group.
- a carboxyl group, an isocyanate group, an amino group, etc. often remain at the terminal, and these can also be used as crosslinkable functional groups.
- Such a crosslinkable functional group may be present in the precursor of the polymer.
- An imide resin (polyimide resin, polyamideimide resin, polyetherimide resin) is a precursor in which the imide group part is completely unreacted (amic acid), or a part of the precursor is unreacted Some can be produced in the form of a body (amic acid), and some are actually sold in that form. Generally, it is used as an imide resin by converting an amic acid to an imide by heating, but in the present invention, an amide group or a carboxyl group constituting this precursor amic acid is used as a crosslinkable functional group. Including that.
- a crosslinkable functional group may be introduced into these resins by modifying a polyimide resin, a polyamideimide resin, a polyamide resin, or a polyetherimide resin.
- the crosslinkable functional group may be present in the main chain of the resin or may be present in the side chain. Furthermore, it may exist in the middle of the molecular chain or may exist at the end. Moreover, the crosslinkable functional group may exist in the benzene ring contained in the polymer.
- polymer components may be used singly or in combination of two or more, and copolymers of the above resins (graft polymer, block copolymer, random copolymer) alone or in combination. It is also possible to use it. Furthermore, you may use the polymer which contains the frame
- polyetherimide resins in addition to polyimide resins, polyamideimide resins, polyamide resins, and polyetherimide resins, other resins such as polyethersulfone can be used as long as they do not impair these characteristics.
- the crosslinking agent can react with the crosslinkable functional group of the polymer to crosslink.
- examples of the cross-linking agent include compounds containing two or more epoxy groups, polyisocyanate compounds, and silane coupling agents.
- the compound containing two or more epoxy groups is a crosslinkable functional group (amide group, carboxy group, amino group, isocyanate group, hydroxyl group, epoxy group, aldehyde group, acid anhydride, etc. possessed by the polymer. Group).
- the compound containing two or more epoxy groups is generally often referred to as an epoxy resin.
- epoxy resins such as 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 modified resins thereof, etc. Resins can be mentioned.
- Commercially available epoxy resins include “Araldite” from Huntsman Advanced Materials, “Denacol” from Nagase ChemteX, “Celoxide” from Daicel Chemical Industries, “Epototo” from Toto Kasei, Japan Epoxy Resin “JER” or the like can be used.
- the polyisocyanate compound can react with a crosslinkable functional group (a carboxy group, an amino group, a hydroxyl group, an epoxy group, an acid anhydride group) possessed by the polymer.
- a crosslinkable functional group a carboxy group, an amino group, a hydroxyl group, an epoxy group, an acid anhydride group
- polyisocyanate compounds include aromatic diisocyanates such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate (HDI), lysine diisocyanate, and the like.
- Aliphatic polyisocyanates such as isophorone diisocyanate (IPDI), cyclohexane-1,4-diisocyanate, and hydrogenated MDI.
- IPDI isophorone diisocyanate
- cyclohexane-1,4-diisocyanate cyclohexane-1,4-diisocyanate
- hydrogenated MDI hydrogenated polyisocyanate compounds
- the silane coupling agent can react with a crosslinkable functional group (amide group, carboxy group, amino group, isocyanate group, hydroxyl group, epoxy group, aldehyde group, acid anhydride group) possessed by the polymer.
- a crosslinkable functional group amide group, carboxy group, amino group, isocyanate group, hydroxyl group, epoxy group, aldehyde group, acid anhydride group
- Examples of the silane coupling agent include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane and 3-glycidoxypropyltriethoxysilane.
- a silane coupling agent from Shin-Etsu Chemical Co., Ltd. can be used.
- a metal foil base material it is effective for improving the adhesion between the porous layer and the metal foil base material.
- a surface-treated resin film substrate it is effective for improving the adhesion between the porous layer and the resin film substrate.
- crosslinking agent other than the above examples include melamine resin, phenol resin, urea resin, guanamine resin, alkyd resin, dialdehyde compound, acid anhydrides and the like.
- the melamine resin can react with a crosslinkable functional group (amino group, hydroxyl group, aldehyde group) possessed by the polymer.
- a crosslinkable functional group amino group, hydroxyl group, aldehyde group
- the melamine resin for example, “Uban 20SB” from Mitsui Chemicals, Inc. and “Super Becamine” from DIC can be used.
- the phenol resin can react with a crosslinkable functional group (a carboxy group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, an aldehyde group, an acid anhydride group) possessed by the polymer.
- a crosslinkable functional group a carboxy group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, an aldehyde group, an acid anhydride group
- a crosslinkable functional group a carboxy group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, an aldehyde group, an acid anhydride group
- a crosslinkable functional group a carboxy group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, an aldehyde group, an acid anhydride group
- the urea resin can react with a crosslinkable functional group (amino group, hydroxyl group, aldehyde group) possessed by the polymer.
- a crosslinkable functional group amino group, hydroxyl group, aldehyde group
- “Uban 10S60” manufactured by Mitsui Chemicals, Inc. can be used as the urea resin.
- the guanamine resin can react with a crosslinkable functional group (aldehyde group) possessed by the polymer.
- a crosslinkable functional group aldehyde group
- the guanamine resin for example, “Nicarac BL-60” manufactured by Sanwa Chemical Co., Ltd. can be used.
- the alkyd resin can react with a crosslinkable functional group (a carboxy group, a hydroxyl group, an epoxy group, an isocyanate group, an acid anhydride group) possessed by the polymer.
- a crosslinkable functional group a carboxy group, a hydroxyl group, an epoxy group, an isocyanate group, an acid anhydride group
- the alkyd resin for example, “Becozole” manufactured by DIC can be mentioned.
- the dialdehyde compound can react with a crosslinkable functional group (amino group, hydroxyl group) possessed by the polymer.
- a crosslinkable functional group amino group, hydroxyl group
- An example of the dialdehyde compound is glyoxal.
- Acid anhydrides can react with crosslinkable functional groups (amino group, epoxy group, isocyanate group) possessed by the polymer.
- acid anhydrides include tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (Me-THPA), methylhexahydrophthalic anhydride (Me-HHPA), methyl nadic anhydride (NMA), hydrogenated methylnadic acid anhydride (H-NMA), trialkyltetrahydrophthalic anhydride (TATHPA), methylcyclohexenetetracarboxylic dianhydride (MCTC), phthalic anhydride (PA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), ethylene glycol bisanhydro trimellitate (TMEG), glycerin bis (anhydro
- a crosslinking agent may be selected in consideration of reactivity depending on the type of the polymer used. You may use a crosslinking agent 1 type or in combination of 2 or more types.
- Examples of the method of reacting a crosslinkable functional group in a polymer with a crosslinking agent include physical treatment by irradiation with heat and active energy rays (visible light, ultraviolet rays, electron beams, radiation). It is preferably used because the heat treatment is simple. In addition, irradiation with active energy rays such as ultraviolet rays, electron beams, and radiations is preferably used because it can give large energy in a short time and promote the reaction. Further, the reaction of the crosslinking agent can be allowed to proceed without a catalyst, but a catalyst can be added to promote the reaction.
- active energy rays visible light, ultraviolet rays, electron beams, radiation
- the blending ratio of the polymer having a crosslinkable functional group and the crosslinker capable of crosslinking with the functional group is not particularly limited, and a desired crosslink It is appropriately determined in consideration of the degree, the kind of polymer and crosslinking agent, the reactivity between the functional group and the crosslinking agent, the adhesion between the porous layer and the substrate, and the like.
- the crosslinking agent may be 2 to 312.5 parts by weight with respect to 100 parts by weight of the polymer. If the crosslinking agent is less than 2 parts by weight relative to 100 parts by weight of the polymer, the degree of crosslinking will be small.
- the crosslinking agent exceeds 312.5 parts by weight with respect to 100 parts by weight of the polymer, the crosslinking agent becomes excessive, and there is a possibility that the crosslinking agent that does not contribute to the crosslinking reaction remains in the porous layer after the crosslinking treatment.
- About the minimum amount of a crosslinking agent 10 weight part or more of crosslinking agents are preferable with respect to 100 weight part of polymers, and 20 weight part or more of crosslinking agents are more preferable.
- About the upper limit of a crosslinking agent 200 weight part or less of a crosslinking agent is preferable with respect to 100 weight part of polymers, and 150 weight part or less of a crosslinking agent is more preferable.
- the thickness of the porous layer is, for example, 0.1 to 100 ⁇ m, preferably 0.5 to 70 ⁇ m, and more preferably 1 to 50 ⁇ m. If the thickness is too thin, it will be difficult to produce stably, and cushion performance may be degraded, and printing characteristics may be degraded. On the other hand, when it is too thick, it becomes difficult to uniformly control the pore size distribution.
- the cross-linking agent contained in the porous layer is in an unreacted state in which the base material and the porous layer are directly passed through other layers. However, they are laminated with an interlayer adhesion strength that does not cause interface peeling in the tape peeling test.
- the porous layer in the base material is laminated.
- Side blast treatment (sand mat treatment), 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.
- the silane coupling agent those exemplified above can be used.
- a plurality of the surface treatments may be performed in combination, and depending on the substrate, it is preferable that the surface treatment is performed in combination with a silane coupling agent treatment and other treatments.
- each component constituting the base material and the porous layer is the same.
- the structure which at least one part of the monomer unit of each high molecular compound which comprises a base material and a porous layer is common is mentioned.
- the material constituting the substrate / porous layer is polyimide / polyimide, polyamideimide / polyimide, polyimide / polyamideimide, polyetherimide / polyimide, polyimide / polyetherimide, polyamideimide / polyetherimide, polyetherimide.
- the average pore diameter is outside the above range, the pore characteristics are inferior in that it is difficult to obtain a desired effect according to the application.
- the average pore diameter is smaller than 0.01 ⁇ m, cushion performance may be deteriorated or heat insulation may be deteriorated, and the porous layer is difficult to produce by the phase separation method of the present invention.
- the average pore diameter exceeds 10 ⁇ m, it is difficult to uniformly control the pore size distribution in the porous layer, and the relative dielectric constant may be inhomogeneous in each part of the porous layer.
- the average porosity (porosity) inside the porous layer is, for example, 30 to 85%, preferably 35 to 85%, and more preferably 40 to 85%.
- 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 May decrease, and printing characteristics may deteriorate. If the porosity is too high, the strength and folding resistance may be inferior.
- the surface area porosity (surface area ratio) of the porous layer is, for example, 90% or less (for example, 0 to 90%), and preferably about 0 to 80%. If the surface area ratio is too high, the mechanical strength and folding resistance may be easily lowered. Depending on the intended use, the higher the porosity of the surface of the porous layer, the lower the better.
- the adhesive when manufacturing a copper-clad laminate with a low dielectric constant substrate by bonding a porous layer and copper foil, the adhesive may penetrate into the copper foil during bonding with the copper foil, which may reduce the relative dielectric constant.
- the etching solution when a circuit is formed by further etching, the etching solution may penetrate into the porous layer and undesired etching may occur from the inside, so that the surface porosity is preferably low.
- an appropriate opening may be preferable in order to exhibit an anchor effect and ensure adhesion with plating or ink.
- an appropriate opening may be preferable in order to sufficiently wash the water-soluble polar solvent and the water-soluble polymer used when forming the porous layer.
- the porous layer should just be formed in the at least single side
- a porous layer laminate having low dielectric constant, cushioning property, heat insulating property, good printability, etc. on both sides is obtained by taking advantage of its pore characteristics. be able to.
- porous layer by functionalizing the surface of the porous layer, circuit boards, heat dissipation 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
- heat dissipation 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
- substrate materials such as ink image-receiving sheets, insulating materials, heat insulating materials, cell culture substrates, and electrolyte membrane substrates.
- the porous layer laminate of the present invention is, for example, A porous layer forming material solution containing a polymer and a cross-linking agent that constitute the porous layer is cast into a film on the base material, and then brought into contact with a coagulation liquid to make it porous.
- the former method is preferably used as described in detail below.
- a solution of a porous layer forming material containing a polymer to form the porous layer and a crosslinking agent is cast on the substrate in a film form. Thereafter, this is introduced into a coagulating liquid, then dried, and a porous layer laminate is obtained by laminating a porous layer on at least one side of a substrate.
- 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.
- porous layer having a large number of micropores is flexible, the porous layer alone is difficult to handle and the lamination process is difficult. And a porous layer laminate in which a porous layer having excellent pore characteristics and a substrate are directly laminated can be easily obtained.
- the solution of the material for forming a porous layer includes, for example, a polymer component that is a main material constituting the porous layer, a crosslinking agent, and a water-soluble polar solvent. It contains a water-soluble polymer as required and water as required.
- the monomer component (raw material) of the polymer component, its oligomer, a precursor before imidization or cyclization, etc. May be used.
- the temperature of the coagulation liquid is not particularly limited, but may be, for example, 0 to 100 ° C. 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.
- water is preferably used from the viewpoints of cost, safety, toxicity and the like. When water is used as the coagulating 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.
- the cleaning time depends on the thickness of the porous layer and the like and cannot be generally specified, but can be about 0.5 to 30 minutes.
- the porous layer solution is cast in the form of a film on a substrate, and then kept in an atmosphere of a relative humidity of 70 to 100% and a temperature of 15 to 100 ° C. for 0.2 to 15 minutes. It is preferable to immerse in.
- a water-soluble polymer or water is effective for making the membrane structure porous like a sponge.
- the water-soluble polymer include polyethylene glycol, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polysaccharides, derivatives thereof, and mixtures thereof.
- polyvinylpyrrolidone is preferable in that it can suppress the formation of micropores inside the porous layer and improve the mechanical strength of the porous layer.
- These water-soluble polymers can be used alone or in combination of two or more.
- the weight average 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 the molecular weight. It may be 1000 or more.
- the pore size can be adjusted by adding water. For example, increasing the amount of water added to the porous layer solution can increase the pore size.
- the water-soluble polymer is very effective for making the membrane structure into a homogeneous sponge-like porous structure, 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.
- the water-soluble polymer is an unnecessary component to be removed that does not ultimately form a porous layer.
- the water-soluble polymer is removed by washing in a step of phase conversion by dipping in a coagulating liquid such as water.
- a coagulating liquid such as water.
- components that do not constitute the porous layer 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.
- the production method of the present invention easily produces a porous layer laminate having desired pore characteristics. This is advantageous in that it can be done.
- the amount of the water-soluble polymer is preferably the minimum amount. Since the strength tends to decrease as the connectivity increases, it is not preferable to add an excessive amount of the water-soluble polymer. Excessive addition is not preferable because it requires a longer washing time. It is also possible not to use a water-soluble polymer.
- water-soluble polar solvent examples include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone, ⁇ -butyrolactone, and these
- DMAc N-dimethylformamide
- NMP N-methyl-2-pyrrolidone
- 2-pyrrolidone ⁇ -butyrolactone
- the amount of each component in the porous layer solution is 8 to 25% by weight of the polymer component, 0.5 to 25% by weight of the crosslinking agent, and 0% of the water-soluble polymer based on the solution for the porous layer. It is preferable that the content be ⁇ 50 wt%, water 0 ⁇ 10 wt%, and water-soluble polar solvent 30 ⁇ 82 wt%. At this time, if the concentration of the polymer component is too low, the thickness of the porous layer becomes insufficient or it is difficult to obtain desired pore characteristics. On the other hand, if the concentration of the polymer component is too high, the porosity is low. Tend to be smaller.
- the concentration of the crosslinking agent is too low, it is difficult to obtain a sufficient improvement effect of chemical resistance and adhesion to the substrate.
- the concentration of the cross-linking agent is too high, the surface of the resulting porous layer tends to be sticky, and there is a risk that excess cross-linking agent may remain even after cross-linking.
- the concentration of the water-soluble polymer is too high, problems such as poor solubility of each component in the solution for the porous layer and a decrease in the strength of the porous layer are likely to occur.
- the amount of water added can be used to adjust the pore size, and the pore size can be increased by increasing the amount added.
- the porous layer solution is cast into a film on a substrate, and the resulting film is held in an atmosphere of 70 to 100% relative humidity and a temperature of 15 to 100 ° C. for 0.2 to 15 minutes. It is desirable to guide into a coagulating liquid composed of a non-solvent of a polymer component.
- a highly homogeneous porous layer can be easily obtained. When placed under humidification, it is considered that moisture penetrates from the surface of the film into the inside and promotes phase separation of the polymer solution efficiently.
- Preferred conditions are a relative humidity of 90 to 100% and a temperature of 30 to 80 ° C., and a more preferred condition is a relative humidity of about 100% (eg, 95 to 100%) and a temperature of 40 to 70 ° C. If the amount of moisture in the air is less than this, the porosity may not be sufficient.
- a porous layer having a large number of micropores and having an average pore diameter of 0.01 to 10 ⁇ m can be easily formed.
- the diameter of the micropores, the porosity, and the porosity of the porous layer constituting the porous layer laminate in the present invention are the types and amounts of the constituent components of the polymer solution, the amount of water used, as described above. It can be adjusted to a desired value by appropriately selecting the humidity, temperature, time, etc. during casting.
- 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.
- a polyamideimide resin or polyamic acid may be used.
- Any solvent can be used, for example, water; monohydric alcohols such as methanol and ethanol; alcohols such as polyhydric alcohols such as glycerin; water-soluble polymers such as polyethylene glycol; water-soluble coagulating liquids such as mixtures thereof Can be used.
- 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. However, the drying process at this time is performed at a temperature lower than the glass transition temperature (Tg) of the composition constituting the porous layer. At the time of drying treatment, care is taken so that the composition constituting the porous layer is not softened and the micropores are not lost. When the micropores disappear, the printing characteristics on the porous layer deteriorate.
- Tg glass transition temperature
- the method for the drying 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 or an oven as long as the laminate can be controlled to a predetermined temperature.
- the atmosphere during the drying process may be air, nitrogen or an inert gas.
- the use of air is the least expensive but may involve an oxidation reaction.
- 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.
- Crosslinking treatment is performed on the obtained porous layer laminate.
- the crosslinking agent contained in the porous layer is usually in an unreacted state.
- a crosslinked structure may be formed by the reaction of a part or all of the crosslinking agent depending on the drying treatment conditions.
- the crosslinking treatment can be performed by heat treatment and / or active energy ray irradiation (visible light, ultraviolet ray, electron beam, radiation, etc.) treatment depending on the type of the crosslinking agent. Appropriate conditions should be set for each.
- the heat treatment is preferably performed at 100 to 400 ° C. for 10 seconds to 5 hours.
- the crosslinkable functional group in the polymer and the functional group of the crosslinking agent react to form a crosslinked structure in the porous layer.
- a laminate having excellent film strength, heat resistance, chemical resistance and durability of the porous layer itself can be obtained.
- crosslinking is formed also in the interface of a board
- a laminate having even more excellent adhesion and rigidity between the substrate and the porous layer can be obtained.
- a functional layer is provided on the surface of the porous layer (functionalization treatment) to obtain the functional laminate of the present invention
- the crosslinking treatment by heating may also serve as the heat treatment for expressing the function of the functional layer.
- the obtained porous layer laminate is subjected to a partial cross-linking treatment, and then a functional layer is provided on the surface of the porous layer, and the cross-linking treatment is performed again to complete the cross-linking treatment.
- the partial cross-linking treatment is intended to be a semi-cured state (so-called B stage).
- a laminate comprising a base material, and a porous layer composed of a composition containing a polymer on one or both sides of the base material and a crosslinking agent, the porous A laminate having an average pore diameter of 0.01 to 10 ⁇ m in the porous layer and a porosity of 30 to 85% can be easily obtained.
- the porous layer laminate of the present invention may be subjected to heat treatment or film formation treatment as necessary in order to impart desired characteristics.
- the porous layer laminate of the present invention has excellent chemical resistance due to the formation of a crosslinked structure, but the porous layer may be further subjected to chemical resistance imparting treatment.
- chemical resistance imparting treatment By imparting chemical resistance to the porous layer, it is possible to avoid problems such as delamination, swelling, dissolution, and alteration when in contact with solvents, acids, alkalis, etc. This is advantageous in that it can.
- 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 compound.
- 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.
- specific examples of such chemicals include dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 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); water Sodium oxide, potassium hydroxide, calcium hydroxide, sodium carbonate, Inorganic salts such as potassium carbonate; amines such as triethylamine; alkaline solutions such as aqueous solutions
- 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.
- 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.
- the porous layer laminate When the porous layer is coated with such a chemical-resistant polymer compound, the porous layer laminate is dissolved even when it comes into contact with the strong polar solvent, alkali, acid or other chemicals. Or can be suppressed to a degree that does not affect the purpose of use or use. 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.
- the chemical-resistant polymer compound often has heat resistance, so that the heat resistance of the porous layer is unlikely to decrease. It is also possible to change the characteristics of the porous layer surface by coating with a chemical resistant polymer compound.
- a chemical resistant polymer compound For example, if a fluororesin is used, the surface can be made water-repellent, and if an ethylene-vinyl alcohol copolymer is used, the surface can be made hydrophilic.
- a phenolic resin is used, the surface can be rendered water repellent with respect to neutral water and the surface can be rendered hydrophilic with respect to an alkaline aqueous solution.
- the affinity (hydrophilicity etc.) with respect to a liquid can be changed by selecting suitably the kind of high molecular compound used for coating
- the porous layer laminate of the present invention has the above configuration, it can be applied to various uses in a wide range of fields. Specifically, it can be used as a substrate material such as a low dielectric constant material, a separator, a cushioning material, an ink image receiving sheet, a test paper, an insulating material, a heat insulating material, etc. by directly utilizing the pore characteristics of the porous layer. . Furthermore, as a functional laminate (composite material) in which other layers (metal plating layer, magnetic plating layer, etc.) are laminated on the porous layer, for example, circuit boards, heat dissipation materials (heat sinks, heat dissipation plates, etc.), electromagnetic wave shields, etc. And an electromagnetic wave control material such as an electromagnetic wave absorber, an antenna, and a cell culture substrate.
- a substrate material such as a low dielectric constant material, a separator, a cushioning material, an ink image receiving sheet, a test paper, an insulating material,
- the functional laminate of the present invention comprises a conductor layer, a dielectric layer, a semiconductor layer, and an insulator layer on the surface of the porous layer of the porous layer laminate described above or the polymer layer derived from the porous layer.
- Such a functional laminate is sometimes referred to as “composite material” in the present specification.
- Formation of various functional layers or precursor layers thereof on the surface of the porous layer described above can be performed by, for example, plating, printing technology, or the like.
- the metal plating layer may be formed as a thin metal coating on the surface of the porous layer, for example.
- 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.
- alloy films are also included.
- 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 has magnetism, and may be either a ferromagnetic material or a paramagnetic material.
- An organic magnetic material made of a compound such as polyacrylonitrile can be exemplified.
- the metal plating layer for example, known methods such as electroless plating and electrolytic plating can be used.
- electroless plating is preferably used from the viewpoint 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 the manufacturer 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.
- 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 layer laminate of the present invention.
- Providing a photosensitive layer exposing the photosensitive layer through a mask, generating a reactive group in the exposed portion, and forming a conductive pattern by combining the reactive group generated in the exposed portion with a metal.
- a method comprising a step of bonding to a metal to form a conductor pattern.
- 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).
- a metal including a metal ion.
- 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.
- 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.
- a cation exchange group is used.
- the cation exchange group includes, for example, an acidic group such as —COOX group, —SO 3 X group or —PO 3 X 2 group (where X is a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium group). ) Etc. are included.
- a cation exchange group having a pKa value of 7.2 or less is preferable because a bond with a sufficient metal per unit area can be formed, and desired conductivity can be easily obtained.
- 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.
- light having a wavelength of 280 nm or more can be used.
- the wavelength is preferably Light of 300 nm or more (about 300 to 600 nm), particularly 350 nm or more is preferably used.
- a pattern composed of reactive groups can be formed in the exposed part or the unexposed part by irradiating with light through a mask after washing as necessary. 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.
- a method by electroless plating 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 surface of the porous layer 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.
- 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.
- 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 Then contact the catalyst metal acid or alkali solution to contact the activator (activation) solution to deposit the catalyst metal (sensitizing (sensitization) -activate (activate) ) Method).
- a metal-salt-containing solution such as a tin-palladium mixed solution or copper sulfate
- the catalyzer-accelerator method is, for example, by immersing the porous layer 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.
- a catalyst nucleus composed of copper fine particles can be formed on the surface of the porous layer of the porous layer laminate.
- 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.
- a catalytic nucleus made of palladium can be precipitated by contacting with a hydrochloric acid solution of palladium chloride.
- a method of bringing the porous layer laminate into contact with these treatment liquids a method of coating the surface of the porous layer on which the metal plating layer is laminated, a method of immersing the porous layer laminate in the treatment liquid, or the like can be used. .
- the substrate is formed with a homogeneous layer. It is preferable that When a porous layer 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 layer laminate, but also on the substrate surface. A large amount of catalyst nuclei adhere to and are easily retained on the surface of a large porous layer, whereas on a homogeneous substrate, the substrate film surface is smooth so that the catalyst nuclei are less likely to precipitate and fall off easily. . 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 in 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 layer laminate subjected to the above treatment in the above plating solution.
- electroless plating is performed only on the other surface by applying electroless plating with a protective sheet applied to one side of the porous layer laminate, for example, metal deposition on the substrate is prevented. can do.
- the thickness of the metal plating layer is not particularly limited and can be appropriately selected depending on the application. For example, it is about 0.01 to 20 ⁇ m, preferably about 0.1 to 10 ⁇ m.
- 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.
- circuit boards are manufactured by a method in which a copper foil is bonded to the surface of a substrate generally made of glass, epoxy resin, polyimide or the like, and wiring is formed by removing unnecessary portions of the copper foil by etching. It was. 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.
- the composite material of the present invention it is also possible to form a fine opening on the surface of the porous layer of the porous layer laminate, and in that case, sufficient adhesion to the metal plating layer is achieved.
- This is suitable for a circuit board material having fine wiring.
- the metal plating layer is preferably made of copper, nickel, silver or the like.
- the porous layer laminate of the present invention is extremely useful as a circuit board manufactured by a method of forming fine wiring directly on the porous layer surface.
- the method described as the method for producing a composite material of the present invention can be used.
- fine wiring firmly entangled with the porous layer can be formed, and wiring can be accurately and easily formed using an exposure technique.
- 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.
- a hole can be formed by a conventionally used drill or laser and filled by conductive paste or plating.
- a method of forming a wiring by using an electroless plating method on a porous body has been known.
- 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.
- the porous layer laminate of the present invention is used, the porous layer is molded in close contact with the base material, so that a sufficient strength can be ensured and the circuit board has excellent handling properties. Can be provided.
- Electromagnetic wave control materials are used as materials for shielding (shielding) or absorbing 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.
- electromagnetic sources such as electric / electronic devices, wireless devices, systems, etc. around 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.
- 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 it is effective to be formed of, for example, 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 materials used when forming a 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 layer laminate of the present invention is also useful as a low dielectric constant material.
- the frequency used in electronic devices is also increasing, and the electronic components used therein must also support high-frequency signals.
- conventional wiring boards mainly glass epoxy resin
- 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.
- the porous layer laminate of the present invention is laminated on the base material and not only has low dielectric constant characteristics, but also is sufficient for handling because the porous layer is in close contact with the base material. Is a preferable medium as a low dielectric constant material.
- the porous layer laminate of the present invention When the porous layer laminate of the present invention is used as a circuit board material having a low dielectric constant, as described above, a copper foil is bonded to the surface of the porous layer, and unnecessary portions of the copper foil are removed by etching. It is conceivable to manufacture by a method of forming a wiring. Although miniaturization and high density of wiring are becoming difficult, most circuit boards are still made by this conventional method, and the porous layer laminate of the present invention can also be used by this method. 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.
- One form of the method for producing the composite material of the present invention is a method using a printing technique. Since the porous layer laminate of the present invention is excellent in printing characteristics, it can be used by forming a pattern on the porous layer by printing. Since it is also used as an ink image receiving sheet (printing medium) in this way, the printing technique will be described in detail next.
- Ink receiving sheets also called print media
- print media are often used in printing technology.
- many printing methods are currently put into practical use and used.
- inkjet printing screen printing, dispenser printing, letterpress printing (flexographic printing), sublimation printing, offset printing, laser, etc.
- 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 can be significantly reduced, it is also true that high-definition printing is required, which is unprecedented and 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.
- the porous layer 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 be in close contact with the printing plate due to its cushioning property, and Since the ink can be sucked or the ink can be fixed precisely, high-definition printing which has never been achieved can be achieved, and it is very preferably used.
- 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.
- an electronic material is manufactured by printing
- the above-described method can be used as a printing method.
- electronic materials produced by printing include electromagnetic wave control materials such as electromagnetic wave shields and electromagnetic wave absorbers, circuit boards, antennas, heat sinks, and the like. More specifically, liquid crystal displays, organic EL displays, Field emission display (FED), IC card, IC tag, solar cell, LED element, organic transistor, capacitor (capacitor), electronic paper, flexible battery, flexible sensor, membrane switch, touch panel, EMI shield and the like can be mentioned.
- electromagnetic wave control materials such as electromagnetic wave shields and electromagnetic wave absorbers, circuit boards, antennas, heat sinks, and the like. More specifically, liquid crystal displays, organic EL displays, Field emission display (FED), IC card, IC tag, solar cell, LED element, organic transistor, capacitor (capacitor), electronic paper, flexible battery, flexible sensor, membrane switch, touch panel, EMI shield and the like can be mentioned.
- the method for producing the electronic material includes a step of printing on the surface of the porous layer (substrate) an ink containing an electronic material such as a conductor, a dielectric, a semiconductor, an insulator, or a resistor.
- an electronic material such as a conductor, a dielectric, a semiconductor, an insulator, or a resistor.
- a 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.
- the semiconductor pentacene, liquid silicon, fluorene-bithiophene copolymer (F8T2), poly (3-hexylthiophene) (P3HT), and the like can be given.
- wiring can be formed by printing with ink containing a conductive material, a flexible substrate, a TAB substrate, an antenna, or the like can be manufactured.
- 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.
- the polythiophene include poly (ethylenedioxythiophene) (PEDOT). These can be used as a solution or a colloidal ink.
- 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.
- the shape of the particles examples 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 ⁇ m to several nanometers can also be used. These particles can be used by mixing a plurality of types.
- 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.
- the silver ink generally contains silver particles, a surfactant, a binder, a solvent and the like as its constituent components.
- an ink containing silver oxide particles is printed and then heated and reduced to form a silver wiring.
- an ink that contains an organic silver compound and is then thermally decomposed to form a silver wiring 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.
- 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 layer laminate of the present invention is an organic material, the firing temperature is preferably relatively low in order to avoid deterioration, but in order to reduce the electrical resistance of the wiring, it is generally fired at a high temperature. Preferably, it is necessary to select and use an ink having an appropriate curing temperature.
- the particle diameter is preferably about 0.01 to 10 ⁇ m.
- the saddle wiring may be formed only on one side of the porous layer, or may be formed on both sides of the substrate when the porous layer exists 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.
- the wiring surface formed of conductive ink can be used by being coated with plating or an insulator.
- 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.
- plating include copper plating, gold plating, and nickel plating. Plating can be performed by a known method.
- the surface of the wiring formed with conductive ink can be used by coating with resin.
- the above configuration can be suitably used for purposes such as wiring protection, wiring insulation, wiring oxidation and migration prevention, and flexibility improvement.
- the silver wiring becomes silver oxide by oxidation and the copper wiring becomes copper oxide, and the conductivity may decrease.
- the wiring surface with the resin 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.
- the porous layer portion has a low dielectric constant, it is preferably used as a high-frequency wiring board.
- the porous layer laminate of the present invention is used in addition to the case where the porous layer voids are left as they are, It is also conceivable to use it by losing it.
- the porous layer is composed of independent micropores with low communication, the resin does not easily enter the pores, and the pore structure tends to be maintained. On the contrary, when the porous layer is composed of fine pores having communication properties, the resin easily enters the pores, so that the pores are filled with the resin and the pore structure tends to disappear.
- resin which coats wiring Although it does not specifically limit as resin which coats wiring, for example, the curable resin used without a solvent, the soluble resin utilized by melt
- the curable resin examples 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.
- 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.
- a latent curing agent commercially available products such as “Sun-Aid SI” manufactured by Sanshin Chemical Industry Co., Ltd. can be used.
- a highly flexible material is used as the cured epoxy resin, it can be made flexible like a flexible substrate. Moreover, when heat resistance and high dimensional stability are requested
- the curable resin composition When using an epoxy resin 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.
- oxetane resin examples 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 irradiation 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”, polyimide material “ULIN COAT” manufactured by NI Material, polyimide ink “Q-PILON” manufactured by PI Research 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.
- the solvent for dissolving the soluble resin used at the time of covering 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.
- 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.
- a plastic spatula is preferably used because it hardly damages the wiring and the porous layer.
- 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.
- an uncured resin having a low viscosity is preferably used.
- the curing reaction rate is increased by heating, so that heating more than necessary is not preferable because workability deteriorates.
- 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 porous layer in addition to the case where the porous structure of the porous layer is maintained, the porous layer has a void after the functional layer is formed on the surface of the porous layer (after functionalization).
- the case where the pore structure is lost and the porous layer is preferably transparent is also included.
- the porous layer laminate of the present invention can achieve high-definition printing on the porous layer due to the pore characteristics of the porous layer.
- the porous structure is whitened and opaque by causing irregular reflection of visible light. Therefore, the usage is limited as it is. Therefore, by selecting a composition that constitutes the porous layer having a glass transition temperature of 20 ° C. or higher, the pore structure of the porous layer is lost by heat treatment to suppress the irregular reflection of visible light. Can be made transparent.
- the porous layer is made transparent by heating the porous layer stack in which various functional layers (patterns) are formed on the surface of the porous layer, so that the porous layer is slightly softened and the pore structure inside the porous layer This is realized by disappearance of.
- the laminated body according to any one of the above (1) to (4) is subjected to a heat treatment at a temperature equal to or higher than a glass transition temperature of the composition constituting the porous layer, A method of eliminating micropores in a porous layer and converting the porous layer into a transparent layer.
- the composition constituting the porous layer usually has a glass transition temperature of 20 ° C. or higher, which is equal to or higher than the glass transition temperature (Tg) of the composition and lower than the heat resistance temperature of the substrate. It is softened and deformed at a temperature lower than the decomposition temperature of the composition (including a polymer as a main component, a crosslinking agent, and other optional components) constituting the porous layer. Therefore, although it depends on the type of the substrate, the composition constituting the porous layer preferably has a glass transition temperature of, for example, 280 ° C. or lower, preferably 200 ° C. or lower, or 130 ° C. or lower.
- the heat treatment for converting the porous layer into a transparent layer is a composition that constitutes the porous layer at a temperature equal to or higher than the glass transition temperature of the composition constituting the porous layer and lower than the heat resistance temperature of the substrate. Can be carried out at a temperature lower than the decomposition temperature. That is, the upper limit of the heat treatment temperature is less than the lower one of the heat-resistant temperature of the substrate and the decomposition temperature of the composition constituting the porous layer.
- the decomposition temperature (decomposition start temperature) of the composition constituting the porous layer is 15 ° C. or higher than the glass transition temperature of the composition constituting the porous layer, preferably It must be 30 ° C or higher, more preferably 50 ° C or higher.
- the larger the temperature difference the more stable heat treatment can be performed. Therefore, although there is no particular upper limit for this temperature difference, in general, polymer components are often decomposed in the region of 200 ° C. or higher (Tg + 200 ° C.) above the glass transition temperature (Tg).
- the upper limit for the temperature difference is 200 ° C.
- the composition constituting the porous layer is softened and deformed, the micropores disappear, and the porous layer is converted into a transparent layer.
- the porous layer is converted into a transparent layer only by heat treatment without using a solvent.
- a group consisting of a substrate, a transparent layer containing the polymer on the substrate as a main component, and a conductor layer, a dielectric layer, a semiconductor layer, an insulator layer, and a resistor layer on the transparent layer A functional laminate having a functional layer more selected, On the surface of the porous layer of the laminate according to any one of (1) to (4) above, a conductor layer, a dielectric layer, a semiconductor layer, an insulator layer, a resistor layer, and the layer Forming a layer selected from the group consisting of the precursor layers of:
- the obtained laminate is subjected to a heat treatment at a temperature equal to or higher than the glass transition temperature of the composition constituting the porous layer, the micropores in the porous layer disappear, and the porous layer becomes a transparent layer. Converting to Performing a heat treatment and / or an active energy ray irradiation treatment to form a crosslinked structure with the crosslinking agent in the porous layer; and Functional laminate obtained by performing
- the “transparent layer containing a polymer as a main component” is a layer corresponding to the “polymer layer derived from the porous layer”.
- a method for producing a functional laminate having a functional layer more selected On the surface of the porous layer of the laminate according to any one of (1) to (4) above, a conductor layer, a dielectric layer, a semiconductor layer, an insulator layer, a resistor layer, and the layer Forming a layer selected from the group consisting of the precursor layers of:
- the obtained laminate is subjected to a heat treatment at a temperature equal to or higher than the glass transition temperature of the composition constituting the porous layer, the micropores in the porous layer disappear, and the porous layer becomes a transparent layer. Converting to Performing a heat treatment and / or an active energy ray irradiation treatment to form a crosslinked structure with the crosslinking agent in the porous layer; and The manufacturing method of a functional laminated body containing this.
- the precursor layer of the layer is a layer that can be converted into a conductor layer, a dielectric layer, a semiconductor layer, an insulator layer, a resistor layer, for example, by heat treatment after the precursor layer is formed. I mean.
- the crosslinking agent may react to form a crosslinked structure.
- the porous layer is immediately heated to a temperature region where the porous layer softens, and the softening and transparency of the porous layer is completed, and then the crosslinking agent is reacted. A cross-linked structure is formed. If the crosslinked structure is formed first, the porous layer will no longer soften and the porous structure will be maintained.
- the material to be used may be selected so that the softening temperature of the porous layer is higher than the heat treatment temperature for forming the crosslinked structure. (The porous structure is maintained even after the crosslinked structure is formed by performing the heat crosslinking treatment at a temperature lower than the softening temperature of the porous layer.)
- the heat treatment is preferably performed below the melting temperature of the composition constituting the porous layer.
- the porous layer composition melts, so that the micropores disappear and the porous layer is converted into a transparent layer, but the porous layer composition is melted. If it does, it will become difficult to maintain the pattern of the patterned functional layer formed on the porous layer.
- a base material As a base material, it is light transmissive, has a heat resistance temperature higher than the glass transition temperature of the composition constituting the porous layer, and is practical at a temperature at which the composition constituting the porous layer softens and deforms.
- the obtained functional laminated body can be used for various uses as which a light transmittance is requested
- the transparency index of the transparent layer converted from the porous layer is the total light transmittance (%) of the used base material itself and the transparent laminate (base material + transparent layer). ) Can be expressed as an absolute value of a difference from the total light transmittance (%).
- Tst total light transmittance of base material itself ⁇ total light transmittance (Tst) of laminate (base material + transparent layer)
- the absolute value of the difference between (Ts) and (Tst) is used because the value of (Tst) may be larger than the value of (Ts).
- the minute irregularities are smoothed by the presence of the transparent layer on the surface to suppress irregular reflection, and the value of (Tst) ) Is considered to be larger.
- the transparency (T) value of the transparent layer is, for example, 0 to 30%, preferably 0 to 20%, more preferably 0 to 10%, especially 0-5%. If the value of the transparency (T) of the transparent layer exceeds 30%, the conversion of the porous layer to the transparent layer will be insufficient.
- the total light transmittance (%) of the laminate (base material + transparent layer) needs to be measured at a portion where a functional layer such as a conductor layer is not formed. The functional layer generally prevents light transmission.
- the total light transmittance can be measured using a NDH-5000W haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136.
- the thickness of the obtained transparent layer is calculated based on the thickness of the porous layer and the porosity.
- Transparent layer thickness porous layer thickness ⁇ (100 ⁇ porosity) / 100
- the thickness of the porous layer is 0.1 to 100 ⁇ m and the porosity is 30 to 85%
- the thickness of the transparent layer can be in the range of 0.015 ⁇ m to 70 ⁇ m.
- the desired thickness of the transparent layer may be appropriately determined with reference to the preferable range of the thickness of the porous layer and the preferable range of the porosity.
- the transparent resin layer derived from the porous layer can facilitate the inspection of the wiring when used for a wiring board, for example, and it is easy to recognize the positional relationship of components when the wiring board is assembled to a device. It is advantageous in that it is excellent in handleability. Furthermore, it is preferable that the substrate of the porous layer laminate has high transparency.
- the substrate of the porous layer laminate used in the present invention is preferable because it has heat resistance that does not deform at the heat treatment temperature for making the porous layer transparent. When the base material is deformed, the dimensional stability as the wiring board is lowered.
- the upper limit temperature of the heat treatment for transparentization of the porous layer varies depending on the substrate and cannot be generally stated.
- the heating temperature is preferably 400 ° C. or lower, preferably 300 ° C. or lower, particularly preferably 260 ° C. or lower.
- the heat treatment time cannot be generally specified depending on the components constituting the porous layer, it is preferably 1 minute to 3 hours, and preferably about 3 minutes to 1 hour. Heating may be performed in one stage or in two stages. For example, when a functional material that can be baked at a low temperature such as silver ink is used, the ink may be printed, the ink baked, and then the temperature may be raised to perform a clearing treatment. You may carry out in one step, setting to the temperature which can be applied to both baking and clearing treatment.
- the composition constituting the porous layer When making the porous layer transparent by heat treatment, the composition constituting the porous layer must have a glass transition temperature of 20 ° C. or higher. If the glass transition temperature is lower than 20 ° C., the porous structure may change even at room temperature, which is not preferable.
- an electromagnetic wave is generated from a display such as a PDP, causing an adverse effect (noise) on peripheral devices.
- a display such as a PDP
- an adverse effect noise
- a film is used.
- the electromagnetic shielding film for the above uses generally has a structure in which a metal layer is laminated on a highly transparent film (highly transparent film).
- 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.
- an electromagnetic wave shielding film there can be mentioned a film having a lattice pattern having a line width of 20 to 30 ⁇ m and a pitch (repetition interval) of about 300 ⁇ m.
- an electromagnetic wave shielding film having the above-described configuration can be provided by forming a lattice-like wiring in the porous layer laminate and then performing a transparent 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.
- the transparency of the wiring part can be further increased by printing using ITO (indium tin oxide) ink, which is a transparent conductor (visible light transmittance of about 90%).
- ITO ink Indium tin oxide
- 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 structure 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.
- 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.
- the solvent treatment is not performed.
- the wiring portion may be covered with a resin by the above-described method.
- the wiring 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.
- the porous structure can be made transparent by the above method, the wiring may remain bare in this case. It is preferable to reliably insulate by covering with resin as described above or forming a coverlay.
- the wiring board is usually joined to other components and boards with solder, connectors or the like in order to allow electricity to flow. Therefore, the contact portion must be filled with a resin in a masked state or coated with a resin while avoiding the contact portion.
- a resin the above-described curable resin or soluble resin can be used as a resin for covering the wiring.
- the wiring board is not only formed by wiring, but semiconductor chips, capacitors, resistors, 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 layer stack, but also on both sides, and a plurality of substrates can be stacked to be multilayered.
- a coverlay may be laminated on the porous layer.
- 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.
- 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.
- a coverlay film such as a polyimide film or a PET film after the solvent treatment to the porous layer. It is done.
- 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 layered product of the present invention can be used for an antenna having higher frequency characteristics.
- 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).
- an antenna with more excellent high frequency characteristics can be manufactured.
- a manufacturing method a subtractive method can be used. Specifically, as shown in the method of manufacturing a low dielectric constant circuit board, a copper layer is bonded to a porous layer laminate or a porous film surface based on a resin film, and after the resist pattern is formed This can be done by removing unnecessary portions of the copper foil by etching. As another method, after forming a resist pattern on a porous layer laminate having a metal foil such as copper as a base material, etching can be performed to remove unnecessary portions of the copper foil. .
- the subtractive method currently performed is a method with a long process, and requires a labor and cost.
- 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.
- Japanese Patent Laid-Open No. 2006-237322 discloses a method for producing a copper polyimide substrate.
- a method for producing a copper polyimide substrate comprising hydrophilizing a surface of a polyimide resin film, providing a physical development nucleus layer, forming a silver film by a silver diffusion transfer method, and then copper plating. Since the polyimide resin film does not have good adhesion, alkali treatment or corona discharge treatment is required for surface modification.
- the porous layer laminate of the present invention since a porous layer having a large number of fine holes can be formed on the polyimide resin film, the adhesive layer thereon can enter the holes, Stronger adhesion can be expected due to the anchor effect. Therefore, the porous layer laminate can be preferably used for the above applications.
- 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.
- 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.
- ⁇ represents a circumference ratio.
- Surface or internal average pore diameter [ ⁇ m] 2 ⁇ (Save / ⁇ ) 1/2
- Porosity The porosity in the porous layer was calculated from the following formula.
- V is the volume of the porous layer [cm 3 ]
- W is the weight of the porous layer [g]
- ⁇ is the density of the porous layer composition [g / cm 3 ] (where the density of the porous layer composition is , Calculated by dividing the density of each component constituting the composition by weight composition ratio).
- the volume V of the porous layer and the weight W of the porous layer were calculated by subtracting the volume or weight of the substrate from the volume or weight of the laminate in which the porous layer was laminated on the substrate, respectively.
- Porosity [%] 100-100 ⁇ W / ( ⁇ ⁇ V)
- the density of each component in the porous layer composition is as follows. Polyamideimide Viromax N-100H density: 1.45 [g / cm 3 ] Polyimide Pyre-M. L. RC5019 density: 1.43 [g / cm 3 ] Density of epoxy resin YDCN-700-5: 1.21 [g / cm 3 ] Density of epoxy resin jER 828: 1.17 [g / cm 3 ] Density of epoxy resin jER 834: 1.18 [g / cm 3 ] Density of epoxy resin jER 1001: 1.19 [g / cm 3 ] Density of epoxy resin jER 1004: 1.19 [g / cm 3 ] Density of epoxy resin jER 152: 1.21 [g / cm 3 ]
- tape peeling test The interlayer adhesion between the base material of the laminate and the porous layer in an uncrosslinked state was determined by the following tape peeling test.
- (I) A 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). ).
- Adhesion evaluation test (cross-cut method) The interlayer adhesion between the base material of the laminate and the porous layer before and after the heat crosslinking treatment was carried out according to the adhesion evaluation test (cross-cut method) of JIS K 5600-5-6. The sample was tested by forming a crosscut with a cut interval of 2 mm.
- As the transparent pressure-sensitive adhesive tape Nichiban's cello tape (registered trademark) NO. 405 24 mm wide (adhesive strength 4.00 N / 10 mm) was used.
- the evaluation after tape peeling was also in accordance with JIS K 5600-5-6.
- Example 1 Porous layer laminate A
- Polyamideimide resin solution (trade name “Bilomax N-100H” manufactured by Toyobo Co., Ltd .; solid content concentration 20% by weight, solvent NMP (N-methyl-2-pyrrolidone), solution viscosity 350 dPa ⁇ s / 25 ° C.), A novolak type epoxy resin (trade name “YDCN-700-5” manufactured by Toto Kasei Co., Ltd.) as a cross-linking agent and NMP as a solvent were mixed at a weight ratio of 15 / polyamideimide resin / NMP / novolac type epoxy resin. Mixing was performed at a ratio of 85/5 to obtain a stock solution for film formation.
- a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m), which is a base material, is fixed on a glass plate with a tape, and this stock solution at 25 ° C. is used as a film applicator. And the substrate was cast under the condition of a gap of 51 ⁇ m. 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, the laminated body A by which the porous layer was laminated
- the substrate and the porous layer did not cause interfacial peeling.
- the porous layer was in close contact with the polyimide film, and a skin layer was basically formed on the surface of the porous layer.
- Independent micropores having an average pore diameter of about 1.5 ⁇ m were present throughout the entire area.
- the porosity inside the porous layer was 80%.
- Example 2 Porous layer laminate B
- the same operation as in Example 1 was carried out except that the weight ratio of polyamideimide resin / NMP / novolak type epoxy resin was mixed at a ratio of 15/85/10 to obtain a stock solution for film formation.
- a laminate B in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 11 ⁇ m, and the total thickness of the laminate was about 61 ⁇ m.
- Example 3 Porous layer laminate C
- the weight ratio of polyamideimide resin / NMP / novolak type epoxy resin was mixed in a ratio of 15/85/15 to obtain a stock solution for film formation. Operation was performed to obtain a laminate C in which a porous layer was laminated on a substrate. The thickness of the obtained porous layer was about 21 ⁇ m, and the total thickness of the laminate was about 71 ⁇ m.
- Example 1 Porous layer laminate D
- the cross-linking agent was not added to the stock solution for film formation, but the mixture was mixed at a ratio of 15/85 of the weight ratio of polyamideimide resin / NMP to obtain a stock solution for film formation.
- the same operation as in Example 1 was performed to obtain a laminate D in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 15 ⁇ m, and the total thickness of the laminate was about 65 ⁇ m.
- Example 4 Porous layer laminate E
- a bisphenol A type epoxy resin (trade name “jER 828” manufactured by Japan Epoxy Resin Co., Ltd.) as a crosslinking agent
- the weight ratio of polyamideimide resin / NMP / bisphenol A type epoxy resin is 20 /
- a laminate E in which a porous layer was laminated on a substrate was obtained by performing the same operation as in Example 1 except that a raw solution for film formation was obtained by mixing at a ratio of 80/10.
- the thickness of the obtained porous layer was about 23 ⁇ m, and the total thickness of the laminate was about 73 ⁇ m.
- Example 5 Porous layer laminate F
- a weight ratio of polyamideimide resin / NMP / bisphenol A type epoxy resin is 20 /
- a film-forming stock solution was obtained by mixing at a ratio of 80/10 to obtain a laminate F in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 29 ⁇ m, and the total thickness of the laminate was about 79 ⁇ m.
- FIG. 1 shows an electron micrograph (x5000 times) of the porous layer surface
- FIG. 2 shows an electron micrograph (x2000 times) of a cross section of the laminate.
- Example 6 Porous layer laminate G
- a bisphenol A type epoxy resin (trade name “jER 1001” manufactured by Japan Epoxy Resin Co., Ltd.) as a crosslinking agent
- the weight ratio of polyamideimide resin / NMP / bisphenol A type epoxy resin is 20 /
- a stock solution for film formation was obtained by mixing at a ratio of 80/10 to obtain a laminate G in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 34 ⁇ m, and the total thickness of the laminate was about 84 ⁇ m.
- the substrate and the porous layer did not cause interface peeling.
- the porous layer was in close contact with the polyimide film, and a skin layer was basically formed on the surface of the porous layer. Independent micropores having an average pore diameter of about 1.8 ⁇ m were present throughout the entire area. The porosity inside the porous layer was 70%.
- Example 7 Porous layer laminate H
- a bisphenol A type epoxy resin (trade name “jER 1004” manufactured by Japan Epoxy Resin Co., Ltd.) was used as a crosslinking agent, and the weight ratio of polyamideimide resin / NMP / bisphenol A type epoxy resin was 20 /
- a film-forming stock solution was obtained by mixing at a ratio of 80/10 to obtain a laminate H in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 30 ⁇ m, and the total thickness of the laminate was about 80 ⁇ m.
- the substrate and the porous layer did not cause interface peeling.
- the porous layer was in close contact with the polyimide film, and a skin layer was basically formed on the surface of the porous layer. There were independent micropores that were almost homogeneous and had an average pore diameter of about 1.8 ⁇ m over the entire area. The porosity inside the porous layer was 71%.
- Example 8 Porous layer laminate I
- a phenol novolac type epoxy resin (trade name “jER 152” manufactured by Japan Epoxy Resin Co., Ltd.) was used as a crosslinking agent, and the weight ratio of polyamideimide resin / NMP / phenol novolac type epoxy resin was 20 /
- a film-forming stock solution was obtained by mixing at a ratio of 80/10 to obtain a laminate I in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 31 ⁇ m, and the total thickness of the laminate was about 81 ⁇ m.
- Example 2 Porous layer laminate J
- a polyamideimide resin solution (trade name “Vilomax N-100H” manufactured by Toyobo Co., Ltd .; solid content concentration 20% by weight, solvent NMP, solution without adding a crosslinking agent to the stock solution for film formation
- solvent NMP solvent
- Example 2 a polyamideimide resin solution (trade name “Vilomax N-100H” manufactured by Toyobo Co., Ltd .; solid content concentration 20% by weight, solvent NMP, solution without adding a crosslinking agent to the stock solution for film formation
- the same operation as in Example 1 was performed except that the viscosity of 350 dPa ⁇ s / 25 ° C.) was directly used as a stock solution for film formation, to obtain a laminate J in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 14 ⁇ m, and the total thickness of the laminate was about 64 ⁇ m. That is, in the stock solution for film formation,
- the substrate and the porous layer did not cause interface peeling.
- the porous layer was in close contact with the polyimide film, the skin layer was basically formed on the surface of the porous layer, and the inside of the porous layer was almost homogeneous. There were independent micropores having an average pore diameter of about 1.2 ⁇ m over the entire area. The porosity inside the porous layer was 77%.
- Example 9 Porous layer laminate K
- Polyamideimide resin (trade name “Torlon AI-10” manufactured by Solvay Advanced Polymers), NMP as a solvent, and bisphenol A type epoxy resin as a crosslinking agent (trade name “jER 828” manufactured by Japan Epoxy Resin Co., Ltd.) ) was mixed at a ratio such that the weight ratio of polyamideimide resin / NMP / bisphenol A type epoxy resin was 25/75/5 to obtain a stock solution for film formation.
- a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m), which is a base material, is fixed on a glass plate with a tape, and this stock solution at 25 ° C.
- the substrate was cast under the condition of a gap of 25 ⁇ m. 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, the laminated body K by which the porous layer was laminated
- Example 10 Porous layer laminate L
- a phenol novolac type epoxy resin (trade name “jER 152” manufactured by Japan Epoxy Resin Co., Ltd.) was used as a crosslinking agent, and the weight ratio of polyamideimide resin / NMP / phenol novolac type epoxy resin was 25 /
- a laminate L in which a porous layer was laminated on a substrate was obtained by performing the same operation as in Example 9 except that a film-forming stock solution was obtained by mixing at a ratio of 75/5.
- the thickness of the obtained porous layer was about 18 ⁇ m, and the total thickness of the laminate was about 68 ⁇ m.
- the substrate and the porous layer did not cause interface peeling.
- the porous layer was in close contact with the polyimide film, and a skin layer was basically formed on the surface of the porous layer. There were independent micropores that were almost homogeneous and had an average pore diameter of about 1.7 ⁇ m over the entire area. The porosity inside the porous layer was 72%.
- Example 9 Porous layer laminate M
- the cross-linking agent was not added to the stock solution for film formation, and the stock solution for film formation was obtained by mixing at a ratio in which the weight ratio of polyamideimide resin / NMP was 25/75.
- Operation similar to Example 9 was performed and the laminated body M by which the porous layer was laminated
- the thickness of the obtained porous layer was about 20 ⁇ m, and the total thickness of the laminate was about 70 ⁇ m.
- Example 11 Porous layer laminate N
- Polyimide resin solution (trade name “Pyre-ML RC5019” manufactured by IST Co .; solid concentration 15.7% by weight, solvent NMP, solution viscosity 69.1 dPa ⁇ s / 25 ° C.), and Bisphenol A type epoxy resin (trade name “jER 828” manufactured by Japan Epoxy Resin Co., Ltd.) as a crosslinking agent is used, and the weight ratio of polyimide resin / NMP / bisphenol A type epoxy resin is 15.7 / 84.3 / 10.
- a stock solution for film formation was obtained by mixing at a ratio of A polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m), which is a base material, is fixed on a glass plate with a tape, and this stock solution at 25 ° C. is used as a film applicator. And the substrate was cast under the condition of a gap of 51 ⁇ m. Immediately after casting, it was kept in a container having a humidity of about 100% and a temperature of 50 ° C. for 4 minutes. Thereafter, the laminate N was solidified by being immersed in water, and then naturally dried at room temperature without being peeled from the substrate, thereby obtaining a laminate N having a porous layer laminated on the substrate. The thickness of the porous layer was about 35 ⁇ m, and the total thickness of the laminate was about 85 ⁇ m.
- Example 4 Porous layer laminate O
- a polyimide resin solution (trade name “Pyre-MLRC5019” manufactured by IST Co., Ltd .; solid content concentration of 15.7 wt. %, Solvent NMP, solution viscosity 69.1 dPa ⁇ s / 25 ° C.) was used as it was as a stock solution for film formation, and the porous layer was laminated on the base material.
- a laminate O was obtained.
- the thickness of the obtained porous layer was about 17 ⁇ m, and the total thickness of the laminate was about 67 ⁇ m. That is, in the stock solution for film formation, the weight ratio of polyimide resin / NMP was 15.7 / 84.3.
- the substrate and the porous layer did not cause interface peeling.
- the porous layer was in close contact with the polyimide film, and a skin layer was basically formed on the surface of the porous layer. There were independent micropores that were almost homogeneous and had an average pore diameter of about 5.0 ⁇ m over the entire area. The porosity inside the porous layer was 65%.
- Example 12 Porous layer laminate P
- polyimide film trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 ⁇ m
- surface-treated rolled copper foil (trade name RCF- manufactured by Fukuda Metal Foil Co., Ltd.) The same operation as in Example 4 was performed except that T5B-18 (thickness: 18 ⁇ m) was used to obtain a laminate P in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 32 ⁇ m, and the total thickness of the laminate was about 50 ⁇ m.
- the substrate and the porous layer did not cause interface peeling.
- the porous layer was in close contact with the polyimide film, and a skin layer was basically formed on the surface of the porous layer. Independent micropores having an average pore diameter of about 1.5 ⁇ m were present throughout the entire area. The porosity inside the porous layer was 70%.
- Example 13 Porous layer laminate Q
- Polyamideimide resin solution (trade name “Vilomax N-100H” manufactured by Toyobo Co., Ltd .; solid content concentration 20 wt%, solvent NMP, solution viscosity 350 dPa ⁇ s / 25 ° C.), NMP as solvent, water-soluble polymer Polyvinylpyrrolidone (molecular weight 50,000) and bisphenol A type epoxy resin (trade name “jER 828” manufactured by Japan Epoxy Resin Co., Ltd.) as a cross-linking agent, polyamideimide resin / NMP / polyvinylpyrrolidone / bisphenol A type epoxy The resin was mixed at a ratio of 15/85/25/15 to obtain a stock solution for film formation.
- a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m), which is a base material, is fixed on a glass plate with a tape, and this stock solution at 25 ° C. is used as a film applicator. And the substrate was cast under the condition of a gap of 51 ⁇ m. 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, the laminated body Q by which the porous layer was laminated
- Example 14 Porous layer laminate R
- a mixture solution of polyamideimide resin / NMP / polyvinylpyrrolidone / bisphenol A type epoxy resin was mixed at a ratio of 15/85/25/20 to form a stock solution for film formation Except having obtained, operation similar to Example 13 was performed and the laminated body R by which the porous layer was laminated
- the thickness of the obtained porous layer was about 20 ⁇ m, and the total thickness of the laminate was about 70 ⁇ m.
- Example 13 a stock solution for film formation was obtained by adding a cross-linking agent to the stock solution for film formation, and mixing the polyamideimide resin / NMP / polyvinylpyrrolidone at a ratio of 15/85/25. Except that, the same operation as in Example 13 was performed to obtain a laminate S in which a porous layer was laminated on a substrate. The thickness of the obtained porous layer was about 16 ⁇ m, and the total thickness of the laminate was about 66 ⁇ m.
- Example 15 Porous layer laminate T
- polyethylene glycol average molecular weight 360 to 440
- the weight ratio of polyamideimide resin / NMP / polyethylene glycol / bisphenol A type epoxy resin is 15/85/25/10.
- the same operation as in Example 13 was performed except that the raw material solution for film formation was obtained by mixing at a ratio to obtain a laminate T in which a porous layer was laminated on a substrate.
- the thickness of the porous layer was about 7 ⁇ m, and the total thickness of the laminate was about 57 ⁇ m.
- Example 16 Porous layer laminate U
- Polyamideimide resin solution (trade name “Vilomax N-100H” manufactured by Toyobo Co., Ltd .; solid content concentration 20 wt%, solvent NMP, solution viscosity 350 dPa ⁇ s / 25 ° C.), NMP as solvent, water-soluble polymer Polyvinyl pyrrolidone (molecular weight 10,000) manufactured by Aldrich, and bisphenol A type epoxy resin (trade name “jER 828” manufactured by Japan Epoxy Resin Co., Ltd.) as a cross-linking agent, polyamideimide resin / NMP / polyvinyl pyrrolidone / bisphenol A weight ratio of the A-type epoxy resin was mixed at a ratio of 15/85/25/10 to obtain a stock solution for film formation.
- a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m), which is a base material, is fixed on a glass plate with a tape, and this stock solution at 25 ° C. is used as a film applicator. And the substrate was cast under the condition of a gap of 51 ⁇ m. 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, the laminated body U by which the porous layer was laminated
- FIG. 3 shows an electron micrograph (x5000 times) of the porous layer surface
- FIG. 4 shows an electron micrograph (x4000 times) of a cross section of the laminate.
- Example 17 Porous layer laminate V
- the weight ratio of polyamideimide resin / NMP / polyvinylpyrrolidone / bisphenol A type epoxy resin was mixed at a ratio of 15/85/25/15 to obtain a stock solution for film formation
- As a base material instead of polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 ⁇ m), plasma-treated polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 ⁇ m)
- the same operation as in Example 13 was performed except that was used to obtain a laminate V in which a porous layer was laminated on a substrate.
- the thickness of the obtained porous layer was about 21 ⁇ m, and the total thickness of the laminate was about 71 ⁇ m.
- Example 6 Porous layer laminate W
- a stock solution for film formation was obtained by adding a cross-linking agent to the stock solution for film formation and mixing at a ratio of 15/85/25 in weight ratio of polyamideimide resin / NMP / polyvinylpyrrolidone. Except that, the same operation as in Example 16 was performed to obtain a laminate W in which a porous layer was laminated on a substrate. The thickness of the obtained porous layer was about 20 ⁇ m, and the total thickness of the laminate was about 70 ⁇ m.
- Example 7 Porous layer laminate X
- a polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 ⁇ m)
- a PET film S type, thickness 100 ⁇ m
- a PET film S type, thickness 100 ⁇ m
- the thickness of the obtained porous layer was about 26 ⁇ m, and the total thickness of the laminate was about 76 ⁇ m.
- Table 1 summarizes the base material and porous layer component of each laminate described above.
- PI Polyimide PAI: Polyamideimide PET: Polyethylene terephthalate.
- Each of the porous membrane laminate samples A to X was heated on a hot plate under the heating conditions (temperature, time) shown in Table 2. In order to heat the entire sample uniformly, the sample was heated with an aluminum vat about 20 mm deep from the top.
- FIG. 5 shows an electron micrograph (x5000 magnification) of the surface of the porous layer of a sample obtained by heat-treating (200 ° C., 30 minutes) the laminate F obtained in Example 5, and FIG. The electron micrograph (x2000 times) of the cross section of is shown.
- FIG. 7 shows an electron micrograph (x5000 magnification) of the porous layer surface of the sample obtained by heat-treating the laminated body U obtained in Example 16 (200 ° C., 30 minutes), and FIG. 8 shows a cross section of the sample.
- the electron micrograph (x4000 times) of is shown.
- FIG. 4 is compared with FIG. 8, in FIG. 8, it is observed that the film thickness of the porous layer portion is reduced by the heat treatment, the micropores are almost disappeared, and the porous layer is made transparent. (Transparent polymer layer derived from porous layer).
- the thickness of the porous layer was reduced by heating. It is thought that shrinkage occurred due to the thermal crosslinking reaction. Moreover, the adhesiveness after heat processing improved remarkably compared with before heat processing. The improvement in the film strength of the porous layer (or the polymer layer derived from the porous layer) and the improvement in the adhesion between the substrate and the porous layer (or the polymer layer derived from the porous layer) were remarkable. In addition, the chemical resistance was significantly improved.
- the membrane of the porous layer (or the polymer layer derived from the porous layer) was obtained by heat treatment. Improvements in strength, adhesion between the substrate and the porous layer (or the polymer layer derived from the porous layer) and chemical resistance were not observed.
- the porous film laminate sample obtained in Comparative Example 7 contained a crosslinking agent, the chemical resistance was improved by heat treatment. However, no improvement in adhesion between the substrate and the porous layer (or the polymer layer derived from the porous layer) was observed.
- Example 18 Conductive pattern formation
- conductive ink [Fujikura Kasei Co., Ltd. silver paste, nano -Dotite XA9053]
- a grid pattern (line width 20 ⁇ m, pitch 300 ⁇ m) was printed by a screen printing method under the conditions of a printing speed of 15 mm / sec, a printing pressure of 0.1 MPa, and a clearance of 1.5 mm.
- the screen printer used was LS-150TVA manufactured by Neurong Seimitsu Kogyo Co., Ltd. A screen version made by Mesh Co., Ltd. was used.
- the ink used was of the type in which silver oxide was reduced to silver by heating, and was black immediately after printing, but showed metallic silver gloss after heating.
- the porous layer that was opaque in yellow and white before heating contracted in the thickness direction when the components (polymer and cross-linking agent) were thermally cross-linked, and the thickness decreased from about 20 ⁇ m to about 7 ⁇ m. The other side can be seen through.
- FIG. 9 shows an electron micrograph (x100 times) of the conductive pattern.
- Example 19 Formation of conductive pattern
- the layered product Q obtained in Example 13 was heated on a hot plate at 200 ° C. for 30 minutes to cause a polymer having a crosslinkable functional group and a crosslinking agent to react (thermal crosslinking).
- the sample was heated with an aluminum vat about 20 mm deep from the top.
- the porous layer which was opaque in yellow and white before heating, shrunk in the thickness direction when the components (polymer and crosslinker) were thermally cross-linked, the thickness decreased from about 20 ⁇ m to about 7 ⁇ m, frosted glass with a slightly opposite side It was in a state where it could see through.
- the surface of the porous layer was screen-printed with conductive ink [Silver paste manufactured by Fujikura Kasei Co., Ltd., Nano-Dotite XA9053] under the same conditions as in Example 18. After printing, a heat treatment was performed at 200 ° C. for 30 minutes to cure the conductive ink and form a wiring. The printed part was black immediately after printing, but showed gloss of metallic silver after heating.
- FIG. 10 shows an electron micrograph (x100 times) of the conductive pattern.
- Example 20 Conductive pattern formation
- the layered product Q obtained in Example 13 was heated on a hot plate at 140 ° C. for 5 minutes to partially react with a polymer having a crosslinkable functional group and a crosslinking agent (thermal crosslinking).
- a stage (semi-cured state) was used.
- the sample was heated with an aluminum vat about 20 mm deep from the top.
- the porous layer that was opaque in white before heating was slightly shrunk in the thickness direction when some of the components (polymer and crosslinking agent) were thermally crosslinked, and the thickness decreased from about 20 ⁇ m to about 14 ⁇ m. There was almost no change in the appearance.
- the surface of the porous layer was screen-printed with conductive ink [Silver paste manufactured by Fujikura Kasei Co., Ltd., Nano-Dotite XA9053] under the same conditions as in Example 18. After printing, a heat treatment was performed at 200 ° C. for 30 minutes to cure the conductive ink and form a wiring. The printed part was black immediately after printing, but showed gloss of metallic silver after heating. In addition, the porous layer that was yellowish white and opaque before heating after printing contracted in the thickness direction when the components (polymer and crosslinking agent) were thermally crosslinked, the thickness decreased to about 7 ⁇ m, and was slightly ground glass. The other side can be seen through.
- FIG. 11 shows an electron micrograph (x100 times) of the conductive pattern.
- Example 21 Conductive pattern formation
- base material / porous layer is polyimide film (50 ⁇ m) / polyamideimide + jER 834 (29 ⁇ m)] obtained in Example 5
- the conductive ink [Silver paste Nano-Dotite XA9053 manufactured by Fujikura Kasei Co., Ltd.]
- the screen printing machine used was LS-25TVA manufactured by Neurong Seimitsu Kogyo Co., Ltd.
- the wiring was formed by holding at 200 ° C. for 30 minutes to cure the conductive ink.
- the ink used was of the type in which silver oxide was reduced to silver by heating, and was black immediately after printing, but showed metallic silver gloss after heating.
- Example 22 Conductive pattern formation
- the laminate F obtained in Example 5 was heated on a hot plate at 200 ° C. for 30 minutes to cause a polymer having a crosslinkable functional group and a crosslinking agent to react (thermal crosslinking).
- the sample was heated with an aluminum vat about 20 mm deep from the top.
- the porous layer that was opaque in yellow and white before heating shrunk slightly in the thickness direction when the components (polymer and crosslinker) were thermally crosslinked, and the thickness decreased from about 29 ⁇ m to about 17 ⁇ m, but remained yellowish white and opaque There was almost no change in appearance.
- the surface of the porous layer was screen-printed with a conductive ink [Fujikura Kasei Co., Ltd. silver paste, Nano-Dotite XA9053] under the same conditions as in Example 21.
- the wiring was formed by holding at 200 ° C. for 30 minutes to cure the conductive ink.
- the printed part was black immediately after printing, but showed gloss of metallic silver after heating.
- Example 21 is the same as Example 21 except that the laminate I [substrate / porous layer is polyimide film (50 ⁇ m) / polyamideimide + jER 152 (31 ⁇ m)] obtained in Example 8 was used as the laminate.
- Example 24 Conductive pattern formation
- Conductive ink (silver paste manufactured by Fujikura Kasei Co., Ltd.] was applied to the porous layer surface of the laminate U [base material / porous layer was polyimide film (50 ⁇ m) / polyamideimide resin + jER 828 (23 ⁇ m)] obtained in Example 16.
- Nano-Dotite XA9053 a grid pattern (line width 20 ⁇ m, pitch 300 ⁇ m) was printed by screen printing under the conditions of a printing speed of 15 mm / sec, a printing pressure of 0.1 MPa, and a clearance of 1.5 mm.
- the screen printer used was LS-150TVA manufactured by Neurong Seimitsu Kogyo Co., Ltd.
- a screen version made by Mesh Co., Ltd. was used. After printing, a heat treatment for 30 minutes was performed on a hot plate set to 200 ° C., and the conductive ink was cured to form wiring. In order to heat the entire sample uniformly, the sample was heated with an aluminum vat about 20 mm deep from the top.
- the ink used was of the type in which silver oxide was reduced to silver by heating, and was black immediately after printing, but showed metallic silver gloss after heating. However, the film contact portion remained black. Moreover, the porous layer which was yellowish white before the heating was transparent. In this way, an electromagnetic wave shielding film was produced. When the obtained electromagnetic wave shielding film was observed with an electron microscope, a grid-like conductive pattern having a line width of 20 ⁇ m and a pitch of 300 ⁇ m was formed.
- the total light transmittance (Ts) of the polyimide film (trade name “Kapton 200H” manufactured by Toray DuPont, thickness 50 ⁇ m) is 41.0%, The total light transmittance (Tsp) of the laminate U is 8.1%.
- the total light transmittance (Tst) of the transparent layered product where no wiring was present was 38.1%. Therefore, the transparency (T) of the transparent layer derived from the porous layer after the heat treatment was 2.9%.
- the opacity (P) of the porous layer not subjected to the heat treatment was 32.9%.
- the measurement of the total light transmittance in the above was performed as follows.
- the total light transmittance (%) was measured using an NDH-5000W haze meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7136.
- the total light transmittance (Ts) of the substrate itself used was measured.
- the total light transmittance (Tsp) of the porous layer laminated body (base material + porous layer) which is not heat-processed was measured.
- the total light transmittance (Tst) of the portion where the wiring of the laminate (base material + transparent layer) made transparent by the heat treatment does not exist was measured.
- Tst total light transmittance of base material itself ⁇ total light transmittance (Tst) of laminate (base material + transparent layer)
Abstract
Description
(1) 基材と、前記基材の少なくとも片面上の多孔質層とを含む積層体であって、
前記基材は、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアミド系樹脂、及びポリエーテルイミド系樹脂からなる群より選ばれる少なくとも1種の樹脂材料からなる樹脂フィルム、又は金属箔であり、
前記多孔質層は、主成分として、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアミド系樹脂、及びポリエーテルイミド系樹脂からなる群より選ばれる少なくとも1種の高分子と、架橋剤とを含む組成物から構成され、
前記多孔質層における微小孔の平均孔径が0.01~10μmであり、空孔率が30~85%である積層体。
前記多孔質層を構成すべき前記高分子と前記架橋剤とを含む多孔質層形成用材料の溶液を、前記基材上にフィルム状に流延し、その後、これを凝固液中に浸漬し、次いで乾燥に付すことを含む、積層体の製造方法。
前記多孔質層又は前記多孔質層由来の高分子層は、前記架橋剤により架橋構造が形成されているものである、機能性積層体。
上記(1) ~(4) のうちのいずれかに記載の積層体の前記多孔質層の表面上に、導電体層、誘電体層、半導体層、絶縁体層、抵抗体層、及び前記層の前駆体層からなる群より選ばれる層を形成し、
加熱処理、及び/又は活性エネルギー線照射処理を行い、前記多孔質層中の前記架橋剤により架橋構造を形成することを含む、機能性積層体を製造する方法。
例えば、本発明の多孔質層積層体は、下記方法に基づくテープ剥離試験:
積層体の多孔質層表面に24mm幅の寺岡製作所社製マスキングテープ[フィルムマスキングテープNo.603(#25)]をテープ一端から50mmの長さ分貼り付け、貼り付けられた前記テープを、直径30mm、200gf荷重のローラー(Holbein Art Materials Inc.社製、耐油性硬質ゴムローラーNo.10)で圧着し、その後、引張試験機を用いてテープ他端を剥離速度50mm/分で引っ張り、T型剥離を行う:
を行ったとき、前記基材と前記多孔質層との間で界面剥離を起こさないものである。すなわち、前記多孔質層中に含まれている前記架橋剤が未反応の状態においても、前記基材と前記多孔質層とが、上記テープ剥離試験で界面剥離が起こらない程度の層間密着強度で直接的に積層されていることを意味している。
前記多孔質層を構成すべき高分子と架橋剤とを含む多孔質層形成用材料の溶液を、前記基材上にフィルム状に流延し、その後、これを凝固液に接触させて多孔化処理を施した後、そのまま乾燥に付して、基材と多孔質層との積層体を得る方法;
前記多孔質層を構成すべき高分子を含む多孔質層形成用材料の溶液を、支持体上にフィルム状に流延し、その後、これを凝固液に接触させて多孔化処理を施した後、得られた多孔質層を支持体から基材表面上に転写し、続いて乾燥に付して、基材と多孔質層との積層体を得る方法;
等により製造できる。本発明では以下に詳述するように前者の方法が好ましく用いられる。
(a) 得られた多孔質層積層体に架橋処理を施し、その後、多孔質層表面に機能性層を設けて、機能性積層体を得る方法。
(b) 得られた多孔質層積層体の多孔質層表面に機能性層を設けて、その後、架橋処理を施し、機能性積層体を得る方法。加熱による架橋処理は、機能性層の機能発現化のための加熱処理を兼ねてもよい。
(c) 得られた多孔質層積層体に部分的架橋処理を施し、その後、多孔質層表面に機能性層を設けて、さらに、再度の架橋処理を施し架橋処理を完全とし、機能性積層体を得る方法。ここで、部分的架橋処理とは、それにより、半硬化状態(いわゆるBステージ)とすることを意図している。
(13) 上記(1) ~(4) のうちのいずれかに記載の積層体を、前記多孔質層を構成している組成物のガラス転移温度以上の温度での加熱処理に付し、前記多孔質層中の微小孔を消失させ、前記多孔質層を透明層に変換する方法。
上記(1) ~(4) のうちのいずれかに記載の積層体の前記多孔質層の表面上に、導電体層、誘電体層、半導体層、絶縁体層、抵抗体層、及び前記層の前駆体層からなる群より選択される層を形成する工程と、
得られた積層体を、前記多孔質層を構成する組成物のガラス転移温度以上の温度での加熱処理に付し、前記多孔質層中の微小孔を消失させ、前記多孔質層を透明層に変換する工程と、
加熱処理、及び/又は活性エネルギー線照射処理を行い、前記多孔質層中の前記架橋剤により架橋構造を形成する工程と、
を行うことにより得られた機能性積層体。
上記(1) ~(4) のうちのいずれかに記載の積層体の前記多孔質層の表面上に、導電体層、誘電体層、半導体層、絶縁体層、抵抗体層、及び前記層の前駆体層からなる群より選択される層を形成する工程と、
得られた積層体を、前記多孔質層を構成する組成物のガラス転移温度以上の温度での加熱処理に付し、前記多孔質層中の微小孔を消失させ、前記多孔質層を透明層に変換する工程と、
加熱処理、及び/又は活性エネルギー線照射処理を行い、前記多孔質層中の前記架橋剤により架橋構造を形成する工程と、
を含む、機能性積層体の製造方法。
多孔質層から変換された透明層の透明度の指標は、次式に示すように、用いられた基材自体の全光線透過率(%)と、透明化された積層体(基材+透明層)の全光線透過率(%)との差の絶対値として表すことができる。
透明層の厚み=多孔質層の厚みx(100-空孔率)/100
ポリイミド樹脂フィルムは接着性がよくないために、表面の改質のためにアルカリ処理やコロナ放電処理が必要とされている。しかし、本発明の多孔質層積層体では、ポリイミド樹脂フィルム上に微細な孔を多数有した多孔質層を形成させることができるために、その上の接着層が孔内に入り込むことができ、そのアンカー効果のためにより強い密着性が期待できる。よって、多孔質層積層体は前記用途に、好ましく利用できる。
電子顕微鏡写真から、積層体の表面又は断面の任意の30点以上の孔についてその面積を測定し、その平均値を平均孔面積Saveとした。孔が真円であると仮定し、下記式を用いて平均孔面積から孔径に換算した値を平均孔径とした。ここでπは円周率を表す。
表面又は内部の平均孔径[μm]=2×(Save/π)1/2
多孔質層内部の空孔率は下記式より算出した。Vは多孔質層の体積[cm3 ]、Wは多孔質層の重量[g]、ρは多孔質層組成物の密度[g/cm3 ](ここで、多孔質層組成物の密度は、該組成物を構成している各成分の密度を重量組成比で分配して算出される)を示す。多孔質層の体積V、多孔質層の重量Wは、それぞれ、基材上に多孔質層が積層された積層体の体積、又は重量から、基材の体積、又は重量を差し引いて算出した。
空孔率[%]=100-100×W/(ρ・V)
ポリアミドイミド バイロマックスN-100Hの密度:1.45[g/cm3 ]
ポリイミド Pyre-M.L.RC5019の密度:1.43[g/cm3 ]
エポキシ樹脂YDCN-700-5の密度:1.21[g/cm3 ]
エポキシ樹脂jER 828の密度:1.17[g/cm3 ]
エポキシ樹脂jER 834の密度:1.18[g/cm3 ]
エポキシ樹脂jER 1001の密度:1.19[g/cm3 ]
エポキシ樹脂jER 1004の密度:1.19[g/cm3 ]
エポキシ樹脂jER 152の密度:1.21[g/cm3 ]
未架橋状態での積層体の基材と多孔質層との層間密着性は、次のテープ剥離試験により行った。
(i) 積層体の多孔質層表面に24mm幅の寺岡製作所社製マスキングテープ[フィルムマスキングテープNo.603(#25)]をテープ一端から50mmの長さ分貼り付け、貼り付けられた前記テープを、直径30mm、200gf荷重のローラー(Holbein Art Materials Inc.社製、耐油性硬質ゴムローラーNo.10)で圧着する。
(ii) 万能引張試験機[(株)オリエンテック社製、商品名「TENSILON RTA-500」]を用いてテープ他端を剥離速度50mm/分で引っ張り、T型剥離を行う。
(iii) 多孔質層と基材との界面剥離の有無を観察する。
加熱架橋処理前及び処理後の積層体の基材と多孔質層との層間密着性は、JIS K 5600-5-6の付着性評価試験(クロスカット法)に従い実施した。
サンプルに、カット間隔2mmのクロスカットを形成して試験を行った。透明感圧付着テープとしては、ニチバン社製セロテープ(登録商標)NO.405 幅24mm(粘着力4.00N/10mm)を使用した。テープ引き剥がし後の評価もJIS K 5600-5-6に従った。
0:どの格子の目にもはがれがない。
1:クロスカット部分で影響を受けるのは、明確に5%を上回ることはない。
2:クロスカット部分で影響を受けるのは、明確に5%を越えるが15%を上回ることはない。
3:クロスカット部分で影響を受けるのは、明確に15%を越えるが35%を上回ることはない。
4:クロスカット部分で影響を受けるのは、明確に35%を越えるが65%を上回ることはない。
5:はがれの程度が分類4を超える場合。
加熱架橋処理前及び処理後の積層体の多孔質層の耐薬品性試験を次のように行った。
積層体サンプルを40mm×30mm程度の大きさに切り出し、スポイトを用いて、N-メチル-2-ピロリドン(NMP)を多孔質層上に1滴(約26mg)滴下した。2分後にサンプルを大量の水(約1リットル)中に浸漬して攪拌し、NMPを洗浄した。その後、サンプルを取り出して、ウエス上で室温にて自然乾燥させた。乾燥後、サンプルの状態を目視で観察した。
ポリアミドイミド系樹脂溶液(東洋紡績社製の商品名「バイロマックスN-100H」;固形分濃度20重量%、溶剤NMP(N-メチル-2-ピロリドン)、溶液粘度350dPa・s/25℃)、架橋剤としてのノボラック型エポキシ樹脂(東都化成株式会社製の商品名「YDCN-700-5」)、及び溶剤としてのNMPを、ポリアミドイミド系樹脂/NMP/ノボラック型エポキシ樹脂の重量比が15/85/5となる割合で混合して製膜用の原液を得た。ガラス板上に、基材であるポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)をテープで固定し、25℃としたこの原液をフィルムアプリケーターを使用して、フィルムアプリケーターと基材とのギャップ51μmの条件でキャストした。キャスト後速やかに湿度約100%、温度50℃の容器中に4分間保持した。その後、水中に浸漬して凝固させ、次いで基材から剥離させることなく室温下で自然乾燥することによって基材上に多孔質層が積層された積層体Aを得た。多孔質層の厚みは約10μmであり、積層体の総厚みは約60μmであった。
実施例1において、ポリアミドイミド系樹脂/NMP/ノボラック型エポキシ樹脂の重量比が15/85/10となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Bを得た。得られた多孔質層の厚みは約11μmであり、積層体の総厚みは約61μmであった。
実施例1において、ポリアミドイミド系樹脂/NMP/ノボラック型エポキシ樹脂との重量比が15/85/15となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Cを得た。得られた多孔質層の厚みは約21μmであり、積層体の総厚みは約71μmであった。
実施例1において、製膜用の原液に架橋剤を添加せず、ポリアミドイミド系樹脂/NMPの重量比が15/85となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Dを得た。得られた多孔質層の厚みは約15μmであり、積層体の総厚みは約65μmであった。
実施例1において、架橋剤としてビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 828」)を用いて、ポリアミドイミド系樹脂/NMP/ビスフェノールA型エポキシ樹脂の重量比が20/80/10となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Eを得た。得られた多孔質層の厚みは約23μmであり、積層体の総厚みは約73μmであった。
実施例1において、架橋剤としてビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 834」)を用いて、ポリアミドイミド系樹脂/NMP/ビスフェノールA型エポキシ樹脂の重量比が20/80/10となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Fを得た。得られた多孔質層の厚みは約29μmであり、積層体の総厚みは約79μmであった。
実施例1において、架橋剤としてビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 1001」)を用いて、ポリアミドイミド系樹脂/NMP/ビスフェノールA型エポキシ樹脂の重量比が20/80/10となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Gを得た。得られた多孔質層の厚みは約34μmであり、積層体の総厚みは約84μmであった。
実施例1において、架橋剤としてビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 1004」)を用いて、ポリアミドイミド系樹脂/NMP/ビスフェノールA型エポキシ樹脂の重量比が20/80/10となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Hを得た。得られた多孔質層の厚みは約30μmであり、積層体の総厚みは約80μmであった。
実施例1において、架橋剤としてフェノールノボラック型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 152」)を用いて、ポリアミドイミド系樹脂/NMP/フェノールノボラック型エポキシ樹脂の重量比が20/80/10となる割合で混合して製膜用の原液を得たこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Iを得た。得られた多孔質層の厚みは約31μmであり、積層体の総厚みは約81μmであった。
実施例1において、製膜用の原液に架橋剤を添加せず、ポリアミドイミド系樹脂溶液(東洋紡績社製の商品名「バイロマックスN-100H」;固形分濃度20重量%、溶剤NMP、溶液粘度350dPa・s/25℃)をそのまま製膜用の原液として用いたこと以外は実施例1と同様の操作を行い、基材上に多孔質層が積層された積層体Jを得た。得られた多孔質層の厚みは約14μmであり、積層体の総厚みは約64μmであった。すなわち、製膜用の原液において、ポリアミドイミド系樹脂/NMPの重量比は20/80であった。
ポリアミドイミド系樹脂(ソルベイアドバンストポリマーズ社製の商品名「トーロンAI-10」)、溶剤としてのNMP、及び架橋剤としてのビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 828」)を、ポリアミドイミド系樹脂/NMP/ビスフェノールA型エポキシ樹脂の重量比が25/75/5となる割合で混合して製膜用の原液を得た。ガラス板上に、基材であるポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)をテープで固定し、25℃としたこの原液をフィルムアプリケーターを使用して、フィルムアプリケーターと基材とのギャップ25μmの条件でキャストした。キャスト後速やかに湿度約100%、温度50℃の容器中に4分間保持した。その後、水中に浸漬して凝固させ、次いで基材から剥離させることなく室温下で自然乾燥することによって基材上に多孔質層が積層された積層体Kを得た。多孔質層の厚みは約20μmであり、積層体の総厚みは約70μmであった。
実施例9において、架橋剤としてフェノールノボラック型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 152」)を用いて、ポリアミドイミド系樹脂/NMP/フェノールノボラック型エポキシ樹脂の重量比が25/75/5となる割合で混合して製膜用の原液を得たこと以外は実施例9と同様の操作を行い、基材上に多孔質層が積層された積層体Lを得た。得られた多孔質層の厚みは約18μmであり、積層体の総厚みは約68μmであった。
実施例9において、製膜用の原液に架橋剤を添加せず、ポリアミドイミド系樹脂/NMPの重量比が25/75となる割合で混合して製膜用の原液を得たこと以外は実施例9と同様の操作を行い、基材上に多孔質層が積層された積層体Mを得た。得られた多孔質層の厚みは約20μmであり、積層体の総厚みは約70μmであった。
ポリイミド系樹脂溶液(I.S.T社製の商品名「Pyre-M.L.RC5019」;固形分濃度15.7重量%、溶剤NMP、溶液粘度69.1dPa・s/25℃)、及び架橋剤としてのビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 828」)を、ポリイミド系樹脂/NMP/ビスフェノールA型エポキシ樹脂の重量比が15.7/84.3/10となる割合で混合して製膜用の原液を得た。ガラス板上に、基材であるポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)をテープで固定し、25℃としたこの原液をフィルムアプリケーターを使用して、フィルムアプリケーターと基材とのギャップ51μmの条件でキャストした。キャスト後速やかに湿度約100%、温度50℃の容器中に4分間保持した。その後、水中に浸漬して凝固させ、次いで基材から剥離させることなく室温下で自然乾燥することによって基材上に多孔質層が積層された積層体Nを得た。多孔質層の厚みは約35μmであり、積層体の総厚みは約85μmであった。
実施例11において、製膜用の原液に架橋剤を添加せず、ポリイミド系樹脂溶液(I.S.T社製の商品名「Pyre-M.L.RC5019」;固形分濃度15.7重量%、溶剤NMP、溶液粘度69.1dPa・s/25℃)をそのまま製膜用の原液として用いたこと以外は実施例11と同様の操作を行い、基材上に多孔質層が積層された積層体Oを得た。得られた多孔質層の厚みは約17μmであり、積層体の総厚みは約67μmであった。すなわち、製膜用の原液において、ポリイミド系樹脂/NMPの重量比は15.7/84.3であった。
実施例4において、基材として、ポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)の代わりに、表面処理圧延銅箔(福田金属箔粉工業社製の商品名RCF-T5B-18、厚み18μm)を用いたこと以外は実施例4と同様の操作を行い、基材上に多孔質層が積層された積層体Pを得た。得られた多孔質層の厚みは約32μmであり、積層体の総厚みは約50μmであった。
ポリアミドイミド系樹脂溶液(東洋紡績社製の商品名「バイロマックスN-100H」;固形分濃度20重量%、溶剤NMP、溶液粘度350dPa・s/25℃)、溶剤としてのNMP、水溶性ポリマーとしてのポリビニルピロリドン(分子量5万)、及び架橋剤としてのビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 828」)を、ポリアミドイミド系樹脂/NMP/ポリビニルピロリドン/ビスフェノールA型エポキシ樹脂の重量比が15/85/25/15となる割合で混合して製膜用の原液を得た。ガラス板上に、基材であるポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)をテープで固定し、25℃としたこの原液をフィルムアプリケーターを使用して、フィルムアプリケーターと基材とのギャップ51μmの条件でキャストした。キャスト後速やかに湿度約100%、温度50℃の容器中に4分間保持した。その後、水中に浸漬して凝固させ、次いで基材から剥離させることなく室温下で自然乾燥することによって基材上に多孔質層が積層された積層体Qを得た。多孔質層の厚みは約20μmであり、積層体の総厚みは約70μmであった。
実施例13において、製膜用の原液として、ポリアミドイミド系樹脂/NMP/ポリビニルピロリドン/ビスフェノールA型エポキシ樹脂の重量比が15/85/25/20となる割合で混合して製膜用の原液を得たこと以外は実施例13と同様の操作を行い、基材上に多孔質層が積層された積層体Rを得た。得られた多孔質層の厚みは約20μmであり、積層体の総厚みは約70μmであった。
実施例13において、製膜用の原液に架橋剤を添加せず、ポリアミドイミド系樹脂/NMP/ポリビニルピロリドンの重量比が15/85/25となる割合で混合して製膜用の原液を得たこと以外は実施例13と同様の操作を行い、基材上に多孔質層が積層された積層体Sを得た。得られた多孔質層の厚みは約16μmであり、積層体の総厚みは約66μmであった。
実施例13において、水溶性ポリマーとしてポリエチレングリコール(平均分子量360~440)を用いて、ポリアミドイミド系樹脂/NMP/ポリエチレングリコール/ビスフェノールA型エポキシ樹脂の重量比が15/85/25/10となる割合で混合して製膜用の原液を得たこと以外は実施例13と同様の操作を行い、基材上に多孔質層が積層された積層体Tを得た。多孔質層の厚みは約7μmであり、積層体の総厚みは約57μmであった。
ポリアミドイミド系樹脂溶液(東洋紡績社製の商品名「バイロマックスN-100H」;固形分濃度20重量%、溶剤NMP、溶液粘度350dPa・s/25℃)、溶剤としてのNMP、水溶性ポリマーとしてのアルドリッチ社製ポリビニルピロリドン(分子量1万)、及び架橋剤としてのビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製の商品名「jER 828」)を、ポリアミドイミド系樹脂/NMP/ポリビニルピロリドン/ビスフェノールA型エポキシ樹脂の重量比が15/85/25/10となる割合で混合して製膜用の原液を得た。ガラス板上に、基材であるポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)をテープで固定し、25℃としたこの原液をフィルムアプリケーターを使用して、フィルムアプリケーターと基材とのギャップ51μmの条件でキャストした。キャスト後速やかに湿度約100%、温度50℃の容器中に4分間保持した。その後、水中に浸漬して凝固させ、次いで基材から剥離させることなく室温下で自然乾燥することによって基材上に多孔質層が積層された積層体Uを得た。多孔質層の厚みは約23μmであり、積層体の総厚みは約73μmであった。
実施例16において、ポリアミドイミド系樹脂/NMP/ポリビニルピロリドン/ビスフェノールA型エポキシ樹脂との重量比が15/85/25/15となる割合で混合して製膜用の原液を得たことと、基材として、ポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)の代わりに、プラズマ処理をしたポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)を用いたこと以外は実施例13と同様の操作を行い、基材上に多孔質層が積層された積層体Vを得た。得られた多孔質層の厚みは約21μmであり、積層体の総厚みは約71μmであった。
実施例16において、製膜用の原液に架橋剤を添加せず、ポリアミドイミド系樹脂/NMP/ポリビニルピロリドンの重量比が15/85/25となる割合で混合して製膜用の原液を得たこと以外は実施例16と同様の操作を行い、基材上に多孔質層が積層された積層体Wを得た。得られた多孔質層の厚みは約20μmであり、積層体の総厚みは約70μmであった。
実施例13において、基材として、ポリイミドフィルム(東レ・デュポン社製の商品名「カプトン200H」、厚み50μm)の代わりに、帝人デュポン社製PETフィルム(Sタイプ、厚み100μm)を用いたこと以外は実施例13と同様の操作を行い、基材上に多孔質層が積層された積層体Xを得た。得られた多孔質層の厚みは約26μmであり、積層体の総厚みは約76μmであった。
PI:ポリイミド
PAI:ポリアミドイミド
PET:ポリエチレンテレフタレート
を表す。
実施例1~17及び比較例1~7でそれぞれ得られた多孔膜積層体サンプルA~Xについて、次のようにして加熱架橋処理を行った。
実施例13で得た積層体Q[基材/多孔質層がポリイミドフィルム(50μm)/ポリアミドイミド+jER 828(20μm)]の多孔質層表面に、導電インク[藤倉化成株式会社製銀ペースト、ナノ・ドータイトXA9053]で、印刷スピード15mm/sec、印圧0.1MPa、クリアランス1.5mmの条件で、格子状パターン(線幅20μm、ピッチ300μm)をスクリーン印刷方式にて印刷を施した。使用したスクリーン印刷機はニューロング精密工業株式会社製LS-150TVAであった。スクリーン版はメッシュ株式会社製のものを使用した。
実施例13で得た積層体Qを200℃、30分間の加熱条件でホットプレート上で加熱して架橋可能な官能基を有する高分子と架橋剤とを反応(熱架橋)させた。サンプル全体が均質に加熱されるように、サンプルの上から深さ約20mmのアルミ製のバットを被せて加熱した。加熱前に黄白色不透明であった多孔質層は成分(高分子と架橋剤)が熱架橋する時に厚み方向に収縮し、厚みは約20μmから約7μmに減少し、すりガラス状でわずかに反対側が透けて見える状態となった。
実施例13で得た積層体Qを140℃、5分間の加熱条件でホットプレート上で加熱して架橋可能な官能基を有する高分子と架橋剤を一部反応(熱架橋)させて、Bステージ(半硬化した状態)とした。サンプル全体が均質に加熱されるように、サンプルの上から深さ約20mmのアルミ製のバットを被せて加熱した。加熱前に黄白色不透明であった多孔質層は成分(高分子と架橋剤)が一部熱架橋する時に少し厚み方向に収縮し、厚みは約20μmから約14μmに減少したが、黄白色不透明のまま外観にはほとんど変化は見られなかった。
実施例5で得た積層体F[基材/多孔質層がポリイミドフィルム(50μm)/ポリアミドイミド+jER 834(29μm)]に、導電インク[藤倉化成株式会社製銀ペースト ナノ・ドータイトXA9053]で、印刷スピード30mm/sec、印圧0.1MPaの条件で、200μmのラインアンドスペース(L/S=200μm/200μm)の配線パターンをスクリーン印刷方式にて印刷を施した。使用したスクリーン印刷機はニューロング精密工業株式会社製LS-25TVAであった。印刷後、200℃で30分間保持し、導電インクを硬化させて配線を形成した。使用したインクは酸化銀が加熱により還元されて銀になるタイプのものであって、印刷直後は黒色であったが、加熱後には金属銀の光沢を示した。電子顕微鏡で観察したところ、L/S=200μm/200μmの配線パターンが形成されていた。
実施例5で得た積層体Fを200℃、30分間の加熱条件でホットプレート上で加熱して架橋可能な官能基を有する高分子と架橋剤を反応(熱架橋)させた。サンプル全体が均質に加熱されるように、サンプルの上から深さ約20mmのアルミ製のバットを被せて加熱した。加熱前に黄白色不透明であった多孔質層は成分(高分子と架橋剤)が熱架橋する時に少し厚み方向に収縮し、厚みは約29μmから約17μmに減少したが、黄白色不透明のまま外観にはほとんど変化は見られなかった。
実施例21において、積層体として実施例8で得た積層体I[基材/多孔質層がポリイミドフィルム(50μm)/ポリアミドイミド+jER 152(31μm)]を用いたこと以外は実施例21と同様の操作を行い、L/S=200μm/200μmの配線パターンをスクリーン印刷方式にて印刷を施して配線基板を製造した。得られた配線基板を電子顕微鏡で観察したところ、L/S=200μm/200μmの配線パターンが形成されていた。
実施例16で得た積層体U[基材/多孔質層がポリイミドフィルム(50μm)/ポリアミドイミド系樹脂+jER 828(23μm)]の多孔質層表面に、導電インク[藤倉化成株式会社製銀ペースト、ナノ・ドータイトXA9053]で、印刷スピードは15mm/sec、印圧0.1MPa、クリアランス1.5mmの条件で、格子状パターン(線幅20μm、ピッチ300μm)をスクリーン印刷方式にて印刷を施した。使用したスクリーン印刷機はニューロング精密工業株式会社製LS-150TVAであった。スクリーン版はメッシュ株式会社製のものを使用した。印刷後、200℃に設定したホットプレート上で30分間の加熱処理を行い、導電インクを硬化させて配線を形成した。サンプル全体が均質に加熱されるように、サンプルの上から深さ約20mmのアルミ製のバットを被せて加熱した。使用したインクは酸化銀が加熱により還元されて銀になるタイプのものであって、印刷直後は黒色であったが、加熱後には金属銀の光沢を示した。ただし、フィルム接触部は黒色のままであった。また、加熱前に黄白色であった多孔質層は透明化していた。このようにして、電磁波シールドフィルムを製造した。得られた電磁波シールドフィルムを電子顕微鏡で観察したところ、線幅20μm、ピッチ300μmの格子状導電パターンが形成されていた。
積層体Uの全光線透過率(Tsp)は8.1%、
透明化された積層体の配線の存在しない部分の全光線透過率(Tst)は38.1%であった。
従って、加熱処理後の多孔質層由来の透明層の透明度(T)は2.9%であった。なお、加熱処理されていない多孔質層の不透明度(P)は32.9%であった。
全光線透過率(%)は、JIS K7136に準拠して、日本電色工業(株)製、NDH-5000Wヘイズメーターを用いて測定した。
そして、加熱処理されていない多孔質層積層体(基材+多孔質層)の全光線透過率(Tsp)を測定した。
最後に、加熱処理により透明化された積層体(基材+透明層)の配線の存在しない部分の全光線透過率(Tst)を測定した。
Claims (12)
- 基材と、前記基材の少なくとも片面上の多孔質層とを含む積層体であって、
前記基材は、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアミド系樹脂、及びポリエーテルイミド系樹脂からなる群より選ばれる少なくとも1種の樹脂材料からなる樹脂フィルム、又は金属箔であり、
前記多孔質層は、主成分として、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアミド系樹脂、及びポリエーテルイミド系樹脂からなる群より選ばれる少なくとも1種の高分子と、架橋剤とを含む組成物から構成され、
前記多孔質層における微小孔の平均孔径が0.01~10μmであり、空孔率が30~85%である積層体。 - 前記架橋剤は、2個以上のエポキシ基を含有する化合物、ポリイソシアネート化合物、及びシランカップリング剤からなる群より選ばれる少なくとも1種である、請求項1に記載の積層体。
- 前記多孔質層は、0.1~100μmの厚みを有する、請求項1又は2に記載の積層体。
- 前記多孔質層は、前記多孔質層を構成すべき前記高分子と前記架橋剤とを含む多孔質層形成用材料の溶液を、前記基材上にフィルム状に流延し、その後、これを凝固液中に浸漬し、次いで乾燥に付すことにより形成されたものである、請求項1~3のうちのいずれか1項に記載の積層体。
- 前記多孔質層中に含まれている前記架橋剤は、未反応の状態である、請求項1~4のうちのいずれか1項に記載の積層体。
- 前記多孔質層は、前記架橋剤により架橋構造が形成されているものである、請求項1~4のうちのいずれか1項に記載の積層体。
- 請求項1~6のうちのいずれか1項に記載の積層体を製造する方法であって、
前記多孔質層を構成すべき前記高分子と前記架橋剤とを含む多孔質層形成用材料の溶液を、前記基材上にフィルム状に流延し、その後、これを凝固液中に浸漬し、次いで乾燥に付すことを含む、積層体の製造方法。 - 前記多孔質層形成用材料の溶液を前記基材上にフィルム状に流延した後、相対湿度70~100%、温度15~100℃の雰囲気下に0.2~15分間保持し、その後、これを凝固液中に浸漬する、請求項7に記載の積層体の製造方法。
- 請求項1~4のうちのいずれか1項に記載の積層体の前記多孔質層又は前記多孔質層由来の高分子層の表面上に、導電体層、誘電体層、半導体層、絶縁体層、及び抵抗体層からなる群より選ばれる機能性層を有する機能性積層体であって、
前記多孔質層又は前記多孔質層由来の高分子層は、前記架橋剤により架橋構造が形成されているものである、機能性積層体。 - 前記機能性層は、パターン化されている、請求項9に記載の機能性積層体。
- 請求項1~4のうちのいずれか1項に記載の積層体の前記多孔質層又は前記多孔質層由来の高分子層の表面上に、導電体層、誘電体層、半導体層、絶縁体層、及び抵抗体層からなる群より選ばれる機能性層を有する機能性積層体を製造する方法であって、
請求項1~4のうちのいずれか1項に記載の積層体の前記多孔質層の表面上に、導電体層、誘電体層、半導体層、絶縁体層、抵抗体層、及び前記層の前駆体層からなる群より選ばれる層を形成し、
加熱処理、及び/又は活性エネルギー線照射処理を行い、前記多孔質層中の前記架橋剤により架橋構造を形成することを含む、機能性積層体を製造する方法。 - 前記機能性層は、パターン化されている、請求項11に記載の機能性積層体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10837447.1A EP2514591A4 (en) | 2009-12-14 | 2010-12-01 | COATED BODY WITH A POROUS LAYER AND FUNCTIONAL COATING THEREWITH |
CN2010800520203A CN102666096A (zh) | 2009-12-14 | 2010-12-01 | 具有多孔层的层叠体以及使用其的功能性层叠体 |
KR1020127011847A KR20120123017A (ko) | 2009-12-14 | 2010-12-01 | 다공질층을 갖는 적층체, 및 그것을 사용한 기능성 적층체 |
JP2011546059A JP5793425B2 (ja) | 2009-12-14 | 2010-12-01 | 多孔質層を有する積層体、及びそれを用いた機能性積層体 |
US13/508,512 US20130020117A1 (en) | 2009-12-14 | 2010-12-01 | Laminated body comprising porous layer and functional laminate using same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009283203 | 2009-12-14 | ||
JP2009-283203 | 2009-12-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011074418A1 true WO2011074418A1 (ja) | 2011-06-23 |
Family
ID=44167174
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/071492 WO2011074418A1 (ja) | 2009-12-14 | 2010-12-01 | 多孔質層を有する積層体、及びそれを用いた機能性積層体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20130020117A1 (ja) |
EP (1) | EP2514591A4 (ja) |
JP (1) | JP5793425B2 (ja) |
KR (1) | KR20120123017A (ja) |
CN (1) | CN102666096A (ja) |
TW (1) | TW201129476A (ja) |
WO (1) | WO2011074418A1 (ja) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011122124A (ja) * | 2009-12-14 | 2011-06-23 | Daicel Chemical Industries Ltd | 多孔質膜及びその製造方法 |
JP2014028326A (ja) * | 2012-07-31 | 2014-02-13 | Daicel Corp | 多孔質層を有する積層体及びその製造方法 |
JP2014110514A (ja) * | 2012-11-30 | 2014-06-12 | Toppan Forms Co Ltd | アンテナ構造体、通信機器及びアンテナ構造体の製造方法 |
US20140183507A1 (en) * | 2011-09-14 | 2014-07-03 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Organic field-effect transistor |
JP2014124906A (ja) * | 2012-12-27 | 2014-07-07 | Daicel Corp | 金属薄膜層が設けられた多孔膜積層体及びその製造方法 |
JP2014180787A (ja) * | 2013-03-18 | 2014-09-29 | Ube Ind Ltd | 積層体および積層体の製造方法 |
US20140295168A1 (en) * | 2012-03-29 | 2014-10-02 | Nitto Denko Corporation | Electrically insulating resin sheet |
JP2016222912A (ja) * | 2015-06-01 | 2016-12-28 | ユニチカ株式会社 | 芳香族アミド系高分子溶液および多孔質芳香族アミド系フィルム |
JP2018024262A (ja) * | 2017-11-20 | 2018-02-15 | 宇部興産株式会社 | 積層体および積層体の製造方法 |
JP2018027705A (ja) * | 2017-11-20 | 2018-02-22 | 宇部興産株式会社 | 積層体および積層体の製造方法 |
JP2019010740A (ja) * | 2017-06-29 | 2019-01-24 | 富士ゼロックス株式会社 | ポリイミド積層膜、及びポリイミド積層膜の製造方法 |
JP2019183153A (ja) * | 2018-04-12 | 2019-10-24 | ユニチカ株式会社 | ポリイミドエアロゲルの製造方法 |
JP2020084096A (ja) * | 2018-11-29 | 2020-06-04 | 株式会社リコー | 多孔質層の製造方法、多孔質層および電極 |
WO2023054591A1 (ja) * | 2021-09-30 | 2023-04-06 | 古河電気工業株式会社 | 紫外線、可視光線および/または赤外線を拡散反射する物品およびその製造方法 |
CN116249592A (zh) * | 2020-09-30 | 2023-06-09 | 富士胶片株式会社 | 导电层叠体及导电层叠体的制造方法 |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2779275B1 (en) | 2011-11-11 | 2017-02-15 | LG Chem, Ltd. | Separator, and electrochemical device comprising same |
JP2014097529A (ja) * | 2012-10-18 | 2014-05-29 | Fuji Electric Co Ltd | 発泡金属による接合方法、半導体装置の製造方法、半導体装置 |
JP5919184B2 (ja) * | 2012-12-17 | 2016-05-18 | 日東電工株式会社 | ポリエーテルイミド多孔質体及びその製造方法 |
KR20140081072A (ko) * | 2012-12-21 | 2014-07-01 | 삼성전자주식회사 | 안테나 및 안테나 제조 방법 |
WO2014119371A1 (ja) * | 2013-01-29 | 2014-08-07 | 東レ株式会社 | 基板及びそれを用いたタッチパネル部材 |
CN105492113B (zh) * | 2013-08-20 | 2018-09-25 | 株式会社大赛璐 | 气体发生器 |
CN103747659B (zh) * | 2014-01-08 | 2017-01-18 | 中国科学院金属研究所 | 一种多孔铜散热片及其制备方法 |
US9251778B2 (en) | 2014-06-06 | 2016-02-02 | Industrial Technology Research Institute | Metal foil with microcracks, method of manufacturing the same, and sound-absorbing structure having the same |
JP6566554B2 (ja) * | 2014-08-20 | 2019-08-28 | 昭和電工株式会社 | 積層シートおよび積層シートの製造方法 |
US9666514B2 (en) * | 2015-04-14 | 2017-05-30 | Invensas Corporation | High performance compliant substrate |
DE102015106828A1 (de) * | 2015-04-30 | 2016-11-03 | At&S Austria Technologie & Systemtechnik Aktiengesellschaft | Vorrichtung zum elektrischen Verbinden von Komponenten mit einem rissminimierenden Haftvermittler und Herstellungsverfahren dafür |
CN105237952B (zh) * | 2015-09-29 | 2017-11-17 | 苏州宽温电子科技有限公司 | 一种电磁波吸收薄膜及其制备方法 |
CN108348871B (zh) | 2015-10-30 | 2021-11-05 | 蓝移材料有限公司 | 高度支化的非交联气凝胶、其制备方法及用途 |
EP3370952A1 (en) | 2015-11-03 | 2018-09-12 | Blueshift Materials, Inc. | Internally reinforced aerogel and uses thereof |
KR101632584B1 (ko) * | 2015-11-03 | 2016-06-23 | 건양테크(주) | 반도체 방열판 제조 방법 |
TWI558740B (zh) | 2015-12-07 | 2016-11-21 | 財團法人工業技術研究院 | 導熱樹脂及包含該導熱樹脂之熱界面材料 |
JP6366564B2 (ja) * | 2015-12-08 | 2018-08-01 | キヤノンファインテックニスカ株式会社 | 転写材、記録物、それらの製造装置および製造方法 |
JP6689880B2 (ja) | 2015-12-16 | 2020-04-28 | テクノUmg株式会社 | レーダー装置が発するビームの経路に配置される樹脂部品、レドーム及びレーダー装置 |
KR20180104085A (ko) * | 2016-01-25 | 2018-09-19 | 주식회사 다이셀 | 이차 전지 |
CA3016132A1 (en) | 2016-06-08 | 2017-12-14 | Blueshift Materials, Inc. | Polymer aerogel with improved mechanical and thermal properties |
KR101809369B1 (ko) * | 2016-06-10 | 2017-12-15 | 한양대학교 산학협력단 | 전도성 구조체 및 그 제조 방법, 그를 포함하는 터치 센서 및 터치 센서의 제조 방법 및 터치 센싱 방법 |
KR20190029649A (ko) * | 2016-07-25 | 2019-03-20 | 닛토덴코 가부시키가이샤 | 밀리파 안테나용 필름 |
CN111433265B (zh) | 2017-12-05 | 2023-09-29 | 蓝移材料有限公司 | 经热处理的聚酰胺酰胺气凝胶 |
CN108847395B (zh) * | 2018-06-25 | 2020-01-07 | 深圳市先进连接科技有限公司 | 一种用于低温快速连接的预烧结纳米网络银膜制备及封装方法 |
CN110787653B (zh) * | 2018-08-01 | 2022-10-11 | 孝感市思远新材料科技有限公司 | 一种含共价有机框架材料的复合膜及制备方法 |
CN115386134A (zh) * | 2018-10-31 | 2022-11-25 | 株式会社理光 | 多孔质层及电极 |
CN113024878B (zh) * | 2019-12-25 | 2023-10-03 | 株式会社理光 | 多孔质结构体,多孔质结构体的制造方法以及制造装置 |
CN114917774B (zh) * | 2022-05-07 | 2023-03-14 | 大连理工大学 | 一种聚丙烯腈基热交联膜的制备方法 |
CN117613517A (zh) * | 2024-01-22 | 2024-02-27 | 宁德新能源科技有限公司 | 隔离膜、二次电池以及电化学装置 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998025997A1 (fr) | 1996-12-10 | 1998-06-18 | Daicel Chemical Industries, Ltd. | Films poreux, leur procede de production et films stratifies et feuilles d'enregistrement fabriques a l'aide desdits films poreux |
JP2000143848A (ja) | 1998-11-13 | 2000-05-26 | Daicel Chem Ind Ltd | インク受像シート及びその製造方法 |
JP2000154273A (ja) * | 1998-09-17 | 2000-06-06 | Matsushita Electric Ind Co Ltd | 多孔質体およびその製造方法 |
JP2000158798A (ja) | 1998-11-24 | 2000-06-13 | Daicel Chem Ind Ltd | インク受像シート及びその製造方法 |
JP2004175104A (ja) | 2002-11-12 | 2004-06-24 | Daicel Chem Ind Ltd | 多孔性フィルムの製造方法、及び多孔性フィルム |
JP2006237322A (ja) | 2005-02-25 | 2006-09-07 | Mitsubishi Paper Mills Ltd | 銅ポリイミド基板の製造方法 |
WO2007097249A1 (ja) | 2006-02-20 | 2007-08-30 | Daicel Chemical Industries, Ltd. | 多孔性フィルム及び多孔性フィルムを用いた積層体 |
JP2009073124A (ja) | 2007-09-21 | 2009-04-09 | Daicel Chem Ind Ltd | 多孔質層を有する積層体及びその製造方法、並びに多孔質膜及びその製造方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001088482A1 (en) * | 2000-05-15 | 2001-11-22 | Mitsubishi Denki Kabushiki Kaisha | Sensor element and its manufacturing method |
JP2002154273A (ja) * | 2000-11-21 | 2002-05-28 | Alps Electric Co Ltd | リライト記録媒体およびリライト記録媒体を用いた記録方法 |
CN1694791B (zh) * | 2002-11-12 | 2010-08-18 | 大赛璐化学工业株式会社 | 多孔膜及其制备方法 |
KR101184540B1 (ko) * | 2003-09-25 | 2012-09-19 | 가부시끼가이샤 다이셀 | 내약품성을 갖는 다공성 필름 |
JP2005212389A (ja) * | 2004-01-30 | 2005-08-11 | Mitsubishi Plastics Ind Ltd | ポリアミド系積層フィルム |
CN101035870B (zh) * | 2004-10-06 | 2010-06-16 | 关西涂料株式会社 | 活化能射线固化性涂料组合物以及涂膜形成方法 |
CN101384425A (zh) * | 2006-02-20 | 2009-03-11 | 大赛璐化学工业株式会社 | 多孔性薄膜及使用了多孔性薄膜的层叠体 |
US20100252310A1 (en) * | 2007-07-27 | 2010-10-07 | Kiyoshige Kojima | Composite for multilayer circuit board |
JP5189379B2 (ja) * | 2008-02-20 | 2013-04-24 | リンテック株式会社 | 樹脂組成物及びこれを用いたフィルム、ならびにフィルムの製造方法 |
KR20110004907A (ko) * | 2008-06-10 | 2011-01-14 | 다이셀 가가꾸 고교 가부시끼가이샤 | 다공질층을 갖는 적층체 및 그것을 사용한 기능성 적층체 |
JP5363227B2 (ja) * | 2009-03-19 | 2013-12-11 | 富士フイルム株式会社 | 電子回路基板製造方法 |
EP2478752A1 (de) * | 2009-09-14 | 2012-07-25 | Felix Schoeller Jr. Foto- Und Spezialpapiere GmbH & Co. KG | Substrat für elektronische schaltungen |
JP5461973B2 (ja) * | 2009-12-14 | 2014-04-02 | 株式会社ダイセル | 多孔質膜及びその製造方法 |
-
2010
- 2010-12-01 CN CN2010800520203A patent/CN102666096A/zh active Pending
- 2010-12-01 US US13/508,512 patent/US20130020117A1/en not_active Abandoned
- 2010-12-01 WO PCT/JP2010/071492 patent/WO2011074418A1/ja active Application Filing
- 2010-12-01 KR KR1020127011847A patent/KR20120123017A/ko not_active Application Discontinuation
- 2010-12-01 JP JP2011546059A patent/JP5793425B2/ja active Active
- 2010-12-01 EP EP10837447.1A patent/EP2514591A4/en not_active Withdrawn
- 2010-12-09 TW TW99142916A patent/TW201129476A/zh unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998025997A1 (fr) | 1996-12-10 | 1998-06-18 | Daicel Chemical Industries, Ltd. | Films poreux, leur procede de production et films stratifies et feuilles d'enregistrement fabriques a l'aide desdits films poreux |
JP2000154273A (ja) * | 1998-09-17 | 2000-06-06 | Matsushita Electric Ind Co Ltd | 多孔質体およびその製造方法 |
JP2000143848A (ja) | 1998-11-13 | 2000-05-26 | Daicel Chem Ind Ltd | インク受像シート及びその製造方法 |
JP2000158798A (ja) | 1998-11-24 | 2000-06-13 | Daicel Chem Ind Ltd | インク受像シート及びその製造方法 |
JP2004175104A (ja) | 2002-11-12 | 2004-06-24 | Daicel Chem Ind Ltd | 多孔性フィルムの製造方法、及び多孔性フィルム |
JP2006237322A (ja) | 2005-02-25 | 2006-09-07 | Mitsubishi Paper Mills Ltd | 銅ポリイミド基板の製造方法 |
WO2007097249A1 (ja) | 2006-02-20 | 2007-08-30 | Daicel Chemical Industries, Ltd. | 多孔性フィルム及び多孔性フィルムを用いた積層体 |
JP2009073124A (ja) | 2007-09-21 | 2009-04-09 | Daicel Chem Ind Ltd | 多孔質層を有する積層体及びその製造方法、並びに多孔質膜及びその製造方法 |
Non-Patent Citations (2)
Title |
---|
NIKKEI ELECTRONICS, 17 June 2002 (2002-06-17), pages 75 |
See also references of EP2514591A4 |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011122124A (ja) * | 2009-12-14 | 2011-06-23 | Daicel Chemical Industries Ltd | 多孔質膜及びその製造方法 |
US20140183507A1 (en) * | 2011-09-14 | 2014-07-03 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Organic field-effect transistor |
US9741953B2 (en) * | 2011-09-14 | 2017-08-22 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Organic field-effect transistor |
US20140295168A1 (en) * | 2012-03-29 | 2014-10-02 | Nitto Denko Corporation | Electrically insulating resin sheet |
JP2014028326A (ja) * | 2012-07-31 | 2014-02-13 | Daicel Corp | 多孔質層を有する積層体及びその製造方法 |
JP2014110514A (ja) * | 2012-11-30 | 2014-06-12 | Toppan Forms Co Ltd | アンテナ構造体、通信機器及びアンテナ構造体の製造方法 |
JP2014124906A (ja) * | 2012-12-27 | 2014-07-07 | Daicel Corp | 金属薄膜層が設けられた多孔膜積層体及びその製造方法 |
JP2014180787A (ja) * | 2013-03-18 | 2014-09-29 | Ube Ind Ltd | 積層体および積層体の製造方法 |
JP2016222912A (ja) * | 2015-06-01 | 2016-12-28 | ユニチカ株式会社 | 芳香族アミド系高分子溶液および多孔質芳香族アミド系フィルム |
JP2019010740A (ja) * | 2017-06-29 | 2019-01-24 | 富士ゼロックス株式会社 | ポリイミド積層膜、及びポリイミド積層膜の製造方法 |
JP7024225B2 (ja) | 2017-06-29 | 2022-02-24 | 富士フイルムビジネスイノベーション株式会社 | ポリイミド積層膜、及びポリイミド積層膜の製造方法 |
JP2018024262A (ja) * | 2017-11-20 | 2018-02-15 | 宇部興産株式会社 | 積層体および積層体の製造方法 |
JP2018027705A (ja) * | 2017-11-20 | 2018-02-22 | 宇部興産株式会社 | 積層体および積層体の製造方法 |
JP2019183153A (ja) * | 2018-04-12 | 2019-10-24 | ユニチカ株式会社 | ポリイミドエアロゲルの製造方法 |
JP2020084096A (ja) * | 2018-11-29 | 2020-06-04 | 株式会社リコー | 多孔質層の製造方法、多孔質層および電極 |
JP7151425B2 (ja) | 2018-11-29 | 2022-10-12 | 株式会社リコー | 多孔質層の製造方法、多孔質層および電極 |
CN116249592A (zh) * | 2020-09-30 | 2023-06-09 | 富士胶片株式会社 | 导电层叠体及导电层叠体的制造方法 |
CN116249592B (zh) * | 2020-09-30 | 2024-04-19 | 富士胶片株式会社 | 导电层叠体及导电层叠体的制造方法 |
WO2023054591A1 (ja) * | 2021-09-30 | 2023-04-06 | 古河電気工業株式会社 | 紫外線、可視光線および/または赤外線を拡散反射する物品およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP5793425B2 (ja) | 2015-10-14 |
EP2514591A1 (en) | 2012-10-24 |
US20130020117A1 (en) | 2013-01-24 |
KR20120123017A (ko) | 2012-11-07 |
JPWO2011074418A1 (ja) | 2013-04-25 |
CN102666096A (zh) | 2012-09-12 |
EP2514591A4 (en) | 2014-02-05 |
TW201129476A (en) | 2011-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5793425B2 (ja) | 多孔質層を有する積層体、及びそれを用いた機能性積層体 | |
JP5117150B2 (ja) | 多孔質層を有する積層体及びその製造方法、並びに多孔質膜及びその製造方法 | |
JP5461973B2 (ja) | 多孔質膜及びその製造方法 | |
JP5474410B2 (ja) | 多孔質層を有する積層体、及びそれを用いた機能性積層体 | |
JP4913663B2 (ja) | 回路基板の製造方法 | |
JP5736186B2 (ja) | 無機粒子を含有する多孔質膜及びその製造方法 | |
EP1995053B1 (en) | Porous film and layered product including porous film | |
KR101464322B1 (ko) | 전자파 차단 구조 및 이를 제조하는 방법 | |
JP5870917B2 (ja) | 樹脂組成物 | |
CN101384425A (zh) | 多孔性薄膜及使用了多孔性薄膜的层叠体 | |
WO2005100435A1 (ja) | エポキシ樹脂組成物 | |
JP6427861B2 (ja) | 回路基板の製造方法 | |
KR102259479B1 (ko) | 프린트 배선판의 제조 방법 | |
CN106548946A (zh) | 布线板的制造方法 | |
JP2014028326A (ja) | 多孔質層を有する積層体及びその製造方法 | |
JP5960989B2 (ja) | 酸化チタン含有多孔質膜積層体及びその製造方法 | |
JP7331812B2 (ja) | 配線板及び半導体装置 | |
WO2023095466A1 (ja) | 樹脂シート | |
JP2023100866A (ja) | 配線板及び半導体装置 | |
TW201043464A (en) | Laminate having porous layers and functional laminate using the same | |
JP2008294059A (ja) | 導体層の形成方法および回路基板の製造方法 | |
JP2016155079A (ja) | 樹脂シートの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080052020.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10837447 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011546059 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13508512 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20127011847 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010837447 Country of ref document: EP |