WO2014115710A1 - 積層体、導電性パターン、電気回路及び積層体の製造方法 - Google Patents
積層体、導電性パターン、電気回路及び積層体の製造方法 Download PDFInfo
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- WO2014115710A1 WO2014115710A1 PCT/JP2014/051077 JP2014051077W WO2014115710A1 WO 2014115710 A1 WO2014115710 A1 WO 2014115710A1 JP 2014051077 W JP2014051077 W JP 2014051077W WO 2014115710 A1 WO2014115710 A1 WO 2014115710A1
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- 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
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- 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
- C08J7/056—Forming hydrophilic coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
- H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4664—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders
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- 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
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- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12542—More than one such component
- Y10T428/12549—Adjacent to each other
Definitions
- the present invention relates to a laminate of a conductive pattern or the like that can be used for manufacturing an electromagnetic wave shield, an integrated circuit, an organic transistor, or the like.
- a conductive material layer is formed by applying and baking a conductive ink containing a conductive material such as silver or a plating nucleating agent on the surface of a support. Then, a conductive pattern in which a plating layer is provided on the surface of the conductive material layer by plating the surface of the conductive material layer is known (see, for example, Patent Document 1).
- the conductive pattern has insufficient adhesion between the support and the conductive material layer, the conductive material is lost from the surface of the support over time and is formed by the conductive material. In some cases, the conductive pattern is disconnected or the conductivity is lowered (resistance value is increased).
- a pattern is drawn by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer on the surface of the support.
- a method for producing a conductive pattern is known (see Patent Document 2).
- the conductive pattern obtained by the above method may still not be sufficient in terms of adhesion between the support and the ink receiving layer, the ink receiving from the surface of the support over time. In some cases, the layer and the conductive material are lost, causing disconnection of the conductive pattern formed by the conductive material or a decrease in conductivity. In addition, when the conductive pattern is used in a high temperature or high humidity environment, the adhesion is remarkably lowered, and the conductive material may be lost.
- the peeling of the ink receiving layer from the surface of the support is not sufficient in terms of moisture and heat resistance, for example, when it is heated to about 100 ° C. to 200 ° C. in the plating process, etc. In some cases, however, the plating treatment cannot be performed for the purpose of improving the strength.
- the surface of the film-like insulating layer is provided for the purpose of providing a film-like insulating layer between the conductive layers or improving the adhesion of the second conductive layer.
- a primer layer is provided on the electronic circuit, which tends to make the electronic circuit thicker than necessary.
- the problem to be solved by the present invention is that the adhesiveness of each layer is excellent, and even when exposed to a high-temperature and high-humidity environment, it has a moisture and heat resistance level that can maintain the excellent adhesiveness. It is providing the thin laminated body provided.
- the problem to be solved by the present invention relates to a manufacturing method capable of efficiently producing a laminate such as a thin conductive pattern.
- the present inventors have provided a primer layer (B) and provided the insulating layer with the role of a primer layer, thereby providing a thin and excellent adhesiveness and heat-and-moisture resistance. It discovered that a laminated body can be manufactured efficiently.
- the present invention comprises at least a support layer (A), a primer layer (B), a first conductive layer (C), an insulating layer (D), and a second conductive layer (E).
- the insulating layer (D) is formed by applying and drying the resin composition (d) on at least a part or the whole of the surface of the first conductive layer (C).
- the second conductive layer (E) is a formed layer, and a fluid (e-1) containing a conductive substance is applied to part or all of the surface of the insulating layer (D).
- a second plating nucleus layer (E-1) formed on the surface of the second plating nucleus layer (E-1). It is related with the laminated body and electroconductive pattern characterized by being a layer.
- the laminate of the present invention can maintain excellent adhesion even when exposed to a high temperature and high humidity environment, and as a result, can maintain excellent conductivity without causing disconnection or the like.
- the top view of the electroconductive pattern which consists of a 1st electroconductive layer (C) printed on the surface of a primer layer (B) is shown.
- the top view of the electroconductive pattern which consists of a 2nd electroconductive layer (E) printed on the surface of the insulating layer (B) is shown. Sectional drawing of a laminated body is shown.
- the laminate of the present invention comprises at least a support layer (A), a primer layer (B), a first conductive layer (C), an insulating layer (D), and a second conductive layer (E ) And the insulating layer (D) is formed by applying and drying the resin composition (d) on part or all of the surface of the first conductive layer (C).
- the second conductive layer (E) is a formed layer, and a fluid (e-1) containing a conductive substance is applied to part or all of the surface of the insulating layer (D).
- the resin composition (d) is applied to at least part or all of the surface of the first conductive layer (C) among the layers having the layers (A) to (D). Then, an insulating layer (D) is formed by drying, and the insulating layer (D) serves as a primer layer that receives the fluid (e-1) that can form the second plating core layer (E-1). Thus, the second plating nucleus layer (E-1) is laminated on the surface of the insulating layer (D).
- the laminate of the present invention may include layers other than the layers (A) to (E).
- the laminate of the present invention has a primer layer (B) between the layer (A) comprising the support and the first conductive layer (C).
- the primer layer (B) is a layer that receives a fluid (c-1) containing a conductive substance that can be used to form the conductive layer (C).
- the primer layer (B) rapidly absorbs the solvent contained in the fluid (c-1) when the fluid (c-1) comes into contact with the primer layer (B-1). ).
- the adhesiveness and heat-and-moisture resistance with the layer (A) which consists of the said support body, a primer layer (B), and the 1st conductive layer (C) comprised from an electroconductive substance can be improved significantly. .
- the primer layer (B) may be provided on a part or all of the surface of the layer (A) composed of the support, or may be provided on one side or both sides thereof.
- the laminate has a primer layer (B) on the entire surface of the layer (A) made of the support, and the conductive layer (C) is provided only in a necessary portion of the primer layer (B). It is also possible to use a laminate of Moreover, the laminated body in which the said primer layer (B) was provided only in the part in which the said conductive layer (C) is provided among the surfaces of the layer (A) which consists of the said support body can also be used.
- the thickness of the primer layer (B) is preferably in the range of 0.01 ⁇ m to 30 ⁇ m, and more preferably in the range of 0.05 ⁇ m to 10 ⁇ m.
- the laminate of the present invention has the first conductive layer (C).
- the first conductive layer (C) a single layer formed of a conductive substance contained in a fluid (c-1) such as a conductive ink or a plating nucleating agent, or a fluid (c-1) And a layer composed of a first plating nucleus layer (C-1) formed of a conductive substance contained in the first plating layer and a first plating layer (C-2) laminated on the surface thereof.
- the first conductive layer (C), the first plating core layer (C-1) and the first plating layer (C-2) are used in order to obtain a laminate having excellent moisture and heat resistance. It is preferable that it is a layer comprised.
- the first plating nucleus layer (C-1) constituting the first conductive layer (C) is preferably composed of the conductive substance, specifically, a layer composed of silver. Is preferred.
- the first plating nucleus layer (C-1) is mainly composed of a conductive substance such as silver as described above, but the solvent, additive, etc. contained in the fluid (c-1) It may remain in the first plating nucleus layer (C-1).
- the first plating layer (C-2) constituting the first conductive layer (C) is a layer laminated on the surface of the first plating nucleus layer (C-1).
- the first plating layer (C-2) is preferably a layer made of a metal such as copper, nickel, chromium, cobalt, tin, etc., and the plating layer made of copper is disconnected over a long period of time. Therefore, it is preferable to produce a conductive pattern such as a highly reliable wiring pattern that can maintain good electrical conductivity without causing any problems.
- the conductive layer (C) may be provided on a part or all of the surface of the primer layer (B). Specifically, examples of the conductive layer (C) provided only on a necessary portion of the surface of the primer layer (B) include a linear layer formed by drawing a line. A laminate having a linear layer as the conductive layer (C) is suitable for producing a conductive pattern, an electric circuit, or the like.
- the width (line width) of the linear layer is about 0.01 ⁇ m to 200 ⁇ m, preferably 0.01 ⁇ m to 150 ⁇ m, more preferably 0.01 ⁇ m to It preferably has a thickness of 100 ⁇ m.
- the first conductive layer (C) constituting the laminate of the present invention preferably has a thickness in the range of 0.01 ⁇ m to 50 ⁇ m, and preferably has a thickness in the range of 0.01 ⁇ m to 30 ⁇ m. More preferably, is used.
- the thickness of the conductive layer (C) can be adjusted by controlling the coating amount of the fluid (c-1) containing a conductive substance that can be used to form the conductive layer (C). .
- the thickness (height) is preferably in the range of 0.01 ⁇ m to 1 ⁇ m.
- the first plating nucleus layer (C-1) that can form the conductive layer (C) preferably has a thickness in the range of 0.01 ⁇ m to 25 ⁇ m.
- the thickness of the first plating nucleus layer (C-1) can be adjusted by controlling the coating amount of the fluid (c-1).
- the first plating layer (C-2) preferably has a thickness in the range of 1 ⁇ m to 45 ⁇ m.
- the thickness of the first plating layer (C-2) is the processing time and current density in the plating process when forming the first plating layer (C-2), the amount of the additive used for plating, etc. Can be adjusted by controlling.
- the laminate of the present invention has an insulating layer (D).
- the insulating layer (D) is a layer provided for the purpose of preventing conduction between the first conductive layer (C) and the second conductive layer (E), and is generally an interlayer insulating material. It is said.
- the insulating layer (D) is included in the fluid (e-1) when it comes into contact with the fluid (e-1) that can form the second plating nucleus layer (E-1) described later. It serves as a primer layer that absorbs the solvent to be carried and carries the conductive substance contained in the fluid (e-1).
- the insulating layer (D) is not a pre-formed film or sheet, but is formed by applying and drying the resin composition (d) on at least the surface of the first conductive layer (C). In order to reduce the thickness of the laminate of the present invention, it is preferable that the layer is a thick layer.
- the insulating layer (D) is preferably laminated on a part or all of the surface of the first conductive layer (C), but the first conductive layer (C) is used as the primer layer (B). In the case where the insulating layer (D) is laminated on a part of the surface, the insulating layer (D) may be laminated directly on the surface of the primer layer (D).
- the thickness of the insulating layer (D) is 1 ⁇ m to 50 ⁇ m in order to achieve both the insulating properties of the first conductive layer (C) and the second conductive layer (E) and the thinned laminate. A range is preferable.
- the laminate of the present invention has a second conductive layer (E).
- the second conductive layer (E) includes a second plating nucleus layer (E-1) formed of a conductive substance contained in a fluid (e-1) such as a conductive ink or a plating nucleating agent; This is a layer constituted by the second plating layer (E-2) laminated on the surface.
- the second plating nucleus layer (E-1) constituting the second conductive layer (E) is preferably composed of the conductive substance, specifically, a layer composed of silver. Is preferred. As described above, the second plating nucleus layer (E-1) is mainly composed of a conductive material such as silver, but the solvent or additive contained in the fluid (e-1) may contain the first plating core layer (E-1). It may remain in the second plating nucleus layer (E-1).
- the second plating layer (E-2) constituting the second conductive layer (E) is a layer laminated on the surface of the second plating core layer (E-1).
- the second plating layer (E-2) is preferably a layer made of a metal such as copper, nickel, chromium, cobalt, tin, etc., and the plating layer made of copper is disconnected over a long period of time. Therefore, it is preferable to produce a conductive pattern such as a highly reliable wiring pattern that can maintain good electrical conductivity without causing any problems.
- the second conductive layer (E) may be provided on a part or all of the surface of the insulating layer (D). Specifically, the conductive layer (E) provided only on a necessary portion of the surface of the insulating layer (D) includes a linear layer formed by drawing a line. A laminate having a linear layer as the conductive layer (E) is suitable for producing a conductive pattern, an electric circuit, or the like.
- the width (line width) of the linear layer is about 0.01 ⁇ m to 200 ⁇ m, preferably 0.01 ⁇ m to 150 ⁇ m, more preferably 0 It is preferable to have a thickness of 0.01 ⁇ m to 100 ⁇ m.
- the second conductive layer (E) constituting the laminate of the present invention preferably has a thickness in the range of 0.01 ⁇ m to 50 ⁇ m, and preferably has a thickness in the range of 0.01 ⁇ m to 30 ⁇ m. More preferably, is used.
- the thickness of the second conductive layer (E) is adjusted by controlling the coating amount of the fluid (e-1) that can be used to form the second plating core layer (E-1). can do.
- the thickness (height) is preferably in the range of 0.01 ⁇ m to 1 ⁇ m.
- the second plating nucleus layer (E-1) forming the second conductive layer (E) preferably has a thickness in the range of 0.01 ⁇ m to 25 ⁇ m.
- the thickness of the second plating nucleus layer (E-1) can be adjusted by controlling the coating amount of the fluid (e-1).
- the second plating layer (E-2) preferably has a thickness in the range of 1 ⁇ m to 45 ⁇ m.
- the thickness of the second plating layer (E-2) is the processing time and current density in the plating processing step when forming the second plating layer (E-2), the amount of additive used for plating, etc. Can be adjusted by controlling.
- a primer for forming the primer layer (B) is applied to a part or all of the surface of the support constituting the layer (A), and a part or all of the application surface thereof is applied.
- a first plating layer is formed on the surface of the first plating nucleus layer (C-1) by plating a part or all of the surface of the first plating nucleus layer (C-1).
- the resin composition (d) for forming the coating is applied, and a conductive substance is contained in part or all of the coated surface.
- the fluid (e-1) By applying the fluid (e-1), the insulating layer (D) is laminated on the surface of the first conductive layer (C), and a second plating nucleus layer is formed on the surface of the insulating layer (D).
- Step (3) of laminating (E-1) and a part or all of the surface of the second plating nucleus layer (E-1) are plated to obtain the second plating nucleus layer (E-1). It can be manufactured through the step [4] of forming the second conductive layer (E) in which the second plating layer (e-2) is laminated on the surface of -1).
- a primer for forming the primer layer (B) is applied to a part or all of the surface of the support constituting the layer (A), dried as necessary, and then the coated surface.
- a fluid (c-1) containing a conductive material is applied to a part or all of the substrate, and dried to provide a layer (A) comprising the support, a primer layer (B), and a first conductive layer
- Examples of the support constituting the layer (A) include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), poly (meth) acrylate, and the like.
- Acrylic resin polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP), polyether ether ketone (PEEK), cellulose nanofiber, silicon, ceramics, glass Etc., a porous support made of them, a support made of a metal such as a steel plate or copper, the surface of which is silicon carbide, diamond-like car Emissions, aluminum, copper, can be used a support obtained by vapor deposition of titanium or the like.
- the support generally used as a support in forming a conductive pattern such as a circuit board, polyimide resin, polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer (LCP), poly It is preferable to use a support made of ether ether ketone (PEEK), glass, cellulose nanofiber or the like.
- PEEK ether ether ketone
- the support when used for applications that require flexibility, it is possible to use a material that is relatively flexible and capable of being bent. It is preferable for obtaining a final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial stretching or the like.
- the film or sheet-like support examples include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.
- the support is preferably one having a thickness of about 1 ⁇ m to 2,000 ⁇ m from the viewpoint of reducing the weight and thickness of a laminate such as a conductive pattern and the final product in which the support is used. More preferably, the thickness is about 1 ⁇ m to 100 ⁇ m. When the laminate is required to be relatively flexible, it is preferable to use a laminate having a thickness of about 1 ⁇ m to 80 ⁇ m.
- the type and thickness of the support constituting the laminate of the present invention vary greatly depending on the use of the laminate and the like. Therefore, in order to reduce the thickness of the laminate, the thickness of the components other than the support, specifically, the primer layer (B) and the first conductive layer (C) constituting the laminate
- the total thickness of the insulating layer (D) and the second conductive layer (E) is preferably in the range of 1 ⁇ m to 100 ⁇ m, and the thickness is preferably 1 ⁇ m to 80 ⁇ m so that the laminated body such as the conductive pattern is thin. It is more preferable for realizing the conversion.
- the primer to be applied to part or all of the surface of the support those containing various resins and solvents can be used.
- the resin examples include urethane resin (b1), vinyl resin (b2), urethane-vinyl composite resin (b3), phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, A fluororesin or the like can be used.
- urethane resin (b1), vinyl resin (b2), and urethane-vinyl composite resin (b3).
- (B1) is a urethane resin having a polycarbonate structure
- an aliphatic polyester structure is a urethane resin
- vinyl resin (b2) is an acrylic resin having a structural unit derived from methyl methacrylate
- urethane-vinyl composite resin (b3) is urethane-acrylic.
- the primer it is preferable to use a primer containing 10% by mass to 70% by mass of the resin with respect to the whole primer, in order to maintain ease of application and the like, and 10% by mass to 50% by mass. It is more preferable to use what is contained.
- a solvent that can be used for the primer various organic solvents and aqueous media can be used.
- organic solvent for example, toluene, ethyl acetate, methyl ethyl ketone and the like can be used.
- aqueous medium include water, organic solvents miscible with water, and mixtures thereof.
- organic solvent miscible with water examples include alcohols such as methanol, ethanol, n- and isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; polyalkylenes such as ethylene glycol, diethylene glycol, and propylene glycol Examples include glycols; alkyl ethers of polyalkylene glycols; and lactams such as N-methyl-2-pyrrolidone.
- only water may be used, or a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
- a resin having a hydrophilic group as the resin in order to impart good water dispersibility to the primer and improve storage stability.
- hydrophilic group examples include an anionic group, a cationic group, and a nonionic group.
- anionic group for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used.
- a sulfonate group is preferable for imparting good water dispersibility.
- Examples of basic compounds that can be used for neutralization of the anionic group include organic bases such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, metal bases including sodium, potassium, lithium, calcium, and the like. Compounds and the like. When forming a conductive pattern or the like, the ammonia, organic amine, or alkanolamine is preferably used because the metal salt compound may inhibit the conductivity and the like.
- the carboxylate group or the sulfonate group is used as the anionic group, they are present in the range of 50 mmol / kg to 2,000 mmol / kg with respect to the whole resin. It is preferable for maintaining the property.
- a tertiary amino group for example, a tertiary amino group can be used.
- Examples of the acid that can be used for neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like. You may use organic sulfonic acid and inorganic acids, such as hydrochloric acid, a sulfuric acid, orthophosphoric acid, orthophosphorous acid, individually or in combination of 2 or more types. In the case of forming a conductive pattern or the like, it is preferable to use acetic acid, propionic acid, lactic acid, maleic acid, or the like because chlorine, sulfur, or the like may inhibit the conductivity.
- nonionic group examples include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.
- urethane resin (b1) that can be used as the resin contained in the primer
- a urethane resin obtained by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender can be used.
- the urethane resin which has a polycarbonate structure and the urethane resin which has an aliphatic polyester structure.
- the polycarbonate structure and the aliphatic polyester structure are structures derived from a polyol used for producing the urethane resin.
- the urethane resin having the polycarbonate structure can be produced by using a polycarbonate polyol described later as the polyol.
- the urethane resin which has the said aliphatic polyester structure can be manufactured by using what contains the aliphatic polyester polyol mentioned later as the said polyol.
- polycarbonate polyol As the polyol that can be used for the production of the urethane resin (b1), as described above, polycarbonate polyol, aliphatic polyester polyol, and the like can be used. Moreover, as said polyol, another polyol can be combined and used as needed.
- polycarbonate polyol for example, those obtained by reacting a carbonic acid ester and a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.
- carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.
- polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-
- aliphatic polyester polyol for example, an aliphatic polyester polyol obtained by an esterification reaction of a low molecular weight polyol and a polycarboxylic acid, a cyclic ester compound such as ⁇ -caprolactone or ⁇ -butyrolactone is subjected to a ring-opening polymerization reaction.
- Aliphatic polyesters obtained as described above, copolymerized polyesters thereof, and the like can be used.
- Examples of the low molecular weight polyol that can be used in the production of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3- Methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more thereof.
- Ethylene glycol 1,2-propanediol
- 1,3-butanediol or 1,4-butanediol in combination with 3-methyl-1,5-pentanediol, neopentyl glycol, or the like.
- polycarboxylic acid examples include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and anhydrides or ester-forming derivatives thereof, and aliphatic polycarboxylic acids such as adipic acid. Is preferably used.
- the polycarbonate polyol and aliphatic polyester polyol preferably have a number average molecular weight of 500 to 4,000, more preferably 500 to 2,000.
- polyol that can be used in the production of the urethane resin (b1) other polyols can be used in combination with the above-described ones as necessary.
- Examples of the other polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylol propane, etc., an acrylic polyol having a hydroxyl group introduced into an acrylic copolymer, and a butadiene copolymer containing a hydroxyl group in the molecule.
- Certain polybutadiene polyols, hydrogenated polybutadiene polyols, partially saponified products of ethylene-vinyl acetate copolymers, and the like can be used as appropriate.
- Examples of the other polyol include 1,4-cyclohexanedimethanol, cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, and tricyclo [5.2.
- a polyol having a hydrophilic group As the urethane resin (b1), it is preferable to use a polyol having a hydrophilic group as the other polyol.
- polyol having a hydrophilic group examples include a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, 5-sulfoisophthalic acid, Polyols having a sulfonic acid group such as sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used.
- a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, 5-sulfoisophthalic acid
- Polyols having a sulfonic acid group such as sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used.
- polyol having a hydrophilic group examples include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. It can also be used.
- Examples of the polyisocyanate that can react with the polyol to form a urethane resin include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene.
- Aliphatic polyisocyanates such as polyisocyanates having an aromatic structure such as diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and aliphatic cyclic structures Po It is possible to use the isocyanate.
- chain extender that can be used in producing the urethane resin
- polyamine, hydrazine compound, other active hydrogen atom-containing compounds, and the like can be used.
- polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like can be used.
- hydrazine compound examples include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide propion Acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.
- Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose.
- Glycols such as methylene glycol, glycerin and sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, water Etc. can be used.
- the chain extender is preferably used, for example, in such a range that the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), and 0.3 to 1 (equivalent ratio) It is more preferable to use in the range.
- the urethane resin (b1) is produced, for example, by reacting the polyol, the polyisocyanate, and, if necessary, the chain extender by a conventionally known method in the absence of a solvent or in the presence of an organic solvent. can do.
- the reaction between the polyol and the polyisocyanate is in consideration of safety by paying careful attention to sudden heat generation and foaming, preferably at a reaction temperature of 50 ° C. to 120 ° C., more preferably 80 ° C. to 100 ° C.
- the polyol and the polyisocyanate can be mixed by batch feeding, or sequentially supplied by a method such as dropping one of them to the other and reacting for approximately 1 to 15 hours.
- the primer containing the water dispersion of the said urethane resin (b1) produces a urethane resin (b1) by making the said polyol, the said polyisocyanate, and a chain extender react as needed by the above-mentioned method. If necessary, by neutralizing a part or all of hydrophilic groups such as anionic groups of the urethane resin (b1), and then mixing it with an aqueous medium used as a solvent for the primer A primer comprising a urethane resin (b1) aqueous dispersion in which the urethane resin (b1) is dispersed or partially dissolved in an aqueous medium can be obtained.
- a urethane prepolymer having an isocyanate group at the terminal is produced, and if necessary, the anionic group possessed by the urethane prepolymer.
- the urethane resin (b1) is aqueous by mixing with the aqueous medium and extending the chain using the chain extender as necessary.
- a primer comprising a urethane resin (b1) aqueous dispersion dispersed or dissolved in a medium can be obtained.
- the reaction between the polyisocyanate and the polyol is preferably performed, for example, in a range where the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol is 0.9-2.
- an organic solvent can be used as a solvent as described above.
- the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. Use or two or more can be used.
- the organic solvent is preferably removed by a distillation method or the like after the production of the urethane resin (b1). However, when the primer containing the urethane resin (b1) and the organic solvent is used, the organic solvent used when the urethane resin (b1) is manufactured is used as the solvent for the primer. Also good.
- urethane resin (b1) a resin having a weight average molecular weight of 5,000 to 500,000 is used for forming a laminate such as a conductive pattern having excellent adhesion and excellent conductivity. It is preferable to use 20,000 to 100,000.
- urethane resin (b1) those having various functional groups can be used as necessary.
- the functional group include crosslinkable functional groups such as an alkoxysilyl group, a silanol group, a hydroxyl group, and an amino group.
- the crosslinkable functional group can be suitably used for forming a conductive layer or a plating layer having excellent durability by forming a crosslinked structure in the primer layer (B).
- the alkoxysilyl group or silanol group can be introduced into the urethane resin by using ⁇ -aminopropyltriethoxysilane or the like when the urethane resin (b1) is produced.
- urethane resin (b1) when used in combination with a crosslinking agent described later, those having a functional group capable of reacting with the functional group of the crosslinking agent can be used.
- a functional group although depending on the selection of the crosslinking agent used in combination, for example, when a crosslinking agent such as a blocked isocyanate compound is used, a hydroxyl group or an amino group can be used.
- the vinyl resin (b2) that can be used as the resin contained in the primer a monomer polymer having a polymerizable unsaturated double bond can be used.
- a monomer polymer having a polymerizable unsaturated double bond can be used.
- polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber, ethylene-vinyl acetate copolymer, acrylic resin, etc. can be used, and a structure derived from methyl methacrylate. It is preferable to use an acrylic resin having units.
- acrylic resin a polymer or copolymer obtained by polymerizing a (meth) acrylic monomer can be used.
- a (meth) acryl monomer points out any one or both of an acrylic monomer and a methacryl monomer.
- acrylic resin having a structural unit derived from methyl (meth) acrylate as the acrylic resin.
- the acrylic resin can be produced, for example, by polymerizing various (meth) acrylic monomers described later.
- Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid t.
- methyl methacrylate makes it possible to use the primer layer (B) and the support layer (A) regardless of the influence of heat or the like in the heating step when producing the conductive pattern. It is preferable to use the above-mentioned methyl methacrylate in order to give excellent adhesiveness.
- the above-mentioned methyl methacrylate is more preferably used in order to enable improvement of the above.
- Alkyl esters are more preferably used, and n-butyl acrylate is preferably used in order to further improve the adhesion and conductivity.
- the methyl (meth) acrylate is preferably 10% by mass to 70% by mass, more preferably 30% by mass to 65% by mass with respect to the total amount of the (meth) acrylic monomer mixture, and
- the acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, preferably the acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms is the total amount of the (meth) acrylic monomer mixture. Is preferably 20% by mass to 80% by mass, and more preferably 35% by mass to 70% by mass.
- (meth) acrylic monomers that can be used for producing the acrylic resin include, in addition to those described above, acrylic acid, methacrylic acid, ⁇ -carboxyethyl (meth) acrylate, 2- (meth) Contains carboxyl groups such as acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, ⁇ - (meth) acryloyloxyethyl hydrogen succinate Vinyl monomers can be used.
- the carboxyl group-containing vinyl monomer may be neutralized with ammonia, potassium hydroxide, or the like.
- the (meth) acrylic monomer includes one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, a hydroxyl group, and a glycidyl group.
- amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, a hydroxyl group, and a glycidyl group.
- the crosslinkable functional group such as amino group, silyl group, aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carbonyl group, acetoacetyl group, etc.
- the body can be used.
- Examples of the vinyl monomer having one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group that can be used for the (meth) acrylic monomer having a crosslinkable functional group include N- Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, Nn-butoxymethyl ( (Meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N, N′-dimethylol (meth) acrylamide, N -Ethoxymethyl-N-propyl Poxymethyl (meth) acrylamide, N, N'-dipropoxymethyl (meth) acrylamide
- Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide can provide a level of durability that can prevent peeling of the conductive material (a2) in the plating process. It is preferable when forming the electroconductive pattern provided with.
- Examples of the (meth) acrylic monomer having a crosslinkable functional group include those other than those described above, for example, a vinyl monomer having an amide group such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid (4-hydroxymethyl) Cyclohexyl) methyl, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, vinyl monomers having a hydroxyl group such as N-hydroxyethyl (meth) acrylamide: glycidyl (meth) acrylate, allyl (meth) acrylate Polymerizable monomer having a glycidyl group such as glycidyl ether Polymerizable monomers having amino groups such as aminoethyl (meth
- the (meth) acrylic monomer having a crosslinkable functional group can be used in the range of 0% by mass to 50% by mass with respect to the total amount of the (meth) acrylic monomer mixture.
- the (meth) acrylic monomer having the amide group has a (meth) acrylic group for introducing a self-crosslinking reactive methylolamide group. It is preferably used in the range of 0.1% by mass to 50% by mass and more preferably in the range of 1% by mass to 30% by mass with respect to the total amount of the monomer mixture.
- the (meth) acrylic monomer having another amide group used in combination with the self-crosslinking reactive methylolamide group and the (meth) acrylic monomer having a hydroxyl group are the (meth) acrylic monomer. It is preferably used in the range of 0.1% by mass to 30% by mass, and more preferably in the range of 1% by mass to 20% by mass with respect to the total amount.
- the (meth) acrylic monomer having a hydroxyl group and the acid group-containing (meth) acrylic monomer are used as a crosslinking agent (D ), But is preferably used in a range of approximately 0.05% by mass to 50% by mass with respect to the total amount of the (meth) acrylic monomer mixture, and 0.05% by mass to 30% by mass.
- the acrylic resin when the acrylic resin is produced, together with the (meth) acrylic monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl Vinyl ether, hexyl vinyl ether, (meth) acrylonitrile, styrene, ⁇ -methylstyrene, vinyl toluene, vinyl anisole, ⁇ -halostyrene, vinyl naphthalene, divinyl styrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N -Vinylpyrrolidone, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, vinyl sulfonic acid, styrene sulfonic acid, Allyl s
- the acrylic resin can be produced by polymerizing a mixture of various vinyl monomers as described above by a conventionally known method, but produces a conductive pattern having excellent adhesion and excellent conductivity. In addition, it is preferable to apply an emulsion polymerization method.
- emulsion polymerization method for example, water, a (meth) acrylic monomer mixture, a polymerization initiator, and if necessary, a chain transfer agent, an emulsifier, a dispersion stabilizer, and the like are collectively supplied into a reaction vessel.
- a pre-emulsion method that drops and polymerizes in a reaction vessel can be applied.
- the reaction temperature of the emulsion polymerization method varies depending on the type of (meth) acrylic monomer and polymerization initiator to be used.
- the reaction time is about 30 ° C. to 90 ° C., and the reaction time is about 1 hour to 10 hours. preferable.
- polymerization initiator examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, hydrogen peroxide Radical polymerization using only these peroxides, or aspercolic acid, erythorbic acid, sodium erythorbate, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, Polymerization can also be achieved by a redox polymerization initiator system combined with a reducing agent such as ferric chloride, and 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-amidino). It is also possible to use an azo initiator such as propane) dihydrochloride, It may be a good combination of two or more types may be use.
- persulfates such as potassium persulf
- anionic surfactant examples include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, and polyoxyethylene alkyl ethers.
- non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl phenyl ether.
- Ethylene diphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, acetylenic diol surfactant and the like can be used.
- cationic surfactant for example, an alkyl ammonium salt or the like can be used.
- alkyl (amido) betaine alkyldimethylamine oxide and the like can be used.
- emulsifier in addition to the above-mentioned surfactants, fluorine-based surfactants, silicone-based surfactants, and emulsifiers having a polymerizable unsaturated group generally called “reactive emulsifier” in the molecule Can also be used.
- Examples of the reactive emulsifier include “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, and “Eleminol JS-2, RS-30” (manufactured by Sanyo Chemical Industries).
- lauryl mercaptan can be used, and 0% by mass to 1.0% by mass with respect to the total amount of the (meth) acrylic monomer mixture. Is preferably used, and more preferably in the range of 0% by mass to 0.5% by mass.
- the urethane-vinyl composite resin (b3) usable as the resin contained in the primer the urethane resin (b3-1) and the vinyl polymer (b3-2) form composite resin particles in an aqueous medium. Can be dispersed.
- the composite resin particles include those in which part or all of the vinyl polymer (b3-2) is contained in the resin particles formed by the urethane resin (b3-1).
- the core-shell type composite resin particles that do not require the use of a surfactant or the like that can lower the electrical characteristics.
- the vinyl polymer (b3-2) is almost completely covered with the urethane resin (b3-1), but this is not essential and the effect of the present invention is impaired.
- a part of the vinyl polymer (b3-2) may be present on the outermost part of the composite resin particles as long as it is not present.
- the vinyl polymer (b3-2) when the vinyl polymer (b3-2) is more hydrophilic than the urethane resin (b3-1), the vinyl polymer (b3- In the resin particles formed in 2), a part or all of the urethane resin (b3-1) may be present to form composite resin particles.
- the urethane resin (b3-1) and the vinyl polymer (b3-2) may form a covalent bond, but preferably do not form a bond.
- urethane-vinyl composite resin (b3) it is preferable to use a urethane-acrylic composite resin in which the vinyl polymer (b3-2) is an acrylic resin.
- the composite resin particles preferably have an average particle diameter in the range of 5 nm to 100 nm from the viewpoint of maintaining good water dispersion stability.
- the average particle diameter here refers to the average particle diameter on a volume basis measured by a dynamic light scattering method.
- the same resin as the urethane resin (b1) can be used.
- the urethane resin (b3-1) constituting the urethane-vinyl composite resin has, for example, a urethane resin having a polyether structure or an aromatic polyester structure other than those exemplified as the urethane resin (b1). Urethane resin can also be used.
- the urethane resin (b3-1) usable for the production of the urethane-vinyl composite resin (b3) an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg, a hydrophilic group
- a urethane resin having a 3,000 mmol / kg to 5,000 mmol / kg aliphatic cyclic structure which further improves the adhesion and moist heat resistance
- Examples of the polyol, polyisocyanate, and chain extender that can be used in the production of the urethane resin (b3-1) include the polyol, polyisocyanate, and chain extension exemplified as those that can be used in the production of the urethane resin (b1). The same agent can be used.
- the polyol and the polyisocyanate have an aliphatic cyclic structure and an aliphatic cyclic structure. It is preferable to select and use a polyisocyanate having
- the urethane resin which has the said polyether structure can be manufactured by using what contains the polyether polyol mentioned later as the said polyol.
- the polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
- the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.
- alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like can be used.
- an aromatic polyester polyol can also be used as the polyol.
- aromatic polyester polyol for example, those obtained by an esterification reaction of a low molecular weight polyol and an aromatic polycarboxylic acid can be used.
- Examples of the low molecular weight polyol that can be used in the production of the aromatic polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-Methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. can be used alone or in combination of two or more thereof.
- Ethylene glycol 1,2-propane It is preferable to use a combination of diol, 1,3-butanediol, 1,4-butanediol, or the like, and 3-methyl-1,5-pentanediol, neopentyl glycol, or the like.
- aromatic polycarboxylic acid for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or esterified products thereof can be used.
- polyether polyol or the aromatic polyester polyol those having a number average molecular weight of 500 to 4,000 are preferably used, more preferably 500 to 2,000.
- the vinyl polymer (b3-2) constituting the urethane-vinyl composite resin use of a polymer having a glass transition temperature of 10 ° C. to 70 ° C. improves adhesion to the conductive layer (C). In addition, it is preferable.
- the glass transition temperature of the vinyl polymer (b3-2) is a value determined by calculation mainly based on the composition of the vinyl monomer used in the production of the vinyl polymer (b3-2). is there. Specifically, the vinyl polymer (b3-2) having the predetermined glass transition temperature can be obtained by using a combination of the vinyl polymer (b3-2) described later.
- the vinyl polymer (b3-2) is 800,000 or more in order to improve the adhesion of the conductive layer (C) and the conductivity of the resulting conductive pattern and to make the pattern thin. It is preferable to use those having a weight average molecular weight of 1, more preferably those having a weight average molecular weight of 1 million or more.
- the upper limit of the weight average molecular weight of the vinyl polymer (b3-2) is not particularly limited, but is preferably approximately 10 million or less, and preferably 5 million or less.
- the vinyl polymer (b3-2) may have various functional groups as necessary.
- the functional group include an amide group, a hydroxyl group, a glycidyl group, an amino group, a silyl group, Examples thereof include crosslinkable functional groups such as an aziridinyl group, an isocyanate group, an oxazoline group, a cyclopentenyl group, an allyl group, a carboxyl group, and an acetoacetyl group.
- the same polymer as the vinyl polymer (b3) can be used.
- the same as the (meth) acrylic monomer can be used.
- the vinyl polymer (b3-2) it is preferable to use the same acrylic resin having a structural unit derived from methyl methacrylate exemplified as usable for the vinyl resin (b2).
- urethane-vinyl composite resin (b3) for example, an aqueous dispersion of the urethane resin (b3-1) is produced by reacting the polyisocyanate, a polyol and, if necessary, a chain extender and dispersing in water. And the step (W) of polymerizing the (meth) acrylic monomer in the aqueous dispersion to produce a vinyl polymer (b3-2).
- the urethane resin (b3-1) is obtained by reacting the polyisocyanate with a polyol in the absence of a solvent or in an organic solvent or in the presence of a reactive diluent such as a (meth) acrylic monomer. Then, a part or all of the hydrophilic group of the urethane resin (b3-1) is neutralized with a basic compound or the like as necessary, and further reacted with a chain extender as necessary. And dispersing it in an aqueous medium to produce an aqueous dispersion of the urethane resin (b3-1).
- a vinyl monomer such as the (meth) acrylic monomer is supplied into the aqueous dispersion of the urethane resin (b3-1) obtained above, and the urethane resin (b3-1) particles
- a vinyl resin (b3-2) is produced by radical polymerization of a vinyl monomer.
- the production of the urethane resin (b3-1) is followed by supplying a polymerization initiator and the like.
- a vinyl resin (b3-2) is produced by radical polymerization of a vinyl monomer such as a (meth) acrylic monomer.
- the urethane resin (b3-1) has a high viscosity and is not excellent in workability
- a normal organic material such as methyl ethyl ketone, N-methylpyrrolidone, acetone, dipropylene glycol dimethyl ether or the like is used.
- Solvents and reactive diluents can be used.
- a vinyl monomer such as a (meth) acrylic monomer that can be used in the production of the vinyl polymer (b3-2) as the reactive diluent. It is preferable for improving the production efficiency.
- resins that can be used for the primer for example, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, fluorine resin, etc. can be used. it can.
- the above-mentioned resins may be used in appropriate combination.
- two or more of the urethane resin (b1), vinyl resin (b2), and urethane-vinyl composite resin (b3) can be used in appropriate combination.
- the urethane resin (b1) a polyether structure-containing urethane resin and a urethane resin having a polycarbonate structure can be used in combination.
- the urethane resin (b1) and the vinyl resin (b2) may be used in combination.
- those having a crosslinkable functional group can be used as described above.
- the crosslinkable functional group forms a cross-linked structure in the primer layer (B), thereby causing no bleeding or the like, and the conductive layer (C) excellent in adhesion and conductivity, or the first constituting the first conductive layer. It can be suitably used for forming the plating nucleus layer (C-1).
- crosslinkable functional group examples include an alkoxysilyl group, a silanol group, an amino group, and a hydroxyl group.
- the alkoxysilyl group or silanol group is hydrolyzed and condensed in an aqueous medium that is a solvent for the primer to form a crosslinked structure.
- the crosslinkable functional group is one that can form a crosslink structure by causing a crosslink reaction between the crosslinkable functional groups or a crosslinker described later by heating to 100 ° C or higher, preferably 120 ° C or higher.
- alkoxymethylamide group examples include an amide group formed by bonding a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or the like to a nitrogen atom, and among them, a methylolamide group and It is preferable to use one having at least one selected from the group consisting of alkoxymethylamide groups in order to greatly improve the durability of the primer layer (B) and the adhesion to various supports.
- a primer including a resin having a functional group capable of undergoing a crosslinking reaction by heating to about 100 ° C. or more, preferably about 120 ° C. as described above, when the primer is applied to the support surface and dried.
- the temperature is preferably less than 100 ° C.
- a primer layer having a crosslinked structure can also be formed.
- a plating agent made of a strong alkali or strongly acidic substance is used in the plating process described later. Even when exposed, it is possible to form a conductive pattern with exceptional durability that does not cause peeling of the primer layer (B) from the support.
- the phrase “substantially has no cross-linked structure” includes an embodiment in which the cross-linked structure is not formed at all, and within about 5% of the number of functional groups capable of forming the cross-linked structure is partially cross-linked. Refers to the structure formed.
- the crosslinkable functional group may be included in a total range of 0.005 equivalent / kg to 1.5 equivalent / kg with respect to the total amount of resin used in the primer.
- the primer is known as a cross-linking agent, a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent, an antifoaming agent, etc., as long as the effects of the present invention are not impaired. These may be added as appropriate.
- crosslinking agent for example, a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, an isocyanate compound, etc., a thermal crosslinking agent that can react at a relatively low temperature of about 25 ° C. to less than 100 ° C. to form a crosslinked structure ( x1-1), one or more selected from the group consisting of a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound, etc., react at a relatively high temperature of approximately 100 ° C. or higher to form a crosslinked structure.
- a thermal crosslinking agent (x1-2) that can be used and various photocrosslinking agents can be used.
- the primer containing the thermal crosslinking agent (x1-1) for example, it is applied to the surface of the support, dried at a relatively low temperature, and then applied (printed) to the fluid (c-1).
- the primer containing the thermal crosslinking agent (x1-1) is applied to the surface of the support, dried at a relatively low temperature, and then applied (printed) to the fluid (c-1).
- a primer containing the thermal crosslinking agent (x1-2) for example, it is applied to the support surface and dried at a low temperature of room temperature (25 ° C.) to about 100 ° C. to form a crosslinked structure.
- the fluid (c-1) After forming the primer layer that has not been formed and then applying the fluid (c-1), it is heated at a temperature of, for example, 150 ° C. or higher, preferably 200 ° C. or higher to form a cross-linked structure. Regardless of the influence of heat, external force, etc., it is possible to obtain a conductive pattern having exceptionally excellent durability that does not cause peeling of the conductive material.
- thermal crosslinking agent (x1-1) instead of the thermal crosslinking agent (x1-2) as the crosslinking agent.
- Examples of the metal chelate compound that can be used for the thermal crosslinking agent (x1-1) include acetylacetone, which is a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Coordination compounds, acetoacetate coordination compounds and the like can be used, and it is preferable to use acetylacetone aluminum which is an acetylacetone coordination compound of aluminum.
- a polyamine compound that can be used for the thermal crosslinking agent (x1-1) for example, a tertiary amine such as triethylamine, triethylenediamine, dimethylethanolamine or the like can be used.
- aziridine compound that can be used in the thermal crosslinking agent (x1-1) examples include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethylene urea. Diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like can be used.
- Examples of the metal salt compound that can be used as the crosslinking agent (x1-1) include aluminum sulfate, aluminum alum, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and aluminum chloride hexahydrate.
- Water-soluble metal salts such as aluminum-containing compounds such as titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate can be used.
- isocyanate compounds that can be used for the thermal crosslinking agent (x1-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexamethylene.
- a polyisocyanate such as diisocyanate and xylylene diisocyanate, an isocyanurate type polyisocyanate compound obtained by using them, an adduct comprising them and trimethylolpropane, the polyisocyanate compound and a polyol such as trimethylolpropane.
- Polyisocyanate group-containing urethane obtained by reacting can be used.
- hexamethylene diisocyanate nurate adduct of hexamethylene diisocyanate and trimethylolpropane
- adduct of tolylene diisocyanate and trimethylol propane adduct of xylylene diisocyanate and trimethylol propane, etc. are used. It is preferable.
- Examples of the melamine compound that can be used in the thermal crosslinking agent (x1-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyl.
- Oxymethyl melamine or a mixed etherified melamine obtained by combining these two types can be used.
- trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used.
- Examples of commercially available products include Becamine M-3, APM, J-101 (manufactured by DIC Corporation), and the like.
- the melamine compound can form a crosslinked structure by a self-crosslinking reaction.
- a catalyst such as an organic amine salt may be used to promote the self-crosslinking reaction.
- catalyst ACX, 376 etc. can be used.
- the catalyst is preferably in the range of approximately 0.01% by mass to 10% by mass with respect to the total amount of the melamine compound.
- Examples of the epoxy compound that can be used for the thermal crosslinking agent (x1-2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, and glycerin diglycidyl ether.
- Polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether
- Polyglycidyl ethers of polyalkylene glycols such as 1,3-bis (N, Polyglycidylamines such as' -diglycidylaminoethyl) cyclohexane; polyglycidyl esters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] Bisphenol A epoxy resin
- polyglycidylamines such as 1,3-bis (N, N′-diglycidylaminoethyl) cyclohexane and polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin diglycidyl ether.
- Examples of the epoxy compound include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -glycidoxypropyl other than those described above.
- a glycidyl group-containing silane compound such as ⁇ -glycidoxypropyltriisopropenyloxysilane can be used.
- oxazoline compounds that can be used for the thermal crosslinking agent (x1-2) include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2 , 2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'- Hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2 , 2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'- Dimethyl-2-oxa Phosphorus), bis - (2-oxazolinyl sulfonyl
- oxazoline compound for example, an oxazoline group-containing polymer obtained by polymerizing a combination of the following addition polymerizable oxazoline and other monomers as required may be used.
- Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., alone or in combination Can do. Of these, the use of 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
- carbodiimide compounds that can be used for the thermal crosslinking agent (x1-2) include poly [phenylenebis (dimethylmethylene) carbodiimide] and poly (methyl-1,3-phenylenecarbodiimide).
- Commercially available products include Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 (manufactured by Nisshinbo Co., Ltd.), UCALINK XL-29SE, XL-29MP (Union Carbide Corp.) Can be used.
- the blocked isocyanate compound that can be used in the thermal crosslinking agent (x1-2) a part or all of the isocyanate groups of the isocyanate compound exemplified as the thermal crosslinking agent (x1-1) What was sealed can be used.
- the blocking agent examples include phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, methyl acetoacetate, Ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetanilide, acetic acid amide, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, succinimide, maleic imide, imidazole, 2-methylimidazole, urea, thiourea, Ethyleneurea, formamide oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexa N'okishimu,
- Elastolon BN-69 (Daiichi Kogyo Seiyaku Co., Ltd.) or the like can be used as a water-dispersed commercial product.
- the crosslinking agent it is preferable to use a resin having a group capable of reacting with the crosslinkable functional group of the crosslinking agent as the resin contained in the primer.
- a resin having a group capable of reacting with the crosslinkable functional group of the crosslinking agent as the resin contained in the primer.
- the (block) isocyanate compound, the melamine compound, the oxazoline compound, and the carbodiimide compound as a crosslinking agent, and use a resin having a hydroxyl group or a carboxyl group as the resin.
- the cross-linking agent is preferably used in a range of 0.01% by mass to 60% by mass with respect to a total mass of 100 parts by mass of the resin contained in the primer, although it varies depending on the type and the like. It is more preferable to use in the range of 10% to 10% by weight, and it is preferable to use in the range of 0.1% to 5% by weight with excellent adhesion and electrical conductivity and excellent durability. This is preferable because a pattern can be formed.
- the cross-linking agent is preferably added in advance before coating or impregnating the primer of the present invention on the surface of the support.
- the additive various fillers such as inorganic particles can be used.
- the amount of the filler used in the primer of the present invention is preferably as small as possible, and more preferably 5% by mass or less based on the total amount of the primer of the present invention.
- the amount of the additive used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 0.01% by mass to 40% by mass with respect to the total nonvolatile content in the primer. .
- Examples of a method for applying the primer to a part or all of the surface of the support include a gravure method, a coating method, a screen method, a roller method, a rotary method, and a spray method.
- a method for removing the solvent contained in the coating layer after applying the primer by the above method for example, a method of drying by using a dryer and volatilizing the solvent is common.
- the drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.
- the amount of the primer applied onto the support is preferably adjusted so that the thickness of the primer layer (B) is within the above-described preferable range from the viewpoint of imparting excellent adhesion and conductivity.
- a fluid (c-1) Is applied to the surface of the primer layer (B) and dried.
- Examples of the fluid (c-1) that can be used for forming the conductive layer (C) or the first plating nucleus layer (C-1) constituting the conductive layer (C-1) include the conductive substance and, if necessary, a solvent, Those containing additives and generally usable for conductive inks and plating nucleating agents are mentioned.
- a transition metal or a compound thereof can be used as the conductive substance.
- an ionic transition metal for example, it is preferable to use a transition metal such as copper, silver, gold, nickel, palladium, platinum, cobalt, and to use copper, silver, gold, or the like. Further, it is more preferable because a conductive pattern having a low electric resistance and strong against corrosion can be formed, and it is more preferable to use silver.
- the surface is coated with the transition metal oxide or organic substance, including the metal particles made of the transition metal as described above as the conductive substance.
- the transition metal oxide or organic substance including the metal particles made of the transition metal as described above as the conductive substance.
- One or more types can be used.
- the oxide of the transition metal is usually in an inactive (insulating) state.
- the metal is exposed by, for example, treatment with a reducing agent such as dimethylaminoborane to impart activity (conductivity). Is possible.
- examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state, but by removing the organic substance using, for example, a laser or the like, it becomes possible to expose the metal and impart activity (conductivity).
- the conductive substance it is preferable to use particles having an average particle diameter of about 1 nm to 100 nm, and it is preferable to use those having an average particle diameter of 1 nm to 50 nm. Compared to the case of using a conductive substance having a particle size, it is more preferable because a fine conductive pattern can be formed and the resistance value after firing can be further reduced.
- the “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance with a good dispersion solvent. For this measurement, Nanotrac UPA-150 manufactured by Microtrac can be used.
- the conductive substance is preferably used in a range of 5% by mass to 90% by mass with respect to the total amount of the fluid (c-1), and is preferably used in a range of 10% by mass to 60% by mass. More preferably.
- the fluid (c-1) preferably contains a solvent from the viewpoint of improving ease of application and the like.
- a solvent an organic solvent or an aqueous medium can be used.
- the solvent examples include aqueous media such as distilled water, ion-exchanged water, pure water, and ultrapure water, and organic solvents such as alcohol, ether, ester, and ketone.
- Examples of the alcohol include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, and tetradecanol.
- ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol or the like can be used for the fluid (c-1) together with the conductive substance and the solvent.
- the fluid (c-1) has a viscosity of approximately 0.1 mPa ⁇ s to 500,000 mPa ⁇ s, preferably 0.5 mPa ⁇ s to 10,000 mPa ⁇ s, as measured with a B-type viscometer at approximately 25 ° C. It is preferable to use a liquid or viscous liquid.
- the fluid (c-1) is applied (printed) by a method such as the inkjet printing method, it is preferable to use a fluid having a viscosity in the range of about 5 mPa ⁇ s to 20 mPa ⁇ s.
- Examples of the method for applying the fluid (c-1) include an ink jet printing method, an electric field ink jet method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method, and a die coating method. , Slit coating method, roll coating method, dip coating method, dispenser method and the like.
- the conductive layer (C) or the thin conductive layer (C) of about 0.01 ⁇ m to 100 ⁇ m, which is required when the fluid (c-1) is used to achieve high density of electronic circuits or the like.
- the fluid (c-1) is preferably applied by an ink jet printing method or a reverse printing method.
- an ink jet printer As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100 and XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like. .
- conductive materials such as metals contained in the fluid (c-1) are joined to each other, and a conductive layer (C)
- a method of firing the coated material for the purpose of forming the first plating nucleus layer (C-1) constituting the first plating nucleus layer.
- the firing is preferably performed in the range of approximately 80 ° C. to 300 ° C. for approximately 2 minutes to 200 minutes.
- the firing may be performed in the air, but from the viewpoint of preventing oxidation of the metal, part or all of the firing step may be performed in a reducing atmosphere.
- the firing step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, photo sintering (light baking), light pulse irradiation, microwave, or the like.
- a part or all of the surface of the first plating core layer (C-1) that can be formed by applying and firing the fluid (c-1) may be subjected to an oxidation treatment.
- the surface of the first plating nucleus layer (C-1) may be subjected to plasma discharge treatment such as corona treatment.
- the plasma discharge treatment is not particularly limited.
- a normal pressure plasma discharge treatment method such as a corona discharge treatment method, or a vacuum plasma discharge treatment such as a glow discharge treatment method and an arc discharge treatment method performed under vacuum or reduced pressure. It is processing done by law.
- the atmospheric pressure plasma discharge treatment method is a plasma discharge treatment method in an atmosphere having an oxygen concentration of approximately 0.1% by mass to 25% by mass.
- a corona discharge treatment method in which the plasma discharge treatment is preferably performed in the range of 10 to 22% by weight, more preferably in the air (oxygen concentration is about 21% by weight). It is preferable when providing adhesiveness.
- the atmospheric pressure plasma discharge treatment method can be performed in an environment containing an inert gas together with the oxygen without giving excessive unevenness to the surface of the first plating nucleus layer (C-1). This is preferable because it can provide more excellent adhesion.
- Argon, nitrogen, or the like can be used as the inert gas.
- an atmospheric pressure plasma treatment apparatus (AP-T01) manufactured by Sekisui Chemical Co., Ltd. can be used for the treatment by the atmospheric pressure plasma discharge treatment method.
- the flow rate of gas such as air is preferably within a range of approximately 5 liters / minute to 50 liters / minute.
- the output is preferably in the range of about 50 W to 500 W.
- the time for the treatment with plasma is preferably in the range of approximately 1 second to 500 seconds.
- the corona discharge treatment method as the atmospheric pressure plasma discharge treatment method.
- a corona surface modification evaluation apparatus TEC-4AX manufactured by Kasuga Electric Co., Ltd. can be used.
- the output is preferably in the range of approximately 5 W to 300 W.
- the time for the corona discharge treatment is preferably in the range of approximately 0.5 seconds to 600 seconds.
- a part or all of the surface of the first plating core layer (C-1) is subjected to plating treatment, and the first plating layer (
- a conductive layer (C) composed of the first plating nucleus layer (C-1) and the first plating layer (C-2) is formed by laminating C-2).
- Examples of the plating method include a dry plating method such as a sputtering method and a vacuum deposition method, a wet plating method such as an electroless plating method and an electroplating method, or a method of combining two or more of these plating methods. .
- the first plating layer (C-2) formed by the above plating method has excellent adhesion to the surface of the first plating nucleus layer (C-1).
- the first plating layer (C-2) formed by electroplating on the surface of the first plating nucleus layer (C-1) can exhibit particularly excellent adhesion. it can.
- a sputtering method, a vacuum deposition method, or the like can be used as the dry plating process.
- an inert gas mainly argon
- negative ions are applied to the first plating layer (C-2) forming material to generate glow discharge
- the inert gas atoms are ionized, gas ions are struck violently at the surface of the plating layer (C-2) forming material at high speed, and the atoms and molecules constituting the plating layer (C-2) forming material are ejected vigorously.
- the plating layer (C-2) is formed by adhering to the surface of one plating nucleus layer (C-1).
- the plating layer (C-2) forming material includes chromium (Cr), copper (Cu), titanium (Ti), silver (Ag), platinum (Pt), gold (Au), nickel-chromium (Ni-Cr). ), SUS, copper-zinc (Cu—Zn), ITO, SiO 2, TiO 2, Nb 2 O 5, ZnO, or the like can be used.
- a magnetron sputtering apparatus or the like When performing the plating process by the sputtering method, for example, a magnetron sputtering apparatus or the like can be used.
- the vacuum deposition method includes heating the various metals and metal oxides that form the plating layer (C-2) in a vacuum to melt, evaporate, and sublimate the first plating core layer.
- the plating layer (C-2) is formed by attaching the metal atoms and molecules to the surface of (C-1).
- aluminum (Al), silver (Ag), gold (Au), titanium (Ti), nickel (Ni), copper (Cu) can be used as a material for forming the plating layer (C-2) usable in the vacuum deposition method.
- Cr Chromium
- Ti tin
- In indium
- the electroless plating process that can be used as the plating process is, for example, bringing an electroless plating solution into contact with a conductive material such as palladium or silver constituting the first plating core layer (C-1).
- This is a method for forming an electroless plating layer (coating) made of a metal film by depositing a metal such as copper contained in the electroless plating solution.
- a material containing a conductive material made of a metal such as copper, nickel, chromium, cobalt, tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent may be used. it can.
- reducing agent for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenols and the like can be used.
- monocarboxylic acids such as acetic acid and formic acid
- dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid
- malic acid lactic acid, glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid
- amino acids such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid
- It may contain complexing agents such as organic acids such as carboxylic acids, soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine.
- the temperature of the electroless plating solution when using the electroless plating solution is preferably in the range of about 20 ° C to 98 ° C.
- the electroplating method usable as the plating method is, for example, a conductive material constituting the first plating core layer (C-1), or an electroless plating layer formed by the electroless treatment.
- a metal containing metals such as copper, nickel, chromium, cobalt and tin, sulfides thereof, sulfuric acid and the like, and an aqueous medium
- a metal containing metals such as copper, nickel, chromium, cobalt and tin, sulfides thereof, sulfuric acid and the like, and an aqueous medium
- those containing copper sulfate, sulfuric acid and an aqueous medium can be used.
- the temperature of the electroplating solution when using the electroplating solution is preferably in the range of about 20 ° C to 98 ° C.
- the electroplating method it is preferable to form a layer made of copper by an electroplating method because workability is good without using a highly toxic substance.
- the step [3] that can be performed when the laminate is manufactured includes insulating a part or all of the surface of the first plating layer (C-2) formed in the step [2].
- the resin composition (d) for forming the layer (D) is applied, and the fluid (e-1) containing a conductive substance is applied to a part or all of the application surface, followed by drying.
- the insulating layer (D) is laminated on the surface of the first conductive layer (C), and the second plating nucleus layer (E-1) is laminated on the surface of the insulating layer (D).
- the same resin composition as that exemplified for the primer capable of forming the primer layer (B) can be used.
- resins that can be used in the resin composition (d) include urethane resin (d1), vinyl resin (d2), urethane-vinyl composite resin (d3), phenol resin, epoxy resin, melamine resin, urea resin, A saturated polyester resin, alkyd resin, polyimide resin, fluororesin, or the like can be used.
- the above-mentioned resins it is preferable to use at least one resin selected from the group consisting of urethane resin (d1), vinyl resin (d2), and urethane-vinyl composite resin (d3).
- the heat and moisture resistance can be further improved, and ion migration between the first conductive layer (C) and the second conductive layer (E) can be prevented.
- urethane resin (d1) the same ones exemplified as the urethane resin (b1) can be used.
- vinyl resin (d2) the thing similar to what was illustrated as said vinyl resin (b2) can be used.
- urethane-vinyl composite resin (d3) those exemplified as the urethane-vinyl composite resin (b3) can be used.
- the urethane resin (d3-1) and the vinyl resin (d3-2) that can be used for the production of the urethane-vinyl composite resin (d3) are also the urethane resin (b3-1) and the vinyl resin (b3), respectively. -2) can be used.
- Examples of the method for applying the resin composition (d) to at least part or all of the surface of the first conductive layer (C) include a gravure method, a coating method, a screen method, a roller method, a rotary method, and a spray. Examples of the method include a method.
- a method for removing the solvent contained in the coating layer after applying the resin composition (d) by the above method for example, a method of drying using a dryer and volatilizing the solvent is common.
- the drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.
- the said resin composition (d) may be formed by coating on the surface of the primer layer (B) as well as the first conductive layer (C).
- the coating amount of the resin composition (d) is an insulating layer in order to achieve both the insulation between the first conductive layer (C) and the second conductive layer (E) and the thinning of the laminate. It is preferable to adjust so that the thickness of (D) is within the above-described preferable range.
- the composition of the insulating layer (D) formed by the above method may be the same as or different from the composition of the primer layer (B), but is the same for further improving the adhesion.
- a composition is preferred.
- the primer layer (B) is a layer containing the urethane-vinyl composite resin (b3)
- the insulating layer (D) is a layer containing the urethane-vinyl composite resin (d3). It is preferable.
- a fluid containing a conductive substance As a method of laminating the second plating core layer (E-1) constituting the second conductive layer (E) on the surface of the insulating layer (D), a fluid containing a conductive substance ( There is a method in which e-1) is applied to the surface of the insulating layer (D) and dried.
- the same fluid (c-1) exemplified as that which can be used for forming the first conductive layer (C) can be used.
- the method for applying and drying the fluid (e-1) can also employ the same method as the method for applying and drying the fluid (c-1).
- the fluid (c-1) and the fluid (e-1) may have the same composition or different compositions.
- a coating apparatus adjusted to be suitable for the fluid can be used, and the production efficiency of the laminate of the present invention It is preferable to use the same composition.
- the step [4] that can be performed when the laminate is manufactured includes the step of plating a part or all of the surface of the second plating nucleus layer (E-1), thereby This is a step of forming a second conductive layer (E) in which the second plating layer (E-2) is laminated on the surface of the plating nucleus layer (E-1).
- the same method as the plating method exemplified as the method for laminating the first plating layer (C-2) is adopted. can do.
- the laminate obtained by the above method can be used as a conductive pattern.
- formation of electronic circuits using silver ink or the like formation of organic solar cells or electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, layers constituting peripheral RFID, peripheral wiring, electromagnetic waves of plasma display It can be suitably used for forming a conductive pattern in manufacturing a shield wiring or the like, more specifically, a circuit board.
- a conductive pattern having a desired pattern can be manufactured by applying the body and baking.
- a laminate such as a conductive pattern obtained by the above method can maintain good current conduction without causing separation between layers, and is thin, so that an electronic circuit or integrated circuit using silver ink or the like is used.
- the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time, for example, a copper-clad laminate is generally used.
- CCL Copper Clad Laminate
- FPC flexible printed circuit board
- TAB automatic tape bonding
- COF chip-on-film
- PWB printed wiring board
- Synthesis Example 1 Production of Aqueous Dispersion of Urethane Resin (Y-1) 100 parts by mass of polyester polyol (1,4-cyclohexane) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer Polyester polyol obtained by reacting dimethanol, neopentyl glycol and adipic acid, hydroxyl group equivalent of 1000 g / equivalent), 17.4 parts of 2,2-dimethylolpropionic acid and 1,4-cyclohexanedimethanol.
- aqueous dispersion of urethane resin (Y-1) was obtained.
- the urethane resin obtained here had an acid value of 30 and a weight average molecular weight of 55,000.
- the reaction vessel contains 46 parts by weight of methyl methacrylate, 45 parts by weight of n-butyl acrylate, 2 parts by weight of methacrylic acid, 5 parts by weight of 2-hydroxyethyl methacrylate and 2 parts by weight of N-methylolacrylamide.
- Part of monomer pre-emulsion obtained by mixing vinyl monomer mixture 4 parts by weight of Aqualon KH-1025 (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 25% by weight) and 15 parts by weight of deionized water (5 parts by mass) was added, and then 0.1 part by mass of potassium persulfate was added, and polymerization was performed for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.
- the remaining monomer pre-emulsion 114 parts by mass
- 30 parts by mass of an aqueous solution of potassium persulfate active ingredient 1.0% by mass
- the temperature in the reaction vessel was cooled to 40 ° C., and aqueous ammonia (active ingredient 10% by mass) was used so that the pH of the aqueous dispersion in the reaction vessel was 8.5.
- an aqueous solution of trimethoxymethylol melamine (DIC Co., Ltd., Becamine M-3) is used as a crosslinking agent with respect to the nonvolatile content of the aqueous dispersion.
- aqueous dispersion of a vinyl polymer (Y-2) having a carboxyl group and an N-methylolacrylamide group is used as a crosslinking agent with respect to the nonvolatile content of the aqueous dispersion.
- urethane-acrylic composite resin constituted by the shell layer made of the urethane resin and the core layer made of the vinyl polymer having Nn-butoxymethyl group by filtering with a cloth Got the body.
- Example 1 Polyurethane film (Toray DuPont Co., Ltd.) treated with corona treatment so that the water dispersion of urethane-acrylic composite resin (Y-3) obtained in Synthesis Example 3 is used as a primer and the primer layer thickness is 1 ⁇ m.
- the support made of Kapton 150EN-C made by company, thickness 37.5 ⁇ m
- each was coated using a spin coater and dried at 80 ° C. for 3 minutes using a hot air dryer.
- a laminate including a primer layer not forming a crosslinked structure was obtained.
- a fluid 1 to be described later is used with an ink jet printer (ink tester EB100 manufactured by Konica Minolta IJ Co., Ltd., evaluation printer head KM512L, discharge amount 42 pl), a line width of 100 ⁇ m, a film A line having a thickness of 0.5 ⁇ m is printed in an inverted U-shape indicated by reference numeral 2 in FIG. 1, and a 2 mm square tab to which a BSP probe can be connected is installed at the end, and then at 150 ° C.
- an ink jet printer ink tester EB100 manufactured by Konica Minolta IJ Co., Ltd., evaluation printer head KM512L, discharge amount 42 pl
- a line width of 100 ⁇ m a film A line having a thickness of 0.5 ⁇ m is printed in an inverted U-shape indicated by reference numeral 2 in FIG. 1, and a 2 mm square tab to which a BSP probe can be connected is installed at the end, and then at 150 ° C.
- the surface of the first plating nucleus layer is set as a cathode, phosphorous copper is set as an anode, and electroplating is performed for 15 minutes at an electric current density of 2 A / dm 2 using an electroplating solution containing copper sulfate.
- a first copper plating layer having a thickness of 8 ⁇ m was laminated on the surface of the first plating nucleus layer to form a first conductive layer, thereby obtaining a laminate (I).
- an aqueous dispersion of urethane-acrylic composite resin (Y-4) obtained in Synthesis Example 4 is used as a resin composition that can form an insulating layer, and this is used as the first composition constituting the laminate (I).
- the surface of the conductive layer is coated with a spin coater and dried at 80 ° C. for 3 minutes using a hot air dryer, thereby providing an insulating layer having no cross-linked structure on the surface of the first conductive layer.
- a laminate (II) was obtained.
- a fluid 1 to be described later is used by using an ink jet printer (an ink jet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., an evaluation printer head KM 512L, a discharge amount 42 pl).
- an ink jet printer an ink jet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., an evaluation printer head KM 512L, a discharge amount 42 pl.
- a line having a line width of 100 ⁇ m and a film thickness of 0.5 ⁇ m is printed in a U-shape indicated by reference numeral 2 in FIG.
- the surface of the second plating nucleus layer is set as a cathode, phosphorous copper is set as an anode, and electroplating is performed at an electric current density of 2 A / dm2 for 15 minutes using an electroplating solution containing copper sulfate.
- a second conductive layer in which a second copper plating layer having a thickness of 8 ⁇ m was laminated was formed on the surface of the second plating nucleus layer.
- a laminate (IV) was obtained in which a layer comprising a support, a primer layer having a crosslinked structure, a first conductive layer, an insulating layer having a crosslinked structure, and a second conductive layer were laminated.
- a cross-sectional view taken along one-dot chain line 23 of the laminate (IV) is shown in FIG.
- the laminate (IV) was formed by laminating the first conductive layer and the second conductive layer via an insulating layer in the cross-section.
- the product is then washed with 100 ml of 5% by weight aqueous hydrochloric acid, then with 100 ml of saturated aqueous sodium bicarbonate solution and then with 100 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered, After concentration, washing with hexane several times, filtration and drying under reduced pressure at 80 ° C., methoxypolyethylene glycol having p-toluenesulfonyloxy group was obtained.
- a mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the silver dispersion and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes.
- a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes.
- 20 g of water was further added to the precipitate, followed by stirring for 2 minutes, and the organic solvent was removed under reduced pressure.
- the fluid 1 which can be used for the conductive ink for inkjet printing was prepared by mixing 25.9g of silver containing powders obtained above with 45g of ethylene glycol, and 55g of ion-exchange water, and stirring for 3 hours ( Silver content 20% by mass, polyethyleneimine 1% by mass, viscosity 10 mPa ⁇ s).
- Example 2 As a primer for forming the primer layer, water of the urethane-acrylic composite resin (Y-4) obtained in Synthesis Example 4 was used instead of the water dispersion of the urethane-acrylic composite resin (Y-3) obtained in Synthesis Example 3. Except for the use of the dispersion, in the same manner as in Example 1, the support layer, the primer layer formed with the crosslinked structure, the first conductive layer, the insulating layer formed with the crosslinked structure, and the second conductive A laminate in which the layers were laminated was obtained.
- Example 3 Instead of the urethane-acrylic composite resin (Y-4) aqueous dispersion obtained in Synthesis Example 4 as the resin composition for forming the insulating layer, the urethane resin (Y-1) obtained in Synthesis Example 1 was dispersed in water. Except for using the body, in the same manner as in Example 2, the support layer, the primer layer formed with the crosslinked structure, the first conductive layer, the insulating layer formed with the crosslinked structure, and the second conductive layer To obtain a laminated body.
- Example 4 In place of the urethane-acrylic composite resin (Y-3) aqueous dispersion, the vinyl polymer (Y-2) aqueous dispersion obtained in Synthesis Example 2 was used as a primer for forming the primer layer, and As a resin composition for forming an insulating layer, the urethane-acrylic composite resin (Y-3) obtained in Synthesis Example 3 was used instead of the aqueous dispersion of the urethane-acrylic composite resin (Y-4) obtained in Synthesis Example 4.
- Example 2 In the same manner as in Example 1, except that the aqueous dispersion is used, a layer comprising the support, a primer layer having a crosslinked structure, a first conductive layer, an insulating layer having a crosslinked structure, and a second layer are formed. A laminate in which the conductive layer was laminated was obtained.
- Comparative Example 1 An attempt was made to produce a laminate in the same manner as in Example 4 except that the primer layer was not provided, but the conduction of the first conductive layer was insufficient. Further, since the conduction of the first conductive layer was insufficient, the first plating layer could not be formed on the surface of the first plating core layer.
- Example 2 Comparative Example 2 except that a film for coverlay (CISA 2535 (DB) manufactured by Nikkan Kogyo Co., Ltd., polyimide film 25 ⁇ m, thickness of adhesive layer 35 ⁇ m) made in advance as an insulating layer is used.
- a film for coverlay CISA 2535 (DB) manufactured by Nikkan Kogyo Co., Ltd., polyimide film 25 ⁇ m, thickness of adhesive layer 35 ⁇ m
- the production of the laminate was attempted in the same manner as described, but the second plating layer could not be formed because the conduction of the second conductive layer was insufficient, and a laminate was produced. I could't.
- the thickness of the laminate was measured with a laser microscope (VK-9700 manufactured by Keyence Corporation) at the section where the layer consisting of the support, the primer layer, the first conductive layer, the insulating layer, and the second conductive layer overlapped. did. If the thickness is 100 ⁇ m or less, it is determined that the total thickness of the primer layer, the first conductive layer, the insulating layer, and the second conductive layer is also 100 ⁇ m or less. Judged to be advantageous in reducing the thickness.
- the adhesive surface of the peeled cellophane pressure-sensitive adhesive tape is “A” in which the components constituting the conductive layer, the insulating layer and the primer layer were not attached at all, and the area where the second conductive layer and the pressure-sensitive adhesive tape were in contact with each other
- the content of the second conductive layer in the range of less than 3% peeled off and adhered to the adhesive surface of the adhesive tape was “B”, and the area where the second conductive layer and the adhesive tape contacted was 3 % And less than 30% of the second conductive layer peeled off and adhered to the adhesive surface of the adhesive tape was "C", 30% with respect to the area where the second conductive layer and the adhesive tape were in contact
- the second conductive layer in the above range peeled off and adhered to the adhesive tape was evaluated as “D”.
- the adhesion was evaluated by the same method as described in [Adhesion evaluation method] except that the laminate after standing was used.
- the insulating property was evaluated by the same method as described in [Conductivity evaluation method (first conductive layer)] except that the laminate after standing was used.
- the insulating property was evaluated by the same method as described in [Conductivity evaluation method (second conductive layer)] except that the laminate after standing was used.
- the insulating property was evaluated by the same method as that described in [Method for evaluating insulating property of insulating layer] except that the laminate after being left standing was used.
- “Kapton150EN-C” in Table 1 represents a polyimide film (thickness: 37.5 ⁇ m) manufactured by Toray DuPont Co., Ltd.
- “CISA 2535 (DB)” represents a Nikkan Kogyo Co., Ltd. coverlay film (polyimide film 25 ⁇ m, adhesive layer thickness 35 ⁇ m).
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Abstract
Description
前記ポリエーテルポリオールとしては、例えば活性水素原子を2個以上有する化合物の1種または2種以上を開始剤として、アルキレンオキサイドを付加重合させたものを使用することができる。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール100質量部(1,4-シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール、水酸基当量1000g/当量)と2,2―ジメチロールプロピオン酸17.4質量部と1,4-シクロヘキサンジメタノール21.7質量部とジシクロヘキシルメタンジイソシアネート106.2質量部とを、メチルエチルケトン178質量部中で混合し反応させることによって、末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
撹拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に、脱イオン水115質量部、ラテムルE-118B(花王株式会社製、有効成分25質量%)4質量部を入れ、窒素を吹き込みながら75℃まで昇温した。
攪拌機、還流冷却管、窒素導入管、温度計、単量体混合物滴下用滴下漏斗、重合触媒滴下用滴下漏斗を備えた反応容器に脱イオン水280質量部、合成例1で得たウレタン樹脂(Y-1)の水分散体333質量部を入れ、窒素を吹き込みながら80℃まで昇温した。
攪拌機、還流冷却管、窒素導入管、温度計、単量体混合物滴下用滴下漏斗、重合触媒滴下用滴下漏斗を備えた反応容器に脱イオン水280質量部、合成例1で得たウレタン樹脂(Y-1)の水分散体333質量部を入れ、窒素を吹き込みながら80℃まで昇温した。
合成例3で得たウレタン-アクリル複合樹脂(Y-3)の水分散体をプライマーとして使用し、それをプライマー層の膜厚が1μmになるように、コロナ処理したポリイミドフィルム(東レ・デュポン株式会社製Kapton150EN-C,厚さ37.5μm)からなる支持体の表面に、スピンコーターを用いてそれぞれ塗工し、熱風乾燥機を用いて80℃で3分間乾燥することによって、前記支持体上に、架橋構造を形成していないプライマー層を備えた積層体を得た。
窒素雰囲気下、メトキシポリエチレングリコール(数平均分子量2,000)20g、ピリジン8.0g及びクロロホルム20mlを含む混合物に、p-トルエンスルホン酸クロライド9.6gを含むクロロホルム(30ml)溶液を、氷冷撹拌しながら30分間滴下した後、浴槽温度40℃で4時間攪拌し、クロロホルム50mlを混合した。
プライマー層を形成するプライマーとして、合成例3で得たウレタン-アクリル複合樹脂(Y-3)の水分散体の代わりに、合成例4で得たウレタン-アクリル複合樹脂(Y-4)の水分散体を使用すること以外は、実施例1と同様の方法で、支持体からなる層と架橋構造を形成したプライマー層と第一の導電層と架橋構造を形成した絶縁層と第二の導電層とが積層した積層体を得た。
絶縁層を形成する樹脂組成物として、合成例4で得たウレタン-アクリル複合樹脂(Y-4)の水分散体の代わりに、合成例1で得たウレタン樹脂(Y-1)の水分散体を使用すること以外は、実施例2と同様の方法で、支持体からなる層と架橋構造を形成したプライマー層と第一の導電層と架橋構造を形成した絶縁層と第二の導電層とが積層した積層体を得た。
プライマー層を形成するプライマーとして、ウレタン-アクリル複合樹脂(Y-3)の水分散体の代わりに、合成例2で得たビニル重合体(Y-2)の水分散体を使用し、かつ、絶縁層を形成する樹脂組成物として、合成例4で得たウレタン-アクリル複合樹脂(Y-4)の水分散体の代わりに、合成例3で得たウレタン-アクリル複合樹脂(Y-3)の水分散体を使用すること以外は、実施例1と同様の方法で、支持体からなる層と架橋構造を形成したプライマー層と第一の導電層と架橋構造を形成した絶縁層と第二の導電層とが積層した積層体を得た。
プライマー層を設けないこと以外は、実施例4と同様の方法で積層体を製造することを試みたが、第一の導電層の導通が不十分であった。また、前記第一の導電層の導通が不十分であったため、前記第一のめっき核層の表面に第一のめっき層を形成することができなかった。
絶縁層として、予めフィルム化されている、カバーレイ用フィルム(ニッカン工業株式会社製 CISA 2535(DB)、ポリイミドフィルム25μm、接着剤層の厚さ35μm)をそれぞれ使用すること以外は、実施例1記載の方法と同様の方法で、積層体の製造を試みたが、第二の導電層の導通が不十分であるため、第二のめっき層を形成することができず、積層体を作製することができなかった。
積層体の厚さは、支持体からなる層とプライマー層と第一の導電層と絶縁層と第二の導電層とが重なった部分の断面をレーザー顕微鏡(キーエンス社製VK-9700)で測定した。前記厚さが100μm以下であれば、プライマー層と第一の導電層と絶縁層と第二の導電層との厚さの合計も100μm以下であると判断し、導電性パターン等の積層体の薄型化を図るうえで有利であると判断した。
前記積層体を構成する第二の導電層の表面にセロハン粘着テープ(ニチバン(株)製,CT405AP-24,24mm)を指で圧着した後、前記セロハン粘着テープを、前記積層体の表面に対して90度方向に剥離した。剥離したセロハン粘着テープの粘着面を目視で観察し、その付着物の有無に基づいて前記密着性を評価した。
実施例及び比較例で得た積層体を、温度85℃及び相対湿度85%の環境下に1000時間放置した。
ロレスタGP MCP T610型(三菱化学アナリティック社製の抵抗率計)を用い、前記積層体を構成する第一の導電層に接続した2つのタブにBSPプローブを接触させ、導通があるかを確認した。導通があったものを「○」、導通がなかったもの、または、導通せずめっき層を形成できなかったものを「×」と評価した。
実施例及び比較例で得た積層体を、温度85℃及び相対湿度85%の環境下に1000時間放置した。
ロレスタGP MCP T610型(三菱化学アナリティック社製の抵抗率計)を用い、前記積層体を構成するの第二の導電層に接続した2つのタブにBSPプローブを接触させ、導通があるかを確認した。導通があったものを「○」、導通がなかったもの、または、導通せずめっき層を形成できなかったものを「×」と評価した。
実施例及び比較例で得た積層体を、温度85℃及び相対湿度85%の環境下に1000時間放置した。
ロレスタGP MCP T610型(三菱化学アナリティック社製の抵抗率計)を用い、第一の導電層に接続した1つのタブにBSPプローブの一方を接触させ、他方のBSPプローブを第二の導電層に接続した1つのタブに接触させ、導通の有無を確認した。導通がなく、第一の導電層と第二の導電層との絶縁性が維持できていたものを「○」、導通があったものを「×」と評価した。
実施例及び比較例で得た積層体を、温度85℃及び相対湿度85%の環境下に1000時間放置した。
2・・・・・第一の導電層(C)
3・・・・・タブ
4・・・・・絶縁層(D)の上面
5・・・・・支持体からなる層(A)
6・・・・・プライマー層(B)
7・・・・・第一の導電層(C)
8・・・・・絶縁層(D)
9・・・・・第二の導電層(E)
20・・・・・積層体(I)の上面図
21・・・・・積層体(IV)の上面図
22・・・・・積層体(IV)の一点破線23における断面図
Claims (13)
- 少なくとも、支持体からなる層(A)と、プライマー層(B)と、第一の導電層(C)と、絶縁層(D)と、第二の導電層(E)とが積層した積層体であって、前記絶縁層(D)が、少なくとも前記第一の導電層(C)の表面の一部または全部に、樹脂組成物(d)を塗布し乾燥することによって形成された層であり、前記第二の導電層(E)が、前記絶縁層(D)の表面の一部または全部に、導電性物質を含有する流動体(e-1)を塗布することによって形成された第二のめっき核層(E-1)と、前記第二のめっき核層(E-1)の表面に設けられた第二のめっき層(E-2)とによって構成される層であることを特徴とする積層体。
- 前記絶縁層(D)が、ウレタン樹脂(d1)、ビニル樹脂(d2)、及び、ウレタン-ビニル複合樹脂(d3)からなる群より選ばれる1種以上の樹脂を含有するものである請求項1に記載の積層体。
- 前記ウレタン-ビニル複合樹脂(d3)が、ウレタン樹脂(d3-1)であるシェル層と、前記ビニル樹脂(d3-2)であるコア層とによって構成される複合樹脂である請求項2に記載の積層体。
- 前記ウレタン樹脂(d3-1)が、2,000mmol/kg~5,500mmol/kgの脂肪族環式構造を有するものである請求項3に記載の積層体。
- 前記プライマー層(B)が、ウレタン樹脂(b1)、ビニル樹脂(b2)、及び、ウレタン-ビニル複合樹脂(b3)からなる群より選ばれる1種以上の樹脂を含有するものである請求項1に記載の積層体。
- 前記ウレタン-ビニル複合樹脂(b3)が、ウレタン樹脂(b3-1)であるシェル層と、前記ビニル樹脂(b3-2)であるコア層とによって構成される複合樹脂である請求項5に記載の積層体。
- 前記ウレタン樹脂(b3-1)が、2,000mmol/kg~5,500mmol/kgの脂肪族環式構造を有するものである請求項6に記載の積層体。
- 前記プライマー層(B)及び絶縁層(E)を形成する樹脂が、架橋性官能基を有するものである請求項1に記載の積層体。
- 前記架橋性官能基が、メチロールアミド基及びアルコキシメチルアミド基からなる群より選ばれる1種以上の熱架橋性官能基である請求項8に記載の積層体。
- 前記第一の導電層(C)が、第一のめっき核層(C-1)と第一のめっき層(C-2)とによって構成されるものである請求項1に記載の積層体。
- 請求項1~10のいずれか1項に記載の積層体からなる導電性パターン。
- 請求項11に記載の導電性パターンを有する電気回路。
- 支持体の表面の一部または全部に、プライマー層(B)を形成するプライマーを塗布し、その塗布面の一部または全部に、導電性物質を含有する流動体(c-1)を塗布することによって、支持体からなる層(A)とプライマー層(B)と第一のめっき核層(C-1)とを積層する工程[1]、前記第一のめっき核層(C-1)の表面の一部または全部をめっき処理することによって、前記第一のめっき核層(C-1)の表面に第一のめっき層(C-2)が積層した第一の導電層(C)を形成する工程[2]、少なくとも前記第一のめっき層(C-2)の表面の一部または全部に、絶縁層(D)を形成する樹脂組成物(d)を塗布し、その塗布面の一部または全部に、導電性物質を含有する流動体(e-1)を塗布することによって、前記第一の導電層(C)の表面に前記絶縁層(D)を積層し、前記絶縁層(D)の表面に第二のめっき核層(E-1)を積層する工程[3]、及び、前記第二のめっき核層(E-1)の表面の一部または全部をめっき処理することによって、前記第二のめっき核層(E-1)の表面に第二のめっき層(e-2)が積層した第二の導電層(E)を形成する工程[4]を経ることを特徴とする積層体の製造方法。
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CN201480005817.6A CN104936774B (zh) | 2013-01-23 | 2014-01-21 | 层叠体、导电性图案、电路及层叠体的制造方法 |
US14/762,783 US9374895B2 (en) | 2013-01-23 | 2014-01-21 | Laminate, conductive pattern, electrical circuit, and method for producing laminate |
DE112014000530.4T DE112014000530T5 (de) | 2013-01-23 | 2014-01-21 | Laminat, Leiterbild, Stromkreis und Verfahren zur Herstellung des Laminats |
JP2014556850A JP5696825B2 (ja) | 2013-01-23 | 2014-01-21 | 積層体、導電性パターン、電気回路及び積層体の製造方法 |
KR1020157012419A KR101562494B1 (ko) | 2013-01-23 | 2014-01-21 | 적층체, 도전성 패턴, 전기 회로 및 적층체의 제조 방법 |
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PCT/JP2014/051077 WO2014115710A1 (ja) | 2013-01-23 | 2014-01-21 | 積層体、導電性パターン、電気回路及び積層体の製造方法 |
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US (1) | US9374895B2 (ja) |
JP (1) | JP5696825B2 (ja) |
KR (1) | KR101562494B1 (ja) |
CN (1) | CN104936774B (ja) |
DE (1) | DE112014000530T5 (ja) |
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JP2016120604A (ja) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | 積層体、導電性パターン及び電子回路 |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE102013104577B3 (de) * | 2013-05-03 | 2014-07-24 | Heraeus Noblelight Gmbh | Vorrichtung zum Trocknen und Sintern metallhaltiger Tinte auf einem Substrat |
US9613915B2 (en) | 2014-12-02 | 2017-04-04 | International Business Machines Corporation | Reduced-warpage laminate structure |
JP6961942B2 (ja) * | 2015-04-16 | 2021-11-05 | 東洋紡株式会社 | フレキシブル基板用透明フィルム及びフレキシブル回路基板 |
US10057981B2 (en) * | 2015-06-10 | 2018-08-21 | Industry Foundation Of Chonnam National University | Stretchable circuit board and method of manufacturing the same |
KR102320490B1 (ko) * | 2016-06-03 | 2021-11-02 | 디아이씨 가부시끼가이샤 | 치환 또는 비치환 알릴기 함유 말레이미드 화합물 및 그 제조 방법, 그리고 상기 화합물을 사용한 조성물 및 경화물 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6139966B2 (ja) * | 1978-07-24 | 1986-09-06 | Mitsui Toatsu Chemicals | |
JPH08139458A (ja) * | 1994-11-10 | 1996-05-31 | Hitachi Chem Co Ltd | 多層配線板の製造方法 |
JP2004259899A (ja) * | 2003-02-25 | 2004-09-16 | Matsushita Electric Works Ltd | プリント配線板用樹脂組成物、プリント配線板及び多層プリント配線板 |
JP2004288818A (ja) * | 2003-03-20 | 2004-10-14 | Seiko Epson Corp | 配線基板およびその製造方法、ならびに電子機器 |
WO2008018589A1 (fr) * | 2006-08-11 | 2008-02-14 | National Starch And Chemical Investment Holding Corporation | Résine réactive hydrocompatible et son procédé de production |
JP2012246533A (ja) * | 2011-05-27 | 2012-12-13 | Achilles Corp | めっき物 |
WO2013147050A1 (ja) * | 2012-03-30 | 2013-10-03 | Dic株式会社 | 積層体、導電性パターン、電気回路及び積層体の製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5985220A (ja) * | 1983-09-09 | 1984-05-17 | ヤンマー農機株式会社 | コンバインの扱深さ調節装置 |
JPH06107834A (ja) * | 1992-09-28 | 1994-04-19 | Dainippon Printing Co Ltd | 易接着コーティング芳香族ポリアミド樹脂基材及びその製造方法 |
US5382447A (en) * | 1993-12-02 | 1995-01-17 | International Business Machines Corporation | Process for fabricating improved multilayer interconnect systems |
JP2005286158A (ja) | 2004-03-30 | 2005-10-13 | Seiko Epson Corp | パターン形成方法、電子デバイス及びその製造方法並びに電子機器 |
US8404388B2 (en) * | 2005-08-09 | 2013-03-26 | Polyplus Battery Company | Compliant seal structures for protected active metal anodes |
JP5137575B2 (ja) * | 2005-08-19 | 2013-02-06 | 旭化成イーマテリアルズ株式会社 | 積層体及びその製造方法 |
CA2625777A1 (en) * | 2005-10-13 | 2007-04-26 | Velocys, Inc. | Electroless plating in microchannels |
US8084684B2 (en) * | 2006-10-09 | 2011-12-27 | Solexel, Inc. | Three-dimensional thin-film solar cells |
JP2009049124A (ja) | 2007-08-17 | 2009-03-05 | Konica Minolta Holdings Inc | 導電性パターン及びその作製方法 |
JP4932758B2 (ja) * | 2008-02-06 | 2012-05-16 | 富士フイルム株式会社 | 発光デバイス及びその製造方法 |
KR101397771B1 (ko) * | 2008-12-26 | 2014-05-20 | 히타치가세이가부시끼가이샤 | 포지티브형 감광성 수지 조성물, 레지스트 패턴의 제조 방법, 반도체 장치 및 전자 디바이스 |
EP2475234A3 (en) * | 2009-04-24 | 2012-09-19 | Sumitomo Electric Industries, Ltd. | Substrate for printed wiring board, printed wiring board, and methods for producing same |
JP2012218318A (ja) | 2011-04-11 | 2012-11-12 | Dic Corp | 導電性インク受容層形成用樹脂組成物、導電性インク受容基材及び回路形成用基板ならびに印刷物、導電性パターン及び回路基板 |
KR101905893B1 (ko) * | 2012-06-13 | 2018-10-08 | 에스케이하이닉스 주식회사 | 복수의 유전층을 포함하는 임베디드 패키지 및 제조 방법 |
-
2014
- 2014-01-21 JP JP2014556850A patent/JP5696825B2/ja active Active
- 2014-01-21 US US14/762,783 patent/US9374895B2/en active Active
- 2014-01-21 KR KR1020157012419A patent/KR101562494B1/ko active IP Right Grant
- 2014-01-21 DE DE112014000530.4T patent/DE112014000530T5/de not_active Ceased
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6139966B2 (ja) * | 1978-07-24 | 1986-09-06 | Mitsui Toatsu Chemicals | |
JPH08139458A (ja) * | 1994-11-10 | 1996-05-31 | Hitachi Chem Co Ltd | 多層配線板の製造方法 |
JP2004259899A (ja) * | 2003-02-25 | 2004-09-16 | Matsushita Electric Works Ltd | プリント配線板用樹脂組成物、プリント配線板及び多層プリント配線板 |
JP2004288818A (ja) * | 2003-03-20 | 2004-10-14 | Seiko Epson Corp | 配線基板およびその製造方法、ならびに電子機器 |
WO2008018589A1 (fr) * | 2006-08-11 | 2008-02-14 | National Starch And Chemical Investment Holding Corporation | Résine réactive hydrocompatible et son procédé de production |
JP2012246533A (ja) * | 2011-05-27 | 2012-12-13 | Achilles Corp | めっき物 |
WO2013147050A1 (ja) * | 2012-03-30 | 2013-10-03 | Dic株式会社 | 積層体、導電性パターン、電気回路及び積層体の製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016120604A (ja) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | 積層体、導電性パターン及び電子回路 |
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TW201438916A (zh) | 2014-10-16 |
CN104936774B (zh) | 2017-11-14 |
JP5696825B2 (ja) | 2015-04-08 |
KR20150063160A (ko) | 2015-06-08 |
US9374895B2 (en) | 2016-06-21 |
DE112014000530T5 (de) | 2015-10-22 |
CN104936774A (zh) | 2015-09-23 |
US20150359095A1 (en) | 2015-12-10 |
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TWI513588B (zh) | 2015-12-21 |
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