WO2014142005A1 - 積層体、導電性パターン及び積層体の製造方法 - Google Patents
積層体、導電性パターン及び積層体の製造方法 Download PDFInfo
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- WO2014142005A1 WO2014142005A1 PCT/JP2014/055830 JP2014055830W WO2014142005A1 WO 2014142005 A1 WO2014142005 A1 WO 2014142005A1 JP 2014055830 W JP2014055830 W JP 2014055830W WO 2014142005 A1 WO2014142005 A1 WO 2014142005A1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/067—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components
- G06K19/07—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components with integrated circuit chips
- G06K19/077—Constructional details, e.g. mounting of circuits in the carrier
- G06K19/0772—Physical layout of the record carrier
- G06K19/07722—Physical layout of the record carrier the record carrier being multilayered, e.g. laminated sheets
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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
- H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
- H05K1/0298—Multilayer circuits
-
- 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
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
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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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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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
-
- 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
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 a conductive ink containing a conductive material such as silver or a plating nucleating agent on the surface of a support and baking it. 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 support surface is not sufficient in terms of durability against acid or alkaline chemicals used in the plating process, for example. In some cases, the plating treatment could not be performed.
- 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 laminated body provided.
- the present inventors have found a laminate having excellent adhesion and heat-and-moisture resistance.
- the present invention includes at least a layer (A) comprising a support, a first primer layer (B-1), a first conductive layer (C), an insulating layer (D), and a second layer.
- the present invention relates to a laminate and a conductive pattern characterized by having a structure in which a primer layer (B-2) and a second conductive layer (E) are laminated.
- 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.
- a top view of a conductive pattern composed of the first conductive layer (C) formed on the surface of the first primer layer (B-1) is shown.
- the top view of the electroconductive pattern which consists of a 2nd conductive layer (E) formed in the surface of a 2nd primer layer (B-2) is shown. Sectional drawing of a laminated body is shown.
- the laminate of the present invention comprises at least a support layer (A), a first primer layer (B-1), a first conductive layer (C), an insulating layer (D), and a second layer.
- the primer layer (B-2) and the second conductive layer (E) have a laminated structure.
- the laminate of the present invention may include layers other than the layers (A) to (E).
- the laminate of the present invention has the first primer layer (B-1) between the layer (A) comprising the support and the first conductive layer (C).
- the first primer layer (B-1) is a layer that receives a fluid (c-1) containing a conductive substance that can be used to form the first conductive layer (C).
- the primer layer (B-1) quickly absorbs the solvent contained in the fluid (c-1) when the fluid (c-1) comes into contact with the primer layer (B-1) It is carried on the surface of (B-1). Thereby, the adhesion and wet heat resistance between the layer (A) made of the support and the primer layer (B-1) and the first conductive layer (C) made of a conductive material are remarkably improved. Can do.
- the primer layer (B-1) may be provided on a part or all of the surface of the layer (A) comprising the support, or may be provided on one side or both sides thereof.
- the laminate has a first primer layer (B-1) on the entire surface of the layer (A) comprising the support, and only a necessary portion of the primer layer (B-1) is present.
- a laminate of the conductive layers (C) can also be used. Further, it is also possible to use a laminate in which the primer layer (B-1) is provided only on the portion where the conductive layer (C) is provided on the surface of the layer (A) comprising the support.
- the thickness of the primer layer (B-1) is preferably in the range of 0.01 ⁇ m to 30 ⁇ m, 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 containing at least one of copper, nickel, chromium, cobalt, tin, gold, etc. More preferably, the plating layer made of nickel is laminated to form the first plating layer (C-2), and the plating layer made of nickel is laminated on the plating layer made of copper, and further the plating layer made of gold
- the first plating layer (C-2) is laminated to form a conductive pattern such as a highly reliable wiring pattern that can maintain good current conduction without causing disconnection or the like over a long period of time. Is more preferable in manufacturing.
- the conductive layer (C) may be provided on part or all of the surface of the primer layer (B-1). Specifically, examples of the conductive layer (C) provided only on a necessary portion of the surface of the primer layer (B-1) include a linear layer formed by drawing a line. It is done. 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 ** width (line width) ** 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.
- an insulating film or insulating sheet previously formed into a film or a sheet can be used.
- an insulating film or an insulating film formed using a resin composition containing various resins or the like. Sheets can be used.
- the insulating layer (D) is formed by applying a resin composition (d) on at least the surface of the first conductive layer (C) instead of a pre-formed film or sheet and drying it. It may be a 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 first primer layer. When laminated on a part of the surface of (B-1), the insulating layer (D) may be laminated directly on the surface of the first primer layer (B-1).
- 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. Further, when a film or sheet formed in advance is used as the insulating layer (D), the thickness is preferably in the range of 5 to 40 ⁇ m from the viewpoint of ease of handling. Moreover, as the film or sheet, a film provided with a pressure-sensitive adhesive layer or an adhesive layer in advance can be used as the film or sheet. The thickness does not include the pressure-sensitive adhesive layer and the adhesive layer and represents the thickness of the film or sheet itself.
- the laminate of the present invention has a second primer layer (B-2).
- the second primer layer (B-2) is a layer that receives the fluid (e-1) containing a conductive substance that can be used to form the second conductive layer (E).
- the primer layer (B-2) rapidly absorbs the solvent contained in the fluid (e-1) when the fluid (e-1) comes into contact with the primer, and the conductive material is absorbed into the primer layer. It is carried on the surface of (B-2). Thereby, the adhesion and wet heat resistance between the insulating layer (D), the primer layer (B-2), and the second conductive layer (E) made of a conductive material can be remarkably improved.
- the primer layer (B-2) may be provided on a part or all of the surface of the insulating layer (D), or may be provided on one side or both sides thereof.
- the laminate has a second primer layer (B-2) on the entire surface of the insulating layer (D), and the first layer is formed only on a necessary portion of the primer layer (B-2). What laminated
- stacked the two electroconductive layer (E) can also be used.
- a laminate in which the primer layer (B-2) is provided only on a portion of the surface of the insulating layer (D) where the second conductive layer (E) is provided can also be used.
- the thickness of the primer layer (B-2) 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 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, for example, a layer made of a metal containing at least one of copper, nickel, chromium, cobalt, tin, gold, and the like.
- the plating layer made of nickel is laminated to form the second plating layer (E-2), and the plating layer made of nickel is laminated on the plating layer made of copper, and further the plating layer made of gold And the second plating layer (E-2) is formed, and the conductive pattern such as a highly reliable wiring pattern capable of maintaining a good electrical conductivity without causing disconnection or the like over a long period of time. Is preferable in manufacturing.
- the second conductive layer (E) may be provided on a part or all of the surface of the second primer layer (B-2). 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 ** width (line width) ** 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 first primer layer (B-1) is applied to a part or all of the surface of the support on which the layer (A) is formed.
- a layer (A), a first primer layer (B-1), and a first plating nucleus layer made of a support are coated on a part or all of the fluid (c-1) containing a conductive substance.
- a process of laminating an insulating layer film or an insulating sheet, or a resin composition (d) is applied to a part or the whole Step [3] of forming an insulating layer (D) by drying, applying a primer for forming the second primer layer (B-2) to a part or all of the insulating layer (D), and applying the primer
- a fluid (e-1) containing a conductive substance to part or all of the surface, the insulating layer (D), the second primer layer (B-2), and the second layer
- the step [4] of laminating the plating nucleus layer (E-1) and the second plating by subjecting a part or all of the surface of the second plating nucleus layer (E-1) to plating. It can be manufactured through the step [5] of forming the second conductive layer (E) in which the second plating layer (E-2) is laminated on the surface of the core layer (E-1).
- a primer for forming the first primer layer (B-1) is applied to part or all of the surface of the support constituting the layer (A), and dried as necessary. Thereafter, a fluid (c-1) containing a conductive material is applied to a part or all of the coated surface, and dried, whereby the layer (A) comprising the support and the first primer layer (B -1) and the first conductive layer (C) or the first plating nucleus layer (C-1) constituting the first conductive layer (C).
- 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.
- a support made of a metal such as a steel plate or copper can be used.
- the support generally used as a support in forming a conductive pattern such as a circuit board, from polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc. It is preferable to use a support.
- 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 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 used in combination as needed.
- polycarbonate polyol for example, those obtained by reacting a carbonate with 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.
- 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 of the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol [isocyanate group / hydroxyl group] is 0.9 to 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 those having a weight average molecular weight of 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. Although it depends on the selection of the crosslinking agent used in combination as the functional group, 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 ( Depending on the type of D), etc., it 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, preferably 0.05% by mass to 30%. It is preferably used in the range of mass%, more preferably 0.1 mass% to 10 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 container 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 or the like can be used, and it is 0% by mass to the total amount of the (meth) acrylic monomer mixture. It is preferably used in the range of 1.0% by mass, 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 examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
- 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 and 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).
- the glass transition temperature of the vinyl polymer (x3-2) is a value determined by calculation mainly based on the composition of the vinyl monomer used for the production of the vinyl polymer (b3-2). is there.
- 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 (x2).
- 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) can be used in combination.
- those having a crosslinkable functional group can be used as described above.
- the crosslinkable functional group is formed by forming a crosslinked structure in the first primer layer (B-1), thereby causing the conductive layer (C) excellent in adhesion and conductivity without causing bleeding or the like. It can be suitably used for forming the first 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 Using one having at least one selected from the group consisting of alkoxymethylamide groups significantly improves the durability of the first primer layer (B-1) and the adhesion to various supports. Is preferable.
- 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 strong alkali or strongly acidic substance is used in the plating process described later. Even when exposed to a plating agent comprising, a conductive pattern with exceptional durability is formed without causing the first primer layer (B-1) to peel off from the support. can do.
- 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.
- polyamine compound that can be used for the thermal crosslinking agent (x1-1) for example, tertiary amines such as triethylenediamine and dimethylethanolamine 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 necessary 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. be able to. 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 coating amount of the primer on the support is adjusted so that the thickness of the first primer layer (B-1) is within the above-mentioned preferred range from the viewpoint of imparting excellent adhesion and conductivity. Is preferred.
- a fluid is used as a method of laminating the first conductive layer (C) or the first plating nucleus layer (C-1) constituting the first conductive layer (C-1) on the surface of the first primer layer (B-1). Examples of the method include applying (c-1) to the surface of the first primer layer (B-1) and drying.
- 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 baking process can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, a heat roll, 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.
- 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].
- an insulating film or sheet formed in advance on part or all of the surface of the first plating layer (C-2) is used using an adhesive or the like. The method to adhere
- stacking the said insulating layer (D) the method of apply
- the pre-formed insulating film or insulating sheet examples include TFA-5602525 (manufactured by Kyocera Chemical Co., Ltd., polyimide film, insulating layer thickness 12 ⁇ m, adhesive layer thickness 20 ⁇ m), NICAFLEX CISA 2535 (manufactured by Nikkan Kogyo Co., Ltd., Polyimide film, insulating layer thickness 25 ⁇ m, adhesive thickness 35 ⁇ m), ABF-GX3 (Ajinomoto Fine Techno Co., epoxy film), CT-F (Kuraray Co., Ltd., liquid crystal polymer film, insulating layer) A film or sheet having a thickness of 25 ⁇ m), BIAC-FILM (manufactured by Primatec Co., Ltd., and a liquid crystal polymer film with an insulating layer thickness of 25 ⁇ m) 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 resin composition (d ) May be applied not only to the first conductive layer (C) but also to the surface of the primer layer (B-1) to form an insulating layer (D).
- 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 step [4] that can be performed when the laminate is manufactured includes a second primer layer (B--) on part or all of the insulating layer (D) formed in the step [2]. 2) is applied, and a fluid (e-1) containing a conductive substance is applied to a part or all of the application surface to thereby form the insulating layer (D) and the second layer.
- the primer layer (B-2) and the second plating nucleus layer (E-1) are laminated.
- Primers that can be used when forming the second primer layer (B-2) on a part or all of the insulating layer (D) include those used when forming the first primer layer (B-1). The thing similar to what was illustrated as a primer which can be used can be used.
- the first primer layer (B-1) and the second primer layer (B-2) may have the same composition or different compositions.
- the method for applying the primer used for forming the second primer layer (B-2), the thickness of the primer layer (B-2), etc. are also the same as those for the first primer layer (B-1). It is preferable to adjust to a method and range similar to the method and range exemplified as the primer application method and thickness used in forming.
- a conductive substance is used as a method of laminating the second plating core layer (E-1) constituting the second conductive layer (E) on the second primer layer (B-2) formed by the above method. Examples thereof include a method in which the contained fluid (e-1) is applied to a part or all of the primer layer (B-2) 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 [5] that can be performed when the laminate is manufactured includes the step of plating the whole or part 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.
- the first conductive layer (C) and the second conductive layer (E) constituting the laminate may be connected to each other by another wiring or the like, and each independently forms a circuit. Also good. Further, the first conductive layer (C) and the second conductive layer (E) may be connected by applying a process such as cutting to a part of the laminate and applying the fluid. .
- a conductive pattern having a desired pattern can be manufactured by applying the body and baking.
- the laminate such as the conductive pattern obtained by the above method can maintain good electrical conductivity without causing separation between layers, and is thin.
- 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 Preparation 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 introduction 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 A polyimide film (Kapton 150EN manufactured by Toray DuPont Co., Ltd.), which was prepared by using the aqueous dispersion of the urethane resin (Y-1) obtained in Synthesis Example 1 as a primer and corona-treating it so that the thickness of the primer layer was 1 ⁇ m. -C, a thickness of 37.5 ⁇ m) is coated on the surface of the support using a spin coater and dried at 80 ° C. for 3 minutes using a hot air dryer to crosslink the support. A laminate provided with a primer layer not forming a 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 at an electric current density of 2 A / dm 2 using an electroplating solution containing copper sulfate for 15 minutes.
- a first copper plating layer having a thickness of 8 ⁇ m was laminated on the surface of the first plating core layer to form a first conductive layer to obtain a laminate (I).
- a NICAFLEX CISA2535 (made by Nikkan Kogyo Co., Ltd., insulating layer thickness 25 ⁇ m, adhesive thickness 35 ⁇ m) capable of forming the insulating layer is formed on the surface including the first plating layer of the laminate (I).
- the insulating layer was laminated on the surface of the laminate (I) by applying pressure in the range of 2 MPa to 4 MPa within a range where the pressurization temperature did not exceed 160 ° C.
- the urethane-acrylic composite resin (Y-4) aqueous dispersion obtained in Synthesis Example 4 is used as the resin composition capable of forming the second primer layer, and this is used as the insulating layer constituting the laminate.
- the surface is coated using a spin coater and dried at 80 ° C. for 3 minutes using a hot air dryer to obtain a laminate (II) in which a second primer layer is laminated on the surface of the insulating layer. It was.
- a fluid 1 to be described later is applied to an ink jet printer (an ink jet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., an evaluation printer head KM512L, 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 KM512L, 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. 2, and a 2 mm square tab to which a BSP probe can be connected is installed at the end.
- the substrate, the first primer layer, the first conductive layer, the insulating layer, the second primer layer, and the second plating core layer are laminated by baking for 30 minutes at 150 ° C.
- laminate (III) was obtained.
- the surface of the second plating nucleus layer constituting the laminate (III) is set as a cathode, phosphorus-containing copper is set as an anode, and an electric plating solution containing copper sulfate is used.
- an electric plating solution containing copper sulfate is used.
- the electroplating solution 70 g / liter of copper sulfate, 200 g / liter of sulfuric acid, 50 mg / liter of chloride ion, and 5 g / liter of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.) were used.
- a laminate (IV) was obtained in which a layer comprising a support, a first primer layer, a first conductive layer, an insulating layer, a second primer layer, 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.
- Example 2 Instead of using the aqueous dispersion of urethane-acrylic composite resin (Y-3) obtained in Synthesis Example 3 as a primer instead of the aqueous dispersion of urethane resin (Y-1) obtained in Synthesis Example 1, In the same manner as in Example 1, a laminate in which a layer made of a support, a first primer layer, a first conductive layer, an insulating layer, a second primer layer, and a second conductive layer was laminated was obtained. .
- 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 3 instead of NICAFLEX CISA2535 (Nikkan Kogyo Co., Ltd., insulating layer thickness 25 ⁇ m, adhesive thickness 35 ⁇ m) that can form an insulating layer, “TFA-5602525” is a film (insulating layer) manufactured by Kyocera Chemical Co., Ltd. In the same manner as in Example 1, except that a thickness of 12 ⁇ m and a thickness of 20 ⁇ m of the adhesive layer are used, the layer made of the support, the first primer layer, the first conductive layer, the insulating layer, and the first layer A laminate in which the two primer layers and the second conductive layer were laminated was obtained.
- Example 4 As a resin composition for forming the insulating layer, instead of NICAFLEX CISA 2535 (Nikkang Kogyo Co., Ltd., insulating layer thickness 25 ⁇ m, adhesive thickness 35 ⁇ m), the polyimide varnish (Y-5) obtained in Synthesis Example 5 was used. In the same manner as in Example 1, except that the layer made of the support, the first primer layer, the first conductive layer, the insulating layer, the second primer layer, and the second conductive layer are prepared in the same manner as in Example 1. A laminated body was obtained.
- NICAFLEX CISA 2535 Nikkang Kogyo Co., Ltd., insulating layer thickness 25 ⁇ m, adhesive thickness 35 ⁇ m
- Example 5 As the primer that can form the first primer layer, the aqueous dispersion of the vinyl polymer (Y-2) obtained in Synthesis Example 2 is used instead of the aqueous dispersion of the urethane-acrylic composite resin (Y-3). Except for the above, the support layer, the first primer layer, the first conductive layer, the insulating layer, the second primer layer, and the second conductive layer were laminated in the same manner as in Example 3. A laminate was obtained.
- Example 1 It tried to manufacture a laminated body by the method similar to Example 1 except not providing a 1st primer layer. However, the first conductive layer was peeled off from the support during the plating process, causing a decrease in conduction or disconnection, so that the insulating layer, the second primer layer, and the second conductive layer were not formed.
- Example 2 It tried to manufacture a laminated body by the method similar to Example 1 except not providing a 2nd primer layer. However, the second conductive layer was peeled off from the insulating layer, causing a decrease in conduction or disconnection of the second conductive layer.
- 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 Tables 1 and 2 represents a polyimide film (thickness 37.5 ⁇ m) manufactured by Toray DuPont Co., Ltd.
- “TFA-5602525” represents a film (insulating layer thickness 12 ⁇ m, adhesive layer thickness 20 ⁇ m) manufactured by Kyocera Chemical Co., Ltd.
- “NICAFLEX CISA 2535” represents a film manufactured by Nikkan Kogyo Co., Ltd. (thickness of insulating layer: 25 ⁇ m, thickness of adhesive layer: 35 ⁇ m).
- Second conductive layer (E) 20 Top view of laminate (I), 21 Top view of laminated body (IV) 22 Cross-sectional view taken along one-dot broken line 23 of laminated body (IV)
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Abstract
Description
また、前記絶縁層(D)は、予め成形されたフィルムまたはシートの代わりに、樹脂組成物(d)を、少なくとも前記第一の導電層(C)の表面に塗布し乾燥することによって形成された層であってもよい。
前記第二のプライマー層(B-2)は、前記第二の導電層(E)の形成に使用可能な導電性物質を含有する流動体(e-1)を受容する層である。前記プライマー層(B-2)は、前記流動体(e-1)が接触した際に、前記流動体(e-1)に含まれる溶媒を速やかに吸収し、かつ前記導電性物質をプライマー層(B-2)の表面に担持する。これにより、前記絶縁層(D)とプライマー層(B-2)と、導電性物質から構成される第二の導電層(E)との密着性及び耐湿熱性を格段に向上することができる。
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。
ン等を使用することができる。
前記絶縁層(D)を積層する方法としては、前記第一のめっき層(C-2)の表面の一部または全部に、予め成形された絶縁フィルムまたは絶縁シートを、接着剤等を用いて接着する方法が挙げられる。
また、前記絶縁層(D)を積層する方法としては、絶縁層(D)を形成可能な樹脂組成物(d)を塗布し、乾燥等する方法が挙げられる。
予め成形された絶縁フィルムまたは絶縁シートとしては、例えばTFA-5602525(京セラケミカル株式会社製、ポリイミドフィルム、絶縁層の厚さ12μm、接着層の厚さ20μm)、NICAFLEX CISA2535(ニッカン工業株式会社製、ポリイミドフィルム、絶縁層の厚さ25μm、接着剤の厚さ35μm)、ABF-GX3(味の素ファインテクノ株式会社製、エポキシ系フィルム)、CT-F(株式会社クラレ製、液晶ポリマーフィルム、絶縁層の厚さ25μm)、BIAC-FILM(株式会社プライマテック製、液晶ポリマーフィルム 絶縁層の厚さ25μm)等からなるフィルムまたはシートを使用することができる。
また、前記絶縁層(D)の形成に使用可能な前記樹脂組成物(d)としては、例えばポリイミドワニス等を含有する樹脂組成物を使用することができる。
前記絶縁層(D)の一部または全部に第二のプライマー層(B-2)を形成する際に使用可能なプライマーとしては、前記第一のプライマー層(B-1)を形成する際に使用可能なプライマーとして例示したものと同様のものを使用することができる。前記第一のプライマー層(B-1)と前記第二のプライマー層(B-2)は同一の組成であっても、異なる組成であってもよい。
第二のプライマー層(B-2)を形成する際に使用するプライマーの塗布方法、及び、プライマー層(B-2)の厚さ等もまた、前記第一のプライマー層(B-1)を形成する際に使用するプライマーの塗布方法及び厚さとして例示した方法及び範囲と、同様の方法及び範囲に調整することが好ましい。
前記方法で形成した第二のプライマー層(B-2)に、第二の導電層(E)を構成する第二のめっき核層(E-1)を積層する方法としては、導電性物質を含有する流動体(e-1)を、前記プライマー層(B-2)の一部または全部に塗布し乾燥する方法が挙げられる。
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。
2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン410g(1モル)、及び1,2,3,4-シクロブタンテトラカルボン酸二無水物192g(0.98モル)をN-メチルピロリドン3400g中で、室温で8時間反応させることによって、ポリイミドワニス(Y-5)を得た。
合成例1で得たウレタン樹脂(Y-1)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。
次に、前記絶縁層を形成しうるNICAFLEX CISA2535(ニッカン工業株式会社製、絶縁層の厚さ25μm、接着剤の厚さ35μm)を、前記積層体(I)の第一のめっき層を含む表面に載置し、加圧温度が160℃を超えない範囲で、2MPa~4MPaの範囲で加圧することによって、前記積層体(I)の表面に絶縁層を積層した。
合成例1で得たウレタン樹脂(Y-1)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)の水分散体をプライマーとして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第一のプライマー層と第一の導電層と絶縁層と第二のプライマー層と第二の導電層とが積層した積層体を得た。
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。
絶縁層を形成しうるNICAFLEX CISA2535(ニッカン工業株式会社製、絶縁層の厚さ25μm、接着剤の厚さ35μm)の代わりに、「TFA-5602525」は、京セラケミカル株式会社製のフィルム(絶縁層の厚さ12μm、接着層の厚さ20μm)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第一のプライマー層と第一の導電層と絶縁層と第二のプライマー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、NICAFLEX CISA2535(ニッカン工業株式会社製、絶縁層の厚さ25μm、接着剤の厚さ35μm)の代わりに、合成例5で得たポリイミドワニス(Y-5)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第一のプライマー層と第一の導電層と絶縁層と第二のプライマー層と第二の導電層とが積層した積層体を得た。
第一のプライマー層を形成しう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)の水分散体を使用すること以外は、実施例3と同様の方法で、支持体からなる層と第一のプライマー層と第一の導電層と絶縁層と第二のプライマー層と第二の導電層とが積層した積層体を得た。
第一のプライマー層を設けないこと以外は、実施例1と同様の方法で積層体を製造することを試みた。
しかし、めっき工程中に第一の導電層が支持体から剥離し、導通の低下または断線を引き起こしたため、絶縁層、第二のプライマー層及び第二の導電層を形成しなかった。
第二のプライマー層を設けないこと以外は、実施例1と同様の方法で積層体を製造することを試みた。
しかし、第二の導電層が絶縁層から剥離し、第二の導電層の導通の低下または断線を引き起こした。
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「A」、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「D」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「A」、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「D」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「A」、導通があったものを「D」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。
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 (10)
- 少なくとも、支持体からなる層(A)と、第一のプライマー層(B-1)と、第一の導電層(C)と、絶縁層(D)と、第ニのプライマー層(B-2)と、第二の導電層(E)とが積層された構造を有するものであることを特徴とする積層体。
- 前記第一のプライマー層(B-1)及び第二のプライマー層(B-2)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2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3に記載の積層体。
- 前記絶縁層(D)が、ポリイミドワニスを用いて形成される層である請求項1に記載の積層体。
- 前記第一のプライマー層(B-1)及び第二のプライマー層(B-2)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6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1~8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。
- 支持体の表面の一部または全部に、第一のプライマー層(B-1)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)と第一のプライマー層(B-1)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、絶縁層フィルムまたは絶縁シートを積層する工程、または、樹脂組成物(d)を塗布し乾燥することによって絶縁層(D)を積層する工程[3]、
前記絶縁層(D)の一部または全部に、第二のプライマー層(B-2)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(e-1)を塗布することによって、前記絶縁層(D)と、第二のプライマー層(B-2)と、第二のめっき核層(E-1)とを積層する工程[4]
、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[5]を経ることを特徴とする積層体の製造方法。
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JP2014556851A JP5713223B2 (ja) | 2013-03-13 | 2014-03-06 | 積層体、導電性パターン及び積層体の製造方法 |
US14/775,576 US9380701B2 (en) | 2013-03-13 | 2014-03-06 | Laminate, conductive pattern, and method for producing laminate |
DE112014001264.5T DE112014001264T5 (de) | 2013-03-13 | 2014-03-06 | Laminat, Leiterbild sowie Verfahren zur Herstellung eines Laminats |
KR1020157014219A KR20150065946A (ko) | 2013-03-13 | 2014-03-06 | 적층체, 도전성 패턴 및 적층체의 제조 방법 |
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JP2017179227A (ja) * | 2016-03-31 | 2017-10-05 | 日本カーバイド工業株式会社 | 水分散型樹脂組成物及び樹脂フィルム |
JP6667119B1 (ja) * | 2018-06-26 | 2020-03-18 | Dic株式会社 | プリント配線板用積層体及びそれを用いたプリント配線板 |
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EP3185310B1 (en) * | 2015-12-23 | 2019-02-20 | Agfa-Gevaert | A backsheet for a solar cell module |
TWI640424B (zh) * | 2017-02-13 | 2018-11-11 | 亞洲電材股份有限公司 | Nano metal substrate for FPC and COF materials |
US11044802B2 (en) * | 2017-02-16 | 2021-06-22 | Azotek Co., Ltd. | Circuit board |
US11225563B2 (en) | 2017-02-16 | 2022-01-18 | Azotek Co., Ltd. | Circuit board structure and composite for forming insulating substrates |
KR102372638B1 (ko) * | 2017-07-10 | 2022-03-10 | 디아이씨 가부시끼가이샤 | 적층체, 그것을 사용한 프린트 배선판, 플렉서블 프린트 배선판 및 성형품 |
US11907790B2 (en) * | 2020-03-06 | 2024-02-20 | Hutchinson Technology Incorporated | Component identification |
TWI841294B (zh) * | 2023-03-15 | 2024-05-01 | 國立中興大學 | 軟性電路板與其製作方法 |
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DE112014001264T5 (de) | 2016-01-21 |
CN105026140A (zh) | 2015-11-04 |
US9380701B2 (en) | 2016-06-28 |
CN105026140B (zh) | 2017-09-26 |
TW201442863A (zh) | 2014-11-16 |
TWI508855B (zh) | 2015-11-21 |
JPWO2014142005A1 (ja) | 2017-02-16 |
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US20160037632A1 (en) | 2016-02-04 |
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