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WO2005068183A1 - 両面導体ポリイミド積層体の連続製造方法 - Google Patents

両面導体ポリイミド積層体の連続製造方法 Download PDF

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Publication number
WO2005068183A1
WO2005068183A1 PCT/JP2004/019523 JP2004019523W WO2005068183A1 WO 2005068183 A1 WO2005068183 A1 WO 2005068183A1 JP 2004019523 W JP2004019523 W JP 2004019523W WO 2005068183 A1 WO2005068183 A1 WO 2005068183A1
Authority
WO
WIPO (PCT)
Prior art keywords
sided conductor
metal foil
conductive metal
laminate
polyimide
Prior art date
Application number
PCT/JP2004/019523
Other languages
English (en)
French (fr)
Inventor
Kazuya Miyamoto
Akira Tokumitsu
Masakazu Ii
Yoshihiro Shigematsu
Ichiro Higasayama
Masahiro Kanno
Yujiro Nakagawa
Original Assignee
Nippon Steel Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Priority to CN2004800404673A priority Critical patent/CN1906027B/zh
Publication of WO2005068183A1 publication Critical patent/WO2005068183A1/ja

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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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1432—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface direct heating of the surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1454—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface scanning at least one of the parts to be joined
    • B29C65/1458—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface scanning at least one of the parts to be joined once, i.e. contour welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1464—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/78—Means for handling the parts to be joined, e.g. for making containers or hollow articles, e.g. means for handling sheets, plates, web-like materials, tubular articles, hollow articles or elements to be joined therewith; Means for discharging the joined articles from the joining apparatus
    • B29C65/7858—Means for handling the parts to be joined, e.g. for making containers or hollow articles, e.g. means for handling sheets, plates, web-like materials, tubular articles, hollow articles or elements to be joined therewith; Means for discharging the joined articles from the joining apparatus characterised by the feeding movement of the parts to be joined
    • B29C65/7888—Means for handling of moving sheets or webs
    • B29C65/7894—Means for handling of moving sheets or webs of continuously moving sheets or webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/001—Joining in special atmospheres
    • B29C66/0012—Joining in special atmospheres characterised by the type of environment
    • B29C66/0014—Gaseous environments
    • B29C66/00141—Protective gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/024—Thermal pre-treatments
    • B29C66/0242—Heating, or preheating, e.g. drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/03—After-treatments in the joint area
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B29C66/7232—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer
    • B29C66/72321—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer consisting of metals or their alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91411—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the parts to be joined, e.g. the joining process taking the temperature of the parts to be joined into account
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91441—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time
    • B29C66/91443—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time following a temperature-time profile
    • B29C66/91445—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time following a temperature-time profile by steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91941—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined
    • B29C66/91945—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined lower than said glass transition temperature
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    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
    • 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
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7316—Surface properties
    • B29C66/73161—Roughness or rugosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/60—In a particular environment
    • B32B2309/62—Inert
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • 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
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • 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
    • H05K2201/0183—Dielectric layers
    • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure

Definitions

  • the present invention relates to a continuous production method of a double-sided conductor polyimide laminate suitable for a flexible printed circuit board or the like as a wiring material in response to a demand for miniaturization and light weight of electronic devices,
  • the present invention relates to a continuous production method of a double-sided conductor polyimide laminate which can be stably produced as a roll-wound product without using a shim, and having a variable strength and quality.
  • a flexible acid that is applied directly to a conductor such as copper foil by applying the uncured polyamic acid solution without using an adhesive, and then cured by heating.
  • the linear expansion coefficient of the cured product 3. 0 X 10- 5 following Jiamin and the polyamic acid which is synthesized by the tetracarboxylic acid anhydride which is cured by heating is applied to the metal foil (e.g., Patent Document 1 ), A resin solution containing a polyamideimide precursor compound having a specific structural unit is applied onto a conductor and imidized (for example, see Patent Document 2), and diamines containing diaminobenzamide or a derivative thereof.
  • These flexible printed wiring boards relate to a single-sided structure in which an insulating layer is adhered to only one side of a conductive metal foil by heat curing without using an adhesive.
  • the present inventors first used a single-sided conductor laminate having at least three polyimide layers on one side of a conductive metal foil (M),
  • M2 conductive metal foil
  • Patent Document 5 proposes a method for producing a double-sided conductor polyimide laminate in which a conductive metal foil (M2) is laminated on the polyimide layer under heat and pressure (see Patent Document 5, for example).
  • a large double-sided conductor laminate can form a wiring circuit on both sides of a substrate, and has already been put to practical use for high-density mounting, and has recently been widely used in various fields.
  • Patent Document 1 JP-A-62-212140
  • Patent Document 2 JP-A-63-84188
  • Patent Document 3 JP-A-63-245988
  • Patent Document 4 Japanese Patent Publication No. 6-49185
  • Patent Document 5 JP-A-10-323935
  • an object of the present invention is to provide a double-sided conductive polyimide laminate having a stable appearance without poor appearance such as vertical wrinkles in which a conductive metal layer is laminated on both sides of a polyimide resin layer without an adhesive.
  • An object of the present invention is to provide a method for continuously producing a body.
  • Another object of the present invention is to provide a double-sided conductor having excellent heat resistance and flexibility as a wiring circuit board, particularly having excellent wiring circuit strength strongly demanded by users.
  • Rolled polyimide laminate It is to provide a manufacturing method.
  • the present inventors have conducted intensive studies on the above problems, and as a result, pre-heated the single-sided conductor laminate and the conductive metal foil (M) immediately before introduction between the heating press rolls to a specific temperature.
  • the present inventors have found that the above object can be achieved by using a sroll surface which has been roughened to a specific surface roughness (R a ), and completed the present invention.
  • a single-sided conductor laminate having at least three polyimide resin layers of a base layer, an intermediate main layer, and a top layer on a conductive metal foil (M) and a conductive metal foil (M)
  • a continuous production method of a double-sided conductor polyimide laminate characterized by contacting the surface of a heated press roll after preheating to a temperature not lower than ° C and not higher than a glass transition point of a polyimide resin of one top layer.
  • the surface of the pair of press rolls according to the present invention is roughened to an average surface roughness (Ra) of 0.01 to 5 ⁇ m, and the press roll surface temperature is reduced in an inert gas atmosphere. 340—3 90. C, it is preferable to heat and press under the conditions of a linear pressure between press rolls of 50 kggcm to 300 kggcm (490 to 2940 NZcm) and a passage time of 2 to 5 seconds.
  • the pre-heating is performed in a state where the flatness is increased in a nitrogen atmosphere through a plurality of guide rolls each having a different height of a central axis.
  • the preheating in the present invention is desirably performed by a guide roll with a built-in heating means disposed at a position where the base material contacts the surface of the heating press roll.
  • FIG. 1 is a schematic flow chart showing a method for producing a double-sided conductor polyimide laminate of the present invention.
  • FIG. 2 is a schematic longitudinal sectional view showing an example of a guide roll for preheating.
  • FIG. 3 is a schematic longitudinal sectional view showing an example of a heating press roll.
  • Rotation support members such as bearings
  • conductive metal foils (M and M) used in the present invention include copper and aluminum having a thickness of 5 to 150 m.
  • Examples thereof include lithium, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zinc, and alloys thereof, and copper is preferable.
  • a rolled copper foil product which has been avoided from being used because of its low rigidity and difficulty in controlling the pressure by thermocompression bonding can be suitably used.
  • the surface may be subjected to siding, nickel plating, copper-zinc alloy plating, or chemical or mechanical surface treatment with aluminum alcoholate, aluminum chelate, silane coupling agent, or the like. .
  • Patent Document 1-14 a single-sided conductor laminate in which a polyimide resin is heat-cured and adhered as an insulating layer without adhesive to one surface of a conductive metal foil (M) that is strong is described in Patent Document 1-14.
  • the publicly known ones disclosed in and 5 can be used.
  • the polyimide resin used as the insulator layer is a general term for a resin having an imide ring structure, and examples thereof include polyimide, polyamideimide, and polyesterimide.
  • Examples of the polyimide resin layer include, but are not particularly limited to, those having low thermal expansion as described in Patent Documents 14 to 14, and thermoplastic polyimides which melt or soften when heated.
  • the insulating layer is composed of a base layer made of a thermoplastic polyimide resin obtained by heating and curing a polyimide precursor resin solution described in Patent Document 5, and a low thermal expansion polyimide resin.
  • An intermediate main layer and a top layer made of a thermoplastic polyimide resin are preferably composed of at least three polyimide resin layers.
  • the coefficient of linear expansion was determined using a sample that had completed the imidization reaction, heated to 250 ° C using a thermomechanical analyzer (TMA), cooled at a rate of 10 ° CZ, 240-100 The average linear expansion coefficient in the range of ° C was determined.
  • TMA thermomechanical analyzer
  • a polyimide resin having a unit structure represented by the following general formula (I) described in Patent Document 5 is desired. Good
  • thermoplastic polyimide resin used for the base layer and the top layer may have any structure as long as its glass transition point temperature is 350 ° C. or lower. It is preferable that the adhesive strength at the interface is sufficient when pressed under heat and pressure.
  • the thermoplastic polyimide resin as used herein includes those which can be adhered by pressure so that they do not necessarily show sufficient fluidity in a normal state above the glass transition point. Specific examples of the thermoplastic polyimide resin having such properties include those having a unit structure represented by the following general formula (II) or general formula (III) described in Patent Document 5 described above.
  • Ar is a divalent aromatic group having 12 or more carbon atoms.
  • divalent aromatic group Ar or Ar include, for example,
  • CH3 CH 3 or the like can be mentioned, preferably,
  • a curing agent such as a known acid anhydride-based amine-based curing agent is added to a polyimide precursor solution or a polyimide solution as described in Patent Document 5 above.
  • Various additives and catalysts such as a silane coupling agent, a titanate coupling agent, an adhesion-imparting agent such as an epoxy conjugate, and a flexibility-imparting agent such as rubber are added to the conductive metal foil (M). And then heat cured by heat treatment to obtain a single-sided conductor laminate.
  • the single-sided conductor laminate has a conductive metal foil (M) as a base layer, a thermoplastic polyimide resin layer as a base layer, an intermediate main layer as a low thermal expansion polyimide resin layer, and a top layer (outermost surface layer). It is preferable that a thermoplastic polyimide resin layer is laminated as ()).
  • a thermoplastic polyimide resin layer is laminated as ()).
  • the intermediate main layer does not include a low thermal expansion polyimide resin layer
  • the single-sided conductor laminate obtained in the heat curing step has a large warp and curl, and the workability in the subsequent steps is reduced. Significantly reduced.
  • the top layer (outermost layer) does not contain a thermoplastic polyimide resin layer, the adhesive force by thermocompression bonding with the conductive metal foil in the thermocompression bonding roll process will not be sufficiently exhibited. It is not preferred.
  • the ratio (t Zt) of the thickness of the low thermal expansion polyimide resin layer to the thickness t of the thermoplastic polyimide resin layer is in the range of 2-100, preferably 5-20. Good range.
  • the adhesive force by the thermocompression bonding in the second step is not sufficiently exhibited.
  • the application of the plurality of polyimide resins on the conductive metal foil (M) can be performed in the form of the resin solution, and is preferably described in Patent Documents 4 and 5 described above.
  • the heat conversion of the precursor to polyimide is performed simultaneously. It is preferred to do so. If another polyimide-based precursor solution is applied on the layer completely converted to polyimide and heat-treated to close the imide ring, the adhesion between the polyimide-based resin layers may not be fully exhibited. This causes the quality of the double-sided laminate of the product to deteriorate.
  • a knife coater, a die coater, a roll coater, a curtain coater, or the like is used as a method of applying a polyimide resin solution or a precursor solution thereof (polyamic acid solution) on the conductive metal foil (M).
  • the method can be carried out by a known method, particularly when a thick coating is performed, a die coater or a knife coater is suitable.
  • the polymer concentration of the polyimide-based precursor solution used for coating is usually 5 to 30% by weight, preferably 10 to 20% by weight, depending on the degree of polymerization of the polymer. If the polymer concentration is lower than 5% by weight, a single coating cannot provide a sufficient film thickness, and if the polymer concentration is higher than 30% by weight, the solution viscosity becomes too high and coating becomes difficult.
  • the polyamic acid solution applied to the conductive metal foil to a uniform thickness is then subjected to a heat treatment to remove the solvent and further close the imide ring.
  • a heat treatment to remove the solvent and further close the imide ring.
  • the final heat treatment temperature is usually preferably 300 to 400 ° C.
  • the solution gradually starts to occur, and at 300 ° C or lower, the polyimide film does not sufficiently align on the conductive metal foil, and a single-sided conductor laminate having good flatness cannot be obtained.
  • the overall thickness of the polyimide resin layer as an insulator thus formed is usually 10 to 150 m.
  • FIG. 1 shows a single-sided conductor laminate of the present invention and a conductive metal foil (M) introduced between a pair of press rolls, and laminated by heating and pressing.
  • M conductive metal foil
  • FIG. 2 is a schematic longitudinal sectional view showing an example of a guide roll for preheating.
  • FIG. 3 is a schematic longitudinal sectional view showing an example of a press roll.
  • FIG. 1 a single-sided conductor laminate 1 in which an insulating layer made of a polyimide resin is adhered to one surface of the above-described conductive metal foil (M) by heating and curing, and a conductive metal foil (M) 2 And together
  • the roll-winding state force is also continuously drawn out, and after a plurality of guide rolls 3, 3 ′, 4, 4 ′, etc., with different center axis heights, preheating is performed in a state where the flatness is increased, then Heating The conductive metal foil (M) is heated and pressed onto the top layer of the single-sided conductor laminate 1 by passing the pressure point between the press rolls in contact with the surfaces of the press rolls 5 and 6.
  • the double-sided conductor polyimide laminate 7 After forming the double-sided conductor polyimide laminate 7 that has been laminated and integrated, it is pre-cooled by a cooling means c such as spraying an inert gas for cooling as appropriate, and then it is passed through a plurality of guide rolls 8 and 8 'in the outside air. The rolled product 9 is further cooled.
  • a cooling means c such as spraying an inert gas for cooling as appropriate
  • the plurality of guide rolls 3, 3, 4, 4, 8, 8, etc. and the pair of heating press rolls 5, 6 are at atmospheric pressure or higher in order to prevent irritation of the conductive metal foil. It is desirable that the sealing mechanism (labyrinth seal) 11 be provided in the processing chamber 10 held in an atmosphere of an inert gas such as nitrogen gas, and provided at the base material inlet and the laminate outlet.
  • an inert gas such as nitrogen gas
  • Processing room 1 Before being introduced into the processing chamber 10, it is desirable to enhance the flatness under tension by passing through a plurality of guide rolls each having a different center axis height. Processing room 1
  • the double-sided conductor polyimide laminate after being pulled out from 0 is also passed through under tension by a plurality of guide rolls with different center axis heights in the open air before being made into a rolled product 9. It is desirable to further lower the surface temperature.
  • a heating step is used. Less roll 5.6 Force to make guide rolls 3, (4,) just before heating roll with built-in heating means or Heating lamp or heater that emits radiant energy just before heating press roll h or h
  • Preheating may be performed by installing 12 or the like, or both preheating means may be used in combination.
  • An example of a particularly preferred type of preheating guide roll with a built-in heating means will now be described with reference to FIG.
  • a guide roll 3 ′ (4 ′) has a rotation support member 13 such as a bearing in which the outer periphery of the cavity and a central axis 12 from which both ends of the cavity also protrude are disposed inside both ends of the outer periphery of the roll. And the roll outer periphery is freely rotated around the central axis 12 by the rotation support member 13.
  • Heating control means 14 by radiant heat selected from a heating coil by dielectric heating, an infrared heater, a resistance heating coil, and the like are appropriately divided or integrated and fixed to a central axis 12 inside the roll.
  • the radiant heat energy applied to the inner wall surface of the roll is controlled by changing the value of the current flowing to the roll.
  • a jacket or heat pipe filled with an organic heat medium having good heat conductivity to uniformly heat the surface temperature with radiant heat energy irradiated from the heating control means is used.
  • the conductive element 17 is embedded and arranged.
  • the strong heat pipe is instantaneously transmitted to the entire outer surface of the roll by heat transfer of the heating means 14 of the center shaft 12 described above, so that an axial temperature difference with high surface temperature accuracy hardly occurs.
  • the preheating temperature is preferably 200 ° C. or higher and a temperature lower than the glass transition point of the thermoplastic polyimide resin as the top layer resin, preferably 200 to 350 ° C. It is desirable that the temperature of the outer surface of the preheating hole be monitored by a temperature sensor embedded in the surface of the roll, and the current value supplied to the heating control means 14 be controlled so as to always maintain a predetermined temperature. If preheating is not performed, or if the preheating temperature is 200 ° C or less, the temperature is extremely thin! It is not preferable because a large number of vertical stripes, horizontal stripes and converging wrinkles are generated on the surface, which leads to poor appearance and poor adhesiveness. If the temperature is higher than the glass transition point, the polyimide resin deteriorates, which is not preferable.
  • the pair of heating presses 5 (6) are structurally structurally similar to the heating press described in FIG.
  • the same as the guide roll 3 '(4') with built-in means and the same reference numerals as those shown in FIG. 2 have the same meanings as those described in FIG. 2, but have a larger diameter and a heating means. It is divided into three parts: 14, 15, and 16 and is different from that in that it is forcibly rotated by a stirring power mechanism (not shown).
  • a means for uniformizing the surface temperature by embedding a heat conductive element 17 called a jacket or a heat pipe filled with an organic heat medium having good heat conductivity. .
  • the temperature of the outer surface of the press roll is preferably controlled to a temperature not lower than the glass transition point of the thermoplastic polyimide resin, and more preferably to a set value in the range of 360 to 390 ° C. It is desirable that the temperature of the outer surface of the press roll that is strong be monitored by a temperature sensor embedded in the roll surface, and the current value supplied to the heating means 14, 15, 16 be controlled.
  • the pair of heated press rolls 5 and 6 hold at least one press roll (not shown) arranged vertically on both sides of the center shaft 12 under a nitrogen atmosphere, and pressurize the press roll to a predetermined position.
  • the gap is adjusted by moving the gears by pressurizing means using gears, so that the optimal pressing force is transmitted from the press roll cap to the base materials 1 and 2 to be introduced.
  • the line pressure between the heating press rolls should be 50-500KgZcm (490N / cm-4900N / cm), preferably 100-300KgZcm (980NZcm-2940NZcm), and the heat and pressure should be 2-5 seconds. Is desirable.
  • a pair of heated press rolls to be used is used in a roughened state in which the average surface roughness (Ra) of the press roll is 0.01 to 5 m, preferably 0.1 to 3 m. Is desirable. If the surface roughness (R a ) of the press roll is 0.01 ⁇ m or less, the double-sided conductor polyimide laminate coming out from between the heating rolls will cause a sticking due to the roll adhesion, resulting in a seam during running or copper. Inevitably pits (dents or dents of several tens of microns) caused by the adhesion of foreign substances such as foil powder are unavoidable.
  • the unevenness of the roll surface is transferred to the surface of the laminate, which is not preferable.
  • the roughened surface of the roll can be adjusted by spraying a ceramic coating.
  • the surface roughness (Ra) is determined with a stylus-type surface roughness meter using a diamond needle.
  • a double-sided conductor polyimide laminate 7 in which a conductive metal foil (M) is laminated and integrated by heating and pressure bonding on the top layer of the single-sided conductor laminate 1 by heating press rolls 5 and 6 is formed.
  • cooling means C such as blowing inert gas for cooling, but the cooling temperature by cooling means C
  • a temperature below the glass transition point of the thermoplastic polyimide resin as the top layer resin preferably 200 ° C. 300 o C force S desired ⁇ .
  • the double-sided conductor type polyimide laminate obtained in the present invention has a conductive metal layer as a conductor on both sides of a polyimide resin layer as an insulator, and has only a good appearance and no occurrence of shiny.
  • a roll-wound product that does not vary in quality and is used as an electronic wiring material to be used with the advancement of miniaturization and light weight of mobile phones, digital cameras, navigators, and other various electronic devices that are becoming more sophisticated. It is suitable.
  • the coefficient of linear expansion was measured by using a thermomechanical analyzer (TMA100) manufactured by Seiko Denshi Kogyo Co., Ltd. and then cooled at a rate of 10 ° CZ after increasing the temperature to 250 ° C. The average linear expansion coefficient during C was calculated and obtained.
  • TMA100 thermomechanical analyzer manufactured by Seiko Denshi Kogyo Co., Ltd.
  • the average linear expansion coefficient during C was calculated and obtained.
  • the extreme radius of the copper-clad product having dimensions of 100 mm ⁇ 100 mm after imidization by heat treatment was measured.
  • the adhesive strength of a single-sided copper-clad product was measured according to JIS C5016: 7.1, using a pattern with a conductor width of 3mm, and peeling the copper foil in the 180 ° direction at a speed of 50mmZ. It was obtained as a value.
  • a polyimide precursor solution was prepared in the same manner as in Synthesis Example 1, except that 1 mol of DDE was used as the diamine component and 1 mol of BTDA was used as the acid anhydride component.
  • the obtained polyimide precursor solution had a polymer concentration of 15% by weight and an apparent viscosity of 300 mPa ⁇ s at 25 ° C. by a B-type viscometer.
  • the polyimide precursor solution 2 prepared in Synthesis Example 2 was uniformly applied to a roughened surface of a 35 ⁇ m roll-shaped electrolytic copper foil (manufactured by Nippon Gould Co., Ltd.) with a thickness of 12 m using a die coater. The solvent was removed by continuous treatment in a hot air drying oven at 120 ° C. Next, the polyimide precursor solution 1 prepared in Synthesis Example 1 was uniformly coated with a thickness of 200 m from above the polyimide precursor layer using a reverse roll coater, and was continuously applied in a hot air drying oven at 120 ° C.
  • the polyimide precursor solution 2 prepared in Synthesis Example 2 was evenly applied to a thickness of 15 m, and then heated from 120 ° C to 360 ° C in a hot-air drying oven for 30 minutes. The temperature was raised, heat treatment was performed, and imidization was performed to obtain a single-sided copper-clad product a having a polyimide resin layer having a thickness of 25 ⁇ m and having good flatness without warpage or curling.
  • the 180 ° peel strength (JIS C-5016) between the copper foil layer of this single-sided copper clad product a and the polyimide resin layer was 0.8 kgZcm, and the coefficient of thermal expansion of the film after etching was 0.8 kgZcm. was 23. 5 X 10- 6 (1Z ° C).
  • the resin-coated surface of the copper-clad product with a single-sided insulation layer prepared in the production example and the rolled sheet having a width of 500 mm and the roughened surface of a rolled copper foil having a width of 35 m having the same width as the rolled sheet were prepared.
  • a pair of heated press rolls (outer diameter: 300 mm, width: 800 mm, and naphthalene sealed as a uniform heating means near the surface) were passed through guide rolls under a nitrogen atmosphere.
  • a heat pipe of a ket type is embedded, and a structure in which a dielectric heating coil is built in the center axis of the inside).
  • the hot press was performed under the conditions of a surface temperature of 360 ° -390 ° C., a linear pressure between the press opening of 150 ° -170 kg / cm, and a transit time of 2-5 seconds.
  • the double-sided copper obtained was obtained when the preheating was not performed under the same base material and the same heating press roll conditions, and when the preheating temperature was changed to 150 ° C, 250 ° C, and 340 ° C.
  • Table 1 shows the results of a visual inspection of the surface condition of the upholstered product.
  • Example 1 the set temperature of the heated press roll surface was set at 360 ° C, the linear pressure between the press rolls was set at 150 kgZcm, the passage time was set at 3 seconds, and there was no preheating of the base material introduced between the heated press rolls. ⁇
  • the surface roughness (Ra) of the heated press roll is 0.01 or less, 0.05, 0.20, 10.0 for both the case and the case where the preheating temperature is 250 ° C and 340 ° C.
  • Table 2 shows the results of a visual inspection of the surface condition of the double-sided copper-clad product obtained when the distance was changed between four steps of m.
  • the method for producing a double-sided conductor polyimide laminate of the present invention is a method for continuously producing a double-sided conductor polyimide laminate in a roll-wound state with a stable double-sided conductor polyimide-based laminate having no appearance defects such as vertical wrinkles. It is a manufacturing method with high industrial applicability.

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Abstract

　本発明の課題は、縦じわ等の外観不良のない品質の安定した両面導体ポリイミド系積層体をロール巻き状態にて両面導体ポリイミド積層体の連続製造方法を提供することであり、かかる両面導体ポリイミド積層体の連続製造方法は、導電性金属箔（Ｍ1）上にベース層、中間メイン層、トップ層の少なくとも三層のポリイミド系樹脂層を有する片面導体積層体と導電性金属箔（Ｍ2）からなる基材を連続的に一対の加熱プレスロール間に導入し、上記トップ層に導電性金属箔（Ｍ2）を加熱圧着により積層一体化させる両面導体ポリイミド積層体の製造方法において、加熱プレスロール間に導入前の片面導体積層体と導電性金属箔（Ｍ2）をそれぞれ不活性ガス雰囲気下にて２００°C以上、トップ層のポリイミド系樹脂のガラス転移点以下に予備加熱後に加熱プレスロール表面に接触させることを特徴とする。

Description

明 細 書
両面導体ポリイミド積層体の連続製造方法
技術分野
[0001] 本発明は、電子機器類の小型化、軽量ィ匕の要請に対応した配線材料としてのフレ キシブルプリント基板等に好適な両面導体ポリイミド積層体の連続製造方法に関し、 特に加熱プレスロールを利用したシヮの発生のな 、、し力も品質バラツキもな 、ロー ル卷き製品として安定生産が可能な両面導体ポリイミド積層体の連続製造方法に関 する。
背景技術
[0002] 近年、高機能化する携帯電話やデシタルカメラ、ナビゲーター、その他の各種電子 機器類の小型化、軽量ィ匕の進展に伴って、これらに使用される電子配線材料として のフレキシブルプリント基板 (配線基板)の小型高密度化、多層化、ファイン化、低誘 電ィ匕等の要請が高まっている。このフレキシブルプリント配線基板については、以前 はポリイミドフィルムと金属箔とを低温硬化可能な接着剤で張り合わせて製造されて いたが、接着剤層が配線基板としての特性の低下、特にポリイミドベースフィルムの 優れた耐熱性、難燃性等を損ねるという問題がある。さらに接着剤層を有する他の問 題として配線の回路カ卩ェ性が悪くなるという問題もある。
[0003] 具体的には、スルーホールカ卩ェ時のドリリングによる榭脂スミアの発生や、導体スル 一ホール加工時の寸法変化率が大きい等の問題が挙げられる。特に両面スルーホ ール構造の場合 (絶縁体層であるベースフィルムを中心にその両面に接着剤を介し て導体の銅箔等を貼り合わせて形成されたもの等）は、片面構造のフレキシブルプリ ント基板と比較して一般的にその柔軟性が低いという問題がある。一方、 ICの高密度 ィ匕、プリント配線の微細化や高密度化に伴い、発熱が大きくなり、良熱伝導体を貼り 合わせることが必要になる場合がある。また、よりコンパクトにするため、ハウジングと 配線を一体化する方法もある。さらには、電気容量の異なった配線を必要としたり、よ り高温に耐える配線材を必要とすることもある。そこで、接着剤を使用しないで硬化前 のポリアミック酸溶液を銅箔等の導体に直接塗布し、加熱して硬化させるフレキシブ
Figure imgf000004_0001
、る。
[0004] 例えば、硬化物の線膨張係数が 3. 0 X 10— 5以下のジァミンとテトラカルボン酸無水 物で合成されるポリアミック酸を金属箔に塗布し加熱硬化させるもの（例えば特許文 献 1参照)や、特定構造単位を有するポリアミドイミド前駆体化合物を含有する榭脂溶 液を導体上に塗布してイミドィ匕するもの（例えば特許文献 2参照）、ジァミノベンズァ- リド又はその誘導体を含むジァミン類と芳香族テトラカルボンサンとの反応で得られる 構造単位を有する絶縁材の前駆体溶液を導体上に直接塗布して硬化させるもの (例 えば特許文献 3参照)等が挙げられる。さらに金属箔との密着性を高めるために導体 上に複数のポリイミド前駆体榭脂溶液を用いて、複数回塗布と乾燥を行うことによつ て複数のポリイミド榭脂層を有するフレキシブルプリント配線用基板を製造する方法（ 例えば特許文献 4参照)も提案されている。
[0005] これらのフレキシブルプリント配線基板は、導電性金属箔の片面側のみに接着剤な しで絶縁体層を加熱硬化にて接着させた片面構造に関するものである。一方、電子 機器類の小型化、軽量化に対応して本発明者等は、先に導電性金属箔 (M )の片 面に少なくとも三層のポリイミド層を有する片面導体積層体を使用し、そのポリイミド 層に導電性金属箔 (M2)を加熱加圧下に積層する両面導体ポリイミド積層体の製造 方法 (例えば特許文献 5参照）を提案して!/ヽる。カゝかる両面導体積層体は特に基板 の両面に配線回路を形成することが可能であり、高密度実装のために既に実用化さ れて近年では種々の分野で多く採用されて 、る。
[0006] 上記の特許文献 5における両面導体ポリイミド積層体の製造方法では、熱プレス装 置等を利用したバッチ方式の具体例を開示して 、る。このバッチ方式の熱プレス装 置等では熱板と呼ばれる台座の上に、片面導体積層体と導電性金属箔の組合わせ を複数層同時に載せ加熱圧着するものである。通常の加熱は、熱板内に配置した電 気ヒーターによって行われ、圧力は油圧により台座が押し上げられシートを通じて上 部台座に圧力を伝達させて所定圧力を維持する。かかる熱板ではヒーターの温度ば らつきが大きいことから、種々の補正を行っても加熱不足や加熱過剰により部分的に 不良箇所が発生する場合がある。
[0007] また複数層同時に処理する場合、長時間の加熱により積層榭脂層の劣化が促進さ れ、品番毎の最適条件が狭い非常に不安定なプロセスであった。さらに積層基材は 常温から加熱加圧して一定温度に達した後冷却するバッチ方式のサイクルを繰返し て生産されるために生産効率が低いだけでなぐ積層基材の裁断作業が必要であり 、この時点で異物を巻き込みやすぐ異物が付着した場合、積層したもの全てに異物 の形状が転写する外観不良を起こすことが多力つた。そこで連続方式による品質の 安定した両面導体ポリイミド積層体の製造方法が強く要請されている。
特許文献 1：特開昭 62- 212140号公報
特許文献 2 :特開昭 63-84188号公報
特許文献 3：特開昭 63 - 245988号公報
特許文献 4:特公平 6 - 49185号公報
特許文献 5：特開平 10-323935号公報
発明の開示
発明が解決しょうとする課題
[0008] 本発明者等は、先に提案した特許文献 5における両面導体ポリイミド積層体の製造 方法における熱プレス装置等を利用したバッチ方式に代えて、一対の加熱プレス口 ールによる加熱圧着により両面導体ポリイミド積層体を連続製造する方法について検 討を進めた結果、プレスロール間への装入前における基材の搬送条件ゃ予熱手段 とプレスロール出口力 の搬送条件や冷却手段が適切でな 、と基材が通過中に熱 膨張'冷却収縮起因の格子じわ、集束じわ等の 10種類近いシヮの発生が見られるこ と、またロール面があまりに平滑度が高 、状態では基材とロール面との密着度が強く なって走行中に巻き付きによる複雑なシヮ（以下、トラレと称する)や不純物に起因す るピット (製品表面に数十ミクロンの打痕)等が多数発生しやす!/、こと等の種々の解決 すべき課題のあることがわかった。
[0009] 従って、本発明の目的は、ポリイミド系榭脂層の両面に接着剤を介することなく導電 性金属層を積層した縦じわ等の外観不良のない品質の安定した両面導体ポリイミド 系積層体の連続製造方法を提供することにある。また、本発明の他の目的は、特に ユーザー力ゝらの要望の強い優れた配線回路力卩ェ性を有し、また、配線回路基板とし て優れた耐熱性や可撓性を有する両面導体ポリイミド積層体をロール巻き状態にて 製造する方法を提供することにある。
課題を解決するための手段
[0010] 本発明者らは、上記課題について鋭意検討した結果、加熱プレスロール間に導入 直前の片面導体積層体と導電性金属箔 (M )を特定温度に予備加熱すること、プレ
2
スロール表面を特定の表面粗さ (Ra)に粗面化処理したものを使用することにより、上 記の目的が達成されることを見出し本発明を完成した。
[0011] すなわち本発明は、
(1)導電性金属箔 (M )上にベース層、中間メイン層、トップ層の少なくとも三層のポ リイミド系榭脂層を有する片面導体積層体と導電性金属箔 (M )
2からなる基材を連続 的に一対の加熱プレスロール間に導入し、上記トップ層に導電性金属箔 (M )をカロ
2 熱圧着により積層一体化させる両面導体ポリイミド積層体の製造方法において、加熱 プレスロール間に導入直前の片面導体積層体と導電性金属箔 (M それぞれ
2 )を 200
°C以上一トップ層のポリイミド系榭脂のガラス転移点以下に予備加熱後に加熱プレス ロール表面に接触させることを特徴とする両面導体ポリイミド積層体の連続製造方法 である。
[0012] (2)上記本発明における一対のプレスロール表面は平均表面粗さ（Ra)が 0. 01— 5 μ mに粗面化処理され、不活性ガス雰囲気下にてプレスロール表面温度を 340— 3 90。C、プレスロール間の線圧 50KgZcm— 300KgZcm(490— 2940NZcm)、 通過時間 2— 5秒間の条件下で加熱圧着することが望ましい。
[0013] (3)上記本発明における片面導体積層体と導電性金属箔 (M )はロール巻き状態か
2
ら引き出してそれぞれ中心軸の高さが異なる複数のガイドロールを経由させて窒素 雰囲気下の平面性を高めた状態で予備加熱されることが望ましい。
[0014] (4)上記本発明における予備加熱は基材が加熱プレスロール面に接触する位置に 配置された加熱手段内蔵のガイドロールによって行うことが望ましい。
[0015] (5)上記本発明におけるロール表面にセラミック皮膜が溶射されて表面粗さ (Ra)が 形成されて ヽることが望ま ヽ。
発明の効果
[0016] カゝかる本発明によれば、加熱プレスロール間に導入前の片面導体積層体と導電性 金属箔 (M )をそれぞれ不活性ガス雰囲気下にて 200°C以上
2 一ガラス転移点以下 の温度 (好ましくは 200— 350°C)で予備加熱後に加熱プレスロール表面に接触させ ることで、加熱圧着時の急激な温度上昇が緩和される結果、両面導体積層体の表面 への縦すじ等の外観不良が防止される。また加熱プレスロールの表面粗さを特定条 件に保持することで基材とロール面との密着度が減少することで走行中に巻き付きに よる複雑なシヮ（以下、トラレと称する)やピット (製品表面に数十ミクロンの打痕)等の 発生も防止される。
図面の簡単な説明
[0017] [図 1]本発明の両面導体ポリイミド積層体の製造方法を示す概略フローである。
[図 2]予備加熱用ガイドロールの一例を示す概略の縦断面図である。
[図 3]加熱プレスロールの一例を示す概略の縦断面図である。
符号の説明
[0018] 1 片面導体積層体
2 導電性金属箔
3 ガイドロール
3，予備加熱用ガイドロール
4 ガイドロール
4'予備加熱用ガイドロール
5 加熱プレスロール
6 加熱プレスロール
7 両面導体ポリイミド積層体
8 ガイドロール
9 ロール巻き製品
10 窒素ガス雰囲気の処理室
11 窒素シール機構
12 中心軸
13 ベアリング等による回転支持部材
14 加熱手段 17 ヒートパイプ
発明を実施するための最良の形態
[0019] 以下、本発明を実施するための最良の形態を詳細に説明する。先ず本発明におい て使用される導電性金属箔（Mと M )としては、厚みが 5— 150 mである銅、アルミ
1 2
ユウム、鉄、銀、パラジウム、ニッケル、クロム、モリブデン、タングステン、亜鉛及びそ れらの合金等を挙げることができ、好ましくは銅である。特に、剛性が低く加熱圧着に よる圧力制御が困難として使用が敬遠されていた圧延銅箔品も好適に使用できる。 なお接着力の向上を目的として、その表面にサイディング、ニッケルメツキ、銅-亜鉛 合金メッキ、あるいはアルミニウムアルコラート、アルミニウムキレート、シランカップリン グ剤等による化学的又は機械的な表面処理を施してもよい。
[0020] ここで力かる導電性金属箔 (M )の片面に絶縁体層としてポリイミド系榭脂が接着 剤なしに加熱硬化して接着させた片面導体積層体としては、前記特許文献 1一 4や 5 で開示された公知のものを利用することができる。絶縁体層として使用されるポリイミ ド系榭脂とは、イミド環構造を有する榭脂の総称であり、例えばポリイミド、ポリアミドィ ミド、ポリエステルイミドなどが挙げられる。そして、ポリイミド系榭脂層としては、前記 特許文献 1一 4に記載したような低熱膨張性のものや、加熱すると溶融若しくは軟ィ匕 する熱可塑性ポリイミド等が利用でき特に限定されな 、。し力 特に好ま U、絶縁体 層は、特許文献 5に記載されたポリイミド前駆体榭脂溶液の加熱硬化で得られた熱 可塑性ポリイミド系榭脂からなるベース層と低熱膨張性ポリイミド系榭脂からなる中間 メイン層及び熱可塑性ポリイミド系榭脂からなるトップ層の少なくとも三層のポリイミド 系榭脂層からなるものが望まし 、。
[0021] ここで中間メイン層を形成する低熱膨張ポリイミド系榭脂としては、その線膨張係数 が 30 X 10— 6 (1Z°C)以下が好ましぐフィルムの耐熱性、可撓性において優れた性 能を有するものがよい。ここで線膨張係数は、イミド化反応が十分に終了した試料を 用い、サーモメカ-カルアナライザー（TMA)を用いて 250°Cに昇温後、 10°CZ分 の速度で冷却し、 240— 100°Cの範囲における平均の線膨張係数を求めたものであ る。このような性質を有する低熱膨張ポリイミド系榭脂の具体例としては、前記特許文 献 5に記載された下記一般式 (I)で表される単位構造を有するポリイミド系榭脂が望 ましい
[0022] [化 1]
Figure imgf000009_0001
(但し、式中 R— R
1 4は低級アルキル基、低級アルコキシ基、ハロゲン基又は水素を 示す）
[0023] また、ベース層やトップ層に使用される熱可塑性ポリイミド系榭脂としては、そのガラ ス転移点温度が 350°C以下のものであればいかなる構造のものであってもよいが、 好ましくは加熱加圧下で圧着した際にその界面の接着強度が十分であるものがよい 。ここでいう熱可塑性ポリイミド系榭脂とは、ガラス転移点以上の通常の状態で必ずし も十分な流動性を示さなくてもよぐ加圧によって接着可能なものも含まれる。このよう な性質を有する熱可塑性ポリイミド系榭脂の具体例としては、前記特許文献 5に記載 された下記一般式 (Π)や一般式 (III)で表される単位構造を有するものである。
[0024] [化 2]
Figure imgf000009_0002
( 1 )
(但し、式中八 は 2価の芳香族基であってその炭素数が 12以上である。 )
[0025] [化 3]
Figure imgf000009_0003
(但し、式中 Arは 2価の芳香族基であってその炭素数が 12以上である。 )
2
[0026] ここで、 2価の芳香族基 Ar又 Arの具体例としては例えば
1 2 [0027] [化 4]
■ -0 - 、 、 - -^
Figure imgf000010_0001
0 -
CH3 CH3 等を挙げることができ、好ましくは、
[0028] [化 5]
Figure imgf000010_0002
である。
[0029] また片面導体積層体の製造方法としては、前記特許文献 5に記載されているように ポリイミド前駆体溶液又はポリイミド溶液に、公知の酸無水物系ゃァミン系硬化剤等 の硬化剤、シランカップリング剤、チタネートカップリング剤、エポキシィ匕合物等の接 着性付与剤、ゴム等の可撓性付与剤等の各種の添加剤や触媒を加えて導電性金属 箔 (M )へ塗工し、次いで熱処理により熱硬化して片面導体積層体を得ることができ る。なお片面導体積層体は、導電性金属箔 (M )にベース層として熱可塑性ポリイミ ド系榭脂層を、中間メイン層に低熱膨張性ポリイミド系榭脂層を、さらにトップ層（最表 面層）として熱可塑性ポリイミド系榭脂層が積層されていることが好ましい。ここで、中 間メイン層に低熱膨張性ポリイミド系榭脂層を含まな ヽ場合は、加熱硬化工程で得ら れる片面導体積層体の反りやカールが大きくなり、以後の工程での作業性が著しく 低下する。また、トップ層（最表面層）に熱可塑性ポリイミド系榭脂層を含まないと、加 熱圧着ロール工程での導電性金属箔との熱圧着による接着力が十分に発揮されな いので好ましくない。
[0030] その際、低熱膨張性ポリイミド系榭脂層の厚み と熱可塑性ポリイミド系榭脂層の厚 み tの厚さの比（t Zt )は 2— 100の範囲、好ましくは 5— 20の範囲がよい。この厚さ
2 1 2
の比 (t Zt )が 2より小さいと、ポリイミド系榭脂層全体の熱膨張係数が金属箔のそれ
1 2
に比べて高くなりすぎ、この第一の工程で得られる片面導体積層体の反りやカール が大きくなり、次の第二の工程での作業性が著しく低下する。また、熱可塑性ポリイミ ド系榭脂層の厚み t力 、さすぎ、厚さの比 (t Zt )が looを超えるほどに大きくなると
2 1 2
、第二の工程の熱圧着による接着力が充分に、発揮されなくなる場合が生じる。
[0031] 導電性金属箔 (M )上へのこれら複数のポリイミド系榭脂の塗工は、その榭脂溶液 の形で行うことができるが、好ましくは前記特許文献 4や 5に記載されているようにそ の前駆体溶液の形で、複数の前駆体溶液の一括又は逐次の塗工あるいはイミド閉 環温度以下での脱溶剤処理の後、前駆体のポリイミドへの加熱変換を一括して行う のが好ましい。完全にポリイミドに変換された層の上にさらに別のポリイミド系前駆体 溶液を塗工し、熱処理してイミド閉環させると、各ポリイミド系榭脂層間の接着力が充 分に発揮されないことがあり、製品の両面積層体の品質を低下させる原因になる。
[0032] 導電性金属箔 (M )上にポリイミド系榭脂溶液あるいはその前駆体溶液 (ポリアミツ ク酸溶液）の塗工の方法としては、例えばナイフコーター、ダイコーター、ロールコー ター、カーテンコーター等を使用して公知の方法により行うことができ、特に厚塗りを 行う場合にはダイコーターやナイフコーターが適している。また、塗工に使用するポリ イミド系前駆体溶液のポリマー濃度は、ポリマーの重合度にもよる力 通常 5— 30重 量％、好ましくは 10— 20重量％である。ポリマー濃度が 5重量％より低いと一回のコ 一ティングで充分な膜厚が得られず、また、 30重量％より高くなると溶液粘度が高く なりすぎて塗工しずらくなる。
[0033] 導電性金属箔に均一な厚みに塗工されたポリアミック酸溶液は、次に熱処理によつ て溶剤が除去されさらにイミド閉環される。この場合、急激に高温で熱処理すると、榭 脂表面にスキン層が生成して溶剤が蒸発しずらくなつたり、発泡したりするので低温 から徐々に高温まで上昇させながら熱処理していくのが望ましい。この際の最終的な 熱処理温度としては、通常 300— 400°Cが好ましぐ 400°C以上ではポリイミドの熱分 解が徐々に起こり始め、また、 300°C以下ではポリイミド皮膜が導電性金属箔上に充 分に配向せず、平面性の良い片面導体積層体が得られない。このようにして形成さ れた絶縁体としてのポリイミド系榭脂層の全体の厚みは通常 10— 150 mである。
[0034] 以下、図面に従って詳細に説明する。図 1は、本発明の片面導体積層体と導電性 金属箔 (M )を一対のプレスロール間に導入し、加熱圧着により積層一体化させる両
2
面導体ポリイミド積層体の製造方法を示す概略フローである。図 2は予備加熱用ガイ ドロールの一例を示す概略の縦断面図である。図 3はプレスロールの一例を示す概 略の縦断面図である。
[0035] 図 1において、前述した導電性金属箔 (M )の片面にポリイミド系榭脂からなる絶縁 体層を加熱硬化して接着させた片面導体積層体 1と導電性金属箔 (M ) 2とは、共に
2
ロール巻き状態力も連続的に引き出されて中心軸の高さが異なる複数のガイドロー ル 3、 3'、 4、 4'等を経て平面性を高めた状態で予備加熱された後で、一対の加熱 プレスロール 5、 6の表面に接触した状態でプレスロール同士による加圧点を通過さ せることで、上記片面導体積層体 1のトップ層に導電性金属箔 (M )を加熱圧着によ
2
り積層一体化させた両面導体ポリイミド積層体 7を形成した後、適宜冷却用の不活性 ガス吹き付け等の冷却手段 cによって予備冷却し、以下、複数のガイドロール 8、 8'を 経て外気中でさらに冷却されつつロール巻き製品 9とされる。
[0036] ここで、複数のガイドロール 3、 3，、 4、 4，、 8、 8，等や一対の加熱プレスロール 5、 6 は導電性金属箔の酸ィ匕を防ぐために大気圧以上の窒素ガス等の不活性ガス雰囲気 下に保持された処理室 10内に配置され、且つ基材導入口及び積層体の排出口に はシール機構 (ラビリンスシール） 11を設けることが望ましい。ここで、ロール巻き状態 力も連続的に引き出される片面導体積層体 1と導電性金属箔 (M ) 2とは、図示され
2
ていないが処理室 10内に導入される前に、それぞれ中心軸の高さが異なる複数の ガイドロールを経由させて緊張状態で平面性を高めることが望ましい。また、処理室 1
0から引き出された後の両面導体ポリイミド積層体も、図示されていないがロール巻き 製品 9とされる前に外気中にてそれぞれ中心軸の高さが異なる複数のガイドロールに よる緊張状態で経由させて更に表面温度を下げることが望ましい。
[0037] 特に、本発明における平面性を高めた状態で予備加熱する手段としては、加熱プ レスロール 5. 6の直前のガイドロール 3，（4，）を加熱手段内蔵タイプとする力 又は 加熱プレスロール直前に加熱ランプ又は輻射エネルギーを放出するヒーター hや h
1 2 等を設置して予備加熱してもよぐ或いは両方の予備加熱手段を併用してもよい。こ こで特に好ましい加熱手段内蔵タイプの予備加熱用ガイドロールの一例を図 2によつ て説明する。図 2において、ガイドロール 3' (4' )は内部が空洞の外周部と空洞の両 端力も突出される中心軸 12とがロール外周部の両端内部に配置されたベアリング等 の回転支持部材 13を介して一体ィ匕され、且つロール外周部は中心軸 12の回りを該 回転支持部材 13で自由回転させる構造である。
[0038] またロール内部における中心軸 12には誘電加熱による加熱コイル、赤外線ヒータ、 抵抗加熱コイル等から選ばれる輻射熱による加熱制御手段 14が適宜分割又は一体 化されて固定されており、これら加熱手段へ流す電流値を変えることでロールの内壁 面へ照射する輻射熱エネルギーを制御する。また、ロール外表面付近には、加熱制 御手段より照射される輻射熱エネルギーで表面温度を均一加熱化するための熱伝 導性の良好な有機熱媒体が充填されたジャケット又はヒートパイプと呼ばれる熱伝導 素子 17が埋め込まれて配置されている。力かるヒートパイプは上記の中心軸 12の加 熱手段 14力もの熱伝達でロール外表面全体に瞬時に伝達されるので表面温度精度 が高ぐ軸方向の温度差が殆ど生じない。
[0039] ここで加熱プレスロール間に導入前の片面導体積層体 1と導電性金属箔 (M ) 2の
2 予備加熱温度としては、 200°C以上でトップ層榭脂である熱可塑性ポリイミド系榭脂 のガラス転移点以下の温度、好ましくは 200— 350°Cが望ましい。かかる予備加熱口 ール外表面温度はロール表面に埋め込まれた温度センサーにて監視し常時所定温 度を保持するように加熱制御手段 14へ供給する電流値を制御することが望ま 、。 予備加熱しな 、場合、或いは予備加熱温度が 200°C以下にぉ 、ては極めて薄!、金 属箔が加熱プレスロール間を通過時に急激に昇温されて圧着される結果、積層体の 表面で多数の縦すじ、横シヮゃ集束じわ等が発生することで外観不良につながるだ けでなぐ接着性が低くなる点で好ましくない。また、ガラス転移点以上ではポリイミド 系榭脂が劣化するので好ましくない。
[0040] 次に一対の加熱プレス 5 (6)は、図 3に示すように、構造的には図 2で説明した加熱 手段内蔵タイプのガイドロール 3' (4' )と同じで、図 2で付した符号と同じものは、図 2 で説明したものと同一の意味であるが、その直径が大きぐ且つ加熱手段が 14、 15、 16と 3分割されており、図示されていないが攪拌動力機構で強制回転させる構造で ある点が異なる。プレスロール外表面付近には、熱伝導性の良好な有機熱媒体が充 填されているジャケット又はヒートパイプと呼ばれる熱伝導素子 17が埋め込まれて表 面温度を均一化する手段が設けられている。プレスロール外表面温度は、熱可塑性 ポリイミド系榭脂のガラス転移点以上であることが望ましぐより好ましくは 360— 390 °Cの範囲内の設定値に制御する。力かるプレスロール外表面温度はロール表面に 埋め込まれた温度センサーにて監視し加熱手段 14、 15、 16へ供給する電流値を制 御することが望ましい。
[0041] また、上記一対の加熱プレスロール 5、 6は窒素雰囲気下において、図示されてい ないが上下に配置された少なくとも片方のプレスロールを中心軸 12の両側で保持し て所定の位置まで油圧又はギヤによる加圧手段で移動させて両者のギャップ調整を 行わせることで、導入される基材 1, 2に対して相互にプレスロールカゝら最適な加圧力 が伝達される。この場合の加熱プレスロール間の線圧は 50— 500KgZcm (490N /cm— 4900N/cm)、好ましくは 100— 300KgZcm (980NZcm— 2940NZc m)、通過時間 2— 5秒間の条件下で加熱圧着することが望ましい。
[0042] さらに使用される一対の加熱プレスロールは、プレスロールの平均表面粗さ（Ra)を 0. 01— 5 m、好ましくは 0. 1— 3 mの粗面化状態にて使用することが望ましい。 プレスロールの表面粗さ（Ra)が 0. 01 μ m以下では加熱ロール間から出てくる両面 導体ポリイミド積層体のロール密着によるトラレが発生して走行中にシヮが発生したり 、銅箔粉等の異物付着に起因するピット (製品表面に数十ミクロンの打痕、又は凹み )等の発生が避けられない。また 5 μ m以上ではロール表面の凹凸が積層体表面に 転写されるので好ましくない。ロール表面を上記範囲内の粗面とするにはセラミック皮 膜を溶射することで調整することができる。なお、表面粗さ (Ra)はダイヤ針による触 針式表面粗さ計にて求める。
[0043] なお、図 1において加熱プレスロール 5と 6にて片面導体積層体 1のトップ層に導電 性金属箔 (M )を加熱圧着により積層一体化させた両面導体ポリイミド積層体 7を形 成した後は、冷却用の不活性ガス吹き付け等の冷却手段 Cによって予備冷却するの が望ましいが、冷却手段 Cによる冷却温度は、あまりに急激に冷却した場合、積層体
7に反りが発生し好ましくないので、前記した予備加熱温度と同等の 200°C以上でト ップ層榭脂である熱可塑性ポリイミド系榭脂のガラス転移点以下の温度、好ましくは 2 00— 300oC力 S望まし ヽ。
[0044] 本発明で得られる両面導体型ポリイミド積層体は、絶縁体としてのポリイミド系榭脂 層の両面に導体としての導電性金属層を有し、外観が良好でシヮの発生がないしか も品質バラツキもないロール巻き製品であり、高機能化する携帯電話やデシタルカメ ラ、ナビゲーター、その他の各種電子機器類の小型化、軽量ィ匕の進展に伴って、使 用される電子配線材料として好適である。
実施例
[0045] 以下、実施例及び比較例に基づいて，本発明の実施の形態を具体的に説明する。
なお、以下の実施例及び比較例において、線膨張係数、片面銅張品のカール及び 接着力は以下の方法で測定した。
[0046] すなわち、線膨張係数はセイコー電子工業株式会社製サーモメカ-カルアナライ ザ一（TMA100)を用いて、 250°Cに昇温後に 10°CZ分の速度で冷却し、 240°C— 100°Cの間における平均線膨張係数を算出して求めた。片面銅張品のカールとして は、熱処理してイミド化した後における 100mm X 100mmの寸法の銅張品の極率半 径を測定した。
[0047] 片面銅張品の接着力は， JIS C5016 : 7. 1項に順じ、導体幅 3mmのパターンを 使用し、銅箔を 180° の方向に 50mmZ分の速度で引き剥がした時の値として求め た。
[0048] また、実施例及び比較例中では以下の略号を使用した。
PMDA:無水ピロメリット酸
BTDA: 3, 3' , 4, 4'一べンゾフエノンテトラカルボン酸無水物
DDE :4, 4ージアミノジフエ-ルエーテル
MABA： 2，—メトキシ— 4, 4，—ジァミノべンズァユリド
[0049] (合成例 1) ガラス製反応器に窒素を通じながら N, N—ジメチルァセトアミド 2, 532gを仕込み、 続いて攪拌下に 0. 5モルの DDEと 0. 5モルの MABAとを仕込み、その後完全に溶 解させた。この溶液を 10°Cに冷却し、反応液が 30°C以下の温度に保たれるように 1 モルの PMDAを少量ずつ添加し、添加終了後引き続 、て室温で 2時間攪拌を行 ヽ 、重合反応を完結させた。得られたポリイミド前駆体溶液はポリマー濃度 15重量％及 び B型粘度計による 25°Cでのみかけ粘度 lOOOmPa' sであった。
[0050] (合成例 2)
ジァミン成分として DDEの 1モルを使用し、酸無水物成分として BTDAの 1モルを 使用した以外は、合成例 1と同様にしてポリイミド前駆体溶液を調整した。得られたポ リイミド前駆体溶液はポリマー濃度 15重量％及び B型粘度計による 25°Cでのみかけ 粘度 300mPa · sであった。
[0051] (積層体の作製）
35 μ mロール状の電解銅箔（日鉱グールド社製)の粗ィ匕面にダイコーターを用いて 合成例 2で調整したポリイミド前駆体溶液 2を 12 mの厚みで均一に塗工した後、 12 0°Cの熱風乾燥炉で連続的に処理し溶剤を除去した。次にこのポリイミド前駆体層の 上からリバース式ロールコーターを用いて合成例 1で調整したポリイミド前駆体溶液 1 を 200 mの厚みで均一に塗工し、 120°Cの熱風乾燥炉で連続的に処理し溶剤を 除去した後、さらに合成例 2で調整したポリイミド前駆体溶液 2を 15 mの厚みで均 一に塗布し、次いで熱風乾燥炉で 30分間かけて 120°Cから 360°Cまで昇温させて 熱処理しイミドィ匕させ、ポリイミド榭脂層の厚みが 25 μ mで反りやカールのない平面 性の良好な片面銅張品 aを得た。この片面銅張品 aの銅箔層とポリイミド榭脂層との 間の 180° 引き剥がし強さ (JIS C— 5016)を測定した結果は 0. 8kgZcmであり、 エッチング後のフィルムの熱膨張係数は 23. 5 X 10— 6 (1Z°C)であった。
[0052] (実施例 1)
製造例で調整した片面絶縁体層の銅張品の横幅 500mmのロール巻きシートの榭 脂面と同じ横幅寸法の 35 mのロール巻きシートである圧延銅箔の粗ィ匕面とを、そ れぞれ窒素雰囲気下のガイドロールを経由して、一対の加熱プレスロール（外径は 3 00mm,幅 800mmで、表面付近には均一加熱手段としてナフタリンを封入したジャ ケット式のヒートパイプが埋め込まれ、内部の中心軸には誘電加熱コイルを内蔵させ た構造）間に導入する前で加熱手段内蔵タイプのガイドロール 3' (4' )にて予備加熱 後に、カロ熱プレスローノレ表面温度 360— 390oC、プレス口一ノレ間の線圧 150— 170 kg/cm,通過時間 2— 5秒間の範囲内で加熱圧着した。このとき、同じ基材材料、 同じ加熱プレスロール条件下での予備加熱しな ヽ場合と、予備加熱温度を 150°C、 250°C及び 340°Cに変更した場合について、得られた両面銅張品の表面状態を目 視にて調査した結果を表 1に示す。
[0053] [表 1]
Figure imgf000017_0001
[0054] (実施例 2)
上記の実施例 1において、加熱プレスロール表面の設定温度 360°C、プレスロール 間の線圧 150kgZcm、通過時間 3秒間に設定し、且つ加熱プレスロール間へ導入 される基材の予備加熱が無 ヽ場合と、予備加熱温度を 250°C及び 340°Cとした場合 のそれぞれについて、加熱プレスロールの表面粗さ（Ra)を 0. 01以下、 0. 05、 0. 2 0、 10. 0 mの 4段間に変化させた場合に得られた両面銅張品の表面状態を目視 にて調査した結果を表 2に示す。
[0055] [表 2] 温度 （で） R a m) 両面鲴張品の表面状態
予備加熱なし 0. 01以下 不良 （トラレによるシヮとピット発生）
0. 05 不良 （多数の縦すじ、 横シヮ発生）
0. 20 不良 （多数の縦すじ、 横シヮ発生）
10. 0 凹凸の発生
250 0. 01以下 不良 （トラレによるシヮとピット発生）
0. 05 外観良好
0. 20 良好）
10. 0 凹凸の発生
340 0. 01以下 不良 （トラレによるシヮとピット発生）
0. 05 外観良好
0. 20 外観良好
10. 0 凹凸の発生 産業上の利用可能性
本発明の両面導体ポリイミド積層体の製造方法は、縦じわ等の外観不良のない品 質の安定した両面導体ポリイミド系積層体をロール巻き状態にて、両面導体ポリイミド 積層体を連続的に製造できる産業上の利用可能性の高い製造方法である。

Claims

請求の範囲
[1] 導電性金属箔 (M^上にベース層、中間メイン層、トップ層の少なくとも三層のポリィ ミド系榭脂層を有する片面導体積層体と導電性金属箔 (M )
2からなる基材を連続的 に一対の加熱プレスロール間に導入し、上記トップ層に導電性金属箔 (M )を加熱
2 圧着により積層一体化させる両面導体ポリイミド積層体の製造方法において、加熱プ レスロール間に導入前の片面導体積層体と導電性金属箔 (M )をそれぞれ不活性
2
ガス雰囲気下にて 200°C以上一トップ層のポリイミド系榭脂のガラス転移点以下に予 備加熱後に加熱プレスロール表面に接触させることを特徴とする両面導体ポリイミド 積層体の連続製造方法。
[2] 上記一対の加熱プレスロールの平均表面粗さ（Ra)が 0. 01— 5 μ mに粗面化処理 され、且つその表面温度を 340— 390°C、プレスロール間の線圧 50Kg/cm— 300 Kg/cm,通過時間 2— 5秒間の条件下で加熱圧着する請求項 1に記載の両面導体 ポリイミド積層体の連続製造方法。
[3] 上記片面導体積層体と導電性金属箔 (M )はロール巻き状態から引き出してそれ
2
ぞれ中心軸の高さが異なる複数のガイドロールを経由させて平面性を高めた状態で 予備加熱される請求項 1又は 2に記載の両面導体ポリイミド積層体の連続製造方法。
[4] 予備加熱は加熱手段内蔵のガイドロールによって行う請求項 1一 3のいずれかに記 載の両面導体ポリイミド積層体の連続製造方法。
[5] ロール表面にセラミック皮膜が溶射されて表面粗さ (Ra)が形成されて!ヽる請求項 2 に記載の両面導体ポリイミド積層体の連続製造方法。
PCT/JP2004/019523 2004-01-16 2004-12-27 両面導体ポリイミド積層体の連続製造方法 WO2005068183A1 (ja)

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