WO2011089930A1 - 銅張積層板の製造方法、それに用いる銅箔、及び銅張積層板のラミネート装置。 - Google Patents

銅張積層板の製造方法、それに用いる銅箔、及び銅張積層板のラミネート装置。 Download PDF

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Publication number
WO2011089930A1
WO2011089930A1 PCT/JP2011/050085 JP2011050085W WO2011089930A1 WO 2011089930 A1 WO2011089930 A1 WO 2011089930A1 JP 2011050085 W JP2011050085 W JP 2011050085W WO 2011089930 A1 WO2011089930 A1 WO 2011089930A1
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WIPO (PCT)
Prior art keywords
copper foil
copper
clad laminate
laminating
preheating
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PCT/JP2011/050085
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English (en)
French (fr)
Japanese (ja)
Inventor
嘉一郎 中室
小野　俊之
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Jx日鉱日石金属株式会社
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Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020127018565A priority Critical patent/KR101396218B1/ko
Priority to CN2011800067449A priority patent/CN102712138A/zh
Publication of WO2011089930A1 publication Critical patent/WO2011089930A1/ja

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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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/56—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using mechanical means or mechanical connections, e.g. form-fits
    • B29C65/64—Joining a non-plastics element to a plastics element, e.g. by force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
    • 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
    • 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
    • B29C66/9161—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 heat or the thermal flux, i.e. the heat flux
    • B29C66/91641—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 heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time
    • B29C66/91643—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 heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-time profile
    • B29C66/91645—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 heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—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 metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
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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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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • B29C65/44—Joining a heated non plastics element to a plastics element
    • 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
    • B29C66/74—Joining plastics material to non-plastics material
    • B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
    • B29C66/7428—Transition metals or their alloys
    • B29C66/74281—Copper or alloys of copper
    • 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
    • B29C66/94—Measuring or controlling the joining process by measuring or controlling the time
    • B29C66/949—Measuring or controlling the joining process by measuring or controlling the time characterised by specific time values or ranges
    • 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
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • 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
    • H05K1/0393—Flexible materials
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/111—Preheating, e.g. before soldering

Definitions

  • the present invention relates to a flexible copper-clad laminate used for a flexible printed circuit board (FPC: Flexible ⁇ ⁇ Printed Circuit) suitably used for a bent portion of an electric circuit, a copper foil used therefor, and a copper clad laminate laminating apparatus. is there.
  • FPC Flexible ⁇ ⁇ Printed Circuit
  • FPCs used for bent parts of mobile phones, etc. are coated with a polyimide varnish on copper foil, dried and cured by heating, and a method called the cast method, which is bonded in advance. It is manufactured by a method called a laminating method in which a polyimide film coated with a strong thermoplastic polyimide and a copper foil are stacked and pressure-bonded through a heating roll or the like.
  • the flexible copper-clad laminate obtained by these methods is called a two-layer flexible copper-clad laminate.
  • a three-layer flexible copper-clad laminate in which a copper foil and a polyimide film are bonded with an epoxy-based adhesive is also known.
  • Patent Documents 1 and 2 As these FPC copper foils, a technique is known in which the I / I0 of the 200 plane that gives reflex annealing and gives flexibility is 40 or more (Patent Documents 1 and 2). Furthermore, the present inventors have reported a technique for reducing the laminating speed to some extent, increasing the crystal grain size of the copper foil, and improving the flexibility when producing a two-layer flexible copper-clad laminate by the laminating method. (Patent Document 3).
  • JP 2001-323354 A (paragraph 0014) Japanese Patent Laid-Open No. 11-286760 JP 2009-292090 A (Claim 3)
  • CCL Copper Clad Laminate: copper clad laminate
  • the degree of orientation of the copper foil in the (200) direction does not increase and the flexibility is lowered.
  • the technique described in Patent Document 3 slows the laminating speed to a certain extent, and slowly heats the copper foil during laminating to increase the degree of orientation in the (200) direction.
  • the objective of this invention is providing the manufacturing method of the copper clad laminated board excellent in both flexibility and productivity, the copper foil used for it, and the laminating apparatus of a copper clad laminated board.
  • the copper foil is heated up to an ultimate temperature of 220 to 280 ° C. within 3 seconds, and Pre-heating is held for 1 to 5 seconds at the ultimate temperature.
  • the area ratio occupied by recrystallized grains in the copper foil is a metal structure on the surface of the copper foil.
  • Preheating is performed so that the tensile strength of the copper foil after the preheating is 10% to 80% and becomes 40 to 90% of the tensile strength before the preheating.
  • the preheating is preferably performed in the same line as the heating lamination.
  • the preheating is preferably performed by direct contact between the copper foil and a heat source or radiant heat from the heat source.
  • the copper foil of the present invention is a copper foil used in the above-described method for producing a copper clad laminate, and when it is brought into direct contact with a heat source maintained at 250 ° C. for 1 to 5 seconds, it re-appears in the metal structure on its surface.
  • the area ratio of the crystal grains is 10 to 80%, and the tensile strength of the copper foil after the contact is 40 to 90% of the tensile strength before the contact, and then the heat source maintained at 350 ° C.
  • I / I0 (200) is 60 or more when in direct contact for 1 to 5 seconds. Further, the area occupied by the recrystallized grains may be 10 to 80%, more preferably 40 to 80%. This is because, in this case, the I / I0 (200) exceeds 65 when it is brought into direct contact with a heat source maintained at 350 ° C. for 1 to 5 seconds, and higher flexibility is obtained.
  • the copper foil of the present invention preferably contains a total of 0.05% by mass or less of one or more selected from the group consisting of Ag and Sn.
  • the copper clad laminate laminating apparatus of the present invention is a copper clad laminate laminating apparatus for continuously laminating a copper foil and a resin layer, the preheating apparatus preheating the copper foil, and the preheating. It is arranged at the rear stage of the apparatus and includes a heat press machine for heating and laminating the resin layer and the preheated copper foil.
  • the most preferable metal structure for flexibility is a structure in which the cubic orientation is very developed and the crystal grain boundary is small, in other words, the crystal grain is large.
  • the degree of development of the cube orientation is expressed by the magnitude of the 200 plane X-ray diffraction intensity ratio I / I0 (I: 200 plane diffraction intensity of copper foil, I0: 200 plane diffraction intensity of copper powder). The larger this value, the more the cube orientation is developed.
  • the copper foil material before being laminated on the flexible copper-clad laminate can be sufficiently annealed in advance in a temperature range suitable for recrystallization in the (200) orientation to increase the degree of orientation in the (200) orientation. Flexibility is improved, but the recrystallized copper foil is very soft, so it tends to cause creases and wrinkles during handling. Therefore, in the copper foil coil before being attached to the laminating apparatus, the copper foil needs a certain degree of strength, and it is difficult to sufficiently increase the degree of orientation in the (200) direction.
  • the CCL can be given flexibility.
  • the copper foil coil is preheated on the line of the continuous laminator and immediately laminated with the resin layer on the same line, the copper foil is partially recrystallized before lamination without considering the strength of the copper foil.
  • the degree of orientation in the (200) direction can be improved and flexibility can be imparted.
  • FIG. 1 shows a configuration example of a laminating apparatus 1 for a copper clad laminate of the present invention.
  • the laminating apparatus 1 in FIG. 1 is an apparatus for double-sided CCL.
  • a varnish-like resin composition 2a is applied to the first copper foil 4 and cured to form the resin layer 2.
  • the 2nd copper foil 6 is piled up on the resin layer 2 surface of this single-sided CCL, and it heat-stacks with the lamination rolls 20 and 21.
  • a laminating apparatus 1 includes a pair of heat rolls (preliminary heating apparatuses) 30 and 31 for preheating a copper foil 6, and a pair of laminating rolls 20 and 21 arranged at the subsequent stage of the heat rolls 30 and 31. (Heating press).
  • the coiled copper foil 6 is unwound and immediately introduced into the laminating rolls 20 and 21 immediately after being preheated by the heat rolls 30 and 31 (on the same line of the laminating apparatus 1).
  • the heat rolls 30 and 31 and the laminating rolls 20 and 21 are on the same line of the laminating apparatus 1.
  • the heat rolls 30 and 31 are located immediately before the laminate rolls 20 and 21 (there are no other rolls between the heat rolls 30 and 31 and the laminate rolls 20 and 21). For this reason, the copper foil 6 can be sufficiently preheated by the heat rolls 30 and 31 and recrystallized without considering the strength of the copper foil, and then introduced into the laminate rolls 20 and 21.
  • the coil-shaped 1st copper foil 4 is continuously unwound, and the varnish-like resin composition 2a is continuously apply
  • FIG. This resin composition 2a becomes the resin layer 2 after curing.
  • coated resin composition 2a is introduce
  • the coil is wound into a coil shape and the process proceeds to the second step.
  • the coiled second copper foil 6 is continuously unwound and heated up to a temperature of 220 to 280 ° C. by the heat rolls 30 and 31 within 3 seconds, and at this temperature reached from 1 second to 5 seconds. Perform preheating for 2 seconds. Thereby, the 2nd copper foil 6 is laminated in the state recrystallized moderately.
  • this preheating may be performed with a single heating device or a plurality of heating devices as long as the conditions of the temperature rise and the holding temperature are within the above condition range.
  • the recrystallization texture of the copper foil 6 does not sufficiently develop when the holding time at the above-described temperature is less than 1 second. This is presumably because nucleation of recrystallized grains occurs randomly before each preferred orientation grows, and each grows.
  • the holding time at the above-mentioned ultimate temperature is 1 second or more, only the preferred orientation that is easy to recrystallize can be nucleated, and the preferred orientation produced by preheating due to the heating during the heat lamination in the subsequent laminating method. Can grow nuclei.
  • the holding time exceeds 5 seconds, the productivity decreases.
  • the ultimate temperature is less than 220 ° C., the recrystallized texture of the copper foil 6 does not sufficiently develop, and the holding time becomes long, so the productivity is lowered.
  • the ultimate temperature exceeds 280 ° C. the entire copper foil is recrystallized and becomes almost completely softened, so that the strength is lowered and heating lamination becomes difficult.
  • the copper foil when the copper foil is heated to a high temperature in a short time, nucleation of recrystallized grains occurs randomly before the preferred orientation grows, and the degree of orientation in the (200) orientation does not increase.
  • the ultimate temperature exceeds 280 ° C., the copper foil surface is oxidized and the etching property and the adhesion to the resin layer are lowered, or the rust preventive agent on the copper foil surface is volatilized and the storability is lowered.
  • the recrystallization rate of copper foil 6 (area ratio occupied by recrystallized grains in the metal structure on the surface of copper foil 6) is adjusted to 10 to 80%, and the tensile strength is adjusted to 40 to 90% before preheating. Is done.
  • the “tensile strength ratio” is defined by ((tensile strength after preheating) / (tensile strength before preheating)) ⁇ 100.
  • FIG. 2 schematically shows the relationship between the recrystallization rate of copper foil and the tensile strength ratio by preheating.
  • the recrystallization rate is less than 10%, the recrystallization texture of the copper foil 6 does not develop sufficiently, and when the recrystallization rate exceeds 80%, the entire copper foil is recrystallized and becomes almost completely softened. Lowering makes heating lamination difficult. If the tensile strength exceeds 90% before preheating, the recrystallization rate is also less than 10%, and the recrystallization texture of the copper foil 6 is not sufficiently developed. When the tensile strength is less than 40% before the preheating, the recrystallization rate also exceeds 80%, and the entire copper foil is recrystallized, which is close to complete softening.
  • Preheating may be performed on a separate line from the heat lamination (laminating press) using the laminating rolls 20, 21 or the like, or may be performed on the same line.
  • the preheating method is not particularly limited, but it is preferably performed by direct contact between the copper foil and the heat source or radiant heat from the heat source.
  • a convection heating device such as an annealing furnace
  • a laminate heating press to increase the equipment size It is difficult to install on the same line as the machine.
  • Specific examples of the direct contact method between the copper foil and the heat source include the heat rolls 30 and 31 described above.
  • Specific examples of the radiant heat method from a heat source include infrared heating (IR heating).
  • the resin layer 2 (having the first copper foil 4 laminated on the back surface) and the second copper foil 6 are continuously passed between the laminating rolls 20 and 21 heated to 350 to 400 ° C. Foil.
  • the 2nd copper foil 6 is match
  • the double-sided copper clad laminate 8 is appropriately wound around a coil.
  • the copper foil (corresponding to the second copper foil 6) used in the method for producing a copper clad laminate of the present invention has its surface metal when directly contacted with a heat source maintained at 250 ° C. for 1 to 5 seconds.
  • the area ratio of the recrystallized grains in the structure is 10 to 80%, and the tensile strength of the copper foil after the contact is 40 to 90% of the tensile strength before the contact, and then maintained at 350 ° C. It has a characteristic that I / I0 (200) is 60 or more when directly in contact with a heat source for 1 to 5 seconds.
  • the characteristics of the copper foil after contact with the heat source maintained at 250 ° C. represent the characteristics obtained by the preheating.
  • the characteristics when directly in contact with a heat source maintained at 350 ° C for 1 to 5 seconds represent the characteristics obtained by heating at the time of laminating, and I / I0 (200) is 60 or more. If it exists, it is excellent in the flexibility of obtained CCL.
  • the composition of the copper foil used for the copper clad laminated board manufacturing method of this invention Tough pitch copper (JIS-1100), oxygen-free copper (JIS-1020), and these from the group of Ag and Sn Those containing a total of 0.05% by mass or less of one or more kinds selected are preferable. If the total amount of one or more selected from the group of Ag and Sn exceeds 0.05% by mass, recrystallization of the copper foil is hindered, so that a predetermined structure may not be obtained by preheating.
  • the semi-softening temperature of the copper foil is preferably 100 ° C. to 200 ° C.
  • the semi-softening temperature is about 100 ° C. to 140 ° C.
  • the semi-softening temperature means an annealing temperature at which the strength after annealing for 30 minutes is an intermediate value between the strength before annealing and the strength in the complete recrystallization state.
  • the resin layer 2 polyimide; PET (polyethylene terephthalate); thermosetting resin such as epoxy resin and phenol resin; and thermoplastic resin such as saturated polyester resin can be used, but not limited thereto.
  • a varnish for example, a polyamic acid solution of a polyimide precursor
  • a solvent is removed by heating to react (for example, The imidization reaction) may proceed to be cured.
  • the thickness of the resin layer 2 can be set to about 1 to 15 ⁇ m, for example.
  • a film-like material may be used as the resin layer 2, and this may be heated and laminated on the first copper foil 4 and / or the second copper foil 6.
  • the copper foil 6 is combined on the surface of the resin layer 2 and heated and laminated. It is good also as an apparatus which heat-stacks copper foil on both surfaces of a resin film other than an apparatus. In the latter case, two copper foils may be simultaneously heated and laminated on both sides of the resin film, or after the first copper foil is heated and laminated on one side of the resin film, the second copper foil may be laminated by heating. Good. In this case, it is preferable to provide a preheating device for preheating both the first copper foil and the second copper foil.
  • Examples of the laminating apparatus for the copper clad laminate for single-sided CCL include an apparatus for heating and laminating the first copper foil on one side of the resin film, and a preheating device for preheating the copper foil is provided. Furthermore, when the copper foil is heated and laminated on the resin film, it is preferable to use a resin film having an adhesive layer formed in advance on the resin film side, but the resin film and the copper foil may be heated and laminated without using the adhesive layer. . In addition, the resin film and the adhesive layer having different compositions are the three-layer CCL. However, when the resin film and the adhesive layer have the same composition, the two-layer CCL in which the copper foil and the resin film are laminated is obtained after the heat lamination. .
  • ⁇ Copper foil> An ingot having the composition shown in Table 1 was manufactured, processed to about 10 mm by hot rolling, repeatedly manufactured by cold rolling and annealing, and pre-heated under the conditions shown in Table 1 after cold rolling. Was used. Preheating was performed by sandwiching a copper foil (CCL in the evaluation of flexibility described later) between two copper plates heated to a predetermined temperature. The composition of the copper foil is as shown in the table. The copper foil was rolled to a final working degree of 99% to a thickness of 18 ⁇ m. One side of the foil after the preheating was subjected to chemical treatment (copper-based rough plating) and provided for CCL lamination.
  • CCL copper foil
  • the recrystallization rate and tensile strength ratio of the copper foil before and after preheating were measured, and the semi-softening temperature of the copper foil after preheating was further measured.
  • the recrystallization rate was measured by observing the surface of the copper foil with an electron microscope, analyzing the binarized image, and calculating the area ratio of the recrystallized portion.
  • the tensile strength conformed to JIS.
  • the preheated copper foil was sandwiched between two copper plates heated to 350 ° C. and held for 1 second, and then the X-ray diffraction intensity ratio I / I0 on the 200 plane was measured.
  • thermoplastic polyimide adhesive on the surface is not a resin different from the polyimide film of the core part, but after being laminated with a copper foil, it becomes a base resin as a whole and becomes a two-layer flexible copper-clad laminate.
  • the two copper foils after the preheating described above are stacked so that the chemically treated surfaces face the films, and the films are sandwiched between the copper foils and laminated,
  • the film was heated and laminated (laminated) with a heating roll of about 300 ° C. at a foil passing rate of 3 m / min.
  • the transportability was evaluated as x when the CCL after lamination had five or more holes or cuts in the copper foil per 1 m of the plate length due to folding or wrinkling.
  • the productivity was evaluated as x when the preheating holding time exceeded 5 seconds.
  • TPC tough pitch copper (JIS-1100)
  • OFC oxygen-free copper
  • Ag 190 ppm-TPC represents a composition in which 190 mass ppm of Ag is added to TPC.
  • FIG. 3 shows a micrograph of the structure of the copper foil of Example 1 after preheating
  • FIG. 4 shows a micrograph of the structure of the copper foil of Example 1 after further heating at 350 ° C. for 1 second after preheating. Show. It can be seen that a recrystallized structure is partially generated by the preheating, and further the recrystallized structure is increased by heating at the time of lamination (350 ° C. ⁇ 1 second).
  • the comparative example 2 is the example which simulated the convection type heating apparatus (annealing furnace etc.) with a slow temperature increase rate.
  • the recrystallization rate was 100%, which was almost completely softened, the strength was lowered, and the transportability was inferior.
  • the degree of orientation of the 200 plane of the copper foil after heating at 350 ° C. for 1 second was also less than 60, and the flexibility of the obtained CCL was inferior.
  • Comparative Example 7 In the case of Comparative Example 7 in which the holding time during the preheating exceeds 5 seconds, the preheating time becomes long and the productivity is inferior, and the recrystallization rate becomes 100%, which is close to complete softening and the strength is lowered. Inferior transportability.
  • Comparative Example 8 In the case of Comparative Example 8 in which the amount of Sn added in the copper foil exceeded 0.05 mass% (500 ppm), recrystallization did not occur even when preheated, and the copper foil after heating at 350 ° C. for 1 second was 200 The degree of orientation of the surface was less than 60, and the flexibility of the obtained CCL was inferior.

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PCT/JP2011/050085 2010-01-21 2011-01-06 銅張積層板の製造方法、それに用いる銅箔、及び銅張積層板のラミネート装置。 WO2011089930A1 (ja)

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CN110475655B (zh) * 2017-03-28 2022-08-16 电化株式会社 层叠体的制造方法以及层叠体的制造装置
JP6647253B2 (ja) * 2017-08-03 2020-02-14 Ｊｘ金属株式会社 フレキシブルプリント基板用銅箔、それを用いた銅張積層体、フレキシブルプリント基板、及び電子機器
CN108405648B (zh) * 2018-02-27 2019-10-29 首钢京唐钢铁联合有限责任公司 一种抗毛边缺陷镀锡板的生产方法
CN110356093A (zh) * 2019-08-19 2019-10-22 江门建滔电子发展有限公司 一种制备覆铜箔层压板的装置及其方法
CN113211906B (zh) * 2021-05-10 2022-06-28 深圳市华鼎星科技有限公司 一种电路材料的贴合方法及所形成的材料
TWI777760B (zh) * 2021-08-09 2022-09-11 頎邦科技股份有限公司 具散熱片之軟性電路板及其散熱片

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