WO2023171705A1 - Procédé de fabrication d'une plaque stratifiée plaquée de métal unilatérale - Google Patents

Procédé de fabrication d'une plaque stratifiée plaquée de métal unilatérale Download PDF

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Publication number
WO2023171705A1
WO2023171705A1 PCT/JP2023/008788 JP2023008788W WO2023171705A1 WO 2023171705 A1 WO2023171705 A1 WO 2023171705A1 JP 2023008788 W JP2023008788 W JP 2023008788W WO 2023171705 A1 WO2023171705 A1 WO 2023171705A1
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Prior art keywords
adhesive sheet
thermoplastic resin
metal foil
resin layer
main surface
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PCT/JP2023/008788
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English (en)
Japanese (ja)
Inventor
寛司 下大迫
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株式会社カネカ
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Publication of WO2023171705A1 publication Critical patent/WO2023171705A1/fr

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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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

Definitions

  • the present invention relates to a method for manufacturing a single-sided metal-clad laminate.
  • Flexible printed wiring boards which include metal wiring formed by patterning a metal layer such as copper on a heat-resistant resin film such as a polyimide film, are used in various electronic devices.
  • a metal layer such as copper
  • a heat-resistant resin film such as a polyimide film
  • double-sided metal-clad laminates are used, in which metal foil such as copper is laminated on both sides of a heat-resistant resin film, and single-sided metal-clad laminates, in which metal foil is laminated on one side of a heat-resistant resin film. ing.
  • Single-sided metal-clad laminates are mainly used to manufacture multilayer FPCs.
  • a multilayer film As a manufacturing method for metal-clad laminates, a multilayer film is used that has thermoplastic resin layers that function as adhesive layers on both sides of a heat-resistant resin film (core layer), and metal foil is thermally laminated on the thermoplastic resin layer of the multilayer film.
  • a single-sided metal-clad laminate can be obtained by laminating metal foil on only one side of a multilayer film having thermoplastic resin layers on both sides of the core layer.
  • the thermoplastic resin layer on the side on which the metal foil is not laminated is fused to a hot roll, etc. during thermal lamination. This may cause problems such as
  • Patent Document 1 in a method for manufacturing a single-sided metal-clad laminate in which metal foil is laminated on one side of a multilayer film, the metal foil is placed on one side of the multilayer film, and a release film is placed on the other side, and then heat is applied. A method of laminating has been proposed.
  • Patent Document 2 a non-fusible or low-fusible surface layer is provided on the thermoplastic resin layer on one side of the multilayer film, and a metal foil is placed on the thermoplastic resin layer on the other side of the multilayer film.
  • a method of thermal lamination has been proposed.
  • thermoplastic resin layer As proposed in Patent Documents 1 and 2, metal rolls and the like can be manufactured by thermally laminating a release film and a surface layer on the thermoplastic resin layer on the side on which the metal foil is not laminated. It is possible to prevent the thermoplastic resin layer from adhering to the equipment.
  • the present invention uses a multilayer film that has thermoplastic resin layers on both sides of a heat-resistant resin film (core layer), and achieves higher productivity while preventing the thermoplastic resin layer from adhering to manufacturing equipment such as metal rolls.
  • the purpose is to provide a single-sided metal-clad laminate.
  • the present invention relates to an adhesive sheet having thermoplastic resin layers on both sides of a core layer made of a heat-resistant film, and a single-sided metal-clad laminate comprising a metal foil closely laminated to the thermoplastic resin layer on one side of the adhesive sheet. Regarding the manufacturing method.
  • the first metal foil, the first adhesive sheet, the second adhesive sheet, and the second metal foil are arranged so that the first main surface of the first adhesive sheet and the first main surface of the first metal foil face each other, and Heat lamination is performed with the second main surface and the second main surface of the second adhesive sheet facing each other, and the first main surface of the second adhesive sheet and the first main surface of the second metal foil facing each other. conduct.
  • a laminate in which the first metal foil, the first adhesive sheet, the second adhesive sheet, and the second metal foil are laminated is formed (lamination step). By peeling and separating this laminate between the first adhesive sheet and the second adhesive sheet (peeling step), the first metal foil is tightly laminated on the first main surface of the first adhesive sheet.
  • a single-sided metal-clad laminate and a second single-sided metal-clad laminate in which the second metal foil is closely laminated on the first main surface of the second adhesive sheet are obtained at the same time.
  • the first adhesive sheet and the second adhesive sheet include thermoplastic resin layers on both sides of a core layer made of a heat-resistant film.
  • the core layer of the adhesive sheet may be a non-thermoplastic polyimide film.
  • the thermoplastic resin layer of the adhesive sheet may contain thermoplastic polyimide resin.
  • the adhesive sheet may have a tensile modulus of elasticity of 0.05 to 1.5 GPa at a temperature of 350°C.
  • the metal foil is brought into contact with a thermocompression bonding means to carry out thermal lamination without placing other layers on the second main surface of the first metal foil and the second main surface of the second metal foil.
  • a surface protection film may be disposed on the second main surface of the first metal foil and/or on the second main surface of the second metal foil, and the surface of the metal foil is protected by the surface protection film.
  • Thermal lamination may be carried out.
  • peeling step in addition to peeling between the first adhesive sheet and the second adhesive sheet, peeling is also performed at the interface between the metal foil and the surface protection film.
  • thermoplastic resin layer (second thermoplastic resin layer) on the second main surface of the first adhesive sheet and the second Lamination may be performed so that the thermoplastic resin layer on the second main surface of the adhesive sheet (second thermoplastic resin layer) is in contact with the adhesive sheet, and an intermediate protective film is placed between the first adhesive sheet and the second adhesive sheet.
  • Lamination may be performed by doing so.
  • the second thermoplastic resin layer of the first adhesive sheet and the second thermoplastic resin layer of the second adhesive sheet are separated in the peeling process. By peeling at the interface, the first adhesive sheet and the second adhesive sheet are peeled off.
  • the interface between the second thermoplastic resin layer of the first adhesive sheet and the intermediate protective film, and the interface of the second adhesive sheet Peeling occurs between the first adhesive sheet and the second adhesive sheet by peeling at the interface between the second thermoplastic resin layer and the intermediate protective film.
  • thermocompression bonding means such as a hot roll
  • problems such as fusion of the thermoplastic resin layer to the thermocompression bonding means can be prevented.
  • two single-sided metal laminates can be obtained at the same time through one-time thermal lamination, the productivity of single-sided metal-clad laminates can be greatly improved.
  • FIG. 1 is a cross-sectional view of a single-sided metal-clad laminate according to an embodiment.
  • FIG. 2 is a cross-sectional view schematically showing an example of a manufacturing process of a single-sided metal-clad laminate.
  • FIG. 2 is a cross-sectional view schematically showing an example of a manufacturing process of a single-sided metal-clad laminate.
  • FIG. 2 is a cross-sectional view schematically showing an example of a manufacturing process of a single-sided metal-clad laminate.
  • FIG. 2 is a cross-sectional view schematically showing an example of a manufacturing process of a single-sided metal-clad laminate.
  • FIG. 1 is a cross-sectional view showing the laminated structure of a single-sided metal-clad laminate.
  • the single-sided metal-clad laminate 20 includes a metal foil 5 closely laminated on one side of the adhesive sheet 1.
  • the adhesive sheet 1 is a multilayer film that includes thermoplastic resin layers 11 and 12 that function as adhesive layers on both sides of a core layer 10.
  • the metal foil 5 is laminated on the first thermoplastic resin layer 11 on one side of the adhesive sheet 1.
  • No metal foil is provided on the second thermoplastic resin layer 12 on the other side of the adhesive sheet 1, and the thermoplastic resin layer 12 is exposed.
  • first principal surface the main surface of the adhesive sheet on which the metal foil is placed
  • second principal surface the side on which the metal foil will not be placed
  • first principal surface The principal surface on the side that is exposed
  • second principal surface The principal surface on the side that is exposed
  • first principal surface the principal surface on the side that is exposed
  • second principal surface the other principal surface
  • thermoplastic resin layer 11 provided on the first main surface of the core layer 10 is referred to as a "first thermoplastic resin layer”
  • thermoplastic resin layer 12 provided on the second main surface of the core layer 10 is referred to as "a first thermoplastic resin layer”. It may be described as "second thermoplastic resin layer”.
  • FIGS. 2A to 2C are cross-sectional views schematically showing the manufacturing process of a single-sided metal-clad laminate according to an embodiment of the present invention.
  • two adhesive sheets 101, 102 and two metal foils 151, 152 are stacked and thermally laminated to produce a laminate 502 (FIGS. 2A and 2B: lamination step), Peeling is performed between the two adhesive sheets 101 and 102 (FIG. 2C: peeling process).
  • FIGS. 2A to 2C peeling process
  • a second single-sided metal-clad laminate 122 in which the second metal foil 152 is bonded to the thermoplastic resin layer 121 is simultaneously obtained. That is, according to the method of the present invention, two single-sided metal-clad laminates can be obtained by one heat lamination.
  • the single-sided metal-clad laminate includes the metal foil 5 on one side of the adhesive sheet 1.
  • the adhesive sheet 1 is a multilayer film that includes thermoplastic resin layers 11 and 12 that function as adhesive layers on both sides of a core layer 10.
  • the core layer 10 is required to be able to withstand use at heating temperatures during thermal lamination in the FPC manufacturing process. Therefore, a highly heat resistant film is used as the core layer 10.
  • the resin material for the core layer 10 is preferably a polyimide film, a polyethylene naphthalate film, or the like, and a non-thermoplastic resin material that does not have thermoplasticity is particularly preferred.
  • a non-thermoplastic polyimide film is preferable for the core layer 10 because it has high heat resistance and excellent electrical properties.
  • the core layer 10 preferably contains 80% by weight or more, more preferably 90% by weight or more, of non-thermoplastic polyimide.
  • Non-thermoplastic polyimide is a polyimide that does not soften even when heated and does not exhibit adhesive properties. Specifically, “non-thermoplastic polyimide” includes polyimide that retains its shape without wrinkles or stretching when a single-layer polyimide film is heated at 380° C. for 2 minutes. Polyimides that do not substantially exhibit a glass transition temperature are also included in non-thermoplastic polyimides. The glass transition temperature is the temperature at which the storage modulus measured by a dynamic viscoelasticity analyzer (DMA) shows an inflection point.
  • DMA dynamic viscoelasticity analyzer
  • a resin material that "substantially does not have a glass transition temperature” refers to one that begins to thermally decompose before reaching the glass transition state.
  • Polyimide is generally obtained by preparing a polyimide precursor (polyamic acid) by polymerizing diamine and tetracarboxylic dianhydride, and then dehydrating and ring-closing the polyamic acid to imidize it.
  • a polyimide precursor polyamic acid
  • tetracarboxylic dianhydride a combination of an aromatic diamine and an aromatic tetracarboxylic dianhydride is preferably used as a monomer.
  • Aromatic diamines include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ propane, 2, 2-bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ hexafluoropropane, bis ⁇ 4-(3-aminophenoxy)phenyl ⁇ sulfone, bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ sulfone, 1,3- Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone , 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'
  • aromatic tetracarboxylic dianhydride examples include 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4 '-Oxydiphthalic dianhydride, 3,4'-oxyphthalic dianhydride, ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid anhydride), pyromellitic acid dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-te
  • Polyamic acid can be obtained by reacting diamine and tetracarboxylic dianhydride in substantially equimolar amounts.
  • the order of addition, combination of monomers, and composition are not particularly limited.
  • the organic solvent used in the polymerization of polyamic acid is not particularly limited as long as it can dissolve the diamine, tetracarboxylic dianhydride, and polyamic acid.
  • amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.
  • the polymerization temperature is preferably -10°C to 50°C.
  • the reaction time is not particularly limited, but is usually several minutes to several hours.
  • the solid content concentration of the polyamic acid solution is usually 5 to 35% by weight, preferably 10 to 30% by weight.
  • Polyimide is obtained by imidizing (dehydration ring closure) polyamic acid as a polyimide precursor.
  • a curing agent may be added to the polyamic acid solution.
  • Curing agents include dehydrating agents and imidization catalysts.
  • Dehydrating agents include aliphatic acid anhydrides, aromatic acid anhydrides, N,N'-dialkylcarbodiimides, lower aliphatic halides, halogenated lower aliphatic acid anhydrides, arylsulfonic acid dihalides, thionyl halides, etc. can be mentioned.
  • the imidization catalyst include aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines.
  • the core layer may contain a filler in addition to the non-thermoplastic polyimide resin.
  • a filler examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
  • thermoplastic resin layer examples of materials for the thermoplastic resin layers 11 and 12 provided on both sides of the core layer 10 include polycarbonate resins, acrylonitrile-styrene copolymer resins, thermoplastic polyimide resins, and the like. Among these, from the viewpoint of heat resistance and adhesion with the core layer, the thermoplastic resin layers 11 and 12 preferably contain a thermoplastic polyimide resin, and preferably contain 50% by weight or more of the thermoplastic polyimide resin.
  • thermoplastic resin layer 11 provided on the first main surface of the core layer 10 and the thermoplastic resin layer 12 provided on the second main surface of the core layer 10 may have the same composition, or may have different compositions. You may do so. From the viewpoint of suppressing warping of the adhesive sheet and single-sided metal-clad laminate and simplifying the manufacturing process, it is preferable that the thermoplastic resin layers 11 and 12 provided on both sides of the core layer have the same composition.
  • the thermoplastic resin layers 11 and 12 preferably have a glass transition temperature in the range of 150°C to 320°C.
  • the glass transition temperature of the thermoplastic resin layers 11 and 12 may be 200°C to 300°C.
  • the glass transition temperature is the temperature at which the storage modulus measured by a dynamic viscoelasticity analyzer (DMA) shows an inflection point.
  • DMA dynamic viscoelasticity analyzer
  • Thermoplastic polyimide like non-thermoplastic polyimide, is obtained by dehydration and ring closure of polyamic acid as a polyimide precursor. Also in the preparation of thermoplastic polyimide, a combination of an aromatic diamine and an aromatic tetracarboxylic dianhydride is preferably used as a monomer. Various properties of the polyimide can be adjusted by selecting the diamine and the tetracarboxylic dianhydride.
  • thermoplastic polyimide resin benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, biphenylsulfone tetracarboxylic dianhydride, etc. are used as the tetracarboxylic dianhydride. , those using an aromatic diamine having an aminophenoxy group as the diamine.
  • the ratio of aromatic diamine having a rigid structure in the diamine used for preparing the thermoplastic polyimide is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.
  • thermoplastic resin layers 11 and 12 on both sides of the core layer 10.
  • Polyimide obtained by imidization of polyamic acid obtained by polymerization of aromatic diamine and aromatic tetracarboxylic dianhydride has low solubility in organic solvents after imidization. Therefore, when the core layer 10 and the thermoplastic resin layers 11 and 12 are made of polyimide, it is preferable to perform imidization after forming a polyamic acid solution (polyimide precursor) into a film.
  • thermoplastic polyimide layers 11 and 12 When producing a multilayer polyimide film comprising thermoplastic polyimide layers 11 and 12 on both sides of a non-thermoplastic polyimide core layer 10 by multilayer coextrusion, as a precursor of the non-thermoplastic polyimide constituting the core layer 10.
  • a polyamic acid solution and a polyamic acid solution as a precursor of the thermoplastic polyimide constituting the thermoplastic resin layers 11 and 12 are coated in a film form on a supporting substrate by three-layer coextrusion, and heated as necessary. It is preferable to perform imidization by further heating after removing the solvent.
  • a curing agent may be added to the polyamic acid solution to promote imidization.
  • the curing agent may be added only to the polyimide precursor of the core layer 10, or to both the polyimide precursor of the core layer 10 and the polyimide precursors of the thermoplastic resin layers 11 and 12. may be added.
  • the polyimide of the core layer 10 and the thermoplastic resin layers 11 and 12 may be completely imidized, or may partially contain a structure that is not imidized (polyamic acid in an open ring state).
  • the thickness of the core layer 10 and the thickness of the thermoplastic resin layers 11 and 12 are not particularly limited, but the balance of the thicknesses is adjusted by considering the coefficient of linear expansion of each layer, etc. so that warpage does not occur in the multilayer film state. It is preferable.
  • the thickness of the core layer 10 is preferably 3 to 50 ⁇ m, more preferably 5 to 40 ⁇ m.
  • the thickness of each of the thermoplastic resin layers 11 and 12 is preferably 0.5 to 15 ⁇ m, more preferably 1 to 10 ⁇ m.
  • the thicknesses of the thermoplastic resin layers 11 and 12 provided on both sides of the core layer 10 may be the same or different. From the viewpoint of suppressing warpage, it is preferable that the difference between the thickness of the thermoplastic resin layer 11 and the thickness of the thermoplastic resin layer 12 is small.
  • the ratio of the thickness of the thermoplastic resin layer 11 to the thickness of the thermoplastic resin layer 12 is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. .
  • each of the thermoplastic resin layers 11 and 12 is preferably 0.05 to 0.5 times the thickness of the core layer 10, and may be about 0.1 to 0.4 times.
  • the total thickness of the adhesive sheet 1 is preferably 5 to 50 ⁇ m. If the thickness is within this range, it can be suitably used as a base material for FPC.
  • a commercially available product may be used as a multilayer film having thermoplastic resin layers on both sides of the core layer.
  • a multilayer polyimide film having a three-layer structure comprising a core layer of non-thermoplastic polyimide and thermoplastic polyimide layers on both sides
  • the "Pixio" series manufactured by Kaneka may be mentioned.
  • the adhesive sheet 1 preferably has a tensile modulus of 0.05 to 1.5 GPa at a temperature of 350°C. If the elastic modulus of the adhesive sheet 1 at the temperature during thermal lamination is too large, the adhesive sheet will be hard and lack cushioning properties against lamination pressure, which may cause poor appearance such as wrinkles during lamination. On the other hand, if the elastic modulus of the adhesive sheet 1 at the temperature during thermal lamination is excessively small, the adhesive sheet is likely to be deformed by the lamination pressure, resulting in the transfer of minute scratches on the surface of the heat roll or protective film, or due to adhering foreign matter. Visual defects due to dents, etc. are likely to occur.
  • the tensile modulus of the adhesive sheet 1 at a temperature of 350° C. is more preferably 0.08 to 1 GPa, even more preferably 0.1 to 0.7 GPa, and 0.12 to 0.6 GPa or 0.14 to 0.5 GPa. Good too.
  • the glass transition temperature of the thermoplastic resin layers 11 and 12 of the adhesive sheet 1, which is a multilayer film is generally less than 350°C
  • the tensile modulus at a temperature of 350°C is largely influenced by the characteristics of the core layer 10.
  • the core layer 10 is a non-thermoplastic polyimide film
  • a typical example of a tetracarboxylic dianhydride with a rigid structure is pyromellitic dianhydride (PMDA), and a typical example of a diamine with a rigid structure is p-phenylenediamine (PDA).
  • PMDA pyromellitic dianhydride
  • PDA p-phenylenediamine
  • Metal foil As the metal material of the metal foil 5, copper or a copper alloy, stainless steel or an alloy thereof, nickel or a nickel alloy (including 42 alloy), aluminum or an aluminum alloy, etc. are preferable because they have high conductivity. Since the metal foil 5 can be easily laminated, a metal foil is preferable, and like a general FPC, a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. A rust-proofing layer, a heat-resistant layer, an adhesive layer, etc. may be provided on the surface of the metal foil. The thickness of the metal foil 5 is not particularly limited, and may be selected depending on the configuration of the FPC and the required conductivity.
  • the thickness of the metal foil 5 is, for example, 3 to 30 ⁇ m, preferably 5 to 20 ⁇ m. From the viewpoint of adhesion to the thermoplastic resin layer, the surface roughness (Rz) of the metal foil 5 is preferably 0.01 ⁇ m to 1 ⁇ m.
  • the first metal foil 151 is a metal foil that is bonded to the thermoplastic resin layer 111 on the first main surface of the first adhesive sheet 101
  • the second metal foil 152 is a metal foil that is bonded to the thermoplastic resin layer 111 on the first main surface of the second adhesive sheet 102. This is a metal foil that is bonded to the plastic resin layer 121.
  • thermoplastic resin layer 111 on the first main surface of the first adhesive sheet 101 and the first main surface of the first metal foil 151 face each other
  • thermoplastic resin layer 111 on the first main surface of the second adhesive sheet 102 faces each other.
  • the resin layer 121 and the first main surface of the first metal foil 152 face each other
  • the thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 and the thermoplastic resin layer 112 on the second main surface of the second adhesive sheet 102 face each other.
  • the resin layers 122 are facing each other.
  • opposite means that two surfaces are arranged facing each other, and another layer may be interposed between the two surfaces.
  • an intermediate protective film 71 may be disposed between the first adhesive sheet 101 and the second adhesive sheet 102 (see FIGS. 3A and 5A).
  • the intermediate protective film 71 is disposed between the thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 and the thermoplastic resin layer 122 on the second main surface of the second adhesive sheet 102. Since the second main surface of the first adhesive sheet 101 and the second main surface of the second adhesive sheet 102 are arranged to face each other, the second main surface of the first adhesive sheet 101 and the second main surface of the second adhesive sheet 102 The two principal surfaces are opposite.
  • thermal lamination examples include batch-type thermo-compression bonding using a single plate press, continuous processing using a double belt press (DBP) device, thermo-compression bonding using a hot roll, and the like. From the viewpoint of productivity, it is preferable to carry out thermal lamination in a roll-to-roll manner using a thermal roll laminating device equipped with thermal rolls for heating and pressing the materials.
  • the hot roll laminating device is equipped with one or more pairs (two) of hot rolls, and thermal lamination is performed by sandwiching the object to be laminated between the two hot rolls and applying pressure while heating.
  • the nip rolls are preferably metal rolls because heating and temperature control are easy.
  • the heating temperature during thermal lamination is determined by the heat of the adhesive sheet. It is preferable that the temperature is higher than the glass transition temperature (Tg) of the plastic resin layer.
  • Tg glass transition temperature
  • the heating temperature is preferably (Tg+0)°C to (Tg+180)°C, more preferably (Tg+10)°C to (Tg+160)°C, and may be (Tg+20)°C to (Tg+150)°C.
  • the heating temperature may be 280-400°C, 300-380°C or 320-370°C.
  • a single-sided metal-clad laminate 122 is tightly laminated with the thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 and the thermoplastic resin layer 122 on the second main surface of the second adhesive sheet 102 interposed therebetween.
  • a stack 502 is formed (FIG. 2B). By peeling and separating this laminate 502 between the first adhesive film 101 and the second adhesive film 102, two single-sided metal-clad laminates 121 and 122 are obtained.
  • the interface between the thermoplastic resin layer 111 on the first main surface of the first adhesive sheet 101 and the first metal foil 151, and the thermoplastic resin layer on the first main surface of the second adhesive sheet 102 At the interface between the adhesive sheet 121 and the second metal foil 152, the adhesive sheet and the metal foil are firmly adhered, whereas the thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 and the second adhesive sheet Since the adhesive force at the interface of the thermoplastic resin layer 122 on the second main surface of the thermoplastic resin layer 102 is small, the laminate 502 can be easily peeled off between the first adhesive sheet and the second adhesive sheet.
  • the second main surfaces of the two adhesive sheets 101, 102 are arranged to face each other, and the thermoplastic resin layers 112, 122 on the second main surfaces of the adhesive sheets Since it does not come into contact with the thermocompression bonding means such as a hot roll, it is possible to prevent problems such as fusion of the thermoplastic resin layer to the thermocompression bonding means.
  • two single-sided metal laminates can be obtained at the same time by forming the laminate 502 through one-time thermal lamination and separating it between the adhesive sheets 101 and 102, which doubles the productivity of single-sided metal-clad laminates. do.
  • thermal lamination is preferably carried out using a hot roll laminating device that performs thermocompression bonding using hot rolls.
  • the first metal foil 151, the first adhesive sheet 101, the second adhesive sheet 102, and the second metal foil 152 constituting the laminate 502 are thermally laminated while being continuously conveyed, which improves productivity. Excellent.
  • the hot roll laminating device is equipped with a feeding device that unwinds and continuously feeds the laminated materials from the roll of each laminated material on the upstream side of the hot roll serving as a thermocompression bonding device, and a feeding device that continuously unwinds the laminated materials from the roll of each laminated material, and a laminating device on the downstream side of the hot roll.
  • a device equipped with a winding means for winding up the body into a rolled body is used.
  • a specific example of the feeding means and the winding means is a roll winding machine.
  • the laminate 502 formed by hot roll lamination may be wound up by a winding means with two single-sided metal-clad laminates stacked together, or a peeling process may be performed after hot lamination to separate the two sheets. After separating into single-sided metal-clad laminates, each of the two single-sided metal-clad laminates 121 and 122 may be wound up by a winding means.
  • thermoplastic resin layer 112 and the thermoplastic resin layer 122 on the second main surface of the second adhesive sheet 102 are in contact with each other.
  • the laminate obtained by the lamination step has an intermediate protective film 71 between the thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 and the thermoplastic resin layer 122 on the second main surface of the second adhesive sheet 102. may be placed.
  • the intermediate protective film 71 by performing thermal lamination with the intermediate protective film 71 disposed between the first adhesive sheet 101 and the second adhesive sheet 102, as shown in FIG. 3B, the intermediate protective film 71
  • the thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 is in contact with one surface (first main surface) of the intermediate protective film 71
  • the second adhesive sheet 102 is in contact with the other surface (second main surface) of the intermediate protective film 71.
  • a laminate 503 is obtained in which the thermoplastic resin layer 122 on the second main surface of the laminate 503 is in contact with the thermoplastic resin layer 122 .
  • thermoplastic resin layer 112 on the second main surface of the first adhesive sheet 101 and the intermediate protective film 71 are separated. Peeling occurs between the first adhesive sheet 101 and the second adhesive sheet 102 by peeling at the interface and the interface between the thermoplastic resin layer 122 on the second main surface of the second adhesive sheet 102 and the intermediate protective film 71. be exposed.
  • the second thermoplastic resin layer 112 of the first adhesive sheet 101 and the second thermoplastic resin layer 122 of the second adhesive sheet 102 do not come into contact with each other. Therefore, even if the adhesive strength of the thermoplastic resin layer of the adhesive sheet is high, the thermoplastic resin layers 112 and 122 of the two adhesive sheets 101 and 102 will not adhere to each other, making it possible to perform the peeling process stably. It becomes possible.
  • a surface protection material may be placed between a thermocompression bonding means (not shown) such as a heat roll and the metal foils 151 and 152.
  • a thermocompression bonding means such as a heat roll
  • a first surface protection film 91 is placed on the second main surface of the first metal foil 151
  • a second surface protection film 92 is placed on the second main surface of the second metal foil 152.
  • the first surface protection film 91 is laminated on the second main surface of the first metal foil 151, and the second main surface of the second metal foil 152 is laminated.
  • a laminate 504 on which the second surface protection film 92 is laminated is obtained.
  • the first metal Peeling is performed at the interface between the foil 151 and the first surface protection film 91 and the interface between the second metal foil 152 and the second surface protection film 92 to remove and remove the surface protection film from the surface of the single-sided metal-clad laminate.
  • thermocompression bonding means such as a heat roll and the metal foils 151 and 152 during heat lamination, and since the thermocompression bonding means and the metal foils do not come into direct contact with each other, the heat Appearance defects such as scratches on the metal foil during crimping can be reduced.
  • FIGS. 4A to 4C show a form in which surface protection films 91 and 92 are placed on the metal foils 151 and 152 on both sides, the surface protection films may be placed only on the metal foils on one side.
  • FIG. 4B when the laminate 504 after thermal lamination has a symmetrical laminate structure, the warping of the laminate and single-sided metal-clad laminate tends to be suppressed, so surface protection is applied on the metal foil.
  • an intermediate protective film 71 is disposed between the first adhesive sheet 101 and the second adhesive sheet 102, and a first surface protective film 91 is further disposed on the second main surface of the first metal foil 151.
  • heat lamination may be performed with the second surface protection film 92 disposed on the second main surface of the second metal foil 152.
  • the laminate 505 after thermal lamination is composed of first surface protection film 91/first adhesive sheet 101/intermediate protection film 71/second adhesive sheet 102/second surface protection film, as shown in FIG. 4B. 92 are laminated in order.
  • This laminate 505 is applied to the interface between the first surface protection film 91 and the first metal foil 151, the interface between the second surface protection film 92 and the second metal foil 152, the interface between the first adhesive sheet 101 and the intermediate protection film 71, and By peeling and separating the second adhesive sheet 102 and the intermediate protective film 71 at the interface, two single-sided metal-clad laminates 101 and 102 are obtained, as shown in FIG. 5C.
  • the surface protection films 91 and 92 placed on the surface of the metal foil and the intermediate protection film 71 placed between the two adhesive sheets prevent the thermocompression bonding means from fusing with the thermoplastic resin layer of the adhesive sheet, It can have functions such as preventing excessive fusion between thermoplastic resin layers and preventing wrinkles during thermal lamination.
  • These protective films are not particularly limited as long as they can withstand the heating temperature during thermocompression bonding, and heat-resistant resin films such as non-thermoplastic polyimide films, metal foils such as copper foil, aluminum foil, and SUS foil are suitable. used for.
  • heat-resistant resin films such as non-thermoplastic polyimide films, metal foils such as copper foil, aluminum foil, and SUS foil are suitable.
  • non-thermoplastic polyimide films are particularly preferred from the viewpoints of heat resistance, recyclability, and the like.
  • the thickness of the protective film is preferably 25 to 300 ⁇ m, more preferably 50 to 250 ⁇ m, and may be 75 to 200 ⁇ m.
  • non-thermoplastic polyimide film When using a non-thermoplastic polyimide film as a protective film, various known films can be used, such as the “Apical” series manufactured by Kaneka, the “Upilex” series manufactured by Ube Industries, and the “Kapton” series manufactured by DuPont Toray. You may use the commercially available polyimide film, such as.
  • the protective film When carrying out the process using the protective film shown in Figures 3 to 5 using a hot roll laminating device, the protective film is continuously fed out from the feeding means and then thermocompressed with the hot roll along with the metal foil and adhesive sheet. Just go. After the peeling process, the protective film peeled from the single-sided metal-clad laminate is wound into a roll by a winding means. This protective film may be reused. When reusing the protective film, it is preferable to wind it up so that the positions of both ends of the protective film in the width direction are constant. In order to align the positions of both ends of the film in the width direction, an end position detecting means and a winding position correcting means may be provided on the pass line of the hot roll laminating apparatus.
  • the single-sided metal-clad laminate 20 described above is suitably used for producing a flexible printed wiring board (FPC).
  • the FPC may be a multilayer printed wiring board in which a plurality of wiring layers are laminated with an insulating layer interposed therebetween.
  • adhesive sheet 1 serves as an insulating layer between multiple wiring layers.
  • a wiring layer (first wiring layer) is formed by patterning the metal foil 5 of the single-sided metal-clad laminate 20. Multilayering is achieved by laminating this single-sided wiring board with a board containing another wiring layer (second wiring layer). For example, the wiring layer-free surface (second thermoplastic resin layer 12) of a single-sided metal-clad laminate having a first wiring layer patterned with metal foil 5 may be bonded to the wiring layer (second wiring layer) of another board. By combining them, multilayering is achieved.
  • the thermoplastic resin layer 12 of the adhesive sheet 1 and the wiring layer of another board may be bonded together via an adhesive sheet such as a bonding sheet.
  • Polyamic acid solution A 50 parts by weight of a curing agent solution containing acetic anhydride/isoquinoline/DMF in a weight ratio of 33/10/57 was added, and the mixture was stirred and degassed at 0°C or lower to form a core layer forming solution. And so.
  • Polyamic acid solution B was diluted by adding DMF to a solid content concentration of 10% by weight, and stirred and defoamed at 0° C. or lower to obtain a solution for forming a thermoplastic resin layer.
  • thermoplastic resin layer dry thickness: 4 ⁇ m
  • solution for forming a core layer dry thickness: 17 ⁇ m
  • solution for forming a thermoplastic resin layer dry thickness: 4 ⁇ m
  • the self-supporting gel film was peeled off from the metal belt. Thereafter, it was heated at 300° C. for 56 seconds and at 380° C. for 49 seconds to obtain a multilayer polyimide film 1 having a total thickness of 25 ⁇ m and having thermoplastic polyimide layers on both sides of a core layer made of non-thermoplastic polyimide.
  • Polyamic acid solution D is used instead of polyamic acid solution A as the core layer forming solution
  • polyamic acid solution E is used instead of polyamic acid solution B as the thermoplastic resin layer forming solution, and added to the core layer forming solution.
  • Table 1 shows the compositions of the core layer and thermoplastic resin layer in the multilayer polyimide films of Production Examples 1 to 3, as well as the glass transition temperature (Tg) of the thermoplastic resin layer and the tensile modulus of the multilayer film at 350°C.
  • Tg glass transition temperature
  • diamines and tetracarboxylic dianhydrides are indicated by the following abbreviations.
  • Example 1 Using the multilayer polyimide film 1 as the adhesive sheet and the rolled copper foil with a thickness of 12 ⁇ m ("GHY5-93F-HA-V2" manufactured by JX Metals) as the metal foil, as shown in FIG. 2, copper foil/adhesive sheet/ With the laminated structure of adhesive sheet/copper foil, heat lamination was performed using a hot roll laminating device under the conditions of lamination temperature of 360°C, lamination pressure of 244 N/cm, and lamination speed of 1 m/min, and then between the two adhesive sheets. By peeling, two single-sided copper-clad laminates were obtained.
  • Example 2 Using a multilayer polyimide film 1 as an adhesive sheet, the laminated structure of protective film/copper foil/adhesive sheet/adhesive sheet/copper foil/protective film was used as shown in FIG. After thermal lamination was performed under the following conditions, peeling was performed between the two adhesive sheets and between the copper foil and the protective film to obtain two single-sided copper-clad laminates.
  • a non-thermoplastic polyimide film (“Apical 125NPI” manufactured by Kaneka) was used as the surface protection film disposed outside the upper and lower rolled copper foils.
  • Example 3 A single-sided copper-clad laminate was obtained in the same manner as in Example 1 except that the multilayer polyimide film 2 was used as the adhesive sheet.
  • Example 4 A single-sided copper-clad laminate was obtained in the same manner as in Example 1 except that the multilayer polyimide film 3 was used as the adhesive sheet.
  • ⁇ Warp> A single-sided copper-clad laminate was cut into a 5 cm x 5 cm square, and placed on a horizontal stand with the copper foil bonded side facing upward. The distance from the stand (amount of uplift) was measured for each of the four vertices of the square, and the average value was taken as the amount of warpage.
  • Table 2 shows the type and 350°C tensile modulus of the adhesive sheet (multilayer polyimide film) used in the Examples and Comparative Examples, the laminated structure during thermal lamination, and the evaluation results of the single-sided copper-clad laminate.
  • thermoplastic resin layer of the multilayer polyimide film stuck to the hot roll, and a single-sided copper temporary laminate could not be obtained.
  • thermoplastic resin layer of the multilayer polyimide film did not come into contact with the thermal roll, so thermal lamination was possible without any problems.
  • the copper-clad laminate of Example 1 which was obtained by peeling the laminate after thermal lamination at the interface of two adhesive sheets, was similar to the copper-clad laminate of Comparative Example 2, with the adhesion of the copper foil (peel It had high strength) and little warpage. A similar tendency was observed in the comparison between Example 3 and Comparative Example 3 and the comparison between Example 4 and Comparative Example 4.
  • Example 1 in which two adhesive sheets and two copper foils were thermally laminated, thermal lamination was possible without any problems because the thermoplastic resin layer of the multilayer polyimide film did not come into contact with the hot roll.
  • the copper-clad laminate of Example 1 which was obtained by peeling the laminate after heat lamination at the interface of two adhesive sheets, had the same adhesion of copper foil as the copper-clad laminate of Comparative Example 2. (peel strength) was high and warpage was small.
  • the single-sided copper-clad laminates of Examples 3 and 4 using multilayer polyimide films 2 and 3 showed no wrinkles or streaks, whereas the single-sided copper-clad laminates of Examples 1 and 2 using multilayer polyimide film 1 (and comparative The single-sided copper-clad laminate of Example 2) had poor appearance. Since the multilayer polyimide films 2 and 3 have a lower elastic modulus at high temperatures than the multilayer polyimide film 1, it is thought that the cushioning properties during thermal lamination are high, which suppresses the occurrence of wrinkles and streaks.
  • Adhesive sheet (multilayer film) 10,110,120 Core layer 11,12,111,112,121,122 Thermoplastic resin layer 5,151,152 Metal foil 20,121,121 Single-sided metal-clad laminate 71 Intermediate protective film 91,92 Surface protective film

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Abstract

La présente invention se rapporte à un procédé de fabrication d'une plaque stratifiée plaquée de métal unilatérale comprenant : des couches centrales (110, 120) constituées d'un film résistant à la chaleur ; et une feuille métallique (151, 152) stratifiée de manière adhésive sur des couches de résine thermoplastique (111, 121) sur un côté d'une feuille adhésive comprenant des couches de résine thermoplastique (111, 112, 121, 122) disposées des deux côtés des couches centrales. Une première feuille métallique (151), une première feuille adhésive (101), une seconde feuille adhésive (102) et une seconde feuille métallique (152) sont stratifiées thermiquement pour former un corps stratifié, et par pelage du corps stratifié entre la première feuille adhésive et la seconde feuille adhésive, une première plaque stratifiée plaquée de métal unilatérale (121) de la première feuille adhésive qui présente la première feuille métallique stratifiée de manière adhésive sur une première surface principale de celle-ci, et une seconde plaque stratifiée revêtue de métal unilatérale (122) de la seconde feuille adhésive qui présente la seconde feuille métallique stratifiée de manière adhésive sur une première surface principale de celle-ci sont obtenues en même temps.
PCT/JP2023/008788 2022-03-09 2023-03-08 Procédé de fabrication d'une plaque stratifiée plaquée de métal unilatérale WO2023171705A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07302977A (ja) * 1994-04-28 1995-11-14 Ibiden Co Ltd 多層プリント配線板の製造方法とそれに用いる銅張積層板
JP2007090581A (ja) * 2005-09-27 2007-04-12 Matsushita Electric Works Ltd 片面板の製造方法及びプリント配線板の製造方法
JP2007109694A (ja) * 2005-10-11 2007-04-26 Toray Ind Inc 片面フレキシブル金属積層板の製造方法
JP2009248409A (ja) * 2008-04-04 2009-10-29 Hitachi Chem Co Ltd ２枚合わせ片面金属箔張積層板およびその製造方法、ならびに、片面プリント配線板およびその製造方法
JP2011513965A (ja) * 2008-02-29 2011-04-28 エルジー イノテック カンパニー，リミティド プリント回路基板及びその製造方法
JP2017205948A (ja) * 2016-05-18 2017-11-24 株式会社カネカ 両面金属張積層板の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07302977A (ja) * 1994-04-28 1995-11-14 Ibiden Co Ltd 多層プリント配線板の製造方法とそれに用いる銅張積層板
JP2007090581A (ja) * 2005-09-27 2007-04-12 Matsushita Electric Works Ltd 片面板の製造方法及びプリント配線板の製造方法
JP2007109694A (ja) * 2005-10-11 2007-04-26 Toray Ind Inc 片面フレキシブル金属積層板の製造方法
JP2011513965A (ja) * 2008-02-29 2011-04-28 エルジー イノテック カンパニー，リミティド プリント回路基板及びその製造方法
JP2009248409A (ja) * 2008-04-04 2009-10-29 Hitachi Chem Co Ltd ２枚合わせ片面金属箔張積層板およびその製造方法、ならびに、片面プリント配線板およびその製造方法
JP2017205948A (ja) * 2016-05-18 2017-11-24 株式会社カネカ 両面金属張積層板の製造方法

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