WO2020145695A1 - 필름, 금속박 적층판, 플렉시블 기판, 필름의 제조 방법, 금속박 적층판의 제조 방법, 및 플렉시블 기판의 제조 방법 - Google Patents

필름, 금속박 적층판, 플렉시블 기판, 필름의 제조 방법, 금속박 적층판의 제조 방법, 및 플렉시블 기판의 제조 방법 Download PDF

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Publication number
WO2020145695A1
WO2020145695A1 PCT/KR2020/000409 KR2020000409W WO2020145695A1 WO 2020145695 A1 WO2020145695 A1 WO 2020145695A1 KR 2020000409 W KR2020000409 W KR 2020000409W WO 2020145695 A1 WO2020145695 A1 WO 2020145695A1
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WIPO (PCT)
Prior art keywords
precursor
polyamic acid
layer
film
adhesive layer
Prior art date
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Ceased
Application number
PCT/KR2020/000409
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English (en)
French (fr)
Korean (ko)
Inventor
키노타카시
박순용
박영석
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to KR1020207028772A priority Critical patent/KR102452787B1/ko
Priority to US17/056,885 priority patent/US11845246B2/en
Priority to EP20738489.2A priority patent/EP3769959B1/en
Priority to CN202080002404.8A priority patent/CN112020427A/zh
Publication of WO2020145695A1 publication Critical patent/WO2020145695A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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
    • B32B27/08—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 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
    • B32B37/0015—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 to avoid warp or curl
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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—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 being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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    • B32B37/15—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 being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—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 being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
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Definitions

  • the present invention relates to a film, a metal foil laminate, a flexible substrate, a method for producing a film, a method for producing a metal foil laminate, and a method for manufacturing a flexible substrate.
  • the FPC can realize three-dimensional wiring, movable wiring, and the like, and high-density mounting is possible in a limited space in the electronic device.
  • FCCL Flexible Copper Clad Laminate
  • metal base layers such as a flexible insulator and a metal foil layer such as a copper foil layer are pasted through an adhesive layer
  • metal foil layer By etching the metal foil layer, an arbitrary wiring pattern is formed on the laminate.
  • FCCL when the symmetry of the layer structure on both sides of the gas is low, warpage may occur naturally.
  • the FCCL etching treatment may include a cleaning process such as an etchant, but when the dehydration property of the FCCL is low, the washing water may remain in the FCCL structure for a long time. In this case, since the dimensions of the FCCL are not stable until the washing water is completely removed from the FCCL, the efficiency of mass production of the FCCL may be deteriorated.
  • Patent Document 1 Japanese Patent Application Publication No. 2006-051800
  • An object of the present invention is to provide a polyimide film and a metal foil laminate having high structural symmetry and excellent dimensional stability.
  • An aspect of the present invention is a gas layer composed of a gaseous polyimide obtained from pyromellitic dianhydride and m-tolidine, and a first layer formed of a first thermoplastic polyimide formed on one surface of the gas layer.
  • An adhesive layer, and a second adhesive layer formed of a second thermoplastic polyimide formed on the other side of the gas layer, the maximum height roughness of the first interface between the gas layer and the first adhesive layer, and the gas layer and The film has a maximum height roughness of 1.0 ⁇ m or less at the second interface between the second adhesive layers.
  • the first thermoplastic polyimide and the second thermoplastic polyimide may be the same polyimide.
  • the first thermoplastic polyimide and the second thermoplastic polyimide may be polyimide obtained from pyromellitic anhydride and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. do.
  • the thickness of the first adhesive layer and the thickness of the second adhesive layer may be approximately the same.
  • Another aspect of the present invention is a metal foil laminate plate comprising the film of the above aspect and a metal foil layer formed on at least one surface of the film.
  • metal foil layers may be formed on both sides of the film, and peeling strength for peeling the metal foil layer from the film may be 10 kg/cm or more on both sides of the film.
  • Another aspect of the present invention is a flexible substrate comprising the film of the above aspect and a conductive pattern formed on at least one surface of the film.
  • Another aspect of the present invention comprises the steps of preparing a first precursor comprising a first polyamic acid obtained from pyromellitic dianhydride and m-tolidine, and a second precursor and a third polya comprising a second polyamic acid.
  • It is a manufacturing method of the film by the thermal imidation method including the step of forming the laminated body which is pinched, and obtaining a three-layer film by heating the said laminated body.
  • thermoplastic polyimide derived from the second polyamic acid in the step of obtaining the three-layer film, heat imidization of the first polyamic acid, the second polyamic acid, and the third polyamic acid is performed by heating the laminate.
  • the second polyamic acid and the third polyamic acid may be the same polyamic acid.
  • the second polyamic acid and the third polyamic acid are polyamic acid obtained from pyromellitic anhydride and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. May be
  • Another aspect of the present invention comprises the steps of preparing a first precursor comprising a first polyamic acid obtained from pyromellitic dianhydride and m-tolidine, and a second precursor and a third polya comprising a second polyamic acid. Preparing a third precursor containing a mixed acid, and simultaneously extruding the first precursor, the second precursor, and the third precursor, thereby simultaneously forming the first precursor between the second precursor and the third precursor.
  • a method of manufacturing a metal foil-clad laminate by a thermal imidization method comprising forming a sandwiched body, obtaining a three-layer film by heating the laminate, and laminating a metal foil layer on the three-layer film. to be.
  • Another aspect of the present invention comprises the steps of preparing a first precursor comprising a first polyamic acid obtained from pyromellitic dianhydride and m-tolidine, and a second precursor and a third polya comprising a second polyamic acid.
  • Forming a laminated body sandwiched therebetween obtaining a three-layer film by heating the laminate, laminating a metal foil layer to the three-layer film, and etching the metal foil layer to form the three-layer film. It includes a step of forming a conductive pattern on at least one surface of, is a method of manufacturing a flexible substrate by a thermal imidization method.
  • FIG. 1 is a schematic cross-sectional view showing a metal foil laminate according to an embodiment.
  • FIG. 2 is a flow chart showing an example of a method of manufacturing a metal foil laminate according to an embodiment.
  • FIG 3 is a schematic cross-sectional view showing an example of a metal foil laminate according to an embodiment.
  • FIG. 1 is a schematic cross-sectional view showing a metal foil laminate according to an embodiment.
  • the metal foil laminate 1 includes at least a first metal foil layer 10, a first adhesive layer 12, a gas layer 14, a second adhesive layer 16, and a second metal foil layer 18.
  • the metal foil laminate 1 has metal foil layers 10 and 18 on both sides thereof, and the first adhesive layer 12, the gas layer 14, and the second adhesive layer are interposed between the metal foil layers 10 and 18. (16) is pinched.
  • the metal foil laminate 1 has a symmetrical structure around the base layer 14 with respect to a plane orthogonal to the lamination direction.
  • one of the first metal foil layer 10 and the second metal foil layer 18 may be omitted.
  • the metal foil laminated board 1 may further have a layer other than the above.
  • the metal material constituting the metal foil layers 10 and 18 is not particularly limited.
  • the metal material is any metal material such as copper, aluminum, stainless steel, iron, nickel, silver, or an alloy of two or more of them.
  • the metal foil layers 10 and 18 are made of copper foil in terms of conductivity, flowability, and cost.
  • the material of the metal foil layers 10 and 18 may be the same or different from each other.
  • the adhesive layers 12 and 16 are interposed between the metal foil layers 10 and 18 and the base layer 14 to adhere them.
  • the first adhesive layer 12 is located between the first metal foil layer 10 and the base layer 14, and the second adhesive layer 16 is between the second metal foil layer 18 and the base layer 14. Located.
  • the adhesive layers 12 and 16 are made of thermoplastic polyimide.
  • polyimide' in the present specification means a polymer having an imide bond in a molecular structure.
  • the adhesive layers 12 and 16 may contain a plasticizer, a filler, or the like in addition to the thermoplastic polyimide. Since the thermoplastic polyimide softens at a high temperature, it can function as an adhesive material for bonding the metal foil layers 10 and 18 and the gas layer 14 to each other.
  • polyimide constituting the adhesive layers 12 and 16
  • pyromellitic dianhydride (PMDA) is used as the tetracarboxylic acid component
  • 2,2-bis[4-(4-aminophenoxy) is used as the diamine component.
  • )Phenyl]propane (4,4-BAPP) is preferred.
  • tetracarboxylic acid component of the polyimide of the adhesive layers 12 and 16 in addition to the above, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4' -Biphenyltetracarboxylic dianhydride (a-BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3 And',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), and derivatives thereof (for example, tetracarboxylic acid not anhydride, esters thereof, halogens, and the like).
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3',4' -Biphenylt
  • Two or more types of tetracarboxylic acid compounds may be used in combination.
  • the diamine component of the polyimide of the adhesive layers 12 and 16 other than the above, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(4-aminophenoxy) )Benzene (APB) and derivatives thereof (for example, a benzene ring in a structure having a lower alkyl substituent or a lower alkoxy substituent) and the like.
  • TPE-R 1,3-bis(4-aminophenoxy)benzene
  • APIB 1,4-bis(4-aminophenoxy) )Benzene
  • derivatives thereof for example, a benzene ring in a structure having a lower alkyl substituent or a lower alkoxy substituent
  • Two or more types of diamine compounds may be used in combination.
  • the polyimide constituting the first adhesive layer 12 and the polyimide constituting the second adhesive layer 16
  • the thickness of the first adhesive layer 12 is approximately equal to the thickness of the second adhesive layer 16.
  • the difference in thickness between the first adhesive layer 12 and the second adhesive layer 16 is 10% or less of the thickness of the first adhesive layer 12, and also 10% of the thickness of the second adhesive layer 16. It means the following.
  • the base layer 14 functions as a base of the metal foil laminate 1.
  • 'gas' means a component of the metal foil laminate, and has a function of supporting the metal foil laminate itself.
  • the gas layer 14 is composed of a non-thermoplastic polyimide.
  • non-thermoplasticity' in the present specification means a property that does not soften to a temperature that decomposes even when the temperature is increased, and includes a polymer having a softening temperature higher than the decomposition temperature or a thermosetting polymer.
  • the base layer 14 may contain a plasticizer, a filler, or the like in addition to the non-thermoplastic polyimide.
  • PMDA polyimide constituting the gas layer 14
  • a derivative thereof for example, pyromellitic acid or an esterified product or a halide thereof
  • m-tolidine It is preferred to use 2,2'-dimethylbenzidine, 4,4'-diamino-2,2'-dimethylbiphenyl.
  • the first precursor for the gas layer and the second precursor for the adhesive layer are prepared by reacting each of the raw materials of the polyimide constituting the gas layer and the adhesive layer in a solvent (S100).
  • the reaction temperature is, for example, 20°C to 60°C.
  • the first precursor and the second precursor are obtained in a state in which a polyamic acid produced by reacting a tetracarboxylic acid compound and a diamine compound, which are raw materials for polyimide, is dissolved in a solvent (also called varnish).
  • the obtained first precursor and the second precursor are extruded in the form of a three-layer laminate (three-layer sheet) in which the second precursor, the first precursor, and the second precursor are stacked in the order of a three-layer extrusion molding die. It is molded (S102).
  • the die for three-layer extrusion molding is continuously supplied to the three-layer laminate extruded on a rotating smooth seamless belt (S104).
  • the three-layer stacked body disposed on the seamless belt is appropriately dried by a heater or a hot air blower while being carried by the belt (S106).
  • the drying temperature is, for example, 100°C to 200°C, preferably 130°C to 200°C.
  • the three-layer laminate is peeled from the belt (S108), and heat treatment is performed by another dryer (for example, a tenter dryer) (S110).
  • the drying temperature is, for example, 200°C to 500°C, preferably 200°C to 450°C.
  • the solvent is completely removed, and polyimide by heat of the polyamic acid of the first precursor and the second precursor is performed to obtain a three-layer polyimide film (S112).
  • the three-layer polyimide film has a layer structure laminated in the order of the first adhesive layer obtained from the second precursor, the gas layer obtained from the first precursor, and the second adhesive layer obtained from the second precursor.
  • the three-layer polyimide film is passed between two rotating nip rollers together with the metal foil, and is laminated with the metal foil (S114). Thereby, a metal foil is formed on one side or both sides of a three-layer polyimide film, and a metal foil laminate is obtained (S116).
  • the obtained metal foil laminated board is masked with a mask material according to the desired wiring pattern shape (S118), and the mask material and the etchant are cleaned after the etching treatment of the non-mask portion is performed with the etchant (S120) ( As S122), a flexible substrate on which a desired wiring pattern is formed is obtained (S124).
  • a method of performing polyimide by heating without using a catalyst as described above is referred to as a'thermal imidization method', and a method of performing polyimide using a catalyst is referred to as'chemical imidization'. It is called.
  • the polyimide film is produced by a thermal imidization method in which a catalyst is unnecessary, simplification of the manufacturing process and reduction of manufacturing cost can be achieved.
  • all of the polyamic acids produced in the following synthesis examples are generally polyimide-formed by a thermal imidization method, and application of a chemical imidation method by a catalytic reaction is impossible or at least difficult.
  • a polyamic acid solution was prepared in the same manner as in Synthesis Example 1-1, except that the concentration of the solid content was changed so that the viscosity was 500 poise (50 Pa ⁇ s) to obtain polyamic acid a1.
  • the chemical composition of polyamic acid a1 is the same as that of polyamic acid A1.
  • Polyamic acid solutions were prepared as in Synthesis Examples 2-1 and 2-20, except that the concentration of the solid content was changed so that the viscosity was 500 poise (50 Pa ⁇ s), and polyamic acids b1 to b20 were obtained, respectively. .
  • the chemical composition of the polyamic acids b1 to b20 is the same as that of the polyamic acids B1 to B20, respectively.
  • Tetracarboxylic acid component Diamine component PMDA s-BPDA a-BPDA DSDA ODPA BTDA m-tolidine PDA 4,4-BAPP TPE-R APB A1/a1 One One A2 One One One B1/b1 One One B2/b2 0.9 0.1 One B3/b3 0.5 0.5 One B4/b4 One One B5/b5 One One B6/b6 0.8 0.2 One B7/b7 0.5 0.5 One B8/b8 One One B9/b9 One One B10/b10 One One B11/b11 One One B12/b12 One One B13/b13 One One B14/b14 One One B15/b15 One One B16/b16 One One B17/b17 One One B18/b18 One One B19/b19 One One B20/b20 One One One One One
  • Extrusion molding of the polyamic acid solution A1 and the polyamic acid solution B1 was performed using a die for three-layer extrusion molding. Specifically, while supplying the polyamic acid solution A1 to the inner layer portion of the die for three-layer extrusion molding, the polyamic acid solution B1 was supplied to the outer layer portions on both sides of the inner layer portion, and the polyamic acid solution B1, the polyamic acid solution A1, and the polya Polyamic acid solutions A1 and B1 were continuously extruded onto a seamless belt made of stainless steel from the outlet of the die in the form of a three-layer sheet laminated in the order of the mixed acid solution B1.
  • the DMAc in the solvent was removed by heating the three-layer sheet under conditions of 5 minutes at 130°C, 5 minutes at 160°C, and 5 minutes at 180°C. Next, while stretching the three-layer sheet by a tenter dryer, by heating under conditions of 200°C 3 minutes, 250°C 3 minutes, 300°C 3 minutes, 350°C 3 minutes, 400°C 3 minutes, 450°C 3 minutes, The three-layer sheet was completely dried, and polyimide of the polyamic acid component of each layer was performed. Thus, a polyimide film c1-1 having a three-layer structure was obtained.
  • a copper foil and a commercially available polyimide film (used as a buffer layer) were prepared, and nitrogen-substituted so as to be laminated in the order of a commercially available polyimide film (buffer layer), copper foil, polyimide film c1-1, copper foil, and commercially available polyimide film (buffer layer).
  • Lamination was performed by passing them through two nip rollers heated to about 400°C under the environment. As the nip roller, an iron roller having a chrome surface was used.
  • a copper foil laminated plate C1-1 in which copper foil was laminated on both sides of the polyimide film c1-1 was obtained.
  • the thickness of the three-layer structure polyimide film c1-1 in the copper foil laminate C1-1 was 20 ⁇ m.
  • the above manufacturing method is referred to as a'lamination method'.
  • a copper-clad laminate was produced in the same manner as in Example 1-1, except that the amount of each polyamic acid solution supplied from the die was adjusted so that the thickness of the resulting polyimide film c1-2 was 15 ⁇ m. Thereby, the copper foil laminated board C1-2 containing the three-layer structure polyimide film c1-2 (thickness 15 micrometers) was obtained.
  • a copper foil laminate was produced in the same manner as in Example 1-1, except that polyamic acid solutions B2 to B20 were used instead of polyamic acid solution B1 as a precursor for the adhesive layer.
  • the base layer obtained from the polyamic acid solution A1 and the adhesive layer obtained from the polyamic acid solutions B2 to B20 were stacked in the order of the adhesive layer, the gas layer, and the adhesive layer, respectively, and the three-layer structure polyimide films c2-1 to c20-1 (thickness) 20 ⁇ m) to obtain copper foil laminates C2-1 to C20-1.
  • a copper foil laminate was manufactured in the same manner as in Example 1-2, except that polyamic acid solutions B2 to B20 were used instead of polyamic acid solution B1 as a precursor for the adhesive layer.
  • the base layer obtained from the polyamic acid solution A1 and the adhesive layer obtained from the polyamic acid solutions B2 to B20 were stacked in the order of the adhesive layer, the gas layer, and the adhesive layer, respectively, and the three-layer structure polyimide films c2-2 to c20-2 (thickness) 15 ⁇ m) to obtain copper foil laminates C2-2 to C20-2.
  • the solvent was partially removed by uniformly coating the polyamic acid solution b1 on one side of the copper foil (first adhesive layer) and heating under conditions of 40°C for 3 minutes, 60°C for 3 minutes, 80°C for 3 minutes, and 120°C for 3 minutes. . Subsequently, the polyamic acid solution a1 was uniformly applied on the first adhesive layer (opposite to the copper foil) (gas layer), and the conditions were 40°C 3 minutes, 60°C 3 minutes, 80°C 3 minutes, and 120°C 3 minutes. Some solvents were removed by heating.
  • polyamic acid solution b1 was uniformly applied to the base layer (opposite to the first adhesive layer) (second adhesive layer), and the conditions were 40°C 3 minutes, 60°C 3 minutes, 80°C 3 minutes, and 120°C 3 minutes. By heating with, some solvent was removed. Subsequently, this laminate was rolled in a nitrogen-based air flow dryer in a roll-to-roll process at 100°C for 3 minutes, 150°C for 3 minutes, 200°C for 3 minutes, 250°C for 3 minutes, 300°C for 3 minutes, and 350°C for 3 minutes. It dried under the conditions of, and completely imidized to prepare a single-sided copper foil laminate D1-1'.
  • a copper foil and a surface smooth copper foil (used as a buffer layer) are prepared, laminated so as to be laminated in the order of surface smooth copper foil (buffer layer), single-sided copper foil laminate D1-1', copper foil, surface smooth copper foil (buffer layer), and nitrogen substitution. Under one environment, they were passed through two nip rollers heated to about 400°C to perform lamination treatment. As the nip roller, an iron roller having a chrome surface was used.
  • the thickness of the three-layer structure polyimide film d1-1 in the copper foil laminate D1-1 was 20 ⁇ m.
  • the above manufacturing method is referred to as a'cast method'.
  • Copper foil laminates were manufactured in the same manner as in Comparative Example 1-1, except that the coating amount of each polyamic acid solution was prepared so that the final thickness was 15 ⁇ m. Thereby, the copper foil laminated board D1-2 containing the three-layer structure polyimide film d1-2 (thickness 15 micrometers) was obtained.
  • a copper foil laminate was manufactured in the same manner as in Comparative Example 1-1, except that polyamic acid solutions b2 to b20 were used instead of polyamic acid solution b1 as a precursor for the adhesive layer.
  • the base layer obtained from the polyamic acid solution A1 and the adhesive layer obtained from the polyamic acid solutions b2 to b20 are stacked in the order of the adhesive layer, the gas layer, and the adhesive layer, respectively, and the three-layer structure polyimide films d2-1 to d20-1 (thickness) 20 ⁇ m) to obtain copper foil laminates D2-1 to D20-1.
  • a copper foil laminate was produced in the same manner as in Comparative Example 1-2, except that polyamic acid solutions b2 to b20 were used instead of polyamic acid solution b1 as a precursor for the adhesive layer.
  • the gas layer obtained from the polyamic acid solution a1 and the adhesive layers obtained from the polyamic acid solutions b2 to b20 are stacked in the order of the adhesive layer, the gas layer, and the adhesive layer, respectively, so that the three-layer structure polyimide films d2-2 to d20-2 (thickness) 15 ⁇ m) to obtain copper foil laminated plates D2-2 to D20-2.
  • a copper foil laminate was produced in the same manner as in Example 1-1, except that polyamic acid solution A2 was used instead of polyamic acid solution A1 as a precursor for the gas layer. Thereby, the gas layer obtained from the polyamic acid solution A2 and the adhesive layer obtained from the polyamic acid solution B1 were each laminated in this order in the order of the adhesive layer, the gas layer, and the adhesive layer.
  • a copper foil laminate D21-1 was obtained.
  • a copper foil laminate was manufactured in the same manner as in Comparative Example 21-1, except that the amount of each polyamic acid solution supplied from the die was adjusted so that the thickness of the resulting polyimide film d21-2 was 15 ⁇ m. Thereby, the copper foil laminated board D21-2 containing the three-layer structure polyimide film d21-2 (thickness 15 micrometers) was obtained.
  • a copper foil laminate was manufactured in the same manner as in Comparative Example 21-1, except that polyamic acid solutions B2 to B20 were used instead of polyamic acid solution B1 as a precursor for the adhesive layer.
  • the base layer obtained from the polyamic acid solution A2 and the adhesive layer obtained from the polyamic acid solutions B2 to B20 were stacked in the order of the adhesive layer, the gas layer, and the adhesive layer, respectively, and the three-layer structure polyimide films d22-1 to D40-1 (thickness) 20 ⁇ m) to obtain copper foil laminates D22-1 to D40-1.
  • a copper foil laminate was manufactured in the same manner as in Comparative Example 21-2, except that polyamic acid solutions B2 to B20 were used instead of polyamic acid solution B1 as a precursor for the adhesive layer.
  • the base layer obtained from the polyamic acid solution A2 and the adhesive layer obtained from the polyamic acid solutions B2 to B20 are stacked in the order of the adhesive layer, the gas layer, and the adhesive layer, respectively, and the three-layer structure polyimide films D22-2 to D40-2 (thickness) 15 ⁇ m) to obtain copper foil laminated plates D22-2 to D40-2.
  • Example Gas layer material Adhesive layer material Thickness of 3-layer polyimide film Manufacturing method Copper foil laminate 1-1 A1 B1 20 ⁇ m Lamination method C1-1 2-1 B2 C2-1 3-1 B3 C3-1 4-1 B4 C4-1 5-1 B5 C5-1 6-1 B6 C6-1 7-1 B7 C7-1 8-1 B8 C8-1 9-1 B9 C9-1 10-1 B10 C10-1 11-1 B11 C11-1 12-1 B12 C12-1 13-1 B13 C13-1 14-1 B14 C14-1 15-1 B15 C15-1 16-1 B16 C16-1 17-1 B17 C17-1 18-1 B18 C18-1 19-1 B19 C19-1 20-1 B20 C20-1
  • Example Gas layer material Adhesive layer material Thickness of 3-layer polyimide film Manufacturing method Copper foil laminate 1-2 A1 B1 15 ⁇ m Lamination method C1-2 2-2 B2 C2-2 3-2 B3 C3-2 4-2 B4 C4-2 5-2 B5 C5-2 6-2 B6 C6-2 7-2 B7 C7-2 8-2 B8 C8-2 9-2 B9 C9-2 10-2 B10 C10-2 11-2 B11 C11-2 12-2 B12 C12-2 13-2 B13 C13-2 14-2 B14 C14-2 15-2 B15 C15-2 16-2 B16 C16-2 17-2 B17 C17-2 18-2 B18 C18-2 19-2 B19 C19-2 20-2 B20 C20-2
  • each copper foil laminate obtained in the above Examples and Comparative Examples with a scanning electron microscope (SEM), for each copper foil laminate, the thickness t T1 of the first adhesive layer of the polyimide film and the thickness t C of the gas layer , And the thickness t T2 of the second adhesive layer, and the interface roughness Rz1 between the first adhesive layer and the gas layer, and the interface roughness Rz2 between the second adhesive layer and the gas layer.
  • SEM scanning electron microscope
  • the interfacial roughnesses Rz1 and Rz2 are calculated according to the'maximum height roughness Rz' defined by JIS B 0601, and the sum of the maximum peak height and the maximum curved depth of the roughness curve R of the two-layer interface (Ie, the difference between the height of the highest and deepest parts).
  • the peel strength when peeling one copper foil of each copper foil laminated board obtained in the said Example and a comparative example from the said copper foil laminated board was measured in accordance with JIS_C_6481 on both front and back sides by a tensile tester.
  • each copper foil laminated board obtained in the said Example and a comparative example the dimension was measured before and after the etching process of copper foil, and dimensional stability was investigated. Specifically, markers for alignment were displayed on the four corners of the copper foil laminate, and the length and length of the width between the markers of the copper foil laminate were measured using a microscope IM7000 from KEYENCE. Next, the copper foil was etched, and thereafter, while measuring the length and length between the markers, the time required to reach the same length as that measured before the etching was measured. The time required for such dimensional stability is generally equivalent to the dehydration time of the washing water after the etching treatment.
  • Each of the copper foil laminates obtained in Examples and Comparative Examples was soldered at about 340° C. to investigate whether the copper foil laminates had heat resistance ( ⁇ ) or not ( ⁇ ) so as not to cause damage that could not be used.
  • the results of the evaluation 1-4 for each copper-clad laminate are shown in the table below.
  • the adhesiveness column the peeling strength of the first adhesive layer was described on the left side, and the peeling strength of the second adhesive layer was described on the right side.
  • coating film formation was performed in the order of the first adhesive layer of thickness t T1 to the gas layer ⁇ second adhesive layer of thickness t T2 .
  • the interfacial roughness was suppressed on both sides of the base layer of the copper-clad laminate produced by the lamination method compared to the copper-clad laminate produced by the cast method.
  • the cast method in which coating is performed in the same order as the first adhesive layer ⁇ gas layer ⁇ second adhesive layer, the mixing of the two layers at the layer interface increases, and , It is considered that the interface roughness becomes asymmetric at both sides of the gas layer. That is, in the laminate method, compared to the cast method, a copper-clad laminate having high structural symmetry, including not only the thickness of the layer but also the interface roughness, was obtained.
  • the peel strength of the copper foils was 10 kg/cm on both sides of the copper foil laminates.
  • the peel strength on the first adhesive layer side was 8 kg/cm, which was smaller than the value of the copper foil laminates by the laminate method.
  • the peel strength on the second adhesive layer side was 10 kg/cm. That is, the copper-clad laminate produced by the lamination method was superior in the adhesion of the copper foil to the copper-clad laminate produced by the cast method.
  • Comparative Examples 21-1 to 40-2 Comparative Example 21-1, Comparative Example 21-2, Comparative Example 22-1 and Comparative Example 22- using polyamic acid B1 or B2 as the polyimide material forming the adhesive layer Except for 2, the copper foil laminate was damaged at the soldering temperature, regardless of the thickness of the polyimide film.
  • a polyimide film comprising a gas layer formed of PMA and polyamic acid solution A1 using 4,4-BAPP as a raw material by a lamination method
  • adhesion, dimensional stability and heat resistance are excellent, and 2 at the layer interface.
  • the copper foil laminated board manufactured by the lamination method had higher structure symmetry than the copper foil laminated board manufactured by the cast method.
  • the lamination method when compared with the copper foil laminate by the cast method, because of high structural symmetry, the warpage of the laminate due to the asymmetrical structure of both sides of the laminate can be suppressed, so that the structural stability of the laminate can be improved. have. Moreover, since the interface roughness of the both sides of a base layer is smaller than the copper foil laminated board by a cast method, the copper foil laminated board by a cast method has less uniformity in a film, and it is easy to handle. In addition, the lamination method is more efficient than the cast method in which application and drying are repeated for each layer because the entire laminate can be dried all at once.

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