Classifications

• • 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
  • B32B37/0007—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
• • 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
  • B32B2310/00—Treatment by energy or chemical effects
  • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
  • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
  • B32B2310/0825—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using IR radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2311/00—Metals, their alloys or their compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
  • B32B2379/08—Polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0393—Flexible materials
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/0154—Polyimide
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0183—Dielectric layers
  • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
  • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Definitions

• the present invention relates to a flexible metal laminate used for manufacturing a flexible printed circuit board, and more particularly, to a flexible metal laminate prepared by heating a polyamic acid, which is a polyimide precursor, at high temperature to be converted into a final polyimide, and a method of manufacturing the same. It is about.
• Flexible Metal Clad Laminate used in the manufacture of Flexible Printed Circuit Boards, is a laminate of conductive foil and insulating resin, which enables fine circuit processing and Flexion is possible.
• flexible metal laminates have been increasingly utilized in notebook computers, portable information terminals, small video cameras, and storage disks, in accordance with the trend of miniaturization and lightweight electronic devices.
• the flexible metal laminates related to this technique are mainly used by laminating a thermoplastic polyimide film on a film on a conductive metal foil and a casting method by directly applying a polyamic acid solution, which is a polyimide precursor, on a metal foil. .
• a polyamic acid solution which is a polyimide precursor
• a heating step is required. Therefore, the flexible metal laminate manufactured by the casting method may be divided into a roll-to-roll and a batch process according to the curing method.
• the batch process requires a back and forth process for preventing adhesion occurring between the metal foil and the polyimide before and after the batch hardening, and the processable length per roll must be short, thereby resulting in a problem of lowering productivity.
• the roll-to-roll process is a method in which a polyamic acid solution, which is a polyimide precursor, is coated on a metal foil, dried, and then uncured by applying heat before being wound up.
• a polyamic acid solution which is a polyimide precursor
• This has the advantage of overcoming the decrease in productivity, which is a problem of the existing batch method, and reducing processing time and cost.
• various defects such as foaming, peeling, and wrinkles due to rapid shrinkage / expansion are likely to occur as a rapid heat is applied during curing. .
• there is a method of lowering the production speed but a problem of lowering productivity is caused.
• the flexible metal laminate is composed of one or more layers of polyimide, and constitutes one layer of polyimide metal laminate to increase productivity.
• the two or more layers of polyimide metal laminate prevents warpage and curl between the metal foil and the laminate, and may improve physical properties such as adhesion, mechanical properties, and electrical properties.
• the glass transition temperature of the polyimide resin in contact with the metal foil as mentioned in the existing Korean Patent Publication No. 10-2010-0048474 and 10-2010-0127125 (Patent Documents 1 and 2)
• the temperature is 300 ° C or higher
• the appearance of poor appearance after heating can be suppressed.
• the aforementioned flexible metal laminate has a problem of low adhesive strength with ACF (anisotropic conductive film) used in liquid crystal displays or touch screens.
• Patent Document 1 Republic of Korea Patent Publication 10-2010-0048474
• Patent Document 2 Republic of Korea Patent Publication 10-2010-0127125
• the present invention is to solve the above problems and to solve the adhesive force with the ACF (Anisotropic Conductive Film) using a thermoplastic polyimide resin in contact with the metal foil, and at the same time to provide a flexible metal laminate having a good appearance and physical properties.
• ACF Adisotropic Conductive Film
• thermoplastic polyimide resin in contact with the metal foil
• the present invention relates to a metal foil, a first polyimide layer having a glass transition temperature of 300 ° C. or less, a second polyimide layer located on a first polyimide layer, and a second polyimide layer located on the metal foil. It includes a multi-layer polyimide film comprising a 3 polyimide layer, the multi-layer polyimide film provides a flexible metal laminate that satisfies the following formula (1).
• C1 is the linear thermal expansion coefficient of the first polyimide layer
• C2 is the linear thermal expansion coefficient of the second polyimide layer
• C3 is the linear thermal expansion coefficient of the third polyimide layer.
• the flexible metal laminates satisfy the following Equations 2 to 3, and the ACF adhesive force may be 0.8kgf / cm or more.
• S MD is the mechanical direction (MD) the standard deviation of the percentage of dimensional change after heating in the formula 2
• S TD is the transverse direction (TD) the standard deviation of the percentage of dimensional change after heating in the formula 3.
• the first polyimide layer may have a linear thermal expansion coefficient of 30 to 50 ppm / K and a glass transition temperature of 200 to 300 ° C.
• the second polyimide layer may have a linear thermal expansion coefficient of 1 to 20 ppm / K and a glass transition temperature of 300 to 420 ° C.
• the third polyimide layer may have a linear thermal expansion coefficient of 30 to 70 ppm / K.
• the multi-layer polyimide film is imidized by infrared heating, and the infrared heating may be a heating performed so that a heating time of 300 ° C. or more is 40% or more of the whole.
• the flexible metal foil laminate which is produced by laminating a metal foil on a third polyimide layer included in the multilayer polyimide film according to the present invention, is included in the scope of the present invention.
• the multi-layer polyimide film provides a method for producing a flexible metal laminate laminate satisfying the following formula 1.
• C1 is the coefficient of linear thermal expansion of the first polyimide layer imidated with the first polyimide precursor layer
• C2 is the coefficient of linear thermal expansion of the second polyimide layer imidated with the second polyimide precursor layer
• C3 is It is a coefficient of linear thermal expansion of the 3rd polyimide layer in which the 3rd polyimide precursor layer was imidated.
• step c) is imidized through infrared heating, and may be performed so that the infrared heating time of 300 ° C. or more is 40% or more of the whole.
• the present invention may further comprise the step of laminating the metal foil on the third polyimide layer included in the multi-layer polyimide film of step d) c).
• the flexible metal laminate prepared by the above manufacturing method satisfies the following Equations 2 to 3, and the ACF adhesive force may be 0.8kgf / cm or more.
• S MD is the mechanical direction (MD) the standard deviation of the percentage of dimensional change after heating in the formula 2
• S TD is the transverse direction (TD) the standard deviation of the percentage of dimensional change after heating in the formula 3.
• the first polyimide layer may have a linear thermal expansion coefficient of 30 to 50 ppm / K and a glass transition temperature of 200 to 300 ° C.
• the second polyimide layer may have a linear thermal expansion coefficient of 1 to 20 ppm / K and a glass transition temperature of 300 to 420 ° C.
• the third polyimide layer may have a linear thermal expansion coefficient of 30 to 70 ppm / K.
• the flexible metal laminate according to the present invention suppresses the appearance defects caused by foaming and the like in the curing process in a continuous curing machine using infrared rays as a heat source, and has excellent adhesion between the metal foil and the polyimide layer or another polyimide layer adjacent to the polyimide layer. It has an effect that the interlayer peeling does not occur, which is excellent in ACF adhesive strength and dimensional stability while solving the problem of the conventional flexible metal laminate, and is expected to be useful for manufacturing a flexible printed circuit board.
• the present invention provides a metal foil, a first polyimide layer having a glass transition temperature of 300 ° C. or lower in contact with the metal foil, a second polyimide layer in contact with the first polyimide layer, and a third polyimide in contact with the second polyimide layer.
• a multilayer polyimide film comprising a layer,
• the multilayer polyimide film formed after imidization satisfies the following formula 1,
• C1 is the linear thermal expansion coefficient of the first polyimide layer
• C2 is the linear thermal expansion coefficient of the second polyimide layer
• C3 is the linear thermal expansion coefficient of the third polyimide layer.
• the flexible metal laminated body containing the multilayer polyimide film characterized by imidating by infrared heating can be provided.
• the present invention is a technique for suppressing foaming or interlaminar peeling that may occur during the high temperature curing process in a high-speed roll-to-roll curing machine, especially a continuous curing machine using infrared as a heat source with excellent ACF adhesion
• the flexible metal laminate according to an embodiment of the present invention may provide a flexible metal laminate prepared by heating a polyamic acid resin, which is a polyimide precursor resin that can be converted into a polyimide resin, onto a metal foil, and drying after heating. Can be.
• the flexible metal laminate according to an embodiment of the present invention has a structure that satisfies Equation 1 below, and the dimensional stability is high when the residence time is higher than a certain ratio in a high temperature region of 300 ° C. or higher in a continuous curing machine using infrared rays as a heat source. It is improved and there is an effect of improving ACF adhesion. In addition, during the curing process, the effect of inhibiting foaming and interlayer peeling is great.
• C1 is the linear thermal expansion coefficient of the first polyimide layer
• C2 is the linear thermal expansion coefficient of the second polyimide layer
• C3 is the linear thermal expansion coefficient of the third polyimide layer.
• Metal foil used in the present invention is not limited, electrolytic copper foil, rolled copper foil, stainless steel foil, aluminum foil, nickel foil or two or more alloy foils and the like can be used.
• the thickness of the metal foil is not limited, but the thickness may be advantageous in the process of 3 ⁇ 70 ⁇ m. Also physical or chemical surface treatments, such as surface sanding, plating of nickel or copper-zinc alloys, coating of silane coupling agents to increase the bond strength between the metal layer and the insulating layer coated thereon. You may do so.
• the multi-layered polyimide film formed after imidization according to an embodiment of the present invention may be prepared by imidization after forming a polyamic acid solution as a precursor layer, and the polyamic acid solution used may be prepared within the technical scope of the present invention. If it is a polyamic acid solution normally used, it is not restrict
• the glass transition temperature (T g ) after the full imidization is 300 ° C. or less, more preferably. It is 200-300 degreeC
• the thermoplastic polyimide resin and polyamic-acid resin which have a thermoplastic characteristic whose adhesive force with copper foil is 0.8 kgf / cm or more can be used, A kind is not specifically limited.
• the thermoplastic polyimide of the first polyimide layer may have a coefficient of linear thermal expansion of 30 to 50 ppm / K. Within such a glass transition temperature and coefficient of thermal expansion coefficient, it is possible to provide a flexible metal laminate having an ACF adhesion force of 0.8 kgf / cm or more.
• the coefficient of linear thermal expansion after full imidization may have a range of 30 to 70 ppm / K.
• a thermoplastic polyimide resin or a polyamic acid resin having a thermoplastic property having an adhesive force of 0.8 kgf / cm or more with copper foil bonded by a high temperature lamination method may be used, and the type thereof is not particularly limited. It is possible to provide a flexible metal foil laminate having excellent copper foil adhesive force and good adhesion state with the copper foil within the linear thermal expansion coefficient range.
• a polyimide resin or a polyamic acid resin having a linear thermal expansion coefficient of 1 to 20 ppm / K after complete imidization may be used.
• the glass transition temperature may be 300 ⁇ 420 °C.
• the second polyimide layer having a linear thermal expansion coefficient of 1 to 20 ppm / K and a glass transition temperature of 300 to 420 ° C. according to an embodiment of the present invention is located between the first polyimide layer and the third polyimide layer.
• the method of applying the polyamic acid solution includes knife coating, roll coating, die coating, curtain coating, and the like, as long as the present invention satisfies the object of the present invention. There is no limit to that method.
• the drying step is preferably hot air drying, it is preferable to perform the drying at 100 ⁇ 150 °C.
• a polyamic acid precursor layer in the form of a film is formed by this drying step, and then imidized by performing infrared heating in a continuous curing machine using infrared light as a heat source under a nitrogen atmosphere to form a flexible metal laminate.
• Infrared heating uses an infrared heating device.
• the main emission region of the infrared wavelength is in the range of 2 ⁇ 25 ⁇ m
• the generation method of infrared rays can be applied to a variety of known methods such as infrared filament, infrared emitting ceramics, without limiting the method.
• the infrared heating according to an embodiment of the present invention can be a heating time of more than 300 °C 40% or more of the total.
• the present inventors use a thermoplastic polyimide having a glass transition temperature of 300 ° C. or lower in the first polyimide layer in order to improve ACF adhesion, which is a problem in the prior art, and solves an appearance defect such as foaming that may occur in this case.
• the coefficient of linear thermal expansion of the first polyimide layer of the multi-layer polyimide film is C1
• the coefficient of linear thermal expansion of the second polyimide layer is C2
• the coefficient of linear thermal expansion of the third polyimide layer is C3.
• the infrared heating time of more than 300 °C to be more than 40% of the total solve the problem of the foaming failure of the flexible metal laminate according to the present invention, the dimensional stability is improved, it was possible to increase the ACF adhesion.
• the multilayer polyimide film is imidized by infrared heating, and the infrared heating may be a residence time in a high temperature region of 300 ° C. or higher at least 40% of the total heating time. It can be 40 to 70%.
• the flexible metal laminate according to an embodiment of the present invention may be heated together with hot air heating in conjunction with infrared heating.
• the flexible metal foil laminate characterized in that the metal foil is laminated on the third polyimide layer included in the multi-layer polyimide film according to an embodiment of the present invention is included in the scope of the present invention.
• various known methods such as a hot roll laminator, a hot press, and a high temperature belt press may be applied.
• the present invention is a.
• the multi-layered polyimide film can provide a method for producing a flexible metal laminate that satisfies the following formula 1.
• C1 is the coefficient of linear thermal expansion of the first polyimide layer imidated with the first polyimide precursor layer
• C2 is the coefficient of linear thermal expansion of the second polyimide layer imidated with the second polyimide precursor layer
• C3 is It is a coefficient of linear thermal expansion of the 3rd polyimide layer in which the 3rd polyimide precursor layer was imidated.
• each precursor layer is formed and then imidized to form a multi-layer polyimide film, the imidization can be imidized through infrared heating.
• the present invention has been found to solve the foaming problem and excellent dimensional stability through the infrared heating, in particular the infrared heating to be carried out so that the infrared heating time of more than 300 °C more than 40% of the total, it can be improved ACF adhesion The present invention was completed.
• step d) laminating the metal foil on the third polyimide layer included in the multi-layer polyimide film of step c) may provide a method for producing a flexible metal laminate.
• the flexible metal laminates satisfy the following Equations 2 to 3, and the ACF adhesive force may be 0.8kgf / cm or more.
• S MD is the mechanical direction (MD) the standard deviation of the percentage of dimensional change after heating in the formula 2
• S TD is the transverse direction (TD) the standard deviation of the percentage of dimensional change after heating in the formula 3.
• the first polyimide layer may have a linear thermal expansion coefficient of 30 to 50 ppm / K and a glass transition temperature of 200 to 300 ° C.
• the second polyimide layer may have a linear thermal expansion coefficient of 1 to 20 ppm / K and a glass transition temperature of 300 to 420 ° C.
• the third polyimide layer may have a linear thermal expansion coefficient of 30 to 70 ppm / K.
• the polyamic acid as a component of the multilayer polyimide will first be described.
• the polyamic acid is used to form a multilayer polyimide precursor layer, which is prepared through synthesis.
• Abbreviations used in the following Synthesis Examples are as follows.
• the coefficient of linear thermal expansion was obtained by averaging the value between 100 ° C and 200 ° C of the thermal expansion values measured using TMA (Thermomechanical Analyzer) at a rate of 10 ° C per minute.
• Instron's universal testing machine was used in accordance with IPC-TM-650, 2.4.19.
• the ACF is inserted between the glass plates, and then bonded by applying a pressure of 25 kgf / cm 2 for 10 seconds at a temperature of 230 ° C. Since 90 degrees peel strength was measured using a universal testing machine of Instron.
• the interface between the copper foil and the polyimide layer was observed through FE-SEM.
• the unbonded portion at the copper foil and polyimide layer interface is a lamination bubble, and as a result of the observation, it is regarded as defective when there is an unbonded interface exceeding the size of 10 ⁇ m at the interface between the metal foil and the insulating layer. It was. However, when the non-bonded interface of several micrometers is adjacent, the length thereof was measured continuously and the value was regarded as the size of the non-bonded interface.
• the copper foil of the flexible copper clad laminate was patterned to a width of 1 mm, and then the peel strength was measured using a universal testing machine.
• the polyamic acid solution prepared through Synthesis Example 1 was applied to one surface of the first polyimide precursor layer so as to have a thickness of 13 ⁇ m after final curing, and then dried at 150 ° C. to form a second polyimide precursor layer.
• thermoplastic polyamic acid solution prepared through Synthesis Example 3 was applied to one surface of the second polyimide precursor layer so as to have a thickness of 3.5 ⁇ m after final curing, and dried at 150 ° C. to form a third polyimide precursor layer.
• the copper foil multilayer polyimide precursor layer thus prepared was completely imidized according to the curing conditions 1 of Table 2 using an infrared heater under a nitrogen atmosphere to prepare a flexible metal laminate laminated on the copper foil.
• the first polyimide precursor layer is imidated as the first polyimide layer, the second polyimide precursor layer as the second polyimide layer, and the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• the polyamic acid solution prepared through Synthesis Example 1 was applied to one surface of the first polyimide precursor layer so as to have a thickness of 13 ⁇ m after final curing, and dried at 150 ° C. to form a second polyimide precursor layer. Thereafter, the thermoplastic polyamic acid solution prepared through Synthesis Example 2 was applied to one surface of the second polyimide precursor layer so as to have a thickness of 4 ⁇ m after final curing, and then dried at 150 ° C.
• the copper foil multilayer polyimide precursor layer thus prepared was completely imidized according to the curing conditions 1 of Table 2 using an infrared heater under a nitrogen atmosphere to prepare a flexible metal laminate laminated on the copper foil.
• the first polyimide precursor layer is imidated as the first polyimide layer
• the second polyimide precursor layer as the second polyimide layer
• the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• the first polyimide precursor layer is imidated as the first polyimide layer
• the second polyimide precursor layer as the second polyimide layer
• the third polyimide precursor layer as the third polyimide layer.
• the polyamic acid solution prepared through Synthesis Example 1 was applied to one surface of the first polyimide precursor layer so as to have a thickness of 14 ⁇ m after the final curing, and dried at 150 ° C. to form a second polyimide precursor layer.
• thermoplastic polyamic acid solution prepared in Synthesis Example 4 was applied to one surface of the second polyimide precursor layer so as to have a thickness of 3 ⁇ m after the final curing, and dried at 150 ° C. to form a third polyimide precursor layer.
• the copper foil multilayer polyimide precursor layer thus prepared was completely imidized under the nitrogen atmosphere according to the curing conditions 2 shown in Table 2 using an infrared heater to prepare a flexible metal laminate laminated on the copper foil.
• the first polyimide precursor layer is imidated as the first polyimide layer, the second polyimide precursor layer as the second polyimide layer, and the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• Example 2 The flexible metal laminates prepared in Example 2 and copper foils of the same type as used in Example 2 were prepared using a high-temperature laminator at a process speed of 3 m / min, and the double-sided flexible metal laminates having copper foil adhered to both sides of the multilayer polyimide film.
• Manufacture Adhesion and cross-sectional observation results of the manufactured product are shown in Table 4.
• Example 1 The flexible metal laminates prepared in Example 1 and copper foils of the same type as used in Example 1 were fabricated using a high temperature laminator at a process speed of 5 m / min. Manufacture. Adhesion and cross-sectional observation results of the manufactured product are shown in Table 4.
• Example 4 A flexible metal laminate laminated in Example 4 and a copper foil of the same type as used in Example 4 were prepared using a high-temperature laminator at a process speed of 5 m / min to give a double-sided flexible metal laminate laminated with copper foil on both sides of the multilayer polyimide film.
• Manufacture Adhesion and cross-sectional observation results of the manufactured product are shown in Table 4.
• the first polyimide precursor layer is imidated as the first polyimide layer
• the second polyimide precursor layer as the second polyimide layer
• the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• the first polyimide precursor layer is imidated as the first polyimide layer
• the second polyimide precursor layer as the second polyimide layer
• the third polyimide precursor layer as the third polyimide layer.
• the polyamic acid solution prepared through Synthesis Example 1 was applied to one surface of the first polyimide precursor layer so as to have a thickness of 14 ⁇ m after the final curing, and dried at 150 ° C. to form a second polyimide precursor layer.
• thermoplastic polyamic acid solution prepared through Synthesis Example 2 was applied to one surface of the second polyimide precursor layer so as to have a thickness of 3.5 ⁇ m after final curing, and dried at 150 ° C. to form a third polyimide precursor layer.
• the copper foil multilayer polyimide precursor layer thus prepared was imidized completely under the nitrogen atmosphere according to the curing conditions 2 shown in Table 2 using an infrared heater to prepare a flexible metal laminate laminated on the copper foil.
• the first polyimide precursor layer is imidated as the first polyimide layer, the second polyimide precursor layer as the second polyimide layer, and the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• the polyamic acid solution prepared through Synthesis Example 1 was applied to one surface of the first polyimide precursor layer so as to have a thickness of 14 ⁇ m after final curing, and then dried at 150 ° C. to form a second polyimide precursor layer.
• thermoplastic polyamic acid solution prepared through Synthesis Example 2 was applied to one surface of the second polyimide precursor layer so as to have a thickness of 3.5 ⁇ m after final curing, and dried at 150 ° C. to form a third polyimide precursor layer.
• the copper foil-like multilayer polyimide precursor layer thus prepared was completely imidized according to the curing conditions 2 of Table 2 using an infrared heater under a nitrogen atmosphere to prepare a flexible metal laminate laminated on the copper foil.
• the first polyimide precursor layer is imidated as the first polyimide layer, the second polyimide precursor layer as the second polyimide layer, and the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• the polyamic acid solution prepared through Synthesis Example 1 was applied to one surface of the first polyimide precursor layer so as to have a thickness of 13 ⁇ m after the final curing, and dried at 150 ° C. to form a second polyimide precursor layer.
• the thermoplastic polyamic acid solution prepared through Synthesis Example 3 was applied to one surface of the second polyimide precursor layer so as to have a thickness of 3 ⁇ m after final curing, and then dried at 150 ° C.
• the copper foil multilayer polyimide precursor layer thus prepared was completely imidated under the nitrogen atmosphere by using an infrared heater under the curing conditions 4 in Table 2 to prepare a flexible metal laminate laminated on the copper foil.
• the first polyimide precursor layer is imidated as the first polyimide layer
• the second polyimide precursor layer as the second polyimide layer
• the third polyimide precursor layer as the third polyimide layer.
• the physical properties and appearance of the soft metal laminate thus prepared are shown in Table 3.
• the copper foil of the same type as used in Example 2 was laminated on the third polyimide layer of the flexible metal laminate prepared in Example 2 at a process speed of 5 m / min using a high temperature laminator, and the copper foil was laminated on both sides of the multilayer polyimide film. A double-sided flexible metal laminate is bonded. Adhesion and cross-sectional observation results of the manufactured product are shown in Table 4.
• the coefficient of linear thermal expansion of the first polyimide layer is C1 and the coefficient of linear thermal expansion of the second polyimide layer is C2 after the complete imidization contacting the copper foil layer.
• the coefficient of thermal expansion of the polyimide layer is set to C3, when a multilayer polyimide precursor layer having a structure of C2 ⁇ C1 < It can be seen that it does not appear.
• the heating time when the heating time is short at a high temperature of 300 ° C. or higher, the appearance is good, but the rate of dimensional change, especially after heating, increases. Able to know. It was also confirmed that the standard deviation value of the dimensional change rate after heating increased.
• the heating time In order to produce a flexible metal laminate having a good appearance and at the same time excellent dimensional stability and ACF adhesion, it is necessary that the heating time of 300 °C or more to be more than 40% of the total heating time. However, if the heating time exceeds 80%, appearance defects are likely to occur due to an increase in the heating rate up to 300 ° C.
• the CTE of the first polyimide layer is C1
• the CTE of the second polyimide layer is C2
• the CTE of the third polyimide layer is C3.
• the heating time of more than 300 °C more than 40% of the total heating time, specifically 40 ⁇ 70% has a good appearance and at the same time can secure excellent dimensional stability and ACF adhesion It can be seen that.
• thermoplastic polyimide having a glass transition temperature (Tg) of 300 ° C. or lower it was confirmed through Comparative Example 5 that the adhesive strength with ACF was superior to that of the polyimide layer having a Tg of 300 ° C. or higher. Can be.
• Tg glass transition temperature
• CTE of the second polyimide layer is C2
• CTE of the third polyimide layer is C3 after complete imidization in contact with the metal foil layer proposed in the present invention.
• the CTE difference between the first polyimide layer and the second polyimide layer is reduced compared to the structure having C2 ⁇ C3 ⁇ C1, which is effective for improving appearance defects such as foaming.
• the lamination process speed for manufacturing the double-sided flexible metal laminate is increased, and the copper foil and the polyimide are fine.
• the CTE (C3) value of the polyimide layer in contact with the copper foil is large, it can be seen that the lamination bubble has a fine size within 10 ⁇ m even though the lamination process speed is high.
• the C3 value is small, it is limited to increasing the process speed. It can be seen that it has a. If lamination bubbles are formed to be 10 ⁇ m or more, a problem may occur in manufacturing a flexible circuit board because an etching solution may penetrate into the unbonded portion between the copper foil and the polyimide layer and cause a poor pattern formation.

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Citations (5)

• 2012
  • 2012-12-27 WO PCT/KR2012/011562 patent/WO2013100627A1/fr not_active Ceased

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