WO2016031960A1 - Stratifié revêtu de métal flexible à trois couches et stratifié revêtu de métal flexible à trois couches double face - Google Patents

Stratifié revêtu de métal flexible à trois couches et stratifié revêtu de métal flexible à trois couches double face Download PDF

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Publication number
WO2016031960A1
WO2016031960A1 PCT/JP2015/074414 JP2015074414W WO2016031960A1 WO 2016031960 A1 WO2016031960 A1 WO 2016031960A1 JP 2015074414 W JP2015074414 W JP 2015074414W WO 2016031960 A1 WO2016031960 A1 WO 2016031960A1
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WIPO (PCT)
Prior art keywords
layer
clad laminate
adhesive layer
flexible metal
metal
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PCT/JP2015/074414
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English (en)
Japanese (ja)
Inventor
雄二 石川
鈴木　直樹
孝之 間山
秀一 藤田
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株式会社有沢製作所
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Publication of WO2016031960A1 publication Critical patent/WO2016031960A1/fr

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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
    • 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
    • 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
    • B32B15/088—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 comprising polyamides
    • 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
    • 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

Definitions

  • the present invention relates to a three-layer flexible metal-clad laminate and a double-sided three-layer flexible metal-clad laminate.
  • the flexible metal laminate is widely used in the field of electronic materials, and is a two-layer flexible metal-clad laminate comprising a metal layer and a polyimide layer, and a three-layer flexible metal laminate comprising a metal layer, a polyimide layer and an adhesive layer. It has been known.
  • the thickness of each layer of the flexible metal-clad laminate is made as thin as possible and a higher definition wiring pattern is formed. Therefore, there is a tendency to use a low profile copper foil.
  • the adhesiveness decreases when the thickness of the adhesive layer is reduced.
  • the low profile copper foil has a feature that the anchor effect is difficult to obtain because the surface roughness of the copper foil is small.
  • Patent Document 1 discloses a flexible printed circuit board having a three-layer structure in which the thickness of an adhesive layer is 0.5 to 25 ⁇ m.
  • the surface roughness (Rz) of the copper foil is made as small as possible, the surface shape of the copper foil is made a complicated surface shape, and both high-definition of the wiring pattern and adhesion to the substrate are compatible.
  • the illustrated copper foil and a laminate using the copper foil are disclosed.
  • the present invention relates to a flexible metal-clad laminate, particularly a three-layer flexible metal-clad laminate and a double-sided three-layer that can maintain sufficient adhesion even when the thickness of the adhesive layer in the three-layer flexible metal-clad laminate is extremely thin.
  • An object is to provide a flexible metal-clad laminate.
  • a three-layer flexible metal-clad laminate including a metal layer, an adhesive layer, and a resin layer, the main surface of the resin layer being
  • the 10-point average roughness (Rz) of the surface on the adhesive layer side of the metal layer laminated on the formed adhesive layer is 0.05 to 0.25 ⁇ m, and the surface area ratio is 1.0001 to 1.010.
  • the adhesive layer has a thickness of 0.3 to 3.0 ⁇ m.
  • a resin layer having a first main surface and a second main surface, and a first adhesive layer and a first metal layer in this order on the first main surface.
  • a double-sided three-layer flexible metal-clad laminate in which a second adhesive layer and a second metal layer are laminated in this order on the second main surface, wherein the first metal layer has the first metal layer.
  • the 10-point average roughness (Rz) of the surface of the second metal layer and the surface of the second metal layer on the second adhesive layer side is 0.05 to 0.25 ⁇ m, and the surface area ratio is 1.0001 to 1. 010, and the thickness of the first adhesive layer and the second adhesive layer is 0.3 to 3.0 ⁇ m.
  • FIG. 1 is a schematic cross-sectional view of a three-layer flexible metal-clad laminate according to an embodiment. It is a schematic sectional drawing of the double-sided three-layer flexible metal-clad laminate concerning an embodiment. It is an expansion schematic sectional drawing of a 3 layer flexible metal laminated board.
  • FIG. 1 is a schematic cross-sectional view of a three-layer flexible metal-clad laminate according to this embodiment.
  • the three-layer flexible metal-clad laminate 10 includes a resin layer 13, an adhesive layer 12 formed on the surface (main surface) of the resin layer 13, and a metal layer 11 adhered to the resin layer 13 via the adhesive layer 12.
  • a resin layer 13 an adhesive layer formed on the surface (main surface) of the resin layer 13
  • a metal layer 11 adhered to the resin layer 13 via the adhesive layer 12.
  • the surface of the metal layer 11 to be bonded to the adhesive layer 12 is preferably as smooth as possible. Smoothness here means that both the 10-point average roughness (Rz) and the surface area ratio (S ratio) of the surface of the metal layer 11 are small. Specifically, from the viewpoint of adhesion between the metal layer 11 and the adhesive layer 12, the surface of the metal layer 11 has a 10-point average roughness (Rz) in the range of 0.05 to 0.25 ⁇ m, and the surface
  • the surface area ratio (S ratio) is preferably in the range of 1.0001 to 1.010, Rz is in the range of 0.05 to 0.20 ⁇ m, and S ratio is in the range of 1.0001 to 1.005. More preferably.
  • the thickness of the adhesive layer 12 cannot be reduced. Thereby, for example, the influence on flame retardancy, solder heat resistance, dimensional stability, and the like is increased. When the value is less than the lower limit, the surface of the metal layer 11 is in a mirror state, but this is not practically present.
  • 10-point average roughness (Rz) and a surface area ratio (S ratio) can be measured by the method as described in the Example mentioned later.
  • the material of the metal layer 11 is not particularly limited, and various metals can be used. For example, copper, aluminum, stainless steel, etc. are mentioned. Among these, it is preferable that the metal layer 11 is a copper foil layer from the viewpoint of improving functionality as a flexible metal-clad laminate and forming a circuit. Moreover, although copper foil has electrolytic copper foil and rolled copper foil, when manufacturing copper foil, electrolytic copper foil is preferable from the few dents formed on the surface of copper foil.
  • the thickness of the metal layer 11 is not particularly limited, and a suitable thickness can be selected as appropriate. In the present embodiment, the thickness is preferably 3 to 35 ⁇ m from the viewpoint of workability.
  • the adhesive layer 12 can be appropriately selected from thermoplastic polyimide resin, epoxy resin, acrylic resin, urethane resin, or polyester resin as a main ingredient. Depending on the characteristics required for the flexible metal-clad laminate, two or more kinds of resins may be selected and combined. Moreover, a hardening
  • thermoplastic polyimide resin those obtained using at least one tetracarboxylic dianhydride and one or more diamines as raw materials are shown.
  • thermoplastic means that it has a glass transition temperature in the range of 100 ° C. to 400 ° C., melts and flows by heating at a temperature equal to or higher than the glass transition temperature, and can be molded.
  • the tetracarboxylic dianhydride and diamine used as raw materials are not particularly limited as long as they have thermoplasticity, and known raw materials can be used.
  • Examples of the raw material tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Ether tetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (trimellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride) ), TABP, p-methylphenylenebis (trimellitic acid monoester anhydride), 3,3 ′, 4,4′
  • diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4′-diamino.
  • thermoplastic polyimide resin When a thermoplastic polyimide resin is used for the adhesive layer 12, the thermoplastic polyimide precursor dissolved in a solvent is applied to the metal layer 11 or the resin layer 13, dried, and an imidization reaction is performed as necessary.
  • the adhesive layer 12 made of a thermoplastic polyimide resin can be obtained.
  • Known methods can be applied to the method of polymerizing the thermoplastic polyimide precursor and the imidization reaction of the precursor.
  • the timing for polymerizing the precursor is preferably performed before being applied to the metal layer 11 or the resin layer 13.
  • the imidation reaction of the precursor is preferably performed after the precursor is applied to the metal layer 11 or the resin layer 12.
  • the epoxy resin is not particularly limited.
  • bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc.
  • examples thereof include an epoxy resin, a biphenyl type epoxy resin, and a naphthalene ring-containing epoxy resin. From the viewpoint of heat resistance and flame retardancy, it is preferable to use a biphenyl type epoxy resin or a naphthalene ring-containing epoxy resin.
  • acrylic resin a polymer obtained by polymerizing monomers such as (meth) acrylic acid alkyl ester and (meth) acrylic acid is shown.
  • Urethane resin is not particularly limited, and examples thereof include those obtained by polymerizing polyester polyol and polyisocyanate.
  • the polyester resin is not particularly limited, and examples thereof include those obtained by polycondensation of dicarboxylic acid and polyalcohol.
  • the curing agent is not particularly limited, and examples thereof include an epoxy resin, an isocyanate curing agent, and an imidazole curing agent.
  • the compounding amount of the curing agent is 0.5 to 50 parts by weight, preferably 5 to 20 parts by weight, with respect to 100 parts by weight (in terms of solid content) of the main resin constituting the adhesive layer.
  • the isocyanate curing agent is not particularly limited, and examples thereof include isocyanate compounds such as TDI-TMP (tolylene diisocyanate-trimethylpropane adduct) and HMDI-TMP (hexamethylene diisocyanate-trimethylpropane adduct).
  • TDI-TMP tolylene diisocyanate-trimethylpropane adduct
  • HMDI-TMP hexamethylene diisocyanate-trimethylpropane adduct
  • the imidazole curing agent is not particularly limited, and examples thereof include imidazole compounds such as 2-methylimidazole and 2-methyl-4-methylimidazole.
  • rubber resins such as nitrile butadiene rubber and acrylic rubber can be added.
  • the compounding amount (in terms of solid content) of the rubber-based resin is 10 to 200 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight (in terms of solid content) of the main resin constituting the adhesive layer.
  • the thickness of the adhesive layer 12 is preferably 0.3 to 3.0 ⁇ m, more preferably 0.3 to less than 2.0 ⁇ m from the viewpoint of flame retardancy, and 0.3 to 1.5 ⁇ m or less. It is particularly preferred.
  • the resin composition of the adhesive layer 12 is composed of an epoxy resin composition, an acrylic resin composition, a urethane resin composition, or a polyester resin composition. Addition of flame retardants such as halogen flame retardants and phosphorus flame retardants becomes unnecessary.
  • the thickness exceeds the upper limit value, the dimensional change rate at the time of circuit formation increases due to curing shrinkage or thermal expansion when the adhesive layer is cured. Moreover, when thickness becomes less than a lower limit, sufficient adhesiveness cannot be obtained.
  • the resin composition of the adhesive layer 12 is composed of an epoxy resin composition, an acrylic resin composition, a urethane resin composition, or a polyester resin composition, and the thickness of the adhesive layer 12 is 2.0 to 3.0 ⁇ m. In such a case, it is preferable to impart flame retardancy to the resin composition.
  • a flammable skeleton can be incorporated into a skeleton having a resin structure as a main component in the resin composition.
  • organic skeletons such as benzene, naphthalene and anthracene can be incorporated.
  • a halogen-based flame retardant or a phosphorus-based flame retardant may be added to the resin composition.
  • the method for forming the adhesive layer 12 on the surface of the metal layer 11 or the resin layer 13 is not particularly limited, and various methods can be employed.
  • the resin composition diluted with a solvent can be applied to the metal layer 11 or the resin layer 13 by a known application method.
  • the application means include a comma coater, a gravure coater, and a bar coater.
  • solvent for example, alcohol (for example, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellsolve), ketone (for example, acetone, methyl ethyl ketone, cyclohexanone), aromatic hydrocarbon (for example, toluene, xylene), aliphatic Hydrocarbon (for example, hexane, octane, decane, dodencan), ester (for example, ethyl acetate, methyl propionate), ether (for example, tetrahydrofuran, ethyl butyl ether) and the like can be mentioned. These may be used alone or in combination of two or more.
  • alcohol for example, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellsolve
  • ketone for example, acetone, methyl ethyl ketone, cyclohexanone
  • aromatic hydrocarbon for
  • Examples of the material used for the resin layer 13 include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, liquid crystal polymer, syndiotactic polystyrene, polyphenylene sulfide, and the like. From the viewpoint of lowering the dielectric constant and dielectric loss tangent of the flexible metal-clad laminate, liquid crystal polymers, syndiotactic polystyrene and polyphenylene sulfide are preferred.
  • a polyimide is preferable from the viewpoint of heat resistance and flame retardancy, and a polyimide containing silica is more preferable from the viewpoint of the smoothness and laminating properties of the resin layer surface.
  • the surface (main surface) of the resin layer 13 may be subjected to a plasma treatment or a corona treatment for increasing the surface activity from the viewpoint of expressing adhesiveness more strongly.
  • laminate refers to whether the metal layer and the resin layer are in close contact with each other through the adhesive layer. For example, when it adheres without a gap, it is evaluated that the laminating property is good.
  • the thickness of the resin layer 13 is not particularly limited, and a suitable thickness can be selected as appropriate. From the viewpoint of thinning and miniaturization of the flexible metal-clad laminate, the thickness is preferably 5 to 25 ⁇ m, more preferably 4 to 15 ⁇ m.
  • the resin composition according to the adhesive layer 12 diluted with a solvent is applied to the surface (main surface) of the resin layer 13 using a coater, and the resin composition Is cured to form a semi-cured state (B-stage state) to form the adhesive layer 12.
  • the adhesive layer 12 is bonded to the surface of the metal layer 11 having a predetermined 10-point average roughness and surface area ratio, and heated until the adhesive layer 12 is completely cured (C-stage state) (after baking). To do. Thereafter, it is cooled to room temperature to obtain a three-layer flexible metal-clad laminate 10.
  • FIG. 2 is a schematic cross-sectional view of a double-sided three-layer flexible metal-clad laminate according to this embodiment.
  • the double-sided three-layer flexible metal-clad laminate 200 includes a resin layer 210 having a first main surface and a second main surface, and a first adhesive layer 221 and a first metal layer on the first main surface. 231 are stacked in this order, and the second adhesive layer 222 and the second metal layer 232 are stacked in this order on the second main surface.
  • the resin composition according to the adhesive layer 221 diluted with a solvent is applied to the first main surface of the resin layer 210 using a coater, and the above resin composition The product is cured so as to be in a semi-cured state (B stage state).
  • the resin composition related to the adhesive layer 222 diluted with a solvent is applied to the second main surface of the resin layer 210 using a coater so that the resin composition is in a semi-cured state (B stage state).
  • FIG. 3 (a) and 3 (b) are enlarged schematic cross-sectional views of a three-layer flexible metal-clad laminate.
  • FIG. 3B is a partially enlarged view of FIG. 3A for easy understanding.
  • the thickness of the adhesive layer 12 existing between the resin layer 13 and the metal layer 11 depends on the shape of the surface of the metal layer 11. It becomes thicker (point a) or thinner (point b). Thereby, it is considered that the angle formed between the adherend (metal layer 11) and the adhesive layer 12 at the time of peeling is not constant, and the peeling force is not stable.
  • the thickness of the adhesive layer 12 is less affected by the surface shape of the metal layer 11, so that the adhesive existing between the resin layer 13 and the metal layer 11 is present.
  • the thickness of the layer 12 is uniform, and the angle formed between the metal layer 11 and the adhesive layer 12 at the time of peeling is also constant. As a result, it is presumed that the peeling interface becomes stable, the peeling force becomes constant, and the decrease in adhesiveness is suppressed.
  • the resin layer 13 is considerably smoother than the metal layer 11, it is considered that the degree that the surface of the resin layer 13 affects the adhesiveness is small.
  • the surface area ratio was calculated using analysis software dedicated to Nanopics 2100 based on data measured under the same conditions as the surface roughness.
  • the surface area rate as used in the field of this invention means the ratio of the area when the designated area
  • peel strength As a sample used for the peel strength (peel strength), a single-sided three-layer flexible copper-clad laminate described below was cut out to a width of 10 mm.
  • the peel strength (peel strength) is a value measured under the following measurement conditions using EZ test (manufactured by Shimadzu Corporation). Peeling speed 50mm / min Peeling angle 180 ° pulling (copper foil drawing)
  • peel strength was evaluated according to the following criteria. ⁇ 7N / cm or more ⁇ ... 5 N / cm or more and less than 7 N / cm ⁇ ... less than 5 N / cm
  • Laminate test The sample used in the laminate test was prepared by removing the copper foil of a single-sided three-layer flexible copper-clad laminate described later by etching with a ferric chloride solution, washing thoroughly with water, and then washing at 30 ° C at 105 ° C. The sample was dried for 1 minute, cooled to room temperature, and then cut into a size of 10 cm ⁇ 10 cm. In the laminate test, this sample was observed at a magnification of 100 times using an optical microscope (manufactured by OLYMPUS, BX51), and evaluated according to the following criteria. ⁇ : There are no voids and voids. X: One or more voids and voids are confirmed.
  • solder heat resistance test The sample used in the solder heat resistance test was obtained by cutting a double-sided three-layer flexible copper-clad laminate described below into a size of 20 mm x 20 mm. In the solder heat resistance test, the sample was immersed in a 300 ° C. solder bath for 10 seconds, and then the appearance of the sample after pulling was visually confirmed. Evaluation was performed according to the following criteria. ⁇ : No peeling or floating. X: There are peeling and floating.
  • Non-flame retardant resin composition (Production of three-layer flexible copper-clad laminate) (1) Preparation of resin composition (1-1) Non-flame retardant resin composition
  • the resin composition is 100 parts by weight of bisphenol A type epoxy resin (AER6121 (75% dissolved product) manufactured by Asahi Kasei E-Materials) in terms of solid content.
  • the resin composition consists of 100 parts by weight of bisphenol A type epoxy resin (AER6121 (75% dissolved product) manufactured by Asahi Kasei E-Materials Co., Ltd.) and 8 parts by weight of diaminodiphenylsulfone. 0.5 parts by weight of boron trifluoride monoethylamine, 0.3 parts by weight of imidazole (C11Z manufactured by Shikoku Kasei Co., Ltd.), nitrile butadiene rubber (S-PNR-20 manufactured by Sakai Chemical Industry Co., Ltd.
  • the resin composition consists of 100 parts by weight of bisphenol A type epoxy resin (AER6121 (75% dissolved product) manufactured by Asahi Kasei E-Materials Co., Ltd.) and 8 parts by weight of diaminodiphenylsulfone.
  • the resin composition is composed of a phosphorus-containing epoxy resin (FX-305EK70 (70% dissolved product) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 90 parts by weight in terms of solid content, bisphenol A type epoxy.
  • (1-1) a copper foil was bonded to the film surface coated with the resin composition using a roll laminator (First Laminator VA-700 manufactured by Taisei Laminator) under the following conditions.
  • Laminate roll temperature 30 ⁇ 150 °C Laminating speed 0.5-30m / min Laminating pressure (linear pressure) 0.1-5MPa
  • the pasted sample was after-baked using an oven at 180 ° C. for 1 hour. Thereafter, the sample was cooled to room temperature to obtain a single-sided three-layer flexible copper-clad laminate.
  • Double-sided, three-layer flexible copper-clad laminate uses the above-mentioned (1-1) resin composition as a polyimide film and a bar coater to give a film thickness after drying.
  • the film is coated to a film thickness, dried using an oven at 100 to 150 ° C. for 5 minutes, and then dried using a bar coater on the polyimide surface not coated with the resin composition.
  • the film was applied so as to have a predetermined thickness, and dried using an oven at 100 to 150 ° C. for 5 minutes.
  • copper foil was bonded together with the roll laminator simultaneously on both surfaces on the above-mentioned lamination conditions. Thereafter, after-baking was performed using an oven at 180 ° C. for 1 hour to obtain a double-sided three-layer flexible copper-clad laminate.
  • Table 1 shows that the adhesive layer of the three-layer flexible copper-clad laminate is the above-mentioned (1-1) resin composition, the thickness after drying is 1.0 ⁇ m, and the resin layer has the same configuration of polyimide film 12.5 ⁇ m And the characteristic results in the respective examples and comparative examples in which the copper foil as the metal layer was appropriately changed.
  • Example 1 As the metal layer of the three-layer flexible metal-clad laminate, electrolytic copper foil T9DA SV (18 ⁇ m) manufactured by Fukuda Metal Foil Powder Co., Ltd. was used. The surface on which the adhesive layer is laminated is the M surface (mat surface).
  • Example 2 As the metal layer of the three-layer flexible metal-clad laminate, rolled copper foil GHSN HA (12 ⁇ m) manufactured by JX Nippon Mining & Metals was used. The surface on which the adhesive layer is laminated is the M surface (mat surface).
  • Comparative Example 1 to Comparative Example 4 do not have sufficient characteristics in terms of laminating properties and solder heat resistance.
  • the comparative example 1 and the comparative example 4 have expressed the peel strength of 5 N / cm or more, sufficient characteristic is not acquired by laminating property and solder heat resistance. This is probably because the surface of the copper foil on which the adhesive layer is laminated is not smooth and air exists between the adhesive layer and the copper foil layer.
  • the copper foil surface on which the adhesive layer is laminated uses the S surface (glossy surface). It is considered that sufficient characteristics could not be obtained because a recess called an oil pit formed during the production of the rolled copper foil was easily formed on the S surface, and air was easily present in the recess.
  • Table 2 shows that the film layer of the three-layer flexible copper-clad laminate is polyimide film 12.5 ⁇ m made by Toray DuPont, the copper foil that is the metal layer is T9DA SV foil 18 ⁇ m made by Fukuda Metal Foil Powder Co., Ltd., and the adhesive layer is It is a characteristic result in each Example and each comparative example which made the above-mentioned (1-1) resin composition, and changed thickness after drying suitably.
  • the adhesive layer was laminated on the M surface side (surface roughness 0.16 ⁇ m, surface area ratio 1.002) of the copper foil.
  • Example 3 In each of Examples 3 to 8, sufficient characteristics were obtained in terms of laminating properties and peel strength.
  • Examples 3 to 6 since the thickness of the adhesive layer is less than 2 ⁇ m, a three-layer flexible metal tension equivalent to UL94VTM-0 is included even in a state where the resin composition of the adhesive layer does not contain a substance that exhibits flame retardancy. A laminate was obtained.
  • Comparative Example 5 the thickness of the adhesive layer was 0.1 ⁇ m, which was insufficient as the thickness of the adhesive layer, so that sufficient characteristics were not obtained in terms of laminating properties and peel strength.
  • Table 3 shows that the resin layer of the three-layer flexible copper-clad laminate is a polyimide film 12.5 ⁇ m, the copper foil as the metal layer is T9DA SV foil 18 ⁇ m manufactured by Fukuda Metal Foil Powder Co., Ltd., and the adhesive layer is described above ( FIG. 6 is a characteristic result in each example when the resin compositions (1-2) to (1-4) other than 1-1) were changed in thickness after drying between 0.7 and 3 ⁇ m.
  • the adhesive layer was laminated on the M surface side (surface roughness 0.16 ⁇ m, surface area ratio 1.002) of the copper foil.
  • the thickness of the adhesive layer is greater than 3 ⁇ m regardless of the presence or absence of flame retardancy of the resin composition as in Comparative Example 6, although not shown in Table 3, the dimensional stability of the three-layer flexible copper-clad laminate is not shown. Decreased. This is considered to be because the laminated board is easily affected by the curing shrinkage of the resin due to the increase in the thickness of the adhesive layer.
  • the dimensional stability was evaluated by measuring the dimensional change rate.
  • the dimensional change rate was measured by preparing a measurement sample in accordance with JIS C-6471 and using a manual two-dimensional measuring machine bestol KANON Y-450 manufactured by Nakamura Seisakusho.
  • the present invention has been described using the single-sided three-layer flexible copper-clad laminate, but also in the double-sided three-layer flexible copper-clad laminate that is another embodiment, the single-sided three-layer flexible copper-clad laminate It was confirmed that the same results were obtained.

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  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

L'invention concerne un stratifié revêtu de métal flexible à trois couches et un stratifié revêtu de métal flexible à trois couches double face dans lequel des propriétés adhésives suffisantes peuvent être maintenues même lorsque l'épaisseur d'une couche adhésive dans un stratifié revêtu de métal flexible à trois couches est considérablement réduite. Le stratifié revêtu de métal flexible à trois couches (10) comprend une couche métallique (11), une couche adhésive (12) et une couche de résine (13), la surface de la couche métallique (11) stratifiée sur la couche adhésive (12) formée sur la surface principale de la couche de résine (13) dans le stratifié revêtu de métal flexible à trois couches (10) présentant une rugosité moyenne sur 10 points (Rz) de 0,05 à 0,25 μm, le rapport d'aire de surface étant de 1,0001 à 1,010 et la couche adhésive (12) présentant une épaisseur de 0,3 à 3,0 μm.
PCT/JP2015/074414 2014-08-28 2015-08-28 Stratifié revêtu de métal flexible à trois couches et stratifié revêtu de métal flexible à trois couches double face WO2016031960A1 (fr)

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JP2014174612 2014-08-28
JP2014-174612 2014-08-28
JP2015140130A JP6297011B2 (ja) 2014-08-28 2015-07-14 ３層フレキシブル金属張積層板及び両面３層フレキシブル金属張積層板
JP2015-140130 2015-07-14

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