CN115397664A - Metal laminated film and method for producing same - Google Patents
Metal laminated film and method for producing same Download PDFInfo
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- CN115397664A CN115397664A CN202180027781.1A CN202180027781A CN115397664A CN 115397664 A CN115397664 A CN 115397664A CN 202180027781 A CN202180027781 A CN 202180027781A CN 115397664 A CN115397664 A CN 115397664A
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- metal
- liquid crystal
- crystal polymer
- polymer film
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 304
- 239000002184 metal Substances 0.000 title claims abstract description 304
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 221
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 220
- 239000005001 laminate film Substances 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 127
- 239000011889 copper foil Substances 0.000 claims description 76
- 239000011888 foil Substances 0.000 claims description 69
- 239000010949 copper Substances 0.000 claims description 53
- 229910052802 copper Inorganic materials 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 44
- 238000000992 sputter etching Methods 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000005096 rolling process Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
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- 238000010030 laminating Methods 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 296
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- 238000003475 lamination Methods 0.000 description 9
- 238000004433 infrared transmission spectrum Methods 0.000 description 8
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- 238000000576 coating method Methods 0.000 description 4
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- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002197 infrared dichroism spectroscopy Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
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- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic silanes Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
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- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- B32B7/03—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 with respect to the orientation of features
-
- 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
-
- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/55—Liquid crystals
-
- 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
- B32B2311/02—Noble metals
- B32B2311/04—Gold
-
- 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
- B32B2311/02—Noble metals
- B32B2311/06—Platinum
-
- 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
- B32B2311/02—Noble metals
- B32B2311/08—Silver
-
- 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
- B32B2311/12—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/18—Titanium
-
- 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
- B32B2311/22—Nickel or cobalt
-
- 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
- B32B2311/30—Iron, e.g. steel
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The main object of the present invention is to provide a metal laminated film capable of optimizing the transmission characteristics of a printed wiring board. The metal laminate film of the present invention is characterized in that a metal layer is laminated on at least one surface of a liquid crystal polymer film, and the liquid crystal polymer film has an orientation degree F at the center in the thickness direction of 0.31 or more.
Description
Technical Field
The present invention relates to a metal laminate film and a method for manufacturing the same.
Background
Conventionally, as a substrate for manufacturing a printed wiring board, a metal laminated film in which a metal layer such as a copper foil is laminated on a rigid plate such as a paper substrate phenol resin and a polymer film such as a liquid crystal polymer film is known. In recent years, with the advent of the fifth generation mobile communication system (5G), a metal laminated film in which a metal layer such as a copper foil is laminated on a liquid crystal polymer film having low dielectric characteristics has been developed in order to improve the high frequency characteristics of a printed wiring board.
As a metal laminate film, a metal laminate film produced by a thermal lamination method using a metal foil whose pressure contact surface is roughened by heat-pressure bonding of a polymer film from the viewpoint of adhesion is generally known. For example, patent document 1 discloses a high-frequency circuit board in which a liquid crystal polymer film is heat-pressure bonded to a rolled copper foil by using a thermal lamination method, the liquid crystal polymer film having a molecular orientation SOR of 1.3 or less. In addition, patent document 2 discloses a laminated board for a flexible printed wiring board, which is produced by: the liquid crystal polymer film and the copper foil having a limited surface roughness Rz of the pressure-bonding surface are continuously supplied, and the liquid crystal polymer film is heated to a temperature of the melting point or higher by using a thermal lamination method, and the copper foil is heat-pressure-bonded to the liquid crystal polymer film.
On the other hand, as a metal laminated film, there is known a metal laminated film produced by using surface activation bonding in which a surface of a laminate is activated by removing an oxide, dirt, or the like by a method such as sputter etching, and the surface of the activated laminate is brought into contact with a surface of another laminate and rolled to bond the laminate. For example, patent document 3 discloses, as a metal laminated film for a flexible circuit board or the like, a multilayer metal laminated film produced by: a metal thin film surface activated by sputter etching on a metal thin film laminated film having a metal thin film formed on a polymer film surface is brought into contact with a metal foil surface.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2000-269616
Patent document 2: japanese patent No. 5411656
Patent document 3: japanese patent No. 4532713.
Disclosure of Invention
Problems to be solved by the invention
When a metal laminated film is produced by thermally pressing a liquid crystal polymer film against a metal layer using the thermal lamination method disclosed in patent documents 1 and 2, the liquid crystal polymer film must be heated to a melting point or higher. Therefore, when the liquid crystal polymer film is heated to a temperature near or above the melting point, the film may be largely deteriorated, and the alignment may be seriously disturbed. This may result in deterioration of dielectric characteristics of the liquid crystal polymer film and deterioration of transmission characteristics of a printed wiring board made of the metal laminated film.
On the other hand, in the multilayer metal laminated film disclosed in patent document 3, which is a metal laminated film produced by surface activation bonding, a liquid crystal polymer film is not used as a polymer film. Therefore, the printed wiring board thus fabricated has low transmission characteristics particularly in a high frequency region (e.g., 28 GHz).
Accordingly, a main object of the present invention is to provide a metal laminate film capable of optimizing transmission characteristics of a printed wiring board and a method for manufacturing the same.
Means for solving the problems
The present inventors have made intensive studies and as a result, have found that, when a liquid crystal polymer film is used as a polymer film of a metal laminated film, alignment disorder of the liquid crystal polymer film can be suppressed by bonding a metal layer to the liquid crystal polymer film by surface activation bonding to produce a metal laminated film, and have completed the present invention. That is, the gist of the present invention is as follows.
(1) A metal laminate film is characterized in that a metal layer is laminated on at least one surface of a liquid crystal polymer film, and the liquid crystal polymer film has an orientation degree F at the center in the thickness direction of 0.31 or more.
(2) A metal laminate film, characterized in that a metal layer is laminated on at least one surface of a liquid crystal polymer film, and the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film before the metal layer is laminated is 77% or more of the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film before the metal layer is laminated.
(3) The metal laminated film according to the above (1) or (2), wherein an average value of the degree of orientation F in the thickness direction of the liquid crystal polymer film is 0.31 or more.
(4) The metallic laminated film according to any one of the above (1) to (3), wherein a dissipation factor of the liquid crystal polymer film is lower than 114% of a dissipation factor of the liquid crystal polymer film before the metallic layer is laminated.
(5) The metallic laminated film according to any one of the above (1) to (4), wherein a bonding strength between the metallic layer and the liquid crystal polymer film is 2.0N/cm or more.
(6) The metal laminate film according to any one of the above (1) to (5), wherein the metal layer has a metal foil.
(7) The metal laminated film according to the above (6), wherein the metal layer further has an intermediate layer containing a metal between the liquid crystal polymer film and the metal foil.
(8) The metal laminated film according to the above (7), wherein the intermediate layer comprises any one metal selected from the group consisting of: copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, and gold.
(9) The metal laminate film according to any one of the above (6) to (8), wherein the metal foil is a copper foil, a copper alloy foil or a copper foil with a carrier.
(10) A method for producing a metal laminated film, wherein the metal laminated film is the metal laminated film according to the item (7), the method comprising: a step (preparation step) of preparing a liquid crystal polymer film and a metal foil; a step of laminating an intermediate layer containing a metal on at least one surface of the liquid crystal polymer film (intermediate layer laminating step); a step (activation step) of activating the surface of the intermediate layer by sputter etching; a step (activation step) of activating the surface of the metal foil by sputter etching; a step (rolling step) of rolling and bonding the intermediate layer and the activated surface of the metal foil to each other at a rolling reduction of 0% to 30%; and a step (heat treatment step) of performing heat treatment on the metal layer having the rolled and bonded intermediate layer and metal foil, and the liquid crystal polymer film at a temperature of from-100 ℃ to-10 ℃ of the melting point of the liquid crystal polymer film.
(11) The method for producing a metal laminated film according to the item (10), wherein the degree of orientation F at the center in the thickness direction of the liquid crystal polymer film after the heat treatment is 0.31 or more.
(12) The method for producing a metal laminated film according to the above (10) or (11), wherein an orientation degree F at a central portion in a thickness direction in the liquid crystal polymer film after the heat treatment is 77% or more of an orientation degree F at a central portion in a thickness direction in the liquid crystal polymer film before the metal layer is laminated.
(13) The method of producing a metal laminated film according to any one of the above (10) to (12), wherein a dissipation factor of the liquid crystal polymer film after the heat treatment is lower than 114% of a dissipation factor of the liquid crystal polymer film before the metal layer is laminated.
The present specification includes the disclosure in japanese patent application No. 2020-075910, which is the basis for priority of the present application.
Effects of the invention
The invention can optimize the transmission characteristics of the printed circuit board.
Drawings
FIG. 1 is a schematic sectional view showing an example of a metal laminated film according to an embodiment;
FIG. 2A is a schematic sectional view of a main part of an example of a method for producing a metal laminated film according to the embodiment;
FIG. 2B is a schematic sectional view of a main part of an example of the method for producing a metal laminated film according to the embodiment;
FIG. 3 is a schematic view showing a measurement region of the degree of orientation F in a cut sheet of a liquid crystal polymer film;
fig. 4 is a graph showing the degree of alignment F at each position of the measurement region in the untreated and cut pieces of the liquid crystal polymer films of example 1 and comparative example 2.
Detailed Description
The following describes embodiments of a metal laminate film and a method for manufacturing the same according to the present invention.
A. Metal laminated film
Embodiments of the metal laminated film according to the present invention will be described herein. Fig. 1 is a schematic cross-sectional view showing an example of a metal laminated film according to an embodiment.
As shown in fig. 1, the metal laminated film 1A of the present example has a metal layer 10 laminated on one surface 20a of a liquid crystal polymer film 20. The metal layer 10 has: a copper-containing intermediate layer 14 laminated on one surface 20a of the liquid crystal polymer film 20; and a copper foil (metal foil) 12 laminated on a surface 14a of the intermediate layer 14 opposite to the liquid crystal polymer layer 20 side.
The degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film 20 before the metal layer 10 was laminated was 0.4. In contrast, in the metal laminate film 1A, the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film 20 is 0.31 or more, and 77% or more of the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film 20 before the metal layer 10 is laminated. Thus, the dissipation factor of the liquid crystal polymer film 20 is lower than 114% of the dissipation factor of the liquid crystal polymer film 20 before the metal layers 10 are laminated. Therefore, the transmission characteristics of the printed wiring board manufactured using the metal laminated film 1A can be optimized. The bonding strength between the metal layer 10 and the liquid crystal polymer film 20 is 2.0N/cm or more, and the adhesion between the metal layer 10 and the liquid crystal polymer film 20 is high. Therefore, the reliability of fine wiring of the printed wiring board manufactured using the metal laminated film 1A can be improved.
Therefore, with the metal laminated film of the embodiment, the transmission characteristics of the printed wiring board can be optimized as with the metal laminated film 1A of the above example. Further, when the bonding strength between the metal layer and the liquid crystal polymer film is 2.0N/cm or more, the transmission characteristics of the printed wiring board and the reliability of fine wiring can be both satisfied.
Next, each composition of the metal laminated film of the embodiment will be described in detail.
1. Liquid crystal polymer film
The degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film is 77% or more of the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film before the metal layers are laminated.
The "liquid crystal polymer film" is a film composed of an aromatic polyester resin having a basic structure of p-hydroxybenzoic acid or the like, which exhibits liquid crystal properties in a molten state.
Here, "degree of orientation F" means the degree of orientation of molecules to the MD (direction of elongation of the film), and is calculated using the following method. First, a polarizer for infrared light was attached to a microscopic infrared spectrometer (microscopic FT-IR device), and the infrared transmission spectrum in the polarization direction parallel to the MD and the infrared transmission spectrum in the polarization direction perpendicular to the MD of a polymer film (here, a liquid crystal polymer film) were measured. Then, 1601cm of these infrared transmission spectra were used -1 The infrared dichroism D (1601 cm of the infrared transmission spectrum in the polarization direction parallel to the MD) was obtained -1 Intensity of peak of (1)/1601 cm of infrared transmission spectrum of polarization direction perpendicular to MD -1 The intensity of the peak a ≠ t). The baseline of the intensities of these peaks was set to 1618.9cm connecting the infrared transmission spectra -1 And 1572.4cm -1 A straight line of (c). In addition, 1601cm therein -1 The peak of (2) is a peak having a transition moment parallel to the molecular chain due to C = C stretching vibration of the benzene ring. Then, the orientation degree F is calculated from the infrared dichroic ratio D. The infrared dichroic ratio D and the degree of orientation F are calculated by the following equations (1) and (2), respectively.
[ number 1]
D＝A///A⊥ (1)
[ number 2]
F＝(D-1)//(D+2) (2)
The "degree of orientation F in the central portion in the thickness direction" means, for example, a degree of orientation F obtained by measuring an infrared dichroic ratio D in a measurement region located at the center in the thickness direction in a cross section (vertical cross section) perpendicular to the surface of the liquid crystal polymer film and parallel to the MD and calculating from the infrared dichroic ratio D measured in the measurement region. The measurement region is not particularly limited, and examples thereof include a rectangular region having a length of 100 μm in the MD × a length of 10 μm in the thickness direction shown in fig. 3.
The term "liquid crystal polymer film before lamination of the metal layer" refers to a liquid crystal polymer film prepared in the preparation step described in the items "b. Method for producing a metal laminated film 1. Preparation step" described later.
The degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film is not particularly limited as long as it is 77% or more of the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film before the metal layer is laminated. The more the orientation degree F in the central portion in the thickness direction of the liquid crystal polymer film before the metal layer is laminated, the more preferable. Specifically, the content is, for example, 0.31 or more, more preferably 0.315 or more, and still more preferably 0.32 or more. This is because especially the transmission characteristics are optimized.
The average value of the degree of orientation F in the thickness direction in the liquid crystal polymer film is not particularly limited. The closer to the average value of the degree of orientation F in the thickness direction in the liquid crystal polymer film before lamination of the metal layer, the more preferable. The average value of the degree of orientation F in the thickness direction in the liquid crystal polymer film before lamination of the metal layers is preferably 79% or more. This is because the transmission characteristics are optimized. Specifically, the average value of the degree of orientation F in the thickness direction in the liquid crystal polymer film is, for example, preferably 0.31 or more, and more preferably 0.315 or more. This is because especially the transmission characteristics are optimized.
The "average value of the degrees of orientation F in the thickness direction" is, for example, an average value of a plurality of degrees of orientation F calculated from infrared dichroic ratios D measured in a plurality of measurement regions (for example, 5 or more measurement regions) each obtained by equally dividing a region of a predetermined MD length in a cross section (vertical cross section) perpendicular to the surface of the liquid crystal polymer film and parallel to the MD in the thickness direction. The plurality of measurement regions are not particularly limited, and examples thereof include 5 rectangular regions located at distances of 5 μm, 15 μm, 25 μm, 35 μm, and 45 μm from the surface shown in fig. 3 in the thickness direction.
The dissipation factor of the liquid crystal polymer film is not particularly limited. The closer to the dissipation factor of the liquid crystal polymer film before lamination of the metal layers, the more preferable. For example, it is preferably lower than 114% of the dissipation factor of the liquid crystal polymer film before the lamination of the metal layers, more preferably lower than 112% of the dissipation factor of the liquid crystal polymer film before the lamination of the metal layers, and further preferably lower than 110%. This is because the transmission characteristics are optimized. Specifically, the dissipation factor of the liquid crystal polymer film is preferably lower than 0.0024, for example. This is because the transmission characteristics in particular are optimized.
The term "dissipation factor" refers to a dissipation factor around 28GHz, and for example, refers to a dissipation factor measured by an open resonator method using a relative dielectric constant/dissipation factor measurement system (DPS 03 manufactured by KEYCOM corporation) at a measurement frequency of 28 GHz.
The thickness of the liquid crystal polymer film may be set as appropriate depending on the use of the metal laminated film and the like. For example, when used as a flexible printed board, the thickness is preferably 10 μm or more and 150 μm or less, more preferably 10 μm or more and 120 μm or less. The thickness of the liquid crystal polymer film may be measured by a micrometer or the like, and is an average value of the thicknesses measured at 10 points randomly selected from the surface of the liquid crystal polymer film as a target. In addition, the deviation from the average value of the measurement values at 10 points with respect to the liquid crystal polymer film is preferably within 20%, more preferably within 15% of all the measurement values.
2. Metal layer
The metal layer is not particularly limited as long as it is a metal foil, and may be a metal layer having an intermediate layer containing a metal between the liquid crystal polymer film and the metal foil, in addition to the metal foil, like the metal layer 10 in the metal laminate film 1A shown in fig. 1. The metal layer may be the metal foil, but is preferably a metal layer having an intermediate layer containing a metal between the liquid crystal polymer film and the metal foil, in addition to the metal foil. The following describes a metal foil provided in the metal layer, and a case where the metal layer includes an intermediate layer and the metal foil.
(1) Metal foil
The metal foil is not particularly limited depending on the application of the metal laminated film, and examples thereof include: single-layer foils such as copper foil, nickel foil, aluminum foil, and iron foil; a laminated foil (clad material), an alloy foil, a rolled sheet, or the like. The metal foil is particularly preferably a copper foil, a copper alloy foil, or the like. This is because, for example, a flexible substrate for forming fine wiring can be obtained by roll bonding these metal foils to a liquid crystal polymer film. In addition, in the case of manufacturing a flexible substrate for forming finer wiring, a copper foil with a carrier composed of an extra thin copper foil, a release layer, and a carrier layer is preferably used as the metal foil. When the copper foil with a carrier is used, the copper foil with a carrier is laminated in the order of an extra thin copper foil, a release layer and a carrier layer from the liquid crystal polymer film side or the intermediate layer side. The copper foil with a carrier layer is not particularly limited, and MT18FL manufactured by Mitsui Metal mining Co., ltd, JXUT-III manufactured by JX Metal Co., ltd, and the like can be mentioned.
The thickness of the metal foil is not particularly limited, depending on the application of the metal laminated film. For example, if used for a flexible printed wiring board, it is preferably 3 μm or more and 100 μm or less, and particularly preferably 10 μm or more and 35 μm or less. When the copper foil with the carrier layer is used as the metal foil, the thickness of the extra thin copper foil is not particularly limited, and is, for example, preferably 0.5 μm or more and 10 μm or less, and more preferably 1 μm or more and 7 μm or less. The thickness of the release layer is not particularly limited, and is preferably 1nm or more and 1 μm or less, for example; the thickness of the support layer is not particularly limited, and is preferably 10 μm or more and 100 μm or less, for example.
Although not shown in fig. 1, the metal layer may be a metal layer having at least one of the following layers (hereinafter, sometimes referred to as a "treatment layer") on the surface of the metal foil on the liquid crystal polymer film side: a grained layer, a rust preventive layer, and a treated layer treated by a silane coupling agent, and the like. The treatment layer may be formed by laminating any one of the layers or may be formed by laminating a plurality of layers. The coarsening particle layer may include, for example, any one metal selected from the group consisting of Cu, co, and Ni, or an alloy thereof, but may also be not limited thereto. Specifically, a cobalt-nickel alloy plating layer, a copper-cobalt-nickel alloy plating layer, and the like can be given. In addition, the rust preventive layer may contain, for example, any one metal selected from the group consisting of Cr, ni, and Zn, or an alloy thereof, but may also be not limited thereto. Specifically, the treatment may be a coating treatment of chromium oxide, a coating treatment of a mixture of chromium oxide and zinc/zinc oxide, a nickel plating layer, or the like. Examples of the silane coupling agent include, but are not limited to, olefinic silanes, epoxy silanes, acrylic silanes, amino silanes, and mercapto silanes. The silane coupling agent can be applied by spraying with a sprayer, coating with a coater, dipping, or the like as appropriate.
(2) Intermediate layer
The intermediate layer is not particularly limited as long as it is a layer containing a metal, and may be a layer containing a metal, or a layer in which 2 or more layers containing a metal are stacked. Examples of the intermediate layer include a layer formed by sputtering, vapor deposition, or electroless plating, which is provided on a liquid crystal polymer film.
The intermediate layer is not particularly limited as long as it is a layer containing a metal, and preferably contains any one metal selected from the group consisting of the following metals, or an alloy containing the metal: copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, gold, aluminum, palladium, and zirconium. The intermediate layer may be a layer in which a plurality of layers containing a metal are stacked. In particular, when the metal foil is a copper foil or a copper alloy foil, the intermediate layer is preferably a layer containing a copper alloy such as copper or a copper-nickel alloy, and particularly preferably a layer containing a metal having the same composition as the metal foil. This is because etching is easily performed.
When the intermediate layer is, for example, a Cu-Ni alloy, the ratio of Ni to Cu is preferably 10 to 90% in at%. However, it is not limited thereto. By providing the intermediate layer, not only the surface of the metal foil or the liquid crystal polymer film can be protected, but also the adhesion between the metal foil and the liquid crystal polymer film can be improved, and a specific function (for example, a function as an etching stopper layer in etching) can be provided to the intermediate layer. The thickness of the intermediate layer is not particularly limited as long as it can exhibit functions such as improving adhesiveness. For example, it is preferably 5nm or more and 200nm or less, and particularly preferably 10nm or more and 100nm or less.
3. Metal laminated film
The metal laminated film is not particularly limited, and it is preferable that the bonding strength between the metal layer and the liquid crystal polymer film is 2.0N/cm or more as in the metal laminated film 1A shown in FIG. 1. This is because the reliability of fine wiring of the printed wiring board can be improved.
In the measurement of the value of the bonding strength, first, a test piece from the metal laminate film was prepared, and a 1cm wide slit was cut in the metal layer using a knife or the like. Thereafter, the metal layer and a part of the liquid crystal polymer film were peeled off, and then the liquid crystal polymer film was fixed to a support, and the metal layer was stretched at a speed of 50mm/min in a 90 ° direction with respect to the liquid crystal polymer film. The force required for peeling at this time was defined as the bonding strength (unit: N/cm). Further, when the metal layer is thin and brittle, the metal layer may be broken when the bonding strength is measured. In this case, the bonding strength may be measured after the thickness of the metal layer is increased to about 5 to 50 μm by applying electrolytic plating or the like (for example, copper plating when the metal layer is copper) to the surface of the metal layer. The method for measuring the value of the bonding strength is the method defined in JIS C6471.
In the present specification, the "bonding strength between the metal layer and the liquid crystal polymer film" refers to not only the bonding strength when the interface between the metal layer and the liquid crystal polymer film is peeled, but also the bonding strength when the interior of the metal layer is broken and peeled, and the bonding strength when the interior of the liquid crystal polymer film is broken and peeled.
The metal laminated film can be used as a metal-clad laminated plate for producing a flexible printed board.
By using the metal laminated film, a printed wiring board having a fine wiring formed thereon can be obtained. In the process of forming the wiring, an additional metal layer may be formed only in the wiring portion. Specifically, conventionally known methods such as a modified semi-addition method (MSAP method), a semi-addition method (SAP method), and a subtractive method can be suitably used to obtain a printed wiring board. For example, when the modified semi-additive process (MSAP process) is used, a non-wiring portion on a metal layer in a metal laminated film is masked, copper plating is performed on the portion not masked to form an additional metal layer, then the mask is removed, and the metal layer hidden by the mask is removed by etching, whereby a printed wiring board can be manufactured. The "printed wiring board" in the present invention includes not only a laminate having wiring formed thereon but also a laminate having wiring formed thereon and mounted with electronic components such as an IC.
The case where a metal layer is laminated on one surface of a liquid crystal polymer film has been described with respect to the metal laminated film 1A shown in fig. 1, but the metal laminated film is not limited thereto. That is, the metal layer may be provided on both surfaces of the liquid crystal polymer film as needed. A flexible printed board in which wirings are formed on both surfaces of a liquid crystal polymer film can be obtained by using a metal laminated film in which metal layers are provided on both surfaces of a liquid crystal polymer film.
B. Method for producing metal laminated film
Here, an embodiment of the method for producing a metal laminated film according to the present invention will be described. Fig. 2A and 2B are schematic sectional views of main portions showing an example of the method for manufacturing a metal laminated film according to the embodiment.
In the method for manufacturing a metal laminated film of the present example, first, a liquid crystal polymer film and a copper foil (metal foil) are prepared. The liquid crystal polymer film had an orientation degree F of 0.4 at the center in the thickness direction.
Thereafter, as shown in fig. 2A (a), one surface 20a of the liquid crystal polymer film 20 is activated by sputter etching at normal temperature using an activation processing apparatus (not shown). Next, as shown in fig. 2A (b), the intermediate layer 14 containing copper on the surface 20a of the activated liquid crystal polymer film 20 is sputtered to form a film at normal temperature using a sputtering apparatus (not shown).
Thereafter, as shown in fig. 2A (c), the surface 14a of the intermediate layer 14 is activated by sputter etching at normal temperature, the surface 12A of the copper foil 12 is activated by sputter etching, and the activated surfaces of the intermediate layer 14 and the copper foil 12 are roll bonded to each other at a rolling reduction of 0% to 30% by using an activation bonding apparatus (not shown).
Thereafter, as shown in fig. 2B (d), the metal layer 10 and the liquid crystal polymer film 20 having the rolled and bonded intermediate layer 14 and the copper foil 12 are subjected to a heat treatment furnace (not shown) in a vacuum atmosphere or N 2 Ar, NH gas (e.g. N) 2 +5％H 2 Mixed gas), and the like, at a temperature of-100 ℃ or higher of the melting point of the liquid crystal polymer film 20 and-10 ℃ or lower of the melting point of the liquid crystal polymer film 20. This improves the adhesion between the metal layer 10 and the liquid crystal polymer film 20. As shown in fig. 2B (e), the metal laminated film 1A can be produced.
The method for manufacturing a metal laminated film of the present example performs the following processes at normal temperature: a process of activating the surface 20a of the liquid crystal polymer film 20 by sputter etching; a process of sputtering the intermediate layer 14 to form a film; a process of activating the surfaces of the intermediate layer 14 and the copper foil 12 by sputter etching; and a process of rolling and bonding the activated surfaces of the intermediate layer 14 and the copper foil 12 to each other. In addition, the adhesion between the metal layer 10 and the liquid crystal polymer film 20 can be improved by performing the heat treatment at a temperature of the melting point of the liquid crystal polymer film 20 to 100 ℃ or higher and the melting point of the liquid crystal polymer film 20 to 10 ℃ or lower. Therefore, unlike the case of producing a metal laminated film by the thermal lamination method, the liquid crystal polymer film 20 is not heated at a temperature near the melting point or at a temperature exceeding the melting point, and therefore, the adhesion between the metal layer 10 and the liquid crystal polymer film 20 can be improved, and in addition, the deterioration of the dielectric properties due to the disorder of the orientation of the liquid crystal polymer film 20 and the deterioration of the surface morphology of the liquid crystal polymer film 20 can be suppressed.
Therefore, according to the method for manufacturing a metal laminated film of the embodiment, a metal laminated film in which adhesion between the metal layer and the liquid crystal polymer film is improved and deterioration of dielectric characteristics is suppressed can be manufactured as in the manufacturing method of the above example. Therefore, a metal laminated film that satisfies both the transmission characteristics of a printed wiring board and the reliability of fine wiring can be manufactured.
Next, each condition of the method for producing a metal laminated film according to the embodiment will be described in detail.
1. Preparation procedure
The liquid crystal polymer film to be prepared as the preparation step is not particularly limited. The liquid crystal polymer film having an orientation degree F of 0.4 or more in the central portion in the thickness direction is preferable, and Vecstar CTQ and the like, which are produced by Korea, K.K., are particularly preferable. This is because the dissipation factor is low and the dielectric characteristics are excellent.
The metal foil prepared in the preparation step is the same as the metal foil described in the item "a. Metal laminated film 2. Metal layer (1) metal foil", and therefore, the details thereof are not repeated.
2. Intermediate layer lamination step
The method for laminating the intermediate layer containing a metal on at least one surface of the liquid crystal polymer film in the intermediate layer laminating step is not particularly limited. For example, a method of activating at least one surface of a liquid crystal polymer film by sputter etching and then sputtering an intermediate layer containing a metal on the activated surface to form a film is preferable. The conditions for sputtering film formation by this method can be appropriately set depending on the kind of metal constituting the intermediate layer and the thickness of the intermediate layer. The kind of metal constituting the intermediate layer and the thickness of the intermediate layer are the same as those described in the item "a. Metal laminate film 2. Metal layer (2) intermediate layer", and therefore, no further description is given here.
3. Activation step
The sputter etching treatment in the activation step may be performed, for example, by preparing metal foils to be bonded or a liquid crystal polymer film provided with an intermediate layer, forming a long coil having a width of 100mm to 600mm, using the bonding surface of the metal foils or the intermediate layer as one electrode to be grounded, applying an alternating current of 1MHz to 50MHz between the other electrodes of the insulating support to generate a glow discharge, and setting the area of the electrode exposed to plasma generated by the glow discharge to 1/3 or less of the area of the other electrode. In the sputter etching process, the grounded electrode acts as a cooling roller, preventing the temperature of the conveyed material from rising.
In the sputter etching treatment in the activation step, the surface to be bonded of the metal foil or the liquid crystal polymer film provided with the intermediate layer is sputtered with an inert gas under vacuum to completely remove adsorbed substances on the surface and remove a part or all of the oxide layer on the surface. The oxide layer of copper is preferably completely removed. As the inert gas, argon, neon, xenon, krypton, or the like, or a mixed gas including at least one of them can be used. Depending on the type of metal, the adsorbate on the surface of the metal foil and the intermediate layer can be completely removed by etching about 1nm, and particularly, the oxide layer of copper can be usually 5nm to 12nm (SiO) 2 Conversion) is removed.
The processing conditions for the sputter etching may be set as appropriate depending on the kind of the metal foil and the intermediate layer, and the like. For example, the plasma treatment can be performed under vacuum at a plasma power of 100W to 10kW and a linear velocity of 0.5 m/min to 30 m/min. The degree of vacuum at this time is preferably high to prevent the adsorbate from adsorbing to the surface again, for example, 1X 10 -5 Pa-10 Pa.
When the surface of the metal foil is provided with the roughened particle layer and the rust preventive layer, the roughened particle layer and the rust preventive layer surface are activated by sputter etching. In this case, the roughened particle layer and the rust-preventive layer may be completely removed by sputter etching or may remain without being removed.
In addition, the surface of the metal foil or the surface of the intermediate layer before activation by sputter etching may be subjected to nickel plating, chromate treatment, silane coupling agent treatment, or the like as necessary to prevent oxidation and improve adhesion. The surface of the metal foil may be roughened as necessary to improve adhesion to the intermediate layer.
4. Rolling and joining process
The active surfaces of the sputter-etched metal foil and the intermediate layer may be pressed against each other by roll pressing. The rolling line load of the roll nip is not particularly limited, and may be set to a range of 0.1tf/cm to 10tf/cm, for example. However, when the thickness of the liquid crystal polymer film provided with the metal foil or the intermediate layer before bonding is large, the pressure at the time of bonding may be required to be secured by increasing the roll line load, and the numerical range is not limited thereto. On the other hand, when the roll line load is too high, not only the surface layer of the metal foil or the intermediate layer but also the joining interface is easily deformed, and therefore the thickness accuracy of each layer in the metal laminated film may be lowered. Further, when the roll line load is high, the work strain applied at the time of joining may become large.
The rolling reduction in the rolling and joining is set to 0% to 30%. Preferably 0% to 15%. Since the reduction ratio can be reduced by the above method using surface activation bonding, a metal layer having excellent thickness accuracy can be formed without generating wrinkles, cracks, and the like. Further, since the undulation at the interface between the metal foil and the intermediate layer and the liquid crystal polymer film can be reduced, the thickness accuracy is excellent when the metal layer having the metal foil and the intermediate layer is subjected to sputter etching to form the wiring, and thus a precise wiring can be obtained.
The bonding by roll bonding is preferably performed in a non-oxidizing atmosphere, for example, a vacuum atmosphere or an inert gas atmosphere such as Ar, in order to prevent the bonding strength between the metal foil and the intermediate layer from being reduced by oxygen re-adsorption on the surface thereof.
5. Heat treatment Process
The heat treatment temperature is-100 ℃ or higher of the melting point of the liquid crystal polymer film and-10 ℃ or lower of the melting point of the liquid crystal polymer film, and particularly preferably-70 ℃ or higher of the melting point of the liquid crystal polymer film and-20 ℃ or lower of the melting point of the liquid crystal polymer film. When the heat treatment temperature is set to be not lower than the lower limit of these ranges, the bonding strength between the metal layer and the liquid crystal polymer film can be increased to a desired strength, and the shape of the metal laminated film bent at the time of rolling bonding can be flattened. When the heat treatment temperature is not more than the upper limit of these ranges, the alignment disorder of the liquid crystal polymer film can be avoided, and the variation in thickness and width of the metal laminated film due to softening can be suppressed. The melting point of the liquid crystal polymer film varies depending on the material, and therefore the heat treatment temperature can be set appropriately depending on the material. For example, when the material is Vecstar CTQ (melting point: 310 ℃ C.) produced by Coli, the heat treatment temperature is 210 ℃ or higher and 300 ℃ or lower, and particularly preferably 240 ℃ or higher and 290 ℃ or lower, for the same reason.
The atmosphere for carrying out the heat treatment is not particularly limited, and is preferably a vacuum atmosphere, or N 2 And an inert gas atmosphere such as Ar or NH gas, and a vacuum atmosphere is particularly preferable. This is because it is possible to avoid a decrease in the bonding strength between the metal layer and the liquid crystal polymer film due to oxidation of the metal layer by heat treatment.
The time for performing the heat treatment is not particularly limited as long as the bonding strength between the metal layer and the liquid crystal polymer film can be set to a desired strength and the alignment disorder of the liquid crystal polymer film can be avoided. For example, it is preferably 180 seconds or more and 18000 seconds or less, and particularly preferably 200 seconds or more and 15000 seconds or less. This is because, by setting the time to be equal to or more than the lower limit of these ranges, sufficient adhesion between the metal layer and the liquid crystal polymer film can be ensured; setting the time to be equal to or less than the upper limit of these ranges enables high production efficiency and low cost of the metal laminated film.
Examples of the method for performing the heat treatment include: using a batch type heat treatment furnace, in a desired atmosphere (e.g., in a vacuum atmosphere or N) 2 Ar, NH gas, or the like) is used, and a method of maintaining the metal layer and the liquid crystal polymer film at a desired heat treatment temperature for a desired time only, and the like. Further, the heat treatment may be performed by a roll-to-roll method using a continuous heat treatment furnace depending on the heat treatment temperature and atmosphere. In this case, there can be mentioned: at least the heating part and the cooling part in the continuous heat treatment furnace are set to a desired atmosphere (for example, a vacuum atmosphere or N 2 And an inert gas atmosphere such as Ar or NH gas) at a desired temperature, and then, the metal layer and the liquid crystal polymer film are passed through the heating section and the cooling section at a desired speed, thereby maintaining the metal layer and the liquid crystal polymer film at a desired heat treatment temperature for a desired time.
6. Method for producing metal laminated film
In the method for producing a metal laminated film according to the embodiment, the degree of orientation F in the central portion in the thickness direction in the liquid crystal polymer film after the heat treatment is preferably 77% or more of the degree of orientation F in the central portion in the thickness direction in the liquid crystal polymer film before the metal layer is laminated. The liquid crystal polymer film after heat treatment has an orientation degree F in the central portion in the thickness direction of 0.31 or more. In addition, the dissipation factor of the liquid crystal polymer film after the heat treatment is preferably lower than 114% of the dissipation factor of the liquid crystal polymer film before the lamination of the metal layers, particularly preferably lower than 112% of the dissipation factor of the liquid crystal polymer film before the lamination of the metal layers, and further preferably lower than 110%.
Since joining and/or heat treatment under high pressure in the production of a metal laminated film significantly changes the structure of each layer of the metal laminated film before and after joining and/or before and after heat treatment, and there is a possibility that the characteristics of the metal laminated film are impaired, joining and heat treatment conditions that can avoid such a change in structure are preferable.
Examples
The present invention will be described in further detail below based on examples and comparative examples, but the present invention is not limited to these examples.
(example 1)
First, a liquid crystal polymer film (Vecstar CTQ-50, produced by Korea corporation) having a thickness of 50 μm was prepared, and 2 rolled copper foils having a thickness of 16 μm were prepared as metal foils. Then, after both surfaces of the liquid crystal polymer film were activated one by sputter etching, an intermediate layer (copper layer) (thickness 40 nm) containing copper was sputter-formed one by one on the activated both surfaces. Thereafter, one surface of the intermediate layer and one surface of the rolled copper foil were activated by sputter etching, the activated surface of the intermediate layer was butted against the activated surface of the rolled copper foil, and on this basis, the intermediate layer and the activated surface of the rolled copper foil were roll-bonded to each other with a line load of 1.5 tf/cm. Then, the surface of the intermediate layer on the side on which the rolled copper foil was not laminated was activated by sputter etching, the surface of the other rolled copper foil was activated by sputter etching, the activated surface of the intermediate layer was butted against the activated surface of the rolled copper foil, and on this basis, the activated surfaces of the intermediate layer and the rolled copper foil were rolled and joined to each other at a line load of 1.5 tf/cm. The reduction rate was 2.4%. Next, the intermediate layer, the metal layer having the rolled copper foil, and the liquid crystal polymer film were subjected to heat treatment at 250 ℃ for 10800 seconds in a vacuum atmosphere. Thus, a metal laminate film [ layer composition: rolled copper foil/intermediate layer (copper layer)/liquid crystal polymer film/intermediate layer (copper layer)/rolled copper foil ].
(example 2)
First, a liquid crystal polymer film (Vecstar CTQ-25, manufactured by Korea corporation) having a thickness of 25 μm was prepared, and a rolled copper foil having a thickness of 16 μm was prepared as a metal foil. Then, after one surface of the liquid crystal polymer film was activated by sputter etching, an intermediate layer (copper layer) (thickness 40 nm) containing copper was sputter-formed on the activated surface. Thereafter, the surface of the intermediate layer and the surface of the rolled copper foil were activated by sputter etching, the activated surface of the intermediate layer and the activated surface of the rolled copper foil were butted, and on this basis, the intermediate layer and the activated surface of the rolled copper foil were rolled and joined to each other with a line load of 1.5 tf/cm. The reduction rate was 2.4%. Next, the metal layer having the intermediate layer and the rolled copper foil and the liquid crystal polymer film were subjected to heat treatment at 280 ℃ for 10800 seconds in a vacuum atmosphere. Thus, a metal laminate film [ layer composition: rolled copper foil/interlayer (copper layer)/liquid crystal polymer film ].
(example 3)
Except that the heat treatment after the calender bonding is in N 2 A metal laminate film [ layer composition: rolled copper foil/interlayer (copper layer)/liquid crystal polymer film]。
(example 4)
A metal laminated film [ layer composition: rolled copper foil/second intermediate layer (copper layer)/first intermediate layer (nickel layer)/liquid crystal polymer film ].
(example 5)
First, a liquid crystal polymer film (Vecstar CTQ-25 manufactured by Colly, inc.) having a thickness of 25 μm was prepared, and a copper foil with a carrier layer, which was formed by providing an extra thin copper layer having a thickness of 1.5 μm on a copper-containing carrier layer having a thickness of 18 μm via a release layer (organic release layer) and further providing a roughened particle layer and an anti-rust layer on the surface of the extra thin copper layer [ MT18FL manufactured by Mitsui Metal mining Co., ltd ], was prepared as a metal foil. Then, after one surface of the liquid crystal polymer film was activated by sputter etching, an intermediate layer (copper layer) (thickness 40 nm) containing copper was sputter-formed on the activated surface. Then, the surface of the intermediate layer and the surface of the extremely thin copper layer were activated by sputter etching, the activated surface of the intermediate layer and the activated surface of the extremely thin copper layer were butted, and then the intermediate layer and the activated surface of the extremely thin copper layer were roll-bonded to each other with a line load of 1.5 tf/cm. The reduction rate was 2.4%. Next, the metal layer having the intermediate layer and the copper foil with the carrier layer and the liquid crystal polymer film were subjected to heat treatment at 250 ℃ in a vacuum atmosphere for 10800 seconds. Thus, a metal laminate film [ layer composition: copper foil with carrier layer/intermediate layer (copper layer)/liquid crystal polymer film ].
(example 6)
A copper foil with a carrier layer, which is provided with an extra thin copper layer having a thickness of 5.0 μm on a copper-containing carrier layer having a thickness of 18 μm via a release layer (organic release layer), and which is provided with only a rust-preventive layer on the surface of the extra thin copper layer, was used as a metal foil; a metal laminate film [ layer composition: copper foil with carrier layer/intermediate layer (copper layer)/liquid crystal polymer film ].
(example 7)
First, a liquid crystal polymer film (Vecstar CTQ-25, produced by Korea corporation) having a thickness of 25 μm was prepared, and a copper foil with a carrier layer, which was formed by providing a copper carrier layer having a thickness of 18 μm with an extra thin copper layer having a thickness of 2.0 μm via a release layer (inorganic release layer) and provided with only a rust-preventive layer on the surface of the extra thin copper layer, was prepared as a metal foil. Then, after one surface of the liquid crystal polymer film was activated by sputter etching, an intermediate layer (copper layer) (thickness 40 nm) containing copper was sputter-formed on the activated surface. Then, the surface of the intermediate layer and the surface of the extremely thin copper layer are activated by sputter etchingThe activated surface of the intermediate layer was butted against the activated surface of the extremely thin copper layer, and on this basis, the intermediate layer and the activated surface of the extremely thin copper layer were roll-bonded to each other with a line load of 1.5 tf/cm. The reduction rate was 2.4%. Next, the metal layer and the liquid crystal polymer film of the copper foil having the intermediate layer and the carrier layer are coated with a coating solution containing N 2 The heat treatment was carried out at 280 ℃ in an atmosphere for 10800 seconds. Thus, a metal laminate film [ layer composition: copper foil/intermediate layer (copper layer)/liquid crystal polymer film with carrier layer]。
(example 8)
A metal laminated film [ layer composition: copper foil with carrier layer/second intermediate layer (copper layer)/first intermediate layer (nickel layer)/liquid crystal polymer film ].
Comparative example 1
A rolled copper foil having a treated layer composed of a roughened particle layer and the like and having a thickness of 12 μm was thermally pressure-bonded one by one to both surfaces of a liquid crystal polymer film (Vecstar CTQ-50 produced by Korea) having a thickness of 50 μm by a thermal lamination method, thereby producing a metal laminated film (layer composition: rolled copper foil/liquid crystal polymer film/rolled copper foil). The metal laminate film is obtained by sandwiching a liquid crystal polymer film with 2 rolled copper foils so that both surfaces of the liquid crystal polymer film are respectively butted against the surfaces of the treated layers of the 2 rolled copper foils, heating the liquid crystal polymer film to a temperature of 310 ℃ or higher, and subjecting the liquid crystal polymer film and the rolled copper foils to hot press molding, thereby bonding the surfaces of the liquid crystal polymer film and the rolled copper foils to each other.
Comparative example 2
A metal laminate film (layer composition: electrodeposited copper foil/liquid crystal polymer film/electrodeposited copper foil) was produced by thermocompression bonding a 12 μm thick electrodeposited copper foil having a treated layer of a roughened particle layer or the like on one surface of a 50 μm thick liquid crystal polymer film (Vecstar CTQ-50 produced by Coli) by a thermal lamination method. The metal laminate film is formed by sandwiching a liquid crystal polymer film with 2 electrolytic copper foils so that both surfaces of the liquid crystal polymer film are in contact with the surfaces of the treated layers of the 2 electrolytic copper foils, respectively, and then heating the liquid crystal polymer film to a temperature of 310 ℃ or higher to perform hot press molding of the liquid crystal polymer film and the electrolytic copper foils, thereby joining the surfaces of the liquid crystal polymer film and the electrolytic copper foils to each other.
[ degree of orientation F of liquid Crystal Polymer film ]
The copper layer and the electrolytic copper foil were chemically removed from the metal laminate films of examples 1 and comparative example 2 by etching with an iron chloride solution or the like, respectively, and cut pieces having a size of about 4 μm in the width direction were cut out from the liquid crystal polymer film after the removal of the copper layer and the electrolytic copper foil, and the degree of orientation F in each region in the thickness direction of each cut piece was measured. For comparison, a cut piece having a size of about 4 μm in the width direction was cut out from the same untreated liquid crystal polymer film as the liquid crystal polymer film used for producing the metal laminated film of example 1 and comparative example 2, and the degree of orientation F of each region in the thickness direction of the cut piece was measured. Fig. 3 is a schematic view showing a measurement region of the degree of orientation F in a cut sheet of a liquid crystal polymer film.
As for the measurement of the degree of orientation F, as shown in fig. 3, in a cross section (vertical cross section) perpendicular to the surface of the cut piece of the liquid crystal polymer film and parallel to the MD, rectangular regions located at distances of 5 μm, 15 μm, 25 μm, 35 μm, and 45 μm from the thickness direction of the surface were set as measurement regions by a diaphragm, an infrared dichroic ratio D was measured by microscopic infrared spectroscopic analysis in each measurement region, and the degree of orientation F was calculated from the infrared dichroic ratio D. The measuring apparatus, measuring method, polarizer and measuring conditions used were as follows.
A measuring device: cary670/620 manufactured by Agilent technologies, inc
The measuring method comprises the following steps: polarization microscopy FT-IR analysis/transmission method
Aperture size: the length of MD is 100 μm × the length in the thickness direction is 10 μm
A polarizer: substrate KRS-5
Resolution ratio: 4cm -1
And (4) accumulating times: 128 times
The infrared dichroism ratio D is C = C stretching vibration attributed to benzene ring according to 1601cm with transition moment parallel to molecular chain -1 The intensity of the peak (b) was determined. Specifically, 1601cm -1 The peak of (3) was used as a quantitative peak, and 1618.9cm of the spectrum was determined -1 Point of (2) and 1572.4cm -1 The infrared dichroic ratio D was obtained by equation (1) based on the intensity a//, of the peak of the infrared transmission spectrum measured in the polarization direction parallel to the MD and the intensity a ±, of the peak of the infrared transmission spectrum measured in the polarization direction perpendicular to the MD, measured as a base line of a straight line connecting the points. The degree of orientation F in the MD was calculated from the formula (2).
[ number 3]
D＝A///A⊥ (1)
[ number 4]
F＝(D-1)/(D+2) (2)
1601cm measured at the position of each measurement area for the untreated liquid crystal polymer film cut pieces of example 1 and comparative example 2 -1 The intensity a// and intensity a ≠ of the peak of (a), the infrared dichroic ratio D, and the average value of the degree of orientation F and the degree of orientation F in the thickness direction of each slice are shown in table 1. Fig. 4 is a graph showing the degree of alignment F at each position of the measurement region in the untreated and cut pieces of the liquid crystal polymer films of example 1 and comparative example 2.
[ Table 1]
As shown in table 1 and fig. 4, the degree of orientation F in the entire thickness direction of the cut pieces of the liquid crystal polymer films of example 1 and comparative example 2 was lower than that of the untreated liquid crystal polymer film. In addition, the cut pieces of the liquid crystal polymer films of example 1 and comparative example 2 were compared, and the degree of orientation F of the cut piece of the liquid crystal polymer film of example 1 was higher than that of the cut piece of the liquid crystal polymer film of comparative example 2 in the entire thickness direction. In addition, regarding the chips of the untreated and liquid crystal polymer films of example 1, unlike the chips of the liquid crystal polymer film of comparative example 2, a tendency was observed that the degree of orientation of the measurement regions located on the center side in the thickness direction (distances from the thickness direction of the chip surface: 15 μm, 25 μm, and 35 μm) was higher than that of the measurement regions located on the surface side in the thickness direction (distances from the thickness direction of the chip surface: 5 μm and 45 μm).
[ dielectric characteristics of liquid Crystal Polymer film ]
The copper layer, rolled copper foil and electrolytic copper foil were chemically removed from the metal laminate films of examples 1, comparative examples 1 and 2 by etching with an iron chloride solution or the like, respectively, to prepare liquid crystal polymer films for measuring the dielectric characteristics of examples 1, comparative examples 1 and 2. Further, the thickness, relative dielectric constant, and dissipation factor were measured with respect to the same untreated liquid crystal polymer film as used for making the metal laminated film of example 1, comparative example 1, and comparative example 2, and the liquid crystal polymer film used for measuring the dielectric characteristics of example 1, comparative example 1, and comparative example 2. The relative permittivity and dissipation factor were measured by an open resonator method using a relative permittivity/dissipation factor measurement system (DPS 03 manufactured by keyom corporation) with a measurement frequency of 28 GHz. The measurement results are shown in table 2.
[ Table 2]
As shown in table 2, the liquid crystal polymer films of comparative examples 1 and 2 had an increase in dissipation factor of more than 14% relative to the untreated liquid crystal polymer film, while the liquid crystal polymer film of example 1 had an increase in dissipation factor of less than 5% relative to the untreated liquid crystal polymer film.
[ bonding strength of Metal layer and liquid Crystal Polymer film ]
The metal laminated films of examples 1 to 8 and comparative examples 1 and 2 were measured for the bonding strength between the metal layer and the liquid crystal polymer film by the measurement method described in the item "a. Metal laminated film 3. Metal laminated film".
In the metal laminated films of examples 5 to 8, after the carrier layer and the release layer of the copper foil with the carrier layer were removed to expose the extra thin copper layer, electrolytic copper plating was performed on the surface of the extra thin copper layer in the same manner as the electrolytic plating method performed on the surface of the metal layer described in the item "a. Metal laminated film 3. Metal laminated film" to prevent the breakage of the thin and fragile extra thin copper layer, and the bonding strength between the metal layer and the liquid crystal polymer film was measured after increasing the thickness of the extra thin copper layer. The measurement results are shown in table 3.
[ Table 3]
As shown in Table 3, the metal layers of the metal laminated films of examples 1 to 8 all had a bonding strength of 2.0N/cm or more to the liquid crystal polymer film. In addition, with respect to the metal laminated films of examples 1 to 8, a tendency was observed that the higher the temperature of the heat treatment, the higher the bonding strength.
Description of the symbols
1A Metal laminate film
10. Metal layer
12. Copper foil (Metal foil)
Surface of 12a copper foil
14. Intermediate layer
14a surface of the intermediate layer opposite to the liquid crystal polymer film side
20. Liquid crystal polymer film
20a one surface of liquid crystalline Polymer film
All publications, patents and patent applications cited in this specification are herein incorporated in their entirety by reference into the specification.
Claims (13)
1. A metal laminate film is characterized in that a metal layer is laminated on at least one surface of a liquid crystal polymer film, and the liquid crystal polymer film has an orientation degree F at the center in the thickness direction of 0.31 or more.
2. A metal laminate film characterized in that a metal layer is laminated on at least one surface of a liquid crystal polymer film, and the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film is 77% or more of the degree of orientation F in the central portion in the thickness direction of the liquid crystal polymer film before the metal layer is laminated.
3. The metallic laminated film according to claim 1 or 2, wherein an average value of the degree of orientation F in the thickness direction in the liquid crystal polymer film is 0.31 or more.
4. The metallic laminate film as recited in any one of claims 1 to 3, wherein the dissipation factor of the liquid crystal polymer film is lower than 114% of the dissipation factor of the liquid crystal polymer film before the metallic layer is laminated.
5. The metallic laminate film according to any one of claims 1 to 4, wherein the bonding strength between the metallic layer and the liquid crystal polymer film is 2.0N/cm or more.
6. The metallic laminate film according to any one of claims 1 to 5, wherein the metallic layer has a metallic foil.
7. The metallic laminate film as recited in claim 6, wherein the metallic layer further has an intermediate layer containing a metal between the liquid crystal polymer film and the metal foil.
8. The metal laminated film according to claim 7, wherein the intermediate layer comprises any one metal selected from the group consisting of: copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, and gold.
9. The metal laminate film according to any one of claims 6 to 8, wherein the metal foil is a copper foil, a copper alloy foil, or a copper foil with a carrier.
10. A method of manufacturing a metal laminated film, wherein the metal laminated film is the metal laminated film according to claim 7, the method comprising:
preparing a liquid crystal polymer film and a metal foil;
a step of laminating an intermediate layer containing a metal on at least one surface of the liquid crystal polymer film;
a step of activating the surface of the intermediate layer by sputter etching;
a step of activating the surface of the metal foil by sputter etching;
rolling and bonding the intermediate layer and the activated surface of the metal foil to each other at a rolling reduction ratio of 0% to 30%; and the number of the first and second groups,
and a step of performing heat treatment on the metal layer having the intermediate layer and the metal foil that are roll-bonded and the liquid crystal polymer film at a temperature of-100 ℃ or higher and-10 ℃ or lower of the melting point of the liquid crystal polymer film.
11. The method of manufacturing a metal laminate film according to claim 10, wherein the degree of orientation F at the center in the thickness direction of the liquid crystal polymer film after the heat treatment is 0.31 or more.
12. The method of manufacturing a metal laminated film according to claim 10 or 11, wherein the degree of orientation F in the central portion in the thickness direction in the liquid crystal polymer film after the heat treatment is 77% or more of the degree of orientation F in the central portion in the thickness direction in the liquid crystal polymer film before the metal layer is laminated.
13. The method of manufacturing a metal laminated film according to any one of claims 10 to 12, wherein the dissipation factor of the liquid crystal polymer film after the heat treatment is lower than 114% of the dissipation factor of the liquid crystal polymer film before the metal layer is laminated.
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| PCT/JP2021/015640 WO2021215353A1 (en) | 2020-04-22 | 2021-04-15 | Metal-laminated film and method for manufacturing same |
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| KR20230006808A (en) | 2023-01-11 |
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| TW202205918A (en) | 2022-02-01 |
| WO2021215353A1 (en) | 2021-10-28 |
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