US20220032575A1 - Liquid crystal polymer film and laminate comprising the same - Google Patents
Liquid crystal polymer film and laminate comprising the same Download PDFInfo
- Publication number
- US20220032575A1 US20220032575A1 US17/502,213 US202117502213A US2022032575A1 US 20220032575 A1 US20220032575 A1 US 20220032575A1 US 202117502213 A US202117502213 A US 202117502213A US 2022032575 A1 US2022032575 A1 US 2022032575A1
- Authority
- US
- United States
- Prior art keywords
- equal
- lcp
- less
- metal foil
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 156
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 156
- 239000011888 foil Substances 0.000 claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 81
- 238000003780 insertion Methods 0.000 abstract description 13
- 230000037431 insertion Effects 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 54
- 239000011889 copper foil Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- -1 aliphatic hydroxy compounds Chemical class 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 3
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 102220625006 2-(3-amino-3-carboxypropyl)histidine synthase subunit 1_E10A_mutation Human genes 0.000 description 1
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- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 description 1
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- 102220502369 Golgin subfamily A member 1_E11A_mutation Human genes 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
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- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
Classifications
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- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- H—ELECTRICITY
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- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0141—Liquid crystal polymer [LCP]
Definitions
- the present application relates to a polymer film for a laminate, more particularly to a liquid crystal polymer (LCP) film and a laminate comprising the same.
- LCP liquid crystal polymer
- 5G fifth generation mobile networks
- 4G fourth generation mobile networks
- the interfacial adhesion between the LCP film and a metal foil is generally insufficient, so components on a circuit board are prone to be detached and thus subsequent lamination processes will be seriously adversely affected. Therefore, the peel strength between the LCP film and the metal foil of conventional laminates still needs improvement in order to develop a laminate that is suitable for 5G products.
- the objective of the present application is to enhance the peel strength between an LCP film and a metal foil.
- the LCP film has a first surface and a second surface opposite each other, and a ratio of a ten-point mean roughness relative to a maximum height (Rz/Ry) of the first surface may be more than or equal to 0.30 and less than or equal to 0.62.
- the adhesion of the LCP film stacked to the metal foil can be increased, thereby enhancing the peel strength between the LCP film and the metal foil. Therefore, the problem such as wire detachment during subsequent processing of a laminate can be avoided.
- Rz/Ry thereof in terms of the second surface of the LCP film, Rz/Ry thereof may also be more than or equal to 0.30 and less than or equal to 0.62.
- the LCP film regardless of whether the LCP film of the present application is laminated with at least one metal foil through either or both of the first surface and the second surface, the LCP film can possess superior adhesion to the at least one metal foil, thus improving the peel strength between the LCP film and the at least one metal foil.
- Rz/Ry of the first surface and/or Rz/Ry of the second surface of the LCP film of the present application may also be more than or equal to 0.36 and less than or equal to 0.61.
- Rz/Ry of the first surface and Rz/Ry of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Rz/Ry of the first surface and Rz/Ry of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- Rz of the first surface of the LCP film may be less than or equal to 2 micrometers ( ⁇ m).
- Rz of the first surface of the LCP film of the present application may be less than or equal to 1.5 ⁇ m; more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.3 ⁇ m and less than or equal to 1.5 ⁇ m; even more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.3 ⁇ m and less than or equal to 1.4 ⁇ m; still more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.3 ⁇ m and less than or equal to 1.3 ⁇ m; yet still more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.35 ⁇ m and less than or equal to 1.2 ⁇ m; even further preferably, Rz of the first surface of the LCP
- Ry of the first surface of the LCP film may be less than or equal to 2.2 ⁇ m. In one of the embodiments, Ry of the first surface of the LCP film of the present application may be less than or equal to 2.0 ⁇ m; preferably, Ry of the first surface of the LCP film of the present application may be more than or equal to 0.5 ⁇ m and less than or equal to 1.8 ⁇ m; more preferably, Ry of the first surface of the LCP film of the present application may be more than or equal to 0.6 ⁇ m and less than or equal to 1.6 ⁇ m. In one of the embodiments, Ry of the first surface and Ry of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Ry of the first surface and Ry of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- arithmetic average roughness (Ra) of the first surface of the LCP film of the present application may be less than or equal to 0.09 ⁇ m.
- applying the LCP film to a laminate can significantly decrease the insertion loss, so that the laminate comprising the LCP film is highly suitable for high-end 5G products.
- Ra of the first surface of the LCP film of the present application may be more than or equal to 0.02 ⁇ m and less than or equal to 0.08 ion; even more preferably, Ra of the first surface may be more than or equal to 0.02 ⁇ m and less than or equal to 0.07 ⁇ m; still more preferably, Ra of the first surface may be more than or equal to 0.02 ⁇ m and less than or equal to 0.06 ⁇ m.
- Ra of the first surface and Ra of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Ra of the first surface and Ra of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- the LCP film may be produced by an LCP resin, which is commercially available or made from conventional raw materials.
- the LCP resin is not particularly restricted.
- aromatic or aliphatic hydroxy compounds such as hydroquinone, resorcin, 2,6-naphthalenediol, ethanediol, 1,4-butanediol, and 1,6-hexanediol
- aromatic or aliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2-chloroterephthalic acid, and adipic acid
- aromatic hydroxy carboxylic acids such as 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, and 4′-hydroxy-4-biphenylcarboxylic acid
- aromatic amine compounds such as p-phenylenediamine, 4,4′-diamin
- 6-hydroxy-2-naphthalenecarboxylic acid, 4-hydroxybenzoic acid, and acetyl anhydride may be chosen to obtain the LCP resin, which can be used to prepare the LCP film of the present application.
- the melting point of the LCP resin may be about 250° C. to 360° C.
- a person having ordinary knowledge in the art may add additives such as, but not limited to, lubricants, antioxidants, electrical insulating agents, or fillers during preparation of the LCP film of the present application based on different needs.
- the applicable additives may be, but are not limited to, polycarbonate, polyamide, polyphenylene sulfide, polyetheretherketone, etc.
- the thickness of the LCP film is not particularly restricted.
- the thickness of the LCP film may be more than or equal to 10 ⁇ m and less than or equal to 500 ⁇ m; preferably, the thickness of the LCP film of the present application may be more than or equal to 10 ⁇ m and less than or equal to 300 ⁇ m; more preferably, the thickness of the LCP film of the present application may be more than or equal to 15 ⁇ m and less than or equal to 250 ⁇ m; even more preferably, the thickness of the LCP film of the present application may be more than or equal to 20 ⁇ m and less than or equal to 200 ⁇ m.
- another aspect of the present application also provides a laminate, which comprises a first metal foil and the LCP film.
- the first metal foil is disposed over the first surface of the LCP film.
- the laminate of the present application may further comprise a second metal foil, which is disposed over the second surface of the LCP film, i.e., the LCP film of the present application is sandwiched between the first metal foil and the second metal foil.
- the adhesion of the LCP film stacked to the first metal foil and the adhesion of the LCP film stacked to the second metal foils are improved simultaneously, and thus the peel strength between the LCP film and the first metal foil as well as the peel strength between the LCP film and the second metal foil are enhanced.
- “stacking” is not limited to direct contact; further, it also includes indirect contact.
- the first metal foil and the LCP film in the laminate are stacked with each other in a direct contact manner, that is, the first metal foil is disposed on and in direct contact with the first surface of the LCP film.
- the first metal foil and the LCP film in the laminate are stacked with each other in an indirect contact manner, that is, the first metal foil is disposed above the LCP film, and the first metal foil and the LCP film are stacked with each other in an indirect contact manner.
- a connection layer may be disposed between the first metal foil and the LCP film based on different needs, so that the first metal foil contacts the first surface of the LCP film via the connection layer.
- the material of the connection layer may be adjusted according to different needs to provide corresponding functions.
- the material of the connection layer may include nickel, cobalt, chromium, or alloys thereof to provide functions such as thermal resistance, chemical resistance, or electrical resistance.
- the second metal foil and the LCP film in the laminate may also be stacked with each other in direct contact or indirect contact. In one of the embodiments of the present application, the stacking manner for the LCP film and the first metal foil and the one for the LCP film and the second metal foil may be the same or different.
- the first metal foil and/or the second metal foil may be, but are not limited to, copper foil, gold foil, silver foil, nickel foil, aluminum foil, stainless steel foil, etc.
- the first metal foil and the second metal foil are made of different materials.
- the first metal foil and/or the second metal foil may be copper foil, so that the copper foil and the LCP film are stacked to form a copper clad laminate (CCL).
- the manufacturing method of the first metal foil and/or the manufacturing method of the second metal foil are not particularly restricted, as long as the methods do not violate the objective of the present application.
- the metal foil may be produced by, but not limited to, a roll-to-roll method or an electrodeposition method.
- surface treatments of the first metal foil and/or the second metal foil of the present application can be conducted based on different needs by a person having ordinary knowledge in the art.
- the surface treatments may be selected from, but not limited to, roughening treatments, acid-base treatments, thermal treatments, degreasing treatments, ultraviolet irradiation treatments, corona discharge treatments, plasma treatments, primer coating treatments, etc.
- a mixture of 6-hydroxy-2-naphthalenecarboxylic acid (540 g), 4-hydroxybenzoic acid (1071 g), acetyl anhydride (1086 g), sodium phosphite (1.3 g), and 1-methylimidazole (0.3 g) was charged into a 3-liter autoclave and stirred for acetylation at 160° C. for about 2 hours under nitrogen atmosphere at normal pressure. Subsequently, the mixture was heated to 320° C. at a rate of 30° C. per hour, and then under this temperature condition, the pressure was reduced slowly from 760 torr to equal to or less than 3 torr or below, and the temperature was increased from 320° C. to 340° C.
- the LCP resin obtained from Preparation Examples 1 to 3 was used as raw materials to prepare LCP films of Examples 1 to 13 (E1 to E13) and Comparative Examples 1 to 5 (C1 to C5) by the methods described below.
- the LCP resin was put into an extruder having a screw diameter of 27 millimeters (mm) (manufacturer: Leistritz, model: ZSE27) and heated to a temperature ranging from 300° C. to 320° C., and then extruded from a T-die of a width of 500 mm with a feeding speed ranging from 3.5 kilograms per hour (kg/hr) to 10 kg/hr.
- the LCP resin was then delivered to a space between two casting wheels having a temperature ranging from about 250° C. to 320° C.
- the casting wheels were spaced about 1 mm to 50 mm from the T-die.
- Examples 1 to 13 differ from those of Comparative Examples 1 to 5 in the kind of the LCP resin, the distance from the T-die to the surfaces of the casting wheels, the feeding speed, and the extrusion temperature.
- the parameters of Examples 1 to 13 and Comparative Examples 1 to 5 are respectively listed in Table 1 below.
- the LCP films of Examples 1 to 13 and Comparative Examples 1 to 5 were used as test samples.
- the surface morphology images of the test samples were each taken using a laser microscope (manufacturer: Olympus, model: LEXT OLS5000-SAF, objective lens: MPLAPON-50 ⁇ LEXT) with an objective lens having a magnification power of 50 ⁇ , 1 ⁇ optical zoom, and a 405 nanometers (nm) wavelength of light source at a temperature of 24 ⁇ 3° C. and a relative humidity of 63 ⁇ 3%.
- Ra, Ry, and Rz of either surface of the test samples were measured according to JIS B 0601:1994 using an evaluation length of 4 mm and a cutoff value ( ⁇ c) of 0.8 mm.
- the results of the test samples are listed in Table 2 below.
- Laminates of Examples 1A to 13A (E1A to E13A) and Comparative Examples 1A to 5A (C1A to C5A) were produced from the LCP films of Examples 1 to 13 as well as Comparative Examples 1 to 5 and commercially available copper foils.
- the product descriptions of the commercially available copper foils are provided as follows:
- Copper foil 1 CF-T49A-HD2, purchased from FUKUDA METAL FOIL & POWDER CO., LTD., Rz: about 1.2 ⁇ m;
- Copper foil 2 CF-H9A-HD2, purchased from FUKUDA METAL FOIL & POWDER CO., LTD., Rz: about 1.0 ⁇ m;
- Copper foil 3 3EC-M2S-HTE-SP2, purchased from MITSUI MINING & SMELTING CO., LTD., Rz: about 1.1 ⁇ m; and
- the LCP film having a thickness about 50 ⁇ m and two identical copper foils each having a thickness about 12 ⁇ m were each first cut to size of 20 cm*20 cm.
- the LCP film was then sandwiched between the two copper foils to form a laminated structure.
- the laminated structure was subjected to a pressure of 5 kilograms per square centimeter (kg/cm 2 ) for 60 seconds at 180° C., followed by a pressure of 20 kg/cm 2 for 25 minutes (min) at 300° C., and then cooled to room temperature to obtain a laminate.
- the peel strength of the laminates was measured according to IPC-TM-650 No.: 2.4.9.
- the laminates of Examples 1A to 13A and Comparative Examples 1A to 5A were each cut to size of a length about 228.6 mm and a width about 3.2 mm as etched specimens.
- Each etched specimen was placed at a temperature of 23 ⁇ 2° C. and a relative humidity of 50 ⁇ 5% for 24 hours to reach stabilization. Subsequently, each etched specimen was adhered to a clamp of a testing machine (manufacturer: Hung Ta Instrument Co., Ltd., model: HT-9102) with a double faced adhesive tape.
- Examples 1A to 13A and Comparative Examples 1A to 5A were each cut to size of a length about 100 mm, a width about 140 mm, and a resistance about 50 Ohm ( ⁇ ) as strip line specimens.
- the insertion loss of the strip line specimens was measured under 10 GHz by a microwave network analyzer (manufacturer: Agilent Technologies, Ltd., model: 8722ES) including a probe (manufacturer: Cascade Microtech, model: ACP40-250).
- the peel strength of the LCP film stacked to metal foils can be specifically improved.
- the laminate having the LCP film not only has improved peel strength but also has reduced insertion loss. Therefore, the laminate of the present application is highly suitable for high-end 5G products.
Abstract
Provided are a liquid crystal polymer (LCP) film and a laminate comprising the same. The LCP film has a first surface and a second surface opposite each other, and a ratio of a ten-point mean roughness relative to a maximum height (Rz/Ry) of the first surface is from 0.30 to 0.62. By controlling Rz/Ry of at least one surface of the LCP film, the peel strength of the LCP film stacked to a metal foil can be increased, and the laminate comprising the same can still maintain the merit of low insertion loss.
Description
- This application is a continuation application of U.S. patent application Ser. No. 16/748,846, filed Jan. 22, 2020, which claims the benefit of Taiwan Patent Application No. 108147226, filed Dec. 23, 2019, each of which is incorporated by reference herein in its entirety.
- The present application relates to a polymer film for a laminate, more particularly to a liquid crystal polymer (LCP) film and a laminate comprising the same.
- The rapid development of mobile communication technology has pushed the telecom industry to actively develop the fifth generation mobile networks, abbreviated as 5G, so as to optimize the performances, such as the data transmission rate, the response time, and the system capacity, etc. of the fourth generation mobile networks (4G).
- Since 5G communication technology uses high-frequency bands for signal transmission, the higher the frequency of the signal, the greater the insertion loss. In order to achieve signal transmission using high-frequency bands, it has been known that an LCP film with low dielectric properties can be chosen to match a metal foil, and they are used to produce a laminate so as to decrease dielectric loss of the signal transmission.
- However, the interfacial adhesion between the LCP film and a metal foil is generally insufficient, so components on a circuit board are prone to be detached and thus subsequent lamination processes will be seriously adversely affected. Therefore, the peel strength between the LCP film and the metal foil of conventional laminates still needs improvement in order to develop a laminate that is suitable for 5G products.
- To overcome the shortcomings, the objective of the present application is to enhance the peel strength between an LCP film and a metal foil.
- To achieve the aforementioned objective, one aspect of the present application provides an LCP film. The LCP film has a first surface and a second surface opposite each other, and a ratio of a ten-point mean roughness relative to a maximum height (Rz/Ry) of the first surface may be more than or equal to 0.30 and less than or equal to 0.62.
- By controlling the Rz/Ry property of either surface (e.g., the first surface) of the LCP film, the adhesion of the LCP film stacked to the metal foil can be increased, thereby enhancing the peel strength between the LCP film and the metal foil. Therefore, the problem such as wire detachment during subsequent processing of a laminate can be avoided.
- In accordance with the present application, in terms of the second surface of the LCP film, Rz/Ry thereof may also be more than or equal to 0.30 and less than or equal to 0.62. Herein, regardless of whether the LCP film of the present application is laminated with at least one metal foil through either or both of the first surface and the second surface, the LCP film can possess superior adhesion to the at least one metal foil, thus improving the peel strength between the LCP film and the at least one metal foil. Preferably, Rz/Ry of the first surface and/or Rz/Ry of the second surface of the LCP film of the present application may also be more than or equal to 0.36 and less than or equal to 0.61. In one of the embodiments, Rz/Ry of the first surface and Rz/Ry of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Rz/Ry of the first surface and Rz/Ry of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- In accordance with the present application, Rz of the first surface of the LCP film may be less than or equal to 2 micrometers (μm). Preferably, Rz of the first surface of the LCP film of the present application may be less than or equal to 1.5 μm; more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.3 μm and less than or equal to 1.5 μm; even more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.3 μm and less than or equal to 1.4 μm; still more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.3 μm and less than or equal to 1.3 μm; yet still more preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.35 μm and less than or equal to 1.2 μm; even further preferably, Rz of the first surface of the LCP film of the present application may be more than or equal to 0.39 μm and less than or equal to 1.2 μm. In one of the embodiments, Rz of the first surface and Rz of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Rz of the first surface and Rz of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- In accordance with the present application, Ry of the first surface of the LCP film may be less than or equal to 2.2 μm. In one of the embodiments, Ry of the first surface of the LCP film of the present application may be less than or equal to 2.0 μm; preferably, Ry of the first surface of the LCP film of the present application may be more than or equal to 0.5 μm and less than or equal to 1.8 μm; more preferably, Ry of the first surface of the LCP film of the present application may be more than or equal to 0.6 μm and less than or equal to 1.6 μm. In one of the embodiments, Ry of the first surface and Ry of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Ry of the first surface and Ry of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- Preferably, arithmetic average roughness (Ra) of the first surface of the LCP film of the present application may be less than or equal to 0.09 μm. Herein, applying the LCP film to a laminate can significantly decrease the insertion loss, so that the laminate comprising the LCP film is highly suitable for high-end 5G products.
- More preferably, Ra of the first surface of the LCP film of the present application may be more than or equal to 0.02 μm and less than or equal to 0.08 ion; even more preferably, Ra of the first surface may be more than or equal to 0.02 μm and less than or equal to 0.07 μm; still more preferably, Ra of the first surface may be more than or equal to 0.02 μm and less than or equal to 0.06 μm. By means of decreasing Ra of the first surface of the LCP film, the insertion loss of the laminate including the LCP film is further reduced, so that the laminate is highly suitable for high-end 5G products. In one of the embodiments, Ra of the first surface and Ra of the second surface of the LCP film of the present application may be the same or different. In one of the embodiments, Ra of the first surface and Ra of the second surface of the LCP film of the present application both fall within the aforementioned ranges.
- In accordance with the present application, the LCP film may be produced by an LCP resin, which is commercially available or made from conventional raw materials. In the present application, the LCP resin is not particularly restricted. For example, aromatic or aliphatic hydroxy compounds such as hydroquinone, resorcin, 2,6-naphthalenediol, ethanediol, 1,4-butanediol, and 1,6-hexanediol; aromatic or aliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2-chloroterephthalic acid, and adipic acid; aromatic hydroxy carboxylic acids such as 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, and 4′-hydroxy-4-biphenylcarboxylic acid; aromatic amine compounds such as p-phenylenediamine, 4,4′-diaminobiphenyl, naphthalene-2,6-diamine, 4-aminophenol, 4-amino-3-methylphenol, and 4-aminobenzoic acid may be used as raw materials to prepare the LCP resin, and the LCP resin is then used to prepare the LCP film of the present application. In one of the embodiments of the present application, 6-hydroxy-2-naphthalenecarboxylic acid, 4-hydroxybenzoic acid, and acetyl anhydride (also called acetic anhydride) may be chosen to obtain the LCP resin, which can be used to prepare the LCP film of the present application. In one of the embodiments, the melting point of the LCP resin may be about 250° C. to 360° C.
- In one of the embodiments, a person having ordinary knowledge in the art may add additives such as, but not limited to, lubricants, antioxidants, electrical insulating agents, or fillers during preparation of the LCP film of the present application based on different needs. For example, the applicable additives may be, but are not limited to, polycarbonate, polyamide, polyphenylene sulfide, polyetheretherketone, etc.
- In accordance with the present application, the thickness of the LCP film is not particularly restricted. For example, the thickness of the LCP film may be more than or equal to 10 μm and less than or equal to 500 μm; preferably, the thickness of the LCP film of the present application may be more than or equal to 10 μm and less than or equal to 300 μm; more preferably, the thickness of the LCP film of the present application may be more than or equal to 15 μm and less than or equal to 250 μm; even more preferably, the thickness of the LCP film of the present application may be more than or equal to 20 μm and less than or equal to 200 μm.
- To achieve the aforementioned objective, another aspect of the present application also provides a laminate, which comprises a first metal foil and the LCP film. The first metal foil is disposed over the first surface of the LCP film.
- In one of the embodiments, the laminate of the present application may further comprise a second metal foil, which is disposed over the second surface of the LCP film, i.e., the LCP film of the present application is sandwiched between the first metal foil and the second metal foil. In this embodiment, when the Rz/Ry properties of both of the first surface and the second surface the LCP film are controlled at the same time, the adhesion of the LCP film stacked to the first metal foil and the adhesion of the LCP film stacked to the second metal foils are improved simultaneously, and thus the peel strength between the LCP film and the first metal foil as well as the peel strength between the LCP film and the second metal foil are enhanced.
- In accordance with the present application, “stacking” is not limited to direct contact; further, it also includes indirect contact. For example, in one of the embodiments of the present application, the first metal foil and the LCP film in the laminate are stacked with each other in a direct contact manner, that is, the first metal foil is disposed on and in direct contact with the first surface of the LCP film. In another embodiment of the present application, the first metal foil and the LCP film in the laminate are stacked with each other in an indirect contact manner, that is, the first metal foil is disposed above the LCP film, and the first metal foil and the LCP film are stacked with each other in an indirect contact manner. For example, a connection layer may be disposed between the first metal foil and the LCP film based on different needs, so that the first metal foil contacts the first surface of the LCP film via the connection layer. The material of the connection layer may be adjusted according to different needs to provide corresponding functions. For example, the material of the connection layer may include nickel, cobalt, chromium, or alloys thereof to provide functions such as thermal resistance, chemical resistance, or electrical resistance. Similarly, the second metal foil and the LCP film in the laminate may also be stacked with each other in direct contact or indirect contact. In one of the embodiments of the present application, the stacking manner for the LCP film and the first metal foil and the one for the LCP film and the second metal foil may be the same or different.
- In accordance with the present application, the first metal foil and/or the second metal foil may be, but are not limited to, copper foil, gold foil, silver foil, nickel foil, aluminum foil, stainless steel foil, etc. In one of the embodiments, the first metal foil and the second metal foil are made of different materials. Preferably, the first metal foil and/or the second metal foil may be copper foil, so that the copper foil and the LCP film are stacked to form a copper clad laminate (CCL). In addition, the manufacturing method of the first metal foil and/or the manufacturing method of the second metal foil are not particularly restricted, as long as the methods do not violate the objective of the present application. For example, the metal foil may be produced by, but not limited to, a roll-to-roll method or an electrodeposition method.
- In accordance with the present application, the thickness of the first metal foil and/or the second metal foil is not particularly restricted and can be adjusted based on different needs by a person having ordinary knowledge in the art. For example, in one of the embodiments, the thickness of the first metal foil and/or the second metal foil may independently be more than or equal to 1 μm and less than or equal to 200 μm; preferably, the thickness of the first metal foil and/or the second metal foil may independently be more than or equal to 1 μm and less than or equal to 40 μm; more preferably, the thickness of the first metal foil and/or the second metal foil may independently be more than or equal to 1 μm and less than or equal to 20 μm; even more preferably, the thickness of the first metal foil and/or the second metal foil may independently be more than or equal to 3 μm and less than or equal to 20 μm.
- In accordance with the present application, surface treatments of the first metal foil and/or the second metal foil of the present application can be conducted based on different needs by a person having ordinary knowledge in the art. For example, the surface treatments may be selected from, but not limited to, roughening treatments, acid-base treatments, thermal treatments, degreasing treatments, ultraviolet irradiation treatments, corona discharge treatments, plasma treatments, primer coating treatments, etc.
- In accordance with the present application, the roughness of the first metal foil and/or the second metal foil is not particularly restricted and can be adjusted according to different needs by a person having ordinary knowledge in the art. In one of the embodiments, Rz of the first metal foil and/or Rz of the second metal foil may independently be more than or equal to 0.1 μm and less than or equal to 2.0 μm; preferably, Rz of the first metal foil and/or Rz of the second metal foil may independently be more than or equal to 0.1 μm and less than or equal to 1.5 μm. In one of the embodiments, Rz of the first metal foil and Rz of the second metal foil may be the same or different. In one of the embodiments, Rz of the first metal foil and Rz of the second metal foil both fall within the aforementioned ranges.
- In one of the embodiments, a third metal foil may be additionally provided based on different needs by a person having ordinary knowledge in the art. The third metal foil may be the same or different from the first metal foil and/or the second metal foil. In one of the embodiments, Rz of the third metal foil may fall within the aforementioned ranges of Rz of the first metal foil and/or Rz of the second metal foil.
- In one of the embodiments, the laminate may comprise multiple LCP films. Based on the premise of not violating the spirit of the present application, multiple LCP films of the present application and multiple metal foils, such as the aforesaid first metal foil, second metal foil, and/or third metal foil, may be stacked based on different needs to produce a laminate having the multiple LCP films and the multiple metal foils by a person having ordinary knowledge in the art.
- In the specification, the terms “ten-point mean roughness (Rz)”, “maximum height (Ry)”, and “arithmetic average roughness (Ra)” are defined according to JIS B 0601:1994.
- Hereinafter, multiple preparation examples are provided to illustrate raw materials used to produce the LCP film of the present application. Multiple examples are further provided to illustrate the implementation of the LCP film and the laminate of the present application, while multiple comparative examples are provided as comparison. A person skilled in the art can easily realize the advantages and effects of the present application from the following examples and comparative examples. The descriptions proposed herein are just preferable embodiments for the purpose of illustrations only, not intended to limit the scope of the present application. Various modifications and variations could be made in order to practice or apply the present application without departing from the spirit and scope of the present application.
- <LCP Resin>
- A mixture of 6-hydroxy-2-naphthalenecarboxylic acid (700 g), 4-hydroxybenzoic acid (954 g), acetyl anhydride (1085 g), and sodium phosphite (1.3 g) was charged into a 3-liter autoclave and stirred for acetylation at 160° C. for about 2 hours under nitrogen atmosphere at normal pressure. Subsequently, the mixture was heated to 320° C. at a rate of 30° C. per hour, and then under this temperature condition, the pressure was reduced slowly from 760 torr to 3 torr or below, and the temperature was increased from 320° C. to 340° C. Afterwards, the stirring power and the pressure were increased, and steps of discharging polymers, drawing strands, and cutting strands into pellets were conducted to obtain an LCP resin having a melting point about 265° C. and a viscosity about 60 pascal-seconds (Pa·s) measured at 300° C. (hereinafter referred to as @300° C.).
- A mixture of 6-hydroxy-2-naphthalenecarboxylic acid (440 g), 4-hydroxybenzoic acid (1145 g), acetyl anhydride (1085 g), and sodium phosphite (1.3 g) was charged into a 3-liter autoclave and stirred for acetylation at 160° C. for about 2 hours under nitrogen atmosphere at normal pressure. Subsequently, the mixture was heated to 320° C. at a rate of 30° C. per hour, and then under this temperature condition, the pressure was reduced slowly from 760 torr to 3 torr or below, and the temperature was increased from 320° C. to 340° C. Afterwards, the stirring power and the pressure were increased, and steps of discharging polymers, drawing strands, and cutting strands into pellets were conducted to obtain an LCP resin having a melting point about 305° C. and a viscosity about 40 Pa·s @300° C.
- A mixture of 6-hydroxy-2-naphthalenecarboxylic acid (540 g), 4-hydroxybenzoic acid (1071 g), acetyl anhydride (1086 g), sodium phosphite (1.3 g), and 1-methylimidazole (0.3 g) was charged into a 3-liter autoclave and stirred for acetylation at 160° C. for about 2 hours under nitrogen atmosphere at normal pressure. Subsequently, the mixture was heated to 320° C. at a rate of 30° C. per hour, and then under this temperature condition, the pressure was reduced slowly from 760 torr to equal to or less than 3 torr or below, and the temperature was increased from 320° C. to 340° C. Afterwards, the stirring power and the pressure were increased, and steps of discharging polymers, drawing strands, and cutting strands into pellets were conducted to obtain an LCP resin having a melting point about 278° C. and a viscosity about 45 Pa·s @300° C.
- LCP Film
- The LCP resin obtained from Preparation Examples 1 to 3 (PE1 to PE3) was used as raw materials to prepare LCP films of Examples 1 to 13 (E1 to E13) and Comparative Examples 1 to 5 (C1 to C5) by the methods described below.
- First, the LCP resin was put into an extruder having a screw diameter of 27 millimeters (mm) (manufacturer: Leistritz, model: ZSE27) and heated to a temperature ranging from 300° C. to 320° C., and then extruded from a T-die of a width of 500 mm with a feeding speed ranging from 3.5 kilograms per hour (kg/hr) to 10 kg/hr. The LCP resin was then delivered to a space between two casting wheels having a temperature ranging from about 250° C. to 320° C. and a diameter ranging from about 35 centimeters (cm) to 45 cm, extruded with a force about 20 kilonewtons (kN) to 60 kN, and then transferred to a cooling wheel for cooling at room temperature to obtain an LCP film having a thickness of 50 μm. Herein, the casting wheels were spaced about 1 mm to 50 mm from the T-die.
- The processes of Examples 1 to 13 differ from those of Comparative Examples 1 to 5 in the kind of the LCP resin, the distance from the T-die to the surfaces of the casting wheels, the feeding speed, and the extrusion temperature. The parameters of Examples 1 to 13 and Comparative Examples 1 to 5 are respectively listed in Table 1 below.
-
TABLE 1 parameters of LCP films of Examples 1 to 13 and Comparative Examples 1 to 5 Parameters Sam- Distance from Feeding Extrusion ple LCP T-die to casting Speed Temp. No. Resin wheels (mm) (kg/hr) (° C.) E1 PE1 20 7.5 310 E2 PE1 20 7.5 315 E3 PE1 20 7.5 320 E4 PE1 20 6.5 290 E5 PE1 20 8.5 310 E6 PE1 20 8.5 315 E7 PE1 20 8.5 320 E8 PE1 20 5.5 310 E9 PE2 20 5.5 315 E10 PE3 20 5.5 320 E11 PE1 20 6.5 310 E12 PE2 20 6.5 315 E13 PE3 20 6.5 320 C1 PE1 20 7.5 300 C2 PE1 20 8.5 290 C3 PE1 5 6.5 310 C4 PE1 5 5.5 320 C5 PE1 5 7.5 315 - The above-mentioned preparation method of LCP film is only used to exemplify implementation of the present application. A person having ordinary knowledge in the art may also use conventional methods such as a laminate extension method and an inflation method to prepare an LCP film.
- In one of the embodiments, after the LCP resin was extruded from the T-die, the LCP resin might be delivered with two high-temperature resistant films to a space between two casting wheels to form a three-layered laminate based on needs by a person having ordinary knowledge in the art. The two high-temperature resistant films were detached from the LCP resin at room temperature to obtain the LCP film of the present application. The high-temperature resistant film may be selected from, but not limited to, poly(tetrafluoroethene) (PTFE) film, polyimide (PI) film, and poly(ether sulfone) (PES) film.
- In addition, post treatments for the obtained LCP film may be conducted based on different needs by a person having ordinary knowledge in the art. The post treatments may be, but are not limited to, polishing, ultraviolet irradiation, plasma, etc. For the plasma treatment, it may be applied with a plasma operated with a power of 1 kW under nitrogen, oxygen, or air atmosphere at a reduced or normal pressure based on different needs, but is not limited thereto.
- In this test example, the LCP films of Examples 1 to 13 and Comparative Examples 1 to 5 were used as test samples. The surface morphology images of the test samples were each taken using a laser microscope (manufacturer: Olympus, model: LEXT OLS5000-SAF, objective lens: MPLAPON-50×LEXT) with an objective lens having a magnification power of 50×, 1× optical zoom, and a 405 nanometers (nm) wavelength of light source at a temperature of 24±3° C. and a relative humidity of 63±3%. Ra, Ry, and Rz of either surface of the test samples were measured according to JIS B 0601:1994 using an evaluation length of 4 mm and a cutoff value (λc) of 0.8 mm. The results of the test samples are listed in Table 2 below.
- Laminates of Examples 1A to 13A (E1A to E13A) and Comparative Examples 1A to 5A (C1A to C5A) were produced from the LCP films of Examples 1 to 13 as well as Comparative Examples 1 to 5 and commercially available copper foils. The product descriptions of the commercially available copper foils are provided as follows:
- Copper foil 1: CF-T49A-HD2, purchased from FUKUDA METAL FOIL & POWDER CO., LTD., Rz: about 1.2 μm;
- Copper foil 2: CF-H9A-HD2, purchased from FUKUDA METAL FOIL & POWDER CO., LTD., Rz: about 1.0 μm;
- Copper foil 3: 3EC-M2S-HTE-SP2, purchased from MITSUI MINING & SMELTING CO., LTD., Rz: about 1.1 μm; and
- Copper foil 4: TQ-M7-VSP, purchased from MITSUI MINING & SMELTING CO., LTD., Rz: about 1.1 μm.
- The kind of the LCP film and the kind of the copper foil used for each of the laminates of Examples 1A to 13A and Comparative Examples 1A to 5A were listed in Table 2, and each of the laminates was produced as follows.
- The LCP film having a thickness about 50 μm and two identical copper foils each having a thickness about 12 μm were each first cut to size of 20 cm*20 cm. The LCP film was then sandwiched between the two copper foils to form a laminated structure. The laminated structure was subjected to a pressure of 5 kilograms per square centimeter (kg/cm2) for 60 seconds at 180° C., followed by a pressure of 20 kg/cm2 for 25 minutes (min) at 300° C., and then cooled to room temperature to obtain a laminate.
- Herein, the lamination method for the laminates is not particularly restricted. A person having ordinary knowledge in the art may use conventional techniques such as a wire lamination or a surface lamination to conduct the lamination process. A laminator applicable to the present application may be, but is not limited to, an intermittent hot-press machine, a roll-to-roll wheeling machine, a double belt press machine, etc. According to different needs, a person having ordinary knowledge in the art can also align the LCP film with the copper foils to form a laminated structure, which may then be processed with surface lamination comprising a heating step and a pressing step.
- In another embodiment, a metal foil, such as a copper foil, on an LCP film may be formed through sputtering, electroplating, chemical plating, evaporation deposition, etc. based on different needs by a person having ordinary knowledge in the art. Or, a connection layer, such as a glue layer, a nickel layer, a cobalt layer, a chromium layer, or an alloy layer thereof, may be formed between an LCP film and a metal foil based on different needs by a person having ordinary knowledge in the art.
- The peel strength of the laminates was measured according to IPC-TM-650 No.: 2.4.9. The laminates of Examples 1A to 13A and Comparative Examples 1A to 5A were each cut to size of a length about 228.6 mm and a width about 3.2 mm as etched specimens. Each etched specimen was placed at a temperature of 23±2° C. and a relative humidity of 50±5% for 24 hours to reach stabilization. Subsequently, each etched specimen was adhered to a clamp of a testing machine (manufacturer: Hung Ta Instrument Co., Ltd., model: HT-9102) with a double faced adhesive tape. Each etched specimen was then peeled from the clamp with a force at a peel speed of 50.8 mm/min, and the value of the force during the peeling process was continuously recorded. Herein, the force should be controlled within a range of 15% to 85% of the bearable force of the testing machine, the peeling distance from the clamp should be at least more than 57.2 mm, and the force for the initial distance of 6.4 mm was neglected and not recorded. The results are shown in Table 2.
-
TABLE 2 roughness of LCP films of Examples 1 to 13 and Comparative Examples 1 to 5, and sample number of copper foil and peel strength of laminates of Examples 1A to 13A and Comparative Examples 1A to 5A LCP Film Laminate Sample Ra Rz Sample Copper Foil Peel Strength No. Rz/Ry (μm) (μm) No. No. (kN/m) E1 0.483 0.029 0.506 E1A Copper Foil 1 0.68 E2 0.548 0.034 0.534 E2A Copper Foil 1 0.60 E3 0.606 0.041 0.826 E3A Copper Foil 1 0.58 E4 0.422 0.092 0.793 E4A Copper Foil 1 0.70 E5 0.361 0.057 1.186 ESA Copper Foil 2 1.44 E6 0.476 0.026 0.390 E6A Copper Foil 2 1.38 E7 0.553 0.036 0.735 E7A Copper Foil 2 1.30 E8 0.492 0.031 0.856 E8A Copper Foil 3 0.53 E9 0.532 0.032 0.547 E9A Copper Foil 3 0.48 E10 0.566 0.033 0.602 E10A Copper Foil 3 0.45 E11 0.495 0.037 0.864 E11A Copper Foil 4 0.83 E12 0.530 0.035 0.609 E12A Copper Foil 4 0.85 E13 0.567 0.037 0.591 E13A Copper Foil 4 0.78 C1 0.829 0.088 1.562 C1A Copper Foil 1 0.56 C2 0.896 0.122 1.839 C2A Copper Foil 1 0.53 C3 0.685 0.043 0.717 C3A Copper Foil 1 0.52 C4 0.632 0.057 1.049 C4A Copper Foil 1 0.50 C5 0.814 0.034 0.442 C5A Copper Foil 2 1.18 - The laminates of Examples 1A to 13A and Comparative Examples 1A to 5A were each cut to size of a length about 100 mm, a width about 140 mm, and a resistance about 50 Ohm (Ω) as strip line specimens. The insertion loss of the strip line specimens was measured under 10 GHz by a microwave network analyzer (manufacturer: Agilent Technologies, Ltd., model: 8722ES) including a probe (manufacturer: Cascade Microtech, model: ACP40-250).
- The LCP films of Examples 1 to 7 as well as Comparative Examples 1 to 5 were chosen as examples to laminate with the commercially available copper foils, the laminates of Examples 1A to 7A and Comparative Examples 1A to 5A were prepared to evaluate insertion loss, and the results are listed in Table 3 below.
-
TABLE 3 descriptions of LCP films and copper foils used for laminates of Examples 1A to 7A and Comparative Examples 1A to 5A and insertion loss of the laminates Laminate LCP Film Insertion Sample Ra Rz Sample Copper Foil Loss No. Rz/Ry (μm) (μm) No. No. (dB) E1 0.483 0.029 0.506 E1A Copper Foil 1 −2.9 E2 0.548 0.034 0.534 E2A Copper Foil 1 −2.9 E3 0.606 0.041 0.826 E3A Copper Foil 1 −2.9 E4 0.422 0.092 0.793 E4A Copper Foil 1 −3.1 E5 0.361 0.057 1.186 E5A Copper Foil 2 −2.9 E6 0.476 0.026 0.390 E6A Copper Foil 2 −2.8 E7 0.553 0.036 0.735 E7A Copper Foil 2 −2.9 C1 0.829 0.088 1.562 C1A Copper Foil 1 −3.1 C2 0.896 0.122 1.839 C2A Copper Foil 1 −3.1 C3 0.685 0.043 0.717 C3A Copper Foil 1 −3.0 C4 0.632 0.057 1.049 C4A Copper Foil 1 −2.9 C5 0.814 0.034 0.442 C5A Copper Foil 2 −2.9 - Discussion on Test Results
- As shown in Table 2 above, Rz/Ry of either surface of the LCP film of each of Examples 1 to 13 was controlled within the range between more than or equal to 0.30 and less than or equal to 0.62, so the laminates (Examples 1A to 13A) produced from such LCP films and various commercially available copper foils with low roughness all exhibited high peel strength. In addition, as shown in Table 3 above, take the results of Examples 1A to 7A as examples, when Rz/Ry of either surface of the LCP films was controlled within the range between more than or equal to 0.30 and less than or equal to 0.62, the insertion loss of the laminates of Examples 1A to 7A was modulated to be −3.1 dB or less.
- The results of Table 2 were further analyzed. For laminates having Copper foil 1, the laminates with the LCP films of Examples 1 to 4 all exhibited higher peel strength than the ones with the LCP films of Comparative Examples 1 to 4. Similarly, for laminates having Copper foil 2, the laminates with the LCP films of Examples 5 to 7 all exhibited higher peel strength than the one with LCP film of Comparative Example 5. Clearly, the peel strength of the laminates produced from the LCP films of the present application is certainly improved, so the laminates are suitable for processing and problems of component detachment will be effectively avoided.
- Furthermore, from the test results of the laminates of Examples 1A to 7A, when either surface of the LCP film has Rz/Ry of more than or equal to 0.30 and less than or equal to 0.62 as well as Ra of less than or equal to 0.09, the peel strength of the laminates (Examples 1A to 3A and 5A to 7A) having the LCP film and copper foils was enhanced, and the insertion loss of the laminates was further reduced to −2.9 dB or less. Thus, the laminates that exhibited high peel strength as well as low insertion loss were provided.
- In summary, by controlling Rz/Ry of at least one surface of the LCP film that is more than or equal to 0.30 and less than or equal to 0.62, the peel strength of the LCP film stacked to metal foils can be specifically improved. In addition, by controlling Ra and Rz/Ry of at least one surface of the LCP film, the laminate having the LCP film not only has improved peel strength but also has reduced insertion loss. Therefore, the laminate of the present application is highly suitable for high-end 5G products.
- Even though numerous characteristics and advantages of the present application have been set forth in the foregoing description, together with details of the structure and features of the present application, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the present application to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
Claims (20)
1. A liquid crystal polymer film, comprising a first surface and a second surface opposite each other, a ratio of a ten-point mean roughness relative to a maximum height of the first surface being more than or equal to 0.36 and less than or equal to 0.61, and the maximum height of the first surface being more than or equal to 1.1 μm and less than or equal to 2.2 μm.
2. The liquid crystal polymer film as claimed in claim 1 , wherein an arithmetic average roughness of the first surface is less than or equal to 0.09 μm.
3. The liquid crystal polymer film as claimed in claim 2 , wherein the arithmetic average roughness of the first surface is more than or equal to 0.02 μm and less than or equal to 0.08 μm.
4. The liquid crystal polymer film as claimed in claim 1 , wherein the ten-point mean roughness of the first surface is less than or equal to 2 μm.
5. The liquid crystal polymer film as claimed in claim 4 , wherein the ten-point mean roughness of the first surface is less than or equal to 1.5 μm.
6. The liquid crystal polymer film as claimed in claim 1 , wherein the maximum height of the first surface is more than or equal to 1.6 μm and less than or equal to 2.2 μm.
7. The liquid crystal polymer film as claimed in claim 1 , wherein a ratio of a ten-point mean roughness relative to a maximum height of the second surface is more than or equal to 0.30 and less than or equal to 0.62.
8. The liquid crystal polymer film as claimed in claim 2 , wherein a ratio of a ten-point mean roughness relative to a maximum height of the second surface is more than or equal to 0.30 and less than or equal to 0.62.
9. The liquid crystal polymer film as claimed in claim 3 , wherein a ratio of a ten-point mean roughness relative to a maximum height of the second surface is more than or equal to 0.30 and less than or equal to 0.62.
10. The liquid crystal polymer film as claimed in claim 4 , wherein a ratio of a ten-point mean roughness relative to a maximum height of the second surface is more than or equal to 0.30 and less than or equal to 0.62.
11. The liquid crystal polymer film as claimed in claim 5 , wherein a ratio of a ten-point mean roughness relative to a maximum height of the second surface is more than or equal to 0.30 and less than or equal to 0.62.
12. The liquid crystal polymer film as claimed in claim 6 , wherein a ratio of a ten-point mean roughness relative to a maximum height of the second surface is more than or equal to 0.30 and less than or equal to 0.62.
13. The liquid crystal polymer film as claimed in claim 7 , wherein an arithmetic average roughness of the second surface is less than or equal to 0.09 μm.
14. The liquid crystal polymer film as claimed in claim 8 , wherein an arithmetic average roughness of the second surface is less than or equal to 0.09 μm.
15. The liquid crystal polymer film as claimed in claim 9 , wherein an arithmetic average roughness of the second surface is less than or equal to 0.09 μm.
16. The liquid crystal polymer film as claimed in claim 10 , wherein an arithmetic average roughness of the second surface is less than or equal to 0.09 μm.
17. The liquid crystal polymer film as claimed in claim 11 , wherein an arithmetic average roughness of the second surface is less than or equal to 0.09 μm.
18. The liquid crystal polymer film as claimed in claim 12 , wherein an arithmetic average roughness of the second surface is less than or equal to 0.09 μm.
19. A laminate, comprising a first metal foil and the liquid crystal polymer film as claimed in claim 1 , the first metal foil disposed over the first surface of the liquid crystal polymer film.
20. The laminate as claimed in claim 19 , wherein the laminate comprises a second metal foil, and the second metal foil is disposed over the second surface of the liquid crystal polymer film.
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2020
- 2020-01-22 US US16/748,846 patent/US20210189075A1/en active Pending
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- 2020-02-12 JP JP2020021487A patent/JP6804673B1/en active Active
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2021
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JP7372898B2 (en) | 2023-11-01 |
TWI697549B (en) | 2020-07-01 |
US20210189075A1 (en) | 2021-06-24 |
TW202124678A (en) | 2021-07-01 |
JP2021098832A (en) | 2021-07-01 |
CN113096900A (en) | 2021-07-09 |
KR102197515B9 (en) | 2022-10-11 |
JP6804673B1 (en) | 2020-12-23 |
JP2021098842A (en) | 2021-07-01 |
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