CN117500867A - Composite film for mobile electronic device components - Google Patents
Composite film for mobile electronic device components Download PDFInfo
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- CN117500867A CN117500867A CN202280043071.2A CN202280043071A CN117500867A CN 117500867 A CN117500867 A CN 117500867A CN 202280043071 A CN202280043071 A CN 202280043071A CN 117500867 A CN117500867 A CN 117500867A
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 88
- 239000000843 powder Substances 0.000 claims description 41
- 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 claims description 30
- 239000004744 fabric Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 239000003365 glass fiber Substances 0.000 claims description 14
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- -1 aromatic diol Chemical class 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000011152 fibreglass Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 4
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 229920000106 Liquid crystal polymer Polymers 0.000 description 9
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000005670 electromagnetic radiation Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- NFTLBCXRDNIJMI-UHFFFAOYSA-N 6-acetyloxynaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OC(=O)C)=CC=C21 NFTLBCXRDNIJMI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 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 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RQMBBMQDXFZFCC-UHFFFAOYSA-N [4-(4-acetyloxyphenyl)phenyl] acetate Chemical group C1=CC(OC(=O)C)=CC=C1C1=CC=C(OC(C)=O)C=C1 RQMBBMQDXFZFCC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
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- 238000002356 laser light scattering Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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Abstract
The present disclosure relates to a composite film comprising at least one liquid crystalline polyester and a fibrous web, for example exhibiting a thickness of less than 0.10mm, and to articles comprising such composite films, which exhibit low dielectric constants and dissipation coefficients and are suitable for use in mobile electronic device components such as flexible printed circuit boards (FPCs).
Description
Cross Reference to Related Applications
The present application claims priority from U.S. provisional patent application number 63/211638 filed on month 17 of 2021 and from European patent application number 21195292.4 filed on month 7 of 2021,each of these applications is intended for all purposesAll of the contentsIncorporated herein by reference。
Technical Field
The present disclosure relates to composite films comprising at least one Liquid Crystalline Polyester (LCP) and at least one fibrous web (F), such composite films exhibiting low dielectric constants and dissipation coefficients, making them well suited for use in mobile electronic device components, such as Copper Clad Laminates (CCL) and flexible printed circuit boards (FPC).
Background
Polymer compositions are widely used for manufacturing mobile electronic device parts due to their reduced weight and high mechanical properties. There is a great need in the market today for polymer compositions to be used in the manufacture of mobile electronic device components with improved dielectric properties (i.e. low dielectric constant and dissipation factor).
In mobile electronic devices, the materials forming the various components and housings may significantly reduce radio signals (e.g., 1MHz, 2.4GHz, and 5.0GHz frequencies) transmitted and received by the mobile electronic device through one or more antennas. The dielectric properties of a material to be used in a mobile electronic device can be determined by measuring the dielectric constant and dissipation factor, as they represent the ability of the material to interact with electromagnetic radiation and interfere with electromagnetic signals (e.g., radio signals) passing through the material. Thus, the lower the dielectric constant of a material at a given frequency, the less interference the material has with electromagnetic signals at that frequency.
Polymeric films find application in the field of mobile electronic devices. For example, aromatic polyimide films in the form of a continuous aromatic polyimide film/copper foil laminate structure have been described for use in the manufacture of flexible printed circuit boards (FPCs), carrier tapes for Tape Automated Bonding (TAB), and tapes of lead-on-chip (LOC) structures. Such films are presented to show good high temperature resistance, good chemical properties, high electrical insulation properties, and high mechanical strength. However, polyimide films do not show the expected dielectric properties, especially the dissipation factor of polyimide films is too high to be used in applications at high frequencies (. Gtoreq.20 GHz). Furthermore, polyimide films have even worse dissipation coefficients at high frequencies due to moisture absorption in humid environments.
It is an object of the present invention to provide a composite film having improved dielectric properties. Such composite films are made of liquid crystalline polyester and fiber fabrics.
Disclosure of Invention
The present invention relates to a composite film comprising:
-at least one liquid crystalline polyester, [ polymer LCP ], and
-at least one fibrous web, [ fibrous web (F) ].
The invention also relates to a method for producing such a composite film.
Other objects of the invention are as follows: an article, or part of an article, comprising at least one composite film of the invention, the use of at least one such composite film for the preparation of a mobile electronic device article, or part thereof, such as a flexible printed circuit board (FPC). Another object is the use of a liquid crystalline polyester powder for the preparation of a composite film, which may for example have a thickness of less than 0.10mm, said composite film further comprising at least one fibrous web.
Disclosure of the invention
In the present application:
any description, even with respect to specific embodiments, is applicable to and interchangeable with other embodiments of the invention;
when an element or component is said to be included in and/or selected from the list of enumerated elements or components, it is to be understood that in the relevant embodiments explicitly contemplated herein, the element or component may also be any one of these enumerated independent elements or components, or may also be selected from the group consisting of any two or more of the enumerated elements or components; any elements or components recited in a list of elements or components may be omitted from this list; and
Any recitation of numerical ranges herein by endpoints includes all numbers subsumed within that recited range, and endpoints and equivalents of that range;
the term "and/or" as used in the phrase in the form of "a and/or B" means a alone, B alone, or a and B together.
Composite membrane
The present invention relates to a composite film comprising:
-at least one liquid crystalline polyester, [ polymer LCP ], and
-at least one fibrous web, [ fibrous web (F) ].
The composite film of the present invention comprises at least one polymeric LCP. Liquid crystal polymers are known polymers and are sometimes described as "rigid-rod" polymers, "rod" polymers, or ordered polymers. These polymers are believed to have a fixed molecular shape, such as linear, etc., due to the nature of the repeating units comprising the polymer chains. The repeating unit typically comprises a rigid molecular moiety. These rigid molecular moieties (mesogens) are generally rod-like or disk-like in shape and are typically aromatic. The rigid molecular moiety may be present in the main chain or in the side chain of the polymer.
In some embodiments, the polymeric LCP comprises 40.0mol.% or more of repeat units derived from 6-hydroxy-2-naphthoic acid (HNA) or derivatives thereof (e.g., acetates). The polymeric LCP may include 50.0mol.% or more, even 60.0mol.% or more, of repeating units derived from 6-hydroxy-2-naphthoic acid based on the total moles in the polymeric LCP. According to the same embodiment, the polymeric LCP comprises less than 99.0mol.%, e.g., less than 98.0mol.% or less than 97.0mol.%, of recurring units derived from 6-hydroxy-2-naphthoic acid (HNA) or derivatives thereof, based on the total moles in the polymeric LCP.
Alternatively or additionally, the polymeric LCP may comprise a specific amount of repeating units derived from 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB).
The polymeric LCP may comprise repeat units derived from 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB) in combination with repeat units derived from 6-hydroxy-2-naphthoic acid (HNA), preferably in combination with 40.0mol.% or more of repeat units derived from 6-hydroxy-2-naphthoic acid (HNA). This particular combination of components has been shown to provide good dielectric properties for composite films comprising such polymeric LCPs. The introduction of the selected ratio of 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB) may be advantageous in the sense that it is able to control the melting temperature (Tm) and crystallization temperature (Tc) of the polymer LCP while maintaining liquid crystallinity, which is desirable for various processing requirements.
The polymeric LCP advantageously comprises:
-40.0mol.% or more of recurring units derived from 6-hydroxy-2-naphthoic acid (HNA), and
1.0mol.% or more, for example more than 1.5mol.%, or even more than 2.0mol.%, of recurring units derived from 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB),
Based on the total moles in the polymer LCP.
The polymeric LCP comprises:
less than 99.0mol.% of recurring units derived from HNA,
less than 23.0mol.%, for example less than 22.0mol.%, even less than 21.0mol.% of recurring units derived from 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB),
based on the total moles in the polymer LCP.
In some embodiments, the polymeric LCP comprises:
a) 40.0 to 98.0mol.% of a repeating unit having formula (I):
b) 1.0 to 30.0mol.% of recurring units derived from at least one aromatic diol selected from the group consisting of diols having the following formulas (IIa) to (IId) (collectively, "formula (II)"):
and/or
And
c) Repeat units derived from an aromatic compound having two carboxyl groups:
-1.0 to 23.0mol.% of a repeating unit having formula (IIIa):
and/or
-1.0 to 13.0mol.% of a repeating unit having formula (IIIb):
the polymeric LCPs described herein may be polymers that substantially comprise the repeating units described above, or polymers that comprise such repeating units and optionally comprise additional repeating units as described below.
In some embodiments, when the polymeric LCP comprises additional repeating units, these repeating units may be selected from the group consisting of those having the formula:
Each of the repeating units having formulae (IV) and (V) may be present in the polymer LCP in a molar amount ranging from 0.1 to 15.0mol.%, e.g., 0.5 to 13.0mol.%, 1.0 to 11.0mol.%, 2.0 to 9.0mol.%, or 3.0 to 8.0mol.%, based on the total moles in the polymer LCP.
Each of the repeating units having formulae (VI) and (VII) may be present in the polymer LCP in a molar amount ranging from 0.1 to 25.0mol.%, e.g., 0.5 to 22.0mol.%, 1.0 to 21.0mol.%, 2.0 to 20.0mol.%, or 3.0 to 18.0mol.%, based on the total moles in the polymer LCP.
In some other embodiments, when the polymeric LCP comprises additional repeating units, these additional repeating units may be selected from the group consisting of those having the formula:
each of the repeating units having formulae (VIII), (IX), (X), (XI), and (XII) may be present in the polymer LCP in a molar amount ranging from 0.1 to 20.0mol.%, e.g., 0.5 to 18.0mol.%, 1.0 to 15.0mol.%, 2.0 to 13.0mol.%, or 3.0 to 10.0mol.% based on the total moles in the polymer LCP.
According to the present invention, when the polymeric LCP used in the composite film of the present invention comprises additional repeating units, these additional repeating units may be selected from the group consisting of those having the formulae (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII). The polymeric LCP may include one, two, three, four, five, six, or seven of these repeating units. Each of these repeating units may be present in the polymer LCP in a molar amount ranging from 0.1 to 15.0mol.%, e.g., 0.5 to 13.0mol.%, 1.0 to 11.0mol.%, 2.0 to 9.0mol.%, or 3.0 to 8.0mol.% based on the total moles in the polymer LCP.
In some embodiments, the polymeric LCP used in the composite films of the present invention comprises 40.0 to 98.0mol.% of the repeating units of formula (I), preferably 40.0 to 90.0mol.%, more preferably 50.0 to 85.0mol.%, or 60.0 to 81.0mol.% of the repeating units of formula (I), based on the total moles in the polymeric LCP. The polymeric LCP may further comprise 1.0 to 30.0mol.% of repeating units derived from at least one aromatic diol, preferably repeating units selected from the group consisting of those having formulae (IIa), (IIb), (IIc), and (IId). Preferably, the polymeric LCP comprises 5.0 to 25.0mol.% or 10.0 to 22.0mol.% of the repeating units of formula (II), based on the total moles in the polymeric LCP.
The polymeric LCP may also include repeat units having formula (III). It may comprise a repeating unit having formula (IIIa) or a repeating unit having formula (IIIb). The polymeric LCP may include repeat units having formula (IIIa) and repeat units having formula (IIIb).
When the polymeric LCP comprises repeating units having formula (IIIa), the molar amount of these repeating units varies from 1.0 to 23.0mol.%, preferably from 2.0 to 22.0mol.% or from 3.0 to 21.0mol.% or from 4.0 to 20.0mol.% based on the total moles in the polymeric LCP.
When the polymeric LCP comprises repeating units having formula (IIIb), the molar amount of these repeating units varies from 1.0 to 13.0mol.%, preferably from 2.0 to 12.0mol.% or from 3.0 to 11.0mol.% or from 4.0 to 10.0mol.% based on the total moles in the polymeric LCP.
When the polymeric LCP comprises repeating units having formula (IIIa) and having formula (IIIb), the molar amount of the sum of the repeating units having formulae (IIIa) and (IIIb) may vary, for example, from 1.0 to 25.0mol.%, preferably from 2.0 to 23.0mol.% or from 3.0 to 21.0mol.% or from 4.0 to 20.0mol.%, based on the total moles in the polymeric LCP. The molar ratio (IIIa)/(IIIb) may vary from 1:99 to 99:1, preferably from 10:90 to 90:10, even more preferably from 20:80 to 80:20.
The polymeric LCP may include repeat units derived from: 6-hydroxy-2-naphthoic acid (HNA), biphenol (BP), hydroquinone (HQ), and diphenic acid (BB). Esters of monomers can be used to prepare polymeric LCPs, such as 6-acetoxy-2-naphthoic acid (AcHNA), diacetoxybiphenyl (AcBP), diacetoxybenzene (AcHQ).
The various isomers of diphenic acid (BB) can be used to prepare polymeric LCP. The diphenic acid (BB) may be in the form of 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB). The polymeric LCP may comprise, even consist of: repeat units derived from hydroxy-2-naphthoic acid (HNA), diphenol (BP) and/or Hydroquinone (HQ), and 4,4 '-diphenic acid (4, 4' -BB).
The polymeric LCP may further comprise, even consist of: repeat units derived from hydroxy-2-naphthoic acid (HNA), diphenol (BP) and/or Hydroquinone (HQ), and 3,4 '-diphenic acid (3, 4' -BB). The polymeric LCP may further comprise, even consist of: repeat units derived from a combination of 3,4'-BB and 4,4' -BB. For example, the polymeric LCP may comprise, even consist of: repeat units derived from hydroxy-2-naphthoic acid (HNA), diphenol (BP) and/or Hydroquinone (HQ), 3,4 '-diphenic acid (3, 4' -BB) and 4,4 '-diphenic acid (4, 4' -BB). The polymeric LCP may be made from only these three, four, or five monomers.
Various isomers of Biphenol (BP) may be used to prepare the polymeric LCP. The diphenol (BP) may, for example, be in the form of 4,4 '-diphenol (4, 4' -BP), 3,4 '-diphenol (3, 4' -BP) or 3,3 '-diphenol (3, 3' -BP). One or more of these isomers may be used. Preferably, at least 4,4' -biphenol is used to prepare the polymeric LCP. Various isomers of Hydroquinone (HQ) may also be used in the context of the present invention.
The polymeric LCP used in the composite film of the present invention may additionally comprise repeating units having the formula (IV), (V), (VI) and/or (VII). In these embodiments, the polymeric LCP may be made from repeat units derived from: hydroxybenzoic acid (HBA) (or derivatives such as acetoxybenzoic acid (AcHBA)), terephthalic acid (TPA), isophthalic acid (IPA). Various isomers of hydroxybenzoic acid (HBA) may be used in the preparation of polymeric LCPs. Notably, the HBA may be in the form of 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA).
In some embodiments, the polymeric LCP used in the composite films of the present invention comprises repeating units derived from terephthalic acid (TPA) in addition to hydroxy-2-naphthoic acid (HNA), biphenol (BP), and diphenic acid (BB).
In some preferred embodiments, the polymeric LCP comprises, consists essentially of, or consists of:
50.0 to 80.0mol.% of a repeating unit of formula (I),
-9.0 to 25.0mol.% of a repeating unit having formula (II), and
-2.0 to 12.0mol.% of a repeating unit having formula (IIIb).
In some other preferred embodiments, the polymeric LCP used in the composite films of the present invention comprises, consists essentially of, or consists of:
50.0 to 80.0mol.% of a repeating unit of formula (I),
-9.0 to 25.0mol.% of a repeating unit having formula (II), and
-2.0 to 21.0mol.% of a repeating unit having formula (IIIa).
In some other mentioned embodiments, the polymeric LCP used in the composite film of the present invention comprises or consists essentially of:
50.0 to 80.0mol.% of a repeating unit of formula (I),
9.0 to 25.0mol.% of a repeating unit of formula (II),
-2.0 to 15.0mol.% of a repeating unit having formula (IIIa), and
-2.0 to 11.0mol.% of a repeating unit having formula (IIIb).
For the avoidance of doubt, the repeat units of formula (II) are those selected from the group consisting of those of formulae (IIa) to (IId).
The polymeric LCP used in the composite film of the present invention may additionally comprise repeating units having the formula (VIII), (IX), (Xa), (Xb) and/or (XI). In these embodiments, the polymeric LCP may be made from the following monomers: cyclohexane dicarboxylic acid (CHDA) is preferably 1,4-CHDA, 2, 6-Naphthalene Dicarboxylic Acid (NDA) (or derivative), resorcinol (RS) (or derivative) and/or Catechol (CT) (or derivative). In these embodiments, the polymeric LCP may comprise, even consist of, repeat units derived from: 6-hydroxy-2-naphthoic acid (HNA), biphenol (BP), terephthalic acid (TPA), and diphenic acid (BB). For example, the polymeric LCP may be made only of HNA, BP, TPA and BB.
The polymer LCP may also be made of only HNA, BP, CHDA, HNA, TPA and BB. The polymeric LCP may also be made of only HNA, BP, HQ, and BB (e.g., 4' -BB, 3,4' -BB, or a combination of both, preferably 3,4' -BB).
In some embodiments, the polymeric LCP is such that the number of moles of repeating units is as follows:
-repeat units of formula (I) + (II) + (III) + (IV) + (V) + (VI) + (VII) + (VIII) + (IX) + (X) + (XI) + (XII) =100 mol%, wherein the number of moles of repeat units of formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and/or (XII) is ∈0 mol%,
-recurring units of formula (I) + (II) + (III) + (IV) + (V) + (VI) =100 mol.%, wherein the number of moles of recurring units of formula (IV), (V) and/or (VI) is ≡0mol.%, and
-recurring units of formula (I) + (II) + (III) + (VII) + (VIII) + (IX) + (X) + (XI) + (XII) =100 mol.%, wherein the number of moles of recurring units of formula (VII), (VIII), (IX), (X), (XI) and/or (XII) is ≡0mol.%.
In these embodiments, the polymeric LCP may be made from only the following monomers: 6-hydroxy-2-naphthoic acid (HNA), biphenol (BP), hydroquinone (HQ), diphenic acid (BB), hydroxybenzoic acid (HBA) (e.g., 4-hydroxybenzoic acid (4-HBA) and/or 3-hydroxybenzoic acid (3-HBA)), and diphenic acid (BB).
For example, the polymeric LCP may be such that the number of moles of repeating units is as follows:
repeat units of formula (I) + (II) + (III) =100 mol.%, for example of formula (I) + (IIa) + (IIIa) =100 mol.%, or of formula (I) + (IIa) + (IIIb) =100 mol.%,
Repeat units of formula (I) + (II) + (III) + (VII) =100 mol.%, for example of formula (I) + (IIa) + (IIIa) + (VII) =100 mol.%, or of formula (I) + (IIa) + (IIIb) + (VII) =100 mol.%,
repeat units of formula (I) + (II) + (III) + (IV) =100 mol%,
repeat units of formula (I) + (II) + (III) + (V) =100 mol%,
-recurring units of formula (I) + (II) + (III) + (X) =100 mol.%, or
-recurring units of formula (I) + (II) + (III) + (XI) =100 mol.%.
The polymeric LCPs used in the composite films of the present invention are prepared from a variety of entities, some of which are diols, dicarboxylic acids, hydroxycarboxylic acids, esters, or diesters. The term "diol" refers to an organic compound having two hydroxyl groups, and preferably no other functional groups that can form ester bonds. The term "dicarboxylic acid" refers to an organic compound having two carboxyl groups, and preferably no other functional groups that can form ester bonds. The term "hydroxycarboxylic acid" refers to an organic compound having one hydroxyl group and one carboxyl group, and preferably no other functional groups that can form ester bonds. The term "ester" or "diester" refers to a polymer having one or two carboxyl groups (R 1 CO 2 -, wherein R is 1 Is alkyl or substituted alkyl). In other words, the polymer LCP may be made of a polymer having [ -OH ]、[-OCOR 1 ]And [ -COOH]And (3) preparing a functional group monomer. In some embodiments, the polymeric LCP consists of a molar ratio ([ -OH) ranging from 0.8 to 1.2, preferably 0.9 to 1.1, even more preferably 0.95 to 1.05]+[-OCOR 1 ])/[-COOH]And (3) preparation. As an example, according to these embodiments, the repeating unit ([ II)]+[IX]+[XII]) Repeating units ([ III ]]+[VI]+[VII]+[VIII]+[X]+[XI]) The molar ratio of (2) is equal to 1.00.+ -. 0.20, preferably 1.00.+ -. 0.10, more preferably 1.00.+ -. 0.05, even more preferably 1.00.+ -. 0.01.
According to embodiments, the polymeric LCP used in the composite films described herein has a melting temperature (Tm) above 255 ℃, e.g., in the range between 256 ℃ and 340 ℃, even between 260 ℃ and 335 ℃, or between 261 ℃ and 330 ℃. The melting temperature may be determined using Differential Scanning Calorimetry (DSC) according to ASTM D3418 (heat up 2, heat up/cool down rate 20 ℃/min).
According to embodiments, the polymeric LCP has a crystallization temperature (Tc) of less than 275 ℃, e.g., in the range between 150 ℃ and 275 ℃, e.g., in the range between 155 ℃ and 260 ℃, or between 160 ℃ and 255 ℃. Crystallization temperatures can be determined using Differential Scanning Calorimetry (DSC) according to ASTM D3418 (Cooling, heating/Cooling Rate of 20 ℃/min).
The polymeric LCPs described herein may be prepared by any conventional method suitable for the synthesis of polyesters, more precisely liquid crystalline polyesters.
According to the present invention, the fiber fabric (F) used in the composite film may be an aramid fabric, a glass fiber fabric, or a quartz fabric. Preferably, the fibrous web (F) comprises glass fibers. The fibrous web (F) may be a woven or nonwoven web.
Preferably, the fibrous web (F) comprises glass fibers. More preferably, the glass fibers, and thus the glass fiber fabrics, are characterized by a low dielectric constant and a low dissipation factor.
In an advantageous embodiment, the glass fiber fabric is made of fibers comprising: at least 33.0 to 48.0 parts by mass of silicon oxide; 1.0 to 5.0 parts by mass of alumina; 5.0 to 10.0 parts by mass of titanium oxide; 0.5 to 4.0 parts by mass of zirconia; and at least one of the following oxides: holmium oxide, alkaline earth metal oxides, neodymium oxide, and iron oxide.
In certain embodiments, the fiberglass fabric is made from fibers having the following composition: 35.0 parts by mass to 48.0 parts by mass of silica relative to the total mass of the fiber; alumina, 1.0 to 5.0 parts by mass; 5.5 to 10.0 parts by mass of titanium oxide; zirconium oxide, 0.5 to 4.0 parts by mass; holmium oxide less than or equal to 3.0 parts by mass; 32.0 to 47.5 parts by mass of an alkaline earth metal oxide. Alternatively, the fiberglass fabric is made from fibers having the following composition: 33.0 parts by mass to 46.0 parts by mass of silica relative to the total mass of the fiber; alumina 1.5 to 5.0 parts by mass; 5.0 to 10.0 parts by mass of titanium oxide; zirconium oxide, 0.5 to 4.0 parts by mass; less than or equal to 2.5 parts by mass of neodymium oxide; iron oxide less than or equal to 1.2 parts by mass; 31.0 to 53.0 parts by mass of an alkaline earth metal oxide.
The fiberglass fabric may additionally or alternatively be characterized by a dielectric constant D of less than 5.5 at 1GHz as measured using a transmission line method and a vector network analyzer k And a dissipation factor D of less than 0.0030 at 1GHz as measured using transmission line method and vector network analyzer f 。
The fiberglass fabric preferably has a dielectric constant D at 1GHz of less than 5.0 as measured using a transmission line method and a vector network analyzer k . Dielectric constant D at 1GHz k Typically not less than 3.0. The fiberglass fabric preferably has a dissipation factor D at 1GHz of less than 0.0025, even less than 0.0020, measured using a transmission line method and a vector network analyzer f . Dissipation coefficient D at 1GHz f Typically not less than 0.0001.
Glass fiber fabrics having the characteristics detailed above are available from Nittobo, inc. and CTG Mount glass fiber company (CTG Taishan Fiberglass).
The fibrous web (F) may, for example, exhibit an average thickness of about 200 μm or less, for example 180 μm or less or 160 μm or less. The fibers in the fibrous web (F) may exhibit an average diameter of about 25 μm or less, for example about 23 μm or less or 21 μm or less.
In some embodiments, the fibrous web (F) is such that it has an average areal weight (in grams per square meter or gsm) comprised between 10gsm and 100gsm, for example between 12gsm and 90gsm or between 15gsm and 80 gsm.
In some embodiments, the fibrous web (F) is such that it has a thickness of between 0.01mm and 0.10 mm.
The use of such a fibrous web in the film of the present invention is advantageous because it imparts additional stiffness or dimensional stability if desired. These features can be advantageously optimized based on the selection of certain fabrics to meet the requirements of certain end uses.
The composite film of the present invention may be a multilayer composite film and may contain several kinds of fiber fabrics (F) each of which is the same or different. These fabrics may have different thicknesses and/or different compositions. They may also be oriented in different directions. For example, the composite membrane may comprise a stack of 2, 3, 4, 5, and up to 10 fibrous webs.
In the multilayer films of the present invention, the same polymeric LCP described herein may be present between the individual fibrous webs, or different polymers including different polymeric LCPs may be used between the individual fibrous webs. Alternatively, chemically different polymers may be used to bond the layers together. An example of such a chemically different polymer is a polyimide polymer.
According to the present invention, the composite film preferably comprises less than about 75wt.% of fibrous web (F), preferably between 5 and 70wt.% or between 10 and 60wt.% of fibrous web (F) per unit area of the composite film. At such weight percentages, the composite film readily accommodates shrinkage of the polymeric LCP as it cools from the elevated lamination temperature.
According to the invention, the composite film is preferably such that its volume fiber is between 20 and 60vol.%, e.g. between 25 and 55vol.%, or between 30 and 50vol.%, wherein Vf is calculated according to the following equation:
the composite film of the present invention may have a wide range of thicknesses. In one embodiment, the composite film has a thickness comprised between 0.100mm and 0.005mm, preferably between 0.090 and 0.010mm, for example between 0.080 and 0.020, even between 0.070 and 0.030 mm.
In alternative embodiments, it may exhibit a greater thickness, for example comprised between 10.00mm and 0.10mm, preferably between 5.00mm and 0.20mm, for example between 3.00mm and 0.40 or between 2.00mm and 0.50 mm. The thickness of the composite film may be measured by any means; for example, it may be measured using a thickness gauge.
The inventors have recognized that films having a thickness within the claimed range retain their desired flexibility for applications while retaining their shape due to the fiber fabric, which makes such films well suited for use as mobile electronic device components, such as Copper Clad Laminates (CCL) and flexible printed circuit boards (FPC). The composite films of the present invention are generally flexible compared to commercially available films. Due to the chemical nature of the resins used to make the films, in combination with the fibrous web, the films of the present invention exhibit not only the proper flexibility for mobile electronic device components, but they also exhibit a suitable set of mechanical properties, including tensile strength and coefficient of thermal expansion.
The composite films of the present invention are also advantageously characterized by excellent dielectric properties for use in mobile electronic device components. In particular, they are characterized by a low dielectric constant and a low dissipation factor even at high frequencies.
In some embodiments, these films have the following dielectric properties:
-a dielectric constant Dk at 5GHz of less than 3.8 as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after drying for 1h at 100 ℃, and/or
-a dissipation coefficient Df of less than 0.0050, even less than 0.0025 at 5GHz as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after drying for 1h at 100 ℃, and/or
A dielectric constant Dk at 20GHz of less than 3.9, even less than 3.85, as measured by splitting a cylindrical resonator, IPC TM-650 2.5.5.13 after drying for 1h at 100 ℃, and/or
Dissipation factor Df of less than 0.0100, even less than 0.0080, still less than 0.0050 at 20GHz as measured by split cylindrical resonator, IPC TM-650 2.5.5.13 after drying for 1h at 100 ℃, and/or
-a dielectric constant Dk at 5GHz of less than 3.8 as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after 24 hours of immersion in water, and/or
-dissipation coefficient Df of less than 0.0050, even less than 0.0030 at 5GHz as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after immersion in water for 24 hours, and/or
-a dielectric constant Dk at 20GHz of less than 3.8 as measured by splitting a cylindrical resonator, IPC TM-650 2.5.5.13 after immersion in water for 24 hours, and/or
Dissipation factor Df of less than 0.0100, even less than 0.0080 at 20GHz as measured by splitting a cylindrical resonator, IPC TM-650 2.5.5.13 after 24 hours immersion in water.
In some embodiments, the film is such that it has a temperature in the range of 0 ℃ to 300 ℃ of less than about 50 x 10 -6 Per DEG C, e.g. less than 40X 10 -6 With a temperature/DEG C or less than 30X 10 -6 Coefficient of Thermal Expansion (CTE) at/DEG C. According to this embodiment, the membrane is such that it has at least 1X 10 -6 At least 4X 10 -6 CTE at DEG C. The coefficient of thermal expansion may be measured in tension mode using TMA equipment according to ASTM D696.
Method for producing a composite film
The composite membrane of the present invention may be prepared according to different methods.
The advantageous method may start with a polymer powder comprising at least one polymer LCP, which is applied to at least one surface of the fibrous web (F). According to a preferred embodiment, the powder comprising at least one polymer LCP is applied to at least one surface of the fibrous web (F) such that it has an average particle size d 50 Is comprised between 0.1 and 250.0 μm, between 0.1 and 100.0 μm, preferably between 1.0 and 90.0 μm or between 5.0 and 80.0 μm. As used herein, the term "d 50 "means the diameter at which 50% of the sample (by volume unless otherwise indicated) consists of particles having a diameter less than the value of the diameter. D of a powder comprising at least one polymer LCP 50 Can be measured by laser light scattering in isopropanol.
The polymer powder may include fillers and other additives well known in the art. Such fillers and additives may include, for example, organic or inorganic particles, plasticizers, light and weather stabilizers, antistatic agents, ultraviolet light absorbers, dyes, pigments, viscosity agents, and lubricants.
According to an embodiment, a method for preparing a composite film of the present invention comprises the steps of:
a) Applying a powder comprising at least one polymer LCP onto at least one surface of a fibrous web (F), wherein the powder is characterized by an average particle size d comprised between 0.1 and 250.0 μm 50 ，
b) Bonding the polymer powder to the fibrous web (F) at a pressure P of at least 0.3MPa and/or at a temperature T such that T.gtoreq.Tm, wherein Tm is the melting temperature (. Degree.C.) of the polymer powder.
At the temperatures and pressures mentioned above, the polymer powder undergoes a melt phase, making it possible to adhere firmly to the fibrous web (F).
In some preferred embodiments, the powder comprising at least one polymer LCP is applied to both surfaces of the fibrous web (F). A protective film may be used to apply the powder comprising at least one polymer LCP to both surfaces of the fibrous web (F).
Preferably, step b) is carried out at a pressure P of at least 0.4MPa, at least 0.5MPa or at least 0.5MPa, and/or at a temperature T such that T.gtoreq.Tm, where Tm is the melting temperature (. Degree.C.) of the polymer powder. In some embodiments, T is such that T.gtoreq.Tm+5℃. In some embodiments, T is such that 280 C.ltoreq.T.ltoreq.400C, e.g., 290 C.ltoreq.T.ltoreq.390C or 305 C.ltoreq.T.ltoreq.380C or 330 C.ltoreq.T.ltoreq.360C.
Step b) may for example comprise subjecting the fibrous web with the polymer powder applied thereto to compression moulding using a hot press.
If a die press is used in the method of the invention, a release film may be used between the film and the press platen of the press so that sticking of the film to the platen does not occur. Any barrier film that does not interfere with or alter the characteristics of the composite film is suitable. For example, the release film may be polyimide, or a release coated metal foil such as aluminum.
Such a process may be a batch process, meaning that a single film may be formed at a time in an autoclave or under vacuum/in an oven using a stack laminator. Alternatively, the process may be a continuous process, for example, wherein polymer powder is continuously laid on at least one fibrous web with or without one or more rolls of fibrous web and bonded thereto by high pressure and high temperature with a twin belt press. When the polymer powder is above its melting point, the residence time in the press is 0.5 to 1,000 seconds. A typical twin belt press may have heating and cooling zones.
The amount of pressure and temperature applied to the film depends on the type of polymer employed and the fibrous web employed and the respective physical and dimensional characteristics, along with the operation, physical and dimensional characteristics of the press. The melting point of the polymer powder is an important feature, along with the size of the polymer powder, the thickness of the fiber web and its heat transfer capability, and of course how thick the composite film is (including multi-layer structures). In addition, the heat transfer characteristics of the platens (of the press), their size and thickness, the residence time of the film in the press, etc. are also important. For example, for a polymer powder comprising a polymer LCP as described above, the temperature should be above about 280 ℃ and a particularly preferred temperature range is 330 ℃ to 380 ℃. When using this particular polymer and a fibrous web having an average thickness of about 0.06mm, the pressure to be applied to such a composite film should be in the range of 0.3MPa to 1.0 MPa.
One of the methods of the present invention for preparing a composite film comprises the steps of:
a) Applying a polymer powder comprising at least one LCP polymer onto at least one surface of a fibrous web (F), said powder being characterized by an average particle size d comprised between 0.1 and 100 μm 50 ，
b) The polymer powder is sintered to the fiber fabric by electromagnetic radiation, infrared or near infrared radiation.
The polymer powder may be applied via electrostatic coating.
According to this method, the polymer powder is sintered at the surface of the fiber web using electromagnetic radiation, infrared or near infrared radiation (e.g. a high power laser source such as an electromagnetic beam source).
Other methods of the present invention for preparing composite films begin with a polymeric material in the form of a slurry or dispersion.
Other methods of the present invention for preparing composite films begin with polymers in the form of films, which may be made from only the polymer LCPs described herein or may contain additional components or additives.
One of these methods for preparing a composite film includes the steps of:
a) Applying a polymer film comprising at least one polymer LCP to at least one surface of a fibrous web (F), an
b) Bonding the polymer film to the fibrous web (F) at a pressure P of at least 0.3MPa and/or at a temperature T such that T.gtoreq.Tm, wherein Tm is the melting temperature (. Degree.C.) of the polymer film.
The polymer film in step a) above preferably has a thickness of less than 0.10 mm.
Yet another method for preparing the composite film of the present invention comprises the steps of:
a) Applying a polymer film comprising at least one LCP polymer to at least one surface of a fibrous web (F), an
b) The polymer film is sintered onto the fibrous web (F), for example by electromagnetic radiation, infrared or near infrared radiation.
The polymer film in step a) above preferably has a thickness of less than 0.10 mm.
According to the present invention, several individual composite films may be stacked on each other to prepare a multi-layered composite film. The composite films may be arranged in the same direction and/or they may be arranged in different directions, for example. The stacked multi-layer structure may be subjected to a new cycle (or several cycles) of compression molding using a hot press, if necessary.
Alternatively, the multilayer composite film may be prepared by:
a) Applying a polymer powder comprising at least one LCP polymer to at least one surface of at least two fibrous webs, preferably fibrous web (F),
b) Stacking the at least two fibrous webs on top of each other
c) The polymer powder is bonded to the fibrous web at a pressure P of at least 0.3MPa and/or at a temperature T such that T.gtoreq.Tm, where Tm is the melting temperature (. Degree.C.) of the polymer powder.
Alternatively, step c) may comprise sintering the polymer powder, as described above.
In some embodiments, the polymer powder is in the form of a slurry, such as a wet slurry.
In some other embodiments, the polymer may be in the form of a film to be melted to adhere to the fibrous web. Preferably, the film has a thickness of less than 0.09 mm.
Several of these options may be used to prepare a multilayer composite film according to the present invention.
End use applications
While the composite films of the present invention may be characterized by a specific thickness, for example less than 0.10mm, the present invention also relates to assemblies of composite films according to the present invention, which may result in final assemblies having a thickness of 0.10mm or more.
The invention also relates to an article or component article comprising at least one composite film as described above, and optionally a metal layer, preferably a copper layer.
The invention also relates to the use of at least one composite film for the preparation of a mobile electronic device article or component, such as a flexible printed circuit board (FPC).
The composite film of the present invention can be notably used for the preparation of flexible printed circuit boards (FPCs), carrier tapes for Tape Automated Bonding (TAB), and tapes of lead-on-chip (LOC) structures.
The invention also relates to the use of a powder comprising, or even consisting of, at least one polymer LCP for the preparation of a composite film further comprising at least one fibrous web (F). The composite film advantageously has a thickness of less than 0.10 mm.
The invention also relates to the use of a composition comprising, even consisting of, at least one polymer LCP comprising recurring units derived from 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB) in combination with an aromatic monomer, including 6-hydroxy-2-naphthoic acid (HNA), for the preparation of a composite film further comprising at least one fibrous web (F). The composite film advantageously has a thickness of less than 0.10 mm.
The disclosure of any patent, patent application, and publication incorporated by reference herein should be given priority if it conflicts with the description of the present application to the extent that the term "does not become clear".
Examples
The present disclosure will now be described in more detail with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the present disclosure.
Starting materials
Glass fabric GF-1: Fabric 108, commercially available from BGF Industries, has a thickness of 48gsm and 0.06 millimeters/2.4 mils and a fiber diameter of 5 μm.
Glass fabric GF-2: fabric LD1035-127, commercially available from CTG Mount glass fiber company; the dielectric constants Dk of 4.3-4.5 at 1GHz and the dissipation factors Df, dk and Df of 0.0016 at 1GHz were both measured using a transmission line method and a vector network analyzer.
LCP preparation
LCP #1 and LCP #2 are prepared as described below, wherein:
AcHNA is 6-acetoxy-2-naphthoic acid;
-Ac4,4'-BP is 4,4' -diacetoxybiphenyl
-4,4'-BP is 4,4' -biphenol
-4,4'-BB is 4,4' -diphenic acid
NDA is 2, 6-naphthalenedicarboxylic acid
IPA is isophthalic acid.
LCP#1
The reaction was performed in a dry 500mL round bottom flask equipped with an overhead stirrer, nitrogen inlet, and a distillation neck attached to a receiving flask. 128.17g of AcHNA (70 mol.%), 32.24g of 4,4'-BP (15 mol.%), 14.45g of 4,4' -BB (7.5 mol.%) and 12.90g (7.5 mol.%) of NDA were added. Subsequent degassing with vacuum and purging with N2 gas (3×) creates an oxygen free environment. The initial temperature was 220 ℃ or the temperature at which all the monomers formed a melt and this temperature was maintained and stirred for 0.5h. The temperature was increased from the starting temperature up to 335 ℃ at 1.0 ℃/min, and maintained at this temperature for 1h. Then an indoor vacuum is applied for 0.5-1h to facilitate removal of acetic acid condensate, followed by a high vacuum to 0.1-2mmHg. The reaction was maintained under high vacuum until no significant condensate was seen to leave the reaction and the polymer sample solidified around the stirring blade. Subsequently, the sample was cooled and removed from the stirring blade. The resulting polymer was dried overnight at 100 ℃ before use. The polymer is obtained in the form of a powder. Two samples with different average particle sizes were prepared as follows: LCP #1-a: d, d 50 ＝137.0μm；LCP#1-B：d50＝65.7μm。
LCP#2
This example followed the procedure described previously, with 129.53g of AcHNA (70 mol.%), 32.59g of Ac4,4'-BP (15 mol.%), 19.47g of 4,4' -BB (10 mol.%) and 6.68g of IPA (5 mol.%) as monomer charges. The polymer is obtained in powder form: LCP #2: d, d 50 ＝236.8μm。
Film preparation method
The LCP polymer powder was dispersed on fabric GF-1 or GF-2 in the following configuration: polymer/fabric/polymer. The resulting combination of parts was then compression molded into a thin composite film using a hot press set at a temperature of 330 ℃ and a pressure of 1 MPa. The film was heated for about 10 minutes. The polymer powder melts and impregnates the fabric fibers. Immediately the film was removed from the press and placed on a cool table and allowed to recover to ambient temperature.
Test method
Dielectric Properties (Dk, df)
The dielectric constant Dk and dissipation factor Df were measured at 5GHz after drying for 1h at 100℃by means of a split column dielectric resonator (SPDR), IEC 61189-2-721:2015 and after immersion in water for 24 hours.
The dielectric constant Dk and dissipation factor Df were measured at 20GHz by splitting a cylindrical resonator, IPC TM-650.5.5.13 after drying at 100℃for 1h and after immersion in water for 24 hours.
Volume of fiber
Vf is calculated according to the following equation:
Results
TABLE 1
The data in table 1 show that the composite film of the present invention has excellent dielectric properties at high frequencies (20 GHz) even after being immersed in water. When the composite material is formed by a material with low d 50 The dielectric properties appear to be further improved when polymer powders of (a) are prepared.
TABLE 2
| Film 2 | |
| Component (A) | LCP#2/GF-2/LCP#2 |
| Vf | 41％ |
| Thickness (mm) | 0.065 |
| Dk at 5GHz after drying at 100℃for 1h | 3.6 |
| Df at 5GHz after drying at 100℃for 1h | 0.0009 |
| Dk at 5GHz after 24h immersion in water | 3.6 |
| Df at 5GHz after 24h immersion in water | 0.0016 |
| Dk at 20GHz after drying at 100℃for 1h | 3.6 |
| Df at 20GHz after drying at 100℃for 1h | 0.0020 |
The data in table 2 show that the composite film of the present invention has excellent dielectric properties even at 20 GHz.
TABLE 3 Table 3
| Film 3 | |
| Component (A) | LCP#1-A/GF-1/LCP#1-A |
| Thickness (mm) | 0.053 |
| Dk at 20GHz after drying at 100℃for 1h | 3.8 |
| Df at 20GHz after drying at 100℃for 1h | 0.0062 |
The data in table 3 show the good dielectric properties of the composite films of the present invention at 20 GHz.
Claims (25)
1. A composite membrane comprising:
at least one liquid crystalline polyester, [ polymer LCP ], and
-at least one fibrous web, [ fibrous web (F) ].
2. A composite film according to claim 1 wherein the polymeric LCP comprises repeat units derived from at least 6-hydroxy-2-naphthoic acid.
3. A composite film according to any preceding claim wherein the polymeric LCP comprises repeat units derived from 4,4 '-diphenic acid and/or 3,4' -diphenic acid.
4. A composite film according to any preceding claim, wherein the polymer LCP comprises 40.0mol.% or more repeat units derived from 6-hydroxy-2-naphthoic acid and 1.0mol.% or more repeat units derived from 4,4 '-diphenic acid and/or 3,4' -diphenic acid based on the total moles in the polymer LCP.
5. A composite film according to any preceding claim, wherein the polymeric LCP comprises:
a) 40.0 to 98.0mol.% of a repeating unit having formula (I):
b) 1.0 to 30.0mol.% of recurring units derived from at least one aromatic diol selected from the group consisting of diols having formulae (IIa) to (IId):
and/or
And
c) Repeat units derived from an aromatic compound having two carboxyl groups:
-1 to 23mol.% of a repeating unit having formula (IIIa):
and/or
-1 to 13mol.% of a repeating unit having formula (IIIb):
all percentages are based on the total moles in the polymer LCP.
6. The composite film of claim 5, wherein the polymeric LCP comprises:
50.0 to 80.0mol.% of a repeating unit of formula (I),
-9.0 to 25.0mol.% of a repeating unit having formula (II), and
-2.0 to 12.0mol.% of a repeating unit having formula (IIIb).
7. The composite film of claim 5, wherein the polymeric LCP comprises:
50.0 to 80.0mol.% of a repeating unit of formula (I),
-9.0 to 25.0mol.% of a repeating unit having formula (II), and
-2.0 to 21.0mol.% of a repeating unit having formula (IIIa).
8. The composite film of claim 5, wherein the polymeric LCP comprises:
50.0 to 80.0mol.% of a repeating unit of formula (I),
9.0 to 25.0mol.% of a repeating unit of formula (II),
-2.0 to 15.0mol.% of a repeating unit having formula (IIIa), and
-2.0 to 11.0mol.% of a repeating unit having formula (IIIb).
9. A composite film according to any preceding claim, wherein the polymeric LCP further comprises:
-0.1 to 15mol.% of a repeating unit having formula (IV):
and/or
-0.1 to 15mol.% of a repeating unit having formula (V):
and/or
-0.1 to 25mol.% of a repeating unit having formula (VI):
and/or
-0.1 to 25mol.% of a repeating unit having formula (VII):
10. a composite film according to any preceding claim, wherein the polymeric LCP further comprises:
-0.1 to 20mol.% of a repeating unit having formula (VIII):
-0.1 to 20mol.% of a repeating unit having formula (IX):
-0.1 to 20mol.% of a repeating unit having formula (X):
-0.1 to 20mol.% of a repeating unit having formula (XI):
and/or
-0.1 to 20mol.% of a repeating unit having formula (XII):
11. a composite film according to any one of the preceding claims, wherein the fibrous web (F) comprises glass fibres.
12. The composite film of claim 11, wherein the glass fibers are selected from fibers comprising:
i) 35.0 parts by mass to 48.0 parts by mass with respect to the total mass of the fiber; alumina, 1.0 to 5.0 parts by mass; 5.5 to 10.0 parts by mass of titanium oxide; zirconium oxide, 0.5 to 4.0 parts by mass; holmium oxide less than or equal to 3.0 parts by mass; 32.0 to 47.5 parts by mass of an alkaline earth metal oxide; or alternatively
ii) 33.0 to 46.0 parts by mass of silica relative to the total mass of the fiber; alumina 1.5 to 5.0 parts by mass; 5.0 to 10.0 parts by mass of titanium oxide; zirconium oxide, 0.5 to 4.0 parts by mass; less than or equal to 2.5 parts by mass of neodymium oxide; iron oxide less than or equal to 1.2 parts by mass; 31.0 to 53.0 parts by mass of an alkaline earth metal oxide.
13. The composite film of claim 11 or 12, wherein the fiberglass fabric is characterized by a dielectric constant D of less than 5.5 at 1GHz measured using a transmission line method and a vector network analyzer k And a dissipation factor D of less than 0.0030 at 1GHz as measured using transmission line method and vector network analyzer f 。
14. A composite film according to any preceding claim having a thickness of less than 0.10 mm.
15. The composite film of any of the preceding claims, wherein the film has:
-a dielectric constant Dk at 5GHz of less than 3.8 as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after drying for 1h at 100 ℃, and/or
-dissipation coefficient Df of less than 0.0050 at 5GHz as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after drying for 1h at 100 ℃, and/or
-a dielectric constant Dk at 20GHz of less than 3.9 as measured by splitting a cylindrical resonator, IPC TM-650 2.5.5.13 after drying for 1h at 100 ℃, and/or
-dissipation coefficient Df of less than 0.0100 at 20GHz as measured by split cylindrical resonator, IPC TM-650 2.5.5.13 after drying for 1h at 100 ℃, and/or
-a dielectric constant Dk at 5GHz of less than 3.8 as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after 24 hours of immersion in water, and/or
-dissipation coefficient Df of less than 0.0050 at 5GHz as measured by split column dielectric resonator (SPDR), IEC 61189-2-721:2015 after 24 hours of immersion in water, and/or
-a dielectric constant Dk at 20GHz of less than 3.8 as measured by splitting a cylindrical resonator, IPC TM-650 2.5.5.13 after immersion in water for 24 hours, and/or
Dissipation factor Df of less than 0.0100 at 20GHz as measured by split cylindrical resonator, IPC TM-650 2.5.5.13 after 24 hours immersion in water.
16. A process for preparing a composite film according to any one of claims 1 to 15, the process comprising applying at least one polymeric LCP to at least one surface of a fibrous web (F).
17. The method of claim 16, comprising the steps of:
a) Applying a powder comprising at least one polymer LCP to at least one surface of a fibrous web (F)Wherein the powder is characterized by an average particle size d comprised between 0.1 and 250.0 μm 50 ，
b) Bonding the polymer powder to the fibrous web (F) at a pressure P of at least 0.3MPa and/or at a temperature T such that T.gtoreq.Tm, wherein Tm is the melting temperature (. Degree.C.) of the polymer powder.
18. The method of claim 17, wherein the powder comprising at least one polymer LCP has an average particle size d comprised between 0.1 and 100.0 μιη 50 。
19. The process according to claim 17 or 18, wherein step b) is carried out at a pressure P of at least 0.5MPa and/or at a temperature T such that t+.tm+5℃.
20. An article or part of an article comprising at least one composite film according to any one of claims 1 to 15, and optionally a metal layer, preferably a copper layer.
21. Use of at least one composite film according to any one of claims 1 to 15 for the preparation of a mobile electronic device article or a component thereof, preferably a flexible printed circuit board (FPC).
22. Use of a powder comprising at least one liquid crystalline polyester comprising repeat units derived from at least one of 4,4 '-diphenic acid (4, 4' -BB) and/or 3,4 '-diphenic acid (3, 4' -BB) for the preparation of a composite film having a thickness of less than 0.10mm, the composite film further comprising at least one fibrous web (F).
23. Use according to claim 22, wherein the fibrous web (F) comprises glass fibers.
24. The use as claimed in claim 22 or 23, wherein the glass fibres are selected from fibres comprising:
-silicon oxide, 35.0 to 48.0 parts by mass; alumina, 1.0 to 5.0 parts by mass; 5.5 to 10.0 parts by mass of titanium oxide; zirconium oxide, 0.5 to 4.0 parts by mass; holmium oxide less than or equal to 3.0 parts by mass; 32.0 to 47.5 parts by mass of an alkaline earth metal oxide; or alternatively
-silicon oxide, 33.0 to 46.0 parts by mass; alumina 1.5 to 5.0 parts by mass; 5.0 to 10.0 parts by mass of titanium oxide; zirconium oxide, 0.5 to 4.0 parts by mass; less than or equal to 2.5 parts by mass of neodymium oxide; iron oxide less than or equal to 1.2 parts by mass; 31.0 to 53.0 parts by mass of an alkaline earth metal oxide.
25. The use as claimed in claims 22 to 24, wherein the glass fibre fabric is characterized by a dielectric constant D at 1GHz of less than 5.5 measured using transmission line method and vector network analyzer k And a dissipation factor D of less than 0.0030 at 1GHz as measured using transmission line method and vector network analyzer f 。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202163211638P | 2021-06-17 | 2021-06-17 | |
| US63/211638 | 2021-06-17 | ||
| EP21195292.4 | 2021-09-07 | ||
| PCT/EP2022/066421 WO2022263572A1 (en) | 2021-06-17 | 2022-06-15 | Composite films for mobile electronic device components |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117500867A true CN117500867A (en) | 2024-02-02 |
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ID=89676877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280043071.2A Pending CN117500867A (en) | 2021-06-17 | 2022-06-15 | Composite film for mobile electronic device components |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117500867A (en) |
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2022
- 2022-06-15 CN CN202280043071.2A patent/CN117500867A/en active Pending
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