WO2022186309A1 - 液晶ポリエステル系樹脂組成物、該組成物を用いた液晶ポリエステル系フィルム、該フィルムを用いた金属ラミネートフィルム、回路基板 - Google Patents
液晶ポリエステル系樹脂組成物、該組成物を用いた液晶ポリエステル系フィルム、該フィルムを用いた金属ラミネートフィルム、回路基板 Download PDFInfo
- Publication number
- WO2022186309A1 WO2022186309A1 PCT/JP2022/008998 JP2022008998W WO2022186309A1 WO 2022186309 A1 WO2022186309 A1 WO 2022186309A1 JP 2022008998 W JP2022008998 W JP 2022008998W WO 2022186309 A1 WO2022186309 A1 WO 2022186309A1
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- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- film
- crystal polyester
- resin composition
- polyetherimide
- Prior art date
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 75
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000004645 polyester resin Substances 0.000 title claims abstract description 21
- 229920006267 polyester film Polymers 0.000 title claims description 42
- 229910052751 metal Inorganic materials 0.000 title claims description 31
- 239000002184 metal Substances 0.000 title claims description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 55
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 46
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 45
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 43
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 41
- 238000001125 extrusion Methods 0.000 claims abstract description 31
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims description 46
- 239000011342 resin composition Substances 0.000 claims description 25
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 10
- 239000005001 laminate film Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 7
- 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 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 23
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 18
- 239000000155 melt Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920006125 amorphous polymer Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 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
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920012287 polyphenylene sulfone Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 101100280469 Salmonella typhimurium (strain LT2 / SGSC1412 / ATCC 700720) fabI gene Proteins 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 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 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
Definitions
- the present invention relates to a liquid crystalline polyester-based resin composition whose main component is a thermoplastic liquid crystalline polyester capable of forming an optically anisotropic melt phase.
- the present invention also relates to a liquid crystal polyester film using the resin composition, and a metal laminate film and a circuit board using the film.
- thermoplastic liquid crystal polyesters are useful in the electronic and electrical fields because they exhibit excellent mechanical and electrical properties, low dimensional change rate, high heat resistance and chemical stability.
- a thermoplastic liquid crystalline polyester having a melting point of 300° C. or more is useful for printed circuit board applications because it can be reflowed with lead-free solder.
- thermoplastic liquid crystalline polyesters have the property that rigid molecular chains are arranged in an orderly manner even in a molten state, and the molecular chains do not get entangled and flow in a slippery manner. alone does not reach a level that can be used.
- Patent Document 1 is an invention relating to an aromatic resin composition characterized by comprising a wholly aromatic copolyester (liquid crystal polyester) and a polyetherimide. Improvements with polyetherimides are described. However, the examples of Patent Document 1 only disclose press molding of the resin composition into a test piece, and do not disclose any continuous film forming.
- Patent Document 2 is an invention relating to a resin composition comprising a thermotropic liquid crystal polyester and a siloxane polyetherimide copolymer, and the anisotropy of the mechanical properties of the liquid crystal polyester can be reduced by the siloxane polyetherimide copolymer. disclosed. However, the examples of Patent Document 2 only disclose that the resin composition was used to prepare sample pieces for various measurements, but do not disclose anything about molding into a film.
- Patent Document 3 is an invention aimed at improving the edge tear strength without impairing the excellent properties of a thermoplastic liquid crystal polymer (liquid crystal polyester) capable of forming an optically anisotropic molten layer.
- Patent Document 3 discloses a polymer alloy comprising a thermoplastic polymer (liquid crystal polyester) capable of forming an optically anisotropic melted layer and an amorphous polymer, and a film comprising the polymer alloy.
- amorphous polymers include polysulfone, polyethersulfone, polyphenylene sulfide, polycarbonate, polyethylene isophthalate, and polyarylate.
- a manufacturing method using an extrusion molding method such as an inflation extrusion molding method is known.
- an extrusion molding method such as an inflation extrusion molding method
- a film is formed by an inflation extrusion method in an example.
- the orientation of the molecular chains can be controlled to some extent by appropriately adjusting the blow ratio.
- thermoplastic liquid crystalline polyesters have the characteristic that the melt viscosity greatly depends on the shear stress, and that a slight increase in shear stress significantly reduces the melt viscosity. For this reason, when the thermoplastic liquid crystalline polyester is melt extruded by the inflation extrusion molding method, the shear stress generated at the die part causes the melt viscosity to drop rapidly, making it difficult to maintain the shape of the film. There is a problem that it is difficult to stably form a film.
- thermoplastic liquid crystalline polyester has a characteristic that the melt viscosity greatly depends on the temperature, and the melt viscosity is remarkably lowered by a slight temperature rise in the vicinity of the melting point. The higher the melting point of the thermoplastic liquid crystalline polyester, the more pronounced this tendency is.
- thermoplastic liquid crystalline polyester with a melting point of 300° C. or more has a low melt viscosity near the melting point, so the film is formed by extrusion such as inflation extrusion. In this case, the bubbles extruded from the die are likely to be perforated, making it difficult to stably form a film.
- the present invention has been made in view of such problems, and a liquid crystal polyester resin composition that is excellent in mechanical properties, electrical properties, and heat resistance that can stably form a film in extrusion molding such as inflation extrusion molding.
- the purpose is to provide goods.
- the present inventors are earnestly interested in a resin composition that enables stable film formation while maintaining the excellent mechanical properties, electrical properties, and heat resistance of a thermoplastic liquid crystal polyester having a melting point of 300 ° C. or higher.
- a thermoplastic liquid crystal polyester having a melting point of 300 ° C. or higher.
- the inventors have found that film formation is possible, and have completed the present invention.
- thermoplastic liquid crystal polyester (A) comprises a structural unit derived from p-hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid.
- the described liquid crystal polyester resin composition is provided, (3) The liquid crystalline polyester resin composition according to (1) or (2) is provided, wherein the resin composition is for inflation extrusion molding, (4) A liquid crystal polyester film characterized by comprising the resin composition according to any one of (1) to (3) is provided, (5) 0.75 ⁇ F (TD)/F (MD) ⁇ 1.25, where F (MD) is the tensile strength in the machine direction of the film and F (TD) is the tensile strength in the width direction of the film.
- the liquid crystalline polyester film according to (4) is provided, (6) A method for producing a liquid crystalline polyester film according to (4) or (5), characterized in that the film is formed by an inflation extrusion method, (7) A metal laminate film is provided, wherein a metal layer is laminated on one side or both sides of the liquid crystal polyester film according to claim 4 or 5, (8) Provided is a circuit board comprising at least one conductor layer and the thermoplastic liquid crystal polyester film described in (4) or (5).
- the liquid crystalline polyester resin composition of the present invention contains polyetherimide having a siloxane bond in the main chain, so that bubbles extruded from a die when forming a film in extrusion molding such as inflation extrusion molding. It is possible to suppress the occurrence of perforation and stably form a film.
- polyetherimide having a siloxane bond in the main chain, the excellent mechanical and electrical properties of a thermoplastic liquid crystal polyester with a melting point of 300 ° C. or higher can be obtained while improving film-forming processability. , it is possible to maintain heat resistance.
- the liquid crystal polyester film made of the liquid crystal polyester resin composition of the present invention and the metal laminate film obtained by bonding the liquid crystal polyester film and the metal layer have excellent mechanical properties, electrical properties, and solder reflow properties. and can be suitably used for applications such as laminates for circuit boards suitable for high-speed communication applications.
- the liquid crystalline polyester resin composition of the present invention comprises a thermoplastic liquid crystalline polyester (A) and a polyetherimide (B) having a siloxane bond in the main chain.
- thermoplastic liquid crystal polyester (A) is a liquid crystalline polyester exhibiting melt anisotropy (polyester capable of forming an optically anisotropic melt phase).
- melt anisotropy polyethyleneter capable of forming an optically anisotropic melt phase.
- the properties of melt anisotropy can be confirmed by a conventional polarization inspection method using crossed polarizers. Specifically, the melting anisotropy was measured by using a polarizing microscope (manufactured by Olympus Co., etc.), melting a sample placed on a hot stage (manufactured by Linkham Co., etc.), and exposing it to a 150-fold magnification in a nitrogen atmosphere. It can be confirmed by observation.
- a liquid crystalline resin exhibiting optical anisotropy when melted is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted, for example, even in the still molten liquid state.
- thermoplastic liquid crystal polyester (A) used in the resin composition of the present invention is a resin having a melting point of 300°C or higher among thermoplastic liquid crystal polyesters. If the melting point is lower than 300° C., the reflowability of the solder is poor, so if it is used for printed circuit boards and the like, the processing method will be restricted.
- thermoplastic liquid crystal polyester (A) used in the resin composition of the present invention is derived from structural units derived from p-hydroxybenzoic acid (sometimes referred to as monomer component A) and 6-hydroxy-2-naphthoic acid. It is preferable to contain a structural unit (sometimes referred to as monomer component B) as an essential unit.
- the thermoplastic liquid crystalline polyester (A) may contain a monomer component C other than the monomer component A and the monomer component B, and the monomer component C includes an aromatic or aliphatic dicarboxylic acid; an aromatic or aliphatic dihydroxy compounds; aromatic hydroxycarboxylic acids; aromatic diamines, aromatic hydroxyamines or aromatic aminocarboxylic acids;
- thermoplastic liquid crystal polyester (A) examples include binary polycondensates of p-hydroxybenzoic acid (monomer component A) and 6-hydroxy-2-naphthoic acid (monomer component B); p-hydroxy Ternary polycondensate of benzoic acid (monomer component A), 6-hydroxy-2-naphthoic acid (monomer component B), and terephthalic acid (monomer component C); p-hydroxybenzoic acid (monomer component A) and 6-hydroxy-2-naphthoic acid (monomer component B), terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol, bisphenol A, hydroquinone, and ethylene terephthalate.
- the blending ratio of each structural unit of the thermoplastic liquid crystal polyester (A) is not particularly limited. 85 mol % or less is more preferable, and 40 mol % or more and 80 mol % or less is even more preferable.
- the monomer component B is preferably 10 mol% or more and 80 mol% or less, more preferably 15 mol% or more and 70 mol% or less, and 20 mol% or more and 60 mol% or less, based on all structural units of the thermoplastic liquid crystal polyester (A). mol % or less is more preferable.
- thermoplastic liquid crystal polyester (A) contains the monomer component C
- the blending ratio of each structural unit of the thermoplastic liquid crystal polyester (A) is not particularly limited.
- A is preferably 15 mol % or more and 90 mol % or less, more preferably 20 mol % or more and 85 mol % or less.
- the monomer component B is preferably 5 mol % or more and 60 mol % or less, more preferably 15 mol % or more and 50 mol % or less, based on all structural units of the thermoplastic liquid crystal polyester (A).
- the monomer component C is preferably 0.5 mol % or more and 60 mol % or less, more preferably 1 mol % or more and 50 mol % or less, based on the total structural units of the thermoplastic liquid crystal polyester (A).
- the melting point of the thermoplastic liquid crystal polyester (A) is not particularly limited as long as it is 300°C or higher. It is more preferably 370° C. or higher, more preferably 310° C. or higher and 360° C. or lower, and particularly preferably 315° C. or higher and 345° C. or lower.
- the melting point of the thermoplastic liquid crystal polyester (A) was obtained by heating the sample at a rate of 10 ° C./min using a differential scanning calorimeter (DSC) to completely melt it, and then heating the melt at 10 ° C./min.
- the melting point is the position of the endothermic peak that appears when the temperature is increased again at a rate of 10°C/min.
- Polyetherimide (B) having a siloxane bond in the main chain is a non-crystalline thermoplastic resin obtained by introducing siloxane groups into polyetherimide to impart the flexibility of a silicone elastomer.
- Polyetherimide is a resin having an imide bond and an ether bond in its molecule, and is represented by the following general formula (1), for example.
- n represents the degree of polymerization, preferably 10 or more, more preferably 10 or more and 200 or less, and even more preferably 10 or more and 100 or less.
- Polyetherimide (B) having a siloxane bond in the main chain is obtained by block-copolymerizing a polyetherimide represented by general formula (1) with a siloxane group represented by general formula (2) below. It is a silicone-modified polyetherimide.
- m represents the degree of polymerization, preferably 1 or more, more preferably 1 or more and 20 or less, and even more preferably 1 or more and 10 or less.
- silicone-modified polyetherimide an appropriately synthesized one may be used, or a commercially available product may be used.
- commercially available products include SILTEM TM STM1500, SILTEM TM STM1600 and SILTEM TM STM1700 manufactured by SHPP Japan LLC.
- the glass transition temperature of the silicone-modified polyetherimide is not particularly limited, for example, it is preferably 190°C or higher, more preferably 195°C or higher, and even more preferably 200°C or higher. If the glass transition temperature of the silicone-modified polyetherimide is within the above range, a liquid crystalline polyester resin composition having excellent heat resistance can be obtained.
- the glass transition temperature of the silicone-modified polyetherimide was determined by heating the sample at a rate of 10 ° C./min using a differential scanning calorimeter (DSC) to completely melt it, and then heating the melt at 10 ° C./min.
- the glass transition temperature is the intersection of the original baseline and the tangent line at the inflection point at the position where the baseline that appears when the temperature is increased again at a rate of 10 ° C. / min is shifted to 30 ° C. at a rate of .
- the ratio of (A):(B) is preferably 94-96% by weight: 4-6% by weight.
- the blending ratio of the polyetherimide (B) having a siloxane bond in the main chain is less than the above range, the film forming processability of the film by extrusion molding of the liquid crystal polyester resin composition cannot be improved, and stable A film cannot be formed. If the blending ratio of the polyetherimide (B) having a siloxane bond in the main chain is more than the above range, the mechanical properties of the liquid crystal polyester film made of the liquid crystal polyester resin composition are significantly lowered.
- the liquid crystalline polyester-based resin composition of the present invention includes other resin components other than the thermoplastic liquid crystalline polyester (A) and the polyetherimide (B) having a siloxane bond in the main chain as long as the effects of the present invention are not impaired.
- Other resin components include thermoplastic resins such as polyarylates, polyphenylene sulfides, polyphenylene ethers, polyetheretherketones, polyetherimides, cycloolefin polymers, polyamides, polyamideimides, polyimides, and epoxy group-containing olefinic copolymers. mentioned.
- the liquid crystal polyester resin composition of the present invention may also contain additives such as lubricants, antioxidants and fillers.
- the present invention also proposes a film made of the resin composition described above and a method for producing the film.
- the liquid crystalline polyester film of the present invention is obtained by blending the thermoplastic liquid crystalline polyester (A) and the polyetherimide (B) having a siloxane bond in the main chain by a known method to form a film.
- the resin composition of the present invention contains a small amount of polyetherimide (B) having a siloxane bond in the main chain, in order to provide a stable kneading state, prior to film formation, melt kneading and Granulation is preferred.
- Equipment for melt-kneading is not particularly limited, but various known extruders such as batch kneaders, kneaders, co-kneaders, Banbury mixers, roll mills, single-screw or twin-screw extruders, etc. is mentioned. Among these, single-screw extruders and twin-screw extruders are preferably used because of their excellent kneading ability and productivity.
- the resin composition of the present invention contains a small amount of polyetherimide (B) having a siloxane bond in the main chain, thereby suppressing a rapid decrease in the melt viscosity of the resin composition due to shear stress or the like.
- the film is preferably formed by an extrusion method such as a T-die extrusion method or an inflation extrusion method. Among them, it is preferable to form the film by the inflation extrusion method in consideration of the balance of the mechanical properties of the film.
- the above-described resin composition is supplied to a melt extruder equipped with an annular slit die, and the molten resin composition is extruded upward or downward in a bubble shape from the annular slit of the extruder. and a method for obtaining a film by blowing air or an inert gas into bubbles made of a resin composition in a molten state to expand and stretch the bubbles in a direction (TD direction) perpendicular to the flow direction (MD direction).
- the cylinder temperature of the melt extruder is usually 280-400°C, preferably 320-380°C.
- the interval between the annular slits is usually 0.1-5 mm, preferably 0.2-2 mm.
- the diameter of the annular slit is usually 20-1000 mm, preferably 25-600 mm.
- the blow ratio is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 4.0 or more, and 4.5 or more. Especially preferred.
- the upper limit of the blow ratio is not particularly limited, the blow ratio is, for example, 10 or less.
- the draft ratio is preferably 1.5 or more and 20 or less, more preferably 1.5 or more and 10 or less.
- the blow ratio is the draw ratio in the TD direction
- the draft ratio is the draw ratio in the MD direction.
- the blow ratio in order to improve the anisotropy of the film tends to destabilize the shape retention of the bubbles made of the resin composition in a molten state. Perforations are more likely to occur.
- the resin composition of the present invention contains a small amount of polyetherimide (B) having a siloxane bond in the main chain, thereby suppressing rapid decrease in melt viscosity of the resin composition due to shear stress or the like. Therefore, even if the blow ratio is 4.0 or more, it is possible to stably form a film while suppressing the occurrence of holes in the bubbles and improving the anisotropy of the film.
- the thickness of the liquid crystal polyester-based film of the present invention is not particularly limited, but is, for example, 0.5 ⁇ m or more and 1000 ⁇ m or less, and considering the handleability and productivity during melt extrusion, it is 5 ⁇ m or more and 500 ⁇ m or less. more preferably 20 ⁇ m or more and 300 ⁇ m or less, even more preferably 30 ⁇ m or more and 200 ⁇ m or less.
- the liquid crystal polyester film of the present invention preferably has a tensile strength of 180 MPa or more in the machine direction (MD direction) and the width direction (TD direction). More preferably, the tensile strength is 200 MPa or more, and even more preferably 220 MPa or more. Although the upper limit of the tensile strength is not particularly limited, for example, it is preferably 500 MPa or less, more preferably 400 MPa or less, and even more preferably 350 MPa or less. When the tensile strength is within the above range, the film is excellent in handleability when processed into a circuit board laminate suitable for high-speed communication applications, and can be prevented from being damaged or cracked at the ends of the film.
- the liquid crystal polyester film of the present invention preferably has low anisotropy in the machine direction (MD direction) and width direction (TD direction).
- the tensile strength F(TD) in the film width direction relative to the tensile strength F(MD) in the film machine direction is preferably 0.5 or more and 1.5 or less. , more preferably 0.75 or more and 1.25 or less, still more preferably 0.85 or more and 1.25 or less, and particularly preferably 0.90 or more and 1.20 or less.
- the anisotropy of the mechanical properties and electrical properties of the film is small, and it is suitable for high-speed communication applications. It can be suitably used for applications such as laminates for circuit boards.
- the liquid crystalline polyester film of the present invention can be further heat-treated to relax the orientation of the molecular chains and improve the dimensional stability of the film.
- a conventionally known method can be used for heat treatment, and examples thereof include contact heat treatment, non-contact heat treatment, and the like, and the type thereof is not particularly limited.
- the liquid crystalline polyester film of the present invention may be used as a metal laminate film by laminating a metal layer thereon.
- the surface of the liquid crystalline polyester film on which the metal layer is to be laminated may be subjected to corona discharge treatment, ultraviolet irradiation treatment or plasma treatment in order to increase adhesive strength.
- Methods for laminating a metal layer on the liquid crystal polyester film of the present invention include, for example, (1) a method of attaching the liquid crystal polyester film to a metal foil by thermocompression bonding, and (2) bonding the liquid crystal polyester film and the metal foil. (3) a method of forming a metal layer on a liquid crystal polyester film by vapor deposition; Among them, the lamination method (1) is a method of press-bonding the liquid crystal polyester film to the metal foil near the flow initiation temperature using a press machine or a heating roll, and is recommended because it can be easily carried out. Examples of adhesives used in the lamination method (2) include hot-melt adhesives and polyurethane adhesives. Among them, an epoxy group-containing ethylene copolymer is preferably used as an adhesive.
- Examples of the lamination method (3) include an ion beam sputtering method, a high frequency sputtering method, a DC magnetron sputtering method, and a glow discharge method. Among them, the high frequency sputtering method is preferably used.
- the structure of the metal laminate film thus obtained includes, for example, a two-layer structure of a liquid crystal polyester film and a metal layer, a three-layer structure in which metal layers are laminated on both sides of the liquid crystal polyester film, and a liquid crystal polyester film and a metal layer. A five-layer structure in which metal layers are alternately laminated can be mentioned. For the purpose of developing high strength, the laminate may be subjected to heat treatment, if necessary.
- the thickness of the metal layer is not particularly limited, it is preferably 1.5 to 1000 ⁇ m, more preferably 2 to 500 ⁇ m, even more preferably 5 to 150 ⁇ m, particularly preferably 7 to 100 ⁇ m. If the thickness is less than the above range, the mechanical strength is inferior, and if the thickness is greater than the above range, the handleability and workability are inferior.
- the circuit board of the present invention includes at least one conductor layer and at least one insulator (or dielectric) layer. Its form is not particularly limited, and it can be used as various high-frequency circuit boards by known or common means. Also, the circuit board may be a circuit board (or a semiconductor element mounting board) on which a semiconductor element (for example, an IC chip) is mounted.
- the conductor layer used in the circuit board of the present invention is formed, for example, from at least a metal having conductivity, and a circuit pattern is formed on this conductor layer using a known circuit processing method.
- a circuit pattern is formed on the metal layer portion of the metal laminate film described above.
- LCP A liquid crystal polyester (LAPEROS (manufactured by Polyplastics Co., Ltd. Registered trademark) C950RX, melting point: 320°C)
- PEI-SS Siloxane-modified polyetherimide (SILTEM TM STM-1700 manufactured by SHPP Japan LLC, glass transition temperature: 197° C.)
- PEI polytherimide (ULTEM TM 1000 manufactured by SHPP Japan LLC, glass transition temperature: 217°C)
- PSU Polysulfone (Ultrason (registered trademark) S2010 manufactured by BASF Japan, glass transition temperature: 187°C)
- PPSU polyphenylene sulfone (Ultrason (registered trademark) P3010 manufactured by BASF Japan, glass transition temperature: 220°C)
- PES Polyethersulfone (Ultrason (registered trademark) E2010 manufactured by BASF Japan, glass transition temperature: 225°C)
- Examples 2 and 3 Liquid crystalline polyester films of Examples 2 and 3 and Comparative Examples 1 to 8 were obtained in the same manner as in Example 1, except that the liquid crystalline polyester resin composition was changed as shown in Table 1.
- Table 1 shows the film formability and tensile strength of the obtained film.
- liquid crystal polyester films of Examples 1 to 3 containing 1, 3, and 5% by weight of siloxane-modified polyetherimide as an amorphous polymer were extruded from a die at a draw ratio exceeding 4.0. Stable film formation was possible without holes in the bubbles.
- the liquid crystal polyester films of Examples 1 to 3 maintained the excellent mechanical properties, electrical properties, and heat resistance of the thermoplastic liquid crystal polyester having a melting point of 300 ° C. or higher, and had anisotropic tensile strength. showed small results.
- the liquid crystalline polyester films of Comparative Examples 1 and 2 containing 10% and 15% by weight of siloxane-modified polyetherimide had no holes in the molten resin bubbles extruded from the die at a draw ratio exceeding 4.0. Although stable film formation was possible, compared with the liquid crystal polyester film of Comparative Example 4 containing no amorphous polymer, the tensile strength was significantly reduced and the anisotropy of the tensile strength was relatively large. rice field. Further, the liquid crystalline polyester film of Comparative Example 3 containing 50% by weight of siloxane-modified polyetherimide had many holes at a draw ratio exceeding 4.0, and the film could not be formed.
- the liquid crystalline polyester film of Comparative Example 4 which is made of only a thermoplastic liquid crystalline polyester with a melting point of over 300° C., had small holes in bubbles of the molten resin extruded from the die at a draw ratio of over 4.0 with a blow ratio. , the bubble shape became unstable due to the air inside the bubble.
- the liquid crystalline polyester film of Comparative Example 5 which contains 5% by weight of non-siloxane-modified polyetherimide as an amorphous polymer, is extruded from the die at a draw ratio of more than 4.0. Although stable film formation was possible without gaps, compared to the liquid crystal polyester film of Comparative Example 4, which does not contain an amorphous polymer, the tensile strength was significantly reduced, and the anisotropy of the tensile strength was relatively large. showed that.
- the liquid crystalline polyester films of Comparative Examples 6 to 8 each containing 5% by weight of polysulfone, polyphenylenesulfone, and polyethersulfone as amorphous polymers were extruded from a die at a draw ratio exceeding 4.0 with a blow ratio. A small hole was generated in the molten resin bubble, and the bubble shape became unstable due to the air inside the bubble.
- the liquid crystalline polyester film obtained by the present invention can be used for electrical insulation of motors and transformers, flexible solar cell element forming films, etc. by taking advantage of its excellent electrical properties, dimensional stability and heat resistance. It's being used. It can also be used in acoustic fields such as surface protective films and diaphragms.
- the metal laminate film of the present invention can also be used for circuit boards, capacitors, electromagnetic shielding materials, and the like.
- the circuit board of the present invention may be used for various transmission lines and antennas (for example, microwave or millimeter wave antennas), and may be used for antenna devices in which an antenna and a transmission line are integrated.
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Abstract
Description
(1)熱可塑性液晶ポリエステル(A)とポリエーテルイミド(B)とを含む液晶ポリエステル樹脂組成物であって、前記液晶ポリエステル(A)は、融点が300℃以上であり、前記ポリエーテルイミド(B)は、主鎖にシロキサン結合を有し、前記液熱可塑性晶ポリエステル(A)と前記ポリエーテルイミド(B)との配合割合が(A):(B)=92~99.5重量%:0.5~8重量%であることを特徴とする液晶ポリエステル系樹脂組成物が提供され、
(2)前記熱可塑性液晶ポリエステル(A)は、p-ヒドロキシ安息香酸に由来する構成単位と、6-ヒドロキシ-2-ナフトエ酸に由来する構成単位とを含むことを特徴とする(1)に記載の液晶ポリエステル系樹脂組成物が提供され、
(3)前記樹脂組成物がインフレーション押出成形法用であることを特徴とする(1)又は(2)に記載の液晶ポリエステル系樹脂組成物が提供され、
(4)(1)乃至(3)のいずれかに記載の樹脂組成物からなることを特徴とする液晶ポリエステル系フィルムが提供され、
(5)フィルムの流れ方向の引張強度をF(MD)、フィルム幅方向の引張強度F(TD)とするとき、0.75≦F(TD)/F(MD)≦1.25であることを特徴とする(4)記載の液晶ポリエステル系フィルムが提供され、
(6)インフレーション押出成形法により製膜することを特徴とする(4)又は(5)記載の液晶ポリエステル系フィルムの製造方法が提供され、
(7)請求項4又は5記載の液晶ポリエステル系フィルムの片面又は両面に金属層がラミネートされていることを特徴とする金属ラミネートフィルムが提供され、
(8)少なくとも1つの導体層と、(4)又は(5)記載の熱可塑性液晶ポリエステル系フィルムとを備える回路基板が提供される。
本発明の液晶ポリエステル系樹脂組成物は、熱可塑性液晶ポリエステル(A)と、主鎖にシロキサン結合を有するポリエーテルイミド(B)とを含む樹脂組成物からなる。
熱可塑性液晶ポリエステル(A)は、溶融異方性を示す液晶ポリエステル(光学的に異方性の溶融相を形成し得るポリエステル)である。溶融異方性の性質は直交偏光子を利用した慣用の偏光検査方法により確認することができる。具体的には、溶融異方性は、偏光顕微鏡(オリンパス(株)製等)を使用し、ホットステージ(リンカム社製等)にのせた試料を溶融し、窒素雰囲気下で150倍の倍率で観察することにより確認できる。溶融時に光学的異方性を示す液晶性の樹脂は、光学的に異方性であり、直交偏光子間に挿入したとき光を透過させる。試料が光学的に異方性であると、例えば溶融静止液状態であっても偏光が透過する。
主鎖にシロキサン結合を有するポリエーテルイミド(B)は、ポリエーテルイミドにシロキサン基を導入してシリコーンエラストマーが示す柔軟性を付与した非結晶性の熱可塑性樹脂である。ポリエーテルイミドは、イミド結合と、エーテル結合とを分子内に有する樹脂であり、例えば、下記一般式(1)で表される。
<一般式(1)>
<一般式(2)>
本発明では、上述した樹脂組成物からなるフィルム、及び該フィルムの製造方法も提案する。本発明の液晶ポリエステル系フィルムは、上述した熱可塑性液晶ポリエステル(A)と主鎖にシロキサン結合を有するポリエーテルイミド(B)とを、公知の方法によりブレンドして製膜することにより得られる。尚、本発明の樹脂組成物は、主鎖にシロキサン結合を有するポリエーテルイミド(B)の配合割合が少ないことから、安定した混錬状態を提供するため、製膜に先立ち、溶融混錬・造粒しておくことが好ましい。
本発明の液晶ポリエステル系フィルムは、これに金属層を積層して、金属ラミネートフィルムとして用いてもよい。金属層を積層するにあたって、液晶ポリエステル系フィルムの金属層を積層する面には、接着力を高めるため、コロナ放電処理、紫外線照射処理又はプラズマ処理を実施してもよい。
本発明の回路基板は、少なくとも1つの導体層と、少なくとも1つの絶縁体(または誘電体)層とを含んでおり、本発明の液晶ポリエステル系フィルムを絶縁体(または誘電体)として用いる限り、その形態は特に限定されず、公知または慣用の手段により、各種高周波回路基板として用いることが可能である。また、回路基板は、半導体素子(例えば、ICチップ)を搭載している回路基板(または半導体素子実装基板)であってもよい。
インフレーション押出成形法によりフィルムを製膜した際に、ダイスから押し出された溶融状態の樹脂からなるバブルの外観を目視にて下記基準で評価した。
○:バブルに穴あき無し
△:バブルに小さな穴あきが発生(バブル内部のエア抜けにより、バブル形状が不安定)
×:バブルに穴あきが発生し、フィルム製膜不可
(引張強度)
ASTM D882に準拠し、190mm×15mmの大きさに切断したサンプルを、オートグラフAGS-500NX(株式会社島津製作所製)を用いて引張速度12.5mm/分、チャック間距離を125mmとして測定した。測定温度は23℃である。なお、フィルムの流れ方向(MD方向)と幅方向(TD方向)の双方を測定した。
LCP:p-ヒドロキシ安息香酸に由来する構成単位と、6-ヒドロキシ-2-ナフトエ酸に由来する構成単位と、テレフタル酸に由来する構成単位と、からなる液晶ポリエステル(ポリプラスチックス社製 LAPEROS(登録商標)C950RX、融点:320℃)
PEI―SS:シロキサン変性ポリエーテルイミド(SHPPジャパン合同会社製 SILTEMTM STM-1700、ガラス転移温度:197℃)
PEI:ポリーテルイミド(SHPPジャパン合同会社製 ULTEMTM 1000、ガラス転移温度:217℃)
PSU:ポリサルフォン(BASFジャパン社製 Ultrason(登録商標) S2010、ガラス転移温度:187℃)
PPSU:ポリフェニレンサルフォン(BASFジャパン社製 Ultrason(登録商標) P3010、ガラス転移温度:220℃)
PES:ポリエーテルサルフォン(BASFジャパン社製 Ultrason(登録商標) E2010、ガラス転移温度:225℃)
LCP99重量%とPEI-SS1重量%とをドライブレンドし、環状スリット(直径25mm)のダイスを備えた溶融押出機に供給して押出機の環状スリットから吐出量3kg/hで溶融押出し、ドラフト比=2、ブロー比=5の条件で延伸し、インフレーション押出成形法により厚み50μmの液晶ポリエステル系フィルムを得た。得られたフィルムの製膜性、引張強度を表1に示す。
液晶ポリエステル系樹脂組成物を表1に示すように変更した以外は、実施例1と同様にして実施例2及び3、比較例1乃至8の液晶ポリエステル系フィルムを得た。得られたフィルムの製膜性、引張強度を表1に示す。
本発明の金属ラミネートフィルムは、回路基板やコンデンサー、電磁波シールド材等に用いることもできる。本発明の回路基板は、各種伝送線路やアンテナ(例えば、マイクロ波またはミリ波用アンテナ)に用いられてもよく、また、アンテナと伝送線路が一体化したアンテナ装置に用いられてもよい。
Claims (8)
- 熱可塑性液晶ポリエステル(A)とポリエーテルイミド(B)とを含む液晶ポリエステル樹脂組成物であって、前記液晶ポリエステル(A)は、融点が300℃以上であり、前記ポリエーテルイミド(B)は、主鎖にシロキサン結合を有し、前記液熱可塑性晶ポリエステル(A)と前記ポリエーテルイミド(B)との配合割合が(A):(B)=92~99.5重量%:0.5~8重量%であることを特徴とする液晶ポリエステル系樹脂組成物。
- 前記熱可塑性液晶ポリエステル(A)は、p-ヒドロキシ安息香酸に由来する構成単位と、6-ヒドロキシ-2-ナフトエ酸に由来する構成単位とを含むことを特徴とする請求項1に記載の液晶ポリエステル系樹脂組成物。
- 前記樹脂組成物がインフレーション押出成形法用であることを特徴とする請求項1又は2に記載の液晶ポリエステル系樹脂組成物。
- 請求項1乃至3のいずれかに記載の樹脂組成物からなることを特徴とする液晶ポリエステル系フィルム。
- フィルムの流れ方向の引張強度をF(MD)、フィルム幅方向の引張強度F(TD)とするとき、0.75≦F(TD)/F(MD)≦1.25であることを特徴とする請求項4記載の液晶ポリエステル系フィルム。
- インフレーション押出成形法により製膜することを特徴とする請求項4又は5記載の液晶ポリエステル系フィルムの製造方法。
- 請求項4又は5記載の液晶ポリエステル系フィルムの片面又は両面に金属層がラミネートされていることを特徴とする金属ラミネートフィルム。
- 少なくとも1つの導体層と、請求項4又は5記載の熱可塑性液晶ポリエステル系フィルムとを備える回路基板。
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JPH04246458A (ja) * | 1991-01-31 | 1992-09-02 | Nippon G Ii Plast Kk | 液晶ポリエステル組成物 |
JP2007138143A (ja) * | 2005-10-21 | 2007-06-07 | Toray Ind Inc | 液晶性樹脂組成物およびその製造方法 |
JP2017026820A (ja) * | 2015-07-22 | 2017-02-02 | 富士ゼロックス株式会社 | 無端ベルト、転写ユニット、及び画像形成装置 |
CN111040448A (zh) * | 2019-12-16 | 2020-04-21 | 中广核高新核材科技(苏州)有限公司 | 一种核电航空用热塑性聚酰亚胺电缆料 |
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