CN112980004A - Liquid composition, liquid crystal polyester film, method for producing liquid crystal polyester film, laminated film, and method for producing laminated film - Google Patents
Liquid composition, liquid crystal polyester film, method for producing liquid crystal polyester film, laminated film, and method for producing laminated film Download PDFInfo
- Publication number
- CN112980004A CN112980004A CN202011399031.0A CN202011399031A CN112980004A CN 112980004 A CN112980004 A CN 112980004A CN 202011399031 A CN202011399031 A CN 202011399031A CN 112980004 A CN112980004 A CN 112980004A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal polyester
- film
- polyester film
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 375
- 229920006267 polyester film Polymers 0.000 title claims abstract description 206
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000007788 liquid Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 229920000728 polyester Polymers 0.000 claims abstract description 181
- 239000002904 solvent Substances 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 104
- 229910052751 metal Inorganic materials 0.000 claims description 84
- 239000002184 metal Substances 0.000 claims description 84
- 238000000034 method Methods 0.000 claims description 62
- 239000000945 filler Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000010304 firing Methods 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 32
- 238000005266 casting Methods 0.000 claims description 26
- 239000005001 laminate film Substances 0.000 claims description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 239000013557 residual solvent Substances 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 183
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 41
- 239000011889 copper foil Substances 0.000 description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 20
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- -1 polypropylene Polymers 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000011256 inorganic filler Substances 0.000 description 12
- 229910003475 inorganic filler Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 229920000106 Liquid crystal polymer Polymers 0.000 description 9
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000010933 acylation Effects 0.000 description 8
- 238000005917 acylation reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005187 foaming Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide 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
- 125000003277 amino group Chemical group 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000001408 amides Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004512 die casting Methods 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- HTFUZOUJKZBUAL-UHFFFAOYSA-N n-[amino(dimethylamino)phosphoryl]-n-methylmethanamine Chemical compound CN(C)P(N)(=O)N(C)C HTFUZOUJKZBUAL-UHFFFAOYSA-N 0.000 description 2
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- FFWNCSWLUYKKKA-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1.NC1=CC=CC(O)=C1 FFWNCSWLUYKKKA-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- XKIWZZJNBVOFIE-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1.NC1=CC=C(O)C=C1 XKIWZZJNBVOFIE-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- PSAGPCOTGOTBQB-UHFFFAOYSA-N 4-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(O)C2=C1 PSAGPCOTGOTBQB-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 238000003887 surface segregation Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Images
Classifications
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/0929—Conductive planes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a liquid composition for producing a liquid crystal polyester film, a liquid crystal polyester film obtained from the liquid composition, a method for producing the liquid crystal polyester film, a laminated film having the liquid crystal polyester film, and a method for producing the laminated film. The liquid composition 1 of the present invention is a liquid composition in which a liquid crystal polyester powder identical or homologous to the liquid crystal polyester is dispersed in a solution obtained by dissolving the liquid crystal polyester in a solvent, and the solid content concentration is increased.
Description
Technical Field
The present invention relates to a liquid composition for producing a liquid crystal polyester film, a liquid crystal polyester film obtained from the liquid composition, and a method for producing the liquid crystal polyester film, and further relates to a laminated film having the liquid crystal polyester film and a method for producing the laminated film.
Background
Liquid crystal polyester films are excellent in low moisture absorption, high frequency characteristics, flexibility, high gas barrier properties, thin-wall formability, and the like, and therefore are suitable for use as insulating films or surface protective films for electronic substrates such as flexible printed wiring boards, rigid printed wiring boards, module substrates, and the like, and the demand for such films has been increasing in recent years.
Various methods (film forming methods) for producing the above-described liquid crystal polyester film have been proposed, and patent document 1 discloses an example of a solution type coating film forming (so-called casting method). In addition, as a method other than the solution-type coating film formation, a method of forming a resin-formed pellet into a film by extrusion by a T-die casting method in a state of being heated to a melting point temperature or higher, or a method of forming a resin-formed pellet into a film by a hot-melt blowing method is performed (patent document 2).
Documents of the prior art
[ patent document 1 ] Japanese patent application laid-open No. 2011-167847
[ patent document 2 ] Japanese patent laid-open publication No. 2013-193438
However, for example, in the case of a wiring board on which electronic components are mounted, when the liquid crystal polyester film is formed into a film on a metal foil to be used as an insulating film and the liquid crystal polyester film is used as a metal-clad laminate or a laminate by performing sputtering or plating, the above-described conventional method for producing a liquid crystal polyester film has problems in productivity and film formation.
For example, the conventional solution-type coating film formation (casting method) of a monomer or oligomer of a liquid crystal polyester is excellent in quality such as orientation and thickness, and requires time for thermal drying and baking, resulting in a problem of low productivity.
On the other hand, film formation by a hot melt inflation method or a T-die casting method of a liquid crystal polyester after resinification (polymerization) has difficulty in reproducibility of orientation, thickness, and the like.
Since the liquid crystal polyester has a property called "liquid crystal" having crystallinity in a molten state (liquid state) and a property of being instantaneously oriented from a glass transition Tg state (amorphous state), if the film is formed by the above-mentioned hot melt blowing method or T-die casting method, a film having anisotropy is formed by molecular orientation in a flow Direction (MD: Machine Direction) of the molten resin, and thus a liquid crystal polyester film which is weak in a TD (Transverse Direction) Direction orthogonal to the MD is formed, and a metal-clad laminate formed by bonding the liquid crystal polyester film as an insulating film to a metal foil has a problem that the film is easily broken in the MD if the film is stretched in the TD Direction.
In particular, if a metal foil is etched to form conductor patterns with the MD direction as the longitudinal direction, there is a problem that the insulating film (liquid crystal polyester film) between the conductor patterns is easily broken along the conductor patterns.
The anisotropy of the liquid crystal polyester film causes warpage or deformation of a metal-clad laminate obtained by laminating such liquid crystal polyester films as insulating films.
Therefore, when the insulating film of the metal-clad laminate is formed of a liquid crystal polymer, it preferably has no alignment properties in any of the MD and TD directions, and more preferably has no alignment properties in any of the MD, TD and Z (thickness) directions. In addition, as a method for modifying a liquid crystal polyester to cope with the alignment property and linear expansion, addition of a filler such as nano-diameter silica has been attempted, but when a liquid crystal polyester film is subjected to sputtering, plating, or the like of silver, copper, or the like to be a circuit pattern layer (metal layer), the inorganic filler segregates on the surface of the liquid crystal polyester film, and is likely to cause generation of pinholes, and also causes dielectric loss.
Further, as described in patent document 1, a method for producing a liquid crystal polyester film by a casting method using a liquid composition containing a solvent and a liquid crystal polyester (precursor of the liquid crystal polyester) dissolved in the solvent has been proposed, and although the alignment properties (MD, TD, and Z) are solved by this method, there are problems that drying of the solvent at the time of casting and further firing require a load (time), and that foaming occurs in the film at the time of film forming.
Disclosure of Invention
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a technique for forming a film by dispersing a filler (liquid crystal polyester powder) of a liquid crystal polyester in the liquid composition in order to improve the efficiency of the drying time and the baking time and to suppress the foaming of the film during the forming in the production of a liquid crystal polyester film.
The following describes a solution to the problem together with reference numerals used in the embodiment for carrying out the invention. The reference numerals are used to clearly describe the correspondence between the description of the technical scope and the description of the embodiment for carrying out the invention, and are not used to limit the explanation of the technical scope of the invention.
In order to achieve the above object, the liquid composition 1 of the present invention comprises a liquid crystal polyester powder which is the same as or similar to the liquid crystal polyester and is 10 to 1000 parts by weight, preferably 10 to 800 parts by weight, more preferably 60 to 300 parts by weight with respect to 100 parts by weight of the liquid crystal polyester dissolved in a solvent, in a solution containing the solvent and the liquid crystal polyester dissolved in the solvent, and has an increased solid content concentration.
The liquid crystal polyester film 10 of the present invention is non-oriented and is formed using the liquid composition 1.
The method for producing a liquid crystal polyester film of the present invention comprises: casting the liquid composition 1 on a substrate; and a step of removing the solvent from the liquid composition on the substrate.
The laminated film 20 of the present invention has a liquid crystal polyester film layer 21 and a metal layer 26 laminated on the surface of the liquid crystal polyester film layer 21, and the liquid crystal polyester film layer 21 has a liquid crystal polyester film formed using the liquid composition 1, and may have a structure (laminated structure) in which liquid crystal polyester layers 22 and 24 formed of a liquid crystal polyester to which no filler is added are laminated on both sides of a filler addition layer 23 formed of a liquid crystal polyester to which a filler, preferably silica, talc, silicon nitride, aluminum nitride, or fluorine-based powder is added.
The method for producing the laminated film 20 of the present invention is characterized by comprising:
a step of forming a metal layer 26 on the surface of a substrate (for example, an OPP film (stretched polypropylene), a CPP film (unstretched polypropylene), or an HPPE film (high-pressure polyethylene))40 by vapor deposition or sputtering, casting the liquid composition 1 on the metal layer 26, drying the cast liquid composition, and then peeling the substrate 40 to produce a laminated film precursor 30 including the metal layer 26 and a liquid crystal polyester film precursor 31; and
taking the laminated film precursor 30 as an example, a step of moving (bending) the laminated film precursor 30 up and down in a direction perpendicular to a horizontal plane (conveyance direction) of the laminated film precursor 30 in a state where a tension acting on the laminated film precursor 30 is released in a firing furnace 51, and performing a heat treatment to remove a residual solvent contained in the liquid crystal polyester film precursor 31, thereby producing the laminated film 20 having the metal layer 26 and the liquid crystal polyester film layer 21.
In the firing furnace 51, gas nozzles (not shown) are alternately arranged above and below the laminated film precursor 30 through the continuously transported laminated film precursor 30 with respect to the traveling direction of the laminated film precursor 30, and a gas (inert gas) is blown from the gas nozzles to the laminated film precursor 30, so that the laminated film precursor 30 can be moved (bent) vertically in a direction perpendicular to the horizontal plane of the laminated film precursor 30.
In addition, a conductor pattern may be formed on the metal layer 26 of the laminate film 20 to form a printed wiring board.
The following significant effects can be obtained by the configuration of the present invention described above.
First, the liquid composition 1 of the present invention is a composition in which a powder of a liquid crystal polyester (liquid crystal polyester powder) identical or homologous to the liquid crystal polyester is dispersed in a solution containing a solvent and a liquid crystal polyester dissolved in the solvent to increase the solid content concentration, whereby the amount of the solvent can be reduced, the drying time and the baking time in the production of a liquid crystal polyester film by a casting method using the liquid composition 1 of the present invention can be reduced, and foaming occurring in film formation can be suppressed.
This is presumed to be a reciprocal effect between the film formation and the firing. That is, in the production of a liquid crystal polyester film, a liquid crystal polyester dissolved in a solvent (hereinafter, the liquid crystal polyester dissolved in a solvent is also referred to as a "liquid crystal polyester precursor") does not exhibit thixotropy or the like with respect to the same or homologous liquid crystal polyester powder, and can be uniformly coated with a comma coater or the like, it is also presumed that in the initial drying step after the coating (in the range of about 4 to 30% of the residual solvent in the liquid composition 1), the film formation is completed by the liquid crystal polyester precursor functioning as a binder for the liquid crystal polyester powder, in the firing step after the drying step, the liquid crystal polyester powder is melted and, at the same time, the liquid crystal polyester precursor undergoes a condensation reaction (polymerization), and finally the liquid crystal polyester powder and the liquid crystal polyester precursor undergo cocrystallization to form a liquid crystal polyester film. In conclusion, the drying time and the baking time were significantly reduced, and a non-foamed liquid crystal polyester film was obtained.
The liquid crystal polyester film 10 obtained from the liquid composition 1 of the present invention may be non-oriented, may not have anisotropy of a general liquid crystal polyester film, and may have improved mechanical strength such as tensile force in the width direction.
In the method for producing the laminated film 20 of the present invention, as described above, the sputtering or vapor deposition of the metal layer 26 is performed not after the liquid crystal polyester film is fired but before the liquid crystal polyester film is fired.
This can solve the problem of pinholes caused by sputtering or vapor deposition of the metal layer 26. That is, the following remarkable effects are exhibited: when the liquid crystal polyester film is condensed during firing, the metal layer 26 follows the liquid crystal polyester film to close the pinholes.
Further, in the firing of the liquid crystal polyester film, high bonding with the sputtering interface of the metal layer 26 is obtained together with thermal activity, and thus, for example, in the case where the laminated film 20 of the present invention is used as a flexible substrate (printed wiring board), the metal layer 26 can withstand fine etching in a post-process.
Drawings
Fig. 1 is a process diagram showing a method for producing a liquid crystal polyester film 10 of the present invention, and is a diagram showing a step of producing a 1 st laminate L1.
Fig. 2 is a view showing the steps of producing the 1 st laminate L1 to the 2 nd laminate L2 in fig. 1.
Fig. 3 is a view showing a step of producing a 3 rd laminate L3 from the 2 nd laminate L2 in fig. 2 and peeling off the liquid crystal polyester film 10.
Fig. 4 is a schematic sectional view showing the laminate film 20 of the present invention (the liquid crystal polyester film layer 21 is a single-layer laminate film 20).
Fig. 5 is a schematic sectional view showing the laminate film 20 of the present invention (the liquid crystal polyester film layer 21 is the laminate film 20 having a 3-layer structure).
Fig. 6 is a view showing an example of a method for manufacturing the laminated film 20 of fig. 4.
Fig. 7 is a view showing an example of a method for manufacturing the laminated film 20 of fig. 5.
Fig. 8 is a view showing another example of the manufacturing method of the laminated film 20 of fig. 5.
Fig. 9 shows a chemical formula of an example of the fluorine-based powder.
In the figure: 1-liquid composition, 1 a-1 st liquid composition, 1 b-2 nd liquid composition, 1 c-3 rd liquid composition, 10-liquid crystal polyester film, 11-liquid crystal polyester film precursor, 13-coating machine, 14-drying machine, 15-substrate, 16-metal substrate, 17-heating furnace (firing furnace), 18-peeling roll, 19-roll, 20-laminated film, 21-liquid crystal polyester film layer, 22-liquid crystal polyester layer (1 st liquid crystal polyester layer), 23-filler addition layer, 24-liquid crystal polyester layer (2 nd liquid crystal polyester layer), 26-metal layer (copper foil), 30-laminated film precursor, 31(31a, 31b, 31c) -liquid crystal polyester film precursor, 40-substrate (OPP film), 51-firing furnace, 52-heating calender, 61(61a, 61b, 61c) -coating machine, 63(63a, 63b, 63c) -drying machine, L1-1 st laminate, l2-stack 2, L3-stack 3.
Detailed Description
Hereinafter, a liquid composition 1, a liquid crystal polyester film 10 produced from the liquid composition 1, and a method for producing the liquid crystal polyester film 10 according to the present invention will be described with reference to the drawings, and a laminated film 20 in which a metal layer 26 is laminated on a liquid crystal polyester film layer 21 having the liquid crystal polyester film 10, and a method for producing the laminated film 20 will be described.
[ liquid composition ]
The liquid composition 1 of the present invention is a composition in which a liquid crystal polyester powder (hereinafter, also referred to as LCP powder) identical or homologous to the liquid crystal polyester is immersed in a solution obtained by dissolving the liquid crystal polyester in a solvent to increase the solid content concentration. The liquid crystal polyester, the solvent, and the liquid crystal polyester powder will be described below.
[ liquid Crystal polyester ]
The liquid crystal polyester used in the present invention is a polyester having a property of exhibiting optical anisotropy at the time of melting and forming an anisotropic melt at a temperature of 450 ℃ or lower.
The preferred liquid crystal polyester is a liquid crystal polyester having a structural unit represented by the following formula 1 (hereinafter referred to as a "structural unit of formula 1"), a structural unit represented by the following formula 2 (hereinafter referred to as a "structural unit of formula 2"), and a structural unit represented by the following formula 3 (hereinafter referred to as a "structural unit of formula 3"), wherein the content of the structural unit represented by the following formula 1 is 30 to 80 mol%, the content of the structural unit represented by the following formula 2 is 10 to 35 mol%, and the content of the structural unit represented by the following formula 3 is 10 to 35 mol%, based on the total content of all the structural units.
－O－Ar1-CO- (formula 1)
－CO－Ar2-CO- (formula 2)
－X－Ar3-Y- (formula 3)
(in the formulae 1 to 3, Ar1Represents phenylene or naphthylene, Ar2Represents phenylene, naphthylene or a group represented by the following formula 4, Ar3Represents phenylene or a group represented by the following formula 4, and X and Y are each independently O or NH. In addition, Ar is1、Ar2And Ar3The hydrogen atom bonded to the aromatic ring of (a) may be substituted with a halogen atom, an alkyl group or an aryl group. )
－Ar11－Z－Ar12- (type 4)
(in the formula, Ar11、Ar12Each independently represents phenylene or naphthylene, Z represents O, CO or SO2。)
The structural unit of formula 1 is a structural unit derived from an aromatic hydroxycarboxylic acid, and examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, and 4-hydroxy-1-naphthoic acid.
The structural unit of formula 2 is a structural unit derived from an aromatic dicarboxylic acid, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 4' -diphenyletherdicarboxylic acid, 4' -dicarboxybiphenylsulfone, 4' -dicarboxybenzophenone, and the like.
The structural unit of formula 3 is a structural unit derived from an aromatic diol, an aromatic amine having a phenolic hydroxyl group, or an aromatic diamine. Examples of the aromatic diol include hydroquinone, resorcinol, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, bis (4-hydroxyphenyl) ether, bis- (4-hydroxyphenyl) ketone, and bis- (4-hydroxyphenyl) sulfone.
Examples of the aromatic amine having a phenolic hydroxyl group include 4-aminophenol (p-aminophenol) and 3-aminophenol (m-aminophenol), and examples of the aromatic diamine include 1, 4-phenylenediamine and 1, 3-phenylenediamine.
The liquid crystal polyester used in the present invention is solvent-soluble, which means that it is dissolved in a solvent (solvent) at a temperature of 50 ℃ at a concentration of 1 mass% or more. The solvent is as described later.
As such a solvent-soluble liquid crystal polyester, it is preferable that the structural unit of formula 3 contains a structural unit derived from an aromatic amine having a phenolic hydroxyl group and/or a structural unit derived from an aromatic diamine. That is, it is preferable that the structural unit of formula 3 includes a structural unit represented by a structural unit (formula 3 ') in which at least one of X and Y is NH (hereinafter, referred to as "structural unit of formula 3'), because the solvent solubility to an appropriate solvent (aprotic polar solvent) described later tends to be excellent. It is particularly preferred that substantially all of the structural units of formula 3 are structural units of formula 3'. In addition, the 3' structural unit of the formula makes the liquid crystal polyester have lower water absorption, in addition to making the liquid crystal polyester solvent soluble enough, which is also advantageous.
－X－Ar3-NH- (formula 3')
(wherein Ar is3And X has the same meaning as previously described. )
More preferably, the content of the structural unit of formula 3 is in the range of 25 to 33 mol% based on the total content of all the structural units, so that the solvent solubility can be improved. Thus, the liquid-crystalline polyester having the structural unit of formula 3' as the structural unit of formula 3 also has the following advantages: the solubility to a solvent is improved, and a liquid crystal polyester film having low water absorption can be obtained.
The content of the structural unit of formula 1 in the total of all the structural units is preferably in the range of 30 to 80 mol%, more preferably in the range of 35 to 50 mol%. The liquid-crystalline polyester containing the structural unit of formula 1 at such a mole fraction has a tendency as follows: can sufficiently maintain liquid crystallinity and has excellent heat resistance. Furthermore, if the availability of the aromatic hydroxycarboxylic acid from which the structural unit of formula 1 is derived is also taken into consideration, p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid are suitable as the aromatic hydroxycarboxylic acid.
The content of the structural unit of formula 2 is preferably in the range of 10 to 35 mol%, more preferably 25 to 33 mol%, based on the total content of all the structural units. The liquid-crystalline polyester containing the structural unit of formula 2 at such a mole fraction has a tendency as follows: the liquid crystal properties can be sufficiently maintained, and the heat resistance is further excellent. Furthermore, if the availability of the aromatic dicarboxylic acid from which the structural unit of formula 2 is derived is also taken into consideration, the aromatic dicarboxylic acid is preferably at least one selected from the group consisting of terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid.
In addition, in the liquid crystal polyester can achieve higher liquid crystallinity, the formula 2 structural unit and formula 3 structural unit mole fraction is [ formula 2 structural unit ]/[ formula 3 structural unit ] is preferably in the range of 0.9/1 to 1/0.9.
Next, a method for producing the above-mentioned liquid crystal polyester will be described.
The liquid-crystalline polyester can be produced by various well-known methods. In the case of producing a suitable liquid crystal polyester, that is, a liquid crystal polyester containing the structural unit of formula 1, the structural unit of formula 2, and the structural unit of formula 3, a method of converting a monomer derived from these structural units into an ester-forming amide-forming derivative and then polymerizing the ester-forming amide-forming derivative to produce a liquid crystal polyester is preferable in view of ease of operation.
The ester-forming amide-forming derivatives are exemplified.
Examples of the ester-forming and amide-forming derivatives of the monomer having a carboxyl group, such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid, include: a substance having a carboxyl group which is a group having high reactivity such as acid chloride or acid anhydride so as to promote a reaction for forming polyester or polyamide; and those in which the carboxyl group forms an ester with an alcohol, ethylene glycol, or the like, so that a polyester or a polyamide is produced by an ester exchange or amide exchange reaction.
Examples of the ester-forming and amide-forming derivatives of monomers having a phenolic hydroxyl group, such as aromatic hydroxycarboxylic acids and aromatic diols, include those in which the phenolic hydroxyl group forms an ester with a carboxylic acid in such a manner that a polyester or a polyamide is formed by an ester exchange reaction.
Examples of the amide-forming derivative as a monomer having an amino group such as an aromatic diamine include a compound in which an amino group and a carboxylic acid form an amide so that a polyamide is produced by an amide exchange reaction.
Among them, in order to more easily produce the liquid crystal polyester, particularly preferred is a method for producing a liquid crystal polyester as follows: a liquid crystal polyester is produced by acylating a monomer having a phenolic hydroxyl group and/or an amino group, such as an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic amine having a phenolic hydroxyl group, or an aromatic diamine, with a fatty acid anhydride to form an ester-forming amide-forming derivative (acylate), and then polymerizing the acylate so that the acyl group of the acylate is transesterified with the carboxyl group of the monomer having a carboxyl group.
The method for producing such a liquid crystal polyester is described in, for example, Japanese patent laid-open Nos. 2002-220444 and 2002-146003.
In the acylation, the amount of the fatty acid anhydride to be added is preferably 1 to 1.2 times by equivalent, more preferably 1.05 to 1.1 times by equivalent, to the total of the phenolic hydroxyl group and the amino group. When the amount of the fatty acid anhydride added is less than 1 equivalent, the acylate and the raw material monomer tend to sublimate during polymerization and easily clog the reaction system, and when the amount exceeds 1.2 equivalents, the resultant liquid crystal polyester tends to be significantly colored.
Acylation is preferably carried out at 130 to 180 ℃ for 5 minutes to 10 hours, and more preferably at 140 to 160 ℃ for 10 minutes to 3 hours.
From the viewpoint of cost and handleability, the fatty acid anhydride used for acylation is preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, or a mixture of 2 or more selected from them, and particularly preferably acetic anhydride.
The polymerization for the subsequent acylation is preferably carried out while raising the temperature at 130 to 400 ℃ at a rate of 0.1 to 50 ℃/min, more preferably at 150 to 350 ℃ at a rate of 0.3 to 5 ℃/min.
In addition, in the polymerization, the acyl group of the acylate is preferably 0.8 to 1.2 times equivalent to the carboxyl group.
In the acylation and/or polymerization, it is preferable to distill the by-produced fatty acid and unreacted fatty acid anhydride out of the system by evaporation or the like in order to shift the equilibrium according to the law of le chateli-brownian (principle of equilibrium shift).
In the acylation and polymerization, the reaction may be carried out in the presence of a catalyst. As the catalyst, those conventionally known as a catalyst for polymerization of polyester can be used, and examples thereof include metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide; organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
Among these catalysts, heterocyclic compounds containing 2 or more nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole are preferably used (see Japanese patent application laid-open No. 2002-146003).
The catalyst is usually charged at the time of charging the monomer, and it is not always necessary to remove the catalyst after acylation, and the catalyst can be transferred from acylation to polymerization as it is without removing the catalyst.
The liquid crystal polyester obtained by such polymerization can be used as it is in the present invention, but in order to further improve the characteristics such as heat resistance and liquid crystallinity, it is preferable to further increase the molecular weight, and in the above-mentioned increase in molecular weight, it is preferable to perform solid phase polymerization. A series of operations involved in the solid-phase polymerization will be described. The liquid crystalline polyester having a relatively low molecular weight obtained by the polymerization is taken out and pulverized into a powder or a sheet. Then, the pulverized liquid crystal polyester is subjected to a heat treatment in a solid phase state at 20 to 350 ℃ for 1 to 30 hours in an atmosphere of an inert gas such as nitrogen gas, for example, and solid phase polymerization can be carried out by this operation. The solid-phase polymerization may be carried out while stirring, or may be carried out in a state of standing without stirring. In addition, from the viewpoint of obtaining a liquid crystal polyester having an appropriate flow initiation temperature as described later, if the conditions appropriate for the solid phase polymerization are described in detail, the reaction temperature is preferably in the range of more than 210 ℃ and more preferably 220 to 350 ℃. The reaction time is preferably selected from 1 to 10 hours.
The liquid-crystalline polyester used in the present invention preferably has a flow initiation temperature of 250 ℃ or higher. If the flow starting temperature of the liquid crystal polyester is in this range, when a conductive metal layer (electrode) is formed on the layer containing the liquid crystal polyester, there is a tendency that higher adhesion can be obtained between the layer containing the liquid crystal polyester and the metal layer. The flow start temperature herein means a temperature at which the melt viscosity of the liquid crystal polyester becomes 4800 pas or less under a pressure of 9.8MPa in the evaluation of the melt viscosity by a flow tester. The flow initiation temperature is known to those skilled in the art as a measure of the molecular weight of a liquid-crystalline polyester (see, for example, Wako Junyaku, ed. "liquid-crystal Synthesis, Molding, and application" - "pp. 95-105, CMC (シーエムシー), published 6/5/1987).
The upper limit of the flow initiation temperature of the liquid-crystalline polyester is determined by the range in which the liquid-crystalline polyester is soluble in a solvent, but is preferably 350 ℃ or lower. If the upper limit of the flow start temperature is within this range, the liquid crystal polyester becomes more soluble in a solvent, and the viscosity does not increase significantly when the liquid composition of the present invention is obtained, so that the liquid composition tends to be more easily handled. In order to control the flow start temperature of the liquid crystal polyester within such an appropriate range, the polymerization conditions for the solid-phase polymerization may be appropriately optimized.
[ solvent ]
The solvent used for dissolving the liquid crystal polyester is not particularly limited as long as it can dissolve the liquid crystal polyester, and examples thereof include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N-dimethylformamide, N-diethylformamide, N-diethylacetamide, N-methylpropionamide, dimethylsulfoxide, γ -butyrolactone, dimethylimidazolidinone, tetramethylphosphoramide, and ethyl cellosolve acetate; and halogenated phenols such as p-fluorophenol, p-chlorophenol and perfluorophenol. These solvents may be used alone, or 2 or more of them may be used in combination.
Among the above solvents, aprotic polar solvents selected from the group consisting of N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N-dimethylformamide, N-diethylformamide, N-diethylacetamide, N-methylpropionamide, dimethylsulfoxide, γ -butyrolactone, dimethylimidazolidinone, tetramethylphosphoramide, and ethyl cellosolve acetate are suitable from the viewpoint of handling.
The amount of the solvent to be used may be appropriately selected depending on the kind of the solvent to be used as long as the liquid composition containing 0.1 mass% or more of the liquid crystal polyester is produced, but is preferably 0.5 to 50 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the solvent.
If the liquid crystal polyester is less than 0.5 parts by mass, the viscosity of the liquid composition of the present invention is too low and the liquid composition tends not to be uniformly applied; when the amount exceeds 50 parts by mass, the viscosity tends to be high.
In the liquid composition of the present invention, the liquid crystal polyester is preferably present in a state dissolved in the solvent (hereinafter, the liquid crystal polyester dissolved in the solvent is also referred to as a "liquid crystal polyester precursor", and the liquid crystal polyester precursor is a low molecular weight liquid crystal polyester including monomers, oligomers, and the like of the liquid crystal polyester), and the liquid composition is further diluted with the organic solvent, and the inherent viscosity at 25 ℃ when the liquid crystal polyester is a 0.5g/dl solution is 0.1 to 10.
[ liquid Crystal polyester powder ]
The liquid composition 1 of the present invention is a composition obtained by dissolving the liquid crystal polyester in the solvent and further containing a liquid crystal polyester powder (LCP powder) in order to increase the solid content concentration.
The liquid crystal polyester powder of the present invention is a powder using a liquid crystal polyester which is the same as or homologous to the liquid crystal polyester dissolved in the solvent.
The term "homologous" means that, although the side chain functional group of a unit structure and a part of the main skeleton of the unit structure are different, the main skeletons having the unit structure or the side chain functional group have a similar chemical structure such as partially repeated, and the homologous polyesters include, for example, compounds having a chemical structure with a plurality of carboxylic acid functional groups such as phthalic acid, which are called homologous polyesters. Further, the powder of the homologous liquid crystal polyester preferably shows compatibility with the liquid crystal polyester dissolved in the solvent.
The film is formed by containing a powder of a liquid crystal polyester which is the same as or similar to the liquid crystal polyester dissolved in a solvent, and in the production of a liquid crystal polyester film described later, the liquid crystal polyester dissolved in a solvent (liquid crystal polyester precursor) does not show thixotropy or the like with respect to the same or similar liquid crystal polyester powder, and can be uniformly coated with a comma coater or the like, and in the initial drying step after the coating (in the range of about 4 to 30% of the residual solvent in the liquid composition 1), the liquid crystal polyester precursor functions as a binder for the liquid crystal polyester powder, and further, in the firing step performed after the drying step, the liquid crystal polyester powder is melted and the liquid crystal polyester precursor is subjected to a condensation reaction (polymerization), and it is estimated that the liquid crystal polyester powder and the liquid crystal polyester precursor are co-crystallized finally.
The particle shape of the liquid crystal polyester powder (LCP powder) is preferably 0.01 to 1000. mu.m, more preferably 0.1 to 30 μm, even more preferably 0.1 to 10 μm, from the viewpoint of smoothness of the fired film.
The amount of the liquid crystal polyester powder (LCP powder) dispersed in the solution obtained by dissolving the liquid crystal polyester in the solvent is 10 to 1000 parts by weight, preferably 10 to 800 parts by weight, based on 100 parts by weight of the liquid crystal polyester precursor (liquid crystal polyester dissolved in the solvent), and more preferably 60 to 300 parts by weight, from the viewpoint of preventing shrinkage.
In addition, in order to increase the weight part, it is necessary to increase the amount of a polar solvent such as NMP (N-methyl-2-pyrrolidone) in view of kneading viscosity and casting characteristics by a coater, and this is not reasonable from the viewpoint of drying efficiency and solvent cost.
[ liquid Crystal polyester film ]
The liquid crystal polyester film 10 of the present invention is a film formed from the above-mentioned liquid composition 1, and preferably has a thickness of 0.5g/m2Moisture permeability of 24 hours or less, and the thickness of the liquid crystal polyester film is preferably 0.1 to 100 μm, more preferably 0.3 to 20 μm.
Further, by using the liquid composition 1 and forming it by a casting method, the liquid crystal polyester film 10 of the present invention can be non-oriented, does not have anisotropy which is possessed by a general liquid crystal polyester film, and can improve mechanical strength such as tensile force in the width direction.
As described above, the amount of the liquid crystal polyester powder (LCP powder) contained in the liquid composition 1 used for forming the liquid crystal polyester film 10 is preferably 10 to 800 parts by weight, and more preferably 60 to 300 parts by weight, based on 100 parts by weight of the liquid crystal polyester precursor (liquid crystal polyester dissolved in a solvent).
In addition, in order to increase the weight part, it is necessary to increase the amount of a polar solvent such as NMP (N-methyl-2-pyrrolidone) in view of kneading viscosity and casting characteristics by a coater, and this is not reasonable from the viewpoint of drying efficiency and solvent cost.
[ method for producing liquid Crystal polyester film ]
The method for producing the liquid crystal polyester film 10 of the present invention can be carried out, for example, by a so-called casting method including a step of casting the liquid composition 1 of the present invention on a substrate and a step of removing the solvent from the liquid composition on the substrate, and is not particularly limited as long as the casting method is used.
First, a step of producing a liquid crystal polyester film precursor 11 is performed. In the step of producing the liquid crystal polyester film precursor 11, as shown in fig. 1, the liquid composition 1 of the present invention is cast from the coater 13 onto the substrate 15, and the liquid composition 1 is dried by the dryer 14 at a predetermined temperature for a predetermined time, thereby forming the liquid crystal polyester film precursor 11 containing the residual solvent on the substrate 15.
Further, as shown in fig. 1, the 1 st laminate L1 in which the polyester film precursor 11 was laminated on the substrate 15 was wound into a roll.
Here, the liquid crystal polyester film precursor 11 refers to a film as follows: in the production process of a liquid crystal polyester film, the liquid crystal polyester (liquid crystal polyester precursor) in the residual solvent is polymerized (polymerized) by heat treatment (firing) at a stage before the liquid crystal polyester film as the final object to be produced.
The substrate 15 is not particularly limited as long as the liquid crystal polyester film precursor 11 can be peeled, but is preferably a glass plate, a stainless steel foil, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polytetrafluoroethylene sheet, or the like.
Further, as a method of casting the liquid composition 1 on the substrate 15, for example, a roll coating method, a gravure coating method, a knife coating method, a blade coating method, a bar coating method, a dip coating method, a spray coating method, a curtain coating method, a slit coating method, a screen printing method, and the like can be cited, and among them, a knife coating method or a slit coating method is preferable from the viewpoint of easy control and uniform film thickness with high accuracy.
The temperature and time for drying the liquid composition 1 are not particularly limited. For example, the temperature is preferably 160 ℃ or lower, more preferably 150 ℃ or lower, and further preferably 140 ℃ or lower. If the temperature is too high, defects may be generated on the coating surface. On the other hand, if the temperature is too low, the time required for removing the solvent becomes long, and the productivity may be lowered. Therefore, the drying of the liquid composition 1 is preferably performed at least at 60 ℃.
The amount of the residual solvent in the liquid crystal polyester film precursor 11 is preferably 30 to 4% by mass, and more preferably 15 to 5% by mass. It is preferable that the residual solvent amount is 18 mass% or less because the occurrence of tackiness on the surface of the liquid crystal polyester film precursor 11 can be suppressed, and the mutual adhesion between the films can be prevented. Further, if the amount of the residual solvent is 2 mass% or more, the film strength of the liquid crystal polyester film precursor 11 can be maintained, and the liquid crystal polyester film 10 produced can be prevented from being damaged when the liquid crystal polyester film precursor 11 is peeled from the substrate 15 in the second laminate production step described below and when heat treatment (firing) is further performed in the third laminate production step described below.
Next, after the 1 st laminate L1 was produced, the process proceeds to the 2 nd laminate production step, and as shown in fig. 2, the 1 st laminate L1 in a roll form is fed out, the liquid crystal polyester film precursor 11 is peeled from the substrate 15 by the peeling roller 18, and then the liquid crystal polyester film precursor 11 is transferred to the surface of the metal substrate 16 having a rubber-like elastic layer on the surface. Then, a 2 nd laminate L2 was obtained in which the metal base material 16 was laminated on the back surface of the liquid crystal polyester film precursor 11. Further, the 2 nd laminate L2 was wound into a roll.
In this case, the metal substrate 16 is laminated on the back surface of the liquid crystal polyester film precursor 11 (that is, the surface in contact with the substrate 15), and if the surface of the substrate 15 is smooth, the back surface of the liquid crystal polyester film precursor 11 is also smooth, and the adhesion between the liquid crystal polyester film precursor 11 and the metal substrate 16 can be ensured.
Here, examples of the material of the metal base 16 include aluminum, stainless steel, iron, and copper. Among these, stainless steel is particularly preferable from the viewpoint of strength and corrosion resistance.
The thickness of the metal base material 16 is preferably in the range of 20 to 200 μm. If the thickness of the metal base material 16 is 20 μm or more, the metal base material 16 has high resistance to scratches and is excellent in recycling property. If the thickness of the metal base material 16 is 200 μm or less, it becomes easy to wind it into a roll.
The surface of the metal substrate 16 may be subjected to any surface treatment as long as it can ensure adhesion to the liquid crystal polyester film precursor 11 and releasability of the liquid crystal polyester film 10 in a film-releasing step described later. For example, in order to make it difficult for the rubber-like elastic layer to peel off from the metal base material 16, embossing may be performed on the surface of the metal base material 16.
Examples of the rubber-like elastic layer include a silicone rubber elastic layer, a fluorine rubber elastic layer, and an acrylic rubber elastic layer. Among these, a silicone rubber elastic layer is particularly preferable, and if it is a silicone rubber elastic layer, the adhesion to the metal base 16 is good, and the releasability of the liquid crystal polyester film 10 in the film releasing step described later is also good.
The thickness of the rubber-like elastic layer is preferably in the range of 5 to 100 μm. If the thickness of the rubber-like elastic layer is 5 μm or more, the difference in elastic modulus of the metal base material 16 can be sufficiently relaxed. If the thickness of the rubber-like elastic layer is 100 μm or less, the rubber-like elastic layer can be prevented from being peeled off (chipping) at the time of processing the metal base material 16.
The method of transferring the liquid crystal polyester film precursor 11 is not particularly limited, but as shown in fig. 2, it is preferable to sandwich the liquid crystal polyester film precursor 11 and the metal substrate 16 by a pair of rollers 19 and 19 from the viewpoint of improving productivity.
The transfer temperature of the liquid crystal polyester film precursor 11 is not particularly limited, but is preferably within a range of 10 to 200 ℃. When the transfer temperature is 10 ℃ or higher, the adhesion to the metal base 16 is good. When the transfer temperature is 200 ℃ or lower, the liquid crystal polyester film 10 has good releasability in the film-releasing step described later.
After the 2 nd laminate L2 was produced in this manner, the process proceeds to the 3 rd laminate L3 production step, and as shown in fig. 3, the 2 nd laminate L2 in a roll form is sent out, and the 2 nd laminate L2 is continuously heat-treated (fired) at a predetermined temperature in a heating furnace (firing furnace) 17 in a nitrogen atmosphere for a predetermined time. By this heat treatment, a 3 rd laminate L3 including the liquid crystal polyester film 10 and the metal substrate 16 substantially free of the solvent was obtained.
At this time, since the heat treatment of the 2 nd laminate L2 is performed in a nitrogen atmosphere, the deterioration of the liquid crystal polyester film 10 due to the oxidation of the liquid crystal polyester can be prevented.
Here, the heat treatment temperature of the 2 nd laminate L2 is preferably in the range of 200 to 350 ℃. When the heat treatment temperature is 200 ℃ or higher, the molecular weight of the liquid crystal polyester increases (becomes polymeric) by the heat treatment, and the liquid crystal polyester film precursor 11 can exhibit the characteristics as the liquid crystal polyester film 10. When the heat treatment temperature is 350 ℃ or lower, thermal decomposition of the liquid crystal polyester film 10 can be suppressed.
On the other hand, the heat treatment time of the 2 nd laminate L2 is not particularly limited, but is usually carried out by raising the temperature to the heat treatment temperature at a temperature raising rate of 10 ℃/min or less and then holding the same at the same temperature for 0 to 10 hours.
The method of heat treatment of the 2 nd laminate L2 is not particularly limited, but may be a method of continuously passing the laminate through the heating furnace 17 roll-to-roll (a method of supplying a raw material roll with a roll and winding a product around a roll), for example, a method described in japanese patent application laid-open No. 2008-207537.
After the 3 rd laminate L3 was produced in this manner, the process proceeds to a film peeling step, and the liquid crystal polyester film 10 is peeled from the metal substrate 16 as shown in fig. 3. At this time, since the rubber-like elastic layer is provided on the surface of the metal base 16, that is, on the surface on the liquid crystal polyester film 10 side, the liquid crystal polyester film 10 is easily peeled from the metal base 16.
Here, the method for peeling the liquid crystal polyester film 10 is not particularly limited, but as shown in fig. 3, a method for continuously peeling the metal substrate 16 and the liquid crystal polyester film 10 using a pair of peeling rollers 18, 18 is preferable.
After the liquid crystal polyester film 10 is peeled off, contaminants (silicone, fluorine-containing substances, etc.) can be removed from the metal base 16 by solvent cleaning, UV treatment, corona treatment, plasma treatment, flame treatment, or other methods as needed.
By doing so, the liquid crystal polyester film 10 is peeled from the metal base material 16, and the manufacturing process of the liquid crystal polyester film 10 is completed.
According to the above-described method for producing the liquid crystal polyester film 10, the liquid crystal polyester film 10 is peeled after the heat treatment in a state where the liquid crystal polyester film precursor 11 is transferred to the metal substrate 16 having the rubber-like elastic layer on the surface.
In the production of a polyester film by the casting method as described above, the use of the liquid composition 1 of the present invention can significantly reduce the drying time in the drying step and the baking time in the heat treatment step, and further can suppress foaming of the film during molding.
[ laminated film ]
Next, the laminated film 20 of the present invention will be described.
The laminate film 20 of the present invention is a film having the liquid crystal polyester film layer 21 formed from the liquid composition 1 of the present invention and the metal layer 26.
[ liquid Crystal polyester film layer ]
The liquid crystal polyester film layer 21 is a liquid crystal polyester film having the liquid composition 1 and preferably has a moisture permeability of 0.5g/m2The layer of the liquid crystal polyester film having a thickness of 24 hours or less is, for example, 3 to 100 μm.
Further, by forming the liquid composition 1 by a casting method, the liquid crystal polyester film layer 21 of the present invention can be made non-oriented, does not have anisotropy which is possessed by a general liquid crystal polyester film, and can improve mechanical strength such as tensile force in the width direction.
The liquid crystal polyester film layer 21 has a single-layer structure as shown in fig. 4, or has a multi-layer structure (3-layer structure in the figure) as shown in fig. 5.
As an example of the case where the liquid crystal polyester film layer 21 has a multilayer structure, as shown in fig. 5, the liquid crystal polyester film layer 21 laminated on the surface of the metal layer 26 may have a three-layer structure in which liquid crystal polyester layers 22 and 24 (for convenience, reference numeral 22 is also referred to as a 1 st liquid crystal polyester layer, and reference numeral 24 is also referred to as a 2 nd liquid crystal polyester layer) are laminated on both surfaces of a filler-added layer 23 which is a liquid crystal polyester film to which a filler is added, as a liquid crystal polyester film containing no filler.
Hereinafter, as shown in fig. 5, the liquid crystal polyester layers 22 and 24 and the filler addition layer 23 will be described.
[ liquid Crystal polyester layer ]
As shown in FIG. 5, the liquid crystal polyester layers 22 and 24 are liquid crystal polyester films formed using the above-mentioned liquid composition 1 of the present invention, have a structure containing no filler, and preferably have a structure of 0.5g/m2Moisture permeability of 24h or less.
The amount of the liquid crystal polyester powder (LCP powder) contained in the liquid composition used for forming the liquid crystal polyester layers 22 and 24 is preferably 10 to 800 parts by weight, and more preferably 60 to 300 parts by weight, based on 100 parts by weight of the liquid crystal polyester precursor (liquid crystal polyester dissolved in a solvent), as described above.
In addition, in order to increase the weight part, it is necessary to increase the amount of a polar solvent such as NMP (N-methyl-2-pyrrolidone) in view of kneading viscosity and casting characteristics by a coater, and this is not reasonable from the viewpoint of drying efficiency and solvent cost.
In addition, as the liquid crystal polyester layers 22 and 24, a liquid composition containing a solvent and a liquid crystal polyester dissolved in the solvent, which does not contain the liquid crystal polyester film powder, may be used instead of the liquid composition 1 of the present invention. In the case of not containing the liquid crystal polyester film powder, the liquid crystal polyester film can be produced by a casting method as in the case of the liquid composition containing the liquid crystal polyester film powder.
The thickness of the liquid crystal polyester layers 22 and 24 is preferably 0.3-20 μm.
In addition, if the thickness of the liquid crystal polyester layers 22 and 24 is 1 μm or less, for example, variations in surface irregularities of the laminated metal layers may not be absorbed, and as a result, an increase in dielectric loss may occur, so that the thickness of the liquid crystal polyester layers 22 and 24 is preferably 2 to 15 μm from the viewpoint of adhesiveness to the metal layer 26 and maintenance of dielectric properties.
The thickness of the liquid crystal polyester layers 22 and 24 is preferably not more than the thickness of the filler addition layer 23 described later, for example, 50% or less, more preferably 40% or less of the thickness of the filler addition layer 23, from the viewpoint of the necessity of reducing the linear expansion coefficient of the entire liquid crystal polyester film layer 21.
In addition, the thickness of the 1 st liquid crystal polyester layer 22 and the thickness of the 2 nd liquid crystal polyester layer 24 may not be uniform.
It is not preferable to add an inorganic filler to the liquid crystal polyester layers 22 and 24 from the viewpoint of dielectric loss.
[ Filler addition layer ]
As shown in fig. 5, the laminated film 20 of the present invention is provided with a filler addition layer 23 made of a liquid crystal polyester film to which an inorganic filler and fluorine-based powder, which will be described later, are added, whereby the linear expansion coefficient of the entire liquid crystal polyester film layer 21 can be reduced and is close to the linear expansion coefficient of the metal layer 26 laminated on the liquid crystal polyester film layer 21.
The liquid crystal polyester film constituting the filler-added layer 23 is formed of a material obtained by adding a filler described later to the liquid crystal composition 1 of the present invention, but it is preferable to use a liquid crystal polyester identical or homologous to the liquid crystal polyester layers 22 and 24 as the liquid crystal polyester contained in the liquid crystal composition 1 used for forming the filler-added layer 23.
The filler added to the filler addition layer 23 is added for adjusting the linear expansion coefficient of the entire liquid crystal polyester film layer 21 (mainly for the purpose of reducing the linear expansion coefficient), and preferably an insulating inorganic filler, for example, silica, talc, silicon nitride, aluminum nitride, or the like can be used. In addition to the inorganic filler, fluorine-based powder described later may be added. Hereinafter, the inorganic filler will be described first.
The blending ratio of the inorganic filler is in the range of 0.5 to 30 parts by mass with respect to 100 parts by mass of the solid content of the liquid crystal polyester, preferably 1 to 15 parts by mass from the viewpoint of maintaining the toughness of the finished film, and more preferably 0.5 to 7 parts by mass from the viewpoint of low dielectric constant.
The inorganic filler used has an average particle diameter of 0.001 to 15 μm, and is preferably 0.05 to 3 μm, more preferably 0.05 to 1 μm, in terms of the thickness of the filler-added layer 23, and the particle shape may be needle-like, other shapes, or amorphous, in addition to spherical.
In order to provide the entire liquid crystal polyester film layer 21 with a low dielectric constant, it is preferable to use a filler obtained by a combustion method such as fumed silica containing no moisture as the inorganic filler.
In addition, powder of an insulating inorganic substance produced by a method other than the above-described method, for example, wet grinding method or normal grinding method, may be used as the filler, but in this case, in order to obtain a filler having a low water content, it is preferable to heat-dry the powder at a temperature of 100 to 400 ℃ or higher for 30min to 12 h.
In the present invention, in addition to the inorganic filler, fluorine-based powder may be added as a linear expansion modifier or an extender to the filler addition layer 23.
The fluorine-based powder is a powder of a composition containing fluorine, and preferably has hydrophobicity.
As the fluorine-based powder, for example, powder of PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxyalkane), FEP (perfluoroethylene propylene copolymer), or the like can be used. For example, a copolymer containing tetrafluoroethylene (component a) and a monomer (component B) containing an unsaturated hydrocarbon as a main component (see fig. 9. it is preferable that R in the figure is a hydrogen atom, a hydroxyl group, an organic group having a hydroxyl group, or an alkyl group) can be used.
As the monomer containing an unsaturated hydrocarbon as a main component, a substance having a hydroxyl group may be used. The hydroxyl group is, for example, involved in an ester bond accompanying the polymerization of the liquid crystal polyester forming the filler-added layer 23, and the hydroxyl group is detached to become hydrophobic.
The fluorine-containing powder preferably has a powder particle size of 0.01 to 5 micrometers (μm), but is not limited thereto. The average particle diameter of the fluorine-containing powder is preferably 0.2 to 0.25 μm, but is not limited thereto.
The amount of the fluorine-based powder is in the range of 1 to 10 parts by mass, preferably 2 to 4 parts by mass, per 100 parts by mass of the solid content of the liquid crystal polymer forming the filler-added layer 23.
The amount of the liquid crystal polyester powder (LCP powder) contained in the liquid composition 1 used for forming the filler-added layer 23 is preferably 10 to 800 parts by weight, more preferably 60 to 300 parts by weight, based on 100 parts by weight of the liquid crystal polyester precursor (liquid crystal polyester dissolved in a solvent), from the viewpoint of uniform dispersion of the inorganic filler and the fluorine-based powder.
In addition, in order to increase the weight part, it is necessary to increase the amount of a polar solvent such as NMP (N-methyl-2-pyrrolidone) in view of kneading viscosity and casting characteristics by a coater, and this is not reasonable from the viewpoint of drying efficiency and solvent cost.
As described above, the linear expansion coefficient of the entire liquid crystal polyester film layer 21 is adjusted by adjusting the filler in the above-described range of the addition amount and adjusting the thicknesses of the liquid crystal polyester layers 22 and 24 and the filler addition layer 23, for example, so as to be close to the linear expansion coefficient of the metal layer 26 laminated on the liquid crystal polyester film layer 21. For example, the difference between the linear expansion coefficient of the metal layer 26 and the linear expansion coefficient of the liquid crystal polyester film layer 21 may be adjusted so that the value of the linear expansion coefficient of the liquid crystal polyester film layer 21 becomes 125% or less of the linear expansion coefficient of the metal layer 26.
For example, when the coefficient of linear expansion of the copper foil forming the metal layer 26 is 19ppm, 25% thereof is 4.75, and in this case, the coefficient of linear expansion of the liquid crystal polyester film layer 21 may be adjusted so as to be 23.75ppm or less.
As described above, by making the linear expansion coefficient of the entire liquid crystal polyester film layer 21 close to the linear expansion coefficient of the metal layer 26 by the filler addition layer 23, the warpage or deformation of the entire laminate film 20 due to the difference in the linear expansion coefficient can be further reduced.
In the laminated film 20 of fig. 5, both surfaces (front and back surfaces) of the filler-added layer 23 are covered with the liquid crystal polyester layers 22 and 24 formed of the liquid crystal polyester film to which no filler is added, whereby the low water absorption property which the original liquid crystal polyester film has can be maintained irrespective of the moisture absorption property of the inorganic filler, the surface segregation of the filler is prevented, the dielectric loss due to the surface unevenness of the filler can be reduced, and the falling-off of the filler from the filler-added layer 23 can be prevented.
The surface of the filler-added layer 23 may be rough and matte due to the addition of the filler, but the liquid crystal polyester film layers of the liquid crystal polyester layers 22 and 24 to which no filler is added are laminated on both surfaces of the filler-added layer 23, and the surface thereof can be finished to a smooth and glossy and beautiful surface.
In fig. 5, an example in which filler addition layer 23 has a single-layer structure is shown, but filler addition layer 23 may have a multilayer structure, and the amount of filler added may be changed for each layer so that the amount of filler added has a gradient in the thickness direction.
In this case, it is preferable that the structure shown in fig. 5 is an inclined structure as follows: the amount of the filler added was decreased toward the first liquid crystal polyester layer 22 side and the second liquid crystal polyester layer 24 side.
[ Metal layer ]
As a material of the metal layer 26 constituting the laminated film of the present invention, various metals having conductivity such as aluminum, iron, gold, silver, and alloys thereof can be used in addition to copper and copper alloys.
In addition, the method for forming the metal layer 26 of the present invention uses vacuum deposition or sputtering, and particularly preferably uses a deposition method having a smaller molecular energy and a weaker adhesion than sputtering.
In addition, the thickness of the metal layer of the present invention is preferably 1 to 6 μm.
[ method for producing laminated film ]
Next, a method for producing the laminated film 20 of the present invention will be described.
First, an example of a method for producing a laminate film 20 in which a liquid crystal polyester film layer 21 has a single-layer structure as shown in fig. 4 will be described.
First, as the base material 40, copper is vapor-deposited on one surface of an OPP (biaxially oriented polypropylene) film to form a copper foil (metal layer) 26 (vapor deposition step, not shown).
The thickness of the OPP film 40 is 10 to 200 μm, preferably 25 to 50 μm, and the deposition thickness of copper is preferably 1 to 6 μm.
The liquid composition 1 of the present invention is cast on the surface of the deposited copper foil 26 by a coater (coating step, not shown), and the liquid composition 1 coated on the surface of the copper foil is dried by a dryer until the residual solvent is 4 to 30%, preferably 4 to 12% (drying step, not shown), and a liquid crystal polyester film precursor 31 is formed on the surface of the copper foil. Thus, a laminate in which the copper foil 26 and the liquid crystal polyester film precursor 31 are laminated on the OPP film 40(OPP film 40/copper foil (metal layer) 26/liquid crystal polyester film precursor 31) was obtained.
Here, the liquid crystal polyester film precursor 31 refers to a film as follows: in the production process of the liquid crystal polyester film as described above, the residual solvent is removed by heat treatment (firing) at a stage before the liquid crystal polyester film as the final object, and the liquid crystal polyester (liquid crystal polyester precursor) in the residual solvent is polymerized (polymerized), whereby the liquid crystal polyester film can be formed.
Examples of the method of casting the liquid composition on the copper foil include roll coating, gravure coating, knife coating, blade coating, bar coating, dip coating, spray coating, curtain coating, slit T die coating, and screen printing, and among them, knife coating and slit T die coating are preferable from the viewpoint of easy control and high accuracy in making the film thickness uniform.
In the drying step, if the drying temperature is too high, the liquid crystal polyester precursor may start to polymerize or the like before the firing step described later and may be polymerized and cause defects on the coating surface, while if the temperature is too low, the time taken to remove the solvent may be prolonged and the productivity may be lowered, and the drying temperature is preferably 60 ℃ or more and 160 ℃ or less, more preferably 150 ℃ or less, and still more preferably 140 ℃ or less.
Next, the OPP film 40 is peeled from the laminate (OPP film 40, copper foil (metal layer) 26, and liquid crystal polyester film precursor 31) (peeling step, not shown) to obtain a laminate film precursor (liquid crystal polyester copper vapor deposition transfer film) 30.
The method for peeling the OPP film 40 is not particularly limited, but for example, there is a method of continuously peeling the OPP film 40 and the laminate film precursor 30 using a pair of peeling rollers.
Next, as shown in fig. 6, the laminated film precursor (copper foil 26/liquid crystal polyester film precursor 31)30 produced through the above-described OPP film peeling step is subjected to continuous heat treatment (continuous firing) at a predetermined temperature for a predetermined time in a firing furnace 51, whereby the liquid crystal polyester film precursor 31 is a liquid crystal polyester film layer 21, and the laminated film (copper foil 26/liquid crystal polyester film layer 21)20 of the present invention having the liquid crystal polyester film layer 21 and the copper foil (metal layer) 26 is obtained (firing step).
At this time, the baking furnace 51 is filled with nitrogen gas, and heat treatment is performed in a nitrogen atmosphere, whereby deterioration of the liquid crystal polyester film due to oxidation of the liquid crystal polyester can be prevented. The heat treatment may be performed in an atmosphere of an inert gas other than nitrogen (e.g., helium, argon, or the like).
It is preferable that the inert gas is always blown to the openings (gaps) of the transfer inlet and the transfer outlet of the firing furnace 51 so that oxygen does not enter the firing furnace 51.
The firing temperature (heat treatment temperature) of the laminated film precursor 30 is preferably in the range of 200 to 350 ℃. When the heat treatment temperature is 200 ℃ or higher, the melt bonding (anchoring) and intermolecular bonding at the interface between the liquid crystal polyester film layer 21 and the copper foil (metal layer) 26 are increased by the heat treatment, and the characteristics as the liquid crystal polyester film layer 21 can be exhibited from the laminate film precursor 30. When the heat treatment temperature is 350 ℃ or lower, thermal decomposition of the liquid crystal polyester film can be suppressed.
Further, gas nozzles (not shown) are alternately arranged above and below the laminated film precursor 30 in the traveling direction of the laminated film precursor 30 through the continuously conveyed laminated film precursor 30 in the firing furnace 51, the laminated film precursor 30 is held in a state where the tension acting on the laminated film precursor 30 is released in the firing furnace 51 (non-contact conveyance), a gas (inert gas) is blown from the gas nozzles from above and below the laminated film precursor 30 toward the laminated film precursor 30, and the laminated film precursor 30 is conveyed while being moved up and down (vibrated) in a direction perpendicular to the conveying direction (plane of the laminated film precursor). As a result, as shown in fig. 6, the laminated film precursor 30 in the firing furnace 51 is conveyed in a suspended state in a continuous substantially wavy state in the conveyance direction, and is subjected to heat treatment.
By performing the heat treatment while moving (vibrating) the laminate film precursor 30 up and down as described above, first, the shrinkage reaction is alleviated at the time of desolvation of the liquid crystal polyester film precursor 31, and the intermolecular behavior is present between the layers of the liquid crystal polyester film layer 21 and the copper foil 26 obtained by the heat treatment, the interface between the liquid crystal polyester film layer 21 and the copper foil 26 has a complicated structure, and integration of the copper foil (metal) and the liquid crystal polyester film, which cannot be measured by delamination, is obtained in the interface region with the copper foil 26 in the finished product, so that the anchoring effect is obtained in the nanometer range of the liquid crystal polyester film layer 21 in the interface region with the copper foil 26 (that is, a state in which the mutual adhesiveness and the bonding strength.
Further, in general, when a liquid crystal polyester film is produced from the liquid crystal polyester film precursor by heat treatment, shrinkage, warpage, deformation in the polymer, and the like occur, and the film is relaxed by the above-described vertical movement during the heat treatment, so that the produced liquid crystal polyester film layer becomes non-oriented, and the deformation in the polymer and the stress of the film are removed, and the laminated film of the present invention having the produced liquid crystal polyester film layer is not shrunk, warped, and deformed and straightened by the polymer.
Therefore, in order to prevent the occurrence of warpage, it is not necessary to use a clip tenter which has been conventionally used.
Further, by loosening the liquid crystal polyester film by the vertical movement, degassing of the solvent, the desorbed water, other residues (including impure gas), and the like in the liquid crystal polyester polymer is promoted, and shrinkage or foaming of the film (bubbling of the desolvation) is avoided, and generation of residual marks such as bubbles and pinholes can be prevented.
The residue and impurities in the liquid crystal polyester polymer cause foaming, and for example, when the laminated film 20 of the present invention is used as a flexible substrate (printed wiring board), the residue and impurities cause noise in electronic devices.
The height of the vertical movement of the laminated film precursor 30 in the firing furnace 51 is 3mm to 900mm, preferably 20mm to 200mm, and more preferably is a non-contact conveyance in which the laminated film precursor 30 is suspended and conveyed between the upper and lower gas nozzles, and the height of the vertical movement of the laminated film precursor (the height of the waves) is 50mm to 200 mm.
The distance between the gas nozzles is preferably 3mm to 900mm, and more preferably 100mm to 500mm, and still more preferably 200mm to 300mm, from the viewpoint of installation cost of the gas nozzles.
Further, since the liquid crystal polyester easily absorbs the far infrared rays into the inside by performing the heat treatment by the far infrared heating in the above-mentioned firing furnace 51, the absorbed far infrared rays (energy) excite the monomer or the polymer and vibrate at the same time, thereby releasing (degassing) the impurity gas in the film and further alleviating the deformation of the polymer.
The wavelength range of the infrared rays emitted from the far-infrared heater is approximately 3 to 25 μm, which corresponds to the wavelength range of the thermal vibration (molecular vibration or lattice vibration) of almost all substances except metal.
After the laminated film precursor 30 is subjected to heat treatment (firing step) as described above to obtain the laminated film 20 having the copper foil (metal layer) 26 and the liquid crystal polyester film layer 21, the laminated film is continuously pressed by a heating calender 52(150 to 200 ℃) to improve the surface smoothness, and is cooled at room temperature to complete winding.
The laminated film 20 having passed through the heating calender 52 may be pressed by a press (not shown) to further press-bond the copper foil 26 and the liquid crystal polyester film layer 21.
Next, an example of a method for producing the laminated film 20 having the liquid crystal polyester film layer 21 having a 3-layer structure shown in fig. 5 will be described.
First, copper is vapor-deposited on an OPP (biaxially oriented polypropylene) film 40 as a base material to form a copper foil (metal layer) 26.
The thickness of the OPP film 40 is 10 to 200 μm, preferably 25 to 50 μm, and the deposition thickness of copper is preferably 1 to 6 μm.
Further, the liquid compositions 1a to 1c of the respective layers of the liquid crystal polyester film layer 21 are sequentially cast from a coater onto the copper foil surface deposited on the OPP film 40 (coating step), and then the residual solvent of the liquid compositions 1a to 1c coated on the copper foil 26 is dried to 4 to 30%, preferably 4 to 12% by a dryer, and the liquid crystal polyester film precursors 31a to 31c are formed on the copper foil 26 (drying step).
More specifically, as shown in FIG. 7, on the copper foil 26 deposited on the OPP film 40, first, the liquid composition 1a of the present invention (for convenience, also referred to as the 1 st liquid composition) for forming the 1 st liquid crystal polyester layer 22 is cast by a coater 61a, drying is carried out by a dryer 63a, a liquid composition (for convenience, also referred to as a 2 nd liquid composition) 1b of the present invention containing the filler forming the filler layer 23 thereon is cast by an applicator 61b, and then dried by the dryer 63b, further, after casting the liquid composition (for convenience, also referred to as a 3 rd liquid composition) 1c on which the 2 nd liquid crystal polyester layer 24 was formed with a coater 61c, the film is dried by a dryer 63c, and the liquid crystal polyester film precursors 31a to 31c are formed on the copper foil 26 through the above steps.
The method of casting the liquid composition 1 in the coating step and the drying temperature in the drying step are as described in the above-mentioned method of producing the laminated film 20 when the liquid crystal polyester film layer 21 is a single layer.
As shown in fig. 8, the above-mentioned 3 liquid compositions 1a to 1c can be simultaneously cast in three layers by a three-layer extrusion die and a three-layer slit coating method on the copper foil 26 deposited on the OPP film 40, and the three layers can be simultaneously dried by a dryer 63.
By the drying, the liquid compositions 1a to 1c of the respective layers on the copper foil 26 become liquid crystal polyester film precursors 31a to 31c containing a residual solvent, and then the OPP film 40 is peeled off (OPP peeling step, not shown), thereby obtaining a laminated film precursor (liquid crystal polyester copper deposition transfer film) 30 in which 3 layers of the liquid crystal polyester film precursors 31a to 31c are laminated on the surface of the copper foil (metal layer) 26.
The laminated film precursor 30 is subjected to a heat treatment (a firing step, not shown) in a heating furnace (a firing furnace) to completely remove the solvent from the liquid crystal polyester film precursors 31a to 31c, thereby obtaining a liquid crystal polyester film layer 21 having a 3-layer structure, and the laminated film 20 of the present invention shown in fig. 5 is produced.
The firing step may be the same as the firing step described in the method for producing the laminate film 20 in the case where the liquid crystal polyester film layer 21 is a single layer.
In the method for producing the laminated film 20 of the present invention described above, as described above, the sputtering or vapor deposition of the copper foil is performed not after the firing of the liquid crystal polyester film but before the firing of the liquid crystal polyester film.
Thus, the problem of pinholes caused by sputtering or vapor deposition of the metal foil can be solved. That is, when the liquid crystal polyester film is condensed during firing, the metal foil follows the liquid crystal polyester film to close the pinholes.
Furthermore, high bonding with the sputtered interface of the metal foil is obtained together with thermal activity at the time of firing of the liquid crystal polyester film, and for example, in the case of using the laminate film 20 of the present invention as a flexible substrate (printed wiring board), the metal layer 26 is resistant to fine etching in a subsequent step.
In addition, in the film formation by the casting method as described above, by using the liquid composition 1 of the present invention, the drying time in the drying step and the baking time in the heat treatment step described above can be significantly reduced, and the foaming of the film at the time of molding can be suppressed.
Further, as described above, the method for producing the laminate film 20 of the present invention does not flow the liquid crystal polyester in a molten state in a certain direction to form a film unlike the melt casting method, and therefore the liquid crystal polyester film layer of the resulting laminate film 20 can be made non-oriented, and the problem of the so-called ordinary liquid crystal polyester which is easily cracked in the orientation direction can be solved, and further the laminate film 20 which is less likely to cause warpage, deformation, or the like by alleviating anisotropy can be obtained.
In the case where the liquid crystal polyester film layer 21 produced by the above method had a 3-layer structure, not only the liquid crystal polyester layers 22 and 24 to which no filler was added but also the filler-added layer 23 was non-oriented, and it was confirmed that the liquid crystal polyester film layer had excellent mechanical strength in any direction.
Further, by providing the filler addition layer 23 on the liquid crystal polyester film layer 21 of the laminate film 20, the linear expansion coefficient of the entire film is made to be close to the linear expansion coefficient of the metal layer (copper foil) 26, whereby warpage or deformation of the entire laminate film 20 can be prevented, and on the other hand, since the laminated surface with the metal layer 26 is the liquid crystal polyester layer 22 (or 24) containing no filler, the adhesiveness between the liquid crystal polyester film layer 21 and the metal layer 26 is not impaired by the addition of the filler, and further, low moisture absorption is maintained, whereby the laminate film 20 can be made to have high functionality by the advantageous characteristics of the liquid crystal polyester exhibited.
Claims (13)
1. A liquid composition characterized in that,
a solution containing a solvent and a liquid crystal polyester dissolved in the solvent contains a liquid crystal polyester powder which is the same as or homologous to the liquid crystal polyester, thereby increasing the solid content concentration.
2. The liquid composition as set forth in claim 1, wherein,
the liquid crystal polyester powder is 10 to 1000 parts by weight relative to 100 parts by weight of the liquid crystal polyester dissolved in the solvent.
3. A liquid crystal polyester film characterized in that,
the liquid crystal polyester film is formed from the liquid composition according to claim 1 or 2.
4. The liquid crystal polyester film according to claim 3,
the liquid crystal polyester film is non-oriented.
5. A method for producing a liquid crystal polyester film, comprising:
casting the liquid composition according to claim 1 or 2 on a substrate; and
and removing the solvent from the liquid composition on the substrate.
6. A laminated film characterized by comprising:
a liquid crystal polyester film layer comprising a liquid crystal polyester film formed using the liquid composition according to claim 1 or 2; and
and a metal layer laminated on the surface of the liquid crystal polyester film layer.
7. The laminate film of claim 6,
the liquid crystal polyester film layer has a laminated structure in which liquid crystal polyester layers made of liquid crystal polyester without filler are laminated on both sides of a filler addition layer made of liquid crystal polyester with filler added.
8. The laminate film of claim 7,
the filler is silicon dioxide, talcum, silicon nitride dioxide, aluminum nitride or fluorine powder.
9. A method for manufacturing a laminated film, comprising:
a step of forming a metal layer on a surface of a substrate by vapor deposition or sputtering, casting the liquid composition according to claim 1 or 2 on the metal layer, drying the cast layer, and then peeling the substrate to produce a laminated film precursor having the metal layer and a liquid crystal polyester film precursor; and
and a step of producing a laminated film having the metal layer and the liquid crystal polyester film layer by removing a residual solvent contained in the liquid crystal polyester film precursor by heat-treating the laminated film precursor in a firing furnace.
10. The method for manufacturing a laminated film according to claim 9,
the substrate is an OPP film, a CPP film or a HPPE film.
11. The method of manufacturing a laminated film according to claim 9 or 10,
and performing a heat treatment in the firing furnace while moving the laminated film precursor up and down in a direction perpendicular to a horizontal plane of the laminated film precursor in a state where a tension acting on the laminated film precursor is released.
12. The method for manufacturing a laminated film according to claim 11,
in the firing furnace, gas nozzles are alternately arranged above and below the laminated film precursor with respect to the traveling direction of the laminated film precursor being continuously transported therebetween, and a gas is blown from the gas nozzles to the laminated film precursor to move the laminated film precursor vertically in a direction perpendicular to the horizontal plane of the laminated film precursor.
13. A printed wiring board characterized in that,
a conductor pattern is formed on a metal layer of the laminate film according to any one of claims 6 to 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-228371 | 2019-12-18 | ||
| JP2019228371A JP2021095520A (en) | 2019-12-18 | 2019-12-18 | Liquid composition, liquid crystal polyester film and method for producing liquid crystal polyester film, and laminate film and method for producing laminate film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112980004A true CN112980004A (en) | 2021-06-18 |
Family
ID=76344873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011399031.0A Pending CN112980004A (en) | 2019-12-18 | 2020-12-04 | Liquid composition, liquid crystal polyester film, method for producing liquid crystal polyester film, laminated film, and method for producing laminated film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2021095520A (en) |
| KR (1) | KR102483681B1 (en) |
| CN (1) | CN112980004A (en) |
| TW (1) | TWI764429B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023032376A1 (en) * | 2021-08-31 | 2023-03-09 | 株式会社村田製作所 | Liquid crystal polymer film and method for producing liquid crystal polymer film |
| WO2024048729A1 (en) * | 2022-08-31 | 2024-03-07 | 富士フイルム株式会社 | Film, method for manufacturing same, and laminate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513895A (en) * | 2002-12-18 | 2004-07-21 | ס�ѻ�ѧ��ҵ��ʽ���� | Aromatic liquid crystal polyester and its film |
| JP2004299216A (en) * | 2003-03-31 | 2004-10-28 | Sumitomo Bakelite Co Ltd | Heat treatment apparatus for film |
| CN104203571A (en) * | 2012-03-30 | 2014-12-10 | 富士胶片株式会社 | Method for producing laminate film containing liquid crystalline compound having high crystallinity |
| JP2019163431A (en) * | 2018-03-20 | 2019-09-26 | 住友化学株式会社 | Liquid crystalline polyester liquid composition, method for producing liquid crystal polyester film, and liquid crystalline polyester film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2942840B2 (en) * | 1989-05-24 | 1999-08-30 | ダイセル化学工業株式会社 | Laminated film |
| JP2000117183A (en) * | 1998-10-13 | 2000-04-25 | Konica Corp | Coating production apparatus and method therefor |
| JP5201131B2 (en) * | 2007-03-01 | 2013-06-05 | 味の素株式会社 | Metal film transfer film, metal film transfer method, and circuit board manufacturing method |
| JP5444581B2 (en) * | 2010-02-16 | 2014-03-19 | 共同技研化学株式会社 | Method for producing liquid crystal polyester film |
| JP6080124B2 (en) * | 2012-03-13 | 2017-02-15 | 住友化学株式会社 | Method for producing laminated substrate |
| JP2013193438A (en) | 2012-03-22 | 2013-09-30 | Sumitomo Chemical Co Ltd | Method of manufacturing liquid crystal polyester film and the liquid crystal polyester film |
| WO2017175067A1 (en) * | 2016-04-06 | 2017-10-12 | Sabic Global Technologies B.V. | Filler-reinforced solid resin multilayered structure |
| TWI650358B (en) * | 2017-09-14 | 2019-02-11 | 佳勝科技股份有限公司 | Liquid crystal polymer composition and high frequency composite substrate |
| TWI647261B (en) * | 2018-02-06 | 2019-01-11 | 佳勝科技股份有限公司 | Liquid crystal polymer film and method for producing flexible copper foil substrate having liquid crystal polymer film |
-
2019
- 2019-12-18 JP JP2019228371A patent/JP2021095520A/en active Pending
-
2020
- 2020-12-04 CN CN202011399031.0A patent/CN112980004A/en active Pending
- 2020-12-11 TW TW109143935A patent/TWI764429B/en active
- 2020-12-18 KR KR1020200179062A patent/KR102483681B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513895A (en) * | 2002-12-18 | 2004-07-21 | ס�ѻ�ѧ��ҵ��ʽ���� | Aromatic liquid crystal polyester and its film |
| JP2004299216A (en) * | 2003-03-31 | 2004-10-28 | Sumitomo Bakelite Co Ltd | Heat treatment apparatus for film |
| CN104203571A (en) * | 2012-03-30 | 2014-12-10 | 富士胶片株式会社 | Method for producing laminate film containing liquid crystalline compound having high crystallinity |
| JP2019163431A (en) * | 2018-03-20 | 2019-09-26 | 住友化学株式会社 | Liquid crystalline polyester liquid composition, method for producing liquid crystal polyester film, and liquid crystalline polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202124576A (en) | 2021-07-01 |
| TWI764429B (en) | 2022-05-11 |
| KR20210078440A (en) | 2021-06-28 |
| KR102483681B1 (en) | 2022-12-30 |
| JP2021095520A (en) | 2021-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI468292B (en) | Laminated body and its manufacturing method, laminated circuit board | |
| TWI480311B (en) | Aromatic polyimide film, laminated material and solar cell | |
| KR101844924B1 (en) | Polyimide resin and metal-clad laminate comprising the same | |
| JP5621768B2 (en) | Polyimide films for metallizing, production methods thereof, and metal laminated polyimide films | |
| TWI417323B (en) | Novel polyimide film and usage thereof | |
| JP5444581B2 (en) | Method for producing liquid crystal polyester film | |
| CN112440539A (en) | Laminated film and method for producing the same | |
| KR20080012300A (en) | Adhesive sheet, metal-laminated sheet and printed wiring board | |
| JP5699454B2 (en) | Film having negative coefficient of thermal expansion, method for producing the same, and laminate | |
| CN112980004A (en) | Liquid composition, liquid crystal polyester film, method for producing liquid crystal polyester film, laminated film, and method for producing laminated film | |
| KR20120101503A (en) | Method for producing a polyimide film, and polyimide film | |
| JP2009056771A (en) | Metal/resin composite, circuit substrate and laminated circuit substrate | |
| KR101027203B1 (en) | Continuous production method for both-sided conductor polyimide laminate | |
| KR20160149171A (en) | Polyimide precursor composition and use thereof and polyimide made therefrom | |
| WO2010119907A1 (en) | Polyimide film, method for producing same, and metal-laminated polyimide film | |
| JP2008302514A (en) | Flexible laminated substrate and its production method | |
| JP2005194318A (en) | Polyimide film | |
| JP3912610B2 (en) | Metalized polyimide film, metalized polyimide film roll, and flexible printed wiring board | |
| TWI387406B (en) | Flexible metal foil laminated board | |
| JP6929555B2 (en) | Manufacturing method of metal-clad laminate | |
| JP4872466B2 (en) | Metallized polyimide film and method for producing the same | |
| JP3912611B2 (en) | Metalized polyimide film, metalized polyimide film roll, and flexible printed wiring board | |
| JP2009029934A (en) | Process for producing resin film and process for producing electrically conductive layer laminated resin film | |
| JP7398771B2 (en) | Metal-clad laminate and method for manufacturing metal-clad laminate | |
| JP2022190826A (en) | Liquid composition, liquid crystal polyester film and method for producing the liquid crystal polyester film, and laminated film and method for producing the laminated film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 40054575 Country of ref document: HK |
|
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210618 |