CN112745676A - Resin composition, resin film, and metal-clad laminate - Google Patents
Resin composition, resin film, and metal-clad laminate Download PDFInfo
- Publication number
- CN112745676A CN112745676A CN202011170486.5A CN202011170486A CN112745676A CN 112745676 A CN112745676 A CN 112745676A CN 202011170486 A CN202011170486 A CN 202011170486A CN 112745676 A CN112745676 A CN 112745676A
- Authority
- CN
- China
- Prior art keywords
- spherical silica
- resin film
- range
- polyimide
- 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.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 129
- 229920005989 resin Polymers 0.000 title claims abstract description 129
- 239000011342 resin composition Substances 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229920001721 polyimide Polymers 0.000 claims abstract description 67
- 239000004642 Polyimide Substances 0.000 claims abstract description 60
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 43
- 238000005259 measurement Methods 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000000790 scattering method Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 94
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 239000002356 single layer Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 abstract description 21
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 21
- 238000007561 laser diffraction method Methods 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011889 copper foil Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- -1 TPE-R) Chemical compound 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IFYXKXOINSPAJQ-UHFFFAOYSA-N 4-(4-aminophenyl)-5,5-bis(trifluoromethyl)cyclohexa-1,3-dien-1-amine Chemical compound FC(F)(F)C1(C(F)(F)F)CC(N)=CC=C1C1=CC=C(N)C=C1 IFYXKXOINSPAJQ-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- UNHOIPHYTXGJQL-UHFFFAOYSA-N 4-(4-propylphenyl)aniline Chemical compound C1=CC(CCC)=CC=C1C1=CC=C(N)C=C1 UNHOIPHYTXGJQL-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 238000007731 hot pressing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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Abstract
The invention provides a resin composition, a resin film and a metal-clad laminate, which can improve dielectric properties without impairing mechanical properties such as bendability due to the addition of an inorganic filler. A resin composition comprising a polyamic acid or polyimide and spherical silica particles, wherein the spherical silica particles obtained by volume-based particle size distribution measurement by a laser diffraction/scattering method have a frequency distribution curve satisfying: a) average particle diameter D with an integrated value of 50%50In the range of 9.0 to 12.0 μm, b) a particle diameter D with an integrated value of 90%90In the range of 15 to 20 μm, c) a particle diameter D at which the integrated value becomes 100%100Is 25 μm or less, and the content of the spherical silica particles is in the range of 20 to 65 vol% based on the polyamic acid or polyimide.
Description
Technical Field
The present invention relates to a resin composition containing spherical silica particles as an inorganic filler, a resin film using the resin composition, and a metal-clad laminate.
Background
In recent years, there has been an increasing demand for downsizing and weight reduction of electronic devices, as represented by mobile phones, Light Emitting Diode (LED) lighting fixtures, and related parts around automobile engines. Along with this, flexible circuit boards, which are advantageous for downsizing and weight reduction of devices, are widely used in the field of electronics. Among them, a flexible circuit board having an insulating layer made of polyimide is widely used because of its excellent heat resistance, chemical resistance, and the like.
On the other hand, with the improvement in performance and functionality of electric and/or electronic devices, the rapid transmission of information has been progressing. Therefore, parts or members for electric and/or electronic equipment are also required to cope with high-speed transmission. In order to provide resin materials used for such applications with electrical characteristics corresponding to high-speed transmission, attempts have been made to reduce the dielectric constant and the dielectric loss tangent. As one example, a resin-coated copper foil having a resin layer containing a resin mixture containing an epoxy resin, a polyimide resin, and an aromatic polyamide resin, an imidazole-based curing catalyst, and an inorganic filler and having dielectric characteristics corresponding to high-frequency transmission has been proposed (for example, patent document 1).
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication WO2017/014079
Disclosure of Invention
[ problems to be solved by the invention ]
Patent document 1 describes that the dielectric loss tangent of the resin layer can be reduced by adding an inorganic filler such as silica, but the specific structure of the inorganic filler suitable for the above purpose has not been studied in detail. Further, the addition of the inorganic filler has a problem of bringing about an influence of reducing the bendability of the resin film.
The present invention aims to provide a resin composition and a resin film which can improve dielectric properties without impairing mechanical properties such as bendability by adding an inorganic filler.
[ means for solving problems ]
The resin composition of the present invention is a resin composition containing polyamic acid or polyimide and spherical silica particles. The resin composition of the present invention has a frequency distribution curve of the spherical silica particles obtained by volume-based particle size distribution measurement by a laser diffraction scattering method, which satisfies the following conditions a to c, and the content of the spherical silica particles is in a range of 20 to 65 vol% with respect to the polyamic acid or the polyimide.
a) Average particle diameter D with an integrated value of 50%50Is in the range of 9.0 to 12.0 μm.
b) Particle diameter D with an integrated value of 90%90Is in the range of 15 to 20 μm.
c) Particle diameter D with an integrated value of 100%100Is 25 μm or less.
The spherical silica particles in the resin composition of the present invention may further satisfy the following condition d.
d) The filter has a frequency maximum value F1 and a frequency maximum value F2, wherein the F1 is in the range of 9.0 to 14.0 μm, and the F2 is in the range of 0.5 to 3.0 μm.
The spherical silica particles in the resin composition of the present invention may further satisfy the following condition e.
e) The frequency maximum value F1 and the frequency maximum value F2 are included, and the ratio of F1 to F2 (F1/F2) is in the range of 3 to 28.
The resin film of the present invention is a resin film having a single layer or a plurality of polyimide layers, at least one of the polyimide layers being a spherical silica-containing polyimide layer containing a cured product of the resin composition, the spherical silica-containing polyimide layer having a thickness in a range of 5 to 150 μm.
In the resin film of the present invention, the spherical silica particles have a particle diameter D relative to the thickness of the spherical silica-containing polyimide layer100Can be in the range of 0.05 to 0.7.
The thickness of the resin film of the present invention may be in the range of 5 to 150 μm, and the ratio of the thickness of the spherical silica-containing polyimide layer may be 50% or more.
The metal-clad laminate of the present invention is a metal-clad laminate comprising an insulating resin layer containing the resin film, and a metal layer laminated on at least one surface of the insulating resin layer.
[ Effect of the invention ]
The resin composition of the present invention contains spherical silica particles having a specific particle size distribution represented by the conditions a to c, and thus can improve dielectric properties without reducing mechanical properties such as bendability. Therefore, in the electric and/or electronic device or electronic part using the resin composition of the present invention, high-speed transmission can be coped with, and reliability can be ensured.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
[ resin composition ]
The resin composition according to one embodiment of the present invention is a resin composition containing polyamic acid or polyimide and spherical silica particles as an inorganic filler. The resin composition may be a varnish (resin solution) containing a polyamic acid, or a polyimide solution containing a solvent-soluble polyimide.
< Polyamic acid or polyimide >
The polyimide is generally represented by the following general formula (1). Such a polyimide can be produced by a conventional method of polymerizing a diamine component and an acid dianhydride component in a substantially equimolar amount in an organic polar solvent. In this case, the molar ratio of the acid dianhydride component to the diamine component can be adjusted to a desired range of viscosity, and is preferably set to a range of, for example, 0.980 to 1.03.
[ solution 1]
Here, Ar1Is a tetravalent organic radical having more than one aromatic ring, Ar2Is a divalent organic group having one or more aromatic rings. And, Ar1It can be said to be a residue of acid dianhydride, Ar2It can be said to be the residue of a diamine. N represents the number of repetitions of the structural unit of the general formula (1), and is 200 or more, preferably 300 to 1000.
The acid dianhydride is preferably, for example, a dianhydride consisting of O (OC)2-Ar1-(CO)2Examples of the aromatic tetracarboxylic dianhydride represented by O include those in which the following aromatic acid anhydride residue is provided as Ar1Acid dianhydride of (1).
[ solution 2]
The acid dianhydride may be used alone or in combination of two or more. Among these, it is preferable to use one selected from pyromellitic dianhydride (PMDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), 3',4,4' -benzophenonetetracarboxylic dianhydride (3,3',4,4' -benzophenonetetracarboxylic dianhydride), 3',4,4' -diphenylsulfonetetracarboxylic dianhydride (DSDA), and 4,4' -Oxydiphthalic Dianhydride (ODPA).
The diamine is preferably, for example, H2N-Ar2-NH2As the aromatic diamine, the following aromatic diamine residue can be exemplified as Ar2The aromatic diamine of (4).
[ solution 3]
Among these diamines, diaminodiphenyl ether (DAPE), 2'-dimethyl-4,4' -diaminobiphenyl (2,2'-dimethyl-4,4' -diaminodiphenyl, m-TB), p-phenylenediamine (p-PDA), 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene, TPE-R), 1,3-bis (3-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene, APB), 1,4-bis (4-aminophenoxy) benzene (1,4-bis (4-aminophenoxy) benzene, TPE-Q), 2-bis [4- (4-aminophenoxy) phenyl ] propane (2), 2-bis [4- (4-amino phenyl) phenyl ] propane, BAPP), and 2,2-bis (trifluoromethyl) benzidine (2,2-bis (trifluoromethyl) benzidine, TFMB) are preferred.
Polyimide can be produced by reacting an acid dianhydride with a diamine compound in a solvent to produce a polyamic acid as a precursor, and then heating the polyamic acid for ring closure (imidization). For example, the polyamic acid is obtained by dissolving an acid dianhydride and a diamine compound in an organic solvent in approximately equimolar amounts, and stirring the solution at a temperature in the range of 0 to 100 ℃ for 30 minutes to 24 hours to effect polymerization. During the reaction, the reaction components are dissolved in the organic solvent so that the produced precursor is present in an amount of 5 to 30 wt%, preferably 10 to 20 wt%. Examples of the organic solvent used in the polymerization reaction include: n, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, Dimethylsulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cresol, and the like. Two or more of these solvents may be used in combination, and an aromatic hydrocarbon such as xylene or toluene may be used in combination. The amount of the organic solvent used is not particularly limited, but is preferably adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 30 wt%.
The polyamic acid synthesized is generally advantageously used as a reaction vehicle solution, which can be concentrated, diluted, or replaced with other organic vehicles as needed to form a resin composition. The method for imidizing the polyamic acid is not particularly limited, and for example, a heat treatment in which heating is performed in the solvent at a temperature in the range of 80 to 400 ℃ for 1 to 24 hours is preferably employed.
< spherical silica particle >
The spherical silica particles are silica particles having a shape close to a sphere and a ratio of an average major axis to an average minor axis of 1 or close to 1. The spherical silica particles have a frequency distribution curve obtained by volume-based particle size distribution measurement by a laser diffraction scattering method, and satisfy the following conditions a to c.
a) Average particle diameter D with an integrated value of 50%50Is in the range of 9.0 to 12.0 μm.
b) Particle diameter D with an integrated value of 90%90Is in the range of 15 to 20 μm.
c) Particle diameter D with an integrated value of 100%100Is 25 μm or less.
With respect to the condition a, if the average particle diameter D of the spherical silica particles50If the thickness is less than 9.0. mu.m, the effect of improving the dielectric characteristics is small. On the other hand, when the average particle diameter D is50When the thickness exceeds 12.0. mu.m, the filling becomes difficult, and the mechanical properties such as the bending property is lowered when the resin film is formed, are difficult to maintain.
In the conditions b and c, the ratio of spherical silica particles having a particle diameter of 15 to 25 μm is suppressed, and the maximum particle diameter is 25 μm or less to exclude coarse particles, so that the bending property in forming the resin film can be improved.
The spherical silica particles preferably further satisfy the following conditions d and e.
d) The frequency maximum value F1 and the frequency maximum value F2 were found, F1 was in the range of 9.0 to 14.0. mu.m, and F2 was in the range of 0.5 to 3.0. mu.m.
e) The frequency maximum value F1 and the frequency maximum values F2, F1 and F2 have a ratio (F1/F2) within a range of 3 to 28.
In the conditions d and e, by containing a certain amount of small spherical silica having a particle diameter in the range of 0.5 to 3.0 μm in the spherical silica particles, it is possible to further improve the dielectric characteristics while suppressing a decrease in bendability when forming a film.
Further, the spherical silica particles can be used by appropriately selecting commercially available ones. For example, spherical cristobalite (cristobalite) silica powder (trade name: CR10-20, manufactured by Nippon iron chemical & materials Co., Ltd.), spherical amorphous silica powder (trade name: SC70-2, manufactured by Nippon iron chemical & materials Co., Ltd.) and the like can be preferably used. Two or more of these may be used in combination.
< composition of blending >
The content of the spherical silica particles in the resin composition is in the range of 20 to 65 vol%, preferably 30 to 60 vol%, with respect to the polyamic acid or polyimide. If the content of the spherical silica particles is less than 20% by volume, the effect of lowering the dielectric loss tangent cannot be sufficiently obtained. When the content of the spherical silica particles exceeds 65% by volume, the spherical silica particles become brittle when a resin film is formed, and the bending property is lowered.
The resin composition of the present embodiment may contain an organic solvent. Examples of the organic solvent include: n, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cresol, and the like. Two or more of these solvents may be used in combination, and an aromatic hydrocarbon such as xylene or toluene may be used in combination. The content of the organic solvent is not particularly limited, and is preferably adjusted to a use amount of about 5 to 30 wt% of the concentration of the polyamic acid or polyimide.
Further, the resin composition of the present embodiment may contain an inorganic filler or an organic filler other than the spherical silica particles having the above conditions a to c as necessary within a range not to impair the effects of the present invention. Specific examples thereof include: inorganic fillers such as silica particles, alumina, magnesia, beryllia, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, and calcium fluoride, and organic fillers such as fluorine-based polymer particles and liquid crystal polymer particles, which do not satisfy the above conditions a to c. These may be used alone or in combination of two or more. Further, as other optional components, plasticizers, curing accelerators, coupling agents, fillers, pigments, flame retardants and the like may be suitably blended as required.
< viscosity >
The viscosity of the resin composition is preferably in the range of 5000cps to 100000cps, more preferably in the range of 10000cps to 50000cps, for example, as a viscosity range in which handling properties in coating the resin composition are improved and a coating film having a uniform thickness can be easily formed. If the viscosity is out of the range, defects such as uneven thickness and streaks are likely to occur in the film during coating work using a coater or the like.
< preparation of resin composition >
In the preparation of the resin composition, for example, spherical silica particles may be directly prepared in a resin solution of polyamic acid. Alternatively, in consideration of the dispersibility of the filler, spherical silica particles may be prepared in advance in a reaction solvent into which either one of an acid dianhydride component and a diamine component, which are raw materials of a polyamic acid, is charged, and then the other raw material may be charged under stirring to carry out polymerization. In either method, the spherical silica particles may be charged all at once, or may be added in portions. In addition, the raw materials may be put together or may be mixed little by little.
[ resin film ]
The resin film of the present embodiment may be a resin film having a single layer or a plurality of polyimide layers, and at least one of the polyimide layers may be a spherical silica-containing polyimide layer containing a cured product of the resin composition.
In the resin film, the thickness of the spherical silica-containing polyimide layer formed from the resin composition is, for example, preferably in the range of 5 to 150 μm, and more preferably in the range of 45 to 100 μm. In addition, the particle diameter D of the spherical silica particles is relative to the thickness of the polyimide layer containing the spherical silica100Preferably in the range of 0.05 to 0.7. Particle diameter D of spherical silica particles100If the thickness of the polyimide layer containing spherical silica is less than 0.05, the effect of improving the dielectric properties may be insufficient, and if the thickness exceeds 0.7, the smoothness of the surface of the polyimide layer containing spherical silica may be impaired, and the bendability may be reduced when a resin film is formed.
The thickness of the entire resin film is, for example, preferably in the range of 5 to 150. mu.m, and more preferably in the range of 45 to 80 μm. If the thickness of the resin film is less than 5 μm, defects such as wrinkles in the metal foil are likely to occur in the conveying step in the production of the metal-clad laminate. Conversely, if the thickness of the resin film exceeds 100 μm, the resin film tends to have a disadvantage in terms of, for example, a decrease in the bendability of the resin film.
The ratio of the thickness of the polyimide layer containing spherical silica to the thickness of the entire resin film is preferably 50% or more. When the ratio of the thickness of the polyimide layer containing spherical silica to the entire thickness of the resin film is less than 50%, the effect of improving the dielectric characteristics cannot be sufficiently obtained.
The method for forming the spherical silica-containing polyimide layer may be any conventional method without particular limitation. The most representative example of which is shown here.
First, a resin composition is directly cast-coated onto an arbitrary supporting substrate to form a coating film. Then, the solvent is dried to some extent at a temperature of 150 ℃ or lower to remove the coating film. When the resin composition contains a polyamic acid, the coating film is then subjected to a heat treatment at a temperature of 100 to 400 ℃, preferably 130 to 360 ℃, for about 5 to 30 minutes in order to further imidize the film. This allows the formation of a polyimide layer containing spherical silica on the support substrate. In the case of providing two or more polyimide layers, the resin solution of the first polyamic acid is applied and dried, and then the resin solution of the second polyamic acid is applied and dried. Thereafter, similarly, the resin solution of polyamic acid is applied and dried sequentially as many times as necessary like the resin solution of third polyamic acid and the resin solution of second polyamic acid. Then, the imidization is preferably carried out by performing a heat treatment at a temperature of 100 to 400 ℃ for about 5 to 30 minutes. If the temperature of the heat treatment is lower than 100 ℃, the dehydration ring-closure reaction of the polyimide may not sufficiently proceed, whereas if it exceeds 400 ℃, the polyimide layer may deteriorate.
Another example of forming a polyimide layer containing spherical silica is described.
First, the resin composition is cast and applied to an arbitrary supporting base material to be formed into a film shape. The film-shaped product is dried by heating on a support base material to prepare a gel film having self-supporting properties. When the resin composition contains polyamic acid after the gel film is peeled from the supporting substrate, the resin composition is further subjected to heat treatment at a high temperature to imidize the resin composition, thereby producing a polyimide resin film.
The support substrate for forming the polyimide layer containing spherical silica is not particularly limited, and any substrate can be used. In addition, when forming a resin film, it is not necessary to form a resin film in which imidization is completely completed on a support substrate. For example, the resin film in the state of a polyimide precursor in a semi-cured state may be separated from the supporting substrate by a method such as peeling, and imidization may be completed after the separation to obtain the resin film.
The resin film may include only a polyimide layer containing an inorganic filler such as spherical silica particles (including the spherical silica-containing polyimide layer), or may have a polyimide layer containing no inorganic filler. When the resin film has a multilayer laminated structure, it is preferable that all layers contain an inorganic filler in view of improvement of dielectric characteristics. In particular, when the adjacent layer of the polyimide layer containing an inorganic filler is a layer containing no inorganic filler or a layer containing a low content of the inorganic filler, the inorganic filler can be prevented from slipping off during processing. When the polyimide layer does not contain an inorganic filler, the thickness of the polyimide layer is preferably in the range of 1/100 to 1/2, preferably 1/20 to 1/3, of the polyimide layer containing an inorganic filler. In the case of having a polyimide layer containing no inorganic filler, adhesion between the metal layer and the insulating resin layer is improved when the polyimide layer is in contact with the metal layer.
The Coefficient of Thermal Expansion (CTE) of the resin film is not particularly limited, and is preferably 5X 10-6/K~40×10-6In the range of/K (5ppm/K to 40ppm/K), more preferably 10X 10-6/K~35×10-6A value of/K (10ppm/K to 35 ppm/K). If the coefficient of thermal expansion of the resin film is less than 5X 10-6and/K, curling is likely to occur after the metal-clad laminate is produced, and handling properties are poor. On the other hand, if the coefficient of thermal expansion of the resin film exceeds 40X 10-6The material/K tends to have poor dimensional stability as an electronic material such as a flexible substrate and to have low heat resistance.
< dielectric loss tangent >
When the resin film is used as an insulating resin layer of a circuit board, for example, in order to reduce dielectric loss at the time of high-frequency signal transmission, the dielectric loss tangent (Tan δ) at 10GHz as measured by a Split Post Dielectric Resonator (SPDR) is preferably 0.005 or less, more preferably 0.004 or less, as the entire film. In order to improve the transmission loss of the circuit board, it is particularly important to control the dielectric loss tangent of the insulating resin layer, and the effect of reducing the transmission loss is increased by setting the dielectric loss tangent within the above range. Therefore, when the resin film is applied to, for example, an insulating resin layer of a high-frequency circuit board, transmission loss can be reduced efficiently. When the dielectric loss tangent at 10GHz exceeds 0.005, when the resin film is applied to an insulating resin layer of a circuit board, problems such as an increase in loss of an electric signal on a transmission path of a high-frequency signal tend to occur. The lower limit of the dielectric loss tangent at 10GHz is not particularly limited, but physical properties should be controlled when the resin film is applied to an insulating resin layer of a circuit board.
< relative dielectric constant >
When the resin film is applied to, for example, an insulating resin layer of a circuit board, the relative dielectric constant of the entire film at 3GHz to 20GHz is preferably 4.0 or less in order to ensure impedance matching. If the relative dielectric constant at 3GHz to 20GHz exceeds 4.0, the dielectric loss is deteriorated when the resin film is applied to an insulating resin layer of a circuit board, and a problem such as an increase in loss of an electric signal on a transmission path of a high-frequency signal is likely to occur.
< Metal-clad laminate >
The metal-clad laminate of the present embodiment is a metal-clad laminate including an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, at least one layer of the insulating resin layer including the resin film. The metal-clad laminate may be a single-sided metal-clad laminate having a metal layer only on one side of the insulating resin layer, or may be a double-sided metal-clad laminate having metal layers on both sides of the insulating resin layer.
The metal-clad laminate of the present embodiment does not exclude the use of an adhesive for bonding a polyimide layer containing an inorganic filler and a metal foil. In the case where the adhesive layer is interposed between the metal-clad laminates having the metal layers on both surfaces of the insulating resin layer, the thickness of the adhesive layer is preferably less than 30%, more preferably less than 20% of the thickness of the entire insulating resin layer so as not to impair the dielectric characteristics. In the case where the adhesive layer is interposed between the single-sided metal-clad laminate having the metal layer only on one side of the insulating resin layer, the thickness of the adhesive layer is preferably less than 15%, more preferably less than 10% of the thickness of the entire insulating resin layer so as not to impair the dielectric characteristics. The adhesive layer is preferably a polyimide layer because it constitutes a part of the insulating resin layer. From the viewpoint of imparting heat resistance, the glass transition temperature of polyimide, which is a main material of the insulating resin layer, is preferably 300 ℃. The acid dianhydride or diamine component constituting the polyimide can be appropriately selected when the glass transition temperature is 300 ℃ or higher.
Examples of the method for producing a metal-clad laminate in which a resin film is used as an insulating resin layer include a method in which a metal foil is heat-pressed onto a resin film directly or via an optional adhesive, and a method in which a metal layer is formed on a resin film by a method such as metal vapor deposition. The double-sided metal-clad laminate can be obtained, for example, by a method of forming a single-sided metal-clad laminate, then pressing and bonding polyimide layers to each other by hot pressing, a method of pressing and bonding a metal foil to a polyimide layer of a single-sided metal-clad laminate, or the like.
< Metal layer >
The material of the metal layer is not particularly limited, and examples thereof include: copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, alloys of these, and the like. Among them, copper or a copper alloy is particularly preferable. The metal layer may be one containing a metal foil or one formed by vapor deposition of a metal on a film. In addition, in terms of the ability to directly apply the resin composition, a metal foil or a metal plate can be used, and a copper foil or a copper plate is preferred.
The thickness of the metal layer is not particularly limited, and is preferably in the range of 5 μm to 3mm, and more preferably in the range of 12 μm to 1mm, for example, because it is appropriately set according to the purpose of use of the metal-clad laminate. If the thickness of the metal layer is less than 5 μm, defects such as wrinkles may occur during transportation, for example, in the production of the metal-clad laminate. On the other hand, if the thickness of the metal layer exceeds 3mm, the metal layer becomes hard and the workability is deteriorated. The thickness of the metal layer is generally a thick metal layer suitable for applications such as a circuit board for a vehicle, and a thin metal layer suitable for applications such as a circuit board for an LED.
[ examples ]
The following examples are presented to more specifically illustrate the features of the present invention. The scope of the present invention is not limited to the examples. In the following examples, unless otherwise specified, various measurements and evaluations were performed as follows.
[ measurement of viscosity ]
The viscosity of the resin solution was measured at 25 ℃ using an E-type viscometer (product name: DV-II + Pro, manufactured by Brookfield corporation). The rotational speed was set so that the torque was 10% to 90%, and the value at which the viscosity was stable was read after 1 minute passed from the start of the measurement.
[ measurement of relative dielectric constant and dielectric loss tangent ]
< silica particles >
The dielectric constant measuring apparatus manufactured by kanto electronics application and development corporation using the resonance cavity perturbation method was set to the dielectric constant measuring mode: TM101, the relative dielectric constant (. epsilon.) of the silica particles at a frequency of 10GHz1) And dielectric loss tangent (Tan. delta.)1). The sample tube had an inner diameter of 1.68mm, an outer diameter of 2.8mm and a height of 8 cm.
< resin film >
The relative dielectric constant and the dielectric loss tangent were measured by using a vector network analyzer (trade name: vector network analyzer E8363C, manufactured by Agilent) and an SPDR resonator, and the relative dielectric constant (. epsilon.) of the resin film (cured resin film) at a frequency of 10GHz1) And dielectric loss tangent (Tan. delta.)1). The resin film used for the measurement was measured at a temperature: 24 ℃ to 26 ℃ and humidity: standing for 24 hours under the condition of 45-55 percent.
[ method for measuring Coefficient of Thermal Expansion (CTE) ]
A resin film having a size of 3mm × 20mm was heated from 30 ℃ to 265 ℃ at a constant heating rate while applying a load of 5.0g using a thermomechanical analyzer (product name: 4000SA manufactured by Bruker Co., Ltd.), and was held at the above temperature for 10 minutes, and then cooled at a rate of 5 ℃/min to obtain an average thermal expansion coefficient (thermal expansion coefficient) from 200 ℃ to 100 ℃.
[ method of measuring particle diameter ]
The particle size was measured by a laser diffraction/scattering measurement method using a laser particle size analyzer (trade name: laser Sizer 3000, manufactured by Malvern corporation).
[ method of measuring true specific gravity ]
The measurement was carried out by a pycnometer method (liquid phase displacement method) using a continuous automatic powder TRUE density measuring apparatus (Seishin corporation, trade name: AUTO TRUE Denser Mat-7000).
[ evaluation of bendability ]
According to Japanese Industrial Standards (JIS) K5600-1, the center of the long side of a resin film having a size of 5cm × 10cm is uniformly bent in 1 to 2 seconds so as to be wound around a metal rod having a diameter of 5mm Φ, and the resin film is "good" when it is not broken or cracked even when it is bent at 180 °, and "failed" when it is broken or cracked.
The abbreviations used in the synthesis examples, comparative examples and examples represent the following compounds.
And (3) PMDA: pyromellitic dianhydride
BPDA: 3,3',4,4' -biphenyltetracarboxylic dianhydride
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl ] propane
m-TB: 2,2'-dimethyl-4,4' -diaminobiphenyl
DMAc: n, N-dimethyl acetamide
Packing 1: chemical of ferric chloride&Manufactured by materials corporation, trade name: CR10-20 (spherical cristobalite silica powder, spherical shape, silica content: 99.4 wt%, cristobalite phase: 98 wt%, true specific gravity: 2.33, specific surface area: 0.63 m)2/g、D50:10.8μm、D90:16.4μm、D100: particle size of 24.1 μm, frequency maximum value F1: 11.2 μm, frequency maximum F1: particle size of 10.6% frequency maximum F2: 1.0 μm, frequency maximum F2: 1.4%, F1/F2: relative dielectric constant at 11.2, 10 GHz: dielectric loss tangent at 3.16, 10 GHz: 0.0008)
And (3) filler 2: chemical of ferric chloride&Products manufactured by Material Co LtdName: SC70-2 (spherical amorphous silica powder, spherical, silica content: 99.9 wt%, true specific gravity: 2.33, specific surface area: 1.1 m)2/g、D50:11.7μm、D90:16.4μm、D100: particle size of 24.1 μm, frequency maximum value F1: 11.2 μm, frequency maximum F1: particle size of 10.8% frequency maximum F2: 1.5 μm, frequency maximum F2: 1.2%, F1/F2: relative dielectric constant at 7.5, 10 GHz: dielectric loss tangent at 3.08, 10 GHz: 0.0015)
And (3) filler: chemical of ferric chloride&Manufactured by materials corporation, trade name: SP40-10 (spherical amorphous silica powder, spherical, silica content: 99.9 wt%, true specific gravity: 2.21, specific surface area: 8.6 m)2/g、D50:2.5μm、D90:3.6μm、D100: particle size of 7.0 μm, frequency maximum value F1: 2.2 μm, frequency maximum F1: particle size of 9.0% frequency maximum F2: 0.9 μm, frequency maximum F2: 4.3%, F1/F2: relative dielectric constant at 2.4, 10 GHz: dielectric loss tangent at 2.78, 10 GHz: 0.0030)
(Synthesis example 1)
A300 ml separable flask was charged with 21.65g of m-TB (101.66mmol) and 255g of DMAc, and the mixture was stirred at room temperature under a nitrogen stream. After complete dissolution, 17.46g of PMDA (80.03mmol) and 5.90g of BPDA (20.01mmol) were added thereto, and the mixture was stirred at room temperature for 18 hours to obtain a polyamic acid solution A (solid content concentration: 15%). The obtained polyamic acid solution A had a viscosity of 22,400 cps.
(Synthesis example 2)
A300 ml separable flask was charged with 29.21g of BAPP (71.15mmol) and 255g of DMAc, and the mixture was stirred at room temperature under a nitrogen stream. After complete dissolution, 14.74g of PMDA (67.60mmol) and 1.05g of BPDA (3.56mmol) were added thereto, and the mixture was stirred at room temperature for 18 hours to obtain a polyamic acid solution B. The obtained polyamic acid solution B (solid content concentration: 15%) had a viscosity of 21,074 cps.
[ example 1]
70.0g of polyamic acid solution A and 7.8g of filler 1 were mixed and stirred until the same solution was visually observed to prepare polyamic acid solution 1 (viscosity: 24,800cps, content of filler to polyamic acid: 32.6 vol%).
A polyamic acid solution 1 was applied on a copper foil 1 (electrolytic copper foil, thickness: 12 μm), and dried at 130 ℃ for 3 minutes. Thereafter, the metal-clad laminate 1 was prepared by performing a stepwise heat treatment from 155 ℃ to 360 ℃ and imidizing the heat treatment.
The copper foil of the metal-clad laminate 1 was removed by etching to prepare a resin film 1. The resin film 1 (thickness: 46.1 μm) had a relative dielectric constant of 2.78, a dielectric loss tangent of 0.0037, a CTE of 34ppm/K, and good bendability. The evaluation results of the resin film 1 are shown in table 1.
[ example 2]
60.0g of polyamic acid solution A and 20.0g of filler 1 were mixed and stirred until the same solution was visually observed to prepare polyamic acid solution 2 (viscosity: 28,400cps, content of filler to polyamic acid: 59.2 vol%).
A metal-clad laminate 2 and a resin film 2 were prepared in the same manner as in example 1. The resin film 2 (thickness: 78.1 μm) had a relative dielectric constant of 2.71, a dielectric loss tangent of 0.0028, a CTE of 34ppm/K, and good bendability. The evaluation results of the resin film 2 are shown in table 1.
[ example 3]
Polyamic acid solution 3 (viscosity: 23,000cps, content of filler to polyamic acid: 30.0 vol%) was prepared by mixing 58.7g of polyamic acid solution B and 6.1g of filler 1 and stirring until the same solution was visually observed.
A metal-clad laminate 3 and a resin film 3 were prepared in the same manner as in example 1. The resin film 3 (thickness: 51.6 μm) had a relative dielectric constant of 3.04, a dielectric loss tangent of 0.0044 and good bendability. The evaluation results of the resin film 3 are shown in table 1.
[ example 4]
70.0g of polyamic acid solution A and 7.8g of filler 2 were mixed and stirred until the same solution was visually observed to prepare polyamic acid solution 4 (viscosity: 23,600cps, content of filler to polyamic acid: 33.8 vol%).
A metal-clad laminate 4 and a resin film 4 were prepared in the same manner as in example 1. The resin film 4 (thickness: 50.4 μm) had a relative dielectric constant of 2.84, a dielectric loss tangent of 0.0038, a CTE of 28.2ppm/K, and good bendability. The evaluation results of the resin film 4 are shown in table 1.
[ example 5]
A polyamic acid solution 5 (viscosity: 30,100cps, content of filler to polyamic acid: 60.5 vol%) was prepared by mixing 60.0g of polyamic acid solution A and 20.0g of filler 2 and stirring until the same solution was visually observed.
A metal-clad laminate 5 and a resin film 5 were prepared in the same manner as in example 1. The resin film 5 (thickness: 79.3 μm) had a relative dielectric constant of 2.75, a dielectric loss tangent of 0.0028, a CTE of 20.4ppm/K, and good bendability. The evaluation results of the resin film 5 are shown in table 1.
[ example 6]
Polyamic acid solution 6 (viscosity: 23,600cps, content of filler to polyamic acid: 30.0 vol%) was prepared by mixing polyamic acid solution B (56.2 g) and filler 2 (5.5 g) and stirring until the same solution was visually observed.
A metal-clad laminate 6 and a resin film 6 were prepared in the same manner as in example 1. The resin film 6 (thickness: 50.7 μm) had a relative dielectric constant of 3.04, a dielectric loss tangent of 0.0047 and good bendability. The evaluation results of the resin film 6 are shown in table 1.
Comparative example 1
70.0g of polyamic acid solution A was coated on copper foil 1 and dried at 130 ℃ for 3 minutes. Thereafter, the metal-clad laminate 7 was prepared by performing a stepwise heat treatment from 155 ℃ to 360 ℃ and imidizing.
Resin film 7 was prepared by etching and removing the copper foil of metal-clad laminate 7 in the same manner as in example 1. The resin film 7 (thickness: 26.7 μm) had a relative dielectric constant of 3.13, a dielectric loss tangent of 0.0056, a CTE of 21.3ppm/K, and good bendability. The evaluation results of the resin film 7 are shown in table 2.
Comparative example 2
60.0g of polyamic acid solution B was coated on copper foil 1, dried at 90 ℃ for 1 minute, and dried at 130 ℃ for 5 minutes. Thereafter, the metal-clad laminate 8 is prepared by performing a stepwise heat treatment from 155 ℃ to 360 ℃ and imidizing.
Resin film 8 was prepared by etching and removing the copper foil of metal-clad laminate 8 in the same manner as in example 1. The resin film 8 (thickness: 41.4 μm) had a relative dielectric constant of 3.16, a dielectric loss tangent of 0.0062, a CTE of 51.3ppm/K, and good bendability. The evaluation results of the resin film 8 are shown in table 2.
(reference example 1)
Polyamic acid solution 9 was prepared in the same manner as in example 1 except that 55.0g of polyamic acid solution A and 36.3g of filler 1 were mixed.
A polyamic acid solution 9 was applied to the copper foil 1, and a metal-clad laminate 9 was prepared in the same manner as in example 1, followed by preparation of a resin film 9. The resin film 9 (thickness: 117.8 μm) had a relative dielectric constant of 2.56, a dielectric loss tangent of 0.0015, a CTE of 31ppm/K, and a bending property of not sufficient. The evaluation results of the resin film 9 are shown in table 3.
(reference example 2)
Polyamic acid solution 10 was prepared in the same manner as in example 1, except that 55.6g of polyamic acid solution a and 36.3g of filler 2 were mixed.
A polyamic acid solution 10 was applied to the copper foil 1, and a metal-clad laminate 10 was prepared in the same manner as in example 1, followed by preparation of a resin film 10. The resin film 10 (thickness: 116.7 μm) had a relative dielectric constant of 2.75, a dielectric loss tangent of 0.0018, a CTE of 13ppm/K, and a bending property of not good. The evaluation results of the resin film 10 are shown in table 3.
(reference example 3)
Polyamic acid solution 11 was prepared in the same manner as in example 1, except that 56.2g of polyamic acid solution B and 5.5g of filler 3 were mixed.
A polyamic acid solution 11 was applied to a copper foil 1, and a metal-clad laminate 11 was prepared in the same manner as in example 1, followed by preparation of a resin film 11. The resin film 11 (thickness: 45.6 μm) had a relative dielectric constant of 3.25, a dielectric loss tangent of 0.0052, a CTE of 40.9ppm/K, and good bendability. The evaluation results of the resin film 11 are shown in table 3.
[ Table 1]
[ Table 2]
[ Table 3]
The polyimide films of examples 1 to 6 each having an average particle diameter D, as compared with the polyimide films of comparative examples 1 and 2 each not containing silica50The polyimide film containing spherical silica particles of 10 μm or more has a reduced relative dielectric constant and a reduced dielectric loss tangent.
In addition, the polyimide films of reference examples 1 and 2 containing 70 vol% or more of spherical silica particles were inferior in the bendability to those of the examples.
Further, the average particle diameter D was adjusted in comparison with the examples50The polyimide film of reference example 3, which was a spherical silica particle having a size of 2.5 μm, had a high relative dielectric constant and a high dielectric loss tangent, and the effect of improving the dielectric characteristics was small.
The embodiments of the present invention have been described in detail for the purpose of illustration, but the present invention is not limited to the embodiments and can be variously modified.
Claims (7)
1. A resin composition comprising a polyamic acid or polyimide and spherical silica particles, characterized in that:
a frequency distribution curve of the spherical silica particles obtained by volume-based particle size distribution measurement by a laser diffraction scattering method satisfies the following conditions a to c;
a) average particle diameter D with an integrated value of 50%50Is in the range of 9.0 to 12.0 μm;
b) particle diameter D with an integrated value of 90%90Is in the range of 15-20 μm;
c) particle diameter D with an integrated value of 100%100Is less than 25 μm;
the content of the spherical silica particles is in the range of 20 to 65 vol% with respect to the polyamic acid or the polyimide.
2. The resin composition according to claim 1, characterized in that:
the spherical silica particles further satisfy the following condition d;
d) the filter has a frequency maximum value F1 and a frequency maximum value F2, wherein the F1 is in the range of 9.0 to 14.0 μm, and the F2 is in the range of 0.5 to 3.0 μm.
3. The resin composition according to claim 1 or 2, characterized in that:
the spherical silica particles further satisfy the following condition e;
e) the frequency maximum value F1 and the frequency maximum value F2 are included, and the ratio of F1 to F2 (F1/F2) is in the range of 3 to 28.
4. A resin film having a single layer or a plurality of polyimide layers, the resin film being characterized in that:
at least one layer of the polyimide layer is a spherical silica-containing polyimide layer comprising a cured product of the resin composition according to any one of claims 1 to 3, the spherical silica-containing polyimide layer having a thickness in the range of 5 μm to 150 μm.
5. The resin film according to claim 4, wherein: the particle diameter D of the spherical silica particles with respect to the thickness of the spherical silica-containing polyimide layer100In the range of 0.05 to 0.7And (4) the following steps.
6. The resin film according to claim 4 or 5, characterized in that: the thickness is in the range of 5-150 μm, and the proportion of the thickness of the polyimide layer containing spherical silica is 50% or more.
7. A metal clad laminate comprising an insulating resin layer, and a metal layer laminated on at least one side of the insulating resin layer, characterized in that:
the insulating resin layer comprises the resin film according to any one of claims 4 to 6.
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CN102149542A (en) * | 2008-09-08 | 2011-08-10 | 新日铁化学株式会社 | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate and method for producing same |
KR20150077317A (en) * | 2013-12-27 | 2015-07-07 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Polyamic acid composition, polymide, resin film and metal-clad laminate |
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JP2002329940A (en) * | 2001-04-27 | 2002-11-15 | Toray Ind Inc | Insulation material for high frequency circuit board and high frequency circuit board using the same |
JP2005171209A (en) * | 2003-12-15 | 2005-06-30 | Toyota Motor Corp | Filler-containing resin composition and its production method |
JP2009096192A (en) * | 2007-09-28 | 2009-05-07 | Nippon Steel Chem Co Ltd | Laminated body for thermally-conductive flexible boards, and thermally-conductive polyimide film |
CN102149542A (en) * | 2008-09-08 | 2011-08-10 | 新日铁化学株式会社 | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate and method for producing same |
KR20150077317A (en) * | 2013-12-27 | 2015-07-07 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Polyamic acid composition, polymide, resin film and metal-clad laminate |
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