CN113045895A - Resin composition, resin film, and metal-clad laminate - Google Patents
Resin composition, resin film, and metal-clad laminate Download PDFInfo
- Publication number
- CN113045895A CN113045895A CN202011446201.6A CN202011446201A CN113045895A CN 113045895 A CN113045895 A CN 113045895A CN 202011446201 A CN202011446201 A CN 202011446201A CN 113045895 A CN113045895 A CN 113045895A
- Authority
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- China
- Prior art keywords
- resin film
- polyimide
- silica particles
- resin
- 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.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 155
- 239000011347 resin Substances 0.000 title claims abstract description 155
- 239000011342 resin composition Substances 0.000 title claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 151
- 229920001721 polyimide Polymers 0.000 claims abstract description 87
- 239000004642 Polyimide Substances 0.000 claims abstract description 84
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 239000010453 quartz Substances 0.000 claims abstract description 9
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 238000001228 spectrum Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 113
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 35
- 235000012239 silicon dioxide Nutrition 0.000 claims description 31
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 23
- 238000005259 measurement Methods 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 4
- 238000000790 scattering method Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 229910016523 CuKa Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 29
- 239000000945 filler Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
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- 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
- 239000011256 inorganic filler Substances 0.000 description 13
- 229910003475 inorganic filler Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
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- 239000000463 material Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 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
- 239000011888 foil Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 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
- 239000002131 composite material Substances 0.000 description 5
- 229920006259 thermoplastic polyimide Polymers 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
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 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
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000003431 cross linking reagent Substances 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
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 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
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- 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
-
- 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
- B32B27/28—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
-
- 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
Abstract
The invention provides a resin composition, a resin film and a metal-clad laminate, which can be used for high frequency of electronic devices by further improving the dielectric properties of the resin film using polyimide as a raw material. The resin composition comprisesComprises the following steps: the resin composition comprises a solid component of an organic compound including polyamic acid or polyimide, and silica particles, wherein the content of the silica particles is within a range of 10 to 85 wt% relative to the total amount of the solid component and the total amount of the silica particles, and the total area of peaks derived from a cristobalite crystal phase and a quartz crystal phase, which are in a range of 10 to 90 DEG 2 theta in an X-ray diffraction analysis spectrum of CuKa rays, is relative to the total area of peaks derived from SiO2The proportion of all peak areas of (a) is 20% by weight or more.
Description
Technical Field
The present invention relates to a resin composition, a resin film, and a metal-clad laminate which are useful as, for example, a material for a circuit board.
Background
In recent years, as electronic devices have been reduced in size, weight, and space, Flexible Printed Circuit (FPC) boards have been increasingly used, which are thin and lightweight. Since FPCs can be mounted in a limited space in a three-dimensional and high-density manner, their applications are expanding to components such as wiring, cables, and connectors of movable parts of electronic devices. In addition to these, communication equipment is becoming faster and the performance of the equipment is becoming higher, and an FPC corresponding to a high-frequency transmission signal for realizing a high transmission speed is also required.
As a problem when transmitting a high-frequency signal, there is a transmission loss in a signal transmission path. If the transmission loss is large, problems such as electrical signal loss and signal delay occur. In order to cope with the increase in frequency of FPCs, it is important to reduce the transmission loss due to the reduction in dielectric constant and dielectric loss tangent of the insulating resin layer. Therefore, in FPCs for high frequency signals, a liquid crystal polymer or a fluorine-based resin having a low dielectric constant and a low dielectric loss tangent is used as an insulating resin layer. However, although the liquid crystal polymer has excellent dielectric characteristics, there is room for improvement in heat resistance and adhesion to metal foil, and the fluorine-based resin has a high thermal expansion coefficient, and therefore, the liquid crystal polymer is not excellent in handling properties.
Polyimide is also used as an insulating resin having excellent heat resistance and adhesion to a metal foil. However, polyimide generally has inferior dielectric characteristics compared to liquid crystal polymers or fluorine-based resins. As a method for reducing the dielectric constant of aromatic polyimide, there is a method of incorporating an aliphatic structure into a resin skeleton. However, the advantage of incorporating an aliphatic structure into the resin skeleton is often in a trade-off relationship with the required properties of the FPC, such as heat resistance and dimensional stability. As another method, when a special monomer or an expensive fluorine-based monomer is used, various obstacles are present in terms of cost and productivity in order to realize low dielectric constant while maintaining excellent heat resistance and required characteristics of FPC only with the polyimide skeleton.
Therefore, a method of improving the characteristics by compounding a resin and a dissimilar material is known. For example, patent document 1 reports a polyimide composition having excellent thermal conductivity, which is obtained by compounding a specific polyimide with a powder of aluminum nitride or silicon nitride.
In addition, in patent document 2, the occurrence of warpage or cracks in the semiconductor package can be suppressed by adding cristobalite silica to the epoxy resin.
Patent document 3 proposes a resin film having a low dielectric loss tangent and low thermal expansion, which is obtained by combining amorphous silica, a thermosetting polyimide resin composed of bismaleimide, and an elastomer, and is effective for improving dielectric characteristics and for making a composite. Patent document 4 discloses a method for producing a low dielectric polyimide film in which polyimide and fluororesin particles are combined.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent No. 3551687 publication
[ patent document 2] Japanese patent laid-open publication No. 2019-
[ patent document 3] Japanese patent laid-open publication No. 2018-12747
[ patent document 4] Japanese patent No. 6387181 publication
Disclosure of Invention
[ problems to be solved by the invention ]
As described above, development of a polyimide that realizes low dielectric constant while maintaining characteristics such as high heat resistance and excellent adhesion has been desired. However, patent document 3 is limited to thermosetting resins, and has a problem in terms of adhesion strength when the resin is multilayered. Patent document 4 has a problem that the thermal expansion coefficient of the composite material is increased by compounding the composite material with a relatively expensive fluororesin filler.
Further, in the composite of the prior art, the composition of the filler is emphasized, and the crystal structure thereof is hardly mentioned.
Accordingly, an object of the present invention is to provide a resin composition and a resin film which can respond to higher frequencies of electronic devices by further improving the dielectric characteristics of polyimide.
[ means for solving problems ]
The present inventors have found the following findings: in the composite formation of a polyimide resin and silica particles, when silica particles having a higher proportion of a cristobalite phase are used as the silica particles than amorphous silica, the dielectric characteristics are improved, and the present invention has been completed.
That is, the resin composition of the present invention contains: a solid component comprising an organic compound of polyamic acid or polyimide, and silica particles,
the content of the silica particles is within a range of 10 to 85 wt% (in terms of polyamic acid converted to imidized polyimide) with respect to the total amount of the solid component and the total amount of the silica particles,
the total area of peaks derived from the cristobalite crystal phase and the quartz crystal phase in the range of 10 ° to 90 ° in the X-ray diffraction spectrum of CuK α rays is determined based on the SiO-based peak area2The proportion of all peak areas of (a) is 20% by weight or more.
The resin composition of the present invention has a median particle diameter D in a frequency distribution curve of the silica particles obtained by volume-based particle size distribution measurement by a laser diffraction scattering method50May be in the range of 6 to 20 μm.
In the resin composition of the present invention, 90% by weight or more of the particles having a particle diameter of 3 μm or more in the silica particles may have a circularity of 0.7 or more.
In the resin composition of the present invention, 90% by weight or more of the silica particles may have a true specific gravity of 2.3 or more.
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 crystalline silica-containing polyimide layer formed of any of the resin compositions, the crystalline silica-containing polyimide layer having a thickness in a range of 15 μm to 200 μm.
The ratio of the thickness of the crystalline silica-containing polyimide layer in the resin film of the present invention to the entire thickness of the resin film may be 50% or more.
The resin film of the present invention may have a relative permittivity of 3.1 or less at a frequency of 3GHz to 20GHz as measured by a split post-dielectric resonator (SPDR).
The resin film of the present invention may have a dielectric loss tangent of 0.005 or less at a frequency of 3GHz to 20GHz when measured by a post-split dielectric resonator (SPDR).
The resin film of the present invention may have a thermal expansion coefficient of 50ppm/K or less.
The metal-clad laminate of the present invention comprises an insulating resin layer, and a metal layer laminated on at least one surface of the insulating resin layer, wherein at least one layer of the insulating resin layer contains any one of the resin films.
[ Effect of the invention ]
The resin composition of the present invention has excellent dielectric properties because it contains silica particles having a specific crystal structure in addition to the heat resistance inherent to polyimide. Therefore, the resin composition and the resin film of the present invention are particularly suitable for use as a substrate material for an electronic device requiring high-speed signal transmission, such as an FPC. Specifically, the present invention is suitable for applications such as an insulating resin layer for an FPC of a mobile device such as a smartphone that handles high-frequency signals, and an insulating resin layer for an FPC mounted on a vehicle that requires heat resistance.
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 a solid component of an organic compound including polyamic acid or polyimide and silica particles,
the content of the silica particles is within a range of 10 to 85 wt% based on the total amount of the solid components and the total amount of the silica particles,
the total area of peaks derived from the cristobalite crystal phase and the quartz crystal phase in the range of 10 ° to 90 ° in the X-ray diffraction spectrum of CuK α rays is determined based on the SiO-based peak area2The proportion of all peak areas of (a) is 20% by weight or more. The resin composition may be a varnish (resin solution) containing a polyamic acid, or a polyimide solution containing a solvent-soluble polyimide.
[ solid content of organic Compound ]
The solid content of the organic compound means a solid content remaining after the solvent and the inorganic solid content are removed from the resin composition. That is, the solid component of the organic compound may contain polyamic acid or polyimide, and as an optional component, a resin other than polyimide, a crosslinking agent, an organic filler, a plasticizer, a curing accelerator, a coupling agent, an organic pigment, an organic flame retardant, a non-volatile organic compound such as a filler, and the like may be contained. Examples of the resin other than polyimide include: epoxy resins, fluorine resins, olefin resins, polyether resins, polyester resins, and the like. Examples of the crosslinking agent include an amino compound (crosslinking-forming amino compound) having at least two primary amino groups as functional groups, which will be described later. Examples of the organic filler include: liquid crystal polymer particles, fluorine-based polymer particles, polyether-based resin particles, olefin-based resin particles, and the like.
The content of the polyamic acid or polyimide in the solid content of the organic compound is preferably 60% by weight or more, more preferably 70% by weight or more, and most preferably 80% by weight or more. If the content of the polyamic acid or polyimide is less than 60% by weight, the toughness of the resin is lowered, and the film holding property when a resin film is formed is lowered. In the case of polyamic acid, the weight ratio is calculated in terms of imidized 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 in order to set the viscosity, and the range is preferably set to a molar ratio in the range of 0.98 to 1.03, for example.
[ 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 72 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.
The polyimide may be a thermoplastic polyimide or a thermosetting polyimide. The "thermoplastic polyimide" is generally a polyimide whose glass transition temperature (Tg) can be clearly confirmed, but in the present invention, it means: the storage modulus of elasticity at 30 ℃ measured using a dynamic viscoelasticity measuring apparatus (dynamic mechanical analyzer, DMA) was 1.0X 108A storage modulus of elasticity of less than 3.0X 10 at 300 ℃ under Pa or higher7Pa of a polyimide. The "non-thermoplastic polyimide" is generally a polyimide which does not soften even when heated and exhibits adhesiveness, but in the present invention, it means: the storage modulus of elasticity at 30 ℃ as measured by a dynamic viscoelasticity measuring apparatus (DMA) was 1.0X 109A storage modulus of elasticity of 3.0X 10 at 300 ℃ under Pa or more8Polyimide having Pa or more.
[ silica particles ]
The silica particles may include crystalline silica particles. In addition, amorphous silica particles may be contained. By blending crystalline silica particles in the resin composition, the dielectric loss tangent at the time of forming a resin film can be reduced. In particular, it is preferable to use silica particles having a cristobalite crystal phase as the crystalline silica particles from the viewpoint of reducing the dielectric loss tangent when forming a resin film. The silica particles having a cristobalite crystal phase are extremely excellent in dielectric properties (for example, the dielectric loss tangent at 10GHz in terms of monomer in the silica particles containing 90 wt% or more of the cristobalite crystal phase is about 0.0008) as compared with those of ordinary silica particles, and can contribute greatly to the reduction of the dielectric loss tangent of a resin film.
The median diameter D in the frequency distribution curve obtained from the volume-based particle size distribution of the silica particles by the laser diffraction scattering method50In the range of 6 to 20 μm, preferably 8 to 15 μm. When the amount is within the above range, the dielectric properties are effectively improved, and a resin film with low dielectric constant can be obtained without deteriorating the surface smoothness when the resin film is blended. Median diameter D50When the amount of the water is less than the above range, the surface area of the silica particles increases, and the water adsorbed on the surface of the silica particles may affect the dielectric characteristics. Median diameter D50When the amount exceeds the above range, the film surface may be uneven and the smoothness of the film surface may be deteriorated.
In addition, spherical silica particles are preferably used as the silica particles. 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. In order to improve the dispersibility of the silica particles and the effect of improving the dielectric characteristics, 90% by weight or more of the silica particles having a particle diameter of 3 μm or more preferably have a circularity of 0.7 or more, more preferably 0.9 or more. The circularity of the silica particle can be obtained by an image analysis method assuming a circle having the same projected area as the imaged particle and using the ratio of the circumference of the circle to the circumference of the particle. If the circularity is less than 0.7, the surface area increases, which may adversely affect the dielectric properties, and the viscosity increases when the resin solution is blended, making handling difficult. In addition, it is preferable that the sphericity obtained three-dimensionally also be a value substantially corresponding to the value of the circularity.
In addition, in order to improve the dispersibility of the silica particles and the effect of improving the dielectric characteristics, the silica particles preferably have a true specific gravity of 2.3 or more. If the true specific gravity is less than 2.3, the crystallinity of the silica particles is small, and the effect of improving the dielectric characteristics is small.
The silica particles may be surface treated. The surface treatment may be carried out by a conventional technique, and is preferably carried out by modification such as corona treatment, plasma treatment, or Ultraviolet (UV) treatment, or by functionalization treatment using a silane coupling agent or the like. By subjecting the silica particles to surface treatment, alkyl groups, amino groups, alkoxy groups, and the like are provided on the particle surfaces, whereby the affinity with a solvent or polyamic acid is improved, or the repulsive force between the particles is improved, whereby the dispersibility of the silica particles and the long-term stability of the varnish are improved.
From the viewpoint of reducing the dielectric loss tangent when forming a resin film, the total area of peaks derived from the cristobalite crystal phase and the quartz crystal phase in the range of 10 ° to 90 ° in the X-ray diffraction analysis spectrum of CuK α rays is determined by the total area of peaks derived from the cristobalite crystal phase and the quartz crystal phase in the SiO-based region as the entire aggregate of the silica particles used2The proportion of the total area of all peaks of (a) is preferably 20% by weight or more, more preferably 40% by weight or more, and ideally 80% by weight or more. By increasing the proportion of the cristobalite crystal phase and/or the quartz crystal phase in the entire silica particle, the polyimide can be further reduced in dielectric loss tangent. When the area ratio of the peaks derived from the cristobalite crystal phase and the quartz crystal phase in the entire silica particles is less than 20% by weight, the effect of improving the dielectric properties is not clear. The proportion of the cristobalite crystal phase can be determined by X-ray diffraction (XRD) using α -radiation with respect to all silica particles in a uniformly mixed state, as a ratio of the total area of diffraction peaks derived from the cristobalite crystal phase and the quartz crystal phase measured in a range of 10 ° ≦ 2 θ ≦ 90 ° to the total area of diffraction peaks derived from all silica particles in the above range. Further, pairs in X-ray diffraction analysis spectraWhen the image peak is difficult to be separated from the amorphous broad peak or overlaps with other crystal phase peaks, various conventional analysis methods, for example, an internal standard method or a PONKCS method can be used.
As a preferred embodiment, an aggregate of silica particles having a cristobalite crystal phase ratio of 50 wt% or more can be used. As a further preferred embodiment, amorphous silica particles can be used in place of a part (for example, 80 wt% or less of the whole) of the aggregate of silica particles having a proportion of the cristobalite crystal phase of 90 wt% or more. The replacement of the amorphous silica particles can be performed as needed, and thus there is an advantage that a resin composition having excellent workability can be produced by enabling cost reduction, high-density filling, and adjustment of solution viscosity.
Further, commercially available silica particles can be suitably selected and used. As the crystalline silica particles, for example, spherical cristobalite silica powder (trade name: CR10-20, manufactured by Nichika chemical & materials Co., Ltd.) can be preferably used. As the amorphous silica particles which can be combined with the crystalline silica particles, spherical amorphous silica powder (trade name: SC70-2, trade name: SP40-10, manufactured by Nichika & materials Co., Ltd.) or the like can be used. Further, two or more different silica particles may be used in combination as the silica particles.
[ blending composition ]
The content of the silica particles in the resin composition is in the range of 10 to 85 wt% (in terms of polyamic acid converted to imidized polyimide) relative to the total amount of the solid content of the organic compound and the silica particles in the resin composition, preferably in the range of 10 to 80 wt%, and more preferably in the range of 15 to 75 wt%. If the content of the silica particles is less than 10% by weight, the effect of lowering the dielectric loss tangent cannot be sufficiently obtained. When the content of the silica particles exceeds 85% by weight, the properties such as adhesiveness of polyimide are deteriorated, and particularly when the content of the silica particles exceeds 80% by weight, the resin composition becomes brittle when formed into a resin film, and the bending property is deteriorated.
[ optional Components ]
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.
The resin composition of the present invention may be appropriately compounded with an inorganic filler other than silica particles, an inorganic pigment, an inorganic flame retardant, an inorganic heat dissipating agent, and the like as optional components as necessary within the range not impairing the effects of the present invention. Examples of the inorganic filler other than the silica particles include: aluminum oxide, magnesium oxide, beryllium oxide, niobium oxide, titanium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, magnesium fluoride, potassium fluorosilicate, metal phosphonate, and the like. These may be used alone or in combination of two or more.
[ viscosity ]
The viscosity of the resin composition is preferably in the range of, for example, 3000cps to 100000cps, more preferably 5000cps to 50000cps, 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, silica particles may be directly prepared in a resin solution of polyamic acid prepared using an arbitrary solvent. Alternatively, in consideration of dispersibility of the silica particles, the silica particles may be prepared in advance in a reaction solvent in which either one of an acid dianhydride component and a diamine component, which are raw materials of the polyamic acid, is charged, and then the other raw material may be charged under stirring to carry out polymerization. In either method, the 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 is a resin film having a single layer or a plurality of polyimide layers, and at least one layer, preferably all, of the polyimide layers may be a polyimide layer containing crystalline silica formed from the resin composition.
In the resin film, the thickness of the crystalline silica-containing polyimide layer formed from the resin composition is, for example, preferably in the range of 15 to 200 μm, and more preferably in the range of 20 to 150 μm. When the thickness of the polyimide layer containing crystalline silica is less than 15 μm, silica particles protrude from the surface of the resin film, and the surface smoothness is deteriorated. On the other hand, if the thickness of the polyimide layer containing crystalline silica exceeds 200 μm, the resin film tends to have a disadvantage in terms of, for example, a reduction in the bendability thereof.
The thickness of the entire resin film is, for example, in the range of 15 to 200. mu.m, preferably in the range of 20 to 200. mu.m, and more preferably in the range of 25 to 200. mu.m. If the thickness of the resin film is less than 15 μm, defects such as wrinkles in the metal foil and cracks in the resin film 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 200 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 crystalline silica to the thickness of the entire resin film is preferably 50% or more of the total thickness. When the ratio of the thickness of the polyimide layer containing crystalline 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 crystalline 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. Thus, a polyimide layer containing crystalline silicon dioxide can be formed 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 as with the third polyamic acid resin solution, the next fourth polyamic acid resin solution, and …, the polyamic acid resin solutions are applied and dried sequentially, generally as many times as necessary. 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 imidization is lower than 100 ℃, the dehydration ring-closure reaction of polyimide may not be sufficiently performed, whereas if it exceeds 400 ℃, the polyimide layer may be deteriorated.
Further, by performing appropriate surface treatment or the like on any polyimide layer to be imidized, the steps of coating with a resin solution, drying, and imidizing can be repeated to superpose the layers again. In this case, the imidization in the intermediate step does not need to be completed, and the imidization can be completed intensively in the final step.
In addition, any polyimide layer that is imidized may be thermally pressure-bonded to a resin film that is separately formed.
Further, the resin film may be in a state of a tape supporting the substrate.
Another example of forming a polyimide layer containing crystalline 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 crystalline 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 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 (including the crystalline 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 10X 10-6/K～50×10-6In the range of/K (10ppm/K to 50ppm/K), more preferably 15X 10-6/K～40×10-6/K(15ppm/K～40ppmK) in the range of (A). If the coefficient of thermal expansion of the resin film is less than 10X 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 50X 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, the dielectric loss tangent (Tan δ) at 3GHz to 20GHz as measured by a post-split dielectric resonator (SPDR) is preferably 0.005 or less, more preferably 0.004 or less, as the entire film, in order to reduce the dielectric loss at the time of high-frequency signal transmission. 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 3GHz to 20GHz 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 electrical signal on a transmission path of a high-frequency signal tend to occur. The lower limit of the dielectric loss tangent at 3GHz to 20GHz is not particularly limited, but physical properties of the resin film when applied to an insulating resin layer of a circuit board need to be controlled.
[ relative dielectric constant ]
When the resin film is used as an insulating resin layer of a circuit board, for example, the relative dielectric constant at 3GHz to 20GHz as measured by a post-split dielectric resonator (SPDR) is preferably 3.1 or less as the entire film in order to ensure impedance matching. If the relative permittivity at 3GHz to 20GHz exceeds 3.1, when the resin film is applied to an insulating resin layer of a circuit board, the dielectric loss is deteriorated, and the loss of an electric signal on a transmission path of a high-frequency signal is likely to increase.
[ 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.
[ insulating resin layer ]
The insulating resin layer comprises a single layer or a plurality of layers, including a layer comprising the resin film. For example, the resin film may form a non-thermoplastic polyimide layer as a main layer of the insulating resin layer for securing mechanical properties or thermal properties. The resin film may be formed as a thermoplastic polyimide layer serving as an adhesive layer for securing adhesion to a metal layer such as a copper foil. The "main layer" is a layer that occupies 50% or more of the total thickness of the insulating resin layer.
In addition, 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. In the case where the crystalline silica-containing polyimide layer constitutes a main layer of the insulating resin layer, the glass transition temperature of the crystalline silica-containing polyimide layer is preferably set to 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. Of these, copper or a copper alloy is particularly preferable. The metal layer may be one containing a metal foil, one formed by metal vapor deposition on a film, or one printed with paste. 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 >
A relative dielectric constant measuring apparatus manufactured by Kanto electronics application and development Co., Ltd, a vector network analyzer (trade name: vector network analyzer E8363C, manufactured by Germany Technologies) and a resonant cavity perturbation method was used, and the relative dielectric constant measuring mode was set as follows: TM020, the relative dielectric constant (∈ 1) and the dielectric loss tangent (Tan δ 1) of the silica particles at a frequency of 10GHz were measured. The silica particles were in the form of powder and filled in a sample tube (inner diameter: 1.68mm, outer diameter: 2.28mm, height: 8cm) to measure.
< resin film >
The relative dielectric constant (. epsilon.1) and the dielectric loss tangent (. DELTA.1) of the resin film at a frequency of 10GHz were measured using a vector network analyzer (trade name: vector network analyzer E8363C, manufactured by Keysight Technologies) and an SPDR resonator. 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.
[ measurement of 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 coefficient of thermal expansion (coefficient of thermal expansion, CTE) from 200 ℃ to 100 ℃.
[ measurement of particle diameter ]
The particle size of the silica particles was measured by a laser diffraction scattering measurement method using a laser particle size analyzer (trade name: laser Sizer 3000, manufactured by Malvern corporation) using water as a dispersion medium under a condition that the refractive index of the particles was 1.54.
[ measurement of true specific gravity ]
The TRUE specific gravity of the silica particles was measured by a densitometer (pycnometer) method (liquid phase displacement method) using a continuous automatic powder TRUE density measuring apparatus (manufactured by Seishin corporation, trade name: AUTO TRUE Denser Mat-7000).
[ measurement of cristobalite Crystal phase ]
The diffraction angle (Cu, Ka) 2 theta was measured by using an X-ray diffraction measuring apparatus (product name: D2PHASER, Bruker) in the range of 10 DEG to 90 DEG from SiO2All diffraction patterns (peak position, peak width, and peak intensity) of the light beam were calculated from SiO2The total area of all peaks. Next, the peak position derived from the cristobalite crystal phase was determined, the total area of all peaks of the cristobalite crystal phase was calculated, and the total area of all peaks derived from SiO2The proportion (wt%) of the total area of all peaks. The peak assignment was made with reference to a database of International Centre for Diffraction Data (ICDD).
[ measurement of circularity ]
The average circularity of the silica particles was measured by dynamic flow particle image analysis using a wet flow particle size and shape analyzer (product name: FPIA-3000, manufactured by Sysmex corporation).
[ evaluation of bendability ]
According to Japanese Industrial Standards (JIS) K5600-5-1, 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, circularity: 0.98, cristobalite crystal phase: 98 wt%, true specific gravity: 2.33, D)50: relative dielectric constant at 10.8 μm and 10 GHz: dielectric loss tangent at 3.16, 10 GHz: 0.0008)
And (3) filler 2: chemical of ferric chloride&Manufactured by materials corporation, trade name: SC70-2 (spherical amorphous silica powder, circularity: 0.98, true specific gravity: 2.21, D)50: relative dielectric constant at 10GHz at 11.7 μm: 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, true specific gravity: 2.21, D)50: relative dielectric constant at 10GHz at 2.5 μm: dielectric loss tangent at 2.78, 10 GHz: 0.0030)
(Synthesis example 1)
A300 ml separable flask was charged with 24g of BAPP (60mmol) and 230g of DMAc, and the mixture was stirred at room temperature under a nitrogen stream. After complete dissolution, 6.5g of PMDA (30mmol) and 8.7g of BPDA (30mmol) were added thereto, and the mixture was stirred at room temperature for 18 hours to obtain a polyamic acid solution A. The obtained polyamic acid solution A had a viscosity of 21,074 cps.
(Synthesis example 2)
A300 ml separable flask was charged with 19g of m-TB (90mmol) and 230g of DMAc, and the mixture was stirred at room temperature under a nitrogen stream. After complete dissolution, 16g of PMDA (72mmol) and 5.3g of BPDA (18mmol) 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 had a viscosity of 22,400 cps.
[ example 1]
Polyamic acid composition 1a (viscosity: 23,000cps) was prepared by mixing 58.7g of polyamic acid solution A and 6.1g of filler 1 and stirring until the same solution was visually observed.
Polyamic acid composition 1a was applied to copper foil 1 (electrolytic copper foil, thickness: 12 μm) and dried at 130 ℃ for 3 minutes. Thereafter, the metal-clad laminate 1b 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 1b is etched away to prepare a resin film 1 c. The resin film 1c (thickness: 51.6 μm) had a relative dielectric constant of 3.04, a dielectric loss tangent of 0.0044, and a "good" bendability.
[ example 2]
70.0g of polyamic acid solution B and 7.8g of filler 1 were mixed and stirred until the same solution was visually observed, thereby obtaining polyamic acid composition 2a (viscosity: 24,800 cps).
A metal-clad laminate 2b and a resin film 2c were prepared in the same manner as in example 1. The resin film 2c (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.
[ example 3]
A polyamic acid composition 3a (viscosity: 28,400cps) was prepared by mixing 60.0g of polyamic acid solution B and 20.0g of filler 1, and stirring until the same solution was visually observed.
A metal-clad laminate 3b and a resin film 3c were prepared in the same manner as in example 1. The resin film 3c (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.
[ example 4]
55.0g of polyamic acid solution B and 36.6g of filler 1 were mixed and stirred until the same solution was visually observed, thereby obtaining polyamic acid composition 4a (viscosity: 29,900 cps).
After preparing the metal-clad laminate 4b in the same manner as in example 1, a resin film 4c was prepared. The resin film 4c (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 bendability of "No".
[ example 5]
Polyamic acid composition 5a (viscosity: 31,000cps) was prepared by mixing 50.0g of polyamic acid solution B, 6.6g of filler 1, and 25.3g of filler 2, and stirring until the same solution was visually observed.
After preparing the metal-clad laminate 5b in the same manner as in example 1, a resin film 5c was prepared. The resin film 5c (thickness: 115.5 μm) had a relative dielectric constant of 2.71, a dielectric loss tangent of 0.0017, a CTE of 27ppm/K, and a bendability of "No".
Comparative example 1
The polyamic acid solution a was coated on the copper foil 1, dried at 90 ℃ for 1 minute, and dried at 130 ℃ for 5 minutes. Thereafter, a metal-clad laminate a1 was prepared by performing a stepwise heat treatment from 155 ℃ to 360 ℃ and imidizing.
In the same manner as in example 1, the copper foil of the metal-clad laminate a1 was removed by etching to prepare a resin film a 1. The resin film A1 (thickness: 41.4 μm) had a relative dielectric constant of 3.16, a dielectric loss tangent of 0.0062, a CTE of 51ppm/K, and "good" bendability.
Comparative example 2
56.2g of polyamic acid solution A and 5.5g of filler 2 were mixed and stirred until the same solution was visually observed, thereby obtaining polyamic acid composition A2 (viscosity: 23,600 cps).
A metal-clad laminate a2 and a resin film a2 were prepared in the same manner as in example 1. The resin film A2 (thickness: 50.7 μm) had a relative dielectric constant of 3.04, a dielectric loss tangent of 0.0047 and a "good" bendability.
Comparative example 3
A polyamic acid composition A3 (viscosity: 30,000cps) was prepared by mixing 56.2g of polyamic acid solution A and 5.5g of filler 3, and stirring until the same solution was visually observed.
After preparing a metal-clad laminate A3 in the same manner as in example 1, a resin film A3 was prepared. The resin film A3 (thickness: 45.6 μm) had a relative dielectric constant of 3.25, a dielectric loss tangent of 0.0052, a CTE of 41ppm/K, and "good" bendability.
The results are summarized in tables 1 and 2.
The crystal phase in table 1 is a ratio of the cristobalite crystal phase, and the filler ratio is a ratio (weight ratio) of the filler to the whole polyamic acid solution (varnish) or the total of the solid content of the organic compound and the silica particles (in terms of the weight of the polyamic acid as converted to the polyimide after imidization). The filler content in table 2 refers to the ratio (weight ratio) of the filler to the resin film.
[ Table 1]
[ Table 2]
Confirming that: the viscosity of polyamic acid composition 1a of example 1 was lower than that of polyamic acid compositions a2 and A3 of comparative examples 2 and 3, respectively. In addition, the resin film 1c of example 1 had a lower relative dielectric constant and a lower dielectric loss tangent than the resin films a2 to A3 of comparative examples 2 to 3, and the higher the proportion of cristobalite crystal phase, the more the effect of low dielectric constant was observed.
From the above results, it was confirmed that the resin film of the present embodiment can be suitably used as a material for a flexible printed circuit board corresponding to a high frequency.
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 (10)
1. A resin composition comprising: a solid component comprising an organic compound of polyamic acid or polyimide, and silica particles, wherein the resin composition is characterized in that:
the content of the silica particles is within a range of 10 to 85 wt% relative to the total amount of the solid components and the total amount of the silica particles, wherein the polyamic acid is converted into imidized polyimide,
the total area of peaks derived from the cristobalite crystal phase and the quartz crystal phase in the range of 10 ° to 90 ° in the X-ray diffraction spectrum of CuK α rays is determined based on the SiO-based peak area2The proportion of all peak areas of (a) is 20% by weight or more.
2. The resin composition according to claim 1, wherein the median diameter D in the frequency distribution curve of the silica particles obtained by volume-based particle size distribution measurement by a laser diffraction scattering method50Is in the range of 6 to 20 μm.
3. The resin composition according to claim 1 or 2, wherein 90% by weight or more of particles having a particle diameter of 3 μm or more in the silica particles have a circularity of 0.7 or more.
4. The resin composition according to claim 1 or 2, wherein 90% by weight or more of the silica particles is a true specific gravity of 2.3 or more.
5. A resin film having a single layer or a plurality of polyimide layers, wherein,
at least one of the polyimide layers is a crystalline silica-containing polyimide layer formed of the resin composition according to any one of claims 1 to 4, the crystalline silica-containing polyimide layer having a thickness in the range of 15 μm to 200 μm.
6. The resin film according to claim 5, wherein a ratio of a thickness of the polyimide layer containing crystalline silica to an entire thickness of the resin film is 50% or more.
7. The resin film according to claim 5 or 6, wherein the relative dielectric constant at a frequency of 3GHz to 20GHz is 3.1 or less as measured by a post-split dielectric resonator.
8. The resin film according to claim 5 or 6, wherein the dielectric loss tangent at a frequency of 3GHz to 20GHz as measured by a dielectric resonator after division is 0.005 or less.
9. The resin film according to claim 5 or 6, wherein the coefficient of thermal expansion is 50ppm/K or less.
10. A metal clad laminate comprising an insulating resin layer, and a metal layer laminated on at least one surface of the insulating resin layer, characterized in that:
at least one layer of the insulating resin layer comprises the resin film according to any one of claims 5 to 9.
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| JP3299333B2 (en) * | 1993-04-02 | 2002-07-08 | 住友ベークライト株式会社 | Polyamic acid film and method for manufacturing flexible printed circuit board using the same |
| JP5038007B2 (en) | 2007-04-17 | 2012-10-03 | 電気化学工業株式会社 | Composition, metal-based circuit board using the composition |
| TWI672267B (en) | 2014-08-25 | 2019-09-21 | 日商日鐵化學材料股份有限公司 | Spherical crystalline cerium oxide particle and method of producing the same |
| TWI677520B (en) | 2015-03-31 | 2019-11-21 | 日商鐘化股份有限公司 | Method for producing polyimide film and use thereof |
| JP2018012747A (en) | 2016-07-19 | 2018-01-25 | 日立化成株式会社 | Thermosetting resin composition, interlayer-insulating resin film, composite film, printed wiring board, and production methods thereof |
| JP6854505B2 (en) | 2016-11-30 | 2021-04-07 | ナミックス株式会社 | Resin composition, thermosetting film using it |
| JP2018145037A (en) | 2017-03-02 | 2018-09-20 | 株式会社アドマテックス | Spherical crystalline silica powder for addition resin composition |
| JP7009790B2 (en) | 2017-06-16 | 2022-01-26 | 住友ベークライト株式会社 | Resin compositions for semiconductor encapsulation and semiconductor devices |
| JP6934344B2 (en) | 2017-07-18 | 2021-09-15 | デンカ株式会社 | Powder for spherical silica filler and its manufacturing method |
-
2019
- 2019-12-27 JP JP2019238109A patent/JP7446814B2/en active Active
-
2020
- 2020-12-11 CN CN202011446201.6A patent/CN113045895A/en active Pending
- 2020-12-14 TW TW109144112A patent/TW202124583A/en unknown
- 2020-12-22 KR KR1020200181167A patent/KR20210084279A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021105148A (en) | 2021-07-26 |
| KR20210084279A (en) | 2021-07-07 |
| TW202124583A (en) | 2021-07-01 |
| JP7446814B2 (en) | 2024-03-11 |
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