TW201904759A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- TW201904759A TW201904759A TW107113110A TW107113110A TW201904759A TW 201904759 A TW201904759 A TW 201904759A TW 107113110 A TW107113110 A TW 107113110A TW 107113110 A TW107113110 A TW 107113110A TW 201904759 A TW201904759 A TW 201904759A
- Authority
- TW
- Taiwan
- Prior art keywords
- resin composition
- resin
- layer
- component
- mass
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 244
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 44
- 239000012762 magnetic filler Substances 0.000 claims abstract description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims description 130
- 229920000647 polyepoxide Polymers 0.000 claims description 130
- 230000035699 permeability Effects 0.000 claims description 61
- 239000004848 polyfunctional curative Substances 0.000 claims description 54
- 239000002313 adhesive film Substances 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 230000001939 inductive effect Effects 0.000 claims description 25
- 239000011256 inorganic filler Substances 0.000 claims description 22
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 20
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 15
- 239000011354 acetal resin Substances 0.000 claims description 15
- 229920006287 phenoxy resin Polymers 0.000 claims description 15
- 239000013034 phenoxy resin Substances 0.000 claims description 15
- 229920006324 polyoxymethylene Polymers 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 441
- 229910052751 metal Inorganic materials 0.000 description 55
- 239000002184 metal Substances 0.000 description 55
- -1 heterocyclic hydroxy compound esters Chemical class 0.000 description 53
- 238000000034 method Methods 0.000 description 46
- 239000000126 substance Substances 0.000 description 45
- 238000001723 curing Methods 0.000 description 40
- 238000007788 roughening Methods 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- 229910045601 alloy Inorganic materials 0.000 description 30
- 239000000956 alloy Substances 0.000 description 30
- 239000010408 film Substances 0.000 description 30
- 238000003475 lamination Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 239000002585 base Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 17
- 229920003986 novolac Polymers 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 239000005060 rubber Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- 206010042674 Swelling Diseases 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 230000008961 swelling Effects 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 229920001721 polyimide Polymers 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 12
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 11
- 125000003700 epoxy group Chemical group 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 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 10
- 229920002799 BoPET Polymers 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 239000002893 slag Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 239000012766 organic filler Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 239000003337 fertilizer Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LARNQUAWIRVQPK-UHFFFAOYSA-N 2-methyloxiran-2-amine Chemical compound NC1(CO1)C LARNQUAWIRVQPK-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 7
- 238000013007 heat curing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000009719 polyimide resin Substances 0.000 description 7
- 238000001029 thermal curing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000004843 novolac epoxy resin Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 239000012756 surface treatment agent Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- 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 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000009499 grossing Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- 229910019819 Cr—Si Inorganic materials 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229940123208 Biguanide Drugs 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229920002098 polyfluorene Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 2
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 description 2
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 2
- 229910017082 Fe-Si Inorganic materials 0.000 description 2
- 229910017133 Fe—Si Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- GHPYAGKTTCKKDF-UHFFFAOYSA-M tetraphenylphosphanium;thiocyanate Chemical compound [S-]C#N.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GHPYAGKTTCKKDF-UHFFFAOYSA-M 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XQQWBPOEMYKKBY-UHFFFAOYSA-H trimagnesium;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O XQQWBPOEMYKKBY-UHFFFAOYSA-H 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
- C08G59/4276—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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Abstract
Description
本發明係關於樹脂組成物。進而,關於使用該樹脂組成物所得之接著薄膜、硬化物、內載電感元件之配線板、晶片電感零件、及印刷配線板。The present invention relates to a resin composition. Furthermore, the adhesive film obtained by using this resin composition, a hardened | cured material, a wiring board with a built-in inductance element, a chip inductance part, and a printed wiring board are mentioned.
因近年來之電子機器的小型化、薄型化之要求,對於印刷配線板或搭載於印刷配線板的電感零件(線圈),小型化、薄型化之要求亦提高。在搭載有電感零件作為晶片零件的情況,於印刷配線板之薄型化產生界限。因而,可推測藉由使用於樹脂組成物層中含有磁性材料的接著薄膜,於印刷基板形成磁性層,而將電感形成於印刷配線板內層(例如,參照專利文獻1)。 [先前技術文獻] [專利文獻]Due to the recent miniaturization and thinning requirements of electronic equipment, the requirements for miniaturization and thinning of printed wiring boards or inductance components (coils) mounted on printed wiring boards have also increased. When an inductive component is mounted as a chip component, there is a limit in reducing the thickness of a printed wiring board. Therefore, it is presumed that by using an adhesive film containing a magnetic material in the resin composition layer to form a magnetic layer on a printed circuit board, an inductor is formed on the inner layer of the printed wiring board (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]
[專利文獻1] 日本特開2015-187260號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-187260
[發明所欲解決之課題][Problems to be Solved by the Invention]
於電感零件中係有電源系與訊號系,於訊號系中係要求吉赫(GHz)以上之區域的相對導磁率(導磁率)。專利文獻1記載的接著薄膜係以使用於訊號系為前提,在1GHz至3GHz之範圍內相對導磁率成為良好。另一方面,於電源系中,要求在比訊號系更低頻的區域之高相對導磁率,一般而言在未達10MHz之頻率使用。因而,以往之樹脂組成物於未達10MHz、或1GHz以上之頻率中為最適化。There are a power supply system and a signal system in the inductive part. In the signal system, the relative permeability (permeability) of the area above the GHz (GHz) is required. The adhesive film described in Patent Document 1 is based on the premise that it is used in a signal system, and the relative magnetic permeability is good in the range of 1 GHz to 3 GHz. On the other hand, in the power supply system, it is required to have a high relative permeability in a lower frequency region than the signal system, and generally, it is used at a frequency less than 10 MHz. Therefore, conventional resin compositions are optimized for frequencies below 10 MHz or above 1 GHz.
相對於此,本發明者們重新著眼於10MHz~200MHz之新的頻率區域,得到只要可實現在此頻率區域之高相對導磁率,則可得到電源系之新穎的電感零件之見解。但,為了將使用有如此之樹脂組成物的接著薄膜,於印刷配線板之層間絕緣層部分作為磁性層來替換使用,亦要求在磁性層形成後不易發生翹曲、難燃性、及疊層性等。In contrast, the present inventors re-focused on a new frequency range of 10 MHz to 200 MHz, and obtained insights into novel inductor parts of power systems as long as high relative permeability in this frequency range can be achieved. However, in order to replace the adhesive film using such a resin composition as a magnetic layer in an interlayer insulating layer portion of a printed wiring board, it is also required that warpage, flame resistance, and lamination are not easily caused after the magnetic layer is formed. Sex, etc.
本發明之課題係提供可得到難燃性優異,翹曲量受到抑制,尤其可提昇頻率10~200MHz之範圍內的相對導磁率之硬化物,進而疊層性優異之樹脂組成物;使用該樹脂組成物所得之接著薄膜、及內載電感元件之配線板、晶片電感零件、及印刷配線板。 [用以解決課題之手段]The object of the present invention is to provide a resin composition which is excellent in flame retardancy and suppresses warpage, and can particularly improve the relative magnetic permeability in the frequency range of 10 to 200 MHz, and further has excellent lamination properties; using the resin The adhesive film obtained from the composition, a wiring board having an inductive element mounted thereon, a chip inductor part, and a printed wiring board. [Means to solve the problem]
一般而言,含有磁性填料的樹脂組成物,由於在頻率10~200MHz之範圍內的相對導磁率為低,因此被限定於1GHz至3GHz之範圍內的高頻用途,或0~10MHz之範圍內的低頻用途中。本發明者們努力探討的結果,發現若以使含有磁性填料之樹脂組成物熱硬化而成之硬化物於23℃時的彈性率成為特定之範圍內的方式來調整樹脂組成物中所包含之各成分,則使用樹脂組成物所得之接著薄膜係疊層性優異,樹脂組成物之硬化物係難燃性優異,翹曲量受到抑制,尤其可提昇頻率10~200MHz之範圍內的相對導磁率,因而完成本發明。Generally speaking, resin compositions containing magnetic fillers have low relative permeability in the frequency range of 10 to 200 MHz, and are therefore limited to high-frequency applications in the range of 1 GHz to 3 GHz, or in the range of 0 to 10 MHz. For low frequency applications. As a result of intensive studies, the present inventors have found that if the elastic modulus of a hardened material obtained by thermally curing a resin composition containing a magnetic filler at 23 ° C. is adjusted to a specific range, the resin composition may be adjusted. For each component, the adhesive film system obtained by using the resin composition is excellent in lamination, the hardened system of the resin composition is excellent in flame retardancy, and the amount of warpage is suppressed. In particular, the relative magnetic permeability in the frequency range of 10 to 200 MHz can be increased. Thus, the present invention has been completed.
亦即,本發明係包含以下之內容。 [1]一種樹脂組成物,其係含有: (A)熱硬化性樹脂、 (B)硬化劑、 (C)熱塑性樹脂、以及 (D)磁性填料, 使樹脂組成物熱硬化而成之硬化物於23℃時的彈性率為7GPa以上18GPa以下。 [2]如[1]之樹脂組成物,其中,在將樹脂組成物中之不揮發性成分設為100質量%的情況時,(D)成分之含量為75質量%以上未達95質量%。 [3]如[1]或[2]之樹脂組成物,其係進一步含有(E)磁性填料以外之無機填充材。 [4]如[3]之樹脂組成物,其中,在將(D)成分之含有質量設為d1,並將(E)成分之含有質量設為e1的情況時,e1/d1為0.02以上0.19以下。 [5]如[1]~[4]中任一項之樹脂組成物,其中,在將樹脂組成物中樹脂成分之含有質量設為a1,並將(C)成分之含有質量設為c1的情況時,(c1/a1)×100為35以上80以下。 [6]如[1]~[5]中任一項之樹脂組成物,其中,(A)成分為環氧樹脂。 [7]如[6]之樹脂組成物,其中,環氧樹脂為選自由具有聯苯骨架之環氧樹脂及具有縮合環構造之環氧樹脂中的1種以上之環氧樹脂。 [8]如[1]~[7]中任一項之樹脂組成物,其中,(B)成分為選自由酚系硬化劑及活性酯系硬化劑中的1種以上之硬化劑。 [9]如[1]~[8]中任一項之樹脂組成物,其中,(C)成分為重量平均分子量3萬以上100萬以下之選自由苯氧基樹脂、聚乙烯縮醛樹脂、丁醛樹脂及丙烯酸系樹脂中的1種以上之熱塑性樹脂。 [10]如[1]~[9]中任一項之樹脂組成物,其中,樹脂組成物係形成由母相與分散相所構成的海島構造,(D)成分集中存在於母相側。 [11]如[1]~[10]中任一項之樹脂組成物,其中,(D)成分之平均粒徑為0.01μm以上8μm以下,且(D)成分之縱橫比為2以下。 [12]如[1]~[11]中任一項之樹脂組成物,其中,(D)成分為包含選自由Si、Al、及Cr中的1種以上之元素的Fe合金類。 [13]如[3]~[12]中任一項之樹脂組成物,其中,(E)成分為二氧化矽。 [14]如[1]~[13]中任一項之樹脂組成物,其中,使樹脂組成物熱硬化而成的硬化物於頻率100MHz時之相對導磁率為5以上。 [15]如[1]~[14]中任一項之樹脂組成物,其中,使樹脂組成物熱硬化而成的硬化物於頻率100MHz時之磁性損失為0.05以下。 [16]如[1]~[15]中任一項之樹脂組成物,其中,使樹脂組成物熱硬化而成的硬化物於頻率10MHz時之相對導磁率為5以上20以下,頻率100MHz時之相對導磁率為5以上20以下,頻率1GHz時之相對導磁率為4以上16以下,頻率3GHz以上時之相對導磁率為2以上10以下。 [17]如[1]~[16]中任一項之樹脂組成物,其係具備電感元件之配線板的磁性層形成用者。 [18]如[17]之樹脂組成物,其中,電感元件發揮功能的頻率為10~200MHz。 [19]一種硬化物,其係使如[1]~[18]中任一項之樹脂組成物熱硬化而成者。 [20]一種接著薄膜,其係包含支撐體,與設置於該支撐體上以如[1]~[18]中任一項之樹脂組成物所形成的樹脂組成物層。 [21]一種內載電感元件之配線板,其係具有:作為如[20]之接著薄膜之樹脂組成物層之硬化物的磁性層,與至少一部分埋入該磁性層的導電性構造體, 且包含:藉由前述導電性構造體,與延伸存在於前述磁性層的厚度方向且被前述導電性構造體所包圍之前述磁性層中的一部分所構成的電感元件。 [22]如[21]之內載電感元件之配線板,其中,電感元件發揮功能的頻率為10~200MHz。 [23]一種印刷配線板,其係使用如[21]或[22]之內載電感元件之配線板作為內層基板。 [24]一種晶片電感零件,其係將如[21]或[22]之內載電感元件之配線板單片化而成。 [25]一種印刷配線板,其係表面安裝有如[24]之晶片電感零件。 [發明效果]That is, the present invention includes the following. [1] A resin composition comprising: (A) thermosetting resin, (B) hardener, (C) thermoplastic resin, and (D) magnetic filler, and 硬化 a hardened product obtained by heat-hardening the resin composition. The elastic modulus at 23 ° C is 7 GPa or more and 18 GPa or less. [2] The resin composition according to [1], wherein when the nonvolatile component in the resin composition is 100% by mass, the content of the component (D) is 75% by mass or more and less than 95% by mass . [3] The resin composition according to [1] or [2], further comprising an inorganic filler other than (E) a magnetic filler. [4] The resin composition according to [3], wherein when the content mass of the (D) component is d1 and the content mass of the (E) component is e1, e1 / d1 is 0.02 or more and 0.19 the following. [5] The resin composition according to any one of [1] to [4], wherein the content of the resin component in the resin composition is a1, and the content of the (C) component is c1 In this case, (c1 / a1) × 100 is 35 or more and 80 or less. [6] The resin composition according to any one of [1] to [5], wherein the component (A) is an epoxy resin. [7] The resin composition according to [6], wherein the epoxy resin is one or more epoxy resins selected from an epoxy resin having a biphenyl skeleton and an epoxy resin having a condensed ring structure. [8] The resin composition according to any one of [1] to [7], wherein the component (B) is one or more hardeners selected from a phenol-based hardener and an active ester-based hardener. [9] The resin composition according to any one of [1] to [8], wherein the component (C) is selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, and a weight average molecular weight of 30,000 to 1 million. One or more thermoplastic resins of butyraldehyde resin and acrylic resin. [10] The resin composition according to any one of [1] to [9], wherein the resin composition forms an island structure composed of a mother phase and a dispersed phase, and the component (D) is concentrated on the mother phase side. [11] The resin composition according to any one of [1] to [10], wherein the average particle diameter of the (D) component is 0.01 μm or more and 8 μm or less, and the aspect ratio of the (D) component is 2 or less. [12] The resin composition according to any one of [1] to [11], wherein the (D) component is an Fe alloy containing one or more elements selected from the group consisting of Si, Al, and Cr. [13] The resin composition according to any one of [3] to [12], wherein the (E) component is silicon dioxide. [14] The resin composition according to any one of [1] to [13], wherein the relative magnetic permeability of the cured product obtained by thermally curing the resin composition at a frequency of 100 MHz is 5 or more. [15] The resin composition according to any one of [1] to [14], wherein the magnetic loss of the cured product obtained by thermally curing the resin composition at a frequency of 100 MHz is 0.05 or less. [16] The resin composition according to any one of [1] to [15], wherein the relative magnetic permeability of the cured product obtained by thermally curing the resin composition at a frequency of 10 MHz is 5 or more and 20 or less, and at a frequency of 100 MHz The relative magnetic permeability is 5 or more and 20 or less, the relative magnetic permeability is 4 or more and 16 or less at a frequency of 1 GHz, and the relative magnetic permeability is 2 or more and 10 or less at a frequency of 3 GHz or more. [17] The resin composition according to any one of [1] to [16], which is for forming a magnetic layer of a wiring board including an inductance element. [18] The resin composition according to [17], wherein the frequency at which the inductance element functions is 10 to 200 MHz. [19] A hardened product obtained by thermally hardening the resin composition according to any one of [1] to [18]. [20] An adhesive film comprising a support and a resin composition layer formed on the support and formed with the resin composition according to any one of [1] to [18]. [21] A wiring board with an inductive element on it, comprising: a magnetic layer as a cured product of the resin composition layer of [20] followed by a thin film; and a conductive structure in which at least a portion is embedded in the magnetic layer. It further includes an inductance element formed by the conductive structure and a part of the magnetic layer extending in a thickness direction of the magnetic layer and surrounded by the conductive structure. [22] The wiring board with inductive elements in [21], wherein the frequency at which the inductive elements function is 10 to 200 MHz. [23] A printed wiring board, which uses a wiring board with an inductive element loaded as in [21] or [22] as the inner substrate. [24] A chip inductor part, which is obtained by singulating a wiring board with an inductive element such as [21] or [22]. [25] A printed wiring board whose surface is mounted with chip inductor parts like [24]. [Inventive effect]
依據本發明,可提供能得到難燃性優異,翹曲量受到抑制,尤其可提昇頻率10~200MHz之範圍內的相對導磁率之硬化物,進而疊層性優異之樹脂組成物;使用該樹脂組成物所得之接著薄膜、內載電感元件之配線板、晶片電感零件、及印刷配線板。According to the present invention, it is possible to provide a resin composition that is excellent in flame retardancy and suppresses warpage, and can particularly improve the relative magnetic permeability in the frequency range of 10 to 200 MHz, and further has excellent lamination properties; using the resin The adhesive film obtained from the composition, a wiring board with an inductive element mounted thereon, a chip inductor part, and a printed wiring board.
以下,參照附圖,針對本發明之實施形態進行說明。另外,各附圖只不過是以可理解發明的程度概略性地顯示構成要素的形狀、大小及配置而已。本發明並非受以下之記述所限定者,各構成要素可在不脫離本發明之要旨的範圍內適當地變更。於以下說明所使用的附圖中,針對相同的構成要素係標示相同的符號,針對重複的說明有時會省略。又,關於本發明之實施形態的構造,不一定因附圖例之配置而使製造或使用受限。Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, each drawing merely shows the shape, size, and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited by the following description, and each constituent element can be appropriately changed without departing from the gist of the present invention. In the drawings used in the following description, the same constituent elements are denoted by the same reference numerals, and duplicate descriptions may be omitted. In addition, regarding the structure of the embodiment of the present invention, manufacturing or use is not necessarily limited due to the arrangement of the drawings.
[樹脂組成物] 本發明之樹脂組成物係含有:(A)熱硬化性樹脂、(B)硬化劑、(C)熱塑性樹脂、以及(D)磁性填料的樹脂組成物,其中,使樹脂組成物熱硬化而成之硬化物於23℃時之彈性率為7GPa以上18GPa以下。[Resin composition] 树脂 The resin composition of the present invention is a resin composition containing (A) a thermosetting resin, (B) a hardener, (C) a thermoplastic resin, and (D) a magnetic filler, wherein the resin composition At 23 ° C, the elasticity of the hardened material obtained by thermal curing of the material is 7 GPa or more and 18 GPa or less.
如前述般,以往,含有磁性填料的樹脂組成物,由於在頻率10~200MHz之範圍內的相對導磁率為低,因此被限定於1GHz至3GHz之範圍內的高頻用途,或0~10MHz之範圍內的低頻用途中。於本發明中,藉由以使熱硬化而成的硬化物於23℃時之彈性率成為7GPa以上8GPa以下的方式來調整樹脂組成物中所包含之(A)成分~(D)成分之含量,而可得到難燃性優異,翹曲量受到抑制,尤其可提昇頻率為10~200MHz之範圍內的相對導磁率之硬化物,進而,使用樹脂組成物所得之接著薄膜係疊層性優異。As mentioned above, conventionally, resin compositions containing magnetic fillers have low relative permeability in the frequency range of 10 to 200 MHz, so they have been limited to high-frequency applications in the range of 1 GHz to 3 GHz, or 0 to 10 MHz. Low frequency range in use. In the present invention, the content of the components (A) to (D) contained in the resin composition is adjusted so that the elastic modulus of the hardened material obtained by heat curing at 23 ° C. is 7 GPa or more and 8 GPa or less. In addition, a hardened product having excellent flame retardancy and suppressed warpage can be obtained. In particular, a cured product having a relative magnetic permeability in the frequency range of 10 to 200 MHz can be improved. Further, the adhesive film obtained by using the resin composition has excellent lamination properties.
樹脂組成物係可因應需要,進一步包含(E)磁性填料以外之無機填充材、(F)硬化促進劑、(G)難燃劑、(H)有機填充材。以下,針對樹脂組成物中所包含之各成分詳細地說明。The resin composition system may further include (E) an inorganic filler other than the magnetic filler, (F) a hardening accelerator, (G) a flame retardant, and (H) an organic filler, if necessary. Hereinafter, each component contained in a resin composition is demonstrated in detail.
<(A)熱硬化性樹脂> 樹脂組成物係含有(A)熱硬化性樹脂。作為(A)成分,可使用在形成配線板之絕緣層時所使用的熱硬化性樹脂,其中,較佳為環氧樹脂。<(A) thermosetting resin> The resin composition system contains (A) a thermosetting resin. As (A) component, the thermosetting resin used when forming the insulation layer of a wiring board can be used, Among these, an epoxy resin is preferable.
作為環氧樹脂,可列舉例如:雙酚A型環氧樹脂;雙酚F型環氧樹脂;雙酚S型環氧樹脂;雙酚AF型環氧樹脂;二環戊二烯型環氧樹脂;三酚型環氧樹脂;酚酚醛清漆型環氧樹脂;tert-丁基-兒茶酚型環氧樹脂;萘酚酚醛清漆型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂等之具有縮合環構造的環氧樹脂;環氧丙基胺型環氧樹脂;環氧丙基酯型環氧樹脂;甲酚酚醛清漆型環氧樹脂;聯苯型環氧樹脂(具有聯苯骨架之環氧樹脂);線狀脂肪族環氧樹脂;具有丁二烯構造之環氧樹脂;脂環式環氧樹脂;雜環式環氧樹脂;含螺環之環氧樹脂;環己烷二甲醇型環氧樹脂;三羥甲基型環氧樹脂;四苯基乙烷型環氧樹脂等。環氧樹脂係可單獨使用1種,亦可將2種以上組合使用。環氧樹脂,較佳為選自由雙酚A型環氧樹脂、具有聯苯骨架之環氧樹脂、萘型環氧樹脂及具有縮合環構造之環氧樹脂中的1種以上,更佳為選自由具有聯苯骨架之環氧樹脂及具有縮合環構造之環氧樹脂中的1種以上。Examples of the epoxy resin include: bisphenol A epoxy resin; bisphenol F epoxy resin; bisphenol S epoxy resin; bisphenol AF epoxy resin; dicyclopentadiene epoxy resin ; Triphenol epoxy resin; phenol novolac epoxy resin; tert-butyl-catechol epoxy resin; naphthol novolac epoxy resin, naphthalene epoxy resin, naphthol epoxy resin And anthracene-type epoxy resins with condensed ring structure epoxy resins; epoxypropylamine epoxy resins; epoxypropyl ester epoxy resins; cresol novolac epoxy resins; biphenyl ring Oxygen resin (epoxy resin with biphenyl skeleton); linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing ring Epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin and the like. The epoxy resins may be used alone or in combination of two or more. The epoxy resin is preferably one or more selected from the group consisting of a bisphenol A epoxy resin, an epoxy resin having a biphenyl skeleton, a naphthalene epoxy resin, and an epoxy resin having a condensed ring structure. One or more of an epoxy resin having a biphenyl skeleton and an epoxy resin having a condensed ring structure are free.
環氧樹脂,較佳係包含於1分子中具有2個以上之環氧基的環氧樹脂。又,環氧樹脂,較佳係具有芳香族構造,在使用2種以上之環氧樹脂的情況,更佳係至少1種具有芳香族構造。在將環氧樹脂之不揮發性成分設為100質量%的情況時,較佳係至少50質量%以上為於1分子中具有2個以上之環氧基的環氧樹脂。其中,較佳係包含於1分子中具有2個以上之環氧基且溫度20℃時為液狀之環氧樹脂(以下稱為「液狀環氧樹脂」),與於1分子中具有3個以上之環氧基且溫度20℃時為固體狀之環氧樹脂(以下稱為「固體狀環氧樹脂」)。藉由併用液狀環氧樹脂與固體狀環氧樹脂作為環氧樹脂,而可得到具有優異的可撓性之樹脂組成物。又,樹脂組成物之硬化物的破斷強度亦會提昇。芳香族構造係指一般定義為芳香族的化學構造,也包含多環芳香族及芳香族雜環。The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. The epoxy resin preferably has an aromatic structure. When two or more epoxy resins are used, it is more preferable that at least one of the epoxy resins has an aromatic structure. When the nonvolatile component of an epoxy resin is 100 mass%, it is preferable that it is an epoxy resin which has 2 or more epoxy groups in 1 molecule at least 50 mass% or more. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) is preferred, and one having 3 in one molecule is preferable. More than two epoxy groups and solid epoxy resin at a temperature of 20 ° C (hereinafter referred to as "solid epoxy resin"). By using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the hardened | cured material of a resin composition will also improve. Aromatic structure refers to a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.
作為液狀環氧樹脂,較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、環氧丙基酯型環氧樹脂、環氧丙基胺型環氧樹脂、酚酚醛清漆型環氧樹脂、具有酯骨架之脂環式環氧樹脂、環己烷二甲醇型環氧樹脂、環氧丙基胺型環氧樹脂、及具有丁二烯構造之環氧樹脂,更佳為環氧丙基胺型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂及萘型環氧樹脂。作為液狀環氧樹脂之具體例,可列舉:DIC公司製之「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)、三菱化學公司製之「828US」、「jER828EL」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「jER152」(酚酚醛清漆型環氧樹脂)、「630」、「630LSD」(環氧丙基胺型環氧樹脂)、新日鐵住金化學公司製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)、Nagase chemteX公司製之「EX-721」(環氧丙基酯型環氧樹脂)、DAICEL公司製之「CELLOXIDE 2021P」(具有酯骨架之脂環式環氧樹脂)、「PB-3600」(具有丁二烯構造之環氧樹脂)、新日鐵住金化學公司製之「ZX1658」、「ZX1658GS」(液狀1,4-環氧丙基環己烷)、三菱化學公司製之「630LSD」(環氧丙基胺型環氧樹脂)、ADEKA公司製之「EP-3980S」(環氧丙基胺型環氧樹脂)等。此等係可單獨使用1種,亦可將2種以上組合使用。The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AF epoxy resin, a naphthalene epoxy resin, an epoxypropyl ester epoxy resin, Epoxypropylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, epoxypropylamine type epoxy resin, and Epoxy resin with butadiene structure, more preferably epoxypropylamine epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin and naphthalene ring Oxygen resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC, "828US", "jER828EL" (double Phenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (epoxypropylamine type epoxy resin) Resin), "ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "EX-721" (epoxypropyl group) manufactured by Nagase chemteX Corporation (Ester type epoxy resin), "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL, "PB-3600" (epoxy resin with butadiene structure), Nippon Steel & Sumitomo Chemical "ZX1658", "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane) made by the company, "630LSD" (epoxypropylamine type epoxy resin) made by Mitsubishi Chemical Corporation, and ADEKA company made "EP-3980S" (epoxypropylamine type epoxy resin), etc. These systems can be used singly or in combination of two or more.
作為固體狀環氧樹脂,較佳為萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、四苯基乙烷型環氧樹脂,更佳為萘型4官能環氧樹脂、萘酚型環氧樹脂、及聯苯型環氧樹脂。作為固體狀環氧樹脂之具體例,可列舉:DIC公司製之「HP4032H」(萘型環氧樹脂)、「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)、「N-690」(甲酚酚醛清漆型環氧樹脂)、「N-695」(甲酚酚醛清漆型環氧樹脂)、「HP-7200」(二環戊二烯型環氧樹脂)、「HP-7200HH」、「HP-7200H」、「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)、日本化藥公司製之「EPPN-502H」(三酚型環氧樹脂)、「NC7000L」(萘酚酚醛清漆型環氧樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵住金化學公司製之「ESN475V」(萘型環氧樹脂)、「ESN485」(萘酚酚醛清漆型環氧樹脂)、三菱化學公司製之「YX4000H」、「YL6121」(聯苯型環氧樹脂)、「YX4000HK」(聯二甲苯酚型環氧樹脂)、「YX8800」(蒽型環氧樹脂)、Osaka Gas Chemicals公司製之「PG-100」、「CG-500」、三菱化學公司製之「YL7760」(雙酚AF型環氧樹脂)、「YL7800」(茀型環氧樹脂)、三菱化學公司製之「jER1010」(固體狀雙酚A型環氧樹脂)、「jER1031S」(四苯基乙烷型環氧樹脂)等。此等係可單獨使用1種,亦可將2種以上組合使用。The solid epoxy resin is preferably a naphthalene type 4-functional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, or a naphthol type epoxy resin. , Biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, more preferably naphthalene type 4-functional epoxy resin Resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type 4-functional epoxy resin), and " "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP -7200HH "," HP-7200H "," EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(dnaphthyl ether ring Oxygen resin), "EPPN-502H" (triphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", `` NC3100 '' (biphenyl type epoxy resin), `` ESN475V '' (naphthalene type epoxy resin), `` ESN485 '' (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and Mitsubishi Chemical Corporation "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG- 100 "," CG -500 "," YL7760 "(bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation," YL7800 "(type epoxy resin)," jER1010 "(solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. These systems can be used singly or in combination of two or more.
在併用液狀環氧樹脂與固體狀環氧樹脂作為環氧樹脂的情況,該等之量比(液狀環氧樹脂:固體狀環氧樹脂),以質量比計,較佳為1:0.1~1:4之範圍。藉由將液狀環氧樹脂與固體狀環氧樹脂之量比設為該範圍,可得到下列效果:i)在以接著薄膜的形態作使用的情況時可獲得適度的黏著性;ii)在以接著薄膜的形態作使用時可得到充分的可撓性,而操作性提昇;以及iii)可得到具有充分的破斷強度之硬化物。就上述i)~iii)之效果的觀點而言,液狀環氧樹脂與固體狀環氧樹脂之量比(液狀環氧樹脂:固體狀環氧樹脂),以質量比計,更佳為1:0.3~1:3.5之範圍,更佳為1:0.6~1:3之範圍,特佳為1:0.8~1:2.5之範圍。When a liquid epoxy resin and a solid epoxy resin are used together as the epoxy resin, the amount ratios (liquid epoxy resin: solid epoxy resin) are preferably 1: 0.1 by mass ratio. The range of ~ 1: 4. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, the following effects can be obtained: i) when the film is used in the form of an adhesive film, moderate adhesion can be obtained; ii) in When it is used in the form of an adhesive film, sufficient flexibility can be obtained and workability can be improved; and iii) a hardened material having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) described above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in terms of mass ratio. A range of 1: 0.3 to 1: 3.5, more preferably a range of 1: 0.6 to 1: 3, and particularly preferably a range of 1: 0.8 to 1: 2.5.
(A)成分之含量(質量%),就得到顯示良好的機械強度、絕緣可靠性的磁性層的觀點而言,在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為0.1質量%以上,更佳為0.5質量%以上,再更佳為1質量%以上。環氧樹脂之含量的上限,只要可發揮本發明之效果則無特別限定,但,較佳為10質量%以下,更佳為5質量%以下,再更佳為3質量%以下。(A) The content (% by mass) of the component is more than 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining a magnetic layer exhibiting good mechanical strength and insulation reliability. It is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and even more preferably at least 1% by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention can be exhibited, but it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.
(A)成分之含量(體積%),在將樹脂組成物中之不揮發性成分設為100體積%的情況,較佳為1質量%以上,更佳為3質量%以上,再更佳為5質量%以上。上限,只要可發揮本發明之效果則無特別限定,但,較佳為25質量%以下,更佳為20質量%以下,再更佳為15質量%以下。(A) The content (vol.%) Of the component is preferably 1% by mass or more, more preferably 3% by mass, or even more preferably when the nonvolatile component in the resin composition is 100% by volume. 5 mass% or more. The upper limit is not particularly limited as long as the effects of the present invention can be exhibited, but it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
環氧樹脂之環氧當量,較佳為50~5000,更佳為50~3000,再更佳為80~2000,又再更佳為110~1000。藉由成為此範圍,可使硬化物之交聯密度變得充分,而獲得表面粗度小的磁性層。另外,環氧當量係可依照JIS K7236進行測定,包含1當量之環氧基的樹脂之質量。The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and still more preferably 110 to 1,000. By setting it as this range, the crosslinking density of hardened | cured material becomes sufficient, and a magnetic layer with small surface roughness can be obtained. The epoxy equivalent is measured in accordance with JIS K7236 and is the mass of a resin containing 1 equivalent of epoxy groups.
環氧樹脂之重量平均分子量,較佳為100~5000,更佳為250~3000,再更佳為400~1500。在此,環氧樹脂之重量平均分子量係藉由凝膠滲透層析(GPC)法所測定之聚苯乙烯換算之重量平均分子量。The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
<(B)硬化劑> 樹脂組成物係含有(B)硬化劑。(B)成分只要具有將(A)成分硬化的功能則無特別限定。在(A)成分為環氧樹脂的情況時,硬化劑為環氧樹脂硬化劑。作為環氧樹脂硬化劑,可列舉例如:酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯并嗪系硬化劑、及氰酸酯系硬化劑。環氧樹脂硬化劑係可單獨使用1種,或者亦可併用2種以上。就絕緣性之可靠性及耐熱性的觀點而言,作為硬化劑,較佳係選自由酚系硬化劑及活性酯系硬化劑中的1種以上。<(B) Hardener> The resin composition system contains (B) a hardener. The component (B) is not particularly limited as long as it has a function of curing the component (A). When (A) component is an epoxy resin, a hardening | curing agent is an epoxy resin hardening | curing agent. Examples of the epoxy resin hardener include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and benzo A azine-based hardener and a cyanate-based hardener. The epoxy resin hardener may be used alone or in combination of two or more. From the viewpoint of insulation reliability and heat resistance, the hardener is preferably one or more selected from the group consisting of a phenol-based hardener and an active ester-based hardener.
作為酚系硬化劑及萘酚系硬化劑,就耐熱性及耐水性的觀點而言,較佳係具有酚醛清漆構造之酚系硬化劑,或者具有酚醛清漆構造之萘酚系硬化劑。又,就與導體層之密著性的觀點而言,較佳為含氮酚系硬化劑,更佳為含三嗪骨架之酚系硬化劑。其中,就高度滿足耐熱性、耐水性、及與導體層之密著性的觀點而言,較佳為含有三嗪骨架之酚酚醛清漆硬化劑。As the phenol-based hardener and naphthol-based hardener, from the viewpoints of heat resistance and water resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. From the viewpoint of adhesion with the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a triazine skeleton-containing phenol-based hardener is more preferred. Among these, a phenol novolak hardener containing a triazine skeleton is preferred from the viewpoint of satisfying high heat resistance, water resistance, and adhesion to a conductor layer.
作為酚系硬化劑及萘酚系硬化劑之具體例,可列舉:明和化成公司製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製之「NHN」、「CBN」、「GPH」、新日鐵住金化學公司製之「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495V」、「SN375」、「SN395」、DIC公司製之「TD-2090」、「LA-7052」、「LA-7054」、「LA-1356」、「LA-3018-50P」、「EXB-9500」、「HPC-9500」、「KA-1160」、「KA-1163」、「KA-1165」、群榮化學公司製之「GDP-6115L」、「GDP-6115H」等。Specific examples of the phenol-based hardener and naphthol-based hardener include "MEH-7700", "MEH-7810", "MEH-7851", and "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395", DIC "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA- 1160 "," KA-1163 "," KA-1165 "," GDP-6115L "," GDP-6115H "manufactured by Qunrong Chemical Company, etc.
作為活性酯系硬化劑雖無特別限制,但一般而言,較佳使用酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之於1分子中具有2個以上反應活性高的酯基之化合物。該活性酯系硬化劑,較佳係藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應所得者。尤其,就耐熱性提昇的觀點而言,較佳係由羧酸化合物與羥基化合物所得之活性酯系硬化劑,更佳係由羧酸化合物與酚化合物及/或萘酚化合物所得之活性酯系硬化劑。作為羧酸化合物,可列舉例如:苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。作為酚化合物或萘酚化合物,可列舉例如:氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥基二苯基酮、根皮三酚、苯三酚、二環戊二烯型二酚化合物、酚酚醛清漆等。在此,「二環戊二烯型二酚化合物」係指二環戊二烯1分子與酚2分子進行縮合所得之二酚化合物。Although it is not particularly limited as an active ester-based hardener, in general, it is preferable to use phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, and the like having 2 in one molecule. More than one ester compound with high reactivity. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improvement in heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester based from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, phlorogallol, pyrogallol, dicyclopentadiene type diphenol compound , Phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.
具體而言,較佳係包含二環戊二烯型二酚構造之活性酯化合物、包含萘構造之活性酯化合物、包含酚酚醛清漆之乙醯化物之活性酯化合物、包含酚酚醛清漆之苯甲醯化物之活性酯化合物,其中,更佳係包含萘構造之活性酯化合物、包含二環戊二烯型二酚構造之活性酯化合物。「二環戊二烯型二酚構造」係表示由伸苯基-二環伸戊基-伸苯基所構成之2價之構造。Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetic acid phenol novolac, and a benzyl containing a novolac Among the active ester compounds of a halogenated compound, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" means a bivalent structure composed of phenylene-bicyclopentyl-phenylene.
作為活性酯系硬化劑之市售品,可列舉:作為包含二環戊二烯型二酚構造之活性酯化合物之「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000-65T」、「HPC-8000H-65TM」、「EXB-8000L-65TM」(DIC公司製)、作為包含萘構造之活性酯化合物之「EXB9416-70BK」(DIC公司製)、作為包含酚酚醛清漆之乙醯化物之活性酯化合物之「DC808」(三菱化學公司製)、作為包含酚酚醛清漆之苯甲醯化物之活性酯化合物之「YLH1026」(三菱化學公司製)、作為酚酚醛清漆之乙醯化物之活性酯系硬化劑之「DC808」(三菱化學公司製)、作為酚酚醛清漆之苯甲醯化物之活性酯系硬化劑之「YLH1026」(三菱化學公司製)、「YLH1030」(三菱化學公司製)、「YLH1048」(三菱化學公司製)等。Examples of commercially available products of the active ester-based hardener include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB9451", active ester compounds containing a dicyclopentadiene-type diphenol structure, `` HPC-8000H-65TM '', `` EXB-8000L-65TM '' (manufactured by DIC Corporation), `` EXB9416-70BK '' (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and acetic acid compound containing phenol novolac Active ester compound "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a phenol novolac benzoic acid compound, and activity as an acetic acid compound of a novolac "DC808" (Mitsubishi Chemical Corporation) as an ester hardener, "YLH1026" (Mitsubishi Chemical Corporation) ("Mitsubishi Chemical Corporation") , "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.
作為苯并嗪系硬化劑之具體例,可列舉:昭和高分子公司製之「HFB2006M」、四國化成工業公司製之「P-d」、「F-a」。As benzo Specific examples of the hydrazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.
作為氰酸酯系硬化劑,可列舉例如:雙酚A二氰酸酯、多酚氰酸酯、寡(3-亞甲基-1,5-伸苯基氰酸酯)、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚、及雙(4-氰酸酯苯基)醚等之2官能氰酸酯樹脂、由酚酚醛清漆及甲酚酚醛清漆等所衍生的多官能氰酸酯樹脂、此等氰酸酯樹脂一部分經三嗪化的預聚物等。作為氰酸酯系硬化劑之具體例,可列舉:Lonza Japan公司製之「PT30」及「PT60」(均為酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部分或全部被三嗪化而成為三聚物的預聚物)等。Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4 ' -Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether, etc. Bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolacs, cresol novolacs, etc., and prepolymers in which some of these cyanate resins are triazinated. Specific examples of the cyanate-based hardener include "PT30" and "PT60" (both phenol novolac-type polyfunctional cyanate resins), "BA230", and "BA230S75" (double Some or all of the phenol A dicyanate is triazinated to form a trimer (a prepolymer), and the like.
環氧樹脂與硬化劑之量比,以[環氧樹脂之環氧基之合計數]:[硬化劑之反應基之合計數]之比率計,較佳為1:0.2~1:2之範圍,更佳為1:0.3~1:1.5之範圍,再更佳為1:0.4~1:1之範圍。在此,硬化劑之反應基係指活性羥基、活性酯基等,依硬化劑之種類而異。又,環氧樹脂之環氧基之合計數係指對於將各環氧樹脂之不揮發性成分之質量除以環氧當量之值,針對全部的環氧樹脂進行合計之值,硬化劑之反應基之合計數係指對於將各硬化劑之不揮發性成分之質量除以反應基當量之值,針對全部的硬化劑進行合計之值。藉由將環氧樹脂與硬化劑之量比設為該範圍內,而更提昇作為硬化劑時之耐熱性。The ratio of the epoxy resin to the hardener is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reaction groups of the hardener], preferably in a range of 1: 0.2 to 1: 2. , More preferably in the range of 1: 0.3 to 1: 1.5, and even more preferably in the range of 1: 0.4 to 1: 1. Here, the reactive group of the hardener refers to an active hydroxyl group, an active ester group, and the like, and it varies depending on the type of the hardener. In addition, the total number of epoxy groups of an epoxy resin refers to a value obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent, and the total value for all epoxy resins, and the reaction of the curing agent. The total number of bases is a value obtained by dividing the mass of the non-volatile component of each hardener by the equivalent of the reactive group, and totaling all hardeners. By setting the amount ratio of the epoxy resin to the hardener within this range, the heat resistance when used as a hardener is further improved.
樹脂組成物,較佳係分別包含作為環氧樹脂之液狀環氧樹脂與固體狀環氧樹脂之混合物,與作為硬化劑之選自由酚系硬化劑及活性酯系硬化劑所成之群中的1種以上。The resin composition preferably contains a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin, and a hardener selected from the group consisting of a phenol-based hardener and an active ester-based hardener. More than 1 kind.
(B)成分之含量,在將樹脂組成物中之不揮發性成分設為100體積%的情況,較佳為5質量%以下,更佳為3質量%以下,再更佳為2質量%以下。又,下限雖無特別限制,但較佳為0.1質量%以上。(B) The content of the component is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less when the nonvolatile component in the resin composition is 100% by volume. . The lower limit is not particularly limited, but is preferably 0.1% by mass or more.
<(C)熱塑性樹脂> 樹脂組成物係含有(C)熱塑性樹脂。藉由含有(C)成分,可使彈性率降低,而減低翹曲。<(C) Thermoplastic resin> The resin composition system contains (C) a thermoplastic resin. By containing the (C) component, the elastic modulus can be reduced, and warpage can be reduced.
作為熱塑性樹脂,可列舉例如:苯氧基樹脂、丙烯酸系樹脂、聚乙烯縮醛樹脂、丁醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚碸樹脂、及聚碸樹脂等,較佳係選自由苯氧基樹脂、聚乙烯縮醛樹脂、丁醛樹脂、及丙烯酸系樹脂中的1種以上。熱塑性樹脂係可單獨使用1種,或者亦可併用2種以上。Examples of the thermoplastic resin include a phenoxy resin, an acrylic resin, a polyvinyl acetal resin, a butyral resin, a polyimide resin, a polyimide resin, a polyetherimide resin, and a polyimide resin. Etc., Preferably it is 1 or more types chosen from the group which consists of a phenoxy resin, a polyvinyl acetal resin, a butyral resin, and an acrylic resin. The thermoplastic resins may be used singly or in combination of two or more kinds.
熱塑性樹脂之聚苯乙烯換算之重量平均分子量,較佳為3萬以上,更佳為5萬以上,再更佳為10萬以上。又,較佳為100萬以下,更佳為75萬以下,再更佳為50萬以下。熱塑性樹脂之聚苯乙烯換算之重量平均分子量係藉由凝膠滲透層析(GPC)法所測定。具體而言,熱塑性樹脂之聚苯乙烯換算之重量平均分子量,可使用作為測定裝置之島津製作所公司製「LC-9A/RID-6A」、作為管柱之昭和電工公司製「Shodex K-800P/K-804L/K-804L」、作為移動相之氯仿等,並以管柱溫度40℃進行測定,並使用標準聚苯乙烯之檢量曲線來算出。The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 30,000 or more, more preferably 50,000 or more, and still more preferably 100,000 or more. In addition, it is preferably 1 million or less, more preferably 750,000 or less, and even more preferably 500,000 or less. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene in terms of thermoplastic resin can be used as a measuring device, "LC-9A / RID-6A" manufactured by Shimadzu Corporation, and "Shodex K-800P / K-804L / K-804L ", chloroform, etc. as a mobile phase, were measured at a column temperature of 40 ° C, and calculated using a calibration curve of standard polystyrene.
作為苯氧基樹脂,可例舉例如:具有選自由雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯骨架、茀骨架、二環戊二烯骨架、降莰烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架、及三甲基環己烷骨架所成之群中的1種以上之骨架的苯氧基樹脂。苯氧基樹脂之末端亦可為酚性羥基、環氧基等之任一種官能基。苯氧基樹脂係可單獨使用1種,或者亦可併用2種以上。作為苯氧基樹脂之具體例,可列舉:三菱化學公司製之「1256」及「4250」(均為含有雙酚A骨架之苯氧基樹脂)、「YX8100」(含有雙酚S骨架之苯氧基樹脂)、及「YX6954」(含有雙酚苯乙酮骨架之苯氧基樹脂),其他,亦可列舉:新日鐵住金化學公司製之「FX280」及「FX293」、三菱化學公司製之「YL7500BH30」、「YX6954BH30」、「YX7553」、「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」及「YL7482」等。Examples of the phenoxy resin include a resin selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and dicyclopentane. One or more types of phenoxy resins in the group consisting of a diene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) and "YX8100" (benzenes containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. Oxyresin) and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), others can also be mentioned: "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and manufactured by Mitsubishi Chemical Corporation "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" and so on.
作為丙烯酸系樹脂,就使熱膨脹率及彈性率更降低的觀點而言,較佳為含有官能基之丙烯酸系樹脂,更佳為玻璃轉移溫度25℃以下之含有環氧基之丙烯酸系樹脂。The acrylic resin is preferably an acrylic resin containing a functional group, and more preferably an epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C or lower, from the viewpoint of further reducing the thermal expansion coefficient and the elastic modulus.
含有官能基之丙烯酸系樹脂之數量平均分子量(Mn),較佳為10000~1000000,更佳為30000~900000。The number average molecular weight (Mn) of the acrylic resin containing a functional group is preferably 10,000 to 1,000,000, and more preferably 30,000 to 900,000.
含有官能基之丙烯酸系樹脂之官能基當量,較佳為1000~50000,更佳為2500~30000。The functional group equivalent of the acrylic resin containing a functional group is preferably 1,000 to 50,000, and more preferably 2500 to 30,000.
作為玻璃轉移溫度為25℃以下之含環氧基之丙烯酸系樹脂,較佳為玻璃轉移溫度為25℃以下之含環氧基之丙烯酸酯共聚物樹脂,作為其具體例,可列舉:Nagase chemteX公司製「SG-80H」(含環氧基之丙烯酸酯共聚物樹脂(數量平均分子量Mn:350000g/mol、環氧價0.07eq/kg、玻璃轉移溫度11℃))、Nagase chemteX公司製「SG-P3」(含環氧基之丙烯酸酯共聚物樹脂(數量平均分子量Mn:850000g/mol、環氧價0.21eq/kg、玻璃轉移溫度12℃))。The epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower is preferably an epoxy group-containing acrylate copolymer resin having a glass transition temperature of 25 ° C. or lower. As a specific example, Nagase chemteX is mentioned. "SG-80H" manufactured by the company (epoxy-containing acrylate copolymer resin (quantity average molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, glass transition temperature 11 ° C)), Nagase chemteX Corporation "SG -P3 "(epoxy-containing acrylate copolymer resin (number average molecular weight Mn: 850,000 g / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C)).
作為聚乙烯縮醛樹脂、丁醛樹脂之具體例,可列舉:電氣化學工業公司製之Denka Butyral「4000-2」、「5000-A」、「6000-C」、「6000-EP」、積水化學工業公司製之S-LEC BH系列、BX系列、「KS-1」等之KS系列、「BL-1」等之BL系列、BM系列等。Specific examples of the polyvinyl acetal resin and the butyral resin include Denka Butyral "4000-2", "5000-A", "6000-C", "6000-EP", and Sekisui manufactured by Denki Chemical Industry Co., Ltd. S-LEC BH series, BX series, KS series such as "KS-1", BL series such as "BL-1", and BM series manufactured by Chemical Industry Corporation.
作為聚醯亞胺樹脂之具體例,可列舉:新日本理化公司製之「RIKACOAT SN20」及「RIKACOAT PN20」。作為聚醯亞胺樹脂之具體例,又可列舉:使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐進行反應所得之線狀聚醯亞胺(日本特開2006-37083號公報記載之聚醯亞胺)、含聚矽氧烷骨架之聚醯亞胺(日本特開2002-12667號公報及日本特開2000-319386號公報等記載之聚醯亞胺)等之變性聚醯亞胺。Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Rika Chemical Co., Ltd. Specific examples of the polyfluorene imine resin include linear polyfluorene imide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride (Japanese Patent Laid-Open No. 2006-37083). Polyimide described in the Gazette), polyimide containing a polysiloxane skeleton (polyimide described in JP 2002-12667 and JP 2000-319386, etc.) and other modified polymers醯 imine.
作為聚醯胺醯亞胺樹脂之具體例,可列舉:東洋紡公司製之「VYLOMAX HR11NN」及「VYLOMAX HR16NN」。作為聚醯胺醯亞胺樹脂之具體例,又可列舉:日立化成公司製之「KS9100」、「KS9300」(含聚矽氧烷骨架之聚醯胺醯亞胺)等之變性聚醯胺醯亞胺。Specific examples of the polyimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation. Specific examples of the polyimide resin include modified polyimide resins such as "KS9100" and "KS9300" (polysiloxane imine containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. Imine.
作為聚醚碸樹脂之具體例,可列舉住友化學公司製之「PES5003P」等。作為聚苯醚樹脂之具體例,可列舉:Mitsubishi Gas Chemical公司製之具有乙烯基之oligo phenylene ether(OPE)・苯乙烯樹脂「OPE-2St 1200」等。Specific examples of the polyether fluorene resin include "PES5003P" manufactured by Sumitomo Chemical Co., and the like. Specific examples of the polyphenylene ether resin include oligo phenylene ether (OPE) with a vinyl group and a styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical.
作為聚碸樹脂之具體例,可列舉:Solvay Advanced Polymers公司製之聚碸「P1700」、「P3500」等。Specific examples of the polyfluorene resin include polyfluoride "P1700" and "P3500" manufactured by Solvay Advanced Polymers.
其中,作為熱塑性樹脂,較佳為重量平均分子量3萬以上100萬以下之選自由苯氧基樹脂、聚乙烯縮醛樹脂、丁醛樹脂、及丙烯酸系樹脂中的1種以上。Among them, the thermoplastic resin is preferably one or more selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a butyral resin, and an acrylic resin with a weight average molecular weight of 30,000 to 1 million.
(C)成分之含量(c1),在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為0.1質量%以上,更佳為0.2質量%以上,再更佳為0.3質量%以上。又,較佳為10質量%以下,更佳為9質量%以下,再更佳為8質量%以下。藉由將(C)成分之含量設為該範圍內,可使樹脂組成物之黏度成為適度,而形成厚度或塊材性狀均勻的樹脂組成物層。The content (c1) of the component (c1) is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and even more preferably 0.3 when the nonvolatile component in the resin composition is 100 mass%. Above mass%. The content is preferably 10% by mass or less, more preferably 9% by mass or less, and even more preferably 8% by mass or less. By setting the content of the component (C) within this range, the viscosity of the resin composition can be made moderate, and a resin composition layer having a uniform thickness or bulk properties can be formed.
在將樹脂組成物中樹脂成分之含有質量設為a1,並將(C)成分之含有質量設為c1的情況時,較佳係以使(c1/a1)×100成為較佳為35以上的方式來調整(C)成分之含量,更佳為45以上,再更佳為55以上、65以上、或70以上。上限,較佳為80以下,更佳為78以下,再更佳為77以下。藉由以使(C)成分之含量成為如此之範圍內的方式進行調整,而使樹脂組成物熱硬化而成的硬化物於23℃時之彈性率容易為7GPa以上18GPa以下。其結果,可得到難燃性優異,翹曲量受到抑制,尤其是可提昇頻率為10~200MHz之範圍內之相對導磁率,通常磁性損失亦減低之硬化物。進而,使用該樹脂組成物所得之接著薄膜係疊層性優異。 在此,「樹脂成分」係指構成樹脂組成物之不揮發性成分當中,排除(D)成分及(E)成分後的成分。When the content of the resin component in the resin composition is set to a1 and the content of the (C) component is set to c1, it is preferable that (c1 / a1) × 100 is preferably 35 or more. Way to adjust the content of the component (C), more preferably 45 or more, still more preferably 55 or more, 65 or more, or 70 or more. The upper limit is preferably 80 or less, more preferably 78 or less, and even more preferably 77 or less. By adjusting so that the content of the component (C) falls within such a range, a cured product obtained by thermally curing the resin composition is likely to have an elastic modulus at 23 ° C. of not less than 7 GPa and not more than 18 GPa. As a result, it is possible to obtain a hardened product which is excellent in flame retardancy and suppresses the amount of warpage. In particular, it is possible to increase the relative magnetic permeability in the frequency range of 10 to 200 MHz and generally reduce the magnetic loss. Furthermore, the adhesive film obtained by using this resin composition is excellent in lamination property.此 Here, the "resin component" refers to a component excluding the (D) component and the (E) component among the nonvolatile components constituting the resin composition.
<(D)磁性填料> 樹脂組成物係含有(D)磁性填料。磁性填料之材料並無特別限定,可列舉例如:純鐵粉末、Fe-Si系合金粉末、Fe-Si-Al系合金粉末、Fe-Cr系合金粉末、Fe-Cr-Si系合金粉末、Fe-Ni-Cr系合金粉末、Fe-Cr-Al系合金粉末、Fe-Ni系合金粉末、Fe-Ni-Mo系合金粉末、Fe-Ni-Mo-Cu系合金粉末、Fe-Co系合金粉末、或者Fe-Ni-Co系合金粉末等之Fe合金類、Fe基非晶質、Co基非晶質等之非晶質合金類、Mg-Zn系肥粒鐵、Mn-Zn系肥粒鐵、Mn-Mg系肥粒鐵、Cu-Zn系肥粒鐵、Mg-Mn-Sr系肥粒鐵、Ni-Zn系肥粒鐵等之尖晶石型肥粒鐵類、Ba-Zn系肥粒鐵、Ba-Mg系肥粒鐵、Ba-Ni系肥粒鐵、Ba-Co系肥粒鐵、Ba-Ni-Co系肥粒鐵等之六方晶型肥粒鐵類、Y系肥粒鐵等之石榴石型肥粒鐵類。其中,作為(D)成分,較佳係Fe-Si系合金粉末、Fe-Si-Al系合金粉末、Fe-Cr系合金粉末、Fe-Cr-Si系合金粉末、Fe-Ni-Cr系合金粉末、Fe-Cr-Al系合金粉末等之包含選自由Si、Al、及Cr中的1種以上之元素的Fe合金類。<(D) Magnetic Filler> The resin composition system contains (D) a magnetic filler. The material of the magnetic filler is not particularly limited, and examples thereof include pure iron powder, Fe-Si-based alloy powder, Fe-Si-Al-based alloy powder, Fe-Cr-based alloy powder, Fe-Cr-Si-based alloy powder, and Fe -Ni-Cr alloy powder, Fe-Cr-Al alloy powder, Fe-Ni alloy powder, Fe-Ni-Mo alloy powder, Fe-Ni-Mo-Cu alloy powder, Fe-Co alloy powder Or Fe alloys such as Fe-Ni-Co based alloy powders, amorphous alloys such as Fe-based amorphous and Co-based amorphous, Mg-Zn-based fertilizer iron, Mn-Zn-based fertilizer iron , Mn-Mg-based fertilizer granular iron, Cu-Zn-based fertilizer granular iron, Mg-Mn-Sr-based fertilizer granular iron, Ni-Zn-based fertilizer granular spinel iron, Ba-Zn fertilizer Hexagonal crystal grain iron, Ba-Mg type iron, Ba-Ni type iron, Ba-Co type iron, Ba-Ni-Co type iron, etc. Garnet-type fertilizers such as iron. Among them, the component (D) is preferably Fe-Si-based alloy powder, Fe-Si-Al-based alloy powder, Fe-Cr-based alloy powder, Fe-Cr-Si-based alloy powder, and Fe-Ni-Cr-based alloy. Fe alloys such as powders, Fe-Cr-Al-based alloy powders, and the like containing one or more elements selected from the group consisting of Si, Al, and Cr.
作為磁性填料係可使用市售之磁性填料。作為可使用之市售之磁性填料的具體例,可列舉:山陽特殊製鋼公司製「PST-S」、EPSON ATMIX公司製「AW2-08」、「AW2-08PF20F」、「AW2-08PF10F」、「AW2-08PF3F」、「Fe-3.5Si-4.5CrPF20F」、「Fe-50NiPF20F」、「Fe-80Ni-4MoPF20F」、JFE Chemical公司製「LD-M」、「LD-MH」、「KNI-106」、「KNI-106GSM」、「KNI-106GS」、「KNI-109」、「KNI-109GSM」、「KNI-109GS」、戶田工業公司製「KNS-415」、「BSF-547」、「BSF-029」、「BSN-125」、「BSN-714」、「BSN-828」、「S-1281」、「S-1641」、「S-1651」、「S-1470」、「S-1511」、「S-2430」、日本重化學工業公司製「JR09P2」、CIK nanoTech公司製「Nanotek」、KINSEI MATEC公司製「JEMK-S」、「JEMK-H」、ALDRICH公司製「Yttrium iron oxide」等。磁性填料係可單獨使用1種,或者亦可併用2種以上。As the magnetic filler, a commercially available magnetic filler can be used. Specific examples of commercially available magnetic fillers include: "PST-S" made by Sanyo Special Steel Co., Ltd., "AW2-08", "AW2-08PF20F", "AW2-08PF10F", "AW2-08PF10F", "AW2-08PF10F", "EPSON ATMIX" AW2-08PF3F "," Fe-3.5Si-4.5CrPF20F "," Fe-50NiPF20F "," Fe-80Ni-4MoPF20F "," LD-M "," LD-MH "," KNI-106 "manufactured by JFE Chemical , "KNI-106GSM", "KNI-106GS", "KNI-109", "KNI-109GSM", "KNI-109GS", "KNS-415", "BSF-547", "BSF" -029 "," BSN-125 "," BSN-714 "," BSN-828 "," S-1281 "," S-1641 "," S-1651 "," S-1470 "," S-1511 " "," S-2430 "," JR09P2 "manufactured by Japan Heavy Chemical Industries," Nanotek "manufactured by CIK nanoTech," JEMK-S "," JEMK-H "manufactured by KINSEI MATEC," Yttrium iron oxide "manufactured by ALDRICH Wait. The magnetic fillers may be used singly or in combination of two or more kinds.
(D)成分較佳為球狀。作為將(D)成分之粉體的長邊之長度除以短邊之長度的值(縱橫比),較佳為2以下,更佳為1.5以下,再更佳為1.2以下。一般而言,磁性填料係以非球狀的扁平形狀較容易提昇相對導磁率。但,為了將(A)成分~(C)成分組合來實現特定之彈性率,尤其是使用球狀之(D)成分者較可容易得到具有所期望之特性的樹脂組成物。The (D) component is preferably spherical. The value (aspect ratio) in which the length of the long side of the powder of the component (D) is divided by the length of the short side is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. Generally speaking, it is easier to increase the relative magnetic permeability of the magnetic filler in an aspherical flat shape. However, in order to achieve a specific modulus of elasticity by combining the components (A) to (C), it is easier to obtain a resin composition having desired characteristics especially when the spherical (D) component is used.
(D)成分之平均粒徑,較佳為0.01μm以上,更佳為0.5μm以上,再更佳為1μm以上。又,較佳為8μm以下,更佳為5μm以下,再更佳為4μm以下。(D)成分之平均粒徑,可以與後述之(E)成分之平均粒徑相同的方法進行測定。The average particle diameter of the component (D) is preferably 0.01 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. The thickness is preferably 8 μm or less, more preferably 5 μm or less, and even more preferably 4 μm or less. The average particle diameter of the component (D) can be measured by the same method as the average particle diameter of the component (E) described later.
作為(D)成分,若使用平均粒徑為0.01μm以上8μm以下之磁性填料,則在頻率為0~10MHz的情況,相較於使用平均粒徑超過25μm之磁性填料的情況之相對導磁率稍差。但,即使超過10MHz相對導磁率也不會急遽地降低,尤其可維持在0~200MHz之範圍之高相對導磁率。亦即,維持在0~200MHz之廣範圍,尤其是在10MHz~200MHz之相對導磁率,並且通常磁性損失亦減低。As the component (D), if a magnetic filler having an average particle diameter of 0.01 μm to 8 μm is used, the relative magnetic permeability at a frequency of 0 to 10 MHz is slightly smaller than that when a magnetic filler having an average particle diameter of more than 25 μm is used. difference. However, even if the relative magnetic permeability exceeds 10 MHz, the relative magnetic permeability does not decrease sharply, and particularly, a high relative magnetic permeability in the range of 0 to 200 MHz can be maintained. That is, it maintains a wide range from 0 to 200 MHz, especially from 10 MHz to 200 MHz, and generally has a reduced magnetic loss.
(D)成分之含量(體積%),就提昇相對導磁率及難燃性的觀點而言,在將樹脂組成物中之不揮發性成分設為100體積%的情況,較佳為10體積%以上,更佳為20體積%以上,再更佳為30體積%以上。又,較佳為85體積%以下,更佳為75體積%以下,再更佳為65體積%以下。(D) The content (vol.%) Of the component is preferably 10 vol.% When the nonvolatile component in the resin composition is set to 100 vol.% From the viewpoint of improving the relative magnetic permeability and flame retardancy. The above is more preferably 20% by volume or more, and even more preferably 30% by volume or more. In addition, it is preferably 85 vol% or less, more preferably 75 vol% or less, and even more preferably 65 vol% or less.
(D)成分之含量(質量%:d1),就提昇相對導磁率及難燃性的觀點而言,在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為75質量%以上,更佳為76質量%以上,再更佳為77質量%以上。又,較佳為未達95質量%,更佳為94質量%以下,再更佳為93質量%以下。The content of the component (D) (mass%: d1) is preferably 75% in the case where the nonvolatile component in the resin composition is set to 100% by mass from the viewpoint of improving the relative magnetic permeability and flame retardancy. Mass% or more, more preferably 76 mass% or more, and still more preferably 77 mass% or more. The content is preferably less than 95% by mass, more preferably 94% by mass or less, and still more preferably 93% by mass or less.
在使用活性酯系硬化劑作為(B)成分的情況,及/或使用丙烯酸系樹脂作為(C)成分的情況,有時(A)成分~(C)成分之相溶性會變低。因此,樹脂組成物有時會形成由母相(海)與分散相(島)所構成的海島構造,且(D)成分集中存在於母相側。其結果,作為樹脂組成物之硬化物全體的相對導磁率會提昇。於此情況中,較佳係母相為(A)成分、(B)成分之混合成分,分散相為(C)成分。When the active ester hardener is used as the (B) component and / or when the acrylic resin is used as the (C) component, the compatibility between the (A) component to the (C) component may be lowered. Therefore, the resin composition may form an island structure composed of a mother phase (sea) and a dispersed phase (island), and the (D) component may be concentrated on the mother phase side. As a result, the relative magnetic permeability of the entire cured product as the resin composition is improved. In this case, it is preferable that the mother phase is a mixed component of the component (A) and the component (B), and the dispersed phase is the component (C).
藉由將含有(A)成分~(D)成分的樹脂組成物之組成以使熱硬化而成之硬化物於23℃時之彈性率成為7GPa以上18GPa以下的方式進行調整,可將頻率為10MHz~200MHz,尤其是頻率為10MHz~100MHz時之相對導磁率設為5以上,進而通常可將頻率為10MHz~100MHz時之磁性損失設為0.05以下。By adjusting the composition of the resin composition containing the components (A) to (D) so that the elastic modulus of the hardened material obtained by thermal curing at 23 ° C becomes 7 GPa or more and 18 GPa or less, the frequency can be 10 MHz The relative magnetic permeability at a frequency of ~ 200 MHz, especially at a frequency of 10 MHz to 100 MHz, is set to 5 or more, and further, the magnetic loss at a frequency of 10 MHz to 100 MHz can be generally set to 0.05 or less.
<(E)磁性填料以外之無機填充材> 於一實施形態中,樹脂組成物係可含有(E)磁性填料以外之無機填充材。藉由含有(E)成分,可減低磁性損失,並可抑制磁性層之熱膨脹,提昇可靠性。<(E) Inorganic Filler Other than Magnetic Filler> In one embodiment, the resin composition may contain an inorganic filler other than (E) a magnetic filler. By containing the (E) component, magnetic loss can be reduced, thermal expansion of the magnetic layer can be suppressed, and reliability can be improved.
(E)成分之材料雖只要為無機化合物則無特別限定,但可列舉例如:二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁礦、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鋯鈦酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯、及磷鎢酸鋯等。該等當中,以二氧化矽特別適合。作為二氧化矽,可列舉例如:無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等。又,作為二氧化矽,較佳為球狀二氧化矽。(E)成分係可單獨使用1種,亦可將2種以上組合使用。The material of the component (E) is not particularly limited as long as it is an inorganic compound, but examples thereof include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, Zinc oxide, hydrotalcite, gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, titanium Calcium acid, magnesium titanate, bismuth titanate, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate. Among these, silicon dioxide is particularly suitable. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. The silicon dioxide is preferably spherical silicon dioxide. (E) A component system may be used individually by 1 type, and may use 2 or more types together.
無機填充材之平均粒徑,為了使樹脂組成物之流動性及成形性成為良好,改善作為硬化物時之相對導磁率及磁性損失、以及初期電阻值,較佳為0.01μm以上,更佳為0.05μm以上,再更佳為0.1μm以上、0.3μm以上。又,較佳為5μm以下,更佳為2.5μm以下,再更佳為1.5μm以下、1μm以下。The average particle diameter of the inorganic filler is preferably 0.01 μm or more, in order to improve the fluidity and moldability of the resin composition, and to improve the relative permeability and magnetic loss and initial resistance when used as a hardened material. 0.05 μm or more, more preferably 0.1 μm or more and 0.3 μm or more. The thickness is preferably 5 μm or less, more preferably 2.5 μm or less, and even more preferably 1.5 μm or less and 1 μm or less.
無機填充材之平均粒徑係可藉由根據米氏(Mie)散射理論的雷射繞射/散射法進行測定。具體而言,可藉由雷射繞射散射式粒度分布測定裝置,以體積基準製成無機填充材之粒度分布,將其中位直徑作為平均粒徑而測定。測定樣品係可較佳使用使無機填充材藉由超音波而分散於甲基乙基酮中者。作為雷射繞射散射式粒度分布測定裝置,可使用堀場製作所公司製「LA-500」、島津製作所公司製「SALD-2200」等。The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measurement device, and the median diameter can be measured as the average particle diameter. As the measurement sample, those in which the inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., and "SALD-2200" manufactured by Shimadzu Corporation can be used.
無機填充材,就提高耐濕性及分散性的觀點而言,較佳係以含氟矽烷偶合劑、胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等的1種以上之表面處理劑進行處理。作為表面處理劑之市售品,可列舉例如:信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧型矽烷偶合劑)、信越化學工業公司製「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)等。From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably a fluorine-containing silane coupling agent, an amino silane coupling agent, an epoxy silane coupling agent, a mercapto silane coupling agent, or a silane coupling agent. One or more surface treatment agents such as a mixture, an alkoxysilane, an organosilazane compound, and a titanate-based coupling agent are treated. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, "KBM573" (N-phenyl-3-aminopropyltrimethyl) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM- 4803 "(long-chain epoxy-type silane coupling agent)," KBM-7103 "(3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
以表面處理劑進行之表面處理的程度,就提昇無機填充材之分散性的觀點而言,相對於無機填充材100質量份而言,較佳係以0.2質量份~5質量份之表面處理劑進行表面處理,較佳係以0.2質量份~3質量份進行表面處理,較佳係以0.3質量份~2質量份進行表面處理。In terms of the degree of surface treatment performed by the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, the surface treatment agent is preferably 0.2 to 5 parts by mass relative to 100 parts by mass of the inorganic filler. For the surface treatment, the surface treatment is preferably performed at 0.2 to 3 parts by mass, and the surface treatment is preferably performed at 0.3 to 2 parts by mass.
以表面處理劑所進行之表面處理的程度,可藉由無機填充材之每單位表面積之碳量進行評估。無機填充材之每單位表面積之碳量,就無機填充材之分散性提昇的觀點而言,較佳為0.02mg/m2 以上,更佳為0.1mg/m2 以上,再更佳為0.2mg/m2 以上。另一方面,就抑制樹脂清漆之溶融黏度及薄片形態下之溶融黏度的上昇之觀點而言,較佳為1mg/m2 以下,更佳為0.8mg/m2 以下,再更佳為0.5mg/m2 以下。The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler. / m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and still more preferably 0.5 mg. / m 2 or less.
無機填充材之每單位表面積之碳量,可在將表面處理後之無機填充材藉由溶劑(例如,甲基乙基酮(MEK))進行洗淨處理之後進行測定。具體而言,將作為溶劑為充分之量的MEK添加於以表面處理劑進行表面處理後的無機填充材,以25℃進行5分鐘超音波洗淨。可在將上澄液去除,使固體成分乾燥之後,使用碳分析計來測定無機填充材之每單位表面積之碳量。作為碳分析計係可使用堀場製作所公司製「EMIA-320V」等。The carbon content per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK was added in a sufficient amount as a solvent to an inorganic filler subjected to a surface treatment with a surface treatment agent, and ultrasonically washed at 25 ° C for 5 minutes. After removing the upper liquid and drying the solid content, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.
在樹脂組成物含有(E)成分的情況,(E)成分之含量(質量%:e1),就提高將樹脂組成物作為硬化物時之絕緣性的可靠性及難燃性的觀點而言,在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為1質量%以上,更佳為1.5質量%以上,再更佳為2質量%以上。又,較佳為25質量%以下,更佳為20質量%以下,再更佳為15質量%以下。When the resin composition contains the (E) component, the content (mass%: e1) of the (E) component is, from the viewpoint of improving the reliability and flame retardancy of the insulation properties when the resin composition is used as a cured product, When the nonvolatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. The content is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
在樹脂組成物含有(E)成分的情況,(E)成分之含量(體積%),較佳為1體積%以上,更佳為3體積%以上,再更佳為5體積%以上。又,上限,較佳為30體積%以下,更佳為25體積%以下,再更佳為20體積%以下。When the resin composition contains the (E) component, the content (vol%) of the (E) component is preferably 1 vol% or more, more preferably 3 vol% or more, and even more preferably 5 vol% or more. The upper limit is preferably 30% by volume or less, more preferably 25% by volume or less, and even more preferably 20% by volume or less.
在樹脂組成物含有(E)成分的情況,在將樹脂組成物中之(D)成分之含有質量設為d1,並將(E)成分之含有質量設為e1的情況,就將樹脂組成物作為硬化物時之頻率為10~200MHz之範圍內的相對導磁率及磁性損失設為良好的範圍,並且抑制磁性層之熱膨脹,提高可靠性的觀點而言,e1/d1較佳為0.02以上,更佳為0.025以上,再更佳為0.03以上。又,上限較佳為0.19以下,更佳為0.185以下,再更佳為0.18以下。When the resin composition contains the (E) component, when the content mass of the (D) component in the resin composition is d1 and the content mass of the (E) component is e1, the resin composition is The relative permeability and magnetic loss in the range of 10 to 200 MHz as a hardened material are in a good range, and from the viewpoint of suppressing thermal expansion of the magnetic layer and improving reliability, e1 / d1 is preferably 0.02 or more. It is more preferably 0.025 or more, and even more preferably 0.03 or more. The upper limit is preferably 0.19 or less, more preferably 0.185 or less, and still more preferably 0.18 or less.
(E)成分之平均粒徑,較佳係小於(D)成分之平均粒徑。只要將(D)成分及(E)成分之含量的比例如前述般設定,且使(E)成分之平均粒徑小於(D)成分之平均粒徑,則可以包圍磁性填料粒子之周圍的方式將無機填充材有效地配置。藉此,由於可防止磁性填料粒子彼此凝聚而互相接觸,使磁性填料粒子彼此互相分離,因此可因所摻合的磁性填料而提高相對導磁率並且實現良好的絕緣性。The average particle diameter of the component (E) is preferably smaller than the average particle diameter of the component (D). As long as the ratio of the content of the (D) component and the (E) component is set as described above and the average particle diameter of the (E) component is smaller than the average particle diameter of the (D) component, a method of surrounding the magnetic filler particles The inorganic filler is efficiently arranged. Thereby, since the magnetic filler particles can be prevented from agglomerating and coming into contact with each other, and the magnetic filler particles can be separated from each other, the relative magnetic permeability can be improved due to the magnetic filler to be blended, and good insulation can be achieved.
<(F)硬化促進劑> 於一實施形態中,樹脂組成物係可含有(F)硬化促進劑。作為硬化促進劑,可列舉例如:磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑等,較佳為磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑,更佳為咪唑系硬化促進劑。硬化促進劑係可單獨使用1種,亦可將2種以上組合使用。<(F) hardening accelerator> In one embodiment, the resin composition system may contain (F) a hardening accelerator. Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Preferred are phosphorus-based hardening accelerators and amines. Hardening accelerator, imidazole hardening accelerator, metal hardening accelerator, more preferably imidazole hardening accelerator. The hardening accelerators may be used alone or in combination of two or more.
作為磷系硬化促進劑,可列舉例如:三苯基膦、鏻硼酸鹽化合物、四苯基鏻四苯基硼酸鹽、n-丁基鏻四苯基硼酸鹽、四丁基鏻癸酸鹽、(4-甲基苯基)三苯基鏻硫氰酸鹽、四苯基鏻硫氰酸鹽、丁基三苯基鏻硫氰酸鹽等,較佳為三苯基膦、四丁基鏻癸酸鹽。Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, preferably triphenylphosphine and tetrabutylphosphonium Decanoate.
作為胺系硬化促進劑,可列舉例如:三乙基胺、三丁基胺等之三烷基胺、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6,-參(二甲基胺基甲基)酚、1,8-二氮雜雙環(5,4,0)-十一烯等,較佳為4-二甲基胺基吡啶、1,8-二氮雜雙環(5,4,0)-十一烯。Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc., preferably 4-dimethylaminopyridine, 1,8-bis Azabicyclo (5,4,0) -undecene.
作為咪唑系硬化促進劑,可列舉例如:2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一烷基偏苯三酸咪唑鹽、1-氰乙基-2-苯基偏苯三酸咪唑鹽、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2,3-二羥-1H-吡咯[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鹽氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂之加合物,較佳為2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑。Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole , 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl trimellitic acid imidazole salt, 1-cyanoethyl-2-phenyl trimellitic acid Imidazole salt, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Undecyl imidazolyl- (1 ')-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1') ] -Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct , 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-4,5-dimethylol imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 -Dihydroxy-1H-pyrrole [1,2-a] benzimidazole, 1-dodecyl-2- Methyl-3-benzylimidazolium chloride, imidazole compounds such as 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4 -Methylimidazole, 1-benzyl-2-phenylimidazole.
作為咪唑系硬化促進劑,亦可使用市售品,可列舉例如:三菱化學公司製之「P200-H50」等。A commercially available product may be used as the imidazole-based hardening accelerator, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.
作為胍系硬化促進劑,可列舉例如:二氰二胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(o-基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(o-基)雙胍等,較佳為二氰二胺、1,5,7-三氮雜雙環[4.4.0]癸-5-烯。Examples of the guanidine-based hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, and 1- (o- Guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n- Octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o- Group) biguanide and the like, preferably dicyandiamine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene.
作為金屬系硬化促進劑,可列舉例如:鈷、銅、鋅、鐵、鎳、錳、錫等之金屬之有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物之具體例,可列舉:乙醯丙酮鈷(II)、乙醯丙酮鈷(III)等之有機鈷錯合物、乙醯丙酮銅(II)等之有機銅錯合物、乙醯丙酮鋅(II)等之有機鋅錯合物、乙醯丙酮鐵(III)等之有機鐵錯合物、乙醯丙酮鎳(II)等之有機鎳錯合物、乙醯丙酮錳(II)等之有機錳錯合物等。作為有機金屬鹽,可列舉例如:辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) acetoacetone, cobalt (III) acetoacetonate, and organocopper complexes of copper (II) acetoacetone and the like , Organic zinc complexes of acetamidine zinc (II), etc., organic iron complexes of acetammonium iron (III), etc., organic nickel complexes of acetammonium nickel (II), etc. (II) and other organic manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
在樹脂組成物含有硬化促進劑的情況,硬化促進劑之含量,在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為0.001質量%~1質量%,更佳為0.001質量%~0.1質量%,再更佳為0.005質量%~0.05質量%。When the resin composition contains a hardening accelerator, the content of the hardening accelerator is preferably 0.001% by mass to 1% by mass when the nonvolatile component in the resin composition is set to 100% by mass. 0.001% by mass to 0.1% by mass, and more preferably 0.005% by mass to 0.05% by mass.
<(G)難燃劑> 於一實施形態中,樹脂組成物係可含有(G)難燃劑。作為難燃劑,可列舉例如:有機磷系難燃劑、有機系含氮之磷化合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物等。難燃劑係可單獨使用1種,或者亦可併用2種以上。<(G) Flame Retardant> In one embodiment, the resin composition may contain (G) a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polysiloxane flame retardant, and a metal hydroxide. The flame retardants may be used alone or in combination of two or more.
作為難燃劑,亦可使用市售品,可列舉例如:三光公司製之「HCA-HQ」、大八化學工業公司製之「PX-200」等。難燃劑係可單獨使用1種,或者亦可併用2種以上。As the flame retardant, a commercially available product can also be used, and examples thereof include "HCA-HQ" manufactured by Sanko, and "PX-200" manufactured by Daiba Chemical Industries. The flame retardants may be used alone or in combination of two or more.
在樹脂組成物含有難燃劑的情況,難燃劑之含量,在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為0.5質量%~10質量%之範圍,更佳為1質量%~9質量%之範圍,再更佳為1.5質量%~8質量%之範圍。When the resin composition contains a flame retardant, the content of the flame retardant is preferably in the range of 0.5% to 10% by mass when the nonvolatile component in the resin composition is set to 100% by mass. It is preferably in a range of 1 to 9% by mass, and even more preferably in a range of 1.5 to 8% by mass.
<(H)有機填充材> 於一實施形態中,樹脂組成物係可含有(H)有機填充材。作為有機填充材之例,可列舉橡膠粒子。作為有機填充材之橡膠粒子,例如:使用不溶解於後述之有機溶劑中,且與(A)成分~(C)成分等不相溶的橡膠粒子。如此之橡膠粒子,一般而言,藉由使橡膠粒子之成分的分子量大到不溶解於有機溶劑、樹脂的程度,且設為粒子狀而調製。<(H) Organic Filler> In one embodiment, the resin composition system may contain (H) an organic filler. Examples of the organic filler include rubber particles. As the rubber particles of the organic filler, for example, rubber particles that are insoluble in an organic solvent to be described later and are incompatible with the components (A) to (C) and the like are used. Such rubber particles are generally prepared by making the molecular weight of the components of the rubber particles so large that they do not dissolve in organic solvents and resins, and they are made into particles.
作為有機填充材之橡膠粒子,可列舉例如:核殼型橡膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯酸橡膠粒子等。核殼型橡膠粒子係具有核層與殼層的橡膠粒子,可列舉例如:外層之殼層以玻璃狀聚合物構成,內層之核層以橡膠狀聚合物構成的2層構造,或者外層之殼層以玻璃狀聚合物構成,中間層以橡膠狀聚合物構成,內層之核層以玻璃狀聚合物構成的3層構造之橡膠粒子等。玻璃狀聚合物層,例如:以甲基丙烯酸甲酯聚合物等所構成,橡膠狀聚合物層,例如:以丁基丙烯酸酯聚合物(丁基橡膠)等所構成。作為可使用之橡膠粒子之例,可列舉GANZ公司製「STAPHYLOID AC3816N」。橡膠粒子係可單獨使用1種,或者亦可併用2種以上。Examples of the rubber particles of the organic filler include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and examples thereof include a two-layer structure composed of a glass-like polymer in an outer shell layer and a rubber-like polymer in an inner core layer, or an outer layer The shell layer is made of glass-like polymer, the middle layer is made of rubber-like polymer, and the core layer of the inner layer is made of glass-like polymer. The glassy polymer layer is formed of, for example, a methyl methacrylate polymer, and the rubbery polymer layer is formed of, for example, a butyl acrylate polymer (butyl rubber). Examples of usable rubber particles include "STAPHYLOID AC3816N" manufactured by GANZ Corporation. The rubber particles may be used singly or in combination of two or more kinds.
作為有機填充材之橡膠粒子之平均粒徑,較佳為0.005μm~1μm之範圍,更佳為0.2μm~0.6μm之範圍。橡膠粒子之平均粒徑係可使用動態光散射法進行測定。例如,可藉由使橡膠粒子藉由超音波等均勻地分散於適當的有機溶劑中,使用濃厚系粒徑分析儀(大塚電子公司製「FPAR-1000」),以質量基準製成橡膠粒子之粒度分布,並將該中位直徑作為平均粒徑而測定。The average particle diameter of the rubber particles as the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, a rubber particle can be uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and a thick particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) can be used to produce rubber particles on a mass basis. The particle size distribution is measured as the average particle diameter.
在樹脂組成物含有有機填充材的情況,有機填充材之含量,在將樹脂組成物中之不揮發性成分設為100質量%的情況,較佳為0.1~20質量%,更佳為0.2~10質量%,再更佳為0.3~5質量%、或0.5~3質量%。In the case where the resin composition contains an organic filler, the content of the organic filler in the case where the nonvolatile component in the resin composition is 100% by mass, preferably 0.1 to 20% by mass, and more preferably 0.2 to 10% by mass, more preferably 0.3 to 5% by mass, or 0.5 to 3% by mass.
<(I)任意之添加劑> 於一實施形態中,樹脂組成物亦可進一步因應需要而包含其他添加劑,作為該其他添加劑,可列舉例如:有機銅化合物、有機鋅化合物及有機鈷化合物等之有機金屬化合物、以及增黏劑、消泡劑、整平劑、密著性賦予劑、及著色劑等之樹脂添加劑等。<(I) Any Additive> In one embodiment, the resin composition may further include other additives as needed. Examples of the other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. Metal compounds, and resin additives such as tackifiers, defoamers, levelers, adhesion-imparting agents, and colorants.
<樹脂組成物之物性、用途> 使本實施形態之樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物)於23℃時之彈性率為7GPa以上,較佳為7.5GPa以上,更佳為8GPa以上。又,上限為18GPa以下,較佳為17GPa以下,更佳為16GPa以下。藉由將彈性率設為如此之範圍內,可得到難燃性優異,翹曲量受到抑制,尤其是可提昇頻率為10~200MHz之範圍內之相對導磁率,並且亦使磁性損失減低之硬化物。進而,使用樹脂組成物所得之接著薄膜係疊層性優異。彈性率係可藉由調整(A)成分~(D)成分而設為如此之範圍內。彈性率可依照後述之<彈性率之測定>記載的方法進行測定。<Physical properties and uses of resin composition> 的 The cured product obtained by thermally curing the resin composition of this embodiment (for example, a cured product obtained by thermally curing at 180 ° C for 90 minutes) has an elastic modulus of 7 GPa or more at 23 ° C. , Preferably 7.5 GPa or more, and more preferably 8 GPa or more. The upper limit is 18 GPa or less, preferably 17 GPa or less, and more preferably 16 GPa or less. By setting the elastic modulus to be in such a range, excellent flame retardancy and suppressed warpage can be obtained. In particular, it is possible to increase the relative magnetic permeability in the frequency range of 10 to 200 MHz, and also reduce the magnetic loss. Thing. Furthermore, the adhesive film obtained by using a resin composition is excellent in lamination | stacking property. The elastic modulus can be adjusted to be within such a range by adjusting the components (A) to (D). The elastic modulus can be measured in accordance with the method described in "Measurement of Elasticity" described later.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),顯示頻率10MHz時之相對導磁率為高的特性。頻率10MHz時之相對導磁率,較佳為5以上,更佳為6以上,再更佳為7以上。又,較佳為20以下,更佳為18以下,再更佳為15以下。相對導磁率可依照後述之<相對導磁率、磁性損失之測定>記載的方法進行測定。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) exhibits a characteristic of high relative magnetic permeability at a frequency of 10 MHz. The relative magnetic permeability at a frequency of 10 MHz is preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more. Moreover, it is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. The relative permeability can be measured in accordance with the method described in "Measurement of Relative Permeability and Magnetic Loss" described later.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),顯示頻率100MHz時之相對導磁率為高的特性。頻率100MHz時之相對導磁率,較佳為5以上,更佳為6以上,再更佳為7以上。又,較佳為20以下,更佳為18以下,再更佳為15以下。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) exhibits a characteristic of high relative magnetic permeability at a frequency of 100 MHz. The relative magnetic permeability at a frequency of 100 MHz is preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more. Moreover, it is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),亦可頻率1GHz時之相對導磁率為低。頻率1GHz時之相對導磁率,較佳為4以上,更佳為5以上,再更佳為6以上。又,較佳為16以下,更佳為15以下,再更佳為14以下。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) may have a low relative magnetic permeability at a frequency of 1 GHz. The relative magnetic permeability at a frequency of 1 GHz is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. It is preferably 16 or less, more preferably 15 or less, and even more preferably 14 or less.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),亦可頻率3GHz時之相對導磁率為低。頻率3GHz時之相對導磁率,較佳為2以上,更佳為3以上,再更佳為4以上。又,較佳為10以下,更佳為9以下,再更佳為8以下。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) may have a low relative magnetic permeability at a frequency of 3 GHz. The relative magnetic permeability at a frequency of 3 GHz is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Moreover, it is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),顯示頻率10MHz時之磁性損失為低的特性。頻率10MHz時之磁性損失,較佳為0.05以下,更佳為0.04以下,再更佳為0.03以下。下限雖無特別限定,但可設為0.0001以上等。磁性損失可依照後述之<相對導磁率、磁性損失之測定>記載的方法進行測定。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) exhibits a characteristic of low magnetic loss at a frequency of 10 MHz. The magnetic loss at a frequency of 10 MHz is preferably 0.05 or less, more preferably 0.04 or less, and even more preferably 0.03 or less. Although the lower limit is not particularly limited, it may be 0.0001 or more. The magnetic loss can be measured in accordance with the method described in "Measurement of Relative Permeability and Magnetic Loss" described later.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),顯示頻率100MHz時之磁性損失為低的特性。頻率100MHz時之磁性損失,較佳為0.05以下,更佳為0.04以下,再更佳為0.03以下。下限雖無特別限定,但可設為0.0001以上等。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) exhibits a characteristic of low magnetic loss at a frequency of 100 MHz. The magnetic loss at a frequency of 100 MHz is preferably 0.05 or less, more preferably 0.04 or less, and even more preferably 0.03 or less. Although the lower limit is not particularly limited, it may be 0.0001 or more.
由於樹脂組成物含有(C)成分,因此使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),顯示翹曲量減低的特性。翹曲量,較佳為10mm以下,更佳為9mm以下,再更佳為8mm以下。上限雖無特別限定,但可設為0.1mm以上等。翹曲量係可依照後述之<翹曲量之測定>記載的方法進行測定。Since the resin composition contains the component (C), a cured product obtained by thermally curing the resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) has a characteristic of reducing the amount of warpage. The amount of warpage is preferably 10 mm or less, more preferably 9 mm or less, and even more preferably 8 mm or less. Although the upper limit is not particularly limited, it may be 0.1 mm or more. The amount of warpage can be measured in accordance with the method described in "Measurement of the amount of warpage" described later.
使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物),顯示難燃性優異的特性。難燃性,較佳係進行5次UL94垂直難燃試驗,10秒接觸火焰後之燃燒殘留的樣品仍有5個存在。難燃性之評估係可依照後述之<難燃性之評估>記載的方法進行測定。A cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C. for 90 minutes) exhibits characteristics of excellent flame retardancy. Flame retardance, it is better to perform 5 UL94 vertical flame retardance tests, and there are still 5 samples remaining after burning for 10 seconds. The evaluation of flame retardancy can be measured in accordance with the method described in "Evaluation of flame retardancy" described later.
本實施形態之樹脂組成物係磁性層形成時之流動性優異,作為磁性層(硬化物)時之配線層的密封性優異。又,只要形成使用本發明之樹脂組成物所形成的磁性層,則可提昇頻率為10MHz~200MHz,尤其是頻率為10MHz~100MHz之範圍內的相對導磁率,且減低磁性損失。又,使本實施形態之樹脂組成物熱硬化所得之磁性層(硬化物),絕緣性亦優異。The resin composition-based magnetic layer of this embodiment is excellent in fluidity at the time of formation, and is excellent in sealing property of a wiring layer when it is used as a magnetic layer (hardened material). In addition, as long as the magnetic layer formed by using the resin composition of the present invention is formed, the relative magnetic permeability in the frequency range of 10 MHz to 200 MHz, especially in the frequency range of 10 MHz to 100 MHz can be increased, and the magnetic loss can be reduced. In addition, the magnetic layer (cured material) obtained by thermally curing the resin composition of this embodiment is also excellent in insulation properties.
因而,本實施形態之樹脂組成物,可適合使用作為具備於磁性層(複數層之磁性層層合而成之磁性體部)的厚度內內置有線圈之所謂的薄膜構造之電感元件的配線板之磁性層的材料,尤其,可更適合使用於電感元件發揮功能之頻率為10MHz~200MHz的情況。Therefore, the resin composition of the present embodiment can be suitably used as a wiring board having an inductive element with a so-called thin film structure in which a coil is incorporated in the thickness of a magnetic layer (a magnetic body portion in which a plurality of magnetic layers are laminated). The material of the magnetic layer is particularly suitable for a case where the frequency at which the inductive element functions is 10 MHz to 200 MHz.
[硬化物] 本發明之硬化物係將本發明之樹脂組成物熱硬化而得。本發明之硬化物係以180℃進行90分鐘熱硬化時於23℃時的彈性率為7GPa以上18GPa以下,較佳之範圍係如上述般。[Hardened product] The hardened product of the present invention is obtained by thermally curing the resin composition of the present invention. The hardened material of the present invention has an elastic modulus of 7 GPa or more and 18 GPa or less at 23 ° C when thermally cured at 180 ° C for 90 minutes. The preferred range is as described above.
樹脂組成物層之熱硬化條件並無特別限定,例如,亦可使用後述之第1磁性層之形成步驟中的熱硬化步驟之條件。又,亦可在熱硬化之前,以比熱硬化溫度更低的溫度進行預備加熱。The thermal curing conditions of the resin composition layer are not particularly limited, and for example, the conditions of the thermal curing step in the formation step of the first magnetic layer described later can also be used. Alternatively, the pre-heating may be performed at a temperature lower than the heat curing temperature before the heat curing.
硬化物之厚度雖依據用途而異,但在作為內載電感元件之配線板的磁性層使用的情況,較佳為100μm以下,更佳為80μm以下,再更佳為60μm以下,又再更佳為40μm以下。硬化物之厚度的下限雖依據用途而異,但在作為內載電感元件之配線板的磁性層使用的情況,通常為10μm以上。Although the thickness of the hardened material varies depending on the application, when it is used as a magnetic layer of a wiring board with an internally mounted inductance element, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably It is 40 μm or less. Although the lower limit of the thickness of the cured product varies depending on the application, when it is used as a magnetic layer of a wiring board with an internally mounted inductance element, it is usually 10 μm or more.
[接著薄膜] 本發明之接著薄膜係包含支撐體,與設置於該支撐體上以本發明之樹脂組成物所形成的樹脂組成物層。[Adhesive film] 接着 The adhesive film of the present invention includes a support and a resin composition layer formed on the support with the resin composition of the present invention.
樹脂組成物層之厚度並無特別限定。樹脂組成物層,較佳係厚度為0.5μm~80μm,更佳係10μm~60μm。The thickness of the resin composition layer is not particularly limited. The thickness of the resin composition layer is preferably 0.5 μm to 80 μm, and more preferably 10 μm to 60 μm.
作為支撐體,可列舉例如:由塑膠材料所構成之薄膜、金屬箔、脫模紙,較佳為由塑膠材料所構成之薄膜、金屬箔。Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and preferably a film made of a plastic material and a metal foil.
在使用由塑膠材料所構成之薄膜作為支撐體的情況,以使用玻璃轉移溫度(Tg)高的塑膠材料為宜。作為玻璃轉移溫度為100℃以上之塑膠材料,可列舉例如:聚對苯二甲酸乙二酯(以下有時簡稱為「PET」)、聚萘二甲酸乙二酯(以下有時簡稱為「PEN」)等之聚酯、聚碳酸酯(以下有時簡稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等之丙烯酸、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中,較佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚醯亞胺,特佳為低價的聚對苯二甲酸乙二酯。When a thin film made of a plastic material is used as a support, it is preferable to use a plastic material having a high glass transition temperature (Tg). Examples of plastic materials having a glass transition temperature of 100 ° C or higher include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN" ") And other polyesters, polycarbonate (hereinafter sometimes referred to as" PC "), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triethyl cellulose (TAC), polyether Sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate, polyethylene naphthalate, and polyimide are preferred, and low-cost polyethylene terephthalate is particularly preferred.
在使用金屬箔作為支撐體的情況,作為金屬箔,可列舉例如:銅箔、鋁箔等,較佳為銅箔。作為銅箔,可使用由銅之單金屬所構成的箔,亦可使用由銅與其他金屬(例如,錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)之合金所構成的箔。When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil composed of a single metal of copper may be used, and a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. .
支撐體,亦可於與樹脂組成物層接合的面施行霧面處理、電暈處理。The support may be subjected to a matte treatment or a corona treatment on the surface bonded to the resin composition layer.
又,作為支撐體,亦可使用於與樹脂組成物層接合之面具有脫模層之附脫模層支撐體。作為使用於附脫模層支撐體之脫模層的脫模劑,可列舉例如:選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂、及聚矽氧樹脂所成之群中的1種以上之脫模劑。附脫模層支撐體亦可使用市售品,可列舉例如:作為具有以醇酸樹脂系脫模劑作為主成分之脫模層的PET薄膜之LINTEC公司製之「SK-1」、「AL-5」、「AL-7」、Toray公司製之「LUMIRROR T60」、帝人公司製之「PUREX」、Unitika公司製之「Unipeel」等。Moreover, as a support body, it can also be used for the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer. Examples of the release agent used for the release layer with a release layer support include a resin selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. 1 or more release agents. A commercially available product may be used as the support with a release layer, and examples thereof include "SK-1" and "AL" manufactured by LINTEC Corporation as PET films having a release layer containing an alkyd resin-based release agent as a main component. -5 "," AL-7 "," LUMIRROR T60 "manufactured by Toray Corporation," PUREX "manufactured by Teijin Corporation," Unipeel "manufactured by Unitika Corporation, etc.
作為支撐體之厚度雖無特別限定,但較佳為5μm~75μm之範圍,更佳為10μm~60μm之範圍。另外,在使用附脫模層支撐體的情況,較佳係附脫模層支撐體全體的厚度為上述範圍。Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
樹脂組成物層所使用之樹脂組成物,可藉由將已說明的前述成分適當混合,又,因應需要而藉由混練手段(3輥機、球磨機、珠磨機、混砂機等)或攪拌手段(高速混合器、行星式攪拌機等)進行混練或混合而調製。The resin composition used in the resin composition layer can be appropriately mixed by the above-mentioned components, and, if necessary, by kneading means (3-roller, ball mill, bead mill, sand mixer, etc.) or stirred. Means (high-speed mixer, planetary mixer, etc.) are kneaded or mixed to prepare.
具有樹脂組成物層的接著薄膜之製造方法並無特別制限,例如,可藉由調製於有機溶劑中溶解有樹脂組成物的清漆,將此樹脂清漆使用模具塗佈機等塗佈於支撐體,並使所塗佈的樹脂清漆之塗佈膜乾燥而製作。The method for producing an adhesive film having a resin composition layer is not particularly limited. For example, a varnish in which a resin composition is dissolved in an organic solvent can be prepared, and this resin varnish can be applied to a support using a mold coater or the like. The coating film of the applied resin varnish is dried and produced.
作為有機溶劑,可列舉例如:丙酮、甲基乙基酮及環己酮等之酮類;乙酸乙酯、乙酸丁酯、賽路蘇乙酸酯、丙二醇單甲基醚乙酸酯及卡必醇乙酸酯等之乙酸酯類;賽路蘇及丁基卡必醇等之卡必醇類;甲苯及二甲苯等之芳香族烴類;二甲基甲醯胺、二甲基乙醯胺及N-甲基吡咯啶酮等之醯胺系溶媒等。有機溶劑係可單獨使用1種,或者亦可併用2種以上。Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, celex acetate, propylene glycol monomethyl ether acetate, and carbidine Ethyl acetates such as alcohol acetate; carbitols such as cyrus and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethylacetamide And N-methylpyrrolidone and other amidine solvents. The organic solvents may be used alone or in combination of two or more.
乾燥係可藉由加熱、熱風吹附等之周知的方法而實施。乾燥條件雖無特別限定,但以使樹脂組成物層中之有機溶劑的含量成為10質量%以下,較佳為5質量%以下的方式來進行乾燥。雖依據樹脂清漆中之有機溶劑的沸點而異,但例如,在使用包含30質量%~60質量%之有機溶劑的樹脂清漆的情況,例如,可藉由以80℃~150℃進行3分鐘~15分鐘左右乾燥,而形成樹脂組成物層。Drying can be performed by a known method such as heating or hot air blowing. Although the drying conditions are not particularly limited, drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, and preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing an organic solvent in an amount of 30% to 60% by mass, it can be performed at 80 ° C to 150 ° C for 3 minutes to Dry for about 15 minutes to form a resin composition layer.
於接著薄膜中,可於樹脂組成物層之非與支撐體接合之面(亦即,與支撐體相反側之面)進一步層合作為支撐體的保護薄膜。保護薄膜之厚度雖無特別限定,但例如為1μm~40μm。藉由層合保護薄膜,可防止對樹脂組成物層之表面的塵埃等之附著或損傷。接著薄膜係可藉由捲成捲狀來保存。在接著薄膜具有保護薄膜的情況,藉由將保護薄膜剝離而成為可使用狀態。In the adhesive film, a protective film may be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent adhesion or damage to dust and the like on the surface of the resin composition layer. The film can then be stored by being rolled into a roll. In the case where the adhesive film has a protective film, the protective film is peeled to a usable state.
本發明之接著薄膜,由於是以使樹脂組成物熱硬化而成的硬化物(例如以180℃進行90分鐘熱硬化而成的硬化物)於23℃時之彈性率成為7GPa以上18GPa以下的方式來調整(A)成分~(D)成分之含量,因此顯示疊層性優異的特性。即使將接著薄膜疊層於配線板,通常於配線板之電路部分也無空隙,來自接著薄膜的樹脂組成物會充分地流動。Since the adhesive film of the present invention is a cured product obtained by thermally curing a resin composition (for example, a cured product obtained by thermally curing at 180 ° C for 90 minutes), the elastic modulus at 23 ° C is 7 GPa or more and 18 GPa or less. Since content of (A) component-(D) component is adjusted, the characteristic which is excellent in lamination property is shown. Even if an adhesive film is laminated on a wiring board, there is usually no void in the circuit part of the wiring board, and the resin composition from the adhesive film flows sufficiently.
[內載電感元件之配線板及內載電感元件之配線板之製造方法] (第1實施形態) 針對第1實施形態之內載電感元件之配線板的構造例,參照第1圖、第2圖及第3圖進行說明。第1圖係由其厚度方向之一方觀看內載電感元件之配線板的示意俯視圖。第2圖係顯示在以II-II虛線表示之位置切斷的內載電感元件之配線板之切斷端面的示意圖。第3圖係用以說明內載電感元件之配線板中之第1配線層的構造的示意俯視圖。以下,有時將內載電感元件之配線板簡稱為「配線板」。[Manufacturing method of wiring board with internal load inductance element and wiring board with internal load inductance element] (First embodiment) For a structural example of the wiring board with internal load inductance element according to the first embodiment, refer to Figs. 1 and 2 This figure and FIG. 3 are demonstrated. FIG. 1 is a schematic plan view of a wiring board with an inductive element on it, viewed from one of its thickness directions. FIG. 2 is a schematic diagram showing a cut end surface of a wiring board of an internally-loaded inductance element cut at a position indicated by a dotted line II-II. FIG. 3 is a schematic plan view for explaining the structure of a first wiring layer in a wiring board with an inductive element on the inside. Hereinafter, a wiring board having an inductive element mounted thereon may be simply referred to as a "wiring board".
配線板係具有作為樹脂組成物(樹脂組成物層)的硬化體之磁性層,與至少一部分埋入此磁性層的導電性構造體,且包含藉由此導電性構造體,與延伸於磁性層的厚度方向且被導電性構造體所包圍之磁性層中的一部分所構成之電感元件。The wiring board is a magnetic layer having a hardened body of a resin composition (resin composition layer), and at least a portion of the conductive structure embedded in the magnetic layer, and includes the conductive structure and the magnetic layer extending therethrough. An inductive element composed of a part of a magnetic layer in a thickness direction and surrounded by a conductive structure.
可想定本實施形態之配線板所具備的電感元件可發揮功能的頻率為10MHz~200MHz。又,可想定本實施形態之配線板所具備的電感元件為電源系。It is conceivable that the frequency at which the inductive element provided in the wiring board of this embodiment can function is 10 MHz to 200 MHz. It is also conceivable that the inductance element included in the wiring board of this embodiment is a power supply system.
如第1圖及第2圖所示般,配線板10係具有增層磁性層的增層配線板。配線板10具備有芯基材20。芯基材20具有第1主表面20a及與第1主表面20a相反側之第2主表面20b。芯基材20為絕緣性之基板。芯基材20亦可為其厚度內內置有配線等之內層電路基板。As shown in FIGS. 1 and 2, the wiring board 10 is a build-up wiring board having a build-up magnetic layer. The wiring board 10 includes a core substrate 20. The core base material 20 has a first main surface 20a and a second main surface 20b on the side opposite to the first main surface 20a. The core substrate 20 is an insulating substrate. The core substrate 20 may be an inner-layer circuit board having wirings and the like built into the thickness thereof.
作為芯基材20之材料之例,可列舉:玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等之絕緣性基材。Examples of the material of the core substrate 20 include insulating substrates such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.
芯基材20具有設置於第1主表面20a的第1配線層42,與設置於第2主表面20b的外部端子24。第1配線層42及第2配線層44包含複數之配線。於圖示例中,僅顯示構成電感元件之線圈狀導電性構造體40的配線。外部端子24為用以與未圖示之外部之裝置等電連接的端子。外部端子24係可作為設置於第2主表面20b之配線層的一部分而構成。The core base material 20 includes a first wiring layer 42 provided on the first main surface 20 a and an external terminal 24 provided on the second main surface 20 b. The first wiring layer 42 and the second wiring layer 44 include a plurality of wirings. In the illustrated example, only the wiring of the coil-shaped conductive structure 40 constituting the inductance element is shown. The external terminal 24 is a terminal for electrically connecting to an external device (not shown) or the like. The external terminal 24 can be configured as a part of a wiring layer provided on the second main surface 20b.
作為可構成第1配線層42、第2配線層44、外部端子24、其他配線的導體材料,可列舉例如:選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所成之群中的1種以上之金屬。第1配線層42、第2配線層44、外部端子24、其他配線可藉由單金屬所構成,亦可藉由合金所構成,作為合金,可列舉例如:選自由上述之群中的2種以上之金屬的合金(例如,鎳鉻合金、銅鎳合金及銅鈦合金)。其中,就泛用性、成本、圖型化之容易性等的觀點而言,較佳係使用鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅,或者鎳鉻合金、銅鎳合金、銅鈦合金,更佳係使用鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅,或者鎳鉻合金,再更佳係使用銅。Examples of the conductive material that can constitute the first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wirings are selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, and nickel. , Titanium, tungsten, iron, tin and indium in a group of one or more metals. The first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wirings may be composed of a single metal or an alloy. Examples of the alloy include two types selected from the group described above. Alloys of the above metals (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoints of versatility, cost, and ease of patterning, it is preferable to use chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel-chromium alloy, copper-nickel Alloys, copper-titanium alloys, more preferably chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloys, and even more preferably copper.
第1配線層42、第2配線層44、外部端子24、其他配線可為單層構造,亦可為層合2層以上由不同種類之金屬或合金所構成之單金屬層或者合金層的多層構造。在第1配線層42、第2配線層44、外部端子24、其他配線為多層構造的情況,與磁性層接觸的層,較佳為鉻、鋅或鈦之單金屬層、或者鎳鉻合金之合金層。The first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wirings may have a single-layer structure, or a multilayer of a single metal layer or an alloy layer composed of two or more layers made of different types of metals or alloys structure. When the first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wirings have a multilayer structure, the layer in contact with the magnetic layer is preferably a single metal layer of chromium, zinc, or titanium, or a nickel-chromium alloy. Alloy layer.
第1配線層42、第2配線層44、外部端子24、其他配線之厚度,雖依據所期望之多層印刷配線板的設計,但一般為3μm~35μm,較佳為5μm~30μm。Although the thicknesses of the first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wirings are based on the desired design of the multilayer printed wiring board, they are generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.
芯基材20所具有之第1配線層42及外部端子24的厚度並無特別限定。第1配線層42及外部端子24的厚度,就薄型化的觀點而言,較佳為70μm以下,更佳為60μm以下,再更佳為50μm以下,又再更佳為40μm以下,特佳為30μm以下、20μm以下、15μm以下或10μm以下。外部端子24之厚度的下限雖無特別限制,但較佳為1μm以上,更佳為3μm以上,再佳為5μm以上。The thickness of the first wiring layer 42 and the external terminals 24 included in the core base material 20 is not particularly limited. From the viewpoint of thinning, the thickness of the first wiring layer 42 and the external terminal 24 is preferably 70 μm or less, more preferably 60 μm or less, still more preferably 50 μm or less, and still more preferably 40 μm or less, and particularly preferably 30 μm or less, 20 μm or less, 15 μm or less, or 10 μm or less. Although the lower limit of the thickness of the external terminal 24 is not particularly limited, it is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more.
第1配線層42及外部端子24之線(L)/空間(S)比雖無特別制限,但就使表面之凹凸減少而得到平滑性優異之磁性層的觀點而言,通常為900/900μm以下,較佳為700/700μm以下,更佳為500/500μm以下,再更佳為300/300μm以下,又再更佳為200/200μm以下。線/空間比之下限雖無特別制限,但就使對空間之樹脂組成物的埋入成為良好的觀點而言,較佳為1/1μm以上。Although the line (L) / space (S) ratio of the first wiring layer 42 and the external terminal 24 is not particularly limited, it is usually 900/900 μm from the viewpoint of reducing unevenness on the surface and obtaining a magnetic layer having excellent smoothness. Hereinafter, it is preferably 700/700 μm or less, more preferably 500/500 μm or less, even more preferably 300/300 μm or less, and still more preferably 200/200 μm or less. Although the lower limit of the line / space ratio is not particularly limited, it is preferably 1/1 μm or more from the viewpoint that the embedding of the resin composition into the space is good.
作為芯基材20,可列舉例如:藉由使用作為玻璃布基材環氧樹脂兩面貼銅層合板之Panasonic公司製「R1515A」,將銅層進行圖型化而作為配線層的配線板。As the core substrate 20, for example, a wiring board in which a copper layer is patterned as a wiring layer by using "R1515A" manufactured by Panasonic Co., Ltd. as a glass cloth substrate epoxy resin-coated copper laminate on both sides is used.
芯基材20係具有以從第1主表面20a至第2主表面20b的方式貫通芯基材20的複數個貫通孔22。於貫通孔22係設置有貫通孔內配線22a。貫通孔內配線22a係將第1配線層42與外部端子24電連接。The core base material 20 has a plurality of through holes 22 penetrating through the core base material 20 so as to extend from the first main surface 20 a to the second main surface 20 b. A through-hole wiring 22 a is provided in the through-hole 22. The through-hole wiring 22 a electrically connects the first wiring layer 42 and the external terminal 24.
如第3圖所示般,第1配線層42包含用以構成線圈狀導電性構造體40之渦卷狀的配線部,與和貫通孔內配線22a電連接之矩形狀的墊42a。於圖示例中,渦卷狀之配線部包含直線狀部與彎曲成直角的彎曲部與繞過墊42a的繞過部。於圖示例中,第1配線層42之渦卷狀的配線部係全體的輪廓為略矩形狀,在從中心側朝向其外側時具有朝逆時針方向捲繞的形狀。As shown in FIG. 3, the first wiring layer 42 includes a spiral-shaped wiring portion for forming the coil-shaped conductive structure 40, and a rectangular pad 42a electrically connected to the through-hole wiring 22a. In the illustrated example, the spiral-shaped wiring portion includes a straight portion, a bent portion bent at a right angle, and a bypass portion that bypasses the pad 42a. In the example shown in the figure, the outline of the volute wiring portion of the first wiring layer 42 is substantially rectangular, and has a shape that is wound in a counterclockwise direction when going from the center side to the outside.
於設置有第1配線層42的芯基材20之第1主表面20a側係以覆蓋第1配線層42及從第1配線層42露出之第1主表面20a的方式設置有第1磁性層32。A first magnetic layer is provided on the side of the first main surface 20 a of the core base material 20 on which the first wiring layer 42 is provided so as to cover the first wiring layer 42 and the first main surface 20 a exposed from the first wiring layer 42. 32.
第1磁性層32係來自已說明的接著薄膜之層,因此,第1配線層42之密封性優異。又,第1磁性層32,係使用前述接著薄膜所形成,因此,頻率為10MHz~200MHz之範圍內的相對導磁率提昇,進而通常磁性損失減低。Since the first magnetic layer 32 is a layer derived from the adhesive film described above, the first wiring layer 42 is excellent in hermeticity. In addition, since the first magnetic layer 32 is formed using the aforementioned adhesive film, the relative magnetic permeability in the frequency range of 10 MHz to 200 MHz is improved, and the magnetic loss is generally reduced.
於第1磁性層32係設置有於其厚度方向貫通第1磁性層32的通孔36。The first magnetic layer 32 is provided with a through-hole 36 penetrating the first magnetic layer 32 in a thickness direction thereof.
於第1磁性層32係設置有第2配線層44。第2配線層44係包含用以構成線圈狀導電性構造體40的渦卷狀之配線部。於圖示例中,渦卷狀之配線部包含直線狀部與彎曲成直角的彎曲部。於圖示例中,第2配線層44之渦卷狀的配線部係全體的輪廓為略矩形狀,在從中心側朝向其外側時具有朝順時針方向捲繞的形狀。A second wiring layer 44 is provided on the first magnetic layer 32. The second wiring layer 44 includes a spiral-shaped wiring portion for forming the coil-shaped conductive structure 40. In the example shown in the figure, the spiral-shaped wiring portion includes a straight portion and a bent portion bent at a right angle. In the example shown in the figure, the outline of the entire spiral-shaped wiring portion of the second wiring layer 44 is slightly rectangular, and has a shape that is wound in a clockwise direction when going from the center side to the outside.
於通孔36內係設置有通孔內配線36a。第2配線層44之渦卷狀之配線部中的中心側之一端係藉由通孔內配線36a而電連接於第1配線層42之渦卷狀之配線部中的中心側之一端。第2配線層44之渦卷狀之配線部中的外周側之另一端係藉由通孔內配線36a而電連接於第1配線層42之墊42a。因而,第2配線層44之渦卷狀之配線部中的外周側之另一端係經過通孔內配線36a、墊42a、貫通孔內配線22a來電連接於外部端子24。A through-hole wiring 36 a is provided in the through-hole 36. One end of the center side of the spiral-shaped wiring portion of the second wiring layer 44 is electrically connected to the center-side end of the spiral-shaped wiring portion of the first wiring layer 42 through the through-hole wiring 36a. The other end on the outer peripheral side of the spiral-shaped wiring portion of the second wiring layer 44 is electrically connected to the pad 42 a of the first wiring layer 42 through the through-hole wiring 36 a. Therefore, the other end on the outer peripheral side of the spiral-shaped wiring portion of the second wiring layer 44 is electrically connected to the external terminal 24 via the through-hole wiring 36a, the pad 42a, and the through-hole wiring 22a.
線圈狀導電性構造體40係藉由作為第1配線層42的一部分之渦卷狀之配線部、作為第2配線層44的一部分之渦卷狀之配線部、將第1配線層42之渦卷狀之配線部與第2配線層44之渦卷狀之配線部電連接的通孔內配線36a所構成。The coil-shaped conductive structure 40 has a spiral-shaped wiring portion as a part of the first wiring layer 42, a spiral-shaped wiring portion as a part of the second wiring layer 44, and a spiral of the first wiring layer 42. The coil-shaped wiring portion is constituted by a through-hole wiring 36 a which is electrically connected to the spiral-shaped wiring portion of the second wiring layer 44.
於設置有第2配線層44的第1磁性層32係以覆蓋第2配線層44及從第2配線層44露出之第1磁性層32的方式設置有第2磁性層34。The second magnetic layer 34 is provided on the first magnetic layer 32 provided with the second wiring layer 44 so as to cover the second wiring layer 44 and the first magnetic layer 32 exposed from the second wiring layer 44.
第2磁性層34係與第1磁性層32相同地來自已說明之接著薄膜之層,接著薄膜之樹脂組成物層係磁性層形成時之流動性優異,因此,第2配線層44之密封性優異。又,第2磁性層34,係使用前述接著薄膜所形成,因此,頻率為10MHz~200MHz之範圍內的相對導磁率提昇,進而通常磁性損失減低。The second magnetic layer 34 is the same as the first magnetic layer 32. It is derived from the film-adhered layer, and the resin composition layer of the subsequent film is excellent in fluidity when the magnetic layer is formed. Therefore, the sealing property of the second wiring layer 44 Excellent. In addition, since the second magnetic layer 34 is formed using the aforementioned adhesive film, the relative magnetic permeability in the frequency range of 10 MHz to 200 MHz is improved, and the magnetic loss is generally reduced.
第1磁性層32及第2磁性層34係構成可視為一體的磁性層之磁性部30。因而,線圈狀導電性構造體40係以使至少一部分埋入磁性層30的方式設置。亦即,於本實施形態之配線板10中,電感元件係藉由線圈狀導電性構造體40,與延伸於磁性部30之厚度方向且被線圈狀導電性構造體40所包圍之磁性部30中的一部分之芯部所構成。The first magnetic layer 32 and the second magnetic layer 34 constitute a magnetic portion 30 that can be considered as a magnetic layer. Therefore, the coil-shaped conductive structure 40 is provided so that at least a part is embedded in the magnetic layer 30. That is, in the wiring board 10 of this embodiment, the inductive element includes the coil-shaped conductive structure 40 and the magnetic portion 30 extending in the thickness direction of the magnetic portion 30 and surrounded by the coil-shaped conductive structure 40. It consists of a core part.
於本實施形態中,線圈狀導電性構造體40係以包含第1配線層42及第2配線層44之2層的配線層之例進行說明,但,亦可藉由3層以上之配線層(及3層以上之增層磁性層)構成線圈狀導電性構造體40。於此情況中,以挾持最上層之配線層與最下層之配線層的方式作配置之未圖示的配線層之渦卷狀的配線部,其一端電連接於最上層側且最靠近配置的配線層之渦卷狀的配線部之任一方的端部,其另一端電連接於最下層側且最靠近配置的配線層之渦卷狀的配線部之任一方的端部。In this embodiment, the coil-shaped conductive structure 40 is described using an example of a two-layer wiring layer including a first wiring layer 42 and a second wiring layer 44. However, three or more wiring layers may be used. (And three or more layers of added magnetic layers) constitute a coil-shaped conductive structure 40. In this case, one end of the spiral-shaped wiring portion of the unillustrated wiring layer, which is configured to support the uppermost wiring layer and the lowermost wiring layer, is electrically connected to the uppermost layer side and closest to the arranged one. The other end of any one of the spirally-shaped wiring portions of the wiring layer is electrically connected to any one of the spiral-shaped wiring portions of the lowermost layer side and closest to the arranged wiring layer.
依據本實施形態之配線板,由於藉由前述接著薄膜形成磁性層,因此可提高所形成之磁性層的相對導磁率、難燃性,且可減低翹曲量。According to the wiring board of this embodiment, since the magnetic layer is formed by the aforementioned bonding film, the relative magnetic permeability and flame resistance of the formed magnetic layer can be improved, and the amount of warpage can be reduced.
以下,針對第1實施形態之內載電感元件之配線板之製造方法,參照第2圖進行說明。 本實施形態之配線板之製造方法係具有包含第1磁性層及第2磁性層之磁性部,與至少一部分被埋入磁性部之線圈狀導電性構造體,且包含藉由線圈狀導電性構造體與磁性部中的一部分所構成之電感元件的配線板之製造方法,其係包含下列步驟:準備本實施形態之接著薄膜及設置有第1配線層之芯基材的步驟;將接著薄膜之樹脂組成物層疊層於芯基材的步驟;將樹脂組成物層進行熱硬化而形成第1磁性層的步驟;於第1磁性層形成通孔的步驟;對於形成有通孔的第1磁性層進行粗化處理的步驟;於第1磁性層形成第2配線層,並形成將第1配線層與第2配線層電連接之通孔內配線的步驟;於形成有第2配線層及通孔內配線的第1磁性層進一步疊層本實施形態之接著薄膜,進行熱硬化而形成第2磁性層的步驟;以及形成包含:包含第1配線層的一部分與第2配線層的一部分與通孔內配線之線圈狀導電性構造體,及延伸於磁性部之厚度方向且被線圈狀導電性構造體所包圍的磁性部的一部分之電感元件的步驟。Hereinafter, a method for manufacturing a wiring board with an internal load inductance element according to the first embodiment will be described with reference to FIG. 2. The manufacturing method of a wiring board according to this embodiment includes a magnetic portion including a first magnetic layer and a second magnetic layer, and a coil-shaped conductive structure in which at least a portion is embedded in the magnetic portion, and includes a coil-shaped conductive structure. The manufacturing method of a wiring board for an inductive element composed of a part of a body and a magnetic part includes the following steps: a step of preparing an adhesive film of this embodiment and a core substrate provided with a first wiring layer; A step of laminating a resin composition on a core substrate; a step of thermally curing the resin composition layer to form a first magnetic layer; a step of forming a through hole in the first magnetic layer; and a first magnetic layer having a through hole A step of performing a roughening process; a step of forming a second wiring layer on the first magnetic layer, and forming a wiring in a via hole electrically connecting the first wiring layer and the second wiring layer; and forming a second wiring layer and a via hole A step of forming a second magnetic layer by laminating the first magnetic layer of the internal wiring with the first magnetic layer of the present embodiment, and performing thermal curing; and forming a second magnetic layer including a part of the first wiring layer and the second wiring layer The through hole portion coiled conductive wire structure, and a step portion of the inductance element portion is surrounded by a magnetic coil-shaped conductive structure extending in the thickness direction of the magnetic portion of and.
首先,準備設置於第1主表面20a的第1配線層42、設置於第2主表面20b的外部端子24、貫通孔22、設置有貫通孔內配線22a的芯基材(內層電路基板)20及接著薄膜。First, a first wiring layer 42 provided on the first main surface 20a, an external terminal 24 provided on the second main surface 20b, a through hole 22, and a core substrate (inner circuit board) provided with the through-hole wiring 22a are prepared. 20 and subsequent films.
<第1磁性層之形成步驟> 接著,形成第1磁性層32。首先,進行以接觸芯基材之第1配線層42的方式將接著薄膜之樹脂組成物層進行疊層的疊層步驟。<Steps of Forming First Magnetic Layer> Next, a first magnetic layer 32 is formed. First, a lamination step of laminating the resin composition layer of the film to the first wiring layer 42 of the core substrate is performed.
疊層步驟的條件並無特別限定,可採用在使用接著薄膜來形成磁性層(增層磁性層)時所使用的條件。例如,可藉由將經加熱的不鏽鋼鏡板等之金屬板從接著薄膜之支撐體側加壓而進行。於此情況中,較佳係並非對金屬板直接加壓,而是以使接著薄膜充分追隨芯基材20之表面凹凸的方式,隔著由耐熱橡膠等所構成之彈性構件來進行加壓。加壓溫度,較佳為70℃~140℃之範圍,加壓壓力較佳為1kgf/cm2 ~11kgf/cm2 (0.098MPa~1.079MPa)之範圍,加壓時間較佳為5秒鐘~3分鐘之範圍。The conditions of the lamination step are not particularly limited, and the conditions used when forming a magnetic layer (additional magnetic layer) using an adhesive film can be adopted. For example, it can be performed by pressurizing a metal plate, such as a heated stainless steel mirror plate, from the support side which adheres a film. In this case, it is preferable not to press the metal plate directly, but to press through the elastic member made of heat-resistant rubber or the like so that the adhesive film sufficiently follows the surface irregularities of the core substrate 20. The pressing temperature is preferably in the range of 70 ° C to 140 ° C, the pressing pressure is preferably in the range of 1 kgf / cm 2 to 11 kgf / cm 2 (0.098 MPa to 1.079 MPa), and the pressing time is preferably 5 seconds to 3 minutes range.
又,疊層步驟,較佳係在20mmHg(26.7hPa)以下之減壓下實施。疊層步驟係可使用市售之真空疊層機來實施。作為市售之真空疊層機,可列舉例如:名機製作所公司製之真空加壓式疊層機、Nikko-Materials公司製之Vacuum Applicator等。The lamination step is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination step can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators made by Meiki Seisakusho, Vacuum Applicator made by Nikko-Materials, and the like.
疊層步驟結束後,亦可實施將疊層於芯基材20的接著薄膜進行加熱及加壓處理之平滑化步驟。After the lamination step is completed, a smoothing step of heating and pressing the adhesive film laminated on the core substrate 20 may be performed.
平滑化步驟,一般而言,在常壓(大氣壓)下,藉由經加熱的金屬板或金屬輥,將疊層於芯基材20的接著薄膜進行加熱及加壓處理而實施。加熱及加壓處理的條件,可使用與上述疊層步驟的條件相同的條件。The smoothing step is generally performed under normal pressure (atmospheric pressure) by heating and pressing the adhesive film laminated on the core substrate 20 with a heated metal plate or metal roller. As the conditions of the heating and pressing processes, the same conditions as those of the above-mentioned lamination step can be used.
疊層步驟及平滑化步驟亦可使用相同的真空疊層機來連續地實施。The lamination step and the smoothing step may be performed continuously using the same vacuum laminator.
另外,在前述疊層步驟或前述平滑化步驟之實施後的任意時機,進行將來自接著薄膜之支撐體剝離的步驟。將支撐體剝離的步驟,例如,可藉由市售之自動剝離裝置而機械性實施。In addition, at any timing after the implementation of the lamination step or the smoothing step, a step of peeling the support from the adhesive film is performed. The step of peeling the support can be performed mechanically by, for example, a commercially available automatic peeling device.
接著,實施將疊層於芯基材20的樹脂組成物層熱硬化而形成磁性層(增層磁性層)的熱硬化步驟。Next, a thermal curing step of thermally curing the resin composition layer laminated on the core base material 20 to form a magnetic layer (additional magnetic layer) is performed.
熱硬化步驟的條件並無特別限定,可適用在形成多層印刷配線板之絕緣層時所通常採用的條件。The conditions for the heat curing step are not particularly limited, and conditions generally used when forming an insulating layer of a multilayer printed wiring board can be applied.
熱硬化步驟的條件,可依據樹脂組成物層所使用之樹脂組成物的組成而設為任意適合的條件。熱硬化步驟的條件,例如,可將硬化溫度設為120℃~240℃之範圍(較佳為150℃~210℃之範圍,更佳為170℃~190℃之範圍),將硬化時間設為5分鐘~90分鐘之範圍(較佳為10分鐘~75分鐘,更佳為15分鐘~60分鐘)。The conditions of the heat curing step can be set to any appropriate conditions depending on the composition of the resin composition used in the resin composition layer. For the conditions of the thermal curing step, for example, the curing temperature can be set in a range of 120 ° C to 240 ° C (preferably in a range of 150 ° C to 210 ° C, and more preferably in a range of 170 ° C to 190 ° C). The range is 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, and more preferably 15 minutes to 60 minutes).
亦可在實施熱硬化步驟之前,實施將樹脂組成物層以比硬化溫度更低的溫度進行預備加熱的步驟。亦可在熱硬化步驟實施之前,例如,先以50℃以上未達120℃(較佳為60℃以上110℃以下,更佳為70℃以上100℃以下)的溫度,將樹脂組成物層進行5分鐘以上(較佳為5分鐘~150分鐘,更佳為15分鐘~120分鐘)預備加熱。預備加熱,較佳係在大氣壓下(常壓下)進行。Before performing the heat curing step, a step of preheating the resin composition layer at a temperature lower than the curing temperature may be performed. Before the heat curing step is performed, for example, the resin composition layer may be subjected to a temperature of 50 ° C or higher and 120 ° C (preferably 60 ° C or higher and 110 ° C or lower, more preferably 70 ° C or higher and 100 ° C or lower). Preheating for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes). The preliminary heating is preferably performed under atmospheric pressure (under normal pressure).
藉由以上的步驟,可形成設置於芯基材20之第1磁性層32。又,藉由對於形成有磁性層的芯基材20進一步重複1次以上前述疊層步驟及前述熱硬化步驟以及後述之配線層之形成步驟,而可形成包含設置於第1磁性層32的第2磁性層34、進一步層合的磁性層之磁性部30。Through the above steps, the first magnetic layer 32 provided on the core substrate 20 can be formed. Furthermore, by repeating the above-mentioned lamination step, the above-mentioned thermosetting step, and a later-described wiring layer formation step for the core substrate 20 on which the magnetic layer is formed, a first layer including the first magnetic layer 32 can be formed. 2 magnetic layer 34, and magnetic portion 30 of further laminated magnetic layer.
又,於芯基材20形成第1磁性層32的步驟,亦可使用一般的真空熱壓機來進行。例如,可藉由將經加熱的SUS板等之金屬板從支撐體側加壓而進行。加壓條件係將減壓度設為通常為1×10-2 MPa以下,較佳為1×10-3 MPa以下之減壓下。加熱及加壓雖亦可以1階段進行,但就抑制樹脂之滲出的觀點而言,較佳係作為2階段以上之步驟,分別改變加壓條件來進行。例如,較佳係將第1階段的加壓條件設為溫度70℃~150℃、壓力1kgf/cm2 ~15kgf/cm2 之範圍,將第2階段的加壓條件設為溫度150℃~200℃、壓力1kgf/cm2 ~40kgf/cm2 之範圍來進行。各階段的時間較佳係設為30分鐘~120分鐘來進行。作為市售之真空熱壓機,可列舉例如:名機製作所公司製「MNPC-V-750-5-200」、北川精機公司製「VH1-1603」等。The step of forming the first magnetic layer 32 on the core substrate 20 can also be performed using a general vacuum hot press. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support side. The pressure condition is a reduced pressure of usually 1 × 10 -2 MPa or less, preferably 1 × 10 -3 MPa or less. Although heating and pressurization may be performed in one step, from the viewpoint of suppressing the bleeding of the resin, it is preferable to perform the steps by changing the pressurization conditions as two or more steps. For example, it is preferable to set the pressure conditions in the first stage to a temperature of 70 ° C to 150 ° C and a pressure of 1 kgf / cm 2 to 15 kgf / cm 2 , and to set the pressure conditions in the second stage to 150 ° C to 200 ° ℃, a pressure 1kgf / cm 2 ~ 40kgf / cm 2 of the range to. The time of each stage is preferably set to 30 minutes to 120 minutes. Examples of commercially available vacuum hot presses include "MNPC-V-750-5-200" manufactured by Meiji Seisakusho, and "VH1-1603" manufactured by Kitagawa Seiki.
<通孔之形成步驟> 於所形成的第1磁性層32形成通孔36。通孔36係成為用以將第1配線層42與第2配線層44電連接的路徑。通孔36係可考慮第1磁性層32的特性,藉由使用鑽孔、雷射、電漿等之周知的方法而形成。例如,在此時點殘留有保護薄膜的情況時,亦可藉由隔著保護薄膜來對第1磁性層32照射雷射光,而形成通孔36。<Step of Forming Through Hole> A through hole 36 is formed on the formed first magnetic layer 32. The through hole 36 is a path for electrically connecting the first wiring layer 42 and the second wiring layer 44. The through hole 36 is formed by a well-known method using drilling, laser, plasma, etc. in consideration of the characteristics of the first magnetic layer 32. For example, when a protective film remains at this point, the first magnetic layer 32 may be irradiated with laser light through the protective film to form the through hole 36.
作為可使用於通孔36之形成的雷射光源,可列舉例如:二氧化碳雷射、YAG雷射、準分子雷射等。其中,就加工速度、成本的觀點而言,較佳為二氧化碳雷射。Examples of the laser light source that can be used for forming the through hole 36 include a carbon dioxide laser, a YAG laser, and an excimer laser. Among these, from the viewpoints of processing speed and cost, carbon dioxide laser is preferred.
通孔36之形成係可使用市售之雷射裝置來實施。作為市售之二氧化碳雷射裝置,可列舉例如:Hitachi Via Mechanics公司製「LC-2E21B/1C」、三菱電機公司製「ML605GTWII」、Panasonic Welding Systems公司製之基板穿孔雷射加工機。The formation of the through hole 36 can be performed using a commercially available laser device. Examples of commercially available carbon dioxide laser devices include: "LC-2E21B / 1C" manufactured by Hitachi Via Mechanics, "ML605GTWII" manufactured by Mitsubishi Electric Corporation, and substrate perforation laser processing machines manufactured by Panasonic Welding Systems.
<粗化步驟> 接著,進行對於形成有通孔36的第1磁性層32進行粗化處理的粗化步驟。粗化步驟的程序、條件並無特別限定,可採用在多層印刷配線板之製造方法時所通常使用之周知的程序、條件。作為粗化步驟,例如,可依序實施以膨潤液進行之膨潤處理、以氧化劑進行之粗化處理、以中和液進行之中和處理,將第1磁性層32進行粗化處理。<Roughening step> Next, a roughening step of roughening the first magnetic layer 32 in which the through-hole 36 is formed is performed. The procedure and conditions of the roughening step are not particularly limited, and known procedures and conditions generally used in a method for manufacturing a multilayer printed wiring board can be adopted. As the roughening step, for example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, a neutralization treatment with a neutralizing solution, and a roughening treatment may be performed in this order.
作為使用於粗化步驟的膨潤液雖無特別限定,但可列舉鹼溶液、界面活性劑溶液等,較佳為鹼溶液。作為膨潤液之鹼溶液,更佳為氫氧化鈉溶液、氫氧化鉀溶液。作為市售之膨潤液,可列舉例如:Atotech Japan公司製「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。The swelling liquid used in the roughening step is not particularly limited, but examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. The alkali solution of the swelling liquid is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" manufactured by Atotech Japan, "Swelling Dip Securiganth SBU", and the like.
以膨潤液進行之膨潤處理雖無特別限定,例如,可藉由將設置有第1磁性層32的芯基材20浸漬於30℃~90℃之膨潤液中1分鐘~20分鐘而進行。就將構成第1磁性層32之樹脂的膨潤抑制於適度的水準之觀點而言,較佳係將第1磁性層32浸漬於40℃~80℃之膨潤液中5分鐘~15分鐘。Although the swelling treatment with the swelling liquid is not particularly limited, for example, it can be performed by immersing the core substrate 20 provided with the first magnetic layer 32 in a swelling liquid at 30 ° C to 90 ° C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin constituting the first magnetic layer 32 to an appropriate level, the first magnetic layer 32 is preferably immersed in a swelling solution at 40 ° C to 80 ° C for 5 to 15 minutes.
作為使用於以氧化劑進行之粗化處理的氧化劑雖無特別限定,但可列舉例如:於氫氧化鈉之水溶液中溶解有過錳酸鉀或過錳酸鈉的鹼性過錳酸溶液。以鹼性過錳酸溶液等之氧化劑進行之粗化處理,較佳係藉由使第1磁性層32浸漬於加熱至60℃~80℃之氧化劑的溶液中10分鐘~30分鐘而進行。又,於鹼性過錳酸溶液中之過錳酸鹽的濃度較佳係設為5質量%~10質量%。作為市售之氧化劑,可列舉例如:Atotech Japan公司製「Concentrate Compact P」、「Dosing Solution Securiganth P」等之鹼性過錳酸溶液。The oxidizing agent used for the roughening treatment with the oxidizing agent is not particularly limited, but examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the first magnetic layer 32 in a solution of the oxidizing agent heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact P" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.
作為使用於中和處理的中和液較佳為酸性之水溶液,作為市售品,可列舉例如:Atotech Japan公司製之「Reduction solution Securiganth P」。以中和液進行之中和處理,可藉由使以氧化劑溶液進行之粗化處理後的處理面浸漬於30℃~80℃之中和液中5分鐘~30分鐘而進行。就作業性等之點而言,較佳係將經以氧化劑溶液進行之粗化處理的第1磁性層32浸漬於40℃~70℃之中和液中5分鐘~20分鐘的方法。The neutralizing solution used in the neutralization treatment is preferably an acidic aqueous solution. As a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan is mentioned. The neutralization treatment with the neutralization solution can be performed by immersing the treated surface after the roughening treatment with the oxidant solution in a neutralization solution at 30 ° C to 80 ° C for 5 to 30 minutes. In terms of workability and the like, a method of immersing the first magnetic layer 32 subjected to the roughening treatment with an oxidizing agent solution in a neutralization solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferred.
如上述般說明的粗化步驟,亦可兼具用以進行形成於第1磁性層32之通孔36的膠渣去除之所謂的去膠渣步驟。The roughening step described above may also have a so-called slag removing step for removing the slag that is formed in the through holes 36 formed in the first magnetic layer 32.
又,亦可與粗化步驟分別地對於通孔36實施去膠渣步驟。另外,此去膠渣步驟,可為濕式之去膠渣步驟,亦可為乾式之去膠渣步驟。Alternatively, the slag removal step may be performed for the through-hole 36 separately from the roughening step. In addition, the slag removal step may be a wet slag removal step or a dry slag removal step.
去膠渣步驟之具體的步驟並無特別限定,例如,可採用在形成多層印刷配線板之絕緣層時所通常使用之周知的步驟、條件。作為乾式之去膠渣步驟之例可列舉電漿處理等,作為濕式之去膠渣步驟之例可列舉依序進行以與前述粗化步驟相同的膨潤液進行之膨潤處理、以氧化劑所進行之處理及以中和液所進行之處理的方法。The specific steps of the slag removing step are not particularly limited. For example, well-known steps and conditions commonly used in forming an insulating layer of a multilayer printed wiring board can be adopted. Examples of the dry type slag removal step include plasma treatment, and examples of the wet type slag removal step include a swelling treatment sequentially performed with a swelling liquid similar to the roughening step, and an oxidizing agent. The method of treatment and the treatment with a neutralizing solution.
<第2配線層之形成> 接著,於已進行粗化步驟(及去膠渣步驟)的第1磁性層32形成第2配線層44。<Formation of the second wiring layer> (2) Next, the second wiring layer 44 is formed on the first magnetic layer 32 that has been subjected to the roughening step (and the slag removing step).
第2配線層44係可藉由鍍敷而形成。第2配線層44,例如,可藉由包含無電解鍍敷步驟、遮罩圖型形成步驟、電解鍍敷步驟、快閃蝕刻步驟的半加成法、全加成法等之以往周知的技術而形成,藉此作為包含所期望之配線圖型的配線層而形成。另外,藉由此第2配線層44之形成步驟,通孔內配線36a一併被形成於通孔36內。The second wiring layer 44 can be formed by plating. The second wiring layer 44 can be formed by a conventionally well-known technique such as a semi-additive method, a full-additive method including an electroless plating step, a mask pattern forming step, an electrolytic plating step, and a flash etching step. It is thereby formed as a wiring layer including a desired wiring pattern. In addition, through this step of forming the second wiring layer 44, the through-hole wiring 36 a is also formed in the through-hole 36.
在第1磁性層32為增層磁性層,第2磁性層44為增層配線層之視為增層的情況,於本實施形態之配線板中,在增層必須再1層以上的情況時,只要再重複進行1次以上從前述第1磁性層32之形成步驟至前述第2磁性層44之形成步驟為止之已說明的一連串步驟來實施即可。In the case where the first magnetic layer 32 is a build-up magnetic layer, and the second magnetic layer 44 is a build-up wiring layer, it is considered as a build-up. In the wiring board of this embodiment, when the build-up layer needs to be more than one layer It is only necessary to repeat a series of steps described from the step of forming the first magnetic layer 32 to the step of forming the second magnetic layer 44 more than once to implement.
<第2磁性層之形成> 接著,於形成有第2配線層44及通孔內配線36a的第1磁性層32形成第2磁性層34。第2磁性層34係只要使用與包含已說明之接著薄膜的疊層步驟、平滑化步驟、熱硬化步驟的第1磁性層32之形成步驟相同的材料,並藉由相同的步驟而形成即可。<Formation of the second magnetic layer> Next, the second magnetic layer 34 is formed on the first magnetic layer 32 on which the second wiring layer 44 and the through-hole wiring 36a are formed. The second magnetic layer 34 may be formed using the same material as the first magnetic layer 32 forming step including the laminating step, smoothing step, and thermosetting step described above, and formed by the same steps. .
藉由以上的步驟,可製造配線板10,該配線板10具有至少一部分埋入磁性部30的線圈狀導電性構造體40,且包含電感元件,該電感元件包含:包含第1配線層42的一部分與第2配線層44的一部分與通孔內配線36a的線圈狀導電性構造體40與延伸於磁性部30之厚度方向且被線圈狀導電性構造體40所包圍的磁性部30中的一部分。Through the above steps, a wiring board 10 having a coil-shaped conductive structure 40 in which at least a portion of the magnetic portion 30 is embedded and an inductance element including the first wiring layer 42 can be manufactured. A part and a part of the second wiring layer 44 and a coil-shaped conductive structure 40 of the through-hole wiring 36 a and a part of the magnetic portion 30 extending in the thickness direction of the magnetic portion 30 and surrounded by the coil-shaped conductive structure 40 .
(第2實施形態) 針對第2實施形態之內載電感元件之配線板的構造例,參照第4圖(h)進行說明。針對與第1實施形態相同的構成要素係標示相同的符號,有時會省略重複的說明。(Second Embodiment) A structural example of a wiring board with an internally mounted inductance element according to a second embodiment will be described with reference to Fig. 4 (h). The same components as those in the first embodiment are denoted by the same reference numerals, and redundant descriptions may be omitted.
如第4圖(h)所示般,配線板11係具有作為樹脂組成物(樹脂組成物層)的硬化體之磁性層,與至少一部分埋入此磁性層的導電性構造體,且包含電感元件,其係藉由此導電性構造體,與延伸於磁性層的厚度方向且被導電性構造體所包圍之磁性層中的一部分所構成。配線板11係具有增層磁性層的增層配線板。配線板11在不具有芯基材的點上與第1實施形態之配線板10不同。As shown in FIG. 4 (h), the wiring board 11 is a magnetic layer having a hardened body of a resin composition (resin composition layer), a conductive structure at least partially embedded in the magnetic layer, and includes an inductor. The device is composed of a conductive structure and a part of a magnetic layer extending in the thickness direction of the magnetic layer and surrounded by the conductive structure. The wiring board 11 is a build-up wiring board having a build-up magnetic layer. The wiring board 11 is different from the wiring board 10 of the first embodiment in that it does not have a core substrate.
可想定配線板11所具備的電感元件可發揮功能的頻率為10MHz~200MHz。又,可想定配線板11所具備的電感元件為電源系。It is conceivable that the frequency at which the inductance element included in the wiring board 11 can function is 10 MHz to 200 MHz. It is also conceivable that the inductance element included in the wiring board 11 is a power supply system.
配線板11包含第1配線層42、第2配線層44、及第3配線層46。第1配線層42、第2配線層44、及第3配線層46通常包含複數之配線。於圖示例中,僅顯示構成電感元件之線圈狀導電性構造體40的配線。針對第1配線層42、第2配線層44、外部端子24、及其他配線係與第1實施形態中之第1配線層42、第2配線層44、外部端子24、及其他配線相同。The wiring board 11 includes a first wiring layer 42, a second wiring layer 44, and a third wiring layer 46. The first wiring layer 42, the second wiring layer 44, and the third wiring layer 46 usually include a plurality of wirings. In the illustrated example, only the wiring of the coil-shaped conductive structure 40 constituting the inductance element is shown. The first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wiring systems are the same as the first wiring layer 42, the second wiring layer 44, the external terminals 24, and other wirings in the first embodiment.
作為可構成第3配線層46的導體材料係與第1實施形態中之可構成第1配線層42的導體材料相同。又,作為第3配線層46的厚度係與第1實施形態中之第1配線層42的厚度相同。The conductive material that can constitute the third wiring layer 46 is the same as the conductive material that can constitute the first wiring layer 42 in the first embodiment. The thickness of the third wiring layer 46 is the same as that of the first wiring layer 42 in the first embodiment.
第3配線層46可為單層構造,亦可為層合2層以上由不同種類之金屬或合金所構成之單金屬層或者合金層的多層構造。在第3配線層46為多層構造的情況,與絕緣層接觸的層較佳為鉻、鋅或鈦之單金屬層、或者鎳鉻合金之合金層。The third wiring layer 46 may have a single-layer structure or a multilayer structure in which two or more single-metal layers or alloy layers composed of different kinds of metals or alloys are laminated. When the third wiring layer 46 has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.
第1磁性層32、第2磁性層34、及第3磁性層38係構成可視為一體的磁性層之磁性部30。第1磁性層32及第2磁性層34係與第1實施形態中之第1磁性層32及第2磁性層34相同。The first magnetic layer 32, the second magnetic layer 34, and the third magnetic layer 38 constitute a magnetic portion 30 that can be considered as a magnetic layer. The first magnetic layer 32 and the second magnetic layer 34 are the same as the first magnetic layer 32 and the second magnetic layer 34 in the first embodiment.
第3磁性層38係來自已說明之接著薄膜之層,接著薄膜之樹脂組成物層係磁性層形成時之流動性優異,因此,第2配線層44之密封性優異。又,第3磁性層38係使用前述接著薄膜所形成,因此,頻率為10MHz~200MHz之範圍內的相對導磁率提昇,進而通常磁性損失減低。The third magnetic layer 38 is derived from the film-adhered layer, and the resin composition layer of the subsequent film is excellent in fluidity when the magnetic layer is formed. Therefore, the second wiring layer 44 is excellent in sealing property. In addition, since the third magnetic layer 38 is formed using the aforementioned adhesive film, the relative magnetic permeability in the frequency range of 10 MHz to 200 MHz is improved, and the magnetic loss is generally reduced.
於通孔36內係設置有通孔內配線36a。第1配線層42、第2配線層44、及第3配線層46係藉由通孔內配線36a等而電連接。A through-hole wiring 36 a is provided in the through-hole 36. The first wiring layer 42, the second wiring layer 44, and the third wiring layer 46 are electrically connected to each other through the through-hole wiring 36 a and the like.
於本實施形態中,線圈狀導電性構造體40係以包含第1配線層42、第2配線層44、及第3配線層46之3層的配線層之例進行說明,但,亦可藉由4層以上之配線層(及4層以上之增層磁性層)構成線圈狀導電性構造體40。於此情況中,以挾持最上層之配線層與最下層之配線層的方式作配置之未圖示的配線層之渦卷狀的配線部,其一端電連接於最上層側且最靠近配置的配線層之渦卷狀的配線部之任一方的端部,其另一端電連接於最下層側且最靠近配置的配線層之渦卷狀的配線部之任一方的端部。In this embodiment, the coil-shaped conductive structure 40 is described using an example of a three-layer wiring layer including a first wiring layer 42, a second wiring layer 44, and a third wiring layer 46. The coil-shaped conductive structure 40 is composed of four or more wiring layers (and four or more build-up magnetic layers). In this case, one end of the spiral-shaped wiring portion of the unillustrated wiring layer, which is configured to support the uppermost wiring layer and the lowermost wiring layer, is electrically connected to the uppermost layer side and closest to the arranged one. The other end of any one of the spirally-shaped wiring portions of the wiring layer is electrically connected to any one of the spiral-shaped wiring portions of the lowermost layer side and closest to the arranged wiring layer.
依據本實施形態之配線板,由於藉由前述接著薄膜形成磁性層,因此可提高所形成之磁性層的相對導磁率、難燃性,且可減低翹曲量。According to the wiring board of this embodiment, since the magnetic layer is formed by the aforementioned bonding film, the relative magnetic permeability and flame resistance of the formed magnetic layer can be improved, and the amount of warpage can be reduced.
以下,針對第2實施形態之內載電感元件之配線板之製造方法,參照第4圖進行說明。針對與第1實施形態說明重複的地方係適當省略說明。 本實施形態之配線板之製造方法係包含下列步驟: (1)準備具有基材51,與設置於該基材51之至少一方之面的附載體金屬層52之附載體金屬層之基材50的步驟; (2)將接著薄膜之樹脂組成物層疊層於附載體金屬層之基材50,將該樹脂組成物層熱硬化,而形成第1磁性層32的步驟; (3)於第1磁性層32上形成第1配線層42的步驟; (4)將接著薄膜之樹脂組成物層疊層於第1配線層42及第1磁性層32上,將該樹脂組成物層熱硬化,而形成第2磁性層34的步驟; (5)於第2磁性層34形成通孔36,對於形成有通孔36的第2磁性層34進行粗化處理的步驟; (6)於第2磁性層34上形成第2配線層44的步驟; (7)將接著薄膜之樹脂組成物層疊層於第2配線層44及第2磁性層34上,將該樹脂組成物層熱硬化,而形成第3磁性層38的步驟; (8)將附載體金屬層之基材50去除的步驟; (9)於第3磁性層38形成通孔36,對於形成有通孔36的第3磁性層38進行粗化處理的步驟; (10)於第1磁性層32形成通孔36,對於形成有通孔36的第1磁性層32進行粗化處理的步驟; (11)於第3磁性層38上形成第3配線層46的步驟;以及 (12)於第1磁性層32上形成外部端子24的步驟。Hereinafter, a method for manufacturing a wiring board with an internally mounted inductance element according to the second embodiment will be described with reference to FIG. 4. The description of the points that overlap with the description of the first embodiment is appropriately omitted. The method for manufacturing a wiring board according to this embodiment includes the following steps: (1) Preparing a base material 50 having a carrier metal layer 52 and a carrier metal layer 52 provided on at least one side of the base material 51; (2) a step of laminating a resin composition with a film on a substrate 50 with a carrier metal layer, and thermally hardening the resin composition layer to form a first magnetic layer 32; (3) in the first step Step of forming the first wiring layer 42 on the magnetic layer 32; (4) Laminating a resin composition with a thin film on the first wiring layer 42 and the first magnetic layer 32, and thermally curing the resin composition layer to form Step of the second magnetic layer 34; (5) a step of forming a through hole 36 in the second magnetic layer 34, and roughening the second magnetic layer 34 where the through hole 36 is formed; (6) on the second magnetic layer 34 Step of forming a second wiring layer 44; (7) Laminating a resin composition with a thin film on the second wiring layer 44 and the second magnetic layer 34, and thermally curing the resin composition layer to form a third magnetic property; Steps of layer 38; (8) attach the carrier gold Step of removing the substrate 50 of the metal layer; ; (9) forming a through hole 36 in the third magnetic layer 38, and roughening the third magnetic layer 38 where the through hole 36 is formed; (10) on the first magnetic layer A step of forming a through hole 36 in the layer 32, and roughening the first magnetic layer 32 on which the through hole 36 is formed; (11) a step of forming a third wiring layer 46 on the third magnetic layer 38; and (12) a A step of forming an external terminal 24 on the first magnetic layer 32.
步驟(9)與步驟(10)係可順序互換來進行,亦可同時進行。又,步驟(11)與步驟(12)係可順序互換來進行,亦可同時進行。Step (9) and step (10) can be performed interchangeably in sequence or simultaneously. In addition, step (11) and step (12) may be performed sequentially and interchangeably, or may be performed simultaneously.
<步驟(1)> 步驟(1)係準備具有基材51,與設置於該基材51之至少一方之面的附載體金屬層52的附載體金屬層之基材50的步驟。如於第4圖(a)中顯示一例般,通常,附載體金屬層之基材50係設有基材51,與於該基材51之至少一方之面的附載體金屬層52。附載體金屬層52,就提高後述之步驟(8)的作業性的觀點而言,較佳係從基材51側起依序具備第1金屬層521、第2金屬層522的構造。<Step (1)> (1) Step (1) is a step of preparing a base material 50 having a base metal 51 and a carrier metal layer 52 provided with a carrier metal layer 52 provided on at least one side of the base material 51. As shown in an example in FIG. 4 (a), the base material 50 with a carrier metal layer is generally provided with a base material 51 and a carrier metal layer 52 on at least one side of the base material 51. From the viewpoint of improving the workability of the step (8) described later, the metal layer with a carrier preferably has a structure including the first metal layer 521 and the second metal layer 522 in this order from the substrate 51 side.
作為基材51係與第1實施形態中之芯基材相同。作為附載體金屬層52之材料,可列舉例如:附載體之銅箔、其他可剝離之附支撐體之金屬箔等。附載體金屬層之基材50可使用市售品。作為市售品可列舉例如:三井金屬公司製MT-EX等。The base material 51 is the same as the core base material in the first embodiment. Examples of the material of the carrier-attached metal layer 52 include a copper foil with a carrier and other peelable metal foils with a support. As the substrate 50 with a carrier metal layer, a commercially available product can be used. Examples of commercially available products include MT-EX manufactured by Mitsui Metals Corporation.
<步驟(2)> 步驟(2)係如於第4圖(b)顯示一例般,將接著薄膜之樹脂組成物層疊層於附載體金屬層之基材50,將該樹脂組成物層熱硬化,而形成第1磁性層32的步驟。<Step (2)> (2) Step (2) is to laminate the resin composition with a film on the substrate 50 with a carrier metal layer as shown in FIG. 4 (b), and heat-harden the resin composition layer. , And a step of forming the first magnetic layer 32.
步驟(2)中之第1磁性層32之形成可藉由與第1實施形態中之第1磁性層之形成相同的方法而形成。The formation of the first magnetic layer 32 in the step (2) can be formed by the same method as the formation of the first magnetic layer in the first embodiment.
步驟(2)結束後,亦可因應需要,而於所形成之第1磁性層上施行粗化步驟。粗化步驟,可藉由與第1實施形態中之對於第1磁性層進行之粗化步驟相同的方法來進行。After step (2) is completed, a roughening step may also be performed on the formed first magnetic layer as required. The roughening step can be performed by the same method as the roughening step performed on the first magnetic layer in the first embodiment.
<步驟(3)> 步驟(3)係如第4圖(c)顯示一例般,於第1磁性層32上形成第1配線層42的步驟。第1配線層42係可藉由鍍敷而形成。第1配線層42可藉由與第1實施形態中之第2配線層44之形成相同的方法而形成。又,第1配線層42可使用與第1實施形態中之第1配線層相同的導體材料。<Step (3)> Step (3) is a step of forming a first wiring layer 42 on the first magnetic layer 32 as shown in FIG. 4 (c). The first wiring layer 42 can be formed by plating. The first wiring layer 42 can be formed by the same method as the formation of the second wiring layer 44 in the first embodiment. The first wiring layer 42 can be made of the same conductive material as the first wiring layer in the first embodiment.
<步驟(4)> 步驟(4)係如第4圖(d)顯示一例般,將接著薄膜之樹脂組成物層疊層於第1配線層42及第1磁性層32上,將該樹脂組成物層熱硬化,而形成第2磁性層34的步驟。<Step (4)> Step (4) is as shown in FIG. 4 (d). The resin composition of the film is laminated on the first wiring layer 42 and the first magnetic layer 32, and the resin composition is laminated. The step of thermally curing the layer to form the second magnetic layer 34.
第2磁性層34可藉由與前述之步驟(2)相同的方法而形成。形成第2磁性層34之接著薄膜,可使用與形成第1磁性層32時所使用的接著薄膜相同者,亦可使用不同的接著薄膜。The second magnetic layer 34 can be formed by the same method as the aforementioned step (2). The adhesive film for forming the second magnetic layer 34 may be the same as the adhesive film used when forming the first magnetic layer 32, or a different adhesive film may be used.
<步驟(5)> 步驟(5)係如第4圖(e)顯示一例般,於第2磁性層34形成通孔36,對於形成有通孔36的第2磁性層34進行粗化處理的步驟。於通孔36內係設置有通孔內配線36a。通孔36係成為用以將第1配線層42與第2配線層44電連接的路徑。<Step (5)> Step (5) is a process of forming a through hole 36 in the second magnetic layer 34 as shown in FIG. 4 (e), and roughening the second magnetic layer 34 in which the through hole 36 is formed. step. A through-hole wiring 36 a is provided in the through-hole 36. The through hole 36 is a path for electrically connecting the first wiring layer 42 and the second wiring layer 44.
通孔36之形成可藉由與第1實施形態中之通孔之形成步驟相同的方法而形成。又,粗化處理,可藉由與第1實施形態中之對於第1磁性層進行之粗化步驟相同的方法來進行。The formation of the through-hole 36 can be performed by the same method as the formation step of the through-hole in the first embodiment. The roughening process can be performed by the same method as the roughening step performed on the first magnetic layer in the first embodiment.
<步驟(6)> 步驟(6)係如第4圖(e)顯示一例般,於第2磁性層34上形成第2配線層44的步驟。詳細內容係於第2磁性層34中之通孔36上形成第2配線層44。第2配線層44係可藉由鍍敷而形成。第2配線層44可藉由與第1實施形態中之第2配線層44之形成相同的方法而形成。又,第2配線層44可使用與第1實施形態中之第2配線層相同的導體材料。<Step (6)> Step (6) is a step of forming a second wiring layer 44 on the second magnetic layer 34 as shown in FIG. 4 (e) as an example. In detail, the second wiring layer 44 is formed on the through hole 36 in the second magnetic layer 34. The second wiring layer 44 can be formed by plating. The second wiring layer 44 can be formed by the same method as the formation of the second wiring layer 44 in the first embodiment. The second wiring layer 44 can be made of the same conductive material as the second wiring layer in the first embodiment.
<步驟(7)> 步驟(7)係如第4圖(f)顯示一例般,將接著薄膜之樹脂組成物層疊層於第2配線層44及第2磁性層34上,將該樹脂組成物層熱硬化,而形成第3磁性層38的步驟。<Step (7)> Step (7) is as shown in FIG. 4 (f), and a resin composition with a thin film is laminated on the second wiring layer 44 and the second magnetic layer 34, and the resin composition is laminated. The step of thermally curing the layer to form the third magnetic layer 38.
第3磁性層38可藉由與前述之步驟(2)相同的方法而形成。形成第3磁性層38之接著薄膜,可使用與形成第1磁性層32及第2磁性層34時所使用的接著薄膜相同者,亦可使用不同者。The third magnetic layer 38 can be formed by the same method as the aforementioned step (2). The adhesive film for forming the third magnetic layer 38 may be the same as the adhesive film used for forming the first magnetic layer 32 and the second magnetic layer 34, or may be different.
<步驟(8)> 步驟(8)係如第4圖(g)顯示一例般,將附載體金屬層之基材50去除的步驟。附載體金屬層之基材50之去除方法並無特別限定。較佳之一實施形態係在第1金屬層521及第2金屬層522的界面將基材51及第1金屬層521剝離,將第2金屬層522以例如氯化銅水溶液等進行蝕刻去除。亦可因應需要,而在以保護薄膜保護第3磁性層38的狀態下將附載體金屬層之基材50剝離。<Step (8)> (8) The step (8) is a step of removing the base material 50 with a carrier metal layer as shown in FIG. 4 (g) as an example. The method for removing the substrate 50 with a carrier metal layer is not particularly limited. In a preferred embodiment, the substrate 51 and the first metal layer 521 are peeled off at the interface between the first metal layer 521 and the second metal layer 522, and the second metal layer 522 is removed by etching with, for example, an aqueous copper chloride solution. If necessary, the base material 50 with a carrier metal layer may be peeled off in a state where the third magnetic layer 38 is protected by a protective film.
<步驟(9)> 步驟(9)係於第3磁性層38形成第4圖未圖示之通孔,並對於形成有通孔的第3磁性層38進行粗化處理的步驟。於通孔內係設置有通孔內配線。通孔係成為用以將第2配線層44與第3配線層46電連接的路徑。此通孔之形成可藉由與第1實施形態中之通孔之形成步驟相同的方法而形成。又,粗化處理,可藉由與第1實施形態中之對於第1磁性層進行之粗化步驟相同的方法來進行。<Step (9)> Step (9) is a step of forming a through hole (not shown in FIG. 4) in the third magnetic layer 38 and roughening the third magnetic layer 38 in which the through hole is formed. A through-hole wiring is provided in the through-hole. The via hole is a path for electrically connecting the second wiring layer 44 and the third wiring layer 46. This through hole can be formed by the same method as the through hole forming step in the first embodiment. The roughening process can be performed by the same method as the roughening step performed on the first magnetic layer in the first embodiment.
<步驟(10)> 步驟(10)係如第4圖(h)顯示一例般,於第1磁性層32形成通孔36,對於形成有通孔36的第1磁性層32進行粗化處理的步驟。詳細內容係於將第1磁性層32之附載體金屬層之基材50去除後之側的面側形成通孔36,並於該通孔36上形成外部端子24。於通孔36內係設置有通孔內配線36a。此通孔36係成為用以將第1配線層42與外部端子24電連接的路徑。此通孔36之形成可藉由與第1實施形態中之通孔之形成步驟相同的方法而形成。又,粗化處理,可藉由與第1實施形態中之對於第1磁性層進行之粗化步驟相同的方法來進行。<Step (10)> (Step (10) is an example in which the through hole 36 is formed in the first magnetic layer 32 as shown in FIG. 4 (h), and the first magnetic layer 32 having the through hole 36 is roughened. step. The details are that a through hole 36 is formed on the surface side of the first magnetic layer 32 with the carrier metal layer with the carrier metal layer removed, and an external terminal 24 is formed in the through hole 36. A through-hole wiring 36 a is provided in the through-hole 36. This through hole 36 is a path for electrically connecting the first wiring layer 42 and the external terminal 24. This through hole 36 can be formed by the same method as the through hole forming step in the first embodiment. The roughening process can be performed by the same method as the roughening step performed on the first magnetic layer in the first embodiment.
<步驟(11)> 步驟(11)係如第4圖(h)顯示一例般,於第3磁性層38上形成第3配線層46的步驟。詳細內容係在進行了形成於第3磁性層38之未圖示的通孔之粗化處理之後,於該通孔上形成第3配線層46。第3配線層46可藉由與第1實施形態中之第2配線層44相同的方法形成,又,可使用與第1實施形態中之第1及第2配線層相同的導體材料。<Step (11)> (Step (11) is a step of forming a third wiring layer 46 on the third magnetic layer 38 as shown in FIG. 4 (h) as an example. The details are obtained by roughening a through hole (not shown) formed in the third magnetic layer 38 and then forming a third wiring layer 46 on the through hole. The third wiring layer 46 can be formed by the same method as the second wiring layer 44 in the first embodiment, and the same conductive material as the first and second wiring layers in the first embodiment can be used.
<步驟(12)> 步驟(12)係如第4圖(h)顯示一例般,於第1磁性層32上形成外部端子24的步驟。詳細內容係在進行了形成於第1磁性層32之通孔36之粗化處理之後,於該通孔36上連接外部端子24。<Step (12)> Step (12) is a step of forming an external terminal 24 on the first magnetic layer 32 as shown in FIG. 4 (h) as an example. In detail, after roughening the through-hole 36 formed in the first magnetic layer 32, the external terminal 24 is connected to the through-hole 36.
藉由以上的步驟,可製造無基材,且包含電感元件之配線板。此電感元件係包含線圈狀導電性構造體40,與延伸於磁性部30之厚度方向且被線圈狀導電性構造體40所包圍之磁性部30中的一部分。並且,線圈狀導電性構造體40包含第1配線層42的一部分、第2配線層44的一部分、第3配線層46的一部分與通孔內配線36a。Through the above steps, a wiring board without a substrate and including an inductance element can be manufactured. This inductance element includes a coil-shaped conductive structure 40 and a part of the magnetic portion 30 extending in the thickness direction of the magnetic portion 30 and surrounded by the coil-shaped conductive structure 40. The coil-shaped conductive structure 40 includes a part of the first wiring layer 42, a part of the second wiring layer 44, a part of the third wiring layer 46, and the through-hole wiring 36 a.
在第1磁性層32為增層磁性層,第2磁性層44為增層配線層之視為增層的情況,於本實施形態之配線板中,在增層必須再1層以上的情況時,只要再重複進行1次以上從前述第1磁性層32之形成步驟至前述第2磁性層44之形成步驟為止之已說明的一連串步驟來實施即可。In the case where the first magnetic layer 32 is a build-up magnetic layer, and the second magnetic layer 44 is a build-up wiring layer, it is considered as a build-up. In the wiring board of this embodiment, when the build-up layer needs to be more than one layer It is only necessary to repeat a series of steps described from the step of forming the first magnetic layer 32 to the step of forming the second magnetic layer 44 more than once to implement.
使用本發明之接著薄膜,可提昇頻率10MHz~200MHz之相對導磁率,且可形成難燃性優異,翹曲量減低的磁性層,因此,可以更簡便的步驟提供包含無需設為空芯構造而是藉由磁性層的一部分所構成之芯部之內置更高性能的低頻帶域用電感元件的配線板。By using the adhesive film of the present invention, the relative magnetic permeability at a frequency of 10 MHz to 200 MHz can be increased, and a magnetic layer having excellent flame retardancy and reduced warpage can be formed. Therefore, it can be provided in a simpler step without the need to be a hollow core structure It is a wiring board with a high-performance low-frequency-band inductive element built into a core made of a part of a magnetic layer.
本實施形態之配線板,可作為用以搭載半導體晶片等之電子零件的配線板使用,亦可作為將該配線板作為內層基板使用的(多層)印刷配線板使用。又,亦可作為將該配線板單片化之晶片電感零件使用,亦可作為將該晶片電感零件進行表面安裝之印刷配線板使用。 又,可使用該配線板來製造各種樣態之半導體裝置。包含該配線板之半導體裝置,可適合使用於電氣製品(例如,電腦、行動電話、數位相機及電視等)及交通工具(例如,機車、汽車、電車、船舶及航空機等)等。 [實施例]The wiring board of this embodiment can be used as a wiring board for mounting electronic components such as semiconductor wafers, or as a (multi-layer) printed wiring board using the wiring board as an inner layer substrate. Moreover, it can also be used as a chip inductor component which singulates this wiring board, and it can also be used as a printed wiring board which surface mounts this chip inductor component. In addition, this wiring board can be used to manufacture various types of semiconductor devices. The semiconductor device including the wiring board is suitable for use in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, locomotives, automobiles, trams, ships, and aircraft). [Example]
以下,雖藉由實施例更具體地說明本發明,但本發明並非限定於此等之實施例者。另外,於以下之記載中,表示量之「份」及「%」只要無另外說明,則分別意味著「質量份」及「質量%」。Hereinafter, although the present invention will be described more specifically with reference to the examples, the present invention is not limited to these examples. In addition, in the following description, "parts" and "%" indicating amounts, unless otherwise specified, mean "mass parts" and "mass%", respectively.
<實施例1.樹脂組成物1之調製> 使「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品、新日鐵住金化學公司製)7質量份、「HP-4700」(萘型4官能環氧樹脂、DIC公司製)7質量份、「YX7553」(苯氧基樹脂、不揮發性成分30質量%、三菱化學公司製)35質量份、「KS-1」(聚乙烯縮醛樹脂、積水化學工業公司製)30質量份,於MEK 10質量份、環己酮10質量份、乙醇40質量份、甲苯40質量份中一邊攪拌一邊加熱溶解。於其中混合「LA-7054」(含三嗪骨架之酚系硬化劑之不揮發性成分60質量%、DIC公司製)14質量份、「2E4MZ」(硬化促進劑、四國化成工業公司製)0.1質量份、無機填充材(將「SO-C2」(二氧化矽、平均粒徑0.5μm、Admatechs公司製)以「KBM-573」(胺基矽烷系偶合劑、信越化學工業公司製)處理後的二氧化矽)35質量份、「AW2-08PF3F」(磁性填料、Fe-Cr-Si系合金(非晶質)、平均粒徑3.0μm、EPSON ATMIX公司製)850質量份,以高速旋轉混合機均勻地分散,而調製樹脂組成物1。<Example 1. Preparation of resin composition 1> 7 parts by mass of "ZX1059" (a mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), "HP -4700 "(naphthalene-type 4-functional epoxy resin, manufactured by DIC Corporation) 7 parts by mass," YX7553 "(phenoxy resin, 30% by mass of non-volatile components, manufactured by Mitsubishi Chemical Corporation)," KS-1 "(Polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) 30 parts by mass, heated and dissolved in 10 parts by mass of MEK, 10 parts by mass of cyclohexanone, 40 parts by mass of ethanol, and 40 parts by mass of toluene while stirring. 14 parts by mass of "LA-7054" (60% by mass of the non-volatile component of the phenol-based hardener containing a triazine skeleton, manufactured by DIC Corporation), and "2E4MZ" (hardening accelerator, manufactured by Shikoku Chemical Industries, Ltd.) 0.1 parts by mass of an inorganic filler ("SO-C2" (silicon dioxide, average particle size 0.5 μm, manufactured by Admatechs)) treated with "KBM-573" (aminosilane-based coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 35 parts by mass of SiO2, 850 parts by mass of "AW2-08PF3F" (magnetic filler, Fe-Cr-Si-based alloy (amorphous), average particle diameter 3.0 μm, manufactured by EPSON ATMIX), and rotated at high speed The mixer disperses uniformly, and the resin composition 1 is prepared.
<實施例2.樹脂組成物2之調製> 使「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品、新日鐵住金化學公司製)14質量份、「HP-4700」(萘型4官能環氧樹脂、DIC公司製)14質量份、「YX7553」(苯氧基樹脂、不揮發性成分30質量%、三菱化學公司製)35質量份、「KS-1」(聚乙烯縮醛樹脂、積水化學工業公司製)23質量份,於MEK 10質量份、環己酮10質量份、乙醇30質量份、甲苯30質量份中一邊攪拌一邊加熱溶解。於其中混合「LA-7054」(含三嗪骨架之酚系硬化劑、不揮發性成分60質量%、DIC公司製)28質量份、「2E4MZ」(硬化促進劑、四國化成工業公司製)0.1質量份、無機填充材(將「SO-C2」(二氧化矽、平均粒徑0.5μm、Admatechs公司製)以「KBM-573」(胺基矽烷系偶合劑、信越化學工業公司製)處理後的二氧化矽)35質量份、「AW2-08PF3F」(磁性填料、Fe-Cr-Si系合金(非晶質)、平均粒徑3.0μm、EPSON ATMIX公司製)1010質量份,以高速旋轉混合機均勻地分散,而調製樹脂組成物2。<Example 2. Preparation of resin composition 2> 14 parts by mass of "ZX1059" (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), "HP -4700 "(naphthalene type 4-functional epoxy resin, manufactured by DIC Corporation) 14 parts by mass," YX7553 "(phenoxy resin, 30% by mass of non-volatile components, manufactured by Mitsubishi Chemical Corporation)," KS-1 "(Polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) 23 parts by mass, heated and dissolved in 10 parts by mass of MEK, 10 parts by mass of cyclohexanone, 30 parts by mass of ethanol, and 30 parts by mass of toluene while stirring. 28 parts by mass of "LA-7054" (a triazine skeleton-containing phenolic hardener, 60% by mass of nonvolatile components, manufactured by DIC Corporation), and "2E4MZ" (hardening accelerator, manufactured by Shikoku Chemical Industries, Ltd.) 0.1 parts by mass of an inorganic filler ("SO-C2" (silicon dioxide, average particle size 0.5 μm, manufactured by Admatechs)) treated with "KBM-573" (aminosilane-based coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) After 35 parts by mass of silicon dioxide, 1010 parts by mass of "AW2-08PF3F" (magnetic filler, Fe-Cr-Si based alloy (amorphous), average particle diameter 3.0 μm, manufactured by EPSON ATMIX), and rotated at high speed The mixer disperses uniformly to prepare the resin composition 2.
<實施例3.樹脂組成物3之調製> 於實施例1中,將KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)30質量份變更成SG-P3(含環氧基之丙烯酸酯共聚物樹脂、Nagase chemteX公司製、數量平均分子量Mn:850000g/mol、環氧價0.21eq/kg、玻璃轉移溫度12℃、不揮發性成分15質量%)200質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物3。<Example 3. Preparation of resin composition 3> In Example 1, 30 parts by mass of KS-1 (polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was changed to SG-P3 (epoxy-containing acrylic acid). Ester copolymer resin, manufactured by Nagase ChemteX, number average molecular weight Mn: 850,000 g / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C, non-volatile content 15% by mass) 200 parts by mass. Except for the above matters, the resin composition 3 was prepared in the same manner as in Example 1.
<實施例4.樹脂組成物4之調製> 於實施例1中,將KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)30質量份變更成BL-1(丁醛樹脂、積水化學工業公司製)23質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物4。<Example 4. Preparation of resin composition 4> In Example 1, 30 parts by mass of KS-1 (polyethylene acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was changed to BL-1 (butyraldehyde resin, Sekisui Chemical Industry company) 23 parts by mass. Except for the above matters, the resin composition 4 was prepared in the same manner as in Example 1.
<實施例5.樹脂組成物5之調製> 於實施例1中,將YX7553(苯氧基樹脂、不揮發性成分30質量%、三菱化學公司)之量從35質量份變更成135質量份,且不添加KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物5。<Example 5. Preparation of resin composition 5> (1) In Example 1, the amount of YX7553 (phenoxy resin, 30% by mass of non-volatile components, Mitsubishi Chemical Corporation) was changed from 35 parts by mass to 135 parts by mass. KS-1 (polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was not added. Except for the above matters, the resin composition 5 was prepared in the same manner as in Example 1.
<實施例6.樹脂組成物6之調製> 於實施例1中,將AW2-08PF3F(EPSON ATMIX公司製)之量從850質量份變更成1500質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物6。<Example 6. Preparation of resin composition 6> In Example 1, the amount of AW2-08PF3F (made by EPSON ATMIX) was changed from 850 parts by mass to 1500 parts by mass. Except for the above matters, the resin composition 6 was prepared in the same manner as in Example 1.
<實施例7.樹脂組成物7之調製> 於實施例1中,將AW2-08PF3F(EPSON ATMIX公司製)之量從850質量份變更成500質量份,將SO-C2(Admatechs公司製)之量從35質量份變更成52.5質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物7。<Example 7. Preparation of resin composition 7> In Example 1, the amount of AW2-08PF3F (manufactured by EPSON ATMIX) was changed from 850 parts by mass to 500 parts by mass, and SO-C2 (manufactured by Admatechs) was changed. The amount was changed from 35 parts by mass to 52.5 parts by mass. Except for the above matters, the resin composition 7 was prepared in the same manner as in Example 1.
<實施例8.樹脂組成物8之調製> 於實施例1中,將SO-C2(Admatechs公司製)之量從35質量份變更成150質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物8。<Example 8. Preparation of resin composition 8> In Example 1, the amount of SO-C2 (manufactured by Admatechs) was changed from 35 parts by mass to 150 parts by mass. Except for the above matters, the resin composition 8 was prepared in the same manner as in Example 1.
<實施例9.樹脂組成物9之調製> 於實施例1中,將AW2-08PF3F(EPSON ATMIX公司製)之量從850質量份變更成600質量份,且不含有SO-C2 (Admatechs公司製)。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物9。<Example 9. Preparation of resin composition 9> In Example 1, the amount of AW2-08PF3F (manufactured by EPSON ATMIX) was changed from 850 parts by mass to 600 parts by mass, and SO-C2 (manufactured by Admatechs) was not included. ). Except for the above matters, the resin composition 9 was prepared in the same manner as in Example 1.
<實施例10.樹脂組成物10之調製> 於實施例3中,將LA-7054(酚系硬化劑、不揮發性成分60質量%、DIC公司製)之量從14質量份變更成7質量份,且含有HPC-8000-65T(活性酯硬化劑、不揮發性成分65質量%、DIC公司製)7份。除了以上的事項以外,以與實施例3相同的方式來調製樹脂組成物10。 使用掃描型電子顯微鏡(SEM)來測定所調製之樹脂組成物10的表面。將樹脂組成物10之表面的放大照片顯示於第5圖。<Example 10. Preparation of resin composition 10> In Example 3, the amount of LA-7054 (phenol-based hardener, 60% by mass of non-volatile components, manufactured by DIC Corporation) was changed from 14 parts by mass to 7 parts by mass. 7 parts of HPC-8000-65T (active ester hardener, 65% by mass of non-volatile components, manufactured by DIC Corporation). Except for the above matters, the resin composition 10 was prepared in the same manner as in Example 3.扫描 The surface of the prepared resin composition 10 is measured using a scanning electron microscope (SEM). An enlarged photograph of the surface of the resin composition 10 is shown in FIG. 5.
<比較例1.樹脂組成物11之調製> 於實施例1中,將KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)之量從30質量份變更成100質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物11。<Comparative Example 1. Preparation of Resin Composition 11> In Example 1, the amount of KS-1 (polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was changed from 30 parts by mass to 100 parts by mass. Except for the above matters, the resin composition 11 was prepared in the same manner as in Example 1.
<比較例2.樹脂組成物12之調製> 於實施例1中,不含有KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)30質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物12。<Comparative Example 2. Preparation of Resin Composition 12> In Example 1, 30 parts by mass of KS-1 (polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was not included. Except for the above matters, the resin composition 12 was prepared in the same manner as in Example 1.
<比較例3.樹脂組成物13之調製> 於實施例1中,將KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)之量從30質量份變更成5質量份,將AW2-08PF3F(EPSON ATMIX公司製)之量從850質量份變更成1800質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物13。<Comparative example 3. Preparation of resin composition 13> (1) In Example 1, the amount of KS-1 (polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was changed from 30 parts by mass to 5 parts by mass, and AW2- The amount of 08PF3F (manufactured by EPSON ATMIX) was changed from 850 parts by mass to 1,800 parts by mass. Except for the above matters, the resin composition 13 was prepared in the same manner as in Example 1.
<比較例4.樹脂組成物14之調製> 於實施例1中,將AW2-08PF3F(EPSON ATMIX公司製)之量從850質量份變更成250質量份,將SO-C2(Admatechs公司製)之量從35質量份變更成52.5質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物14。<Comparative Example 4. Preparation of Resin Composition 14> In Example 1, the amount of AW2-08PF3F (manufactured by EPSON ATMIX) was changed from 850 parts by mass to 250 parts by mass, and SO-C2 (manufactured by Admatechs) was changed. The amount was changed from 35 parts by mass to 52.5 parts by mass. Except for the above matters, the resin composition 14 was prepared in the same manner as in Example 1.
<比較例5.樹脂組成物15之調製> 於實施例9中,將KS-1(聚乙烯縮醛樹脂、積水化學工業公司製)30質量份變更成SG-P3(含環氧基之丙烯酸酯共聚物樹脂、Nagase chemteX公司製、數量平均分子量Mn:850000g/mol、環氧價0.21eq/kg、玻璃轉移溫度12℃、不揮發性成分15質量%)50質量份,將AW2-08PF3F(EPSON ATMIX公司製)之量從600質量份變更成150質量份。除了以上的事項以外,以與實施例9相同的方式來調製樹脂組成物15。<Comparative Example 5. Preparation of Resin Composition 15> In Example 9, 30 parts by mass of KS-1 (polyvinyl acetal resin, manufactured by Sekisui Chemical Industry Co., Ltd.) was changed to SG-P3 (epoxy-containing acrylic acid). Ester copolymer resin, manufactured by Nagase ChemteX, number average molecular weight Mn: 850,000 g / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C, nonvolatile content 15% by mass) 50 parts by mass of AW2-08PF3F ( EPSON ATMIX Co., Ltd.) was changed from 600 parts by mass to 150 parts by mass. Except for the above matters, the resin composition 15 was prepared in the same manner as in Example 9.
<比較例6.樹脂組成物16之調製> 於實施例1中,將AW2-08PF3F(EPSON ATMIX公司製)850質量份變更成HQ(羰基鐵、BASF公司製)500質量份。除了以上的事項以外,以與實施例1相同的方式來調製樹脂組成物16。<Comparative Example 6. Preparation of Resin Composition 16> In Example 1, 850 parts by mass of AW2-08PF3F (manufactured by EPSON ATMIX) was changed to 500 parts by mass of HQ (iron carbonyl, manufactured by BASF). Except for the above matters, the resin composition 16 was prepared in the same manner as in Example 1.
<疊層性之評估> 作為支撐體,準備聚對苯二甲酸乙二酯(以下稱為「PET」)薄膜(厚度38μm)。將各實施例及各比較例所製作的樹脂組成物,以使乾燥後之樹脂組成物層的厚度成為50μm的方式,以模具塗佈機均勻地塗佈於PET薄膜上,以70℃至120℃(平均100℃)7分鐘,以使樹脂組成物層中之殘留溶媒量成為約0.4質量%的方式進行乾燥,而得到接著薄膜。<Evaluation of stackability> 性 As a support, a polyethylene terephthalate (hereinafter referred to as "PET") film (thickness: 38 μm) was prepared. The resin composition prepared in each example and each comparative example was uniformly coated on a PET film with a die coater so that the thickness of the dried resin composition layer became 50 μm, and the temperature was 70 ° C. to 120. The film was dried at a temperature of 70 ° C (average 100 ° C) for 7 minutes so that the amount of residual solvent in the resin composition layer was about 0.4% by mass, and an adhesive film was obtained.
將接著薄膜分別使用名機製作所公司製之分批式真空加壓疊層機「MVLP-500」,來疊層於配線板的兩面。疊層係藉由進行30秒減壓將氣壓設為13hPa以下,其後,以100℃、壓力0.74MPa進行30秒加壓而實施。評估係藉由依照下述之評估基準,來檢查所得之層合構造體的外觀而進行。將結果顯示於下述表。 評估基準 ○:於配線板之電路部分無空隙,來自接著薄膜的樹脂組成物會充分地流動。 ×:於配線板之電路部分發生空隙,來自接著薄膜的樹脂組成物之疊層時的流動性不足。The adhesive film was laminated on both sides of a wiring board using a batch type vacuum pressure laminator "MVLP-500" manufactured by Nago Seisakusho. The lamination was performed by depressurizing for 30 seconds to set the air pressure to 13 hPa or less, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds. The evaluation was performed by checking the appearance of the obtained laminated structure in accordance with the evaluation criteria described below. The results are shown in the following table. Evaluation Criteria ○: There is no void in the circuit portion of the wiring board, and the resin composition from the adhesive film flows sufficiently. ×: Voids occurred in the circuit portion of the wiring board, and the fluidity was insufficient when the resin composition from the film was laminated.
<相對導磁率、磁性損失之測定> 作為支撐體,準備已施行氟樹脂系脫模劑(ETFE)處理的PET薄膜(三菱樹脂公司製「FLUOROGE RL50KSE」)。將各實施例及各比較例所製作的樹脂組成物,以使乾燥後之樹脂組成物層的厚度成為50μm的方式,以模具塗佈機均勻地塗佈於上述PET薄膜上,以70℃至120℃(平均100℃)7分鐘,以使樹脂組成物層中之殘留溶媒量成為約0.4質量%的方式進行乾燥,而得到接著薄膜。藉由將所得之接著薄膜以180℃進行90分鐘加熱而將樹脂組成物層熱硬化,並將支撐體剝離,藉此而得到薄片狀之硬化體。將所得之硬化體切斷成寬5mm、長度18mm之試驗片,作為評估樣品。對於此評估樣品,使用Agilent Technologies公司製「HP8362B」(商品名),以3匝線圈法將測定頻率設為10MHz至100MHz之範圍,在室溫23℃下測定相對導磁率(μ’)及磁性損失(μ”)。又,以短路條帶線法,將測定頻率設為100MHz至10GHz之範圍,在室溫23℃下測定相對導磁率(μ’)及磁性損失(μ”)。將測定頻率為10MHz、100MHz、1GHz及3GHz的情況之相對導磁率、測定頻率為10MHz及100MHz的情況之磁性損失顯示於下述表。<Measurement of Relative Magnetic Permeability and Magnetic Loss> (1) As a support, a PET film ("FLUOROGE RL50KSE" manufactured by Mitsubishi Resin Co., Ltd.) was prepared and treated with a fluororesin-based release agent (ETFE). The resin composition prepared in each example and each comparative example was uniformly coated on the PET film with a die coater so that the thickness of the dried resin composition layer became 50 μm, and the temperature was 70 ° C. to Drying was performed at 120 ° C. (average 100 ° C.) for 7 minutes so that the amount of residual solvent in the resin composition layer was about 0.4% by mass, and an adhesive film was obtained. The obtained adhesive film was heated at 180 ° C for 90 minutes to thermally harden the resin composition layer and peel off the support, thereby obtaining a sheet-like cured body. The obtained hardened body was cut into a test piece having a width of 5 mm and a length of 18 mm as an evaluation sample. For this evaluation sample, "HP8362B" (trade name) manufactured by Agilent Technologies was used to set the measurement frequency in the range of 10 MHz to 100 MHz by the 3-turn coil method, and the relative permeability (μ ') and magnetic properties were measured at room temperature of 23 ° C. Loss (μ "). The measurement frequency was set in the range of 100 MHz to 10 GHz by the short-strip line method, and the relative magnetic permeability (μ ') and magnetic loss (μ") were measured at room temperature of 23 ° C. The relative magnetic permeability when the measurement frequency is 10 MHz, 100 MHz, 1 GHz, and 3 GHz, and the magnetic loss when the measurement frequency is 10 MHz and 100 MHz are shown in the following table.
<彈性率之測定> 作為支撐體,準備已施行氟樹脂系脫模劑(ETFE)處理的PET薄膜(三菱樹脂公司製「FLUOROGE RL50KSE」)。將各實施例及各比較例所製作的樹脂組成物,以使乾燥後之樹脂組成物層的厚度成為50μm的方式,以模具塗佈機均勻地塗佈於上述PET薄膜上,以70℃至120℃(平均100℃)7分鐘,以使樹脂組成物層中之殘留溶媒量成為約0.4質量%的方式進行乾燥,而得到接著薄膜。藉由將所得之接著薄膜以180℃進行90分鐘加熱而將樹脂組成物層熱硬化,並將支撐體剝離,藉此而得到薄片狀之硬化體。將所得之硬化體,依據日本工業規格(JIS K7127),使用TENSILON萬能試驗機(A&D公司製)來進行拉伸試驗,測定拉伸彈性率。<Measurement of Elasticity> As a support, a PET film ("FLUOROGE RL50KSE" manufactured by Mitsubishi Resin Co., Ltd.) treated with a fluororesin-based release agent (ETFE) was prepared. The resin composition prepared in each example and each comparative example was uniformly coated on the PET film with a die coater so that the thickness of the dried resin composition layer became 50 μm, and the temperature was 70 ° C. to Drying was performed at 120 ° C. (average 100 ° C.) for 7 minutes so that the amount of residual solvent in the resin composition layer was about 0.4% by mass, and an adhesive film was obtained. The obtained adhesive film was heated at 180 ° C for 90 minutes to thermally harden the resin composition layer and peel off the support, thereby obtaining a sheet-like cured body. The obtained hardened body was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a TENSILON universal testing machine (manufactured by A & D Corporation) to measure the tensile elastic modulus.
<翹曲量之測定> 作為支撐體,準備聚對苯二甲酸乙二酯(以下稱為「PET」)薄膜(厚度38μm)。將各實施例及各比較例所製作的樹脂組成物,以使乾燥後之樹脂組成物層的厚度成為50μm的方式,以模具塗佈機均勻地塗佈於PET薄膜上,以70℃至120℃(平均100℃)7分鐘,以使樹脂組成物層中之殘留溶媒量成為約0.4質量%的方式進行乾燥,而得到接著薄膜。將所得之接著薄膜穿孔成100mm平方,將支撐體剝離,並以重疊有8片樹脂組成物層的狀態,於作為100mm平方200μm之玻璃布基材環氧樹脂兩面貼銅層合板之Panasonic公司製「R1515A」的單面,使用名機製作所公司製之分批式真空加壓疊層機「MVLP-500」進行疊層。疊層係藉由進行30秒減壓將氣壓設為13hPa以下,其後,以100℃、壓力0.74MPa進行30秒加壓而進行。接著,以180℃進行30分鐘熱硬化,而得到層合構造體。將層合構造體放置於水平的台上,將從台起至層合構造體端部為止的距離作為翹曲量,評估係依照下述之評估基準來進行。 評估基準 ○:翹曲量為7mm以上、未達20mm ×:翹曲量為20mm以上、或6mm以下<Measurement of Amount of Warpage> As a support, a polyethylene terephthalate (hereinafter referred to as "PET") film (thickness: 38 μm) was prepared. The resin composition prepared in each example and each comparative example was uniformly coated on a PET film with a die coater so that the thickness of the dried resin composition layer became 50 μm, and the temperature was 70 ° C. to 120. The film was dried at a temperature of 70 ° C (average 100 ° C) for 7 minutes so that the amount of residual solvent in the resin composition layer was about 0.4% by mass, and an adhesive film was obtained. The obtained adhesive film was perforated to 100 mm square, the support was peeled off, and a copper laminate was laminated on both sides of the epoxy resin as a glass cloth substrate with a thickness of 200 μm and a glass cloth substrate of 200 μm in a state of overlapping 8 resin composition layers. One side of "R1515A" was laminated using a batch type vacuum pressure laminator "MVLP-500" manufactured by Meiki Seisakusho. The lamination was performed by depressurizing for 30 seconds to set the air pressure to 13 hPa or less, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds. Then, it heat-hardened at 180 degreeC for 30 minutes, and obtained the laminated structure. The laminated structure was placed on a horizontal table, and the distance from the table to the end of the laminated structure was used as the amount of warpage. The evaluation was performed according to the evaluation criteria described below. Evaluation Criteria ○: The amount of warpage is 7mm or more and less than 20mm ×: The amount of warpage is 20mm or more or 6mm or less
<難燃性之評估> 作為支撐體,準備聚對苯二甲酸乙二酯(以下稱為「PET」)薄膜(厚度38μm)。將各實施例及各比較例所製作的樹脂組成物,以使乾燥後之樹脂組成物層的厚度成為50μm的方式,以模具塗佈機均勻地塗佈於PET薄膜上,以70℃至120℃(平均100℃)7分鐘,以使樹脂組成物層中之殘留溶媒量成為約0.4質量%的方式進行乾燥,而得到接著薄膜。將所得之接著薄膜,於將基板厚度0.2mm之貼銅層合板(日立化成公司製「679-FG」)之銅箔蝕刻去除後的基材的兩面,使用分批式真空加壓疊層機MVLP-500(名機公司製),來疊層於層合板的兩面。疊層係藉由進行30秒減壓將氣壓設為13hPa以下,其後,以100℃、壓力0.74MPa進行30秒加壓而進行。將支撐體之PET薄膜剝離後,將接著薄膜以上述之疊層條件疊層於樹脂組成物層的兩面。其後,將PET薄膜剝離,以180℃進行90分鐘熱硬化,而得到難燃試驗用樣品。切出寬12.7mm、長度127mm,將切出的面以研磨機(Struers製、RotoPol-22)進行研磨。將以上5個樣品作為一組,依照UL94垂直難燃試驗來實施難燃試驗。將10秒鐘接觸火焰後之燃燒殘留樣品仍有5個的情況作為「○」,將10秒鐘接觸火焰後無燃燒殘留樣品的情況作為「×」。<Evaluation of flame resistance> As a support, a polyethylene terephthalate (hereinafter referred to as "PET") film (thickness: 38 μm) was prepared. The resin composition prepared in each example and each comparative example was uniformly coated on a PET film with a die coater so that the thickness of the dried resin composition layer became 50 μm, and the temperature was 70 ° C. to 120. The film was dried at a temperature of 70 ° C (average 100 ° C) for 7 minutes so that the amount of residual solvent in the resin composition layer was about 0.4% by mass, and an adhesive film was obtained. The obtained adhesive film was etched and removed on both sides of the substrate after the copper foil of the copper-clad laminated board having a substrate thickness of 0.2 mm ("679-FG" manufactured by Hitachi Chemical Co., Ltd.) was removed, and a batch type vacuum pressure laminator was used. MVLP-500 (manufactured by Meiji Co., Ltd.) is laminated on both sides of the laminate. The lamination was performed by depressurizing for 30 seconds to set the air pressure to 13 hPa or less, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds. After the PET film of the support was peeled off, the adhesive film was laminated on both sides of the resin composition layer under the above-mentioned laminating conditions. After that, the PET film was peeled and heat-cured at 180 ° C for 90 minutes to obtain a flame retardant test sample. A width of 12.7 mm and a length of 127 mm were cut, and the cut surface was polished with a grinder (manufactured by Struers, RotoPol-22). The above 5 samples are taken as a group, and a flame retardance test is performed in accordance with the UL94 vertical flame retardance test. A case where there are still five samples of combustion residues after being exposed to the flame for 10 seconds is regarded as "○", and a case where there are no samples of combustion residues after being exposed to the flame for 10 seconds is regarded as "X".
得知,實施例1~10係疊層性、磁性損失、相對導磁率、彈性率、翹曲量、翹曲試驗及難燃性優異。得知,實施例1~10係10MHz~200MHz之相對導磁率明顯提昇,且磁性損失減低。 得知,實施例10之樹脂組成物係如第5圖所示般,形成由母相與分散相所構成的海島構造,(D)成分集中存在於母相側。可推測,藉由(D)成分集中存在於母相側,而實施例10之樹脂組成物之硬化物係相對導磁率提昇。It was found that Examples 1 to 10 were excellent in lamination properties, magnetic loss, relative magnetic permeability, elastic modulus, warpage amount, warpage test, and flame retardancy. It is known that the relative magnetic permeability of Examples 1 to 10 from 10 MHz to 200 MHz is significantly improved, and the magnetic loss is reduced. It was found that the resin composition of Example 10 formed an island structure composed of a mother phase and a dispersed phase as shown in FIG. 5, and the component (D) was concentrated on the mother phase side. It can be presumed that the relative permeability of the hardened material system of the resin composition of Example 10 is increased by the fact that the component (D) is concentrated on the mother phase side.
另一方面,彈性率為未達7GPa的比較例1、比較例4~6、彈性率為超過18GPa的比較例2~3係疊層性、10MHz~200MHz之相對導磁率、磁性損失、彈性率、翹曲量、翹曲試驗及難燃性之任一者皆比實施例1~10更差,無法作為樹脂組成物使用。另外,比較例1、比較例3係由於翹曲量大,超過測定極限,因此無法測定翹曲量。又,難燃性亦無法評估。On the other hand, Comparative Examples 1, Comparative Examples 4 to 6 whose elasticity is less than 7 GPa, Comparative Examples 2 to 3 having elasticity exceeding 18 GPa, lamination, relative permeability, magnetic loss, and elastic modulus of 10 MHz to 200 MHz. , Warpage amount, warpage test, and flame retardancy were all worse than those of Examples 1 to 10, and could not be used as a resin composition. In addition, Comparative Examples 1 and 3 were unable to measure the amount of warpage because the amount of warpage was large and exceeded the measurement limit. Moreover, the flame retardancy cannot be evaluated.
於各實施例中,確認到即使在不含有(E)~(F)成分的情況,雖程度上有所差異,但亦回歸與上述實施例相同的結果。In each of the examples, it was confirmed that even when the components (E) to (F) were not contained, the results were the same as those of the above-mentioned examples, although the degree was different.
10‧‧‧配線板10‧‧‧ Distribution Board
20‧‧‧芯基材(內層電路基板)20‧‧‧ core substrate (inner circuit board)
20a‧‧‧第1主表面20a‧‧‧1st major surface
20b‧‧‧第2主表面20b‧‧‧Second major surface
22‧‧‧貫通孔22‧‧‧through hole
22a‧‧‧貫通孔內配線22a‧‧‧Wiring in through hole
24‧‧‧外部端子24‧‧‧External Terminal
30‧‧‧磁性部30‧‧‧Magnetic Section
32‧‧‧第1磁性層32‧‧‧ 1st magnetic layer
34‧‧‧第2磁性層34‧‧‧ 2nd magnetic layer
36‧‧‧通孔36‧‧‧through hole
36a‧‧‧通孔內配線36a‧‧‧Wiring in through hole
38‧‧‧第3磁性層38‧‧‧ 3rd magnetic layer
40‧‧‧線圈狀導電性構造體40‧‧‧coil-shaped conductive structure
42‧‧‧第1配線層42‧‧‧The first wiring layer
42a‧‧‧墊42a‧‧‧pad
44‧‧‧第2配線層44‧‧‧ 2nd wiring layer
46‧‧‧第3配線層46‧‧‧ 3rd wiring layer
50‧‧‧附載體金屬層之基材50‧‧‧ substrate with carrier metal layer
51‧‧‧基材51‧‧‧ substrate
52‧‧‧附載體金屬層52‧‧‧ with carrier metal layer
521‧‧‧第1金屬層521‧‧‧The first metal layer
522‧‧‧第2金屬層522‧‧‧Second metal layer
[第1圖] 第1圖係由其厚度方向之一方觀看作為一例之第1實施形態的內載電感元件之配線板的示意俯視圖。 [第2圖] 第2圖係顯示在作為一例之以II-II虛線所表示之位置切斷的第1實施形態的內載電感元件之配線板之切斷端面的示意圖。 [第3圖] 第3圖係用以說明作為一例之第1實施形態的內載電感元件之配線板中之第1配線層的構造的示意俯視圖。 [第4圖] 第4圖係用以說明作為一例之第2實施形態的內載電感元件之配線板之製造方法的示意剖面圖。 [第5圖] 第5圖係實施例10之樹脂組成物之剖面的放大照片。[FIG. 1] FIG. 1 is a schematic plan view of a wiring board of an inductive element with a built-in inductance according to a first embodiment as an example when viewed from one of its thickness directions.第 [Fig. 2] Fig. 2 is a schematic diagram showing a cut end surface of the wiring board of the internally-loaded inductance element of the first embodiment cut at a position indicated by a dotted line II-II as an example.第 [Fig. 3] Fig. 3 is a schematic plan view for explaining the structure of a first wiring layer in a wiring board of an internally-loaded inductor element as an example of the first embodiment.第 [Fig. 4] Fig. 4 is a schematic cross-sectional view for explaining a method for manufacturing a wiring board of an internally-loaded inductance element according to a second embodiment as an example. [Fig. 5] Fig. 5 is an enlarged photograph of a cross section of the resin composition of Example 10.
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JP7031206B2 (en) * | 2017-10-02 | 2022-03-08 | 味の素株式会社 | Resin composition |
JP7222228B2 (en) * | 2018-11-29 | 2023-02-15 | 味の素株式会社 | Substrate manufacturing method |
JPWO2020175590A1 (en) * | 2019-02-27 | 2021-12-23 | 味の素株式会社 | Magnetic film |
JP7368693B2 (en) * | 2019-04-22 | 2023-10-25 | イビデン株式会社 | Inductor built-in board |
EP3730545A1 (en) * | 2019-04-26 | 2020-10-28 | SABIC Global Technologies B.V. | Laser platable thermoplastic compositions |
JP7078016B2 (en) * | 2019-06-17 | 2022-05-31 | 株式会社村田製作所 | Inductor parts |
JP7311618B2 (en) * | 2019-09-30 | 2023-07-19 | 富士フイルム株式会社 | Adhesive sheets and electronic components |
JP7354774B2 (en) * | 2019-11-01 | 2023-10-03 | 味の素株式会社 | resin composition |
JP7463736B2 (en) * | 2020-01-24 | 2024-04-09 | 味の素株式会社 | Resin composition |
JP7387528B2 (en) | 2020-04-28 | 2023-11-28 | 株式会社豊田中央研究所 | Powder magnetic core and its manufacturing method |
CN111640567B (en) * | 2020-05-29 | 2022-02-11 | 深圳顺络电子股份有限公司 | Preparation method of soft magnetic alloy material and soft magnetic alloy material |
JPWO2022065183A1 (en) | 2020-09-24 | 2022-03-31 | ||
CN114479417B (en) * | 2020-10-27 | 2023-09-12 | 广东生益科技股份有限公司 | Magneto-dielectric resin composition, prepreg comprising magneto-dielectric resin composition and copper-clad plate |
CN112652434B (en) * | 2020-12-28 | 2022-11-25 | 横店集团东磁股份有限公司 | Thin film power inductance magnetic sheet and preparation method and application thereof |
CN112967856B (en) * | 2021-03-11 | 2022-11-08 | 横店集团东磁股份有限公司 | Soft magnetic resin slurry and preparation method and application thereof |
CN113234407A (en) * | 2021-04-02 | 2021-08-10 | 广东美信科技股份有限公司 | Magnetic conductive glue and preparation method thereof |
CN113113223A (en) * | 2021-04-13 | 2021-07-13 | 横店集团东磁股份有限公司 | Soft magnetic alloy magnetic sheet and preparation method and application thereof |
WO2023181742A1 (en) * | 2022-03-22 | 2023-09-28 | 味の素株式会社 | Manufacturing method for magnetic substrate |
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US20050007232A1 (en) * | 2003-06-12 | 2005-01-13 | Nec Tokin Corporation | Magnetic core and coil component using the same |
JP2007154041A (en) * | 2005-12-05 | 2007-06-21 | Nissan Motor Co Ltd | Thermosetting resin composition and foamed thermosetting resin produced by foaming and curing the composition |
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JP2016108561A (en) * | 2014-12-04 | 2016-06-20 | 日東電工株式会社 | Soft magnetic resin composition and soft magnetic film |
JP5881027B1 (en) * | 2015-03-16 | 2016-03-09 | パナソニックIpマネジメント株式会社 | Resin sheet, resin sheet manufacturing method, inductor component |
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TWI781166B (en) | 2022-10-21 |
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