JP2005285540A - Insulation sheet, insulation sheet with base material, and multilayer printed circuit board - Google Patents
Insulation sheet, insulation sheet with base material, and multilayer printed circuit board Download PDFInfo
- Publication number
- JP2005285540A JP2005285540A JP2004097528A JP2004097528A JP2005285540A JP 2005285540 A JP2005285540 A JP 2005285540A JP 2004097528 A JP2004097528 A JP 2004097528A JP 2004097528 A JP2004097528 A JP 2004097528A JP 2005285540 A JP2005285540 A JP 2005285540A
- Authority
- JP
- Japan
- Prior art keywords
- insulating sheet
- resin
- weight
- resin composition
- curable resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000009413 insulation Methods 0.000 title abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 125
- 239000011347 resin Substances 0.000 claims abstract description 125
- 239000011342 resin composition Substances 0.000 claims abstract description 71
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 45
- 229920000647 polyepoxide Polymers 0.000 claims description 43
- 239000003822 epoxy resin Substances 0.000 claims description 42
- 239000011256 inorganic filler Substances 0.000 claims description 29
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 29
- 239000013034 phenoxy resin Substances 0.000 claims description 19
- 229920006287 phenoxy resin Polymers 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 69
- 239000002966 varnish Substances 0.000 description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 21
- 239000007822 coupling agent Substances 0.000 description 20
- 239000004020 conductor Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
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- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
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- 239000000758 substrate Substances 0.000 description 10
- 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 9
- 238000006243 chemical reaction Methods 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
- 238000009775 high-speed stirring Methods 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
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- 238000011156 evaluation Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
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- 238000001035 drying Methods 0.000 description 4
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- 239000004593 Epoxy Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- 238000005530 etching Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 238000005829 trimerization reaction Methods 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QKVROWZQJVDFSO-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanamine Chemical compound CC1=NC=CN1CCN QKVROWZQJVDFSO-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- DJUJXSUTUOATMS-UHFFFAOYSA-N 3-(1h-imidazol-2-ylmethoxy)propanenitrile Chemical compound N#CCCOCC1=NC=CN1 DJUJXSUTUOATMS-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- MLLXXNHPVFZVTB-UHFFFAOYSA-N 3-[2-(2-methylimidazol-1-yl)ethylamino]propanenitrile Chemical compound CC1=NC=CN1CCNCCC#N MLLXXNHPVFZVTB-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 102100027340 Slit homolog 2 protein Human genes 0.000 description 1
- 101710133576 Slit homolog 2 protein Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
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- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 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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- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
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- Production Of Multi-Layered Print Wiring Board (AREA)
- Inorganic Insulating Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、絶縁シート、基材付き絶縁シート、及び多層プリント配線板に関するものである。 The present invention relates to an insulating sheet, an insulating sheet with a base material, and a multilayer printed wiring board.
近年、電子機器の高機能化等の要求に伴い、電子部品の高密度集積化、高密度実装化等が進んでいる。そのため、これらに使用される高密度実装対応のプリント配線板等は、従来にも増して、小型化かつ高密度化されている。このようなプリント配線板等の高密度化への対応として、ビルドアップ方式による多層配線板が多く採用されている。 In recent years, with the demand for higher functionality of electronic devices, etc., high density integration and high density mounting of electronic components are progressing. For this reason, printed wiring boards and the like for high-density mounting used for these are smaller and higher in density than conventional ones. As a measure for increasing the density of such printed wiring boards, a multilayer wiring board by a build-up method is often used.
一般的なビルドアップ多層配線板は、樹脂組成物で構成される１００μｍ厚以下の絶縁樹脂層と、導体層とを交互に積層して、これを加熱加圧成形等行って接合することにより得られている。
ここで、絶縁樹脂層と導体層とを接合する方法としては、例えば、銅箔や有機フィルム等の基材に絶縁樹脂層を塗工した樹脂付き基材を、回路加工を施した内層回路基板上に積層し、これを加熱加圧成形する方法がある（例えば、特許文献１参照。）。
この方法では、樹脂付き基材の絶縁樹脂層と内層回路基板とを接合した後、金属箔基材を使用している場合にはこの金属箔を所定のパターンに従ってエッチング処理することにより外層導体回路を形成するか、あるいは、金属箔や有機フィルムを全面除去した後、導体金属メッキを行うことにより、所定の外層導体回路を形成する方法が一般的である。
A general build-up multilayer wiring board is obtained by alternately laminating insulating resin layers having a thickness of 100 μm or less composed of a resin composition and conductor layers and bonding them by performing heat-pressure molding or the like. It has been.
Here, as a method of joining the insulating resin layer and the conductor layer, for example, an inner layer circuit board obtained by subjecting a base material with resin obtained by applying an insulating resin layer to a base material such as copper foil or an organic film to a circuit. There is a method of laminating on top and heating and press-molding this (see, for example, Patent Document 1).
In this method, after joining the insulating resin layer of the base material with resin and the inner layer circuit board, when using the metal foil base material, the outer layer conductor circuit is etched by etching the metal foil according to a predetermined pattern. Or a method of forming a predetermined outer layer conductor circuit by conducting metal plating after removing the entire surface of the metal foil or organic film.
しかし、金属箔からエッチング処理により外層導体回路を形成する場合は、回路の微細化には限界があった。一方、メッキにより外層導体回路を形成する場合は、回路が形成される絶縁樹脂層表面に予め微細な凹凸を形成しておくことが必要であるが、従来の絶縁樹脂層では、薬液処理時に粗化できなかったり、粗化が表面全体に進行して大きく不均一な凹凸を形成したりすることがあり、微細な凹凸を均一に形成することが困難であった。
また、上記基材として片面粗化銅箔を用い、この粗化面のプロファイルを利用する方法もあるが、粗化面の凹凸が大きいため、特に形成する導体回路が微細である場合は導体回路の平滑性が低下し、導体回路の凹凸により導電損失が増大するという問題を生じていた。
そして、これらの方法では、外層導体回路と絶縁樹脂層との密着性（ピール強度）が不充分であり、その部位によってバラツキも生じやすいという問題があった。
However, when forming an outer layer conductor circuit from a metal foil by etching, there is a limit to miniaturization of the circuit. On the other hand, when an outer layer conductor circuit is formed by plating, it is necessary to form fine irregularities on the surface of the insulating resin layer on which the circuit is to be formed. In some cases, roughening proceeds to the entire surface to form large and uneven unevenness, and it is difficult to form fine unevenness uniformly.
In addition, there is a method using a roughened surface profile using a single-sided roughened copper foil as the base material. However, since the roughened surface has large irregularities, the conductive circuit is formed especially when the conductive circuit to be formed is fine. As a result, the smoothness of the conductor deteriorates, and the conductive loss increases due to the unevenness of the conductor circuit.
In these methods, there is a problem that the adhesion (peel strength) between the outer conductor circuit and the insulating resin layer is insufficient, and variations are likely to occur depending on the portion.
本発明は、平滑性、及び、絶縁樹脂層への密着性に優れた微細な外層導体回路を形成することができる絶縁シート、基材付き絶縁シート、及び、この絶縁シートを用いた信頼性の高い多層プリント配線板を提供するものである。 The present invention provides an insulating sheet capable of forming a fine outer layer conductor circuit excellent in smoothness and adhesion to an insulating resin layer, an insulating sheet with a substrate, and reliability using the insulating sheet. A high-layer printed wiring board is provided.
このような目的は、下記の本発明（１）〜（１０）により達成される。
（１）硬化性樹脂と無機充填材とを含有する樹脂組成物から形成される絶縁シートであって、該絶縁シートは、示差走査熱量分析において、第１の発熱ピークと、これより高い温度に位置する第２の発熱ピークとを有することを特徴とする絶縁シート。
（２）上記樹脂組成物は、硬化性樹脂として、上記第１の発熱ピークを発現する第１の硬
化性樹脂と、上記第２の発熱ピークを発現する第２の硬化性樹脂とを含有するものである上記（１）に記載の絶縁シート。
（３）上記第１の発熱ピークは、１５０〜２００℃の範囲内にある上記（１）又は（２）のいずれかに記載の絶縁シート。
（４）上記第２の発熱ピークは、１８０〜２５０℃の範囲内にある上記（１）ないし（３）のいずれかに記載の絶縁シート。
（５）上記第１の硬化性樹脂は、シアネート樹脂及び／又はそのプレポリマーを含有する上記（１）ないし（４）のいずれかに記載の絶縁シート。
（６）上記第２の硬化性樹脂は、エポキシ樹脂を含有する上記（１）ないし（５）のいずれかに記載の絶縁シート。
（７）上記樹脂組成物は、硬化性樹脂成分として、さらに、フェノキシ樹脂を含有する上記（１）ないし（６）のいずれかに記載の絶縁シート。
（８）上記樹脂組成物は、無機充填材成分として球状シリカを含有する上記（１）ないし（７）のいずれかに記載の絶縁シート。
（９）上記（１）ないし（８）のいずれかに記載の絶縁シートと、これを担持する基材とから構成されることを特徴とする基材付き絶縁シート。
（１０）上記（１）ないし（８）のいずれかに記載の絶縁シートを、内層回路基板に接合してなることを特徴とする多層プリント配線板。
Such an object is achieved by the following present inventions (1) to (10).
(1) An insulating sheet formed from a resin composition containing a curable resin and an inorganic filler, the insulating sheet having a first exothermic peak and a temperature higher than that in differential scanning calorimetry. An insulating sheet having a second exothermic peak located.
(2) The resin composition contains, as a curable resin, a first curable resin that expresses the first exothermic peak and a second curable resin that expresses the second exothermic peak. The insulating sheet according to (1), which is a material.
(3) The insulating sheet according to any one of (1) and (2), wherein the first exothermic peak is in a range of 150 to 200 ° C.
(4) The insulating sheet according to any one of (1) to (3), wherein the second exothermic peak is in a range of 180 to 250 ° C.
(5) The insulating sheet according to any one of (1) to (4), wherein the first curable resin contains a cyanate resin and / or a prepolymer thereof.
(6) The insulating sheet according to any one of (1) to (5), wherein the second curable resin contains an epoxy resin.
(7) The insulating sheet according to any one of (1) to (6), wherein the resin composition further contains a phenoxy resin as a curable resin component.
(8) The said resin composition is an insulating sheet in any one of said (1) thru | or (7) containing spherical silica as an inorganic filler component.
(9) An insulating sheet with a base material comprising the insulating sheet according to any one of (1) to (8) above and a base material carrying the same.
(10) A multilayer printed wiring board obtained by bonding the insulating sheet according to any one of (1) to (8) above to an inner circuit board.
本発明により、平滑性、及び、絶縁樹脂層への密着性に優れた微細な外層導体回路を形成することができる絶縁シート、基材付き絶縁シート、及び、この絶縁シートを用いた信頼性の高い多層プリント配線板を提供することができる。 According to the present invention, an insulating sheet capable of forming a fine outer layer conductor circuit excellent in smoothness and adhesion to an insulating resin layer, an insulating sheet with a substrate, and reliability using the insulating sheet A high multilayer printed wiring board can be provided.
以下、本発明の絶縁シート、フィルム付き絶縁シート、及び、多層プリント配線板について説明する。
本発明の絶縁シートは、硬化性樹脂と無機充填材とを含有する樹脂組成物から形成される絶縁シートであって、この絶縁シートは、示差走査熱量分析において、第１の発熱ピークと、これより高い温度に位置する第２の発熱ピークとを有することを特徴とするものである。
また、本発明の基材付き絶縁シートは、上記本発明の絶縁シートと、これを担持する基材とから構成されることを特徴とするものである。
そして、本発明の多層プリント配線板は、上記本発明の絶縁シートを内層回路基板に接合してなることを特徴とするものである。
Hereinafter, the insulating sheet, the insulating sheet with film, and the multilayer printed wiring board of the present invention will be described.
The insulating sheet of the present invention is an insulating sheet formed from a resin composition containing a curable resin and an inorganic filler, and this insulating sheet has a first exothermic peak in differential scanning calorimetry, It has the 2nd exothermic peak located in higher temperature, It is characterized by the above-mentioned.
Moreover, the insulating sheet with a base material of this invention is comprised from the said insulating sheet of this invention, and the base material which carries this.
The multilayer printed wiring board of the present invention is characterized in that the insulating sheet of the present invention is bonded to an inner circuit board.
まず、本発明の絶縁シートについて説明する。
本発明の絶縁シートは、硬化性樹脂と無機充填材とを含有する樹脂組成物から形成される絶縁シートであり、示差走査熱量分析において、第１の発熱ピークと、これより高い温度に位置する第２の発熱ピークとを有する。
これにより、第１の発熱ピークを発現する硬化性樹脂の硬化反応によって、内層回路基板と絶縁シートとを強固に接合することができ、かつ、第２の発熱ピークを発現する硬化性樹脂の硬化反応によって、絶縁シートと外層導体回路（以下、単に「外層回路」という）との密着性を高めることができる。
First, the insulating sheet of the present invention will be described.
The insulating sheet of the present invention is an insulating sheet formed from a resin composition containing a curable resin and an inorganic filler, and is located at a first exothermic peak and a temperature higher than that in differential scanning calorimetry. With a second exothermic peak.
Thereby, the inner layer circuit board and the insulating sheet can be firmly bonded by the curing reaction of the curable resin that exhibits the first exothermic peak, and the curable resin that exhibits the second exothermic peak can be cured. By the reaction, adhesion between the insulating sheet and the outer conductor circuit (hereinafter simply referred to as “outer layer circuit”) can be enhanced.
本発明の絶縁シートの評価に用いられる示差走査熱量分析は、試料に熱を加え、所定の温度条件で昇温した際に、試料から発生した熱エネルギーの変化を定量的に検出する手法であり、例えば市販の示差走査熱量分析装置を用いて行うことができる。
ここで示差走査熱量分析を行う際の昇温条件としては特に限定されないが、５〜１０℃／分で実施することが好ましい。これにより、再現性よく効率的に評価を行うことができ
る。
The differential scanning calorimetry used for the evaluation of the insulating sheet of the present invention is a technique for quantitatively detecting a change in thermal energy generated from a sample when the sample is heated and heated at a predetermined temperature condition. For example, a commercially available differential scanning calorimeter can be used.
Although it does not specifically limit as temperature rising conditions at the time of performing differential scanning calorimetry here, It is preferable to implement at 5-10 degreeC / min. Thereby, evaluation can be performed efficiently with good reproducibility.
本発明の絶縁シートは、上記示差走査熱量分析において、第１の発熱ピークと、これより高い温度に位置する第２の発熱ピークとを有する。
具体的には、上記示差走査熱量分析によって得られた、温度上昇と発熱量との関係を図示したＤＳＣ曲線上に、異なる温度における２つの発熱ピークを有する。
In the differential scanning calorimetry, the insulating sheet of the present invention has a first exothermic peak and a second exothermic peak located at a higher temperature.
Specifically, there are two exothermic peaks at different temperatures on the DSC curve illustrating the relationship between the temperature rise and the calorific value obtained by the differential scanning calorimetry.
ここで第１の発熱ピークとしては特に限定されないが、１２０〜２００℃の範囲内にあることが好ましい。さらに好ましくは１５０〜２００℃である。
また、第２の発熱ピークとしては特に限定されないが、１５０〜２５０℃の範囲内にあることが好ましい。さらに好ましくは１８０〜２５０℃である。
そして、上記第１の発熱ピークと第２の発熱ピークとは、特に限定されないが、３０〜８０℃の差を有することが好ましい。
Although it does not specifically limit as a 1st exothermic peak here, It exists in the range of 120-200 degreeC. More preferably, it is 150-200 degreeC.
The second exothermic peak is not particularly limited, but is preferably in the range of 150 to 250 ° C. More preferably, it is 180-250 degreeC.
The first exothermic peak and the second exothermic peak are not particularly limited, but preferably have a difference of 30 to 80 ° C.
まず、第１の発熱ピークを上記範囲内とすることにより、以下の効果を発現させることができる。絶縁シートを内層回路基板に接合する際の温度、すなわち、通常、多層回路基板を加熱加圧成形して製造する際の温度、あるいは、上記第１の発熱ピーク温度より０〜５０℃低い温度で、この第１の硬化性樹脂の硬化反応を効率的に進めることができる。また、第２の硬化性樹脂の硬化反応が進行するのを実質的に抑制することができる。
First, by setting the first exothermic peak within the above range, the following effects can be exhibited. The temperature at which the insulating sheet is bonded to the inner circuit board, that is, the temperature at which the multilayer circuit board is usually produced by heating and pressing, or the
また、第２の発熱ピークを上記範囲内とすることにより、以下の効果を発現させることができる。本発明の絶縁シートを内層回路基板に接合した後、外層回路を形成したものを上記第２の発熱ピーク温度より０〜５０℃低い温度範囲内で熱処理することにより、第２の硬化性樹脂の硬化反応を効率的に進め、絶縁層と外層回路との密着性を確保することができる。また、導体金属のアニーリングを行うことができるので、導体金属メッキにより外層回路を形成した際の応力歪の開放を併せて行うことができる。 Moreover, the following effects can be expressed by making a 2nd exothermic peak into the said range. After bonding the insulating sheet of the present invention to the inner layer circuit board, the outer layer circuit formed is heat-treated within a temperature range of 0 to 50 ° C. lower than the second exothermic peak temperature, whereby the second curable resin The curing reaction can be efficiently advanced, and the adhesion between the insulating layer and the outer layer circuit can be ensured. Moreover, since the conductor metal can be annealed, the stress strain when the outer layer circuit is formed by the conductor metal plating can be released together.
本発明の絶縁シートは、硬化性樹脂と無機充填材とを含有する樹脂組成物から形成されるものである。そして、この樹脂組成物は、上記第１の発熱ピークを発現する第１の硬化性樹脂と、上記第２の発熱ピークを発現する第２の硬化性樹脂とを含有することが好ましい。 The insulating sheet of the present invention is formed from a resin composition containing a curable resin and an inorganic filler. And it is preferable that this resin composition contains the 1st curable resin which expresses the said 1st exothermic peak, and the 2nd curable resin which expresses the said 2nd exothermic peak.
本発明の絶縁シートに用いられる硬化性樹脂としては特に限定されないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂等のノボラック型フェノール樹脂、レゾール型フェノール樹脂等のフェノール樹脂、ビスフェノールＡエポキシ樹脂、ビスフェノールＦエポキシ樹脂等のビスフェノール型エポキシ樹脂、ノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂等のノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂等のエポキシ樹脂、ノボラック型シアネート樹脂、ビスフェノールＡ型シアネート樹脂、ビスフェノールＥ型シアネート樹脂、ビスフェノールＦ型シアネート樹脂等のビスフェノール型シアネート樹脂等のシアネート樹脂等が挙げられる。 Although it does not specifically limit as curable resin used for the insulating sheet of this invention, For example, phenol novolak resins, such as a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, a phenol resin, such as a resol type phenol resin, bisphenol A Epoxy resin, bisphenol type epoxy resin such as bisphenol F epoxy resin, novolac epoxy resin, novolac type epoxy resin such as cresol novolac epoxy resin, epoxy resin such as biphenyl type epoxy resin, novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol Examples thereof include cyanate resins such as bisphenol type cyanate resins such as E type cyanate resin and bisphenol F type cyanate resin.
まず、第１の硬化性樹脂について説明する。
本発明の絶縁シートを形成する樹脂組成物においては、第１の硬化性樹脂として、シアネート樹脂及び／又はそのプレポリマーを含有することが好ましい。
シアネート樹脂及び／又はそのプレポリマーの入手方法としては特に限定されないが、例えば、ハロゲン化シアン化合物とフェノール類とを反応させ、必要に応じて加熱等の方法でプレポリマー化することにより得ることができる。また、このようにして調製された市販品を用いることもできる。
First, the first curable resin will be described.
In the resin composition which forms the insulating sheet of this invention, it is preferable to contain cyanate resin and / or its prepolymer as 1st curable resin.
The method for obtaining the cyanate resin and / or its prepolymer is not particularly limited. For example, the cyanate resin can be obtained by reacting a cyanogen halide with a phenol and prepolymerizing it by a method such as heating as necessary. it can. Moreover, the commercial item prepared in this way can also be used.
上記第１の硬化性樹脂として、シアネート樹脂及び／又はそのプレポリマーを用いることにより、絶縁シートの弾性率を向上させることができる。また、シアネート樹脂（特にノボラック型シアネート樹脂）は、剛直な化学構造を有するため、耐熱性に優れており、ガラス転移温度以上でも弾性率の低下が小さく、高温においても高弾性率を維持することができる。さらに、硬化反応によって水酸基などの分極率の大きな官能基が生じないため、誘電特性においても優れたものとすることができる。 By using a cyanate resin and / or a prepolymer thereof as the first curable resin, the elastic modulus of the insulating sheet can be improved. Cyanate resins (especially novolac-type cyanate resins) have a rigid chemical structure and are therefore excellent in heat resistance, have a small decrease in elastic modulus even above the glass transition temperature, and maintain a high elastic modulus even at high temperatures. Can do. Furthermore, since a functional group having a high polarizability such as a hydroxyl group is not generated by the curing reaction, the dielectric properties can be improved.
上記シアネート樹脂の中でも、下記一般式（Ｉ）で表されるノボラック型シアネート樹脂を含有することが好ましい。これにより、上記効果に加えて、絶縁シートのガラス転移温度をさらに高くすることができるとともに、硬化後の絶縁シートの難燃性をより向上させることができる。 Among the cyanate resins, it is preferable to contain a novolac-type cyanate resin represented by the following general formula (I). Thereby, in addition to the said effect, while being able to make the glass transition temperature of an insulating sheet still higher, the flame retardance of the insulating sheet after hardening can be improved more.
上記一般式（Ｉ）で表されるノボラック型シアネート樹脂の分子量としては特に限定されないが、ＧＰＣ測定による重量平均分子量が５００〜１０，０００であることが好ましく、さらに好ましくは７００〜５，０００である。重量平均分子量が上記下限値未満であると、機械的強度が低下する場合がある。また、上記上限値を超えると、硬化前の絶縁シートの弾性率が高くなり作業性が低下したり、溶融粘度が高くなり成形性が低下したりする場合がある。 The molecular weight of the novolak cyanate resin represented by the general formula (I) is not particularly limited, but the weight average molecular weight by GPC measurement is preferably 500 to 10,000, and more preferably 700 to 5,000. is there. If the weight average molecular weight is less than the lower limit, the mechanical strength may be lowered. Moreover, when the said upper limit is exceeded, the elasticity modulus of the insulating sheet before hardening may become high and workability | operativity will fall, or melt viscosity may become high and a moldability may fall.
ノボラック型シアネート樹脂の入手方法としては特に限定されないが、例えば、ノボラック型フェノール樹脂と、ハロゲン化シアン化合物等のシアネート化試薬とを反応させることにより得ることができる。また、このようにして調製された市販品を用いることもできる。 The method for obtaining the novolac-type cyanate resin is not particularly limited. For example, the novolac-type cyanate resin can be obtained by reacting a novolac-type phenol resin with a cyanating reagent such as a halogenated cyanide compound. Moreover, the commercial item prepared in this way can also be used.
なお、上記シアネート樹脂としては、これをプレポリマー化したものも用いることができる。すなわち、シアネート樹脂を単独で用いてもよいし、重量平均分子量の異なるシアネート樹脂を併用したり、シアネート樹脂とそのプレポリマーとを併用したりすることもできる。
ここでプレポリマーとは、通常、上記シアネート樹脂を加熱反応などにより、例えば３量化することで得られるものであり、樹脂組成物の成形性、流動性を調整するために好ましく使用されるものである。
ここでプレポリマーとしては特に限定されないが、例えば、３量化率が２０〜５０重量
％であるものを用いることができる。この３量化率は、例えば赤外分光分析装置を用いて求めることができる。
In addition, as said cyanate resin, what prepolymerized this can also be used. That is, a cyanate resin may be used alone, a cyanate resin having a different weight average molecular weight may be used in combination, or a cyanate resin and a prepolymer thereof may be used in combination.
Here, the prepolymer is usually obtained by, for example, trimerizing the cyanate resin by a heat reaction or the like, and is preferably used for adjusting the moldability and fluidity of the resin composition. is there.
Although it does not specifically limit as a prepolymer here, For example, what a trimerization rate is 20 to 50 weight% can be used. This trimerization rate can be determined using, for example, an infrared spectroscopic analyzer.
上記樹脂組成物中、第１の硬化性樹脂の含有量としては特に限定されないが、樹脂組成物全体に対して１０〜５０重量％であることが好ましく、さらに好ましくは１０〜４０重量％である。
これにより、内層回路基板と絶縁シートとを強固に接合することができる。
Although it does not specifically limit as content of 1st curable resin in the said resin composition, It is preferable that it is 10 to 50 weight% with respect to the whole resin composition, More preferably, it is 10 to 40 weight% .
Thereby, an inner layer circuit board and an insulating sheet can be joined firmly.
また、上記樹脂組成物中、第１の硬化性樹脂としてシアネート樹脂を用いる場合、その含有量としては特に限定されないが、樹脂組成物全体に対して１０〜４０重量％であることが好ましく、さらに好ましくは１５〜３５重量％である。
シアネート樹脂の含有量が上記下限値未満であると、絶縁シートに耐熱性や低熱膨張性を付与する場合には、その効果が充分でないことがある。また、上記上限値を超えると、シアネート樹脂による架橋密度が高くなり、自由体積が増加するため、絶縁シートとしての耐湿性が低下することがある。
Moreover, when using cyanate resin as 1st curable resin in the said resin composition, it is although it does not specifically limit as the content, It is preferable that it is 10 to 40 weight% with respect to the whole resin composition, Furthermore, Preferably it is 15 to 35% by weight.
When the content of the cyanate resin is less than the lower limit, the effect may not be sufficient when the insulating sheet is imparted with heat resistance and low thermal expansion. Moreover, since the crosslinking density by cyanate resin will become high and the free volume will increase when the said upper limit is exceeded, the moisture resistance as an insulating sheet may fall.
次に、第２の硬化性樹脂について説明する。
本発明の絶縁シートを構成する樹脂組成物においては、第２の硬化性樹脂として、エポキシ樹脂を含有することが好ましい。これにより、絶縁シート製造時の製膜性や、内層回路基板への密着性を向上させることができる。
また、エポキシ樹脂としては、実質的にハロゲン原子を含まないエポキシ樹脂を含有することが好ましい。
Next, the second curable resin will be described.
In the resin composition which comprises the insulating sheet of this invention, it is preferable to contain an epoxy resin as 2nd curable resin. Thereby, the film-forming property at the time of insulating sheet manufacture and the adhesiveness to an inner-layer circuit board can be improved.
Moreover, as an epoxy resin, it is preferable to contain the epoxy resin which does not contain a halogen atom substantially.
このようなエポキシ樹脂としては特に限定されないが、例えば、フェノールノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、アリールアルキレン型エポキシ樹脂等が挙げられる。
これらの中でも、アリールアルキレン型エポキシ樹脂が好ましい。これにより、多層プリント配線板の吸湿半田耐熱性をさらに向上させることができる。また、上記効果に加えて、ハロゲン化合物を用いることなく絶縁シートに難燃性を付与することができる。
Such an epoxy resin is not particularly limited, and examples thereof include a phenol novolac type epoxy resin, a bisphenol type epoxy resin, a naphthalene type epoxy resin, and an arylalkylene type epoxy resin.
Among these, aryl alkylene type epoxy resins are preferable. Thereby, the moisture absorption solder heat resistance of a multilayer printed wiring board can further be improved. Moreover, in addition to the said effect, a flame retardance can be provided to an insulating sheet, without using a halogen compound.
ここで、アリールアルキレン型エポキシ樹脂とは、繰り返し単位中に一つ以上のアリールアルキレン基を有するエポキシ樹脂を指し、例えば、キシリレン型エポキシ樹脂、ビフェニルジメチレン型エポキシ樹脂等が挙げられる。これらの中でも、下記一般式（ＩＩ）で表されるビフェニルジメチレン型エポキシ樹脂が好ましい。これにより、ハロゲン化合物を用いることなく絶縁シートに高い難燃性を付与することができる。 Here, the aryl alkylene type epoxy resin refers to an epoxy resin having one or more aryl alkylene groups in the repeating unit, and examples thereof include a xylylene type epoxy resin and a biphenyl dimethylene type epoxy resin. Among these, a biphenyl dimethylene type epoxy resin represented by the following general formula (II) is preferable. Thereby, high flame retardance can be imparted to the insulating sheet without using a halogen compound.
上記一般式（ＩＩ）で表されるビフェニルジメチレン型エポキシ樹脂のｎは、特に限定
されないが、ｎ＝１〜１０であることが好ましく、さらに好ましくはｎ＝２〜５である。これにより、示差走査熱量分析において、好適な温度範囲内で第２の発熱ピークを発現させることができる。
ｎの数が上記下限値より少ないとビフェニルジメチレン型エポキシ樹脂は結晶化しやすくなり、汎用溶媒に対する溶解性が若干低下するため、絶縁シートの製造時に樹脂組成物ワニスを調製する際に、取り扱いが難しくなることがある。また、上記上限値より多いと、樹脂の流動性が低下するため、絶縁シートの製膜性に影響を与えることがある。
Although n of the biphenyl dimethylene type | mold epoxy resin represented by the said general formula (II) is not specifically limited, It is preferable that it is n = 1-10, More preferably, it is n = 2-5. Thereby, in the differential scanning calorimetry, the second exothermic peak can be expressed within a suitable temperature range.
When the number of n is less than the above lower limit value, the biphenyldimethylene type epoxy resin is easily crystallized, and the solubility in a general-purpose solvent is slightly reduced. Therefore, when preparing the resin composition varnish during the production of the insulating sheet, handling is difficult. It can be difficult. On the other hand, when the amount is larger than the above upper limit value, the fluidity of the resin is lowered, which may affect the film forming property of the insulating sheet.
なお、ここで実質的にハロゲン原子を含まないエポキシ樹脂としては、例えば、エポキシ樹脂中のハロゲン原子の含有量が１重量％以下であるものを用いることができる。 In addition, as an epoxy resin which does not contain a halogen atom substantially here, the content of the halogen atom in an epoxy resin can be 1 weight% or less, for example.
上記樹脂組成物中、第２の硬化性樹脂の含有量としては特に限定されないが、樹脂組成物全体に対して１０〜５０重量％であることが好ましく、さらに好ましくは１５〜４５重量％である。
これにより、絶縁シートと外層回路との密着性を高めることができる。
Although it does not specifically limit as content of 2nd curable resin in the said resin composition, It is preferable that it is 10 to 50 weight% with respect to the whole resin composition, More preferably, it is 15 to 45 weight% .
Thereby, the adhesiveness of an insulating sheet and an outer layer circuit can be improved.
また、上記樹脂組成物中、第２の硬化性樹脂として上記エポキシ樹脂を用いる場合の含有量としては特に限定されないが、樹脂組成物全体に対して１０〜５０重量％であることが好ましく、さらに好ましくは１５〜３５重量％である。
エポキシ樹脂の含有量が上記下限値未満であると、密着性、製膜性を向上する効果が低下することがある。また、上記上限値を超えると、第１の硬化性樹脂の硬化後、内層回路基板と絶縁シートとの密着性が不十分となったり、耐薬品性が低下したりする場合がある。
Further, the content in the case where the epoxy resin is used as the second curable resin in the resin composition is not particularly limited, but is preferably 10 to 50% by weight with respect to the entire resin composition. Preferably it is 15 to 35% by weight.
When the content of the epoxy resin is less than the above lower limit, the effect of improving the adhesion and film forming property may be lowered. Moreover, when the said upper limit is exceeded, after hardening of 1st curable resin, the adhesiveness of an inner-layer circuit board and an insulating sheet may become inadequate, or chemical resistance may fall.
本発明の絶縁シートに用いる樹脂組成物には、硬化性樹脂として、好ましくは上記シアネート樹脂と上記エポキシ樹脂のほか、実質的にハロゲン原子を含まないフェノキシ樹脂を用いることが好ましい。これにより、絶縁シートを製造する際の製膜性をさらに向上させることができる。 In the resin composition used for the insulating sheet of the present invention, as the curable resin, it is preferable to use a phenoxy resin that substantially does not contain a halogen atom in addition to the cyanate resin and the epoxy resin. Thereby, the film formability at the time of manufacturing an insulating sheet can further be improved.
このようなフェノキシ樹脂としては特に限定されないが、例えば、ビスフェノール骨格を有するフェノキシ樹脂、ナフタレン骨格を有するフェノキシ樹脂、ビフェニル骨格を有するフェノキシ樹脂等が挙げられる。これらの中でも、ビスフェノールＦ型、ビスフェノールＳ型、ビフェニル型が好ましい。これにより、難燃性をより向上させることができる。 Such a phenoxy resin is not particularly limited, and examples thereof include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, and a phenoxy resin having a biphenyl skeleton. Among these, bisphenol F type, bisphenol S type, and biphenyl type are preferable. Thereby, a flame retardance can be improved more.
なお、ここで実質的にハロゲン原子を含まないフェノキシ樹脂としては、例えば、フェノキシ樹脂中のハロゲン原子の含有量が１重量％以下であるものを用いることができる。 In addition, as a phenoxy resin which does not contain a halogen atom substantially here, what has the content of the halogen atom in a phenoxy resin is 1 weight% or less can be used, for example.
上記フェノキシ樹脂の分子量としては特に限定されないが、ＧＰＣ測定による重量平均分子量が１，０００〜１００，０００であるものを用いることが好ましい。さらに好ましくは３，０００〜３０，０００である。
重量平均分子量が上記下限値未満であると、製膜性を向上する効果が充分でないことがあり、上記上限値を超えると、樹脂組成物ワニスを調製する際のフェノキシ樹脂の溶解性が低下することがある。
The molecular weight of the phenoxy resin is not particularly limited, but it is preferable to use one having a weight average molecular weight of 1,000 to 100,000 by GPC measurement. More preferably, it is 3,000-30,000.
If the weight average molecular weight is less than the lower limit, the effect of improving the film-forming property may not be sufficient, and if it exceeds the upper limit, the solubility of the phenoxy resin at the time of preparing the resin composition varnish decreases. Sometimes.
硬化性樹脂として上記フェノキシ樹脂を用いる場合の含有量としては特に限定されないが、樹脂組成物全体に対して３〜２０重量％であることが好ましく、さらに好ましくは５〜１５重量％である。
フェノキシ樹脂の含有量が上記下限値未満であると、製膜性を向上させる効果が低下することがある。また、上記上限値を超えると、絶縁シートの低熱膨張性が低下することが
ある。
The content when the phenoxy resin is used as the curable resin is not particularly limited, but is preferably 3 to 20% by weight, more preferably 5 to 15% by weight, based on the entire resin composition.
When the content of the phenoxy resin is less than the lower limit, the effect of improving the film forming property may be lowered. Moreover, when the said upper limit is exceeded, the low thermal expansibility of an insulating sheet may fall.
本発明の絶縁シートに用いる樹脂組成物には、無機充填材が用いられる。
ここで用いられる無機充填材としては特に限定されないが、例えば、窒化アルミニウム、窒化ホウ素、窒化ケイ素等の窒化物、タルク、焼成クレー、未焼成クレー、マイカ、ガラス等のケイ酸塩、酸化チタン、アルミナ、シリカ、溶融シリカ等の酸化物、炭酸カルシウム、炭酸マグネシウム、ハイドロタルサイト等の炭酸塩、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム等の水酸化物、硫酸バリウム、硫酸カルシウム、亜硫酸カルシウム等の硫酸塩または亜硫酸塩、ホウ酸亜鉛、メタホウ酸バリウム、ホウ酸アルミニウム、ホウ酸カルシウム、ホウ酸ナトリウム等のホウ酸塩等を挙げることができる。
これらの中でも低熱膨張で絶縁信頼性の高いシリカが好ましい。さらには球状シリカが好ましく、球状溶融シリカが特に好ましい。これにより、樹脂組成物中における無機充填材の配合量を多くでき、絶縁シートを特に低熱膨張化させることができる。また、球状シリカを用いることにより樹脂組成物の溶融粘度を低く維持することができるので、多層プリント配線板を製造する際の内層回路基板の凹凸を埋める成形性を向上させることができる。
An inorganic filler is used for the resin composition used for the insulating sheet of the present invention.
The inorganic filler used here is not particularly limited, but for example, nitrides such as aluminum nitride, boron nitride, and silicon nitride, talc, fired clay, unfired clay, mica, silicates such as glass, titanium oxide, Oxides such as alumina, silica and fused silica, carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, barium sulfate, calcium sulfate and calcium sulfite And borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate and the like.
Among these, silica with low thermal expansion and high insulation reliability is preferable. Furthermore, spherical silica is preferable, and spherical fused silica is particularly preferable. Thereby, the compounding quantity of the inorganic filler in a resin composition can be increased, and an insulating sheet can be made especially low thermal expansion. Moreover, since the melt viscosity of the resin composition can be kept low by using spherical silica, it is possible to improve the moldability for filling the irregularities of the inner circuit board when manufacturing the multilayer printed wiring board.
上記無機充填材の粒度としては特に限定されないが、平均粒径が０．０１〜５μｍであることが好ましく、さらに好ましくは０．２〜２μｍである。平均粒径が上記下限値未満であると、樹脂組成物ワニスの粘度が高くなり、また、上記上限値を超えると、樹脂組成物ワニス中で無機充填材の沈降等が起こりやすく、いずれの場合も作業性が低下する場合がある。 Although it does not specifically limit as a particle size of the said inorganic filler, It is preferable that an average particle diameter is 0.01-5 micrometers, More preferably, it is 0.2-2 micrometers. When the average particle size is less than the above lower limit, the viscosity of the resin composition varnish increases. When the average particle size exceeds the upper limit, sedimentation of the inorganic filler easily occurs in the resin composition varnish. However, workability may be reduced.
樹脂組成物中、上記無機充填材の含有量としては特に限定されないが、樹脂組成物全体の２０〜７０重量％であることが好ましく、さらに好ましくは３５〜６０重量％である。
含有量が上記下限値未満であると、高弾性化、低熱膨脹化する効果が充分でない場合がある。また、上記上限値を超えると、流動性の低下により、この絶縁シートを用いて多層プリント配線板を製造する際の成形性が低下することがある。
Although it does not specifically limit as content of the said inorganic filler in a resin composition, It is preferable that it is 20 to 70 weight% of the whole resin composition, More preferably, it is 35 to 60 weight%.
If the content is less than the lower limit, the effect of increasing elasticity and decreasing thermal expansion may not be sufficient. Moreover, when the said upper limit is exceeded, the moldability at the time of manufacturing a multilayer printed wiring board using this insulating sheet may fall by fluid fall.
本発明で用いられる樹脂組成物では、特に限定されないが、さらにカップリング剤を含有することが好ましい。
カップリング剤は、硬化性樹脂と無機充填剤との界面の濡れ性を向上させ、絶縁シートを用いた多層プリント配線板の耐熱性、特に吸湿後の半田耐熱性を向上させることができるとともに、基材付き絶縁シートを製造する際に、基材に対して硬化性樹脂と充填剤とを均一に定着させることができる。
Although it does not specifically limit in the resin composition used by this invention, It is preferable to contain a coupling agent further.
The coupling agent improves the wettability of the interface between the curable resin and the inorganic filler, can improve the heat resistance of the multilayer printed wiring board using the insulating sheet, particularly the solder heat resistance after moisture absorption, When manufacturing an insulating sheet with a substrate, the curable resin and the filler can be uniformly fixed to the substrate.
ここで用いられるカップリング剤としては、通常用いられるものであれば特に限定されないが、エポキシシランカップリング剤、チタネート系カップリング剤、アミノシランカップリング剤及びシリコーンオイル型カップリング剤の中から選ばれる１種以上のカップリング剤を使用することが好ましい。これにより、無機充填剤の界面との濡れ性が良くなり、耐熱性をより向上させることができる。 The coupling agent used here is not particularly limited as long as it is usually used, but is selected from an epoxy silane coupling agent, a titanate coupling agent, an aminosilane coupling agent, and a silicone oil type coupling agent. It is preferred to use one or more coupling agents. Thereby, the wettability with the interface of the inorganic filler is improved, and the heat resistance can be further improved.
カップリング剤の含有量は特に限定されないが、無機充填材１００重量部に対して０．０５〜３重量部であることが好ましく、さらに好ましくは０．１〜２重量部である。含有量が上記下限値未満であると、無機充填材を充分に被覆できず、耐熱性を向上させる効果が低下する場合がある。一方、上記上限値を超えると、絶縁シートの曲げ強度が低下する場合がある。 Although content of a coupling agent is not specifically limited, It is preferable that it is 0.05-3 weight part with respect to 100 weight part of inorganic fillers, More preferably, it is 0.1-2 weight part. If the content is less than the above lower limit, the inorganic filler cannot be sufficiently covered, and the effect of improving heat resistance may be reduced. On the other hand, when the above upper limit is exceeded, the bending strength of the insulating sheet may decrease.
本発明で用いられる樹脂組成物には、硬化性樹脂成分の硬化反応を促進させるため、硬化触媒を用いることができる。
硬化性樹脂としてシアネート樹脂を用いる場合の硬化触媒としては、例えばトリエチルアミン、トリブチルアミン、キノリン、イソキノリン等の三級アミン類、塩化テトラエチルアンモニウム、臭化テトラブチルアンモニウム等の四級アンモニウム塩、フェノール、ノニルフェノール、カテコール、ピロガール、ジヒドロキシナフタレンに代表される芳香族ヒドロキシ化合物、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、ビス（２−エチル−４−メチル−イミダゾール）、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−アミノエチル−２−メチルイミダゾール、１−（シアノエチルアミノエチル）−２−メチルイミダゾール、１−シアノエチル−２−フェニル−４，５−ビス（シアノエトキシメチルイミダゾール）あるいはトリアジン付加型イミダゾール等に代表されるイミダゾール類等がある。また、シアネート樹脂の硬化触媒としては、ナフテン酸亜鉛、ナフテン酸コバルトオクチル酸錫、オクチル酸コバルト等に代表される有機金属塩、銅アセチルアセトナート、アルミニウムアセチルアセトナート、コバルトアセチルアセトナート等に代表される有機金属錯体等がある。これらは単独で使用しても２種以上を併用してもよい。
In the resin composition used in the present invention, a curing catalyst can be used to accelerate the curing reaction of the curable resin component.
Curing catalysts in the case of using a cyanate resin as the curable resin include, for example, tertiary amines such as triethylamine, tributylamine, quinoline, and isoquinoline, quaternary ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide, phenol, and nonylphenol. , Catechol, pyrogal, aromatic hydroxy compounds represented by dihydroxynaphthalene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, bis (2-ethyl-4-methyl-imidazole), 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl 2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, Examples include imidazoles represented by 1-cyanoethyl-2-phenyl-4,5-bis (cyanoethoxymethylimidazole) or triazine addition type imidazole. Also, as a curing catalyst for cyanate resin, organic metal salts typified by zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, etc., copper acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, etc. Organometallic complexes and the like. These may be used alone or in combination of two or more.
また、硬化性樹脂としてエポキシ樹脂を用いる場合の硬化触媒としては、例えば、３級アミン化合物、イミダゾール化合物、ルイス酸などが挙げられる。これらは単独で使用しても２種以上を併用してもよい。 Moreover, as a curing catalyst when using an epoxy resin as curable resin, a tertiary amine compound, an imidazole compound, a Lewis acid, etc. are mentioned, for example. These may be used alone or in combination of two or more.
また、樹脂組成物にはこのほか、絶縁シート製造時に気泡の発生を防止するための消泡剤、難燃性を向上させるための液状又は粉末の難燃剤、靭性、密着性を向上させるための熱可塑性樹脂等を添加することもできる。
ここで用いられる熱可塑性樹脂としては特に限定されないが、例えば、ポリアミド系樹脂、ポリエステル系樹脂、ポリイミド系樹脂、ポリウレタン系樹脂、ポリスチレン系樹脂、アクリル系樹脂、シリコーン系樹脂等が挙げられる。
In addition to the above, the resin composition also includes an antifoaming agent for preventing the generation of bubbles during the production of the insulating sheet, a liquid or powder flame retardant for improving flame retardancy, to improve toughness and adhesion. A thermoplastic resin or the like can also be added.
The thermoplastic resin used here is not particularly limited, and examples thereof include polyamide resins, polyester resins, polyimide resins, polyurethane resins, polystyrene resins, acrylic resins, and silicone resins.
本発明の絶縁シートは、以上に説明した樹脂組成物から形成されるものである。
本発明の絶縁シートの厚みとしては特に限定されないが、１５〜１００μｍとすることが好ましい。これにより、絶縁シートの取り扱いに必要な機械的強度を付与することができるとともに、これを用いて多層プリント配線板を製造する際、内層回路基板の凹凸を充填でき、必要かつ充分な絶縁層の厚みを確保することができる。
また、本発明の絶縁シートの表面形態は、表裏とも、凹凸が極力小さいものであることが好ましい。
The insulating sheet of the present invention is formed from the resin composition described above.
Although it does not specifically limit as thickness of the insulating sheet of this invention, It is preferable to set it as 15-100 micrometers. As a result, the mechanical strength necessary for the handling of the insulating sheet can be imparted, and when producing a multilayer printed wiring board using this, the unevenness of the inner circuit board can be filled, and the necessary and sufficient insulating layer can be formed. Thickness can be ensured.
Moreover, it is preferable that the surface form of the insulating sheet of the present invention is as small as possible on both the front and back sides.
次に、本発明の基材付き絶縁シートについて説明する。
本発明の基材付き絶縁シートは、上記本発明の絶縁シートと、これを担持する基材とから構成されているものである。
Next, the insulating sheet with a substrate of the present invention will be described.
The insulating sheet with a base material of the present invention is composed of the above-described insulating sheet of the present invention and a base material carrying the same.
本発明の基材付き絶縁シートを製造する方法としては特に限定されないが、例えば、予め作製した絶縁シートと基材とを加熱加圧して接合する方法、基材に樹脂組成物ワニスを塗工した後、これを乾燥する方法等が挙げられる。これらの中でも、基材に樹脂組成物ワニスを塗工した後、これを乾燥する方法が好ましい。これにより、効率良く基材付き絶縁シートを製造することができる。 Although it does not specifically limit as a method to manufacture the insulating sheet with a base material of this invention, For example, the resin composition varnish was applied to the base material, the method of joining by heating-pressing the insulating sheet and base material which were produced previously Thereafter, a method of drying the same may be used. Among these, the method of drying the resin composition varnish after applying it to the substrate is preferable. Thereby, the insulating sheet with a base material can be manufactured efficiently.
樹脂組成物ワニスを基材に塗工する方法の場合、まず、樹脂組成物を用いて樹脂組成物ワニスを調製する。樹脂組成物ワニスは、通常、樹脂組成物をアルコール類、エーテル類、アセタール類、ケトン類、エステル類、アルコールエステル類、ケトンアルコール類、
エーテルアルコール類、ケトンエーテル類、ケトンエステル類やエステルエーテル類等の有機溶媒に溶解又は分散させて調製することができる。次いで、この樹脂組成物ワニスを基材上に所定量塗工した後、加温した乾燥装置などを用いて、樹脂組成物中に含有されている上記有機溶剤を実質的に除去して得ることができる。
In the case of a method of applying a resin composition varnish to a substrate, first, a resin composition varnish is prepared using the resin composition. The resin composition varnish is usually obtained by converting the resin composition into alcohols, ethers, acetals, ketones, esters, alcohol esters, ketone alcohols,
It can be prepared by dissolving or dispersing in an organic solvent such as ether alcohols, ketone ethers, ketone esters and ester ethers. Next, after applying a predetermined amount of this resin composition varnish on the substrate, the organic solvent contained in the resin composition is substantially removed using a heated drying device or the like. Can do.
本発明の基材付き絶縁シートに用いられる基材としては特に限定されないが、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステル樹脂のほか、フッ素系樹脂、ポリイミド樹脂などの耐熱性を有した熱可塑性樹脂フィルムを用いることができる。このほか、銅又は銅系合金、アルミ又はアルミ系合金等の金属箔を用いることもできる。
基材の厚みとしては特に限定されないが、５〜５０μｍのものを用いると、基材付き絶縁シートを製造する際の取り扱い性が良好であり好ましい。
なお、本発明の基材付き絶縁シートを製造するにあたっては、絶縁シートと接合される側の基材表面の凹凸は極力小さいものであることが好ましい。
Although it does not specifically limit as a base material used for the insulating sheet with a base material of this invention, For example, in addition to polyester resins, such as a polyethylene terephthalate and a polybutylene terephthalate, thermoplastics which have heat resistance, such as a fluororesin and a polyimide resin A resin film can be used. In addition, a metal foil such as copper or a copper-based alloy, aluminum, or an aluminum-based alloy can also be used.
Although it does not specifically limit as thickness of a base material, When the thing of 5-50 micrometers is used, the handleability at the time of manufacturing an insulating sheet with a base material is favorable, and it is preferable.
In addition, when manufacturing the insulating sheet with a base material of the present invention, it is preferable that the unevenness on the surface of the base material to be bonded to the insulating sheet is as small as possible.
次に、本発明の多層プリント配線板について説明する。
本発明の多層プリント配線板は、上記本発明の絶縁シートを内層回路基板に接合してなるものである。
本発明の絶縁シートを内層回路基板に接合して、本発明の多層プリント配線板を製造する方法としては特に限定されないが、例えば、下記の方法を適用することができる。
まず、内層回路基板の片面または両面に絶縁シートを積層し、平板プレス装置を用いて、これを好ましくは８０〜１８０℃、０．５〜４ＭＰａ、０．５〜１．５時間で加熱加圧成形する方法、あるいは、内層回路基板と絶縁シートとを、真空ラミネーター装置を用いて、好ましくは７０〜１００℃のロールラミネーターで接着後、８０〜１８０℃で０．５〜１時間熱処理する方法などにより、内層回路基板表面の凹凸を絶縁シートで充填して成形するとともに、上記第１の硬化性樹脂成分の硬化を行い、両者を接合する。
次いで、内層回路基板と接合された側と反対側の絶縁シート表面を過マンガン酸カリウム等で酸化処理（デスミア処理）して、絶縁シート表面に存在する上記第２の硬化性樹脂成分を除去することにより、絶縁シートの表面に微細な凹凸を高い均一性で形成することができる。
そして、この凹凸面に、導体金属をメッキ等により付着させて所定の導体回路を作製する。この後、好ましくは上記第２の発熱ピーク温度より０〜５０℃低い温度にて、０．５〜３時間熱処理して、上記第２の硬化性樹脂成分の硬化を行うとともに、表層に形成された導体回路のアニーリングを行うことにより、本発明の多層プリント配線板を製造することができる。
なお、このようにして形成された表層の導体回路面に、再度本発明の絶縁シートを積層・接合し、同様の処理を繰り返してビルドアップして、さらに層を重ねて多層プリント配線板を製造することもできる。
Next, the multilayer printed wiring board of the present invention will be described.
The multilayer printed wiring board of the present invention is formed by bonding the insulating sheet of the present invention to an inner layer circuit board.
Although it does not specifically limit as a method of manufacturing the multilayer printed wiring board of this invention by joining the insulating sheet of this invention to an inner-layer circuit board, For example, the following method is applicable.
First, an insulating sheet is laminated on one side or both sides of the inner layer circuit board, and this is preferably heated and pressurized at 80 to 180 ° C., 0.5 to 4 MPa, and 0.5 to 1.5 hours using a flat plate press. A method of forming, or a method of heat-treating the inner layer circuit board and the insulating sheet at 80 to 180 ° C. for 0.5 to 1 hour after bonding them with a roll laminator preferably at 70 to 100 ° C. using a vacuum laminator device, etc. Thus, the unevenness on the surface of the inner layer circuit board is filled with an insulating sheet and molded, and the first curable resin component is cured and joined together.
Next, the surface of the insulating sheet opposite to the side bonded to the inner layer circuit board is oxidized (desmeared) with potassium permanganate to remove the second curable resin component present on the surface of the insulating sheet. As a result, fine irregularities can be formed on the surface of the insulating sheet with high uniformity.
Then, a conductor metal is attached to the uneven surface by plating or the like to produce a predetermined conductor circuit. Thereafter, the second curable resin component is cured by heat treatment for 0.5 to 3 hours, preferably at a
In addition, the insulating sheet of the present invention is laminated and bonded again to the surface of the conductive circuit surface formed in this way, the same treatment is repeated, build-up is performed, and further layers are stacked to produce a multilayer printed wiring board You can also
本発明の絶縁シートを用いて、好ましくは上記方法により多層プリント配線板を製造することにより、信頼性の高い多層プリント配線板を製造することができる。この理由は、以下のように考えられる。 A highly reliable multilayer printed wiring board can be manufactured using the insulating sheet of the present invention, preferably by manufacturing the multilayer printed wiring board by the above method. The reason is considered as follows.
本発明の絶縁シートは、硬化性樹脂と無機充填材とを含有する樹脂組成物から形成される絶縁シートであり、示差走査熱量分析において、第１の発熱ピークと、これより高い温度に位置する第２の発熱ピークとを有する。
この絶縁シートを、予め導体回路が形成された内層回路基板の表面に積層して接合することにより、上記第１の硬化性樹脂の硬化反応を行い、絶縁シートと内層回路基板とを強固に接合することができる。
次に、この内層回路基板に接合された絶縁シートの外側表面に存在し、上記第２の硬化
性樹脂成分をデスミア処理等により除去することにより、絶縁シートの表面側に微細な凹凸を高い均一性で形成することができる。
このようにして形成された凹凸形状は微小なものであり、大きな凹凸が実質的に存在しないため、この面に導体金属をメッキ等により付着させることにより、平滑性の高い外層回路を形成することができる。この外層回路の裏面側には、絶縁シート表面の微小な凹凸形状と同じプロファイルが形成されるため、アンカー効果により絶縁シートと外層回路との密着性を確保できるとともに、外層回路を形成する部位によらず、この密着強度を実質的に一定にすることができる。
そして、外層回路を形成後に熱処理を行うことにより、上記第２の硬化性樹脂の硬化反応を行うとともに、外層回路のアニーリング処理を行うことができる。これにより、外層回路と絶縁シートとの密着性を向上させることができるとともに、その後の熱履歴によってもこれを安定なものとすることができる。
このようにして、信頼性の高い多層プリント配線板を製造することができる。
The insulating sheet of the present invention is an insulating sheet formed from a resin composition containing a curable resin and an inorganic filler, and is located at a first exothermic peak and a temperature higher than that in differential scanning calorimetry. With a second exothermic peak.
By laminating and bonding the insulating sheet to the surface of the inner layer circuit board on which the conductor circuit is formed in advance, the curing reaction of the first curable resin is performed, and the insulating sheet and the inner layer circuit board are firmly bonded. can do.
Next, it exists on the outer surface of the insulating sheet bonded to this inner layer circuit board, and the second curable resin component is removed by desmearing or the like, so that fine unevenness is highly uniformly formed on the surface side of the insulating sheet. Can be formed.
The uneven shape formed in this way is very small, and there is virtually no large unevenness. Therefore, an outer layer circuit with high smoothness can be formed by attaching a conductive metal to this surface by plating or the like. Can do. Since the same profile as the minute uneven shape on the surface of the insulating sheet is formed on the back surface side of the outer layer circuit, the adhesion between the insulating sheet and the outer layer circuit can be ensured by the anchor effect, and the outer layer circuit is formed at the site where the outer layer circuit is formed. Regardless, this adhesion strength can be made substantially constant.
Then, by performing heat treatment after forming the outer layer circuit, the second curable resin can be cured and the outer layer circuit can be annealed. Thereby, while being able to improve the adhesiveness of an outer layer circuit and an insulating sheet, this can also be stabilized by the subsequent heat history.
In this way, a highly reliable multilayer printed wiring board can be manufactured.
以下、本発明を実施例および比較例により詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
実施例及び比較例において用いた原材料は以下の通りである。
（１）シアネート樹脂Ａ／ノボラック型シアネート樹脂：ロンザ社製・「プリマセットＰＴ−３０」、重量平均分子量７００
（２）シアネート樹脂Ｂ／ノボラック型シアネート樹脂Ｂ：ロンザ社製・「プリマセットＰＴ−６０」、重量平均分子量２６００
（３）エポキシ樹脂Ａ／ビフェニルジメチレン型エポキシ樹脂：日本化薬社製・「ＮＣ−３０００Ｐ」、エポキシ当量２７５
（４）エポキシ樹脂Ｂ／ビスフェノールＦ型エポキシ樹脂：日本化薬社製・「ＲＥ−４０４Ｓ」、エポキシ当量１６５
（５）フェノキシ樹脂／ビスフェノールＦ型フェノキシ樹脂：ジャパンエポキシレジン社製・「エピコート４０１０Ｐ」、数平均分子量６０００
（６）硬化触媒／イミダゾール化合物：四国化成工業社製・「２−フェニル−４，５−ジヒドロキシメチルイミダゾール」
（７）無機充填材／球状溶融シリカ：アドマテックス社製・「ＳＯ−２５Ｈ」、平均粒径０．５μｍ
（８）カップリング剤／エポキシシランカップリング剤：日本ユニカー社製・「Ａ−１８７」
The raw materials used in Examples and Comparative Examples are as follows.
(1) Cyanate resin A / Novolac type cyanate resin: “Primaset PT-30” manufactured by Lonza Corporation, weight average molecular weight 700
(2) Cyanate Resin B / Novolac Cyanate Resin B: “Primaset PT-60” manufactured by Lonza Corporation, weight average molecular weight 2600
(3) Epoxy resin A / biphenyl dimethylene type epoxy resin: Nippon Kayaku Co., Ltd. “NC-3000P”, epoxy equivalent 275
(4) Epoxy resin B / bisphenol F type epoxy resin: “RE-404S” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 165
(5) Phenoxy resin / bisphenol F type phenoxy resin: “Epicoat 4010P” manufactured by Japan Epoxy Resin Co., Ltd., number average molecular weight 6000
(6) Curing catalyst / imidazole compound: “2-phenyl-4,5-dihydroxymethylimidazole” manufactured by Shikoku Kasei Kogyo Co., Ltd.
(7) Inorganic filler / spherical fused silica: manufactured by Admatechs Co., Ltd. “SO-25H”, average particle size 0.5 μm
(8) Coupling agent / epoxysilane coupling agent: Nippon Unicar Co., Ltd. “A-187”
＜実施例１＞
１．樹脂組成物ワニスの調製
第１の硬化性樹脂として、シアネート樹脂Ａ１４．５重量部と、シアネート樹脂Ｂ１０重量部とを用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ３５重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材３９．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
<Example 1>
1. Preparation of Resin Composition Varnish As the first curable resin, 14.5 parts by weight of cyanate resin A and 10 parts by weight of cyanate resin B were used. As the second curable resin, 35 parts by weight of epoxy resin A was used. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 39.8 parts by weight of an inorganic filler and 0.2 parts by weight of a coupling agent were added and stirred for 10 minutes using a high-speed stirring device to obtain a resin composition varnish having a solid content of 60% by weight.
２．絶縁シートの製造
基材として、厚さ２５μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを用い、コンマコーター装置にて、乾燥後の絶縁シート厚さが５０μｍとなるように上記樹脂組成物ワニスを塗工し、１５０℃で５分間乾燥して基材付き絶縁シートを得た。
2. Production of insulating sheet Using a polyethylene terephthalate (PET) film having a thickness of 25 μm as a base material, the above-mentioned resin composition varnish was applied so that the insulating sheet thickness after drying was 50 μm in a comma coater device, It dried at 150 degreeC for 5 minute (s), and obtained the insulating sheet with a base material.
３．多層プリント配線板の製造
下記（１）〜（５）の工程により、内層回路基板の両面側に上記で得られた絶縁シート
を積層し、４層の多層プリント配線板を得た。
（１）所定の内層回路が両面に形成された内層回路基板（銅箔厚み１８μｍ、Ｌ／Ｓ＝１００／１００μｍ、クリアランスホール１ｍｍφ、３ｍｍφ、スリット２ｍｍ）の表裏に、上記で得られた絶縁シートを真空ラミネーター（日立化成社製 ＨＬＭ−Ｖ５７０）を用いて８０℃でロールラミネートし、１５０℃に設定した乾燥機中で３０分間加熱した。（２）炭酸ガスレーザを用いて、１００μｍのビアホールを形成し、内外層の接続部を設けた後、基材付き絶縁シートから基材を剥離した。
（３）内層回路基板と接合された絶縁シート表面を下記の工程でデスミア処理して、絶縁シートの表面に微小な凹凸を形成した。
（ア）膨潤：８０℃／１０分間（シプレイ社製・「ＭＬＢ−２１１」）
（イ）粗化：８０℃／１０分間（シプレイ社製・「プロモーター２１３Ａ、２１３Ｂ」）
（ウ）中和：５０℃／１０分間（シプレイ社製・「ニュートライザー２１６」）
（４）上記（３）で形成した凹凸面に、銅メッキを行い、所定の外層回路（回路厚み２０μｍ、Ｌ／Ｓ＝５０／５０μｍ）を形成した。
（５）温度２００℃で６０分間熱処理し、所定の導体パターンを有する４層多層プリント配線板を作製した。
3. Production of Multilayer Printed Wiring Board By the following steps (1) to (5), the insulating sheet obtained above was laminated on both sides of the inner layer circuit board to obtain a four-layer multilayer printed wiring board.
(1) Insulating sheet obtained above on the front and back of an inner layer circuit board (copper foil thickness 18 μm, L / S = 100/100 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm) on which predetermined inner layer circuits are formed on both sides Was roll-laminated at 80 ° C. using a vacuum laminator (HLM-V570 manufactured by Hitachi Chemical Co., Ltd.) and heated in a dryer set at 150 ° C. for 30 minutes. (2) A carbon dioxide laser was used to form a 100 μm via hole, and after providing the inner and outer layer connecting portions, the substrate was peeled from the insulating sheet with the substrate.
(3) The surface of the insulating sheet bonded to the inner layer circuit board was desmeared in the following steps to form minute irregularities on the surface of the insulating sheet.
(A) Swelling: 80 ° C./10 minutes (manufactured by Shipley, “MLB-211”)
(I) Roughening: 80 ° C./10 minutes (manufactured by Shipley, “Promoter 213A, 213B”)
(C) Neutralization: 50 ° C./10 minutes (manufactured by Shipley Co., Ltd., “New Trizer 216”)
(4) Copper plating was performed on the concavo-convex surface formed in (3) above to form a predetermined outer layer circuit (circuit thickness 20 μm, L / S = 50/50 μm).
(5) A heat treatment was performed at a temperature of 200 ° C. for 60 minutes to prepare a four-layer multilayer printed wiring board having a predetermined conductor pattern.
＜実施例２＞
第１の硬化性樹脂として、シアネート樹脂Ａ１５．５重量部を用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ２４重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材５９．７重量部、カップリング剤０．３重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Example 2>
As the first curable resin, 15.5 parts by weight of cyanate resin A was used. As the second curable resin, 24 parts by weight of epoxy resin A was used. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 59.7 parts by weight of an inorganic filler and 0.3 part by weight of a coupling agent were added and stirred for 10 minutes using a high-speed stirring device to obtain a resin composition varnish having a solid content of 60% by weight.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜実施例３＞
第１の硬化性樹脂として、シアネート樹脂Ａ２４．５重量部を用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ２５重量部を用いた。このほか、硬化性樹脂としてフェノキシ樹脂１０重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材３９．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Example 3>
As the first curable resin, 24.5 parts by weight of cyanate resin A was used. As the second curable resin, 25 parts by weight of epoxy resin A was used. In addition, 10 parts by weight of phenoxy resin was used as the curable resin. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 39.8 parts by weight of an inorganic filler and 0.2 parts by weight of a coupling agent were added and stirred for 10 minutes using a high-speed stirring device to obtain a resin composition varnish having a solid content of 60% by weight.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜実施例４＞
第１の硬化性樹脂として、シアネート樹脂Ａ１０重量部を用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ３４．５重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材５４．７重量部、カップリング剤０．３重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Example 4>
As the first curable resin, 10 parts by weight of cyanate resin A was used. As the second curable resin, 34.5 parts by weight of epoxy resin A was used. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 54.7 parts by weight of an inorganic filler and 0.3 part by weight of a coupling agent were added and stirred for 10 minutes using a high-speed stirrer to obtain a resin composition varnish having a solid content of 60% by weight.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜実施例５＞
第１の硬化性樹脂として、シアネート樹脂Ａ１９．５重量部と、シアネート樹脂Ｂ２０重量部とを用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ２０重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材３９．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Example 5>
As the first curable resin, 19.5 parts by weight of cyanate resin A and 20 parts by weight of cyanate resin B were used. As the second curable resin, 20 parts by weight of epoxy resin A was used. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 39.8 parts by weight of an inorganic filler and 0.2 parts by weight of a coupling agent were added and stirred for 10 minutes using a high-speed stirring device to obtain a resin composition varnish having a solid content of 60% by weight.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜実施例６＞
第１の硬化性樹脂として、シアネート樹脂Ａ２４．５重量部を用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ２０重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材５４．７重量部、カップリング剤０．３重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Example 6>
As the first curable resin, 24.5 parts by weight of cyanate resin A was used. As the second curable resin, 20 parts by weight of epoxy resin A was used. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 54.7 parts by weight of an inorganic filler and 0.3 part by weight of a coupling agent were added and stirred for 10 minutes using a high-speed stirrer to obtain a resin composition varnish having a solid content of 60% by weight.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜実施例７＞
第１の硬化性樹脂として、シアネート樹脂Ａ１９．５重量部を用いた。第２の硬化性樹脂として、エポキシ樹脂Ａ４５重量部を用いた。これに、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材３４．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、固形分６０重量％の樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Example 7>
As the first curable resin, 19.5 parts by weight of cyanate resin A was used. As the second curable resin, 45 parts by weight of epoxy resin A was used. This was mixed with 0.5 part by weight of a curing catalyst and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 34.8 parts by weight of an inorganic filler and 0.2 part by weight of a coupling agent were added and stirred for 10 minutes using a high speed stirring device to obtain a resin composition varnish having a solid content of 60% by weight.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜比較例１＞
エポキシ樹脂Ｂ２０重量部、フェノキシ樹脂４８重量部、硬化触媒２重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材２９．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Comparative Example 1>
20 parts by weight of epoxy resin B, 48 parts by weight of phenoxy resin, and 2 parts by weight of curing catalyst were blended and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 29.8 parts by weight of an inorganic filler and 0.2 part by weight of a coupling agent were added and stirred for 10 minutes using a high speed stirring device to obtain a resin composition varnish.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜比較例２＞
エポキシ樹脂Ａ２５重量部、エポキシ樹脂Ｂ２０重量部、フェノキシ樹脂２３重量部、硬化触媒２重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材２９．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Comparative example 2>
25 parts by weight of epoxy resin A, 20 parts by weight of epoxy resin B, 23 parts by weight of phenoxy resin, and 2 parts by weight of a curing catalyst were blended and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 29.8 parts by weight of an inorganic filler and 0.2 part by weight of a coupling agent were added and stirred for 10 minutes using a high speed stirring device to obtain a resin composition varnish.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
＜比較例３＞
シアネート樹脂Ａ２４．５重量部、シアネート樹脂Ｂ２５重量部、フェノキシ樹脂１０重量部、硬化触媒０．５重量部を配合し、メチルエチルケトンに溶解、分散させた。
さらに、無機充填材３９．８重量部、カップリング剤０．２重量部を添加して、高速攪拌装置を用いて１０分間攪拌して、樹脂組成物ワニスを得た。
この樹脂組成物ワニスを用いて、実施例１と同様にして絶縁シート及び多層プリント配線板を得た。
<Comparative Example 3>
24.5 parts by weight of cyanate resin A, 25 parts by weight of cyanate resin B, 10 parts by weight of phenoxy resin, and 0.5 parts by weight of a curing catalyst were blended and dissolved and dispersed in methyl ethyl ketone.
Furthermore, 39.8 parts by weight of an inorganic filler and 0.2 part by weight of a coupling agent were added and stirred for 10 minutes using a high speed stirring device to obtain a resin composition varnish.
Using this resin composition varnish, an insulating sheet and a multilayer printed wiring board were obtained in the same manner as in Example 1.
実施例及び、比較例で得られた絶縁シートと多層プリント配線板について、下記の評価を以下の方法で行った。得られた結果を表１に示す。 About the insulating sheet and multilayer printed wiring board obtained by the Example and the comparative example, the following evaluation was performed with the following method. The obtained results are shown in Table 1.
１．絶縁シートの評価方法
（１）示差走査熱量分析
示差走査熱量分析装置（ＴＡインスツルメント社製）を用いて、昇温速度１０℃／分で実施した。実施例１で得られた絶縁シートを分析した際のＤＳＣ曲線を図１に、比較例１で得られた絶縁シートを分析した際のＤＳＣ曲線を図２に示す。
ＤＳＣ曲線から、実施例については第１及び第２の発熱ピークを示す温度を読み取った。比較例については発熱ピークが一つであったので、そのピークを示す温度を読み取った。
1. Insulating Sheet Evaluation Method (1) Differential Scanning Calorimetry Analysis Using a differential scanning calorimeter (TA Instruments), the heating rate was 10 ° C./min. The DSC curve when analyzing the insulating sheet obtained in Example 1 is shown in FIG. 1, and the DSC curve when analyzing the insulating sheet obtained in Comparative Example 1 is shown in FIG.
From the DSC curve, the temperature showing the first and second exothermic peaks was read for the examples. Since the comparative example had one exothermic peak, the temperature indicating the peak was read.
（２）熱時弾性率、ガラス転移温度
絶縁シート１枚の両面側に、１８μｍ厚みの銅箔を積層して、真空プレス装置により、圧力２．５ＭＰａ、温度２００℃で９０分間加熱加圧成形を行った後、銅箔を両面全面エッチング除去して、絶縁シート硬化物を得た。
得られた絶縁シート硬化物から５×２５ｍｍの試料を作成した。これを用いて、ＤＭＡ装置（ＴＡインスツルメンツ社製）により、５℃／分で昇温して、２００℃及び２５０℃での貯蔵弾性率をそれぞれ測定し、ｔａｎδのピーク位置をガラス転移温度とした。
(2) Thermal modulus of elasticity, glass transition temperature 18 μm thick copper foil is laminated on both sides of one insulating sheet, and heated and pressed at a pressure of 2.5 MPa and a temperature of 200 ° C. for 90 minutes using a vacuum press. Then, the copper foil was entirely etched away on both sides to obtain a cured insulating sheet.
A 5 × 25 mm sample was prepared from the obtained cured insulating sheet. Using this, the temperature was raised at 5 ° C./min with a DMA apparatus (manufactured by TA Instruments), the storage elastic moduli at 200 ° C. and 250 ° C. were measured, and the peak position of tan δ was defined as the glass transition temperature. .
（３）線膨張係数
上記（２）で得られた絶縁シート硬化物から４×２０ｍｍの試料を作成した。これを用いて、ＴＭＡ装置（ＴＡインスツルメンツ社製）により、１０℃／分で昇温して、５０〜１５０℃の熱膨張率を測定した。
(3) Linear expansion coefficient A 4 × 20 mm sample was prepared from the cured insulating sheet obtained in (2) above. Using this, it heated up at 10 degree-C / min with the TMA apparatus (made by TA Instruments), and measured the thermal expansion coefficient of 50-150 degreeC.
（４）引張り強度
上記（２）で得られた絶縁シート硬化物から１２．５×１９０ｍｍの試料を作成した。これを用いて、ＪＩＳ Ｋ ７１６１ に準拠して試験速度５０ｍｍ／ｍｉｎで行った。
(4) Tensile strength A sample of 12.5 × 190 mm was prepared from the cured insulating sheet obtained in (2) above. Using this, it was carried out at a test speed of 50 mm / min according to JIS K 7161.
（５）誘電率、誘電正接
絶縁シートを、加熱加圧成形後の厚みが１ｍｍとなるように積層し、その両面側に、１８μｍ厚みの銅箔を積層して、真空プレス装置により、圧力２．５ＭＰａ、温度２００℃で９０分間加熱加圧成形を行った後、銅箔を両面全面エッチング除去して、絶縁シート硬化物を得た。
得られた絶縁シート硬化物から、９７×２５ｍｍ、５３×２５ｍｍ、３７×２５ｍｍの試料を作成した。これを用いて、トリプレート線路共振法により測定した。
(5) Dielectric constant, dielectric loss tangent Insulating sheets are laminated so that the thickness after heat and pressure molding is 1 mm, and 18 μm thick copper foil is laminated on both sides of the insulating sheet. After performing heat and pressure molding at 0.5 MPa and a temperature of 200 ° C. for 90 minutes, the copper foil was entirely etched away on both sides to obtain a cured insulating sheet.
Samples of 97 × 25 mm, 53 × 25 mm, and 37 × 25 mm were prepared from the obtained cured insulating sheet. Using this, measurement was performed by a triplate line resonance method.
２．多層プリント配線板の評価
（１）表面粗さ（外層回路作製時）
内層回路基板に接合後の絶縁シートの表面に微小な凹凸を形成した後、この面の表面粗さを、ＪＩＳ Ｂ ０６０１に準拠して、接触式表面粗さ計により測定し、基準長さ８ｍｍにおけるＲｍａｘ（最大高さ）と、Ｒａ（平均粗さ）で表示した。
2. Evaluation of multilayer printed wiring board (1) Surface roughness (when manufacturing outer layer circuit)
After forming minute irregularities on the surface of the insulating sheet after bonding to the inner circuit board, the surface roughness of this surface is measured with a contact surface roughness meter in accordance with JIS B 0601, and the reference length is 8 mm. Rmax (maximum height) and Ra (average roughness).
（２）成形性
多層プリント配線板を目視で観察し、成形ボイドの有無を確認した。
(2) Formability The multilayer printed wiring board was visually observed to check for the presence of molding voids.
（３）外層回路の形状
多層プリント配線板に形成した外層回路を観察した。符号は下記の通りである。
○：５０μｍ幅回路の剥離などがなく、良好。
×：５０μｍ幅回路の一部剥離が発生。
(3) Shape of outer layer circuit The outer layer circuit formed on the multilayer printed wiring board was observed. The symbols are as follows.
◯: Good with no peeling of the 50 μm width circuit.
×: Partial peeling of the 50 μm wide circuit occurred.
（４）外層回路の引き剥がし強さ
多層プリント配線板の外層回路（１０ｍｍ幅）の引き剥がし強さを、５箇所において、ＪＩＳ Ｋ ６９１１ に準拠して測定し、平均値を算出した。
(4) Peeling strength of outer layer circuit The peeling strength of the outer layer circuit (10 mm width) of the multilayer printed wiring board was measured in accordance with JIS K 6911 at five locations, and the average value was calculated.
（５）吸湿半田耐熱性
多層プリント配線板より、５０×５０ｍｍの試料を作製した。これを、１２５℃のプレッシャークッカーで２時間処理した後、２６０℃の半田層に１８０秒間浸漬して、ふくれ、はがれの有無を観察した。
(5) Hygroscopic solder heat resistance A 50 × 50 mm sample was prepared from a multilayer printed wiring board. This was treated with a pressure cooker at 125 ° C. for 2 hours and then immersed in a solder layer at 260 ° C. for 180 seconds to observe the presence or absence of blistering or peeling.
実施例１〜７は、示差走査熱量分析において、第１の発熱ピークと、これより高い温度に位置する第２の発熱ピークとを有する本発明の絶縁シートと、これを用いた多層プリント配線板であり、外層回路形成面の表面平滑性に優れ、外層回路の引き剥がし強さも充分な水準を有し、安定したものであった。
一方、比較例はいずれも、示差走査熱量分析において１つの発熱ピークしか有さないものであるが、比較例１〜２は、絶縁シートのＴｇが低く、熱時弾性率は測定できなかった。そして、外層回路形成面を粗化処理した際に、粗化が表面全体に進行して不均一で大きな凹凸しか形成できず、表面粗さが増大した。そして、形成した外層回路の引き剥がし強さが低下し、回路の一部には剥離が発生した。また、比較例３は、外層回路形成時に絶縁シートが実質的に完全に硬化していたため、粗化処理を行うことができず、外層回路を形成することもできなかった。
In Examples 1-7, in differential scanning calorimetry, the insulating sheet of the present invention having a first exothermic peak and a second exothermic peak located at a higher temperature, and a multilayer printed wiring board using the same Thus, the surface smoothness of the outer layer circuit formation surface was excellent, and the peel strength of the outer layer circuit was at a sufficient level and stable.
On the other hand, all of the comparative examples have only one exothermic peak in the differential scanning calorimetry, but in Comparative Examples 1 and 2, the Tg of the insulating sheet was low, and the thermal elastic modulus could not be measured. Then, when the outer layer circuit formation surface was roughened, the roughening progressed to the entire surface, so that only uneven and large irregularities could be formed, and the surface roughness increased. And the peeling strength of the formed outer layer circuit was lowered, and peeling occurred in a part of the circuit. In Comparative Example 3, since the insulating sheet was substantially completely cured when the outer layer circuit was formed, the roughening treatment could not be performed and the outer layer circuit could not be formed.
本発明の絶縁シートは、特に、高密度配線化に対応でき、信頼性の高い多層プリント配線板を製造するのに好適に用いることができるものである。
そして、本発明の多層プリント配線板は、このような高密度集積化、高密度実装化に対応できる多層プリント配線配線板を提供することができる。
In particular, the insulating sheet of the present invention can be used for manufacturing a highly reliable multilayer printed wiring board that can cope with high density wiring.
And the multilayer printed wiring board of this invention can provide the multilayer printed wiring wiring board which can respond to such high-density integration and high-density mounting.
Claims (10)
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| JP2004097528A JP5055683B2 (en) | 2004-03-30 | 2004-03-30 | Insulating sheet, insulating sheet with substrate, and multilayer printed wiring board |
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| JP2004097528A JP5055683B2 (en) | 2004-03-30 | 2004-03-30 | Insulating sheet, insulating sheet with substrate, and multilayer printed wiring board |
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| JP2010102976A Division JP5168312B2 (en) | 2010-04-28 | 2010-04-28 | Multilayer printed circuit board manufacturing method |
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