JP2007224283A - Resin composition, prepreg and metal foil-clad laminate for print wiring board - Google Patents
Resin composition, prepreg and metal foil-clad laminate for print wiring board Download PDFInfo
- Publication number
- JP2007224283A JP2007224283A JP2007005654A JP2007005654A JP2007224283A JP 2007224283 A JP2007224283 A JP 2007224283A JP 2007005654 A JP2007005654 A JP 2007005654A JP 2007005654 A JP2007005654 A JP 2007005654A JP 2007224283 A JP2007224283 A JP 2007224283A
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- JP
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- Prior art keywords
- compound
- resin composition
- phenol
- cyanate
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- -1 cyanate compound Chemical class 0.000 claims abstract description 111
- 239000003822 epoxy resin Substances 0.000 claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 57
- 239000004643 cyanate ester Substances 0.000 claims abstract description 36
- 150000001913 cyanates Chemical class 0.000 claims abstract description 30
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229920001230 polyarylate Polymers 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004973 liquid crystal related substance Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000009477 glass transition Effects 0.000 abstract description 12
- 238000009413 insulation Methods 0.000 abstract description 10
- 238000005553 drilling Methods 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000002966 varnish Substances 0.000 description 27
- 239000002585 base Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 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 5
- 239000000203 mixture Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000000243 solution 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 3
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- CDFCBRMXZKAKKI-UHFFFAOYSA-N 2-hydroxybenzaldehyde;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1C=O CDFCBRMXZKAKKI-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- JNCRKOQSRHDNIO-UHFFFAOYSA-N [4-[(4-cyanato-3,5-dimethylphenyl)methyl]-2,6-dimethylphenyl] cyanate Chemical compound CC1=C(OC#N)C(C)=CC(CC=2C=C(C)C(OC#N)=C(C)C=2)=C1 JNCRKOQSRHDNIO-UHFFFAOYSA-N 0.000 description 1
- MGURRWJWGJUVEM-UHFFFAOYSA-N [4-[2,6-di(propan-2-yl)phenyl]phenyl] cyanate Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C1=CC=C(OC#N)C=C1 MGURRWJWGJUVEM-UHFFFAOYSA-N 0.000 description 1
- INHGSGHLQLYYND-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OC#N)C=C1 INHGSGHLQLYYND-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 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
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、樹脂組成物、プリプレグ及びプリント配線板用金属箔張積層板に関し、詳しくは低誘電率、低吸水で、ガラス転移温度（Ｔｇ）が高く、絶縁信頼性、耐燃性に優れた、しかも、ドリル切削時の穴壁粗さが小さくかつドリル刃の磨耗が少ないプリント配線板用金属箔張積層板及びそれを得るための樹脂組成物及びプリプレグに関する。 The present invention relates to a resin composition, a prepreg, and a metal foil-clad laminate for printed wiring boards. Specifically, it has a low dielectric constant, low water absorption, high glass transition temperature (Tg), and excellent insulation reliability and flame resistance. In addition, the present invention relates to a metal foil-clad laminate for printed wiring boards having a small hole wall roughness during drill cutting and little wear on the drill blade, and a resin composition and prepreg for obtaining the same.
電子機器用のプリント配線板として、主にエポキシ樹脂を用いた積層板が広く使用されている。しかしながら、電子機器における実装密度の増大に伴うパターンの細密化、表面実装方式の定着並びに信号伝播速度の高速化と取り扱う信号の高周波化に伴い、プリント配線板材料の低誘電損失化、さらに耐熱性及び耐電食性の向上が強く要望されている。また、近年の環境問題に対する意識の高まりを受けて、ハロゲン系の難燃剤を使用せず、非ハロゲン系（ハロゲンフリー）であって、かつ良好な難燃性を有する材料が強く要望されている。 As a printed wiring board for electronic equipment, a laminated board mainly using an epoxy resin is widely used. However, as the mounting density of electronic equipment increases, the pattern density becomes finer, the surface mounting method is fixed, the signal propagation speed is increased, and the signal frequency is increased. There is a strong demand for improvement in resistance to electric corrosion. Further, in response to the recent increase in awareness of environmental issues, there is a strong demand for materials that do not use halogen-based flame retardants, are non-halogen-based (halogen-free), and have good flame retardancy. .
エポキシ樹脂を硬化剤とし、スチレンと無水マレイン酸からなる共重合樹脂を使用する樹脂組成物又は積層板の事例としては、例えば、可撓性付与のために、反応性エポキシ希釈剤とアクリロニトリル−ブタジエン共重合体とを必須とする、可撓性エポキシ樹脂、スチレンと無水マレイン酸からなる共重合樹脂等による可撓性プリント配線板が知られている（例えば特許文献１参照）。 Examples of a resin composition or laminate using an epoxy resin as a curing agent and a copolymer resin composed of styrene and maleic anhydride include, for example, a reactive epoxy diluent and acrylonitrile-butadiene for imparting flexibility. There is known a flexible printed wiring board made of a flexible epoxy resin, a copolymer resin composed of styrene and maleic anhydride, which requires a copolymer (for example, see Patent Document 1).
プリント配線板用金属箔張積層板としては、電気絶縁性樹脂（以下、ベース樹脂という）と繊維基材とからなる積層板が用いられている。ベース樹脂としては、通常、フェノール樹脂、エポキシ樹脂、ポリイミド樹脂、ビスマレイミドートリアジン樹脂等が用いられている。繊維基材としては、紙、例えば、クラフト紙やリンター紙、ガラス繊維の布、例えば、ガラス織布やガラス不織布、有機繊維の布、例えば、アラミド不織布等が用いられている。特にコンピュータや産業用電子機器のプリント配線板用には、エポキシ樹脂をベース樹脂とし、ガラス繊維布を繊維基材とする積層板が広く用いられている。 As a metal foil-clad laminate for a printed wiring board, a laminate comprising an electrically insulating resin (hereinafter referred to as a base resin) and a fiber substrate is used. As the base resin, phenol resin, epoxy resin, polyimide resin, bismaleimide-triazine resin or the like is usually used. As the fiber substrate, paper, for example, craft paper or linter paper, glass fiber cloth, for example, glass woven cloth, glass nonwoven cloth, organic fiber cloth, for example, aramid nonwoven cloth, or the like is used. In particular, for printed wiring boards of computers and industrial electronic devices, laminated boards having epoxy resin as a base resin and glass fiber cloth as a fiber base material are widely used.
近年、コンピュータ等の情報処理機器にみられる高速演算化、及び、移動体通信や衛星通信等にみられる高周波化に対応するため、低誘電率の積層板が求められるようになっており、積層板を低誘電率とするためにベース樹脂と繊維基材に低誘電率の材料を用いられている。
低誘電率のベース樹脂としては、エポキシ樹脂にフェノール類付加ジエン系重合体を配合した樹脂組成物、低誘電率ポリイミド樹脂等が知られている。また、低誘電率の繊維基材としては、Ｓガラス、Ｄガラスのような低誘電率のガラス繊維基材を使用することが知られている。
In recent years, in order to cope with the high-speed computation found in information processing equipment such as computers and the high frequency found in mobile communications and satellite communications, low dielectric constant laminates have been required. In order to make the plate have a low dielectric constant, a low dielectric constant material is used for the base resin and the fiber base material.
As a low dielectric constant base resin, a resin composition in which a phenol addition diene polymer is blended with an epoxy resin, a low dielectric constant polyimide resin, and the like are known. As a low dielectric constant fiber base material, it is known to use a low dielectric constant glass fiber base material such as S glass or D glass.
しかしながら，ベース樹脂にエポキシ樹脂にフェノール類付加ジエン系重合体を配合した樹脂組成物、低誘電率ポリイミド樹脂を用いた場合では、繊維基材にＤガラス又はＳガラスを用いても積層板は誘電率３．６〜４．０（１ＧＨｚ）までしか下がらないのみでなく、ＳガラスやＤガラスを使用するため、ドリル切削時の穴壁粗さが大きくなり、また、ドリル摩耗量も大きくなる。また、繊維基材にアラミド不織布を使用すると、吸水による誘電率変化や吸湿はんだ耐熱が極端に低下するという欠点がある。
本発明の目的は、こうした現状に鑑み、低誘電率、低吸水で、ガラス転移温度（Ｔｇ）が高く、絶縁信頼性、耐燃性に優れ、しかも、ドリル切削時の穴壁粗さが小さくかつドリル刃の磨耗が少ないプリント配線板用金属箔張積層板及びそれを得るための樹脂組成物及びプリプレグを提供することである。 In view of the current situation, the object of the present invention is low dielectric constant, low water absorption, high glass transition temperature (Tg), excellent insulation reliability, flame resistance, and small hole wall roughness during drill cutting. It is to provide a metal foil-clad laminate for a printed wiring board with less wear on a drill blade, and a resin composition and prepreg for obtaining the same.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定のフェノール化合物とシアネート化合物を反応させて得られたフェノール変性シアネートエステルオリゴマーにエポキシ樹脂が配合された樹脂組成物が上記目的に沿うものであり、プリント配線板用金属箔張積層板が有利に製造されることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to achieve the above object, the present inventors have obtained a resin composition in which an epoxy resin is blended with a phenol-modified cyanate ester oligomer obtained by reacting a specific phenol compound with a cyanate compound. It has been found that the metal foil-clad laminate for printed wiring boards is produced advantageously in accordance with the above object. The present invention has been completed based on such findings.
すなわち本発明は、以下の樹脂組成物、プリプレグおよびプリント配線板用金属箔張積層板を提供するものである。
１．分子中に２個以上のシアナト基を含有するシアネート化合物（ａ1）と下記一般式（１）で表されるフェノール化合物（ａ2）を反応させて得られたフェノール変性シアネートエステルオリゴマー（Ａ）に、分子中に２個以上のエポキシ基を含有するエポキシ樹脂（Ｂ）が配合された樹脂組成物であって、シアネート化合物（ａ1）のシアナト基に対するフェノール化合物（ａ2）のフェノール性水酸基の当量比（水酸基／シアナト基比）が０．０１〜０．０３の範囲であることを特徴とする樹脂組成物。
That is, the present invention provides the following resin composition, prepreg, and metal foil-clad laminate for printed wiring boards.
1. Phenol-modified cyanate ester oligomer (A) obtained by reacting a cyanate compound (a 1 ) containing two or more cyanato groups in the molecule with a phenol compound (a 2 ) represented by the following general formula (1) And a phenolic hydroxyl group of the phenol compound (a 2 ) with respect to the cyanate group of the cyanate compound (a 1 ), wherein the epoxy resin (B) contains two or more epoxy groups in the molecule. An equivalent ratio (hydroxyl group / cyanato group ratio) in the range of 0.01 to 0.03.
（式（１）中、Ｒ1およびＲ2は水素原子又はメチル基を表し、それぞれ同じでも異なっていても良い。また、ｎは１〜３の整数を表す。）
２．更に、一般式（１）で表されるフェノール化合物（Ｃ）を配合し、シアネート化合物（ａ1）のシアナト基に対するフェノール化合物（ａ2）のフェノール性水酸基とフェノール化合物（Ｃ）のフェノール性水酸基との合計量の配合当量比（水酸基／シアナト基比）が０．０４〜０．２９の範囲である上記１の樹脂組成物。
３．フェノール変性シアネートエステルオリゴマー（Ａ）が、シアネート化合物（ａ1）の転化率が１０〜７０％となるように反応させて得られたものである上記１又は２の樹脂組成物。
４．フェノール変性シアネートエステルオリゴマー（Ａ）の数平均分子量が３８０〜２５００である上記１ないし３のいずれかの樹脂組成物。
５．シアネート化合物（ａ1）が、下記一般式（２）で表される化合物である上記１〜４のいずれかの樹脂組成物。
(In Formula (1), R 1 and R 2 represent a hydrogen atom or a methyl group, and may be the same or different. N represents an integer of 1 to 3)
2. Further, by blending the phenol compound represented by the general formula (1) (C), the phenolic hydroxyl group of cyanate compound (a 1) phenolic compound to the cyanato group of the phenolic hydroxyl groups and phenolic compound (a 2) (C) The resin composition as described in 1 above, wherein the total equivalent weight ratio (hydroxyl group / cyanato group ratio) is in the range of 0.04 to 0.29.
3. 3. The resin composition according to 1 or 2 above, wherein the phenol-modified cyanate ester oligomer (A) is obtained by reacting the cyanate compound (a 1 ) so that the conversion of the cyanate compound (a 1 ) is 10 to 70%.
4). 4. The resin composition according to any one of 1 to 3 above, wherein the number average molecular weight of the phenol-modified cyanate ester oligomer (A) is 380 to 2500.
5). The resin composition according to any one of 1 to 4 above, wherein the cyanate compound (a 1 ) is a compound represented by the following general formula (2).
（式中、Ｒ5はハロゲンで置換されていてもよい炭素数１〜３のアルキレン基、アルキリデン基、下記一般式（２ａ）、又は一般式（２ｂ）で表される基を表し、Ｒ6〜Ｒ9は、水素原子又は炭素数１〜３のアルキル基を表し、それぞれ同じでも異なっていても良い。） (Wherein, R 5 represents a group represented by C 1-3 alkylene group which may be substituted with a halogen, an alkylidene group, following general formula (2a), or the general formula (2b), R 6 to R 9 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, it may be the same or different.)
（式中、Ｒ10およびＲ11は炭素数１〜１１のアルキル基を表し、それぞれ同じでも異なっていても良い。）
６．エポキシ樹脂（Ｂ）として、下記一般式（３）で表されるジシクロペンタジエン骨格を有するジシクロペンタジエン−フェノール重付加物から誘導されるエポキシ樹脂を含む上記１〜５のいずれかの樹脂組成物。
(In the formula, R 10 and R 11 represent an alkyl group having 1 to 11 carbon atoms, and may be the same or different.)
6). The resin composition according to any one of 1 to 5 above, which contains an epoxy resin derived from a dicyclopentadiene-phenol polyaddition product having a dicyclopentadiene skeleton represented by the following general formula (3) as the epoxy resin (B): .
（式中ｎは０又は正の整数を表す。）
７．エポキシ樹脂（Ｂ）として、臭素化ビスフェノールＡ型エポキシ樹脂を含む上記１〜５のいずれかの樹脂組成物。
８． シアネート化合物（ａ1）１００質量部に対するエポキシ樹脂（Ｂ）の配合量が５０〜３００質量部である上記１〜７の樹脂組成物。
９．更に硬化促進剤（Ｄ）として、鉄、銅、亜鉛、コバルト、ニッケル、マンガンおよびスズから選ばれる少なくとも一種の金属の有機金属塩又は該金属の有機金属錯体と、イミダゾール類化合物を配合する上記１〜８の樹脂組成物。
１０．イミダゾール類化合物が下記一般式（４）で表される化合物である上記９の樹脂組成物。
(In the formula, n represents 0 or a positive integer.)
7). The resin composition according to any one of the above 1 to 5, comprising a brominated bisphenol A type epoxy resin as the epoxy resin (B).
8). The resin composition according to the above 1 to 7, wherein the compounding amount of the epoxy resin (B) with respect to 100 parts by mass of the cyanate compound (a 1 ) is 50 to 300 parts by mass.
9. Furthermore, as the curing accelerator (D), at least one kind of metal organic metal salt selected from iron, copper, zinc, cobalt, nickel, manganese and tin or an organic metal complex of the metal and an imidazole compound are blended. ~ 8 resin composition.
10. 9. The resin composition according to 9 above, wherein the imidazole compound is a compound represented by the following general formula (4).
（式中、Ｒ12は炭素数１〜１１のアルキル基又はフェニル基を表す。）
１１．シアネート化合物（ａ1）１００質量部に対する硬化促進剤（Ｄ）の配合量が０．１〜５質量部である上記９又は１０の樹脂組成物。
１２．更に酸化防止剤（Ｅ）として、フェノール系酸化防止剤または硫黄有機化合物系酸化防止剤の中から選ばれる１種以上の酸化防止剤を含む上記１〜１１のいずれかの樹脂組成物。
１３．シアネート化合物（ａ1）１００質量部に対する酸化防止剤（Ｅ）の配合量が０．１〜２０質量部である上記１２の樹脂組成物。
１４．上記１〜１３のいずれかの樹脂組成物を繊維基材に含浸又は塗工した後、Ｂステージ化して得られるプリプレグ。
１５．上記１４のプリプレグの少なくとも一方に金属箔を重ねた後、加熱加圧して得られたプリント配線板用金属箔張積層板。
１６．繊維基材が、液晶ポリアリレート繊維基材である上記１５のプリント配線板用金属箔張積層板。
(In the formula, R 12 represents an alkyl group having 1 to 11 carbon atoms or a phenyl group.)
11. The resin composition according to 9 or 10 above, wherein the amount of the curing accelerator (D) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the cyanate compound (a 1 ).
12 Furthermore, as antioxidant (E), the resin composition in any one of said 1-11 containing 1 or more types of antioxidant chosen from phenol type antioxidant or sulfur organic compound type antioxidant.
13. 12. The resin composition as described in 12 above, wherein the amount of the antioxidant (E) to be added is from 0.1 to 20 parts by mass per 100 parts by mass of the cyanate compound (a 1 ).
14 A prepreg obtained by impregnating or coating a fiber base material with any of the resin compositions described in 1 to 13 above and then forming a B-stage.
15. A metal foil-clad laminate for a printed wiring board, obtained by heating and pressing a metal foil on at least one of the prepregs of 14.
16. 15. The metal foil-clad laminate for printed wiring board as described in 15 above, wherein the fiber substrate is a liquid crystal polyarylate fiber substrate.
本発明の樹脂組成物は、低誘電率、低吸水で、ガラス転移温度（Ｔｇ）が高く、絶縁信頼性、耐燃性に優れたプリント配線板用金属箔張積層板を提供することができる。
また、繊維基材として液晶ポリアリレート繊維基材を用いることにより、ドリル切削時の穴壁粗さが小さくかつドリル刃の磨耗が少ないプリント配線板用金属箔張積層板を提供することができる。
The resin composition of the present invention can provide a metal foil-clad laminate for printed wiring boards that has a low dielectric constant, low water absorption, high glass transition temperature (Tg), and excellent insulation reliability and flame resistance.
Further, by using a liquid crystal polyarylate fiber base material as the fiber base material, it is possible to provide a metal foil-clad laminate for printed wiring boards that has a small hole wall roughness during drill cutting and little wear on the drill blade.
先ず、本発明の樹脂組成物は、分子中に２個以上のシアナト基を含有するシアネート化合物（ａ1）と下記一般式（１）で表されるフェノール化合物（ａ2）を反応させて得られたフェノール変性シアネートエステルオリゴマー（Ａ）に、分子中に２個以上のエポキシ基を含有するエポキシ樹脂（Ｂ）が配合されたものである。 First, the resin composition of the present invention is obtained by reacting a cyanate compound (a 1 ) containing two or more cyanate groups in the molecule with a phenol compound (a 2 ) represented by the following general formula (1). The obtained phenol-modified cyanate ester oligomer (A) is blended with an epoxy resin (B) containing two or more epoxy groups in the molecule.
（式（１）中、Ｒ1およびＲ2は水素原子又はメチル基を表し、それぞれ同じでも異なっていても良い。また、ｎは１〜３の整数を表す。）
本発明の樹脂組成物に用いる分子中に２個以上のシアナト基を含有するシアネート化合物（ａ1）は、特に限定されるものではないが、下記の一般式（２）で表されるシアネート化合物が好ましい。
(In Formula (1), R 1 and R 2 represent a hydrogen atom or a methyl group, and may be the same or different. N represents an integer of 1 to 3)
The cyanate compound (a 1 ) containing two or more cyanato groups in the molecule used in the resin composition of the present invention is not particularly limited, but is a cyanate compound represented by the following general formula (2). Is preferred.
（式中、Ｒ5はハロゲンで置換されていてもよい炭素数１〜３のアルキレン基、下記一般式（２ａ）、又は一般式（２ｂ）で表される基を表し、Ｒ6〜Ｒ9は、水素原子又は炭素数１〜３のアルキル基を表し、それぞれ同じでも異なっていても良い。） (In the formula, R 5 represents an alkylene group having 1 to 3 carbon atoms which may be substituted with halogen, a group represented by the following general formula (2a) or general formula (2b), and R 6 to R 9. Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, which may be the same or different.
このような分子中に２個以上のシアナト基を含有するシアネート化合物（ａ1）の具体例としては２，２−ビス（４−シアナトフェニル）プロパン、ビス（３，５−ジメチル−４−シアナトフェニル）メタン、２，２−ビス（４−シアナトフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン、α，α'−ビス（４−シアナトフェニル）−ｍ−ジイソプロピルベンゼン、フェノール付加ジシクロペンタジエン重合体のシアネートエステル化物などが挙げられ、これらは１種類又は２種類以上を混合して用いても良い。 Specific examples of the cyanate compound (a 1 ) containing two or more cyanate groups in the molecule include 2,2-bis (4-cyanatophenyl) propane and bis (3,5-dimethyl-4- Cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m -Diisopropylbenzene, a cyanate esterified product of a phenol-added dicyclopentadiene polymer, and the like, and these may be used alone or in combination of two or more.
本発明における一般式（１）で表されるフェノール化合物（ａ2）としては、ｐ−（α−クミル）フェノール、ｐ−ｔｅｒｔ−オクチルフェノール、モノ（又はトリ）（α−メチルベンジル）フェノールなどが挙げられる。これら（Ｂ）フェノール化合物は、１種類単独及び２種類以上を混合しても良い。 Examples of the phenol compound (a 2 ) represented by the general formula (1) in the present invention include p- (α-cumyl) phenol, p-tert-octylphenol, mono (or tri) (α-methylbenzyl) phenol, and the like. Can be mentioned. These (B) phenol compounds may be used alone or in combination of two or more.
分子中に２個以上のシアナト基を含有するシアネート化合物（ａ1）と一般式（１）で表されるフェノール化合物（ａ2）を反応させてフェノール変性シアネートエステルオリゴマー（Ａ）を得る際のフェノール化合物（ａ2）の配合量は、シアネート化合物（ａ1）のシアナト基１当量に対する式（１）で表されるフェノール化合物（ａ2）のフェノール性水酸基の当量比（水酸基／シアナト基比）で、０．０１〜０．０３の範囲とする必要がある。
水酸基／シアナト基比を０．０１以上とすることにより十分な誘電率が得られ、また水酸基／シアナト基比を０．０３以下とすることにより、誘電率の悪化や吸水率の上昇、ワニス作製時にワニスの粘度が増化を回避することができる。
When a phenol-modified cyanate ester oligomer (A) is obtained by reacting a cyanate compound (a 1 ) containing two or more cyanate groups in the molecule with a phenol compound (a 2 ) represented by the general formula (1) phenolic compounds amount of (a 2) is cyanate compound (a 1) the equivalent ratio of phenolic hydroxyl groups (hydroxyl / cyanato group ratio of the phenol compound represented by the formula (1) to the cyanato group 1 equivalent of (a 2) of ) In the range of 0.01 to 0.03.
Sufficient dielectric constant can be obtained by setting the hydroxyl group / cyanato group ratio to 0.01 or more, and by setting the hydroxyl group / cyanato group ratio to 0.03 or less, the dielectric constant deteriorates, the water absorption increases, and the varnish is produced. Sometimes an increase in the viscosity of the varnish can be avoided.
本発明で用いられるシアネート化合物（ａ1）とフェノール化合物（ａ2）を反応させて得られるフェノール変性シアネートエステルオリゴマー（Ａ）は、シアネート化合物（ａ1）が単独で環化反応によりトリアジン環を形成するシアネートエステルオリゴマー（主にシアネート化合物の３、５、７、９及び１１量体を含む）とシアネート化合物（ａ1）のシアナト基にフェノール化合物（ａ2）のフェノール性水酸基が付加したイミドカーボネート化変性オリゴマーとの混合物であることが好ましい。例えばトリアジン環から伸びる３つの鎖のうち１つまたは２つが１価フェノール化合物に由来する分子に置き換わることにより、シアネート化合物の単独オリゴマーよりも架橋点が少ない変性オリゴマーとの混合オリゴマーとなる。 In the phenol-modified cyanate ester oligomer (A) obtained by reacting the cyanate compound (a 1 ) and the phenol compound (a 2 ) used in the present invention, the cyanate compound (a 1 ) alone has a triazine ring formed by a cyclization reaction. formed to cyanate ester oligomer (mainly 3, 5, 7, 9 and 11 containing an amount of cyanate compound) imide phenolic hydroxyl group is added to the cyanate compound (a 1) a phenolic compound cyanato group (a 2) A mixture with a carbonated modified oligomer is preferred. For example, by replacing one or two of the three chains extending from the triazine ring with a molecule derived from a monohydric phenol compound, a mixed oligomer with a modified oligomer having fewer crosslinking points than a single oligomer of a cyanate compound is obtained.
シアネート化合物（ａ1）とフェノール化合物（ａ2）を反応させて得られるフェノール変性シアネートエステルオリゴマー（Ａ）を製造する際には、反応を促進させる触媒機能を有する化合物を用いることが好ましい。シアネート化合物（ａ1）とフェノール化合物（ａ2）との反応を促進させる触媒機能を有する化合物としては、鉄、銅、亜鉛、コバルト、ニッケル、マンガン、スズから選ばれる少なくとも一種の金属の有機金属塩及び該金属の有機金属錯体等が挙げられる。 When producing the phenol-modified cyanate ester oligomer (A) obtained by reacting the cyanate compound (a 1 ) and the phenol compound (a 2 ), it is preferable to use a compound having a catalytic function for promoting the reaction. The compound having a catalytic function for promoting the reaction between the cyanate compound (a 1 ) and the phenol compound (a 2 ) is an organic metal of at least one metal selected from iron, copper, zinc, cobalt, nickel, manganese, and tin. Examples thereof include salts and organometallic complexes of the metal.
本発明におけるフェノール変性シアネートエステルオリゴマー（Ａ）は、シアネート化合物（ａ1）の転化率を１０〜７０％となるように反応させて得られることが好ましい。さらにシアネート化合物（ａ1）の転化率として２０〜７０％がより好ましい。シアネート化合物（ａ1）の転化率を１０％以上とすることにより、シアネート化合物（ａ1）は結晶性が高いためにフェノール変性シアネートエステルオリゴマー（Ａ）を溶剤に溶解しワニス化した際に溶剤中にシアネート化合物モノマーが再結晶するのを回避することができる。また、シアネート化合物（ａ1）の転化率を７０％以下とすることにより、ワニスとした時の粘度が高くなって繊維基材等への含浸性が低下しプリプレグ表面の平滑性が失われることや、ゲル化時間が塗工作業上問題となるまで短くなったり、ワニスの保存安定性（ポットライフ）が失われることを回避することができる。 The phenol-modified cyanate ester oligomer (A) in the present invention is preferably obtained by reacting the cyanate compound (a 1 ) so that the conversion rate is 10 to 70%. Further, the conversion rate of the cyanate compound (a 1 ) is more preferably 20 to 70%. By setting the conversion rate of the cyanate compound (a 1 ) to 10% or more, the cyanate compound (a 1 ) has high crystallinity, so the phenol-modified cyanate ester oligomer (A) is dissolved in a solvent to form a varnish. It is possible to avoid recrystallization of the cyanate compound monomer. In addition, by setting the conversion rate of the cyanate compound (a 1 ) to 70% or less, the viscosity of the varnish is increased, the impregnation property to the fiber base material is lowered, and the smoothness of the prepreg surface is lost. In addition, it is possible to avoid the gelation time from being shortened until it becomes a problem in the coating work, and the loss of storage stability (pot life) of the varnish.
さらに、フェノール変性シアネートエステルオリゴマー（Ａ）は、数平均分子量が３８０〜２５００であることが好ましく、より好ましくは、８００〜２０００である。数平均分子量を３８０以上とすることにより、シアネート化合物は結晶性が高いためにフェノール変性シアネートエステルオリゴマー（Ａ）を溶剤に溶解しワニス化した溶剤中にシアネート化合物モノマーが再結晶するのを回避することができる。また、数平均分子量を２５００以下とすることにより、ワニスとした時の粘度が高くなり繊維基材等への含浸性が低下しプリプレグ表面の平滑性が失われることや、ゲル化時間が塗工作業上問題となるまで短くなったり、ワニスの保存安定性（ポットライフ）が失われることを回避することができる。 Furthermore, the phenol-modified cyanate ester oligomer (A) preferably has a number average molecular weight of 380 to 2500, more preferably 800 to 2000. By setting the number average molecular weight to 380 or more, the cyanate compound has high crystallinity, so that the phenol-modified cyanate ester oligomer (A) is dissolved in the solvent to avoid recrystallization of the cyanate compound monomer in the varnished solvent. be able to. In addition, by setting the number average molecular weight to 2500 or less, the viscosity when used as a varnish is increased, the impregnation property to the fiber base material is lowered, the smoothness of the prepreg surface is lost, and the gelation time is applied. It is possible to avoid shortening until it becomes a problem in work and losing storage stability (pot life) of the varnish.
本発明の樹脂組成物に用いられる分子中に２個以上のエポキシ基を含有するエポキシ樹脂（Ｂ）は、下記一般式（３）で表されるジシクロペンタジエン骨格を含有するジシクロペンタジエン−フェノール重付加物から誘導されるエポキシ樹脂(ｂ1)を含み、これと他の１分子中に２個以上のエポキシ基をもったエポキシ樹脂(ｂ2)を併用することが好ましい。 The epoxy resin (B) containing two or more epoxy groups in the molecule used in the resin composition of the present invention is a dicyclopentadiene-phenol containing a dicyclopentadiene skeleton represented by the following general formula (3). They include epoxy resins derived from polyaddition product (b 1), it is preferable to use epoxy resin (b 2) having two or more epoxy groups in this and in other one molecule.
（式中ｎは０又は正の整数を表す。）
エポキシ樹脂(ｂ2)としては、ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾール型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールサリチルアルデヒドノボラック型エポキシ樹脂等が挙げられる。
エポキシ樹脂(ｂ1)とエポキシ樹脂(ｂ2)を併用する場合の配合量は特に限定されるものではないが、分子中に２個以上のエポキシ基を含有するエポキシ樹脂（Ｂ）の全配合量の少なくとも１５質量％以上がエポキシ樹脂(ｂ1)であることが好ましい。１５質量％以上とすることにより、著しいガラス転移温度（Ｔｇ）の低下や、吸水率が上昇するのを回避することができる。
(In the formula, n represents 0 or a positive integer.)
Examples of the epoxy resin (b 2 ) include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, biphenyl type epoxy resin, phenol salicylaldehyde novolak type epoxy resin and the like.
The compounding amount in the case of using the epoxy resin (b 1 ) and the epoxy resin (b 2 ) is not particularly limited, but the total compounding of the epoxy resin (B) containing two or more epoxy groups in the molecule It is preferable that at least 15% by mass or more of the amount is the epoxy resin (b 1 ). By setting it as 15 mass% or more, it can avoid that a remarkable glass transition temperature (Tg) fall and a water absorption rate rise.
また、樹脂の耐燃性を確保するためは、エポキシ樹脂(ｂ2)として、臭素化エポキシ樹脂を配合することが好ましい。臭素化エポキシ樹脂としては、例えば臭素化ビスフェノールＡ型エポキシ樹脂や臭素化フェノールノボラック型エポキシ樹脂が挙げられ、特に誘電率の点から臭素化ビスフェノールＡ型エポキシ樹脂を配合することが好ましい。臭素化エポキシ樹脂の配合量は、全樹脂に対する臭素含有量が１０質量％以上となるようにすることが好ましい。 In order to ensure the flame resistance of the resin, the epoxy resin (b 2), it is preferable to blend a brominated epoxy resin. Examples of brominated epoxy resins include brominated bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins, and it is particularly preferable to blend brominated bisphenol A type epoxy resins from the viewpoint of dielectric constant. The blending amount of the brominated epoxy resin is preferably such that the bromine content with respect to the total resin is 10% by mass or more.
本発明の樹脂組成物におけるエポキシ樹脂（Ｂ）の配合量は、分子中に２個以上のシアナト基を含有するシアネート類化合物（ａ1）１００質量部に対してエポキシ樹脂（Ｂ）を５０〜３００質量部とすることが好ましい。５０質量部以上とすることにより吸湿時の耐熱性が悪化するのを回避することができ、３００質量部以下とすることにより誘電率の悪化やガラス転移温度（Ｔｇ）が低下するのを回避することができる。 The compounding amount of the epoxy resin (B) in the resin composition of the present invention is such that the epoxy resin (B) is 50 to 100 parts by mass of the cyanate compound (a 1 ) containing two or more cyanato groups in the molecule. It is preferable to set it as 300 mass parts. By setting it as 50 mass parts or more, it can avoid that the heat resistance at the time of moisture absorption deteriorates, and by setting it as 300 mass parts or less, it avoids that a dielectric constant deterioration and a glass transition temperature (Tg) fall. be able to.
本発明の樹脂組成物において、誘電率や吸水性を向上させるために、適正な当量比（水酸基／シアナト基比）を保ちながら、フェノール化合物（ａ1）とシアネート化合物（ａ1）を反応させてフェノール変性シアネートエステルオリゴマー（Ａ）とした後、更に、フェノール化合物（Ｃ）を配合し、シアネート化合物（ａ1）のシアナト基に対するフェノール化合物（ａ2）のフェノール性水酸基とフェノール化合物（Ｃ）のフェノール性水酸基との合計量の配合当量比（水酸基／シアナト基比）が０．０４〜０．２９の範囲とすることが好ましい。水酸基／シアナト基比を０．２９以下とすることにより誘電率の悪化及び吸湿時の耐熱性が悪化するのを回避することができる。
なお、樹脂組成物作製時に配合するフェノール化合物（Ｃ）は一般式（１）で表されるものであるが、フェノール変性シアネートエステルオリゴマー（Ａ）作製時に反応させるフェノール化合物（ａ2）と同じであっても異なってもよい。
In the resin composition of the present invention, the phenol compound (a 1 ) and the cyanate compound (a 1 ) are reacted while maintaining an appropriate equivalent ratio (hydroxyl group / cyanate group ratio) in order to improve dielectric constant and water absorption. The phenol-modified cyanate ester oligomer (A) is further blended with the phenol compound (C), and the phenolic hydroxyl group and phenol compound (C) of the phenol compound (a 2 ) with respect to the cyanate group of the cyanate compound (a 1 ). It is preferable that the blending equivalent ratio (hydroxyl group / cyanato group ratio) of the total amount with the phenolic hydroxyl group is in the range of 0.04 to 0.29. By setting the hydroxyl group / cyanato group ratio to 0.29 or less, deterioration of the dielectric constant and deterioration of heat resistance during moisture absorption can be avoided.
Incidentally, the phenol compound to be blended during resin composition produced (C) are those represented by the general formula (1), the same as the phenol-modified cyanate ester oligomer (A) a phenol compound to be reacted during the production (a 2) It may or may not be.
本発明の樹脂組成物で用いられる硬化促進剤（Ｄ）としてシアネート化合物とフェノール化合物との反応を促進させる触媒機能を有する化合物を用いることが好ましい。このような反応を促進させる触媒機能を有する化合物として、例えば、鉄、銅、亜鉛、コバルト、ニッケル、マンガン、スズから選ばれる少なくとも一種の金属の有機金属塩及び該金属の有機金属錯体等が挙げられる。この硬化促進剤（Ｄ）の配合量はシアネート化合物（ａ1）１００質量部に対して０．１〜５質量部とすることが好ましく、０．１〜３質量部とすることが更に好ましい。０．１質量部以上とすることにより触媒機能が得られ、硬化時間が短縮される。また、５質量部以下とすることによりワニスやプリプレグの保存安定性の低下が避けられるようになる。この硬化促進剤は、その一部又は全部をシアネート化合物（ａ1）とフェノール化合物（ａ2）とを反応させて得られるフェノール変性シアネートエステルオリゴマー（Ａ）を合成する際に配合しても、合成後に配合してもよい。 As the curing accelerator (D) used in the resin composition of the present invention, it is preferable to use a compound having a catalytic function for promoting the reaction between a cyanate compound and a phenol compound. Examples of the compound having a catalytic function for promoting such a reaction include an organic metal salt of at least one metal selected from iron, copper, zinc, cobalt, nickel, manganese, and tin, and an organic metal complex of the metal. It is done. The amount of the curing accelerator (D) is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the cyanate compound (a 1 ). A catalyst function is obtained by setting it as 0.1 mass part or more, and hardening time is shortened. Moreover, the fall of the storage stability of a varnish or a prepreg can be avoided by setting it as 5 mass parts or less. The curing accelerator may be blended in the synthesis thereof a part or all of the cyanate compound (a 1) and the phenol compound (a 2) the phenol-modified cyanate ester oligomer obtained is reacted with (A), You may mix | blend after a synthesis | combination.
また、本発明の樹脂組成物で用いられる硬化促進剤（Ｄ）として、シアネート化合物（ａ1）とフェノール化合物（ａ2）及びからフェノール化合物（Ｃ）選ばれるフェノール化合物との反応を促進させる触媒機能を有する化合物と、エポキシ樹脂（Ｂ）のグリシジル基の硬化反応を促進させる触媒機能を有する化合物を併用することが好ましい。
このエポキシ基を含有するエポキシ樹脂（Ｂ）のグリシジル基の硬化反応を促進させる触媒機能を有する化合物としてはアルカリ金属化合物、アルカリ土類金属化合物、イミダゾール類化合物、有機リン化合物、第二級アミン、第三級アミン、第四級アンモニウム塩等が挙げられるが、イミダゾール化合物がグリシジル基の硬化反応を促進する触媒機能が良好であるので好ましく、下記一般式（４）で表されるイミダゾール類化合物が特に好ましい。
Further, as the curing accelerator (D) used in the resin composition of the present invention, a catalyst that promotes the reaction of the cyanate compound (a 1 ) with the phenol compound (a 2 ) and the phenol compound selected from the phenol compound (C). It is preferable to use together the compound which has a function, and the compound which has a catalyst function which accelerates | stimulates hardening reaction of the glycidyl group of an epoxy resin (B).
As a compound having a catalytic function for promoting the curing reaction of the glycidyl group of the epoxy resin (B) containing this epoxy group, an alkali metal compound, an alkaline earth metal compound, an imidazole compound, an organic phosphorus compound, a secondary amine, Tertiary amines, quaternary ammonium salts and the like can be mentioned, but imidazole compounds are preferable because of their good catalytic function of promoting the curing reaction of glycidyl groups, and imidazole compounds represented by the following general formula (4) are preferred. Particularly preferred.
（式中、Ｒ12は炭素数１〜１１のアルキル基又はフェニル基を表す。）
このように両者の硬化促進剤を併用する場合、両者の硬化促進剤の合計量を、（Ａ）シアネート化合物（ａ1）１００質量部に対して０．１〜５質量部とすることが好ましい。０．１質量部以上とすることにより触媒機能が得られ硬化時間が短縮される。また、５質量部以下とすることにより、ワニスやプリプレグの保存安定性の低下が回避されるようになる。
(In the formula, R 12 represents an alkyl group having 1 to 11 carbon atoms or a phenyl group.)
When such a combination of both curing accelerator, the total amount of both the curing accelerator, it is preferable that 0.1 to 5 parts by mass with respect to (A) the cyanate compound (a 1) 100 parts by weight . By setting it as 0.1 mass part or more, a catalyst function is acquired and hardening time is shortened. Moreover, the fall of the storage stability of a varnish or a prepreg is avoided by setting it as 5 mass parts or less.
本発明の樹脂組成物において酸化防止剤（Ｅ）を配合することが好ましい。この酸化防止剤（Ｅ）としては、フェノール系酸化防止剤または硫黄有機化合物系酸化防止剤が挙げられる。
フェノール系酸化防止剤の具体例としては、ピロガロール、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−４−メチルフェノールなどのモノフェノール系や２，２'−メチレン−ビス−（４−メチル−６−ｔ−ブチルフェノール）、４，４'−チオビス−（３−メチル−６−ｔ−ブチルフェノール）などのビスフェノール系及び１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、テトラキス−〔メチレン−３−（３'−５'−ジ−ｔ−ブチル−４'−ヒドロキシフェニル）プロピオネート〕メタンなどの高分子型フェノール系が挙げられる。これらのフェノール系酸化防止剤の中でも、特にビスフェノール系酸化防止剤が効果の点から好ましい。硫黄有機化合物系酸化防止剤の具体例としては、ジウラリルチオジプロピオネート、ジステアリルチオジプロピオネート等がある。これらの酸化防止剤は何種類かを併用してもよい。
酸化防止剤（Ｅ）はシアネート化合物（ａ1）１００質量部に対して０．１〜２０質量部配合することが好ましい。０．１質量部以上とすることにより絶縁特性が向上し、２０質量部以下とすることにより逆に絶縁特性が低下することが回避される。
It is preferable to mix | blend antioxidant (E) in the resin composition of this invention. Examples of the antioxidant (E) include phenolic antioxidants and sulfur organic compound antioxidants.
Specific examples of the phenol-based antioxidant include monophenols such as pyrogallol, butylated hydroxyanisole, 2,6-di-t-butyl-4-methylphenol, and 2,2′-methylene-bis- (4- Bisphenols such as methyl-6-tert-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol) and 1,3,5-trimethyl-2,4,6-tris (3 Polymeric phenols such as 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3′-5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane System. Among these phenolic antioxidants, bisphenolic antioxidants are particularly preferable from the viewpoint of effects. Specific examples of the sulfur organic compound-based antioxidant include diuraryl thiodipropionate and distearyl thiodipropionate. Several types of these antioxidants may be used in combination.
The antioxidant (E) is preferably blended in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the cyanate compound (a 1 ). When the content is 0.1 parts by mass or more, the insulation characteristics are improved, and when the content is 20 parts by mass or less, the deterioration of the insulation characteristics is avoided.
本発明の樹脂組成物においては、必要に応じて充填剤及びその他の添加剤を配合することができる。配合される充填剤としては、通常、無機充填剤が好適に用いられ、具体的には溶融シリカ、ガラス、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、窒化珪素、窒化ホウ素、ベリリア、ジルコニア、チタン酸カリウム、珪酸アルミニウム、珪酸マグネシウムなどが粉末又は球形化したビーズとして用いられる。また、ウィスカー、単結晶繊維、ガラス繊維、無機系及び有機系の中空フィラーなども配合することができる。 In the resin composition of this invention, a filler and another additive can be mix | blended as needed. As fillers to be blended, inorganic fillers are usually preferably used. Specifically, fused silica, glass, alumina, zircon, calcium silicate, calcium carbonate, silicon nitride, boron nitride, beryllia, zirconia, titanic acid. Potassium, aluminum silicate, magnesium silicate, etc. are used as powdered or spherical beads. In addition, whiskers, single crystal fibers, glass fibers, inorganic and organic hollow fillers, and the like can also be blended.
一般的なエポキシ樹脂の硬化反応は、エポキシ基の開環に伴い極性の高い水酸基が生成するため、低誘電率化には限界がある。また、フェノール類付加ポリブタジエンなどの炭化水素系重合体に代表される特殊な硬化剤を用いた場合、エポキシ樹脂本来の耐熱性を損ねたり、多官能フェノール樹脂等で硬化させた場合と比べガラス転移温度が低い、コスト高になるなどの問題がある。一方、低極性、剛直かつ対称性構造のトリアジン骨格を有するシアネートエステル樹脂の硬化物は低誘電率でかつ高いガラス転移温度を有するという特徴がある。
しかしながら、シアネートエステル樹脂単独の硬化反応においては、シアネートエステル樹脂中のすべてのシアナト基が反応してトリアジン構造を生成するというようなことは不可能であり、硬化反応の進行に伴って反応系が流動性を失い未反応のシアナト基として系内に残存することになる。その結果、これまでは本来の硬化物より誘電率の高い硬化物しか得られなかった。また、シアネートエステル樹脂単独の硬化反応で得られる樹脂硬化物は硬く脆いため加工性が劣ったり、極性の高いシアナト基が残存し吸水率が大きくなるため吸湿時の耐熱性に問題があった。
この問題を改善するためシアネートエステル樹脂に従来のビスフェノールＡ、臭素化ビスフェノールＡ等をベースとしたエポキシ樹脂を併用する方法が図られているが、ガラス転移温度（Ｔｇ）の低下や誘電率の悪化等の問題がある。
A general epoxy resin curing reaction generates a highly polar hydroxyl group as the epoxy group is opened, so there is a limit to lowering the dielectric constant. In addition, when a special curing agent typified by a hydrocarbon polymer such as phenol-added polybutadiene is used, the glass has a glass transition as compared with the case where the inherent heat resistance of the epoxy resin is impaired or the resin is cured with a polyfunctional phenol resin. There are problems such as low temperature and high cost. On the other hand, a cured product of a cyanate ester resin having a triazine skeleton having a low polarity, a rigid and symmetrical structure is characterized by a low dielectric constant and a high glass transition temperature.
However, in the curing reaction of the cyanate ester resin alone, it is impossible for all cyanate groups in the cyanate ester resin to react to form a triazine structure. The fluidity is lost and it remains in the system as an unreacted cyanato group. As a result, only a cured product having a dielectric constant higher than that of the original cured product has been obtained so far. Further, the cured resin obtained by the curing reaction of the cyanate ester resin alone is hard and brittle, so that the processability is inferior, or the highly polar cyanate group remains and the water absorption rate is increased, so that there is a problem in heat resistance during moisture absorption.
In order to solve this problem, a method of using a conventional epoxy resin based on bisphenol A, brominated bisphenol A or the like in combination with a cyanate ester resin has been attempted. However, the glass transition temperature (Tg) is lowered and the dielectric constant is lowered. There are problems such as.
これに対して、本発明は、特定のフェノール変性シアネートオリゴマー（Ａ）とエポキシ樹脂（Ｂ）からなる樹脂組成物であり、ガラス転移温度（Ｔｇ）が高く、誘電率、吸水性、絶縁信頼性、耐燃性に優れる樹脂組成物を得ることができる。特にエポキシ樹脂（Ｂ）としてジシクロペンタジエン−フェノール重付加物から誘導されるものを用い、硬化促進剤（Ｄ）として、鉄、銅、亜鉛、コバルト、ニッケル、マンガンおよびスズから選ばれる少なくとも一種の金属の有機金属塩または該金属の有機金属錯体と、イミダゾール類化合物を含むものを併用することが好ましい。 In contrast, the present invention is a resin composition comprising a specific phenol-modified cyanate oligomer (A) and an epoxy resin (B), having a high glass transition temperature (Tg), dielectric constant, water absorption, and insulation reliability. A resin composition having excellent flame resistance can be obtained. In particular, the epoxy resin (B) is derived from a dicyclopentadiene-phenol polyadduct, and the curing accelerator (D) is at least one selected from iron, copper, zinc, cobalt, nickel, manganese and tin. It is preferable to use a metal organometallic salt or an organometallic complex of the metal in combination with a compound containing an imidazole compound.
本発明のプリント配線板用金属箔張積層板は、前記の樹脂組成物をワニス化して繊維基材に含浸又は塗工した後、Ｂステージ化して得られるプリプレグを１枚又は複数枚重ね、さらにその上下面又は片面に金属箔を積層し、加熱加圧して得られる。
本発明の樹脂組成物をワニス化する場合は必要に応じて溶剤を用いる。用いられる溶剤は特に制限されないが、ケトン系、芳香族炭化水素系、エステル系、アミド系、アルコール系等が挙げられる。具体的には、ケトン系溶剤として、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等が、芳香族炭化水素系としては、トルエン、キシレン等が、エステル系溶剤としてはメトキシエチルアセテート、エトキシエチルアセテート、ブトキシエチルアセテート、酢酸エチル等が、アミド系溶剤としてはＮ−メチルピロリドン、ホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等が、アルコール系溶剤としてはメタノール、エタノール、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノプロピルエーテル等が挙げられる。これらの溶剤は１種または２種以上を混合して用いてもよい。
The metal foil-clad laminate for a printed wiring board of the present invention is obtained by varnishing the resin composition and impregnating or coating the fiber base material, and then stacking one or a plurality of prepregs obtained by B-stage, It is obtained by laminating metal foil on the upper and lower surfaces or one surface and heating and pressing.
When varnishing the resin composition of this invention, a solvent is used as needed. The solvent to be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, esters, amides, and alcohols. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are used as ketone solvents, toluene, xylene, etc. are used as aromatic hydrocarbons, and methoxyethyl acetate, ethoxyethyl acetate, butoxy are used as ester solvents. Ethyl acetate, ethyl acetate, etc. are N-methylpyrrolidone, formamide, N-methylformamide, N, N-dimethylacetamide, etc. as amide solvents, and methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether as alcohol solvents , Ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, pro Glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, and the like. These solvents may be used alone or in combination of two or more.
本発明のプリント配線板用金属箔張積層板に用いられる繊維基材としては、液晶ポリアリレート繊維基材が好ましい。この液晶ポリアリレート繊維基材は、溶融液晶ポリマーであり、紡糸時に高配向するため、超高強度で高耐熱性を示す。液晶ポリアリレートの繊維は、同じ有機繊維基材であるアラミドの繊維に比べて、吸水率が極めて低く、低吸水性の樹脂組成物と組み合わせることで従来のガラスエポキシ積層板よりも低吸水性を有する積層板を作製できる。また、ＤガラスおよびＳガラスよりも誘電率が低いため積層板の低誘電率化も同時に達成できる。 As a fiber base material used for the metal foil clad laminated board for printed wiring boards of this invention, a liquid crystal polyarylate fiber base material is preferable. This liquid crystal polyarylate fiber base material is a molten liquid crystal polymer, and is highly oriented during spinning, and therefore exhibits ultrahigh strength and high heat resistance. The liquid crystal polyarylate fiber has an extremely low water absorption rate compared to the aramid fiber, which is the same organic fiber base material, and when combined with a low water absorption resin composition, it has a lower water absorption than conventional glass epoxy laminates. The laminated board which has can be produced. In addition, since the dielectric constant is lower than that of D glass and S glass, the dielectric constant of the laminated plate can be simultaneously reduced.
本発明において用いられる液晶ポリアリレートとしては、ヒドロキシナフトエ酸とヒドロキシ安息香酸の共重合体である全芳香族ポリエステルを用いることが望ましい。このポリアリレートは、下記一般式（５）に示すような構造をもつポリアリレートである。一般式（５）において、ｍ＝２０〜５０、ｎ＝８０〜５０の範囲で組み合わせることができるが、液晶ポリマーの溶融重合させる際に粘度を小さくする必要があるため、本発明で使用する液晶ポリアリレート繊維では、ｍ＝３５〜４５、ｎ＝５５〜６５のものが好ましい。一般式（５）に示すような構造をもつポリアリレートの外に、ヒドロキシ安息香酸、芳香族ジオール及びフタル酸を共重合させた一般式（６ａ）で示されるような全芳香族ポリエステル及び、ポリエチレンテレフタレートとヒドロキシ安息香酸とを共重合させた一般式（６ｂ）で示されるような全芳香族ポリエステルも使用できる。 As the liquid crystal polyarylate used in the present invention, it is desirable to use a wholly aromatic polyester which is a copolymer of hydroxynaphthoic acid and hydroxybenzoic acid. This polyarylate is a polyarylate having a structure as shown in the following general formula (5). In the general formula (5), m = 20 to 50 and n = 80 to 50 can be combined. However, since it is necessary to reduce the viscosity when the liquid crystal polymer is melt polymerized, the liquid crystal used in the present invention is used. Of the polyarylate fibers, those with m = 35 to 45 and n = 55 to 65 are preferred. In addition to polyarylate having a structure represented by the general formula (5), a wholly aromatic polyester represented by the general formula (6a) obtained by copolymerizing hydroxybenzoic acid, aromatic diol and phthalic acid, and polyethylene A wholly aromatic polyester represented by the general formula (6b) obtained by copolymerizing terephthalate and hydroxybenzoic acid can also be used.
繊維基材の形態としてはドリル切削時の穴壁粗さを小さくし、かつドリル刃の磨耗性を少なくできることから不織布が好ましく用いられる。不織布の形態としては乾式不織布よりも、湿式不織布の方が好ましい。乾式不織布では、引っ張り強度を確保するために熱キャレンダと呼ばれる１８０〜２８０℃に加熱したロールを通過させ、液晶ポリアリレート繊維を溶融圧着させる工程が必要となる。しかし、熱キャレンダにより液晶ポリアリレート繊維は、溶融するばかりでなく熱変形により偏平するため、液晶ポリアリレート繊維基材の見掛け密度が大きくなり樹脂組成物が繊維基材間に含浸し難くなる。従って湿式不織布が好適に用いられる。 As the form of the fiber base material, a non-woven fabric is preferably used since the hole wall roughness at the time of drill cutting can be reduced and the wearability of the drill blade can be reduced. As the form of the nonwoven fabric, the wet nonwoven fabric is preferable to the dry nonwoven fabric. In a dry nonwoven fabric, in order to ensure tensile strength, a process called a heat calender, which is heated to 180 to 280 ° C., is passed, and a process of melt-compressing liquid crystal polyarylate fibers is required. However, since the liquid crystal polyarylate fibers are not only melted but flattened by thermal deformation due to the heat calender, the apparent density of the liquid crystal polyarylate fiber base material is increased and the resin composition is hardly impregnated between the fiber base materials. Accordingly, a wet nonwoven fabric is preferably used.
以下、具体例を挙げて本発明を具体的に説明するが、本発明はこれらに限られるものではない。なお、以下において、％は質量％を表し、また下記表１中の樹脂組成物（ワニス）の配合の単位は質量部である。
実施例及び比較例で作製したワニスの粘度を測定し、銅張積層板は、厚さ、ガラス転移温度（Ｔｇ）、誘電率、吸水率、吸湿はんだ耐熱性、絶縁信頼性、耐燃性を評価した。また、積層板にドリルで穴あけ加工を施したときの穴壁粗さ及びドリル磨耗量を測定した。
Hereinafter, the present invention will be specifically described with specific examples, but the present invention is not limited thereto. In the following, “%” represents “% by mass”, and the unit of compounding of the resin composition (varnish) in Table 1 below is “parts by mass”.
Viscosity of varnishes prepared in Examples and Comparative Examples was measured, and copper clad laminates were evaluated for thickness, glass transition temperature (Tg), dielectric constant, water absorption, moisture absorption solder heat resistance, insulation reliability, and flame resistance did. Moreover, the hole wall roughness and drill wear amount when drilling the laminated plate with a drill were measured.
実施例における評価方法は、次のように行った。
（１）粘度：
配合１日後のワニス約１．４ｍｌをＥ型粘度計により２５℃にて測定した。
（２）厚さ：
マイクロメーターを用いて、各３個の試験片について、各々３か所づつ測定してその平均値を示した。
（３）ガラス転移温度（Ｔｇ）：
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置〔デュポン（株）製ＴＭＡ２９４０〕を用い、評価基板の熱膨張特性を観察することにより評価した。
（４）誘電率：
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、マイクロストリップライン共振器法により、比誘電率測定装置（Ｈｅｗｌｌｅｔ・Ｐａｃｋｅｒｄ社製ＨＰ４２９１Ｂ）を用いて、周波数１ＧＨｚでの比誘電率を測定した。
（５）吸水率：
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、温度１２１℃、圧力０．２２ＭＰａ、飽和水蒸気圧のプレッシャー・クッカー試験装置〔平山製作所（株）製〕内に４時間保持し、保持前後の質量変化を測定して増加した質量を保持前の質量で除し、％で表示した。
Evaluation methods in the examples were performed as follows.
(1) Viscosity:
About 1.4 ml of varnish one day after compounding was measured at 25 ° C. with an E-type viscometer.
(2) Thickness:
Using a micrometer, each of the three test pieces was measured at three locations, and the average value was shown.
(3) Glass transition temperature (Tg):
A 5 mm square evaluation board is prepared by removing the copper foil by immersing the copper-clad laminate in a copper etching solution, and the thermal expansion characteristics of the evaluation board are observed using a TMA test apparatus (TMA2940 manufactured by DuPont). It was evaluated by.
(4) Dielectric constant:
An evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and the frequency was measured by a microstrip line resonator method using a relative dielectric constant measuring apparatus (HP4291B manufactured by Hewlett-Packard Company). The relative dielectric constant at 1 GHz was measured.
(5) Water absorption rate:
A copper-clad laminate was immersed in a copper etching solution to prepare an evaluation substrate from which the copper foil was removed, and a pressure cooker test apparatus (produced by Hirayama Seisakusho Co., Ltd.) having a temperature of 121 ° C., a pressure of 0.22 MPa, and a saturated water vapor pressure. It was held for 4 hours, the mass change before and after holding was measured, and the increased mass was divided by the mass before holding and expressed in%.
（６）はんだ耐熱性：
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板を作製し、プレッシャー・クッカー試験装置〔平山製作所（株）製〕で４時間処理後の試験片を、２６０℃のはんだ槽に２０秒浸漬後の外観を観察し、以下の評価基準により評価した。
○；フクレ、ミーズリングのないもの
△；ミーズリングの発生したもの
×；フクレの発生したもの
（７）絶縁信頼性：
スルーホール穴壁間隔を３５０μｍとしたテストパターンを用いて、各試料について４００穴の絶縁抵抗を経時的に測定した。試験条件は、８５℃、９０％ＲＨ雰囲気中１００Ｖ印加して行い、導通破壊が発生するまでの時間を測定した。
（８）耐燃性：
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた評価基板から、長さ１２７ｍｍ、幅１２．７ｍｍに切り出した評価基板を作製し、ＵＬ９４試験法（Ｖ法）に準拠して評価した。
（９）穴壁粗さ：
直径０．７ｍｍのドリルを用いて、回転数６５，０００ｒｐｍ、送り速度３，５００ｍｍ／分の条件にて積層板を３枚重ねで穴あけを行い、上から３枚目に銅めっきを行い、穴あけヒット数が６，０００穴の位置の断面を実体顕微鏡で観察して、穴壁からの銅めっきのしみこみ距離を測定した。
（１０）ドリル摩耗量：
穴壁粗さを測定する時に用いたドリル刃について、穴あけに使用する前と穴あけヒット数が６，０００穴となったときの刃幅長を実体顕微鏡で観察して、摩耗量を測定した。
(6) Solder heat resistance:
An evaluation board from which the copper foil was removed by immersing the copper-clad laminate in a copper etching solution was prepared, and a test piece treated for 4 hours with a pressure cooker test apparatus (manufactured by Hirayama Seisakusho Co., Ltd.) The appearance after immersion for 20 seconds in a solder bath was observed and evaluated according to the following evaluation criteria.
○: No blistering or mising ring △: Missing ring ×: Fluffing (7) Insulation reliability:
The insulation resistance of 400 holes was measured over time for each sample using a test pattern in which the through hole hole wall interval was 350 μm. The test conditions were performed by applying 100 V in an atmosphere of 85 ° C. and 90% RH, and measuring the time until conduction breakdown occurred.
(8) Flame resistance:
An evaluation board cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation board in which the copper foil was removed by immersing the copper-clad laminate in a copper etching solution, and in accordance with UL94 test method (Method V) evaluated.
(9) Hole wall roughness:
Using a drill with a diameter of 0.7 mm, drill three layers of laminated plates at a rotational speed of 65,000 rpm and a feed rate of 3,500 mm / min. The cross section at the position where the number of hits was 6,000 holes was observed with a stereoscopic microscope, and the penetration distance of the copper plating from the hole wall was measured.
(10) Drill wear amount:
About the drill blade used when measuring the hole wall roughness, the amount of wear was measured by observing the blade width length with a stereomicroscope before use for drilling and when the number of drilling hits was 6,000 holes.
実施例１
温度計、冷却管、攪拌装置を備えた２リットルの４つ口セパラブルフラスコに、トルエン、シアネート化合物（ａ1）として２，２−ビス（４−シアナトフェニル）プロパン（旭チバ株式会社製、商品名：Ａｒｏｃｙ Ｂ−１０）、フェノール化合物（ａ2）としてｐ−（α−クミル）フェノール（東京化成工業株式会社製）を第１表に記載のように配合し、液温を１２０℃に保った後、硬化促進剤としてナフテン酸亜鉛（和光純薬工業株式会社製）を第１表に記載にように添加して４時間加熱反応させてシアネート化合物モノマーの転化率が約５５％のフェノール変性シアネートエステルオリゴマー（Ａ）を合成した。なお、反応液の濃度は７０質量％であった。フェノール変性シアネートエステルオリゴマー（Ａ）のシアネート化合物（ａ1）のシアナト基に対するフェノール化合物の（ａ2）フェノール性水酸基の当量比（水酸基／シアナト基比）は０．０３である。シアネート化合物（ａ1）モノマーの転化率は、液体クロマトグラフィー〔機種、ポンプ；日立製作所（株）製Ｌ−６２００、ＲＩ検出機；Ｌ−３３００、カラム：東ソー（株）製ＴＳＫｇｅｌ−Ｇ４０００Ｈ、Ｇ２０００Ｈ、溶媒：ＴＨＦ、濃度：１％〕で確認した。また、この時のフェノール変性シアネートエステルオリゴマー（Ａ）の数平均分子量（Ｍｎ）は１４３０であった。また同時に、ｐ−（α−クミル）フェノールの溶出ピークが消失していることを確認した。
このフェノール変性シアネートエステルオリゴマー（Ａ）を室温（２５℃）に冷却した後、樹脂組成物におけるエポキシ樹脂（Ｂ）としてジシクロペンタジエン型エポキシ樹脂（大日本インキ化学工業株式会社製、商品名：ＨＰ−７２００Ｈ）と臭素化ビスフェノールＡ型エポキシ樹脂（住友化学工業株式会社製、商品名：ＥＳＢ４００Ｔ）を、フェノール化合物（Ｃ）としてｐ−（α−クミル）フェノールを各々第１表に示す配合量で配合した後、硬化促進剤（Ｄ）としてナフテン酸亜鉛と１−シアノエチル−２−メチルイミダゾールトリメリテート（四国化成工業株式会社製、商品名：２ＭＺ−ＣＮＳ）を、酸化防止剤（Ｅ）としてピロガロールを表１に記載のように配合し、不揮発分７０％のワニスを作製した。なお、溶媒にはメチルエチルケトンを使用した。該樹脂組成物のシアネート化合物（ａ1）のシアナト基に対するフェノール化合物（ａ2）のフェノール性水酸基とフェノール化合物（Ｃ）のフェノール性水酸基との合計量の配合当量比（水酸基／シアナト基比）は０．２９である。
作製したワニスを液晶ポリアリレート繊維（株式会社クラレ製、商品名：ベクルス、坪量５０ｇ／ｍ2）に含浸乾燥して、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Example 1
To a 2-liter four-necked separable flask equipped with a thermometer, a condenser, and a stirrer, 2,2-bis (4-cyanatophenyl) propane (manufactured by Asahi Ciba Co., Ltd.) as toluene and cyanate compound (a 1 ) , Trade name: Arocy B-10), p- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a phenol compound (a 2 ) is blended as shown in Table 1, and the liquid temperature is 120 ° C. Then, zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a curing accelerator as shown in Table 1 and heated for 4 hours to give a cyanate compound monomer conversion of about 55%. A phenol-modified cyanate ester oligomer (A) was synthesized. In addition, the density | concentration of the reaction liquid was 70 mass%. The equivalent ratio (hydroxyl group / cyanato group ratio) of the (a 2 ) phenolic hydroxyl group of the phenol compound to the cyanate group of the cyanate compound (a 1 ) of the phenol-modified cyanate ester oligomer (A) is 0.03. The conversion rate of the cyanate compound (a 1 ) monomer was determined by liquid chromatography [model, pump; L-6200 manufactured by Hitachi, Ltd., RI detector; L-3300, column: TSKgel-G4000H, G2000H manufactured by Tosoh Corporation. , Solvent: THF, concentration: 1%]. Moreover, the number average molecular weight (Mn) of the phenol modified cyanate ester oligomer (A) at this time was 1430. At the same time, it was confirmed that the elution peak of p- (α-cumyl) phenol disappeared.
After this phenol-modified cyanate ester oligomer (A) is cooled to room temperature (25 ° C.), a dicyclopentadiene type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: HP) is used as the epoxy resin (B) in the resin composition. -7200H) and brominated bisphenol A type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: ESB400T), and p- (α-cumyl) phenol as a phenol compound (C) in the blending amounts shown in Table 1 respectively. After blending, zinc naphthenate and 1-cyanoethyl-2-methylimidazole trimellitate (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2MZ-CNS) are used as the antioxidant (E) as the curing accelerator (D). Pyrogallol was blended as shown in Table 1 to prepare a varnish having a nonvolatile content of 70%. Note that methyl ethyl ketone was used as a solvent. Compounding equivalent ratio of total amount of phenolic hydroxyl group of phenol compound (a 2 ) and phenolic hydroxyl group of phenol compound (C) to cyanate group of cyanate compound (a 1 ) of the resin composition (ratio of hydroxyl group / cyanato group) Is 0.29.
The produced varnish was impregnated and dried in liquid crystal polyarylate fibers (manufactured by Kuraray Co., Ltd., trade name: VECRUZ, basis weight 50 g / m 2 ) to prepare a prepreg having a thickness of 0.15 mm after drying. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
実施例２
実施例１において、フェノール変性シアネートエステルオリゴマー（Ａ）を製造する際のシアネート化合物（ａ1）を２，２−ビス（３，５−ジメチル−４−シアネートフェニル）メタン（旭チバ株式会社製、商品名：Ａｒｏｃｙ Ｍ−１０）に、フェノール化合物（ａ2）をｐ−ｔｅｒｔ−オクチルフェノールに代えて第１表に記載のように配合し、フェノール変性シアネートエステルオリゴマー（Ａ）を合成した。該フェノール変性シアネートエステルオリゴマー（Ａ）の水酸基／シアナト基比は０．０１である。
このフェノール変性シアネートエステルオリゴマー（Ａ）を冷却後、実施例１の樹脂組成物において配合したフェノール化合物（Ｃ）をｐ−ｔｅｒｔ−オクチルフェノールに、硬化促進剤（Ｄ）を１−シアノエチル−２−フェニルイミダゾール（四国化成工業株式会社製、商品名：２ＰＺ−ＣＮＳ）に、酸化防止剤（Ｅ）を４，４−チオビス−（３−メチル−６−ｔ−ブチルフェノール）として第１表に従って配合した他は実施例１と同様にしてワニスを作製した。該樹脂組成物全体の水酸基／シアナト基比は０．０４である。
作製したワニスを液晶ポリアリレート繊維（坪量５０ｇ／ｍ2、株式会社クラレ製、商品名：ベクルス）に含浸乾燥して、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Example 2
In Example 1, the cyanate compound (a 1 ) in producing the phenol-modified cyanate ester oligomer (A) was converted to 2,2-bis (3,5-dimethyl-4-cyanatephenyl) methane (Asahi Ciba Co., Ltd., A phenol-modified cyanate ester oligomer (A) was synthesized in the product name: Arocy M-10) by replacing the phenol compound (a 2 ) with p-tert-octylphenol as shown in Table 1. The phenol-modified cyanate ester oligomer (A) has a hydroxyl group / cyanato group ratio of 0.01.
After cooling this phenol-modified cyanate ester oligomer (A), the phenol compound (C) blended in the resin composition of Example 1 is p-tert-octylphenol, and the curing accelerator (D) is 1-cyanoethyl-2-phenyl. In addition to imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2PZ-CNS), 4,4-thiobis- (3-methyl-6-t-butylphenol) as an antioxidant (E) was blended according to Table 1. Produced a varnish in the same manner as in Example 1. The hydroxyl group / cyanato group ratio of the entire resin composition is 0.04.
The prepared varnish was impregnated and dried in liquid crystal polyarylate fibers (basis weight 50 g / m 2 , manufactured by Kuraray Co., Ltd., trade name: Vecrus) to prepare a prepreg having a thickness after drying of 0.15 mm. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
実施例３
実施例１において、硬化促進剤（Ｄ）をナフテン酸マンガンに代え、各成分を第１表に従って配合した他は実施例１と同様にしてワニスを作製した。フェノール変性シアネートエステルオリゴマー（Ａ）の水酸基／シアナト基比は０．０３であり、樹脂組成物全体の水酸基／シアナト基比は０．０４である。
作製したワニスを液晶ポリアリレート繊維（坪量５０ｇ／ｍ2、株式会社クラレ製、商品名ベクルス）を含浸乾燥して、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Example 3
In Example 1, a varnish was prepared in the same manner as in Example 1 except that the curing accelerator (D) was replaced with manganese naphthenate and each component was blended according to Table 1. The hydroxyl group / cyanate group ratio of the phenol-modified cyanate ester oligomer (A) is 0.03, and the hydroxyl group / cyanate group ratio of the entire resin composition is 0.04.
The prepared varnish was impregnated and dried with liquid crystal polyarylate fibers (basis weight 50 g / m 2 , manufactured by Kuraray Co., Ltd., trade name Veculus) to prepare a prepreg having a thickness of 0.15 mm after drying. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
実施例４
実施例１において、液晶ポリアリレート繊維に代えて、Ｓガラスクロス（坪量１０５ｇ／ｍ2、厚さ０．１ｍｍ、日東紡績製、商品名：ＷＴＸ１１６Ｅ）使用し、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Example 4
In Example 1, S glass cloth (basis weight 105 g / m 2 , thickness 0.1 mm, manufactured by Nitto Boseki Co., Ltd., trade name: WTX116E) was used instead of the liquid crystal polyarylate fiber, and the thickness after drying was 0.00. A 15 mm prepreg was prepared. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
比較例１
実施例１においてフェノール変性シアネートエステルオリゴマー（Ａ）を２，２−ビス（４−シアナトフェニル）プロパンのプレポリマ化物（旭チバ株式会社製、商品名：Ａｒｏｃｙ Ｂ−３０）に代えて、ｐ−（α−クミル）フェノールを配合しないでワニス化した他は実施例１と同様にしてワニスを作製した。作製したワニスを液晶ポリアリレート繊維（坪量５０ｇ／ｍ2、株式会社クラレ製、商品名：ベクルス）に含浸乾燥して、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Comparative Example 1
In Example 1, the phenol-modified cyanate ester oligomer (A) was replaced with 2,2-bis (4-cyanatophenyl) propane prepolymerized product (trade name: Arocy B-30, manufactured by Asahi Ciba Co., Ltd.), p- A varnish was prepared in the same manner as in Example 1 except that (α-cumyl) phenol was not added and varnished. The prepared varnish was impregnated and dried in liquid crystal polyarylate fibers (basis weight 50 g / m 2 , manufactured by Kuraray Co., Ltd., trade name: Vecrus) to prepare a prepreg having a thickness after drying of 0.15 mm. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
比較例２
実施例１においてフェノール変性シアネートエステルオリゴマー（Ａ）を２，２−ビス（３，５−ジメチル−４−シアネートフェニル）メタン（旭チバ株式会社製、商品名：Ａｒｏｃｙ Ｍ−３０）のプレポリマ化物に代えた他は実施例１と同様にしてワニスを作製した。作製したワニスを液晶ポリアリレート繊維（坪量５０ｇ／ｍ2、株式会社クラレ製、商品名：ベクルス）に含浸乾燥して、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Comparative Example 2
In Example 1, the phenol-modified cyanate ester oligomer (A) was converted into a prepolymerized product of 2,2-bis (3,5-dimethyl-4-cyanatephenyl) methane (manufactured by Asahi Ciba, trade name: Arocy M-30). A varnish was prepared in the same manner as in Example 1 except that the varnish was used. The prepared varnish was impregnated and dried in liquid crystal polyarylate fibers (basis weight 50 g / m 2 , manufactured by Kuraray Co., Ltd., trade name: Vecrus) to prepare a prepreg having a thickness after drying of 0.15 mm. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
比較例３
比較例１において樹脂組成物に配合したフェノール化合物（Ｃ）としてフェノールノボラック（日立化成工業株式会社製、商品名：ＨＰ８５０Ｎ）を第１表に従って配合した他は比較例２と同様にしてワニスを作製した。作製したワニスはゲル化しており、液晶ポリアリレート繊維（坪量５０ｇ／ｍ2、株式会社クラレ製、商品名：ベクルス）に含浸乾燥してもプリプレグが得られなかった。
Comparative Example 3
A varnish was prepared in the same manner as in Comparative Example 2 except that phenol novolak (manufactured by Hitachi Chemical Co., Ltd., trade name: HP850N) was blended according to Table 1 as the phenol compound (C) blended in the resin composition in Comparative Example 1. did. The produced varnish was gelled, and a prepreg was not obtained even when impregnating and drying liquid crystal polyarylate fibers (basis weight: 50 g / m 2 , manufactured by Kuraray Co., Ltd., trade name: Veculus).
比較例４
比較例１において２，２−ビス（４−シアナトフェニル）プロパンのプレポリマ化物（旭チバ株式会社製、商品名：Ａｒｏｃｙ Ｂ−３０）を配合せず、エポキシ樹脂（Ｂ）としてジシクロペンタジエン型エポキシ樹脂（大日本インク化学工業株式会社製、商品名：ＨＰ７２００Ｈ）および臭素化ビスフェノールＡ型エポキシ樹脂（住友化学工業株式会社製、商品名：ＥＳＢ４００Ｔ）を、フェノール化合物(Ｃ)としてフェノールノボラック樹脂（日立化成工業株式会社製、商品名：ＨＰ８５０Ｎ）をエポキシ樹脂のエポキシ当量とフェノール化合物（Ｃ）の水酸基当量の当量比１：１の割合で配合した後、硬化促進剤（Ｄ）として２−メチルイミダゾール、酸化防止剤（Ｅ）として４，４'−チオビス−（３−メチル−６−ｔ−ブチルフェノール）を第１表に従って配合して不揮発分７０％のワニスを作製した。なお、溶媒としてメチルエチルケトンを使用した。ワニスを液晶ポリアリレート繊維（坪量５０ｇ／ｍ2、株式会社クラレ製、商品名：ベクルス）に含浸乾燥して、乾燥後の厚さが０．１５ｍｍのプリプレグを作製した。次に、このプリプレグを５枚と上下に厚み１８μｍの銅箔を積層し、温度１７５℃、圧力３ＭＰａで９０分間加熱して銅張積層板を作製した。評価結果を第１表に示す。
Comparative Example 4
In Comparative Example 1, 2,2-bis (4-cyanatophenyl) propane prepolymerized product (trade name: Arocy B-30, manufactured by Asahi Ciba Co., Ltd.) was not blended, and the dicyclopentadiene type was used as the epoxy resin (B). Epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: HP7200H) and brominated bisphenol A type epoxy resin (Sumitomo Chemical Co., Ltd., trade name: ESB400T) are used as phenolic compounds (C) and phenol novolac resins ( Hitachi Chemical Co., Ltd., trade name: HP850N) was blended at an equivalent ratio of 1: 1 between the epoxy equivalent of the epoxy resin and the hydroxyl equivalent of the phenol compound (C), and then 2-methyl as a curing accelerator (D). Imidazole, 4,4′-thiobis- (3-methyl-6-tert-butylphenol as antioxidant (E) In accordance with Table 1, a varnish having a nonvolatile content of 70% was prepared. In addition, methyl ethyl ketone was used as a solvent. The varnish was impregnated and dried in liquid crystal polyarylate fibers (basis weight 50 g / m 2 , manufactured by Kuraray Co., Ltd., trade name: Vecruz) to prepare a prepreg having a thickness after drying of 0.15 mm. Next, five prepregs and a copper foil having a thickness of 18 μm were laminated vertically and heated at a temperature of 175 ° C. and a pressure of 3 MPa for 90 minutes to produce a copper-clad laminate. The evaluation results are shown in Table 1.
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| US8674502B2 (en) | 2010-07-16 | 2014-03-18 | Hitachi Chemical Company, Ltd. | Semiconductor-encapsulating adhesive, semiconductor-encapsulating film-form adhesive, method for producing semiconductor device, and semiconductor device |
| US10662304B2 (en) | 2013-12-31 | 2020-05-26 | Saint-Gobain Performance Plastics Corporation | Composites for protecting signal transmitters/receivers |
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| JP2001240723A (en) * | 1999-12-22 | 2001-09-04 | Hitachi Chem Co Ltd | Thermosetting resin composition and prepreg, metal-clad laminate, and printed wiring board using the same |
| JP2002146060A (en) * | 2000-11-07 | 2002-05-22 | Hitachi Chem Co Ltd | Prepreg and laminate |
| JP2004307761A (en) * | 2003-04-10 | 2004-11-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, metal-clad laminate and printed wiring board all using the same |
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| WO2009084861A3 (en) * | 2007-12-28 | 2009-09-24 | Lg Chem, Ltd. | Curing composition and cured product prepared by using the same |
| JP2009256587A (en) * | 2008-03-26 | 2009-11-05 | Hitachi Chem Co Ltd | Adhesive for sealing semiconductor, film-like adhesive for sealing semiconductor, manufacturing method for semiconductor apparatus, and semiconductor apparatus |
| US8674502B2 (en) | 2010-07-16 | 2014-03-18 | Hitachi Chemical Company, Ltd. | Semiconductor-encapsulating adhesive, semiconductor-encapsulating film-form adhesive, method for producing semiconductor device, and semiconductor device |
| US9123734B2 (en) | 2010-07-16 | 2015-09-01 | Hitachi Chemical Company, Ltd. | Semiconductor-encapsulating adhesive, semiconductor-encapsulating film-form adhesive, method for producing semiconductor device, and semiconductor device |
| US10662304B2 (en) | 2013-12-31 | 2020-05-26 | Saint-Gobain Performance Plastics Corporation | Composites for protecting signal transmitters/receivers |
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