TW202325793A - Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-clad laminated sheet, and wiring board - Google Patents
Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-clad laminated sheet, and wiring board Download PDFInfo
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- TW202325793A TW202325793A TW111138420A TW111138420A TW202325793A TW 202325793 A TW202325793 A TW 202325793A TW 111138420 A TW111138420 A TW 111138420A TW 111138420 A TW111138420 A TW 111138420A TW 202325793 A TW202325793 A TW 202325793A
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- Prior art keywords
- resin composition
- aforementioned
- compound
- particle size
- resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 214
- 239000011888 foil Substances 0.000 title claims description 64
- 229910052751 metal Inorganic materials 0.000 title claims description 64
- 239000002184 metal Substances 0.000 title claims description 63
- -1 poly(phenylene ether) Polymers 0.000 claims abstract description 223
- 150000001875 compounds Chemical class 0.000 claims abstract description 120
- 239000002245 particle Substances 0.000 claims abstract description 120
- 239000011256 inorganic filler Substances 0.000 claims abstract description 87
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 87
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 83
- 239000011574 phosphorus Substances 0.000 claims abstract description 83
- 238000009826 distribution Methods 0.000 claims abstract description 56
- 229910052582 BN Inorganic materials 0.000 claims abstract description 48
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000000691 measurement method Methods 0.000 claims abstract description 9
- 229920001955 polyphenylene ether Polymers 0.000 claims description 118
- 239000011347 resin Substances 0.000 claims description 84
- 229920005989 resin Polymers 0.000 claims description 84
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 125000005641 methacryl group Chemical group 0.000 claims description 12
- 239000004848 polyfunctional curative Substances 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 8
- 150000003440 styrenes Chemical class 0.000 claims description 8
- 229920000388 Polyphosphate Polymers 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000001205 polyphosphate Substances 0.000 claims description 7
- 235000011176 polyphosphates Nutrition 0.000 claims description 7
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 6
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 5
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 66
- 239000010408 film Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 31
- 239000002585 base Substances 0.000 description 25
- 150000003018 phosphorus compounds Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 125000000524 functional group Chemical group 0.000 description 19
- 125000001424 substituent group Chemical group 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 239000002966 varnish Substances 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 125000003342 alkenyl group Chemical group 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 230000008901 benefit Effects 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 125000000304 alkynyl group Chemical group 0.000 description 10
- 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 9
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 9
- 125000005090 alkenylcarbonyl group Chemical group 0.000 description 9
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 125000005087 alkynylcarbonyl group Chemical group 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 7
- 239000013039 cover film Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- RGYRCSKRQNNKOE-UHFFFAOYSA-N 1-phenylacenaphthylene Chemical group C=12C3=CC=CC2=CC=CC=1C=C3C1=CC=CC=C1 RGYRCSKRQNNKOE-UHFFFAOYSA-N 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
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- 238000003825 pressing Methods 0.000 description 3
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- MJEDTBDGYVATPI-UHFFFAOYSA-N 4-hydroxy-TEMPO benzoate Chemical compound C1C(C)(C)N([O])C(C)(C)CC1OC(=O)C1=CC=CC=C1 MJEDTBDGYVATPI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthalene Natural products C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
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- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- UFLXKQBCEYNCDU-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CC(C)(C)NC(C)(C)C1 UFLXKQBCEYNCDU-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
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- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- PJEUXMXPJGWZOZ-UHFFFAOYSA-L zinc;diphenylphosphinate Chemical compound [Zn+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 PJEUXMXPJGWZOZ-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本發明涉及一種樹脂組成物、預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及配線板。The invention relates to a resin composition, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate and a wiring board.
各種電子機器伴隨著資訊處理量大增，所搭載之半導體裝置的高積體化、配線的高密度化及多層化等的安裝技術持續發展。且，作為各種電子機器使用之配線板，係要求例如用於車載用途之毫米波雷達基板等對應高頻之配線板。為了提高訊號之傳輸速度，對於各種電子機器中所使用之配線板要求降低訊號傳輸時之損失，且對於對應高頻之配線板特別要求所述需求。為了滿足該需求，對於用以構成可在各種電子機器中使用之配線板之基材的基材材料，要求介電常數及介電正切要低。With the increase in the amount of information processed by various electronic devices, mounting technologies such as high integration of mounted semiconductor devices, high density of wiring, and multilayering continue to develop. Furthermore, as a wiring board used in various electronic devices, wiring boards corresponding to high frequencies, such as millimeter-wave radar boards used in automotive applications, are required. In order to increase the transmission speed of signals, reduction of loss during signal transmission is required for wiring boards used in various electronic devices, and such requirements are particularly required for wiring boards corresponding to high frequencies. In order to meet this demand, a low dielectric constant and a low dielectric tangent are required for a base material constituting a base material of a wiring board used in various electronic devices.
作為所述基材材料，例如有報告提出一種含PPE樹脂組成物具有優異之低介電特性或玻璃轉移溫度(Tg)等，該含PPE樹脂組成物包含：PPE(聚伸苯基醚)、交聯型硬化性化合物及磷雜菲衍生物(專利文獻1)。As the base material, for example, there are reports that a PPE-containing resin composition has excellent low dielectric properties or glass transition temperature (Tg), etc., and the PPE-containing resin composition includes: PPE (polyphenylene ether), A crosslinkable curable compound and a phosphaphenanthrene derivative (Patent Document 1).
另一方面，對於基地台之PA(power amplification，功率放大器)基板等所使用之電子材料，除了要求介電常數及介電正切低外，還要求熱傳導率要高。迄今為止，作為提升樹脂組成物之熱傳導率之手法之一，還有報告提出一種包含各向異性氧化鎂之衍生物用樹脂組成物(專利文獻2)，而為了獲得更高之熱傳導率，有報告提出一種使用氮化硼作為無機充填劑之技術(專利文獻3或專利文獻4)。On the other hand, for the electronic materials used in the PA (power amplification, power amplifier) substrate of the base station, in addition to requiring low dielectric constant and dielectric tangent, high thermal conductivity is also required. So far, as one of the means of improving the thermal conductivity of the resin composition, there is also a report to propose a resin composition for derivatives containing anisotropic magnesium oxide (Patent Document 2), and in order to obtain higher thermal conductivity, there are The report proposes a technology using boron nitride as an inorganic filler (
上述專利文獻3及4中記載之氮化硼填料確實能改善樹脂組成物之熱傳導率。但，將樹脂組成物作為基板材料等成形材料使用時，還要求更優異之阻燃性。關於這點，上述專利文獻1記載之樹脂組成物中，係於聚伸苯基醚樹脂中添加有作為阻燃劑使用之磷雜菲衍生物。磷雜菲衍生物作為無鹵素之磷系阻燃劑廣為人知。The boron nitride fillers described in the
然而，根據本發明人等之研究，可知若分別單獨使用與樹脂相溶之磷系阻燃劑或不與樹脂相溶之磷系阻燃劑，熱傳導率或Tg會變差。 先前技術文獻 專利文獻 However, according to the studies of the inventors of the present invention, it is known that if a phosphorus-based flame retardant compatible with a resin or a phosphorus-based flame retardant not compatible with a resin is used alone, the thermal conductivity or Tg will be deteriorated. prior art literature patent documents
專利文獻1：日本專利特開2015-67700號公報 專利文獻2：日本專利特開2015-168731號公報 專利文獻3：日本專利特開2013-241321號公報 專利文獻4：日本專利特開2014-208818號公報 Patent Document 1: Japanese Patent Laid-Open No. 2015-67700 Patent Document 2: Japanese Patent Laid-Open No. 2015-168731 Patent Document 3: Japanese Patent Laid-Open No. 2013-241321 Patent Document 4: Japanese Patent Laid-Open No. 2014-208818
本發明係有鑑於所述情事而作成之發明，目的在於提供一種樹脂組成物，該樹脂組成物可獲得介電特性低、熱傳導率及玻璃轉移溫度(Tg)高且阻燃性優異之硬化物。又，本發明目的在於提供一種使用前述樹脂組成物所得之預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及配線板。The present invention was made in view of the above circumstances, and an object of the present invention is to provide a resin composition capable of obtaining a cured product having low dielectric properties, high thermal conductivity and glass transition temperature (Tg), and excellent flame retardancy . Another object of the present invention is to provide a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board obtained by using the aforementioned resin composition.
本發明人等經過種種研討，結果發現上述目的可藉由以下構成來達成，並進一步反覆研討而達成本發明。As a result of various researches, the inventors of the present invention found that the above-mentioned object can be achieved by the following configurations, and further conducted repeated researches to achieve the present invention.
亦即，本發明一態樣之樹脂組成物之特徵在於：包含：聚伸苯基醚化合物(A)；硬化劑(B)；含氮化硼之無機充填劑(C)；及磷化合物(D)；且前述無機充填劑(C)之粒度分布中，利用雷射繞射式粒度分布測定法測定之粒度分布的峰值在粒徑1.0~50.0µm範圍中至少存在2個；前述磷化合物(D)包含相溶性磷化合物(D-1)及非相溶性磷化合物(D-2)，該相溶性磷化合物(D-1)係和前述聚伸苯基醚化合物(A)與前述硬化劑(B)之混合物相溶者，該非相溶性磷化合物(D-2)係不與前述混合物相溶者。That is, the resin composition of one aspect of the present invention is characterized in that it contains: a polyphenylene ether compound (A); a hardener (B); an inorganic filler containing boron nitride (C); and a phosphorus compound ( D); and in the particle size distribution of the above-mentioned inorganic filler (C), there are at least two peaks of the particle size distribution measured by the laser diffraction particle size distribution method in the range of particle diameters of 1.0 to 50.0 µm; the above-mentioned phosphorus compound ( D) Comprising a compatible phosphorus compound (D-1) and an incompatible phosphorus compound (D-2), the compatible phosphorus compound (D-1) and the aforementioned polyphenylene ether compound (A) and the aforementioned hardening agent If the mixture of (B) is compatible, the incompatible phosphorus compound (D-2) is not compatible with the aforementioned mixture.
以下，針對本發明實施形態進行具體說明，但本發明不受該等所限。Hereinafter, although embodiment of this invention is demonstrated concretely, this invention is not limited to these.
[樹脂組成物] 本發明實施形態之樹脂組成物之特徵在於：包含：聚伸苯基醚化合物(A)；硬化劑(B)；含氮化硼之無機充填劑(C)；及磷化合物(D)；且前述無機充填劑(C)之粒度分布中，利用雷射繞射式粒度分布測定法測定之粒度分布的峰值在粒徑1.0~50.0µm範圍中至少存在2個；前述磷化合物(D)包含相溶性磷化合物(D-1)及非相溶性磷化合物(D-2)，該相溶性磷化合物(D-1)係和前述聚伸苯基醚化合物(A)與前述硬化劑(B)之混合物相溶者，該非相溶性磷化合物(D-2)係不和前述聚伸苯基醚化合物(A)與前述硬化劑(B)之混合物相溶者。 [Resin composition] The resin composition according to the embodiment of the present invention is characterized by: comprising: polyphenylene ether compound (A); hardener (B); inorganic filler containing boron nitride (C); and phosphorus compound (D); and In the particle size distribution of the above-mentioned inorganic filler (C), there are at least two peaks in the particle size distribution measured by the laser diffraction particle size distribution measurement method in the range of particle diameters from 1.0 to 50.0 µm; the above-mentioned phosphorus compound (D) contains phase A soluble phosphorus compound (D-1) and an incompatible phosphorus compound (D-2). If the mixture is compatible, the incompatible phosphorus compound (D-2) is not compatible with the mixture of the aforementioned polyphenylene ether compound (A) and the aforementioned hardening agent (B).
藉由上述構成可獲得一種樹脂組成物，該樹脂組成物可獲得介電特性(相對介電常數)低、熱傳導率及Tg高、密著性及阻燃性優異之硬化物。又，根據本發明，藉由使用前述樹脂組成物，可提供具有優異性能之預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及配線基板。With the above configuration, a resin composition can be obtained which can obtain a cured product having low dielectric properties (relative permittivity), high thermal conductivity and Tg, and excellent adhesion and flame retardancy. Also, according to the present invention, by using the aforementioned resin composition, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board having excellent performance can be provided.
首先，針對本實施形態之樹脂組成物的各成分進行說明。First, each component of the resin composition of this embodiment is demonstrated.
(聚伸苯基醚化合物(A)) 本實施形態之聚伸苯基醚化合物(A)無特別限定，但由更降低介電特性之觀點來看，宜為改質聚伸苯基醚化合物。更理想的是，若為具有後述式(1)或式(2)所示之基團的改質聚伸苯基醚化合物(A-1)即較理想。吾等認為藉由含有所述聚伸苯基醚化合物，便能成為一種可獲得介電特性低且耐熱性高之硬化物的樹脂組成物。 (polyphenylene ether compound (A)) The polyphenylene ether compound (A) of this embodiment is not particularly limited, but a modified polyphenylene ether compound is preferable from the viewpoint of further lowering the dielectric properties. More preferably, it is a modified polyphenylene ether compound (A-1) having a group represented by the following formula (1) or formula (2). We think that by containing the polyphenylene ether compound, it becomes possible to obtain a cured product having low dielectric characteristics and high heat resistance.
[化學式1] [chemical formula 1]
式(1)中，s表示0~10之整數。又，Z表示伸芳基。又，R 1~R 3分別獨立。即，R 1~R 3可分別為相同基團，亦可為互異之基團。又，R 1~R 3表示氫原子或烷基。 In formula (1), s represents an integer of 0-10. Also, Z represents an extended aryl group. Also, R 1 to R 3 are independently independent. That is, R 1 to R 3 may be the same group or different groups. Also, R 1 to R 3 represent a hydrogen atom or an alkyl group.
此外，式(1)中，s為0時，Z表示直接鍵結於聚伸苯基醚末端。In addition, in formula (1), when s is 0, Z represents that it is directly bonded to the polyphenylene ether terminal.
上述Z之伸芳基無特別限定。該伸芳基可舉例如伸苯基等單環芳香族基、或是芳香族非為單環而為萘環等多環芳香族之多環芳香族基等。又，該伸芳基中還包含鍵結於芳香族環之氫原子被烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基等官能基取代之衍生物。又，前述烷基無特別限定，例如宜為碳數1~18烷基，較宜為碳數1~10烷基。具體上可舉例如甲基、乙基、丙基、己基及癸基等。The above-mentioned arylylene group of Z is not particularly limited. The aryl group includes, for example, a monocyclic aromatic group such as a phenylene group, or a polycyclic aromatic group such as a naphthalene ring instead of a monocyclic aromatic group. In addition, the aryl group also includes derivatives in which the hydrogen atom bonded to the aromatic ring is replaced by a functional group such as alkenyl, alkynyl, formyl, alkylcarbonyl, alkenylcarbonyl or alkynylcarbonyl. Also, the aforementioned alkyl group is not particularly limited, for example, it is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, etc. are mentioned.
[化學式2] [chemical formula 2]
式(2)中，R 4表示氫原子或烷基。前述烷基無特別限定，例如宜為碳數1~18烷基，較宜為碳數1~10烷基。具體上可舉例如甲基、乙基、丙基、己基及癸基等。 In formula (2), R 4 represents a hydrogen atom or an alkyl group. The aforementioned alkyl group is not particularly limited, for example, it is preferably an alkyl group with 1 to 18 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, etc. are mentioned.
前述式(1)所示之取代基之理想具體例可舉例如含乙烯基苄基之取代基等。前述含乙烯基苄基之取代基可舉例如下述式(6)所示之取代基等。又，前述式(2)所示之取代基可舉例如丙烯酸酯基及甲基丙烯酸酯基等。Desirable specific examples of the substituent represented by the aforementioned formula (1) include, for example, a vinylbenzyl group-containing substituent and the like. Examples of the vinylbenzyl group-containing substituent include substituents represented by the following formula (6). Moreover, the substituent represented by said formula (2) is mentioned, for example, an acrylate group, a methacrylate group, etc. are mentioned.
[化學式3] [chemical formula 3]
前述取代基更具體而言可列舉對乙烯基苄基及間乙烯基苄基等乙烯基苄基(vinyl benzyl/ethenyl benzyl)、乙烯基苯基、丙烯酸酯基及甲基丙烯酸酯基等。More specifically, examples of the substituent include vinylbenzyl groups such as p-vinylbenzyl groups and m-vinylbenzyl groups (vinylbenzyl/ethenylbenzyl groups), vinylphenyl groups, acrylate groups, methacrylate groups, and the like.
前述聚伸苯基醚化合物於分子中具有聚伸苯基醚鏈，例如宜於分子中具有下述式(7)所示之重複單元。The aforementioned polyphenylene ether compound has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by the following formula (7) in the molecule, for example.
[化學式4] [chemical formula 4]
式(7)中，t表示1~50。又，R 5~R 8分別獨立。即，R 5~R 8可分別為相同基團，亦可為互異之基團。又，R 5~R 8表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基。其中又宜為氫原子及烷基。 In formula (7), t represents 1-50. Also, R 5 to R 8 are independently independent. That is, R 5 to R 8 may be the same group or different groups. Also, R 5 to R 8 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are preferable.
關於R 5~R 8，所列舉之各官能基具體上可舉如下。 As for R 5 ~R 8 , each functional group enumerated can be specifically listed as follows.
烷基無特別限定，例如宜為碳數1~18烷基，較宜為碳數1~10烷基。具體上可舉例如甲基、乙基、丙基、己基及癸基等。The alkyl group is not particularly limited. For example, it is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, etc. are mentioned.
烯基無特別限定，例如宜為碳數2~18烯基，較宜為碳數2~10烯基。具體上可舉例如乙烯基、烯丙基及3-丁烯基等。The alkenyl group is not particularly limited, for example, it is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms. Specifically, a vinyl group, an allyl group, a 3-butenyl group, etc. are mentioned.
炔基無特別限定，例如宜為碳數2~18炔基，較宜為碳數2~10炔基。具體上可舉例如乙炔基及丙-2-炔-1-基(prop-2-yn-1-yl；炔丙基)等。The alkynyl group is not particularly limited, for example, it is preferably an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms. Specifically, ethynyl and prop-2-yn-1-yl (prop-2-yn-1-yl; propargyl) etc. are mentioned, for example.
烷基羰基若為經烷基取代之羰基即無特別限定，例如宜為碳數2~18烷基羰基，較宜為碳數2~10烷基羰基。具體上可列舉例如乙醯基、丙醯基、丁醯基、異丁醯基、三甲基乙醯基、己醯基、辛醯基及環己基羰基等。The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, it is preferably an alkylcarbonyl group having 2 to 18 carbons, more preferably an alkylcarbonyl group having 2 to 10 carbons. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, trimethylacetyl, hexyl, octyl, and cyclohexylcarbonyl.
烯基羰基若為經烯基取代之羰基即無特別限定，例如宜為碳數3~18烯基羰基，較宜為碳數3~10烯基羰基。具體上可舉例如丙烯醯基、甲基丙烯醯基及巴豆醯基等。The alkenylcarbonyl group is not particularly limited if it is a carbonyl group substituted with an alkenyl group. For example, it is preferably an alkenylcarbonyl group having 3 to 18 carbons, more preferably an alkenylcarbonyl group having 3 to 10 carbons. Specifically, an acryl group, a methacryl group, a crotonyl group, etc. are mentioned, for example.
炔基羰基若為經炔基取代之羰基即無特別限定，例如宜為碳數3~18炔基羰基，較宜為碳數3~10炔基羰基。具體上可舉例如炔丙醯基等。The alkynylcarbonyl group is not particularly limited if it is a carbonyl group substituted by an alkynyl group. For example, it is preferably an alkynylcarbonyl group having 3 to 18 carbons, more preferably an alkynylcarbonyl group having 3 to 10 carbons. Specifically, a propargyl group etc. are mentioned, for example.
前述聚伸苯基醚化合物之重量平均分子量(Mw)無特別限定。具體而言，宜為500~5000，較宜為800~4000，更宜為1000~3000。此外，在此重量平均分子量若為以一般分子量測定方法測得者即可，具體上可舉使用凝膠滲透層析術(GPC)測得之值等。又，聚伸苯基醚化合物於分子中具有前述式(11)所示之重複單元時，t宜為可使聚伸苯基醚化合物之重量平均分子量落在所述範圍內之數值。具體而言，t宜為1~50。The weight average molecular weight (Mw) of the aforementioned polyphenylene ether compound is not particularly limited. Specifically, it is preferably 500-5000, more preferably 800-4000, more preferably 1000-3000. In addition, what is necessary is just to measure a weight average molecular weight here by the general molecular weight measuring method, Specifically, the value measured using gel permeation chromatography (GPC), etc. are mentioned. Also, when the polyphenylene ether compound has a repeating unit represented by the aforementioned formula (11) in the molecule, t is preferably a value that allows the weight average molecular weight of the polyphenylene ether compound to fall within the above-mentioned range. Specifically, t is preferably 1-50.
前述聚伸苯基醚化合物之重量平均分子量若在所述範圍內，便能成為下述者：具有聚伸苯基醚具有之優異的低介電特性，硬化物之耐熱性更優異，不僅如此，成形性亦優異。吾等以為其理由如下。以一般的聚伸苯基醚來說，其重量平均分子量若在所述範圍內，即為分子量較低之物，故有硬化物之耐熱性降低之傾向。關於這點，因為本實施形態之聚伸苯基醚化合物於末端具有1個以上不飽和雙鍵，故可獲得硬化物之耐熱性充分夠高者。又，聚伸苯基醚化合物之重量平均分子量若在所述範圍內，即為分子量較低之物，因此成形性亦優異。所以，吾等認為所述聚伸苯基醚化合物可獲得不僅硬化物之耐熱性更優異且成形性亦優異者。If the weight-average molecular weight of the aforementioned polyphenylene ether compound is within the above-mentioned range, it will not only have the excellent low dielectric properties of polyphenylene ether, but also have excellent heat resistance of the cured product. , excellent formability. We believe the reasons for this are as follows. In the case of general polyphenylene ether, if the weight average molecular weight is within the above-mentioned range, the molecular weight is relatively low, so the heat resistance of the cured product tends to decrease. In this regard, since the polyphenylene ether compound of the present embodiment has one or more unsaturated double bonds at the terminal, it is possible to obtain a cured product with sufficiently high heat resistance. Moreover, if the weight average molecular weight of a polyphenylene ether compound exists in the said range, since it will be a low molecular weight thing, it will also be excellent in formability. Therefore, we think that the above-mentioned polyphenylene ether compound can obtain not only the heat resistance of the cured product but also the excellent formability.
前述聚伸苯基醚化合物中，聚伸苯基醚化合物每分子之分子末端具有之前述取代基的平均個數(末端官能基數)無特別限定。具體而言，宜為1~5個，較宜為1~3個，更宜為1.5~3個。該末端官能基數若太少，有不易獲得就硬化物之耐熱性而言夠充分之物的傾向。又，末端官能基數若太多，反應性會變得過高，而恐發生例如樹脂組成物之保存性降低、或樹脂組成物之流動性降低等不良情況。即，若使用所述聚伸苯基醚化合物，恐有因流動性不足等，而發生例如於多層成形時產生孔隙等的成形不良，從而發生不易獲得可靠性高之印刷配線板等的成形性之問題。In the polyphenylene ether compound, the average number of the substituents (terminal functional group number) per molecule of the polyphenylene ether compound is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, more preferably 1.5 to 3. When the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product which is sufficient in heat resistance. In addition, if the number of terminal functional groups is too large, the reactivity will be too high, which may cause problems such as reduced storage stability of the resin composition or reduced fluidity of the resin composition. That is, if the above-mentioned polyphenylene ether compound is used, there is a possibility that molding defects such as voids during multilayer molding may occur due to insufficient fluidity, and it may be difficult to obtain a formability such as a highly reliable printed wiring board. question.
此外，聚伸苯基醚化合物之末端官能基數可舉：表示聚伸苯基醚化合物1莫耳中存在之所有改質聚伸苯基醚化合物每分子之前述取代基之平均值的數值等。該末端官能基數例如可藉由測定所得之改質聚伸苯基醚化合物中殘存之羥基數，再從改質前之聚伸苯基醚之羥基數算出減少量來測定。從該改質前之聚伸苯基醚之羥基數減少之減少量即為末端官能基數。而且，改質聚伸苯基醚化合物中殘存之羥基數的測定方法，可藉由於改質聚伸苯基醚化合物之溶液中添加能與羥基締合之四級銨鹽(氫氧化四乙銨)，並測定其混合溶液之UV吸光度而求得。In addition, the number of terminal functional groups of the polyphenylene ether compound can be exemplified by a numerical value representing the average value of the aforementioned substituents per molecule of all the modified polyphenylene ether compounds present in 1 mole of the polyphenylene ether compound. The number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound, and then calculating the amount of reduction from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease in the number of hydroxyl groups from the polyphenylene ether before modification is the number of terminal functional groups. Moreover, the method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether compound can be obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) capable of associating with hydroxyl groups to the solution of the modified polyphenylene ether compound. ), and obtain it by measuring the UV absorbance of the mixed solution.
本實施形態之聚伸苯基醚化合物(A)的固有黏度無特別限定。具體而言，若為0.03~0.12dl/g即可，宜為0.04~0.11dl/g，較宜為0.06~0.095dl/g。該固有黏度若太低，有分子量低之傾向，而有不易獲得低介電常數或低介電正切等低介電性的傾向。又，固有黏度若太高，有黏度高、無法獲得充分之流動性，而硬化物之成形性降低的傾向。因此，聚伸苯基醚化合物之固有黏度若在上述範圍內，便可實現優異之硬化物的耐熱性及成形性。The intrinsic viscosity of the polyphenylene ether compound (A) of this embodiment is not specifically limited. Specifically, it is sufficient if it is 0.03-0.12dl/g, preferably 0.04-0.11dl/g, more preferably 0.06-0.095dl/g. If the intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric properties such as low dielectric constant and low dielectric tangent. Also, if the intrinsic viscosity is too high, the viscosity becomes high, sufficient fluidity cannot be obtained, and the formability of the hardened product tends to decrease. Therefore, if the intrinsic viscosity of the polyphenylene ether compound is within the above-mentioned range, excellent heat resistance and moldability of the cured product can be realized.
此外，在此之固有黏度係在25℃之二氯甲烷中測得之固有黏度，更具體而言，例如係以黏度計測定0.18g/45ml之二氯甲烷溶液(液溫25℃)所得之值等。該黏度計可舉例如Schott公司製AVS500 Visco System等。In addition, the intrinsic viscosity here is the intrinsic viscosity measured in dichloromethane at 25°C. More specifically, it is obtained by measuring a 0.18g/45ml dichloromethane solution (liquid temperature: 25°C) with a viscometer, for example. value etc. The viscometer may, for example, be Schott AVS500 Visco System or the like.
本實施形態之改質聚伸苯基醚化合物(A)可舉例如下述式(8)所示之改質聚伸苯基醚化合物及下述式(9)所示之改質聚伸苯基醚化合物等。又，本實施形態之改質聚伸苯基醚化合物可單獨使用該等改質聚伸苯基醚化合物，亦可組合2種改質聚伸苯基醚化合物來使用。The modified polyphenylene ether compound (A) of this embodiment can be, for example, a modified polyphenylene ether compound represented by the following formula (8) and a modified polyphenylene ether compound represented by the following formula (9) ether compounds, etc. In addition, as the modified polyphenylene ether compound of the present embodiment, these modified polyphenylene ether compounds may be used alone, or two types of modified polyphenylene ether compounds may be used in combination.
[化學式5] [chemical formula 5]
[化學式6] [chemical formula 6]
式(8)及式(9)中，R 9~R 16以及R 17~R 24分別獨立表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基。X 1及X 2分別獨立表示具有碳-碳不飽和雙鍵之取代基。A及B分別表示下述式(10)及下述式(11)所示之重複單元。又，式(9)中，Y表示碳數20以下之直鏈狀、支鏈狀或環狀烴。 In formula (8) and formula (9), R 9 ~ R 16 and R 17 ~ R 24 independently represent hydrogen atom, alkyl, alkenyl, alkynyl, formyl, alkylcarbonyl, alkenylcarbonyl or alkyne base carbonyl. X1 and X2 each independently represent a substituent having a carbon-carbon unsaturated double bond. A and B represent repeating units represented by the following formula (10) and the following formula (11), respectively. Also, in formula (9), Y represents a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms.
[化學式7] [chemical formula 7]
[化學式8] [chemical formula 8]
式(10)及式(11)中，m及n分別表示0~20。R 25~R 28以及R 29~R 32分別獨立表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基。 In formula (10) and formula (11), m and n represent 0~20 respectively. R 25 to R 28 and R 29 to R 32 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group.
前述式(8)所示之改質聚伸苯基醚化合物及前述式(9)所示之改質聚伸苯基醚化合物若為滿足上述構成之化合物，則無特別限定。具體來說，前述式(8)及前述式(9)中，R 9~R 16以及R 17~R 24如上述，係分別獨立。即，R 9~R 16以及R 17~R 24可分別為相同基團，亦可為互異之基團。又，R 9~R 16以及R 17~R 24表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基。其中又宜為氫原子及烷基。 The modified polyphenylene ether compound represented by the aforementioned formula (8) and the modified polyphenylene ether compound represented by the aforementioned formula (9) are not particularly limited as long as they satisfy the above constitution. Specifically, in the aforementioned formula (8) and the aforementioned formula (9), R 9 to R 16 and R 17 to R 24 are independent as described above. That is, R 9 to R 16 and R 17 to R 24 may be the same group or different groups. Also, R 9 to R 16 and R 17 to R 24 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are preferable.
式(10)及式(11)中，m及n宜分別如上述，表示0~20。又，以m及n來說，m與n之合計值宜表示成為1~30之數值。因此，較宜為：m表示0~20，n表示0~20，m與n之合計表示1~30。又，R 25~R 28以及R 29~R 32係分別獨立。即，R 25~R 28以及R 29~R 32可分別為相同基團，亦可為互異之基團。又，R 25~R 28以及R 29~R 32表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基。其中又宜為氫原子及烷基。 In the formula (10) and the formula (11), m and n should represent 0~20 respectively as above. Also, for m and n, the total value of m and n should be expressed as a numerical value of 1 to 30. Therefore, it is preferable that m represents 0-20, n represents 0-20, and the total of m and n represents 1-30. Also, R 25 to R 28 and R 29 to R 32 are independently independent. That is, R 25 to R 28 and R 29 to R 32 may be the same group or different groups. Also, R 25 to R 28 and R 29 to R 32 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are preferable.
R 9~R 32係與上述式(7)中之R 5~R 8相同。 R 9 to R 32 are the same as R 5 to R 8 in the above formula (7).
前述式(9)中，Y如上述，為碳數20以下之直鏈狀、支鏈狀或環狀烴。Y可舉例如下述式(12)所示之基團等。In the aforementioned formula (9), Y is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms as described above. As Y, the group represented by following formula (12), etc. are mentioned, for example.
[化學式9] [chemical formula 9]
前述式(12)中，R 33及R 34分別獨立表示氫原子或烷基。前述烷基可舉例如甲基等。又，式(12)所示之基團可舉例如亞甲基、甲基亞甲基及二甲基亞甲基等，該等又中宜為二甲基亞甲基。 In the aforementioned formula (12), R 33 and R 34 each independently represent a hydrogen atom or an alkyl group. The aforementioned alkyl group may, for example, be methyl group or the like. In addition, the group represented by the formula (12) includes, for example, methylene, methylmethylene, and dimethylmethylene, among which dimethylmethylene is preferable.
前述式(8)及前述式(9)中，X 1及X 2分別獨立為具有碳-碳不飽和雙鍵之取代基。該取代基X 1及X 2若為具有碳-碳不飽和雙鍵之取代基，則無特別限定。前述取代基X 1及X 2可舉例如上述式(1)所示之取代基及上述式(2)所示之取代基等。此外，前述式(8)所示之改質聚伸苯基醚化合物及前述式(9)所示之改質聚伸苯基醚化合物中，X 1及X 2可為相同取代基，亦可為互異之取代基。 In the aforementioned formula (8) and aforementioned formula (9), X 1 and X 2 are each independently a substituent having a carbon-carbon unsaturated double bond. The substituents X1 and X2 are not particularly limited as long as they are substituents having a carbon-carbon unsaturated double bond. The aforementioned substituents X 1 and X 2 can be exemplified by the substituents represented by the above formula (1) and the substituents represented by the above formula (2). In addition, in the modified polyphenylene ether compound represented by the aforementioned formula (8) and the modified polyphenylene ether compound represented by the aforementioned formula (9), X 1 and X 2 may be the same substituent, or may be are different substituents.
前述式(8)所示之改質聚伸苯基醚化合物之更具體例示，可舉例如下述式(13)所示之改質聚伸苯基醚化合物等。More specific examples of the modified polyphenylene ether compound represented by the aforementioned formula (8) include, for example, a modified polyphenylene ether compound represented by the following formula (13).
[化學式10] [chemical formula 10]
前述式(9)所示之改質聚伸苯基醚化合物之更具體例示，可舉例如下述式(14)所示之改質聚伸苯基醚化合物及下述式(15)所示之改質聚伸苯基醚化合物等。More specific examples of the modified polyphenylene ether compound represented by the aforementioned formula (9) include the modified polyphenylene ether compound represented by the following formula (14) and the modified polyphenylene ether compound represented by the following formula (15). Modified polyphenylene ether compounds, etc.
[化學式11] [chemical formula 11]
[化學式12] [chemical formula 12]
上述式(13)~式(15)中，m及n係與上述式(10)及上述式(11)中之m及n相同。又，上述式(13)及上述式(14)中，R 1~R 3、p及Z分別係與上述式(1)中之R 1~R 3、s及Z相同。又，上述式(14)及上述式(15)中，Y係與上述(9)中之Y相同。又，上述式(14)中，R 4係與上述式(2)中之R 4相同。 In the above formula (13) to formula (15), m and n are the same as m and n in the above formula (10) and the above formula (11). In addition, in the above formula (13) and the above formula (14), R 1 to R 3 , p and Z are respectively the same as R 1 to R 3 , s and Z in the above formula (1). In addition, in the above-mentioned formula (14) and the above-mentioned formula (15), Y is the same as Y in the above-mentioned (9). Also, in the above formula (14), R 4 is the same as R 4 in the above formula (2).
吾等認為藉由使用如上述之改質聚伸苯基醚化合物，可維持低介電常數等低介電特性與優異之耐熱性等，同時可提升高Tg及密著性。We believe that by using the above-mentioned modified polyphenylene ether compound, low dielectric properties such as low dielectric constant and excellent heat resistance can be maintained, and high Tg and adhesion can be improved at the same time.
此外，改質聚伸苯基醚化合物可單獨使用1種，亦可組合2種以上來使用。In addition, the modified polyphenylene ether compound may be used alone or in combination of two or more.
本實施形態之樹脂組成物中使用之聚伸苯基醚化合物(A)可利用公知方法合成，亦可使用市售物。市售物可舉例如MITSUBISHI GAS CHEMICAL COMPANY製之「OPE-2st 1200」、「OPE-2st 2200」；SABIC Innovative Plastics公司製之「SA9000」等。The polyphenylene ether compound (A) used in the resin composition of this embodiment can be synthesized by a known method, and a commercially available thing can also be used. Commercially available products include "OPE-2st 1200" and "OPE-2st 2200" manufactured by MITSUBISHI GAS CHEMICAL COMPANY; "SA9000" manufactured by SABIC Innovative Plastics; and the like.
(硬化劑(B)) 本實施形態之樹脂組成物更包含硬化劑(B)。 (Hardener (B)) The resin composition of the present embodiment further includes a curing agent (B).
前述硬化劑(B)若為可與前述聚伸苯基醚化合物(A)反應而使含前述聚伸苯基醚化合物(A)之樹脂組成物硬化的硬化劑，即無特別限定。前述硬化劑可舉分子中具有至少1個以上有助於與前述聚伸苯基醚化合物(A)之反應之官能基的硬化劑等。The curing agent (B) is not particularly limited as long as it can react with the polyphenylene ether compound (A) to cure the resin composition containing the polyphenylene ether compound (A). Examples of the curing agent include those having at least one functional group in the molecule that contributes to the reaction with the polyphenylene ether compound (A).
具體而言，可列舉例如：分子中具有丙烯醯基之化合物、分子中具有甲基丙烯醯基之化合物、分子中具有乙烯基之化合物、分子中具有烯丙基之化合物、分子中具有馬來醯亞胺基之化合物、分子中具有苊結構之化合物及分子中具有三聚異氰酸酯基之三聚異氰酸酯化合物、苯乙烯衍生物等。Specifically, for example, compounds having an acryl group in the molecule, compounds having a methacryl group in the molecule, compounds having a vinyl group in the molecule, compounds having an allyl group in the molecule, compounds having a maleic group in the molecule, Compounds with imide group, compounds with acenaphthene structure in the molecule, isocyanate compounds with isocyanate group in the molecule, styrene derivatives, etc.
前述分子中具有丙烯醯基之化合物為丙烯酸酯化合物。前述丙烯酸酯化合物可舉分子中具有1個丙烯醯基之單官能丙烯酸酯化合物、及分子中具有2個以上丙烯醯基之多官能丙烯酸酯化合物。前述單官能丙烯酸酯化合物可舉例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯及丙烯酸丁酯等。前述多官能丙烯酸酯化合物可舉例如三環癸烷二甲醇二丙烯酸酯等。The compound having an acryl group in the aforementioned molecule is an acrylate compound. Examples of the aforementioned acrylate compound include monofunctional acrylate compounds having one acryl group in the molecule, and polyfunctional acrylate compounds having two or more acryl groups in the molecule. The aforementioned monofunctional acrylate compound may, for example, be methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate. The aforementioned polyfunctional acrylate compound may, for example, be tricyclodecane dimethanol diacrylate or the like.
前述分子中具有甲基丙烯醯基之化合物為甲基丙烯酸酯化合物。前述甲基丙烯酸酯化合物可舉分子中具有1個甲基丙烯醯基之單官能甲基丙烯酸酯化合物、及分子中具有2個以上甲基丙烯醯基之多官能甲基丙烯酸酯化合物。前述單官能甲基丙烯酸酯化合物可舉例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯及甲基丙烯酸丁酯等。前述多官能甲基丙烯酸酯化合物可舉例如三環癸烷二甲醇二甲基丙烯酸酯等。The compound having a methacryl group in the aforementioned molecule is a methacrylate compound. Examples of the aforementioned methacrylate compound include monofunctional methacrylate compounds having one methacryl group in the molecule, and polyfunctional methacrylate compounds having two or more methacryl groups in the molecule. The aforementioned monofunctional methacrylate compound may, for example, be methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate. The aforementioned polyfunctional methacrylate compound may, for example, be tricyclodecane dimethanol dimethacrylate or the like.
前述分子中具有乙烯基之化合物為乙烯基化合物。前述乙烯基化合物可舉分子中具有1個乙烯基之單官能乙烯基化合物(單乙烯基化合物)、及分子中具有2個以上乙烯基之多官能乙烯基化合物。前述多官能乙烯基化合物可舉例如二乙烯苯及聚丁二烯等。The compound having a vinyl group in the aforementioned molecule is a vinyl compound. Examples of the aforementioned vinyl compound include a monofunctional vinyl compound (monovinyl compound) having one vinyl group in a molecule, and a polyfunctional vinyl compound having two or more vinyl groups in a molecule. The aforementioned polyfunctional vinyl compound may, for example, be divinylbenzene or polybutadiene.
前述分子中具有烯丙基之化合物為烯丙基化合物。前述烯丙基化合物可舉分子中具有1個烯丙基之單官能烯丙基化合物及分子中具有2個以上烯丙基之多官能烯丙基化合物。前述多官能烯丙基化合物可舉例如酞酸二烯丙酯(DAP)等。The compound having an allyl group in the aforementioned molecule is an allyl compound. The aforementioned allyl compound includes a monofunctional allyl compound having one allyl group in a molecule and a polyfunctional allyl compound having two or more allyl groups in a molecule. The aforementioned polyfunctional allyl compound may, for example, be diallyl phthalate (DAP).
前述分子中具有馬來醯亞胺基之化合物為馬來醯亞胺化合物。前述馬來醯亞胺化合物可舉分子中具有1個馬來醯亞胺基之單官能馬來醯亞胺化合物、分子中具有2個以上馬來醯亞胺基之多官能馬來醯亞胺化合物及改質馬來醯亞胺化合物等。前述改質馬來醯亞胺化合物可舉例如分子中一部分經胺化合物改質之改質馬來醯亞胺化合物、分子中一部分經聚矽氧化合物改質之改質馬來醯亞胺化合物、及分子中一部分經胺化合物及聚矽氧化合物改質之改質馬來醯亞胺化合物等。The compound having a maleimide group in the aforementioned molecule is a maleimide compound. The aforementioned maleimide compounds include monofunctional maleimide compounds having one maleimide group in the molecule, and polyfunctional maleimide compounds having two or more maleimide groups in the molecule. Compounds and modified maleimide compounds, etc. The aforementioned modified maleimide compound can be, for example, a modified maleimide compound in which a part of the molecule is modified by an amine compound, a modified maleimide compound in which a part of the molecule is modified by a polysiloxane compound, And modified maleimide compounds modified by amine compounds and polysiloxane compounds in part of the molecule.
前述分子中具有苊結構之化合物為苊化合物。前述苊化合物可舉例如苊、烷基苊類、鹵化苊類及苯基苊類等。前述烷基苊類可舉例如1-甲基苊、3-甲基苊、4-甲基苊、5-甲基苊、1-乙基苊、3-乙基苊、4-乙基苊、5-乙基苊等。前述鹵化苊類可舉例如1-氯苊、3-氯苊、4-氯苊、5-氯苊、1-溴苊、3-溴苊、4-溴苊、5-溴苊等。前述苯基苊類可舉例如1-苯基苊、3-苯基苊、4-苯基苊、5-苯基苊等。前述苊化合物可為如前述之分子中具有1個苊結構之單官能苊化合物，亦可為分子中具有2個以上苊結構之多官能苊化合物。The compound having an acenaphthene structure in the aforementioned molecules is an acenaphthene compound. The aforementioned acenaphthylene compound may, for example, be acenaphthylene, alkyl acenaphthylene, halogenated acenaphthylene, or phenyl acenaphthylene. The above-mentioned alkyl acenaphthene can be exemplified for example by 1-methyl acenaphthene, 3-methyl acenaphthylene, 4-methyl acenaphthylene, 5-methyl acenaphthylene, 1-ethyl acenaphthylene, 3-ethyl acenaphthylene, 4-ethyl acenaphthylene, 5-Ethylacenaphthene, etc. The above-mentioned halogenated acenaphthylenes include, for example, 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, 5-bromoacenaphthene, and the like. The aforementioned phenylacenaphthylenes include, for example, 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene, and the like. The aforementioned acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule.
前述分子中具有三聚異氰酸酯基之化合物為三聚異氰酸酯化合物。前述三聚異氰酸酯化合物可舉分子中更具有烯基之化合物(三聚異氰酸烯基酯化合物)等，可舉例如三聚異氰酸三烯丙酯(TAIC)等三聚異氰酸三烯基酯化合物等。The compound having a trimeric isocyanate group in the aforementioned molecule is a trimeric isocyanate compound. The above-mentioned isocyanate compound can be a compound having an alkenyl group in the molecule (alkenyl isocyanate compound), etc., such as triallyl isocyanate (TAIC), etc. Alkenyl ester compounds, etc.
前述苯乙烯衍生物可舉例如溴苯乙烯及二溴苯乙烯等。The aforementioned styrene derivatives include, for example, bromostyrene and dibromostyrene.
關於本實施形態中使用之硬化劑(B)，宜包含上述中例如選自下述中之至少一者：分子中具有2個以上丙烯醯基之多官能丙烯酸酯化合物、分子中具有2個以上甲基丙烯醯基之多官能甲基丙烯酸酯化合物、分子中具有2個以上乙烯基之多官能乙烯基化合物、苯乙烯衍生物、分子中具有烯丙基之烯丙基化合物、分子中具有馬來醯亞胺基之馬來醯亞胺化合物、分子中具有苊結構之苊化合物及分子中具有三聚異氰酸酯基之三聚異氰酸酯化合物。The curing agent (B) used in this embodiment preferably contains at least one of the above, for example, selected from the following: a polyfunctional acrylate compound having 2 or more acryl groups in the molecule, a polyfunctional acrylate compound having 2 or more acryl groups in the molecule Multifunctional methacrylate compounds with methacryl groups, multifunctional vinyl compounds with two or more vinyl groups in the molecule, styrene derivatives, allyl compounds with allyl groups in the molecule, horse Maleimide compound with aleimide group, acenaphthylene compound with acenaphthene structure in the molecule, and isocyanate compound with isocyanate group in the molecule.
前述硬化劑(B)可單獨使用如上述之硬化劑，亦可組合2種以上來使用。The aforementioned curing agent (B) may be used alone or in combination of two or more of the above-mentioned curing agents.
前述硬化劑(B)之重量平均分子量宜為100~5000，較宜為100~4000，更宜為100~3000。前述硬化劑之重量平均分子量若過低，有前述硬化劑容易從樹脂組成物之摻混成分系統揮發之虞。又，前述硬化劑之重量平均分子量若過高，有樹脂組成物之清漆黏度、或加熱成形時之熔融黏度變太高之虞。因此，前述硬化劑之重量平均分子量若在所述範圍內，便可獲得硬化物之耐熱性更優異之樹脂組成物。吾等認為其係因藉由與前述聚伸苯基醚化合物之反應，可適宜使含有前述聚伸苯基醚化合物之樹脂組成物硬化之故。此外，在此重量平均分子量若為以一般分子量測定方法測得者即可，具體上可舉使用凝膠滲透層析術(GPC)測得之值等。The weight average molecular weight of the aforementioned curing agent (B) is preferably 100-5000, more preferably 100-4000, more preferably 100-3000. If the weight average molecular weight of the aforementioned curing agent is too low, the aforementioned curing agent may easily volatilize from the compounding component system of the resin composition. In addition, if the weight average molecular weight of the aforementioned curing agent is too high, the varnish viscosity of the resin composition or the melt viscosity during thermoforming may become too high. Therefore, if the weight average molecular weight of the said hardening|curing agent is in the said range, the resin composition which is more excellent in the heat resistance of a cured product can be obtained. We think that this is because the resin composition containing the aforementioned polyphenylene ether compound can be suitably cured by reaction with the aforementioned polyphenylene ether compound. In addition, what is necessary is just to measure a weight average molecular weight here by the general molecular weight measuring method, Specifically, the value measured using gel permeation chromatography (GPC), etc. are mentioned.
前述硬化劑(B)中，前述硬化劑每分子中有助於與前述聚伸苯基醚化合物反應之官能基的平均個數(官能基數)會依前述硬化劑之重量平均分子量而異，例如宜為1~20個，較宜為2~18個。該官能基數若太少，有不易獲得就硬化物之耐熱性而言夠充分之物的傾向。又，官能基數若過多，反應性會變得太高，有發生例如樹脂組成物之保存性降低、或樹脂組成物之流動性降低等不良情況之虞。In the aforementioned hardening agent (B), the average number of functional groups (number of functional groups) per molecule of the aforementioned hardening agent that facilitates the reaction with the aforementioned polyphenylene ether compound will vary depending on the weight average molecular weight of the aforementioned hardening agent, for example It should be 1~20 pieces, more preferably 2~18 pieces. If the number of functional groups is too small, it tends to be difficult to obtain a cured product having sufficient heat resistance. Also, if the number of functional groups is too large, the reactivity becomes too high, and there is a possibility of occurrence of disadvantages such as lowered storage stability of the resin composition or lowered fluidity of the resin composition.
(無機充填劑(C)) 本實施形態之樹脂組成物更包含含氮化硼之無機充填劑(C)。前述氮化硼若為可作為樹脂組成物中所含之無機充填劑來使用且滿足後述粒度分布之規定者，即無特別限定。氮化硼可舉例如六方晶系之常壓相(h-BN)及立方晶系之高壓相(c-BN)等。 (Inorganic filler (C)) The resin composition of this embodiment further includes an inorganic filler (C) containing boron nitride. The aforementioned boron nitride is not particularly limited as long as it can be used as an inorganic filler contained in the resin composition and satisfies the regulation of the particle size distribution described later. Examples of boron nitride include hexagonal normal pressure phase (h-BN) and cubic high pressure phase (c-BN).
關於本實施形態之無機充填劑(C)，在前述無機充填劑之粒度分布中，利用雷射繞射式粒度分布測定法測定之粒度分布的峰值在粒徑1.0~50.0µm之範圍中至少存在有2個。亦即，本實施形態中使用之無機充填劑中混合有至少具有2種以上峰值粒徑(峰頂)之無機充填劑。如所述，藉由使用峰值在前述粒徑範圍內至少存在2個的無機充填劑(C)，可於樹脂組成物之硬化物中達成高熱傳導率與低介電特性(Dk)。Regarding the inorganic filler (C) of this embodiment, in the particle size distribution of the aforementioned inorganic filler, the peak of the particle size distribution measured by the laser diffraction particle size distribution measurement method exists at least in the range of particle diameters of 1.0 to 50.0 µm. There are 2 of them. That is, inorganic fillers having at least two or more types of peak particle diameters (peak tops) are mixed in the inorganic filler used in this embodiment. As mentioned above, by using the inorganic filler (C) having at least two peaks within the aforementioned particle size range, high thermal conductivity and low dielectric properties (Dk) can be achieved in the cured product of the resin composition.
並且，該等峰值宜分別在粒徑1.0~5.0µm範圍中存在至少一個，且在粒徑5.0~50.0µm範圍中存在至少一個。亦即，在較理想實施形態中使用之無機充填劑中混合有較小粒徑之無機充填劑與較大粒徑之無機充填劑，亦即混合有至少具有2種以上峰值粒徑(峰頂)之無機充填劑。吾等認為藉此可兼顧確保與金屬箔之密著性與高熱傳導率。無機充填劑之粒度分布中的峰值若僅一個，當僅在小粒徑範圍中具有峰值時，有無法充分提高所得之樹脂組成物之硬化物與金屬箔之密著性的傾向。又，僅在大粒徑之範圍具有峰值時，有所得之樹脂組成物之熱傳導率降低的傾向。Moreover, it is preferable that at least one of these peaks exists in the range of particle diameter 1.0~5.0µm, and at least one exists in the range of particle diameter 5.0~50.0µm. That is, the inorganic filler used in a more ideal embodiment is mixed with an inorganic filler with a smaller particle size and an inorganic filler with a larger particle size, that is, a mixture with at least two or more peak particle sizes (peak peak ) of inorganic fillers. We believe that this can ensure both the adhesion to the metal foil and high thermal conductivity. If there is only one peak in the particle size distribution of the inorganic filler, if the peak is only in the small particle size range, the adhesion between the cured product of the obtained resin composition and the metal foil tends not to be sufficiently improved. Also, when there is a peak only in the range of large particle diameters, the thermal conductivity of the obtained resin composition tends to decrease.
本說明書中，前述粒度分布係藉由利用雷射繞射散射法之粒度分布測定測得之值，例如可藉由後述實施例中使用之雷射/繞射式粒度分布測定裝置「LA-960V2」(股份公司堀場製作所製)等來測定。又，在本實施形態中，前述峰值係指粒度分布之圖表中的極大值，具體而言係指藉由以橫軸為粒徑、縱軸為相對粒子量(頻率)時之粒度分布之圖表中的極大值所得之數值。In this specification, the aforementioned particle size distribution is the value measured by the particle size distribution measurement using the laser diffraction scattering method, for example, it can be obtained by the laser/diffraction type particle size distribution measuring device "LA-960V2" used in the examples described later. ” (manufactured by Horiba Manufacturing Co., Ltd.) and so on. Also, in this embodiment, the above-mentioned peak refers to the maximum value in the graph of the particle size distribution, and specifically refers to the graph of the particle size distribution when the horizontal axis is the particle diameter and the vertical axis is the relative particle amount (frequency). The value obtained from the maximum value in .
並且，宜為：相對於前述無機充填劑(C)之粒度分布全體100體積%，粒徑0.1~5.0µm範圍之粒子的累積比率為25~75體積%，粒徑5.0~100.0µm之粒子的累積比率為25~75體積%。該等各累積比率(%)係從各粒徑範圍中之相對粒子量的累積值算出藉此求得之值。藉此，具有兼顧確保銅箔密著性與高熱傳導率之優點。In addition, it is preferable that the cumulative ratio of particles in the range of 0.1 to 5.0 µm in particle size is 25 to 75 % by volume, and the particle size of particles in the range of 5.0 to 100.0 µm is 100% by volume of the entire particle size distribution of the inorganic filler (C). The cumulative ratio is 25 to 75% by volume. These respective accumulation ratios (%) are calculated from the accumulation value of the relative particle amount in each particle size range to obtain the value thus obtained. Thereby, it has the advantage of ensuring both the adhesion of the copper foil and high thermal conductivity.
此外，關於本實施形態之無機充填劑(C)中所含之前述氮化硼，藉由將本實施形態之樹脂組成物之硬化物的垂直截面圖進行能量色散X射線分析(EDX分析觀察)來判別氮化硼時，在SEM觀察中存在於邊長50µm之範圍內的氮化硼中，從氮化硼之一端至另一端中最長的長度為10µm以上且50µm以下的氮化硼宜成為3~30個之範圍。藉此，具有可維持高熱傳導率且確保銅箔密著性之優點。In addition, regarding the above-mentioned boron nitride contained in the inorganic filler (C) of this embodiment, energy dispersive X-ray analysis (EDX analysis observation) was carried out on the vertical cross-sectional view of the cured product of the resin composition of this embodiment. When distinguishing boron nitride, among the boron nitride existing within the range of side length 50µm in SEM observation, the boron nitride with the longest length from one end of the boron nitride to the other end is more than 10µm and less than 50µm should be The range of 3~30. Thereby, there is an advantage that high thermal conductivity can be maintained and the adhesion of copper foil can be ensured.
本實施形態之樹脂組成物可僅包含有前述氮化硼，亦可包含有前述氮化硼以外之無機充填劑。相對於前述無機充填劑(C)100質量份，前述無機充填劑(C)中之前述氮化硼之含量宜為20~100質量份，較宜為30~80質量份。吾等認為藉由前述氮化硼之含量在前述範圍內，則具有可確保高熱傳導率之優點。The resin composition of this embodiment may contain only the aforementioned boron nitride, or may include inorganic fillers other than the aforementioned boron nitride. The content of the boron nitride in the inorganic filler (C) is preferably 20-100 parts by mass, more preferably 30-80 parts by mass, relative to 100 parts by mass of the inorganic filler (C). We believe that there is an advantage that high thermal conductivity can be ensured when the content of the aforementioned boron nitride is within the aforementioned range.
僅含前述氮化硼時，係使用2種以上粒徑不同之氮化硼，以使無機充填劑(C)之粒度分布滿足上述規定。又，含前述氮化硼以外之無機充填劑時，亦可調整氮化硼之粒徑與該氮化硼以外之無機充填劑之粒徑，以使無機充填劑(C)之粒度分布滿足上述規定。When only the aforementioned boron nitride is contained, two or more boron nitrides with different particle sizes are used so that the particle size distribution of the inorganic filler (C) satisfies the above-mentioned requirements. In addition, when an inorganic filler other than the aforementioned boron nitride is contained, the particle size of boron nitride and the particle size of the inorganic filler other than boron nitride can also be adjusted so that the particle size distribution of the inorganic filler (C) satisfies the above-mentioned Regulation.
前述氮化硼以外之無機充填劑若為可作為樹脂組成物中所含之無機充填劑使用者，即無特別限定。前述氮化硼以外之無機充填劑可列舉例如二氧化矽、氧化鋁、氧化鈦、氧化鎂及雲母等金屬氧化物、氫氧化鋁及氫氧化鎂等金屬氫氧化物、滑石、硼酸鋁、硫酸鋇、氮化鋁、氮化矽、無水碳酸鎂等碳酸鎂及碳酸鈣等。作為前述氮化硼以外之無機充填劑，其中又宜為二氧化矽、無水碳酸鎂、氧化鋁及氮化矽等。前述二氧化矽無特別限定，可舉例如破碎狀二氧化矽及二氧化矽粒子等，宜為二氧化矽粒子。又，前述碳酸鎂無特別限定，宜為無水碳酸鎂(合成菱鎂礦)。The aforementioned inorganic fillers other than boron nitride are not particularly limited as long as they can be used as the inorganic filler contained in the resin composition. Inorganic fillers other than the aforementioned boron nitride include, for example, metal oxides such as silica, alumina, titanium oxide, magnesium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, and sulfuric acid. Magnesium carbonate such as barium, aluminum nitride, silicon nitride, anhydrous magnesium carbonate and calcium carbonate. As the inorganic filler other than the aforementioned boron nitride, silicon dioxide, anhydrous magnesium carbonate, aluminum oxide, silicon nitride, etc. are preferred. The aforementioned silicon dioxide is not particularly limited, and examples thereof include crushed silicon dioxide and silicon dioxide particles, among which silicon dioxide particles are preferred. Also, the aforementioned magnesium carbonate is not particularly limited, and anhydrous magnesium carbonate (synthetic magnesite) is preferable.
前述氮化硼以外之無機充填劑可為經表面處理之無機充填劑，亦可為未經表面處理之無機充填劑。又，前述表面處理可舉例如利用矽烷耦合劑進行之處理等。The aforementioned inorganic fillers other than boron nitride may be surface-treated inorganic fillers, or may be non-surface-treated inorganic fillers. In addition, the above-mentioned surface treatment may, for example, be treated with a silane coupling agent.
前述矽烷耦合劑可舉例如具有選自於由乙烯基、苯乙烯基、甲基丙烯醯基、丙烯醯基、苯胺基所構成群組中之至少1種官能基的矽烷耦合劑等。即，該矽烷耦合劑之反應性官能基可舉下述化合物等：具有乙烯基、苯乙烯基、甲基丙烯醯基、丙烯醯基及苯胺基中之至少1者，並具有甲氧基或乙氧基等水解性基者。The aforementioned silane coupling agent may, for example, be a silane coupling agent having at least one functional group selected from the group consisting of vinyl, styryl, methacryl, acryl, and anilino. That is, the reactive functional group of the silane coupling agent can include the following compounds: having at least one of vinyl, styryl, methacryl, acryl and anilino, and having methoxy or Hydrolyzable groups such as ethoxy.
關於前述矽烷耦合劑，可舉例如乙烯基三乙氧基矽烷及乙烯基三甲氧基矽烷等作為具有乙烯基者。關於前述矽烷耦合劑，可舉例如對苯乙烯基三甲氧基矽烷及對苯乙烯基三乙氧基矽烷等作為具有苯乙烯基者。關於前述矽烷耦合劑，可列舉例如3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷及3-甲基丙烯醯氧基丙基乙基二乙甲氧基矽烷等作為具有甲基丙烯醯基者。關於前述矽烷耦合劑，可舉例如3-丙烯醯氧基丙基三甲氧基矽烷及3-丙烯醯氧基丙基三乙氧基矽烷等作為具有丙烯醯基者。關於前述矽烷耦合劑，可舉例如N-苯基-3-胺丙基三甲氧基矽烷及N-苯基-3-胺丙基三乙氧基矽烷等作為具有苯胺基者。Regarding the above-mentioned silane coupling agent, for example, vinyltriethoxysilane, vinyltrimethoxysilane, etc. may be mentioned as those having a vinyl group. As for the said silane coupling agent, p-styryl trimethoxysilane and p-styryl triethoxysilane etc. are mentioned as what has a styryl group, for example. Regarding the aforementioned silane coupling agents, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Propyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropylethyldiethylmethoxysilane are used as methacrylic Acyl-based. Regarding the aforementioned silane coupling agent, for example, 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane can be mentioned as those having an acryl group. Regarding the aforementioned silane coupling agent, for example, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane can be cited as those having anilino groups.
此外，本實施形態之無機充填劑含有前述氮化硼以外之無機充填劑時，相對於前述無機充填劑100體積份，前述無機充填劑中之前述氮化硼之含量宜為20~100體積份。吾等認為藉此可更確實達成高熱傳導率。更理想之範圍為30~70體積份。In addition, when the inorganic filler of this embodiment contains an inorganic filler other than the aforementioned boron nitride, the content of the aforementioned boron nitride in the aforementioned inorganic filler is preferably 20 to 100 parts by volume relative to 100 parts by volume of the aforementioned inorganic filler. . We believe that a high thermal conductivity can be more reliably achieved by this. A more ideal range is 30 to 70 parts by volume.
本實施形態中，前述氮化硼之平均粒徑及/或前述述氮化硼以外之無機充填劑之平均粒徑若為可使無機充填劑(C)之粒度分布滿足如上述之規定的範圍，即無特別限定。In this embodiment, if the average particle size of the aforementioned boron nitride and/or the average particle size of the aforementioned inorganic filler other than the aforementioned boron nitride is within the range that allows the particle size distribution of the inorganic filler (C) to satisfy the above-mentioned requirements , that is, there is no special limitation.
本實施形態之無機充填劑(C)中，如上述之粒度分布的峰值不僅在粒徑1.0~50.0µm之範圍中存在2個，亦可更在該範圍內存在有第3個峰值。此時，第3個峰值宜存在於粒徑20.0~50.0µm範圍中。藉此，還可更期待藉由充填材均勻分散於樹脂成分中來提升熱傳導率之優點。In the inorganic filler (C) of this embodiment, not only there are two peaks in the particle size distribution range of 1.0 to 50.0 µm as described above, but a third peak may also exist in this range. At this time, the third peak should exist in the particle size range of 20.0~50.0µm. Thereby, the advantage of improving the thermal conductivity by uniformly dispersing the filler in the resin component can also be expected.
在較理想實施形態中，本實施形態之樹脂組成物宜包含前述氮化硼與二氧化矽作為無機充填劑(C)。並且，在含前述氮化硼與二氧化矽之無機充填劑的粒度分布中，利用雷射繞射式粒度分布測定法測定之粒度分布的峰值在粒徑1.0~50.0µm之範圍中至少存在三個，並且該等峰值在粒徑1.0~5.0µm範圍中至少存在一個，在粒徑5.0~20.0µm範圍中至少存在一個，且在粒徑20.0~50.0µm範圍中至少存在一個。此時，本實施形態之無機充填劑的粒度分布中至少會存在三個峰值，但宜藉由含有具有至少2種不同粒徑之氮化硼與二氧化矽來調整前述粒度分布。吾等認為藉由所述構成，則更具有藉由熱傳導高之充填材均勻分散於樹脂成分中來提升熱傳導率之優點。In a more ideal embodiment, the resin composition of this embodiment preferably includes the aforementioned boron nitride and silicon dioxide as the inorganic filler (C). In addition, in the particle size distribution of the inorganic filler containing boron nitride and silicon dioxide, there are at least three peaks of the particle size distribution measured by the laser diffraction particle size distribution measurement method in the range of particle diameters from 1.0 to 50.0 µm. There are at least one such peak in the range of 1.0~5.0µm in particle size, at least one in the range of 5.0~20.0µm in particle size, and at least one in the range of 20.0~50.0µm in particle size. At this time, there are at least three peaks in the particle size distribution of the inorganic filler of this embodiment, but it is preferable to adjust the particle size distribution by containing boron nitride and silicon dioxide having at least two different particle sizes. We think that with the above structure, there is an advantage that the thermal conductivity can be improved by uniformly dispersing the filler material with high thermal conductivity in the resin component.
(磷化合物(D)) 本實施形態之磷化合物(D)含有相溶性磷化合物(D-1)與非相溶性磷化合物(D-2)，該相溶性磷化合物(D-1)係和前述聚伸苯基醚化合物(A)與前述硬化劑(B)之混合物相溶者，該非相溶性磷化合物(D-2)係不與前述混合物相溶者。 (phosphorus compound (D)) The phosphorus compound (D) of this embodiment contains a compatible phosphorus compound (D-1) and an incompatible phosphorus compound (D-2), and the compatible phosphorus compound (D-1) is combined with the aforementioned polyphenylene ether compound (A) is compatible with the mixture of the aforementioned curing agent (B), and the incompatible phosphorus compound (D-2) is not compatible with the aforementioned mixture.
相溶性磷化合物(D-1)若為可作為阻燃劑發揮作用且與前述混合物相溶之磷化合物，即無特別限定。在此，相溶意指在聚伸苯基醚化合物(A)與硬化劑(B)之混合物中，以例如分子等級微分散之狀態。The compatible phosphorus compound (D-1) is not particularly limited as long as it functions as a flame retardant and is compatible with the aforementioned mixture. Here, compatibility means that the polyphenylene ether compound (A) and the curing agent (B) are in a finely dispersed state, for example, at a molecular level in a mixture of the polyphenylene ether compound (A) and the curing agent (B).
具體之相溶性磷化合物(D-1)可舉磷酸酯化合物、膦氮烯化合物、亞磷酸酯化合物及膦化合物等之含磷且未形成鹽之化合物等。Specific examples of the compatible phosphorus compound (D-1) include phosphorus-containing compounds such as phosphate compounds, phosphazene compounds, phosphite compounds, and phosphine compounds that do not form salts.
膦氮烯化合物可舉例如環狀或鏈狀膦氮烯化合物。此外，環狀膦氮烯化合物亦稱為環膦氮烯，係以磷與氮作為構成元素且於分子中具有雙鍵之化合物，且為具有環狀結構者。又，磷酸酯化合物可列舉例如磷酸三苯酯、磷酸三甲苯酯、磷酸二甲苯基二苯酯、磷酸甲苯二苯酯、1,3-伸苯基雙(二2,6-二磷酸二甲苯酯)、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)、芳香族縮合磷酸酯化合物等縮合磷酸酯化合物及環狀磷酸酯化合物等。又，亞磷酸酯化合物可舉例如亞磷酸三甲酯及亞磷酸三乙酯等。又，膦化合物可舉例如參-(4-甲氧基苯基)膦及三苯膦等。又，前述相溶性磷化合物可單獨使用1種，亦可組合2種以上來使用。The phosphazene compound may, for example, be a cyclic or chain phosphazene compound. In addition, the cyclic phosphazene compound is also called cyclic phosphazene, which is a compound with phosphorus and nitrogen as constituent elements and has a double bond in the molecule, and has a ring structure. In addition, examples of phosphoric acid ester compounds include triphenyl phosphate, tricresyl phosphate, xylyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylene bis(bis-2,6-diphenylene phosphate), ester), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), aromatic condensed phosphoric acid ester compounds and other condensed phosphoric acid ester compounds and cyclic phosphoric acid ester compounds, etc. Moreover, as a phosphite compound, trimethyl phosphite, triethyl phosphite, etc. are mentioned, for example. In addition, examples of the phosphine compound include para-(4-methoxyphenyl)phosphine, triphenylphosphine, and the like. Moreover, the said compatible phosphorus compound may be used individually by 1 type, and may use it in combination of 2 or more types.
非相溶性磷化合物(D-2)若為可作為阻燃劑發揮作用且不與前述混合物相溶之非相溶磷化合物，即無特別限定。在此，非相溶意指在前述聚伸苯基醚化合物(A)與前述硬化劑(B)之混合物中不相溶，而對象物(磷化合物)在混合物中呈島狀分散之狀態。非相溶性磷化合物(D-2)在混合物中分散成島狀時，該成為島狀之磷化合物之粒徑無特別限定，宜為平均粒徑0.1µm~100µm，較宜為平均粒徑0.1µm~70µm，更宜為平均粒徑0.1µm~40µm。The incompatible phosphorus compound (D-2) is not particularly limited as long as it functions as a flame retardant and is incompatible with the aforementioned mixture. Here, incompatibility means that the mixture of the polyphenylene ether compound (A) and the curing agent (B) is not compatible, and the target object (phosphorus compound) is dispersed in the form of islands in the mixture. When the incompatible phosphorus compound (D-2) is dispersed into islands in the mixture, the particle size of the island-shaped phosphorus compound is not particularly limited, and the average particle size is preferably 0.1µm~100µm, and the average particle size is preferably 0.1µm ~70µm, more preferably an average particle size of 0.1µm~40µm.
具體之非相溶性磷化合物(D-2)可舉次磷酸鹽化合物、多磷酸鹽化合物及鏻鹽化合物等之含磷且有形成鹽之化合物、以及膦氧化物化合物等。Specific examples of the incompatible phosphorus compound (D-2) include phosphorus-containing salt-forming compounds such as hypophosphite compounds, polyphosphate compounds, and phosphonium salt compounds, and phosphine oxide compounds.
次膦酸鹽化合物可列舉例如二烷基次膦酸鋁、參二乙基次膦酸鋁、參甲基乙基次膦酸鋁、參二苯基次膦酸鋁、雙二乙基次膦酸鋅、雙甲基乙基次膦酸鋅、雙二苯基次膦酸鋅、雙二乙基次膦酸氧鈦、雙甲基乙基次膦酸氧鈦、雙二苯基次膦酸氧鈦等。又，多磷酸鹽化合物可舉例如多磷酸三聚氰胺、多磷酸蜜白胺、多磷酸蜜勒胺等。又，膦酸鹽化合物可舉例如四苯硼酸四苯鏻及溴化四苯鏻等。又，膦氧化物化合物可舉例如分子中具有2個以上氧化二苯膦基之膦氧化物化合物(氧化二苯膦化合物)等，更具體而言可舉對二甲苯雙(氧化二苯膦)等。前述非相溶性磷化合物可單獨使用1種，亦可組合2種以上來使用。As the phosphinate compound, for example, aluminum dialkylphosphinate, aluminum para-methylethylphosphinate, aluminum para-methylethylphosphinate, aluminum para-diphenylphosphinate, bis-diethylphosphinate Zinc acid, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, bisdiphenylphosphinic acid Titanium oxide, etc. Moreover, as a polyphosphate compound, melamine polyphosphate, melem polyphosphate, melem polyphosphate, etc. are mentioned, for example. Moreover, as a phosphonate compound, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, etc. are mentioned, for example. In addition, the phosphine oxide compound includes, for example, a phosphine oxide compound (diphenylphosphine oxide compound) having two or more diphenylphosphine oxide groups in the molecule, and more specifically, p-xylene bis(diphenylphosphine oxide) wait. The said incompatible phosphorus compound may be used individually by 1 type, and may use it in combination of 2 or more types.
相溶性磷化合物(D-1)與非相溶性磷化合物(D-2)之含有比，以質量比計宜為1：2~2：1，較宜為1：1~3：2。吾等認為若為所述含有比，便可成為在硬化物中具備高Tg且阻燃性更優異之樹脂組成物。The content ratio of the compatible phosphorus compound (D-1) to the incompatible phosphorus compound (D-2) is preferably 1:2~2:1 in terms of mass ratio, more preferably 1:1~3:2. We think that if the content ratio is as described above, a cured product can have a high Tg and a resin composition more excellent in flame retardancy.
本實施形態之樹脂組成物中，作為阻燃劑，可僅包含由前述相溶性磷化合物(D-1)與前述非相溶性磷化合物(D-1)構成之磷化合物(D)，亦可包含該2種以外之阻燃劑。所述阻燃劑亦可含有前述相溶性磷化合物(D-1)及前述非相溶性磷化合物(D-2)以外之阻燃劑，惟由無鹵素之觀點來看，宜不含鹵素系阻燃劑。In the resin composition of the present embodiment, as a flame retardant, only the phosphorus compound (D) composed of the above-mentioned compatible phosphorus compound (D-1) and the above-mentioned incompatible phosphorus compound (D-1) may be contained, or Flame retardants other than these two are included. The flame retardant may also contain flame retardants other than the above-mentioned compatible phosphorus compound (D-1) and the above-mentioned incompatible phosphorus compound (D-2). flame retardant.
(各成分之含量) 本實施形態之樹脂組成物中，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述聚伸苯基醚化合物(A)之含量宜為15~40質量份，較宜為15~30質量份，更宜為15~25質量份。吾等認為前述聚伸苯基醚化合物(A)之含量若在上述範圍內，便可更確實地獲得一種可獲得介電特性低且耐熱性高之硬化物的樹脂組成物。 (content of each ingredient) In the resin composition of the present embodiment, the polyphenylene ether compound ( The content of A) is preferably 15-40 parts by mass, more preferably 15-30 parts by mass, more preferably 15-25 parts by mass. We think that if the content of the aforementioned polyphenylene ether compound (A) is within the aforementioned range, a resin composition capable of obtaining a cured product with low dielectric properties and high heat resistance can be more reliably obtained.
又，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述硬化劑(B)之含量宜為5~20質量份，較宜為6~18質量份，更宜為7~16質量份。前述硬化劑(B)之含量若為上述範圍內之含量，便可成為硬化物之耐熱性更優異之樹脂組成物。吾等認為其係因本實施形態之樹脂成分與前述硬化劑之硬化反應適當進行的緣故。In addition, the content of the curing agent (B) is preferably 5 to 20 parts by mass based on 100 parts by mass of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C) in total. , more preferably 6 to 18 parts by mass, more preferably 7 to 16 parts by mass. If the content of the aforementioned curing agent (B) is within the above-mentioned range, a cured product can have a resin composition with better heat resistance. We think that this is because the hardening reaction between the resin component of this embodiment and the aforementioned hardening agent proceeds appropriately.
相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)與前述無機充填劑(C)之合計100質量份，本實施形態之樹脂組成物中之無機充填劑(C)之含量宜為40~80質量份，較宜為50~80質量份，更宜為60~80質量份。前述無機充填劑(C)之含量若在前述範圍內，便可更確實地獲得具有高熱傳導率之硬化物。Content of the inorganic filler (C) in the resin composition of the present embodiment relative to the total of 100 parts by mass of the aforementioned polyphenylene ether compound (A), the aforementioned hardener (B) and the aforementioned inorganic filler (C) It is preferably 40 to 80 parts by mass, more preferably 50 to 80 parts by mass, more preferably 60 to 80 parts by mass. If the content of the aforementioned inorganic filler (C) is within the aforementioned range, a cured product having high thermal conductivity can be more reliably obtained.
並且，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，本實施形態之樹脂組成物中之前述氮化硼之含量宜為15~50質量份，較宜為20~50質量份。吾等認為藉此可更確實地獲得高熱傳導率。Furthermore, the content of the boron nitride in the resin composition of the present embodiment is relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). It is preferably 15 to 50 parts by mass, more preferably 20 to 50 parts by mass. We believe that high thermal conductivity can be more reliably obtained by this.
又，本實施形態之樹脂組成物中，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述磷化合物(D)之含量宜為2~15質量份，較宜為2~12質量份，更宜為2~10質量份。In addition, in the resin composition of the present embodiment, the phosphorus compound (D) is The content is preferably 2-15 parts by mass, more preferably 2-12 parts by mass, more preferably 2-10 parts by mass.
本實施形態之樹脂組成物中，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述相溶性磷化合物(D-1)之含量宜為2~15質量份，較宜為2~12質量份。又，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述非相溶性磷化合物(D-2)之含量宜為5~25質量份，較宜為5~22質量份。並且，前述樹脂組成物中，相對於前述相溶性磷化合物(D-1)與前述非相溶性磷化合物(D-2)之合計100質量份，前述相溶性磷化合物(D-1)之含量宜為25~65質量份，更宜為40~60質量份。In the resin composition of this embodiment, the aforementioned compatible phosphorus compound (D- 1) The content is preferably 2-15 parts by mass, more preferably 2-12 parts by mass. Furthermore, the content of the incompatible phosphorus compound (D-2) is preferably 5-25 parts by mass, more preferably 5-22 parts by mass. Furthermore, in the aforementioned resin composition, the content of the aforementioned compatible phosphorous compound (D-1) is It is preferably 25 to 65 parts by mass, more preferably 40 to 60 parts by mass.
吾等認為前述相溶性磷化合物(D-1)及前述非相溶性磷化合物(D-2)之含量若在前述範圍內，便具有可兼顧確保阻燃性與確保高Tg之優點。We believe that if the content of the above-mentioned compatible phosphorus compound (D-1) and the above-mentioned incompatible phosphorus compound (D-2) is within the above-mentioned range, it has the advantage of ensuring both flame retardancy and high Tg.
(其他成分) 本實施形態之樹脂組成物亦可在不損及本發明效果之範圍內，視需求含有上述成分以外之成分(其他成分)。本實施形態之樹脂組成物中所含之其他成分可更包含例如：苯乙烯系聚合物、自由基化合物、反應引發劑、矽烷耦合劑、消泡劑、抗氧化劑、熱穩定劑、抗靜電劑、紫外線吸收劑、染料或顏料、分散劑及滑劑等添加劑。又，本實施形態之樹脂組成物中，除了前述聚伸苯基醚化合物(A)及前述硬化劑(B)外，亦可含有環氧樹脂、馬來醯亞胺樹脂、芳香族烴樹脂、脂肪族烴樹脂等熱硬化性樹脂。 (other ingredients) The resin composition of this embodiment may also contain components (other components) other than the above-mentioned components as needed within the range which does not impair the effect of this invention. Other components contained in the resin composition of this embodiment may further include, for example: styrene-based polymers, free radical compounds, reaction initiators, silane coupling agents, defoamers, antioxidants, heat stabilizers, antistatic agents , UV absorbers, dyes or pigments, dispersants and lubricants and other additives. In addition, the resin composition of this embodiment may contain epoxy resin, maleimide resin, aromatic hydrocarbon resin, Thermosetting resins such as aliphatic hydrocarbon resins.
・苯乙烯系聚合物 本實施形態之樹脂組成物除了如上述之成分外，亦可更包含有苯乙烯系聚合物。吾等認為藉由包含苯乙烯系聚合物，則更具有樹脂之低介電常數化等之優點。 ・Styrenic polymer In addition to the above-mentioned components, the resin composition of this embodiment may further include a styrene-based polymer. We think that by including a styrene-based polymer, there are advantages such as lowering the dielectric constant of the resin.
本實施形態中使用之苯乙烯系聚合物例如為含苯乙烯系單體之單體聚合而得之聚合物，亦可為苯乙烯系共聚物。又，前述苯乙烯系共聚物可舉例如使1種以上苯乙烯系單體與1種以上可與苯乙烯系單體共聚之其他單體共聚而得之共聚物等。前述苯乙烯系單體可舉苯乙烯、苯乙烯衍生物、苯乙烯之部分氫原子被取代基取代者等。The styrene-based polymer used in this embodiment is, for example, a polymer obtained by polymerizing monomers containing styrene-based monomers, or may be a styrene-based copolymer. Moreover, the said styrene-type copolymer is mentioned, for example, the copolymer etc. which copolymerized 1 or more types of styrene-type monomers and 1 or more types of other monomers copolymerizable with a styrene-type monomer. The aforementioned styrene-based monomers include styrene, styrene derivatives, and those in which some of the hydrogen atoms of styrene are replaced by substituents.
具體之苯乙烯系聚合物可廣泛使用以往公知之物，並無特別限定，可舉例如分子中具有下述式(3)所示之結構單元(源自苯乙烯系單體之結構)的聚合物等。Specific styrene-based polymers can be widely used conventionally known ones, and are not particularly limited. For example, polymers having a structural unit (derived from a styrene-based monomer) represented by the following formula (3) in the molecule can be used. things etc.
[化學式13] [chemical formula 13]
式(3)中，R 35~R 37分別獨立表示氫原子或烷基，R 38表示選自於由氫原子、烷基、烯基及異丙烯基所構成群組中之基團。前述烷基無特別限定，例如宜為碳數1~18烷基，較宜為碳數1~10烷基。又，前述烯基宜為碳數1~10烯基。具體上可舉例如甲基、乙基、丙基、己基及癸基等。 In formula (3), R 35 to R 37 independently represent a hydrogen atom or an alkyl group, and R 38 represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an isopropenyl group. The aforementioned alkyl group is not particularly limited, for example, it is preferably an alkyl group with 1 to 18 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms. Also, the aforementioned alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, etc. are mentioned.
本實施形態之苯乙烯系聚合物宜包含有至少1種上述式(3)所示之結構單元，但亦可組合互異之2種以上來包含。又，宜包含有重複上述式(3)所示之結構單元之結構。The styrene-based polymer of this embodiment preferably contains at least one structural unit represented by the above formula (3), but may also contain two or more different types in combination. Moreover, it preferably includes a structure in which the structural unit represented by the above formula (3) is repeated.
苯乙烯系聚合物之理想例示可舉苯乙烯、乙烯基甲苯、α-甲基苯乙烯、異丙烯基甲苯、二乙烯苯、烯丙基苯乙烯等苯乙烯系單體之1種以上聚合或共聚而得之聚合物或共聚物。更具體而言，可舉苯乙烯-丁二烯共聚物、苯乙烯-異丁烯共聚物等。又，亦可為加氫(氫化)之苯乙烯系聚合物，可舉例如氫化甲基苯乙烯(乙烯/丁烯)甲基苯乙烯共聚物、氫化甲基苯乙烯(乙烯-乙烯/丙烯)苯乙烯共聚物、氫化苯乙烯異戊二烯共聚物、氫化苯乙烯異戊二烯苯乙烯共聚物、氫化苯乙烯(乙烯/丁烯)苯乙烯共聚物及氫化苯乙烯(乙烯-乙烯/丙烯)苯乙烯共聚物等。Ideal examples of styrene-based polymers include polymerization of one or more styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, isopropenyltoluene, divinylbenzene, and allylstyrene A polymer or copolymer obtained by copolymerization. More specifically, a styrene-butadiene copolymer, a styrene-isobutylene copolymer, etc. are mentioned. In addition, hydrogenated (hydrogenated) styrene-based polymers can also be used, such as hydrogenated methylstyrene (ethylene/butylene) methylstyrene copolymer, hydrogenated methylstyrene (ethylene-ethylene/propylene) Styrene copolymer, hydrogenated styrene isoprene copolymer, hydrogenated styrene isoprene styrene copolymer, hydrogenated styrene (ethylene/butylene) styrene copolymer and hydrogenated styrene (ethylene-ethylene/propylene ) Styrene copolymer, etc.
此外，前述苯乙烯系聚合物可單獨使用上述例示之物，亦可組合2種以上來使用。In addition, the said styrene-type polymer may use what was illustrated above individually, and may use it in combination of 2 or more types.
藉由包含所述苯乙烯系聚合物，除了如上述之效果外，還可發揮抑制樹脂組成物之硬化物的吸濕率，從而可抑制因吸濕量增加所造成之電特性劣化這種進一步的效果。By including the styrene-based polymer, in addition to the above-mentioned effects, the moisture absorption rate of the cured product of the resin composition can be suppressed, thereby suppressing further degradation of electrical characteristics due to an increase in the moisture absorption amount. Effect.
在理想實施形態之前述苯乙烯系聚合物中，包含前述式(3)所示之結構單元之至少一種時，相對於前述聚合物整體，其結構單元之莫耳分率宜為10~70%左右，更宜為15~65%。藉此，可確保與樹脂之相溶性，因此具有確保樹脂組成物內部之特性的均一性等之進一步的優點。In the aforementioned styrene-based polymer in an ideal embodiment, when at least one structural unit represented by the aforementioned formula (3) is included, the molar fraction of the structural unit is preferably 10 to 70% relative to the entire polymer. About, more preferably 15~65%. Thereby, since the compatibility with resin can be ensured, there exists a further advantage, such as ensuring the uniformity of the characteristic inside a resin composition.
前述苯乙烯系聚合物之聚合形態無特別限定，可為嵌段共聚物、交替共聚物、無規共聚物、接枝共聚物等。又，亦可為彈性體之形態。The polymerization form of the aforementioned styrene-based polymer is not particularly limited, and may be a block copolymer, an alternating copolymer, a random copolymer, a graft copolymer, or the like. In addition, it may be in the form of an elastic body.
本實施形態之苯乙烯系聚合物之重量平均分子量宜為10,000~200,000左右，較宜為20,000~150,000左右。重量平均分子量若在上述範圍內，便具有可在樹脂硬化物之B階段確保適當之樹脂流動性之優點。此外，在此重量平均分子量若為利用一般分子量測定方法測得者即可，具體上可舉使用凝膠滲透層析術測得之值等。The weight average molecular weight of the styrene-based polymer in this embodiment is preferably about 10,000-200,000, more preferably about 20,000-150,000. If the weight average molecular weight is within the above range, there is an advantage that appropriate resin fluidity can be secured in the B-stage of the cured resin. In addition, here, the weight average molecular weight should just be what is measured by the general molecular weight measuring method, and the value measured using gel permeation chromatography etc. are mentioned specifically,.
在理想實施形態中，前述苯乙烯系聚合物較宜包含含下述式(16)所示之結構單元之苯乙烯・異丁烯・苯乙烯系嵌段共聚物(SIBS)。藉此，可獲得氣體阻障性高之樹脂組成物，而具有可抑制對樹脂組成物吸濕之優點。In an ideal embodiment, the aforementioned styrene-based polymer preferably includes a styrene-isobutylene-styrene-based block copolymer (SIBS) containing a structural unit represented by the following formula (16). Thereby, a resin composition with high gas barrier property can be obtained, and there is an advantage that moisture absorption to the resin composition can be suppressed.
[化學式14] [chemical formula 14]
式(16)中，a1、a2之合計表示1,000~60,000之整數，b表示1,000~70,000之整數，且a1、a2及b之合計表示10,000~130,000。In formula (16), the total of a1 and a2 represents an integer of 1,000 to 60,000, b represents an integer of 1,000 to 70,000, and the total of a1, a2 and b represents 10,000 to 130,000.
本實施形態中使用之苯乙烯系聚合物之製造方法無特別限定，例如若舉前述SIBS之製造方法之一例，首先可藉由活性陽離子聚合法將異丁烯聚合後，接著添加苯乙烯使其聚合，藉此進行合成。The production method of the styrene-based polymer used in this embodiment is not particularly limited. For example, as an example of the production method of the aforementioned SIBS, isobutylene can be first polymerized by living cationic polymerization, and then styrene is added to polymerize it. Use this to synthesize.
本實施形態之苯乙烯系聚合物亦可使用市售物，可舉例如股份公司Kaneka製之「SIBSTAR(註冊商標)073T」、「SIBSTAR(註冊商標)103T」、「SIBSTAR(註冊商標)102T」、股份公司Kuraray製之「SEPTON V9827」等。Commercially available products can also be used as the styrene-based polymer of this embodiment, and examples thereof include "SIBSTAR (registered trademark) 073T", "SIBSTAR (registered trademark) 103T", and "SIBSTAR (registered trademark) 102T" manufactured by Kaneka Co., Ltd. , "SEPTON V9827" manufactured by Kuraray Co., Ltd., etc.
本實施形態之樹脂組成物包含前述苯乙烯系聚合物時，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述苯乙烯系聚合物之含量宜為1~6質量份，較宜為1~4質量份。When the resin composition of the present embodiment contains the aforementioned styrene-based polymer, the aforementioned The content of the styrene-based polymer is preferably 1-6 parts by mass, more preferably 1-4 parts by mass.
・自由基化合物 本實施形態之樹脂組成物中亦可摻混自由基化合物。吾等認為藉由包含自由基化合物，則具有樹脂之流動性變良好而成形性變良好之優點。自由基化合物若為能作為聚合抑制劑使用之這類自由基化合物，即無特別限定。 ・Free radical compound A radical compound may also be blended in the resin composition of this embodiment. We think that by including the radical compound, there is an advantage that the fluidity of the resin becomes better and the moldability becomes better. The radical compound is not particularly limited as long as it is such a radical compound that can be used as a polymerization inhibitor.
本實施形態中可適宜使用之更具體的自由基化合物可列舉：4-胺基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-乙醯胺-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-胺基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-羧基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-氰基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-環氧丙基氧基-2,2,6,6-四甲基哌啶1-氧自由基自由基、4-羥基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-羥基-2,2,6,6-四甲基哌啶1-氧基苯甲酸酯 自由基、4-異硫氰酸基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-(2-碘乙醯胺)-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-[2-[2-(4-碘苯氧基)乙氧基]羰基]苯并基氧基-2,2,6,6-四甲基哌啶-1-氧自由基、4-甲氧基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-甲基丙烯醯氧基-2,2,6,6-四甲基哌啶1-氧自由基自由基、4-側氧基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、4-側氧基-2,2,6,6-四甲基哌啶1-氧自由基 自由基、2,2,6,6-四甲基哌啶1-氧自由基 自由基、2,2,6,6-四甲基-4-(2-丙烯氧基)哌啶1-氧自由基 自由基、2,2,6,6-四甲基哌啶1-氧自由基 自由基、4,5-二羥基-4,4,5,5-四甲基-2-苯基-1H-咪唑-1-基氧基-1-氧化物、癸二酸雙(2,2,6,6-四甲基-4-哌啶基-1-氧自由基)、3-羧基-2,2,5,5-四甲基吡咯啶1-氧自由基 自由基、4-(2-氯乙醯胺)-2,2,6,6-四甲基哌啶1-氧自由基 自由基、2-(4-硝苯基)-4,4,5,5-四甲基咪唑啉-3-氧化物-1-氧自由基 自由基、2-(14-羧基十四基)-2-乙基-4,4-二甲基-3-㗁唑基氧基 自由基、1,1-二苯基-2-三硝基苯肼 自由基等。該等可單獨使用1種，亦可組合2種以上來使用。如上述之自由基化合物亦可使用市售物，例如可從東京化成工業股份公司等取得。More specific free radical compounds that can be suitably used in this embodiment include: 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-acetamide-2 ,2,6,6-Tetramethylpiperidine 1-oxygen radical, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxygen radical, 4-carboxy- 2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-cyclo Oxypropyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxybenzoate radical, 4-isothiocyanato-2,2,6,6-tetramethylpiperidine Pyridine 1-oxyl radical, 4-(2-iodoacetamide)-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-[2-[2-( 4-iodophenoxy)ethoxy]carbonyl]benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical, 4-methoxy-2,2,6 ,6-Tetramethylpiperidine 1-oxygen radical, 4-methacryloxy-2,2,6,6-tetramethylpiperidine 1-oxygen radical, 4-oxo Base-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperidine 1-oxyl radical radical, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4,5-dihydroxy-4,4,5,5-tetramethyl-2-phenyl-1H-imidazole -1-yloxy-1-oxide, sebacic acid bis(2,2,6,6-tetramethyl-4-piperidinyl-1-oxyl radical), 3-carboxy-2,2, 5,5-Tetramethylpyrrolidine 1-oxygen radical, 4-(2-chloroacetamide)-2,2,6,6-tetramethylpiperidine 1-oxygen radical, 2 -(4-nitrophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl radical, 2-(14-carboxytetradecyl)-2-ethane Radical-4,4-dimethyl-3-oxazolyloxy radical, 1,1-diphenyl-2-trinitrophenylhydrazine radical, etc. These may be used individually by 1 type, and may use it in combination of 2 or more types. Commercially available compounds can also be used as above-mentioned radical compounds, for example, they can be obtained from Tokyo Chemical Industry Co., Ltd. and the like.
本實施形態之樹脂組成物包含前述自由基化合物時，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述自由基化合物之含量宜為0.005~0.05質量份，較宜為0.005~0.03質量份。When the resin composition of the present embodiment contains the radical compound, the radical The content of the compound is preferably 0.005-0.05 parts by mass, more preferably 0.005-0.03 parts by mass.
・反應引發劑 本實施形態之樹脂組成物中，如上述亦可含有反應引發劑(引發劑)。前述樹脂組成物即便為包含前述聚伸苯基醚化合物(A)與前述硬化劑(B)者，硬化反應仍得以進行。然而，依製程條件有時會很難維持高溫直到硬化進行，因此亦可添加反應引發劑。 ・Reaction Initiator The resin composition of this embodiment may contain a reaction initiator (initiator) as described above. Even if the aforementioned resin composition contains the aforementioned polyphenylene ether compound (A) and the aforementioned hardening agent (B), the hardening reaction proceeds. However, depending on the process conditions, sometimes it is difficult to maintain high temperature until hardening, so a reaction initiator can also be added.
前述反應引發劑若為可促進前述樹脂組成物之硬化反應者，即無特別限定。具體而言，可舉例如金屬氧化物、偶氮化合物、有機過氧化物等。The aforementioned reaction initiator is not particularly limited as long as it can accelerate the hardening reaction of the aforementioned resin composition. Specifically, metal oxides, azo compounds, organic peroxides, etc. are mentioned, for example.
金屬氧化物具體而言可舉羧酸金屬鹽等。As the metal oxide, carboxylic acid metal salt and the like are specifically mentioned.
有機過氧化物可列舉α,α'-二(三級丁基過氧基)二異丙基苯、2,5-二甲基-2,5-二(三級丁基過氧基)-3-己炔、苯甲醯基過氧化物、3,3',5,5'-四甲基-1,4-聯苯醌、氯醌、2,4,6-三-三級丁基苯氧基、三級丁基過氧基異丙基單碳酸酯、偶氮雙異丁腈等。Examples of organic peroxides include α,α'-bis(tertiary butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)- 3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-tertiary butyl Phenoxy, tertiary butylperoxyisopropyl monocarbonate, azobisisobutyronitrile, etc.
偶氮化合物具體上可舉2,2'-偶氮雙(2,4,4-三甲基戊烷)、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2'-偶氮雙(2-甲基丁腈)等。Azo compounds specifically include 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide ), 2,2'-azobis(2-methylbutyronitrile), etc.
其中理想之反應引發劑為2,2'-偶氮雙(2,4,4-三甲基戊烷)、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)等。該等反應引發劑對介電特性的影響小。又，其係具有下述優點之故：因反應引發溫度較高，故可抑制在預浸體乾燥時等無須硬化之時間點的硬化反應被促進，從而可抑制前述樹脂組成物之保存性降低。Among them, the ideal reaction initiators are 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide )wait. These reaction initiators have little influence on the dielectric properties. In addition, it has the following advantages: since the reaction initiation temperature is high, it is possible to suppress the acceleration of the curing reaction at a time point when the prepreg is not required to be cured, such as when the prepreg is dried, and it is possible to suppress the reduction in the preservability of the aforementioned resin composition. .
如上述之反應引發劑可單獨使用，亦可組合2種以上來使用。The above reaction initiators may be used alone or in combination of two or more.
本實施形態之樹脂組成物包含前述反應引發劑時，其含量無特別限定，例如相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，宜為0.1~0.5質量份，較宜為0.2~0.4質量份。When the resin composition of this embodiment contains the aforementioned reaction initiator, its content is not particularly limited, for example, relative to the total of the aforementioned polyphenylene ether compound (A), the aforementioned hardener (B) and the aforementioned inorganic filler (C) 100 parts by mass, preferably 0.1 to 0.5 parts by mass, more preferably 0.2 to 0.4 parts by mass.
(製造方法) 製造前述樹脂組成物之方法無特別限定，可舉例如將前述聚伸苯基醚化合物(A)、前述硬化劑(B)、前述磷化合物(D)及視需求之其他有機成分混合，然後添加無機充填劑(C)之方法等。具體而言，於欲獲得含有機溶劑之清漆狀組成物時，可舉後述預浸體之說明中所記載之方法等。 (Manufacturing method) The method for producing the above-mentioned resin composition is not particularly limited, for example, mixing the above-mentioned polyphenylene ether compound (A), the above-mentioned curing agent (B), the above-mentioned phosphorus compound (D) and other organic components as required, and then adding The method of the inorganic filler (C), etc. Specifically, when it is desired to obtain a varnish-like composition containing an organic solvent, the method described in the description of the prepreg described later, etc. may be used.
又，藉由使用本實施形態之樹脂組成物，可如下獲得預浸體、覆金屬積層板、配線板、附樹脂之金屬箔及附樹脂之薄膜。Also, by using the resin composition of this embodiment, a prepreg, a metal-clad laminate, a wiring board, a resin-coated metal foil, and a resin-coated film can be obtained as follows.
前述樹脂組成物之硬化物宜熱傳導率為1.0W/m・K以上，且頻率10GHz下之相對介電常數為4.0以下。如上述藉由使用本實施形態之樹脂組成物，可在該硬化物中兼顧高熱傳導率及Tg與低介電特性，且還可達成優異之阻燃性。The cured product of the aforementioned resin composition preferably has a thermal conductivity of 1.0 W/m·K or higher and a relative dielectric constant of 4.0 or lower at a frequency of 10 GHz. By using the resin composition of this embodiment as described above, high thermal conductivity and Tg and low dielectric properties can be achieved in the cured product, and excellent flame retardancy can also be achieved.
[預浸體]
圖1係顯示本發明實施形態之預浸體1之一例的概略截面圖。此外，在以下說明中，圖式中之各符號分別是指1:預浸體、2:樹脂組成物或樹脂組成物之半硬化物、3:纖維質基材、11:覆金屬積層板、12:絕緣層、13:金屬箔、14:配線、21:配線基板、31:附樹脂之金屬箔、32、42:樹脂層、41:附樹脂之薄膜、43:支持薄膜。
[Prepreg]
Fig. 1 is a schematic cross-sectional view showing an example of a
如圖1所示，本實施形態之預浸體1具備前述樹脂組成物或前述樹脂組成物之半硬化物2、及纖維質基材3。該預浸體1具備前述樹脂組成物或前述樹脂組成物之半硬化物2、及存在於前述樹脂組成物或前述樹脂組成物之半硬化物2之中的纖維質基材3。As shown in FIG. 1 , a
此外，在本實施形態中，半硬化物意指使樹脂組成物在可進一步硬化之程度上硬化至中間狀態者。即，半硬化物係樹脂組成物呈半硬化狀態(經B階段化)者。例如，樹脂組成物一經加熱，剛開始黏度會緩慢地下降，然後開始硬化後，然後開始硬化後，黏度又緩慢地上升。此時，半硬化便可舉從黏度開始上升後至完全硬化前之期間的狀態等。In addition, in the present embodiment, the semi-cured material means that the resin composition is cured to an intermediate state to the extent that it can be further cured. That is, the semi-cured resin composition is in a semi-cured state (B-staged). For example, once the resin composition is heated, the viscosity will decrease slowly at the beginning, and then it will start to harden, and then the viscosity will increase slowly after it starts to harden. In this case, semi-hardening refers to a state in the period from when the viscosity starts to rise until it is completely hardened.
又，使用本實施形態之樹脂組成物獲得之預浸體可為如上述之具備前述樹脂組成物之半硬化物者，亦可為具備未硬化之前述樹脂組成物本身者。即，可為具備前述樹脂組成物之半硬化物(B階段之前述樹脂組成物)與纖維質基材的預浸體，亦可為具備硬化前之前述樹脂組成物(A階段之前述樹脂組成物)與纖維質基材的預浸體。又，前述樹脂組成物或前述樹脂組成物之半硬化物亦可為前述樹脂組成物經乾燥或加熱乾燥者。In addition, the prepreg obtained by using the resin composition of this embodiment may be a semi-cured product of the aforementioned resin composition as described above, or may include the uncured resin composition itself. That is, it may be a prepreg comprising a semi-cured product of the above-mentioned resin composition (the above-mentioned resin composition of the B-stage) and a fibrous base material, or may be provided with the above-mentioned resin composition before curing (the above-mentioned resin composition of the A-stage). objects) and prepregs of fibrous substrates. In addition, the aforementioned resin composition or the semi-cured product of the aforementioned resin composition may be dried or heat-dried.
製造預浸體時，為了浸潤至用以形成預浸體之基材的纖維質基材3，樹脂組成物2多調製成清漆狀來使用。即，樹脂組成物2通常多為調製成清漆狀的樹脂清漆。所述清漆狀樹脂組成物(樹脂清漆)例如可依以下方式調製。When producing a prepreg, the
首先，將樹脂組成物之組成中可溶解於有機溶劑之各成分投入有機溶劑中使其溶解。此時，亦可視需求進行加熱。然後，添加視需求使用之不溶解於有機溶劑的成分(例如無機充填劑等)，並使用球磨機、珠磨機、行星式混合器、輥磨機等進行分散直到成為預定分散狀態為止，藉此調製清漆狀樹脂組成物。在此使用之有機溶劑若為可使前述改質聚伸苯基醚化合物或前述硬化劑等溶解且不阻礙硬化反應之物，即無特別限定。具體上可舉例如甲苯或甲基乙基酮(MEK)等。First, each component that is soluble in an organic solvent in the composition of the resin composition is put into an organic solvent and dissolved. At this time, heating may also be performed as required. Then, add an optional component insoluble in an organic solvent (for example, an inorganic filler, etc.), and disperse using a ball mill, a bead mill, a planetary mixer, a roll mill, etc. until it becomes a predetermined dispersion state, thereby A varnish-like resin composition is prepared. The organic solvent used here is not particularly limited as long as it can dissolve the above-mentioned modified polyphenylene ether compound or the above-mentioned curing agent and the like and does not inhibit the curing reaction. Specifically, toluene, methyl ethyl ketone (MEK), etc. are mentioned, for example.
前述預浸體之製造方法若可製造前述預浸體即無特別限定。具體來說，製造預浸體時，上述本實施形態所用之樹脂組成物如上述，大多係調製成清漆狀作成樹脂清漆來使用。The method for producing the aforementioned prepreg is not particularly limited as long as the aforementioned prepreg can be produced. Specifically, when producing a prepreg, the resin composition used in the above-mentioned embodiment is often prepared in the form of a varnish and used as a resin varnish as described above.
前述纖維質基材具體上可舉例如玻璃布、芳醯胺布、聚酯布、玻璃不織布、芳醯胺不織布、聚酯不織布、紙漿紙及棉絨紙。此外，若使用玻璃布，可獲得機械強度優異之積層板，尤宜為經扁平處理加工之玻璃布。扁平處理加工具體上可舉例如在適當壓力下以壓輥將玻璃布連續加壓，將線股壓縮成扁平的方法。此外，一般使用之纖維質基材的厚度例如為0.01mm以上且0.3mm以下。Specifically, the aforementioned fibrous base material may, for example, be glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, or cotton linter paper. In addition, if glass cloth is used, a laminate with excellent mechanical strength can be obtained, especially glass cloth that has been flattened. Specifically, the flattening process may include, for example, a method in which the glass cloth is continuously pressed with a pressure roller under an appropriate pressure to compress the strands into a flat shape. In addition, the thickness of the generally used fibrous base material is, for example, not less than 0.01 mm and not more than 0.3 mm.
前述預浸體之製造方法若可製造前述預浸體即無特別限定。具體來說，製造預浸體時，上述本實施形態之樹脂組成物如上述，大多係調製成清漆狀作成樹脂清漆來使用。The method for producing the aforementioned prepreg is not particularly limited as long as the aforementioned prepreg can be produced. Specifically, when producing a prepreg, the resin composition of the present embodiment described above is often prepared in the form of a varnish and used as a resin varnish.
製造預浸體1之方法可舉例如使樹脂組成物2、例如使調製成清漆狀之樹脂組成物2浸潤至纖維質基材3中後進行乾燥的方法。樹脂組成物2可藉由浸漬及塗佈等浸潤至纖維質基材3。亦可視需求反覆複數次進行浸潤。又，此時，亦可藉由使用組成或濃度不同的複數種樹脂組成物反覆浸潤，調整成最後所希望的組成及浸潤量。As a method of producing the
浸潤有樹脂組成物(樹脂清漆)2的纖維質基材3，可在所期望的加熱條件下例如80℃以上且180℃以下，加熱1分鐘以上且10分鐘以下。藉由加熱，可獲得硬化前(A階段)或半硬化狀態(B階段)之預浸體1。此外，藉由前述加熱，可使有機溶劑從前述樹脂清漆揮發，減少或去除有機溶劑。The
具備本實施形態之樹脂組成物或該樹脂組成物之半硬化物的預浸體，是一可適宜獲得介電特性低、熱傳導率及Tg高、密著性及阻燃性亦優異之硬化物的預浸體。A prepreg comprising the resin composition of this embodiment or a semi-cured product of the resin composition is suitable for obtaining a cured product with low dielectric properties, high thermal conductivity and Tg, and excellent adhesion and flame retardancy. prepreg.
[覆金屬積層板]
圖2係顯示本發明實施形態之覆金屬積層板11之一例的概略截面圖。
[Metal-clad laminate]
Fig. 2 is a schematic cross-sectional view showing an example of a metal-clad
如圖2所示，覆金屬積層板11係由含如圖1所示之預浸體1之硬化物的絕緣層12、及與絕緣層12積層之金屬箔13構成。即，覆金屬積層板11具有含樹脂組成物之硬化物的絕緣層12與設於絕緣層12上之金屬箔13。又，絕緣層12可為由前述樹脂組成物之硬化物構成者，亦可為由前述預浸體之硬化物構成者。又，前述金屬箔13之厚度會因應對於最終獲得之配線板所要求之性能等而不同，並無特別限定。金屬箔13之厚度可因應所期望之目的適當設定，例如宜為0.2~70µm。又，前述金屬箔13可舉例如銅箔及鋁箔等，當前述金屬箔較薄時，為提升處理性，亦可為具備剝離層及載體的附載體之銅箔。As shown in FIG. 2 , a metal-clad
製造前述覆金屬積層板11之方法若可製造前述覆金屬積層板11即無特別限定。具體上可舉使用預浸體1來製作覆金屬積層板11之方法。該方法可舉以下方法等：取1片預浸體1或層疊複數片預浸體1後，進一步於其上下兩面或單面層疊銅箔等的金屬箔13，並將金屬箔13及預浸體1加熱加壓成形進行積層一體化，而製出雙面覆有金屬箔或單面覆有金屬箔之積層板11。即，覆金屬積層板11係於預浸體1積層金屬箔13後進行加熱加壓成形而得。又，加熱加壓條件可根據欲製造之覆金屬積層板11的厚度及預浸體1之組成物種類等適當設定。例如，可將溫度設為170~210℃，壓力設為3~4MPa，且時間設為60~150分鐘。又，前述覆金屬積層板亦可不使用預浸體來製造。例如，可舉將清漆狀樹脂組成物塗佈於金屬箔上，於金屬箔上形成含樹脂組成物之層後再進行加熱加壓之方法等。The method of manufacturing the metal-clad
具備含本實施形態之樹脂組成物之硬化物的絕緣層之覆金屬積層板，是一具備介電特性低、熱傳導率及Tg高、與金屬箔之密著性及阻燃性亦優異之絕緣層的覆金屬積層板。A metal-clad laminate having an insulating layer containing a cured product of the resin composition of this embodiment is an insulating material having low dielectric properties, high thermal conductivity and Tg, and excellent adhesion to metal foil and flame retardancy. layers of metal-clad laminates.
[配線板]
圖3係顯示本發明實施形態之配線板21之一例的概略截面圖。
[wiring board]
Fig. 3 is a schematic cross-sectional view showing an example of a
如圖3所示，本實施形態之配線板21係由使圖1所示之預浸體1硬化來使用的絕緣層12與配線14構成，該配線14係與絕緣層12積層且將金屬箔13予以部分去除而形成者。即，前述配線板21具有含樹脂組成物之硬化物的絕緣層12與設於絕緣層12上之配線14。又，絕緣層12可為由前述樹脂組成物之硬化物構成者，亦可為由前述預浸體之硬化物構成者。As shown in FIG. 3 , the
製造前述配線板21之方法若可製造前述配線板21即無特別限定。具體上可舉使用前述預浸體1來製作配線板21之方法等。該方法可舉例如將依上述製出之覆金屬積層板11之表面的金屬箔13利用蝕刻加工等形成配線，藉此製出於絕緣層12之表面設有配線作為電路的配線板21之方法等。即，配線板21可藉由將覆金屬積層板11之表面的金屬箔13予以部分去除，形成電路而得。又，形成電路之方法除了上述方法以外，還可舉例如利用半加成法(SAP：Semi Additive Process)或改良半加成法(MSAP：Modified Semi Additive Process)來形成電路等。配線板21具有絕緣層12，該絕緣層12之介電特性低、耐熱性高，且即便在吸水處理後仍可適宜維持低介電特性。The method of manufacturing the
所述配線板是一具備介電特性低、熱傳導率及Tg高、與金屬箔之密著性及阻燃性亦優異之絕緣層的配線板。The wiring board is a wiring board having an insulating layer with low dielectric properties, high thermal conductivity and Tg, and excellent adhesion to metal foil and flame retardancy.
[附樹脂之金屬箔]
圖4係顯示本實施形態之附樹脂之金屬箔31之一例的概略截面圖。
[Metal foil with resin]
FIG. 4 is a schematic cross-sectional view showing an example of the resin-coated
如圖4所示，本實施形態之附樹脂之金屬箔31具備含前述樹脂組成物或前述樹脂組成物之半硬化物的樹脂層32、及金屬箔13。該附樹脂之金屬箔31係於前述樹脂層32之表面上具有金屬箔13。即，該附樹脂之金屬箔31具備前述樹脂層32及與前述樹脂層32積層之金屬箔13。又，前述附樹脂之金屬箔31亦可在前述樹脂層32與前述金屬箔13之間具備其他層。As shown in FIG. 4 , the resin-coated
又，前述樹脂層32亦可為包含如上述之前述樹脂組成物之半硬化物者，或可為包含未硬化之前述樹脂組成物者。即，前述附樹脂之金屬箔31可具備含前述樹脂組成物之半硬化物(B階段之前述樹脂組成物)的樹脂層與金屬箔，亦可為具備含硬化前之前述樹脂組成物(A階段之前述樹脂組成物)之樹脂層與金屬箔的附樹脂之金屬箔。又，前述樹脂層若包含有前述樹脂組成物或前述樹脂組成物之半硬化物即可，而纖維質基材可含或可不含。又，前述樹脂組成物或前述樹脂組成物之半硬化物亦可為前述樹脂組成物經乾燥或加熱乾燥者。又，纖維質基材可使用與預浸體之纖維質基材相同之物。In addition, the
又，金屬箔可不作限定地使用可用於覆金屬積層板的金屬箔。金屬箔可舉例如銅箔及鋁箔等。Moreover, the metal foil which can be used for a metal-clad laminate can be used without limitation. As metal foil, copper foil, aluminum foil, etc. are mentioned, for example.
前述附樹脂之金屬箔31及前述附樹脂之薄膜41亦可視需求具備覆蓋薄膜等。藉由具備覆蓋薄膜可防止異物混入等。前述覆蓋薄膜無特別限定，可舉例如聚烯烴薄膜、聚酯薄膜、聚甲基戊烯薄膜及於該等薄膜上設置脫模劑層而形成之薄膜等。The aforementioned resin-coated
製造前述附樹脂之金屬箔31之方法若可製造前述附樹脂之金屬箔31即無特別限定。前述附樹脂之金屬箔31之製造方法可舉將上述清漆狀樹脂組成物(樹脂清漆)塗佈至金屬箔13上並進行加熱來製造之方法等。清漆狀樹脂組成物例如可使用棒塗機塗佈於金屬箔13上。經塗佈之樹脂組成物例如可在80℃以上且180℃以下及1分鐘以上且10分鐘以下的條件下加熱。經加熱之樹脂組成物係作為未硬化之樹脂層32形成於金屬箔13上。此外，藉由前述加熱，可使有機溶劑從前述樹脂清漆揮發，減少或去除有機溶劑。The method of manufacturing the aforementioned resin-coated
具備包含本實施形態之樹脂組成物或該樹脂組成物之半硬化物的樹脂層之附樹脂之金屬箔，是一可適宜獲得介電特性低、熱傳導率及Tg高、與金屬箔之密著性及阻燃性亦優異之硬化物的附樹脂之金屬箔。The resin-attached metal foil having a resin layer comprising the resin composition of this embodiment or a semi-cured product of the resin composition is suitable for obtaining low dielectric properties, high thermal conductivity and Tg, and adhesion to the metal foil. Resin-attached metal foil of a hardened product that is also excellent in fire resistance and flame retardancy.
[附樹脂薄膜]
圖5係顯示本實施形態之附樹脂之薄膜41之一例的概略截面圖。
[with resin film]
FIG. 5 is a schematic cross-sectional view showing an example of the resin-coated
如圖5所示，本實施形態之附樹脂之薄膜41具備含前述樹脂組成物或前述樹脂組成物之半硬化物的樹脂層42、及支持薄膜43。該附樹脂之薄膜41具備前述樹脂層42及與前述樹脂層42積層之支持薄膜43。又，前述附樹脂之薄膜41亦可在前述樹脂層42與前述支持薄膜43之間具備其他層。As shown in FIG. 5 , the resin-attached
又，前述樹脂層42亦可為含如上述之前述樹脂組成物之半硬化物者，或可為含未硬化之前述樹脂組成物者。即，前述附樹脂之薄膜41可具備含前述樹脂組成物之半硬化物(B階段之前述樹脂組成物)之樹脂層與支持薄膜，亦可為具備含硬化前之前述樹脂組成物(A階段之前述樹脂組成物)之樹脂層與支持薄膜的附樹脂之薄膜。又，前述樹脂層若包含有前述樹脂組成物或前述樹脂組成物之半硬化物即可，而纖維質基材可含或可不含。又，前述樹脂組成物或前述樹脂組成物之半硬化物亦可為前述樹脂組成物經乾燥或加熱乾燥者。又，纖維質基材可使用與預浸體之纖維質基材相同之物。In addition, the
又，支持薄膜43可不作限定地使用可用於附樹脂之薄膜的支持薄膜。前述支持薄膜可列舉例如聚酯薄膜、聚對苯二甲酸乙二酯(PET)薄膜、聚醯亞胺薄膜、聚乙二醯脲薄膜、聚醚醚酮薄膜、聚伸苯硫薄膜、聚醯胺薄膜、聚碳酸酯薄膜及聚芳酯薄膜等之電絕緣性薄膜等。In addition, as the
前述附樹脂之薄膜41亦可視需求具備覆蓋薄膜等。藉由具備覆蓋薄膜可防止異物混入等。前述覆蓋膜薄無特別限定，可舉例如聚烯烴薄膜、聚酯薄膜及聚甲基戊烯薄膜等。The aforementioned resin-attached
前述支持薄膜及覆蓋薄膜亦可為視需求經施行消光處理、電暈處理、脫模處理及粗化處理等表面處理者。The above-mentioned support film and cover film may also be surface treated with matting treatment, corona treatment, mold release treatment, and roughening treatment as required.
製造前述附樹脂之薄膜41之方法若為可製造前述附樹脂之薄膜41即無特別限定。前述附樹脂之薄膜41之製造方法可舉例如將上述清漆狀樹脂組成物(樹脂清漆)塗佈於支持薄膜43上並進行加熱來製造之方法等。清漆狀樹脂組成物例如可使用棒塗機塗佈於支持薄膜43上。經塗佈之樹脂組成物例如可在80℃以上且180℃以下及1分鐘以上且10分鐘以下的條件下加熱。經加熱之樹脂組成物係作為未硬化之樹脂層42形成於支持薄膜43上。此外，藉由前述加熱，可使有機溶劑從前述樹脂清漆揮發，減少或去除有機溶劑。The method of manufacturing the aforementioned resin-coated
具備含本實施形態之樹脂組成物或該樹脂組成物之半硬化物的樹脂層之附樹脂之薄膜，是一可適宜獲得介電特性低、熱傳導率及Tg高、密著性及阻燃性亦優異之硬化物的附樹脂之薄膜。A resin-attached film having a resin layer containing the resin composition of this embodiment or a semi-cured product of the resin composition is suitable for obtaining low dielectric properties, high thermal conductivity and Tg, adhesion and flame retardancy. It is also excellent as a resin-attached film for hardened products.
本說明書如上述揭示了各種態樣之技術，並將其中主要技術彙整如下。This specification discloses technologies in various aspects as described above, and the main technologies are summarized as follows.
本發明第1態樣之樹脂組成物之特徵在於：包含：聚伸苯基醚化合物(A)；硬化劑(B)；含氮化硼之無機充填劑(C)；及磷化合物(D)；前述無機充填劑(C)之粒度分布中，利用雷射繞射式粒度分布測定法測定之粒度分布的峰值在粒徑1.0~50.0µm範圍中至少存在2個；前述磷化合物(D)包含相溶性磷化合物(D-1)及非相溶性磷化合物(D-2)，該相溶性磷化合物(D-1)係和前述聚伸苯基醚化合物(A)與前述硬化劑(B)之混合物相溶者，該非相溶性磷化合物(D-2)係不與前述混合物相溶者。The resin composition of the first aspect of the present invention is characterized by comprising: a polyphenylene ether compound (A); a hardener (B); an inorganic filler containing boron nitride (C); and a phosphorus compound (D) ; In the particle size distribution of the aforementioned inorganic filler (C), there are at least two peaks in the particle size distribution measured by the laser diffraction particle size distribution measurement method in the range of particle diameters from 1.0 to 50.0 µm; the aforementioned phosphorus compound (D) includes Compatible phosphorus compound (D-1) and incompatible phosphorus compound (D-2), the compatible phosphorus compound (D-1) and the aforementioned polyphenylene ether compound (A) and the aforementioned hardener (B) If the mixture is compatible, the non-miscible phosphorus compound (D-2) is not compatible with the aforementioned mixture.
關於第2態樣之樹脂組成物，在第1態樣之樹脂組成物中，前述粒度分布的峰值在粒徑1.0以上且10.0µm以下範圍中至少存在一個，且在粒徑大於10.0µm且在50.0µm以下範圍中至少存在一個。Regarding the resin composition of the second aspect, in the resin composition of the first aspect, at least one of the peaks of the aforementioned particle size distribution exists in the range of a particle diameter of 1.0 to 10.0 µm, and the particle diameter is greater than 10.0 µm and within At least one exists in the range below 50.0µm.
關於第3態樣之樹脂組成物，在第1或第2態樣之樹脂組成物中，相對於前述無機充填劑(C)之粒度分布全體100體積%，粒徑0.1~5.0µm範圍之粒子的累積比率為25~75體積%，粒徑5.0~100.0µm之粒子的累積比率為25~75體積%。Regarding the resin composition of the third aspect, in the resin composition of the first or second aspect, particles with a particle diameter in the range of 0.1 to 5.0 µm are 100% by volume of the particle size distribution of the aforementioned inorganic filler (C) The accumulation ratio of the particles is 25~75% by volume, and the accumulation ratio of particles with a particle size of 5.0~100.0µm is 25~75% by volume.
關於第4態樣之樹脂組成物，在第1~3中任一態樣之樹脂組成物中，前述無機充填劑(C)更包含有選自於由二氧化矽、無水碳酸鎂、氧化鎂、氧化鋁、氮化矽及氮化鋁所構成群組中之至少1種填料。Regarding the resin composition of the fourth aspect, in the resin composition of any one of the first to third aspects, the above-mentioned inorganic filler (C) further contains a compound selected from silicon dioxide, anhydrous magnesium carbonate, magnesium oxide , alumina, silicon nitride and aluminum nitride at least one filler in the group.
關於第5態樣之樹脂組成物，在第4態樣之樹脂組成物中，前述無機充填劑(C)包含二氧化矽填料；前述無機充填劑(C)之粒度分布中，利用雷射繞射式粒度分布測定法測定之粒度分布的峰值在粒徑1.0~50.0µm範圍中至少存在三個，並且該等峰值在粒徑1.0~10.0µm範圍中至少存在一個，在粒徑5.0~20.0µm範圍中至少存在一個，且在粒徑20.0~50.0µm範圍中至少存在一個。Regarding the resin composition of the fifth aspect, in the resin composition of the fourth aspect, the aforementioned inorganic filler (C) includes a silica filler; in the particle size distribution of the aforementioned inorganic filler (C), laser diffraction There are at least three peaks of the particle size distribution measured by the radiographic particle size distribution measurement method in the particle size range of 1.0~50.0µm, and there is at least one of these peaks in the particle size range of 1.0~10.0µm, and there is at least one of these peaks in the particle size range of 5.0~20.0µm There is at least one in the range, and there is at least one in the range of particle size 20.0~50.0µm.
關於第6態樣之樹脂組成物，在第1~5之任一態樣之樹脂組成物中，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述無機充填劑(C)之含量為40~80質量份。Regarding the resin composition of the sixth aspect, in the resin composition of any one of the first to fifth aspects, with respect to the aforementioned polyphenylene ether compound (A), the aforementioned hardener (B) and the aforementioned inorganic filler The total amount of (C) is 100 parts by mass, and the content of the aforementioned inorganic filler (C) is 40 to 80 parts by mass.
關於第7態樣之樹脂組成物，在第6態樣之樹脂組成物中，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述氮化硼之含量為15~50質量份。並且，相對於前述無機充填劑(C)100質量份，前述無機充填劑(C)中之前述氮化硼之含量宜為20~100質量份。Regarding the resin composition of the seventh aspect, in the resin composition of the sixth aspect, relative to the total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C) 100 parts by mass, the content of the aforementioned boron nitride is 15-50 parts by mass. In addition, the content of the boron nitride in the inorganic filler (C) is preferably 20 to 100 parts by mass relative to 100 parts by mass of the inorganic filler (C).
關於第8態樣之樹脂組成物，在第6態樣之樹脂組成物中，相對於前述聚伸苯基醚化合物(A)、前述硬化劑(B)及前述無機充填劑(C)之合計100質量份，前述無機充填劑(C)中之前述氮化硼以外之無機充填劑之含量為20~60質量份。Regarding the resin composition of the eighth aspect, in the resin composition of the sixth aspect, relative to the total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C) 100 parts by mass, the content of inorganic fillers other than the aforementioned boron nitride in the aforementioned inorganic filler (C) is 20 to 60 parts by mass.
關於第9態樣之樹脂組成物，在第1~8態樣之樹脂組成物中，前述相溶性磷化合物(D-1)包含選自於由磷酸酯化合物、膦氮烯化合物、亞磷酸酯化合物及膦化合物所構成群組中之至少1者。Regarding the resin composition of the ninth aspect, in the resin composition of the first to eighth aspects, the above-mentioned compatible phosphorus compound (D-1) contains a phosphoric acid ester compound, a phosphazene compound, a phosphite At least one of the group consisting of a compound and a phosphine compound.
關於第10態樣之樹脂組成物，在第1~9態樣之樹脂組成物中，前述非相溶性磷化合物(D-2)包含選自於由次磷酸鹽化合物、多磷酸鹽化合物、鏻鹽化合物及膦氧化物化合物所構成群組中之至少1者。Regarding the resin composition of the tenth aspect, in the resin composition of the first to ninth aspects, the aforementioned incompatible phosphorus compound (D-2) contains a compound selected from hypophosphite compounds, polyphosphate compounds, phosphonium At least one member of the group consisting of a salt compound and a phosphine oxide compound.
關於第11態樣之樹脂組成物中，在第1~10態樣之樹脂組成物中，相對於前述相溶性磷化合物(D-1)與前述非相溶性磷化合物(D-2)之合計100質量份，前述相溶性磷化合物(D-1)之含量為25~65質量份。Regarding the resin composition of the eleventh aspect, in the resin compositions of the first to tenth aspects, relative to the total of the aforementioned compatible phosphorus compound (D-1) and the aforementioned incompatible phosphorus compound (D-2) 100 parts by mass, the content of the aforementioned compatible phosphorus compound (D-1) is 25 to 65 parts by mass.
關於第12態樣之樹脂組成物，在第1~11之態樣之樹脂組成物中，前述聚伸苯基醚化合物(A)包含改質聚伸苯基醚化合物(A-1)，且該改質聚伸苯基醚化合物(A-1)具有上述式(1)及式(2)所示之基團中之至少一者。Regarding the resin composition of the twelfth aspect, in the resin composition of the first to eleventh aspects, the polyphenylene ether compound (A) includes a modified polyphenylene ether compound (A-1), and The modified polyphenylene ether compound (A-1) has at least one of the groups represented by the above formula (1) and formula (2).
關於第13態樣之樹脂組成物，在第1~12態樣之樹脂組成物中，前述硬化劑(B)包含選自於由以下所構成群組中之至少1種：分子中具有2個以上丙烯醯基之多官能丙烯酸酯化合物、分子中具有2個以上甲基丙烯醯基之多官能甲基丙烯酸酯化合物、分子中具有2個以上乙烯基之多官能乙烯基化合物、苯乙烯衍生物、分子中具有烯丙基之烯丙基化合物、分子中具有馬來醯亞胺基之馬來醯亞胺化合物、分子中具有苊結構之苊化合物及分子中具有三聚異氰酸酯基之三聚異氰酸酯化合物。Regarding the resin composition of the thirteenth aspect, in the resin composition of the first to twelfth aspects, the aforementioned curing agent (B) contains at least one selected from the group consisting of: having two Multifunctional acrylate compounds with the above acryl groups, multifunctional methacrylate compounds with 2 or more methacryl groups in the molecule, multifunctional vinyl compounds with 2 or more vinyl groups in the molecule, and styrene derivatives , Allyl compounds with allyl groups in the molecule, maleimide compounds with maleimide groups in the molecule, acenaphthylene compounds with acenaphthene structure in the molecule, and isocyanate with isocyanate groups in the molecule compound.
關於第14態樣之樹脂組成物，第1~13態樣之樹脂組成物更包含苯乙烯系聚合物。Regarding the resin composition of the fourteenth aspect, the resin compositions of the first to thirteenth aspects further include a styrene-based polymer.
關於第15態樣之樹脂組成物，第1~14態樣之樹脂組成物之硬化物之熱傳導率為1.0W/m・K以上，且頻率10GHz下之相對介電常數為4.0以下。Regarding the resin composition of the fifteenth aspect, the thermal conductivity of the cured product of the resin compositions of the first to fourteenth aspects is 1.0 W/m·K or more, and the relative dielectric constant at a frequency of 10 GHz is 4.0 or less.
本發明第16態樣之預浸體之特徵在於具備：第1~15之態樣之樹脂組成物或前述樹脂組成物之半硬化物；及纖維質基材。A prepreg according to a sixteenth aspect of the present invention is characterized by comprising: the resin composition of the first to fifteenth aspects or a semi-cured product of the aforementioned resin composition; and a fibrous base material.
本發明第17態樣之附樹脂之薄膜之特徵在於具備：樹脂層，其包含第1~15態樣之樹脂組成物或前述樹脂組成物之半硬化物；及支持薄膜。The resin-attached film of the 17th aspect of the present invention is characterized by comprising: a resin layer comprising the resin composition of the 1st to 15th aspects or a semi-cured product of the aforementioned resin composition; and a supporting film.
本發明第18態樣之附樹脂之金屬箔之特徵在於具備：樹脂層，其包含第1~15態樣之樹脂組成物或前述樹脂組成物之半硬化物；及金屬箔。The resin-attached metal foil of the eighteenth aspect of the present invention is characterized by comprising: a resin layer comprising the resin composition of the first to fifteenth aspects or a semi-cured product of the aforementioned resin composition; and a metal foil.
本發明第19態樣之覆金屬積層板之特徵在於具備：絕緣層，其包含第1~15態樣之樹脂組成物之硬化物或第16態樣之預浸體之硬化物；及金屬箔。A metal-clad laminate according to a nineteenth aspect of the present invention is characterized by comprising: an insulating layer comprising a cured product of the resin composition of the first to fifteenth aspects or a cured product of the prepreg of the sixteenth aspect; and a metal foil .
本發明第20態樣之配線板之特徵在於具備：絕緣層，其包含如第1~15態樣之樹脂組成物之硬化物或第16態樣之預浸體之硬化物；及配線。A wiring board according to a twentieth aspect of the present invention is characterized by comprising: an insulating layer including a cured product of the resin composition of the first to fifteenth aspects or a cured product of the prepreg of the sixteenth aspect; and wiring.
以下將藉由實施例更具體地說明本發明，惟本發明範圍不受該等限定。The following examples will illustrate the present invention more specifically, but the scope of the present invention is not limited thereto.
實施例 [實施例1~20及比較例1~4] 在本實施例中，針對調製樹脂組成物時使用之各成分加以說明。 Example [Examples 1-20 and Comparative Examples 1-4] In this example, each component used when preparing a resin composition is demonstrated.
(聚伸苯基醚化合物) ・PPE1：於末端具有甲基丙烯醯基之聚伸苯基醚化合物(聚伸苯基醚之末端羥基經甲基丙烯醯基改質的改質聚伸苯基醚，上述式(15)所示且式(15)中之Y為二甲基亞甲基(式(12)所示且式(12)中之R 33及R 34為甲基之基團)的改質聚伸苯基醚化合物，SABIC Innovative Plastics公司製SA9000，重量平均分子量Mw2000，末端官能基數2個) ・PPE2：使聚伸苯基醚與氯甲基苯乙烯反應所得之改質聚伸苯基醚。具體上係如以下方式進行反應所得之改質聚伸苯基醚。 (Polyphenylene ether compound) ・PPE1: Polyphenylene ether compound having a methacryl group at the end (modified polyphenylene ether compound in which the terminal hydroxyl group of polyphenylene ether is modified with a methacryl group) Ether, shown in the above formula (15) and Y in the formula (15) is dimethyl methylene (shown in the formula (12) and R 33 and R 34 in the formula (12) are methyl groups) Modified polyphenylene ether compound, SA9000 manufactured by SABIC Innovative Plastics, weight average molecular weight Mw2000, two terminal functional groups) ・PPE2: Modified polyphenylene ether obtained by reacting polyphenylene ether with chloromethylstyrene Phenyl ether. Specifically, it is a modified polyphenylene ether obtained by performing the reaction in the following manner.
首先，於具備溫度調節器、攪拌裝置、冷卻設備及滴下漏斗之1公升的三口燒瓶中，饋入聚伸苯基醚(SABIC Innovative Plastics公司製SA90，末端羥基數2個，重量平均分子量Mw1700)200g、對氯甲基苯乙烯與間氯甲基苯乙烯之質量比為50：50的混合物(東京化成工業股份公司製氯甲基苯乙烯：CMS)30g、作為相轉移觸媒之溴化四正丁銨1.227g及甲苯400g，並攪拌。然後，持續攪拌直到聚伸苯基醚、氯甲基苯乙烯及溴化四正丁銨溶解於甲苯為止。此時，緩慢地加熱，並加熱到最後液溫成為75℃為止。接著，於該溶液中耗時20分鐘滴下作為鹼金屬氫氧化物之氫氧化鈉水溶液(氫氧化鈉20g/水20g)。然後進一步在75℃下攪拌4小時。接下來，以10質量%之鹽酸將燒瓶之內容物進行中和後，投入大量的甲醇。依上述方式，而於燒瓶內之液體中產生沉澱物。即，使燒瓶內之反應液中所含之產物再次沉澱。然後，利用過濾取出該沉澱物，以甲醇與水之質量比為80：20的混合液洗淨3次後，在減壓下以80℃乾燥3小時。First, in a 1-liter three-neck flask equipped with a temperature regulator, a stirring device, a cooling device, and a dropping funnel, feed polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, with 2 terminal hydroxyl groups, and a weight average molecular weight Mw1700) 200g, 30g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (chloromethylstyrene manufactured by Tokyo Chemical Industry Co., Ltd.: CMS), tetrabromide as a phase transfer catalyst 1.227g of n-butylammonium and 400g of toluene, and stirred. Then, the stirring was continued until the polyphenylene ether, chloromethylstyrene and tetra-n-butylammonium bromide were dissolved in toluene. At this time, it heated slowly, and heated until the final liquid temperature became 75 degreeC. Next, an aqueous sodium hydroxide solution (sodium hydroxide 20 g/water 20 g) was dropped over 20 minutes in this solution as an alkali metal hydroxide. Then it was further stirred at 75° C. for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass of hydrochloric acid, a large amount of methanol was injected. In the above manner, a precipitate was produced in the liquid in the flask. That is, the product contained in the reaction liquid in the flask was reprecipitated. Then, the precipitate was taken out by filtration, washed three times with a mixture of methanol and water having a mass ratio of 80:20, and then dried at 80° C. under reduced pressure for 3 hours.
將所得之固體以 1H-NMR(400MHz、CDCl 3、TMS)進行分析。測定NMR的結果，於5~7ppm確認有源自乙烯基苄基(vinyl benzyl/ethenyl benzyl)的波峰。藉此得以確認，所得之固體為於分子中在分子末端具有乙烯基苄基(vinyl benzyl/ethenyl benzyl)作為前述取代基之改質聚伸苯基醚化合物。具體而言，可確認為經乙烯基苄基化之聚伸苯基醚。該所得之改質聚伸苯基醚化合物係上述式(14)所示之改質聚伸苯基醚化合物，Y為二甲基亞甲基(式(12)所示且式(12)中之R 33及R 34為甲基之基團)，Z為伸苯基，R 1~R 3為氫原子，且n為1。 The obtained solid was analyzed by 1 H-NMR (400 MHz, CDCl 3 , TMS). As a result of measuring NMR, a peak derived from vinyl benzyl (vinyl benzyl/ethenyl benzyl) was confirmed at 5~7ppm. It was thus confirmed that the obtained solid was a modified polyphenylene ether compound having vinyl benzyl (vinyl benzyl/ethenyl benzyl) as the aforementioned substituent at the molecular terminal in the molecule. Specifically, vinylbenzylated polyphenylene ether was confirmed. The obtained modified polyphenylene ether compound is a modified polyphenylene ether compound shown in the above formula (14), Y is dimethylmethylene (shown in formula (12) and in formula (12) R 33 and R 34 are methyl groups), Z is a phenylene group, R 1 to R 3 are hydrogen atoms, and n is 1.
又，以以下方式測定改質聚伸苯基醚之末端官能基數。Also, the number of terminal functional groups of the modified polyphenylene ether was measured in the following manner.
首先，正確秤量改質聚伸苯基醚。令此時之重量為X(mg)。然後，使該經秤量之改質聚伸苯基醚溶解於25mL二氯甲烷中，並於該溶液中添加100μL之10質量%氫氧化四乙銨(TEAH)之乙醇溶液(TEAH：乙醇(體積比)=15：85)後，使用UV分光光度計(股份公司島津製作所製UV-1600)，測定318nm之吸光度(Abs)。接著，從該測定結果以下述式算出改質聚伸苯基醚之末端羥基數。First, weigh the modified polyphenylene ether correctly. Let the weight at this time be X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25 mL of dichloromethane, and 100 μL of a 10% by mass tetraethylammonium hydroxide (TEAH) ethanol solution (TEAH: ethanol (volume Ratio)=15:85), the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (UV-1600, manufactured by Shimadzu Corporation). Next, from the measurement results, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated by the following formula.
殘存OH量(µmol/g)=[(25×Abs)/(ε×OPL×X)]×10 6 Residual OH content (µmol/g)=[(25×Abs)/(ε×OPL×X)]×10 6
在此，ε表示吸光係數，為4700L/mol・cm。又，OPL為測試槽光徑長度，為1cm。Here, ε represents the light absorption coefficient, which is 4700 L/mol·cm. Also, OPL is the optical path length of the test groove, which is 1 cm.
然後，由該所算出之改質聚伸苯基醚的殘存OH量(末端羥基數)幾乎為零的結果可知，改質前之聚伸苯基醚的羥基幾乎已被改質。由此可知，從改質前之聚伸苯基醚的末端羥基數減少的減少量，即為改質前之聚伸苯基醚的末端羥基數。即可知，改質前之聚伸苯基醚的末端羥基數為改質聚伸苯基醚之末端官能基數。亦即，末端官能基數為2個。Then, from the calculated result that the residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether is almost zero, it can be seen that the hydroxyl groups of the polyphenylene ether before modification are almost modified. It can be seen from this that the decrease in the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal hydroxyl groups of the polyphenylene ether before modification. That is, it can be known that the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups is two.
又，測定改質聚伸苯基醚在25℃之二氯甲烷中之固有黏度(IV)。具體而言，改質聚伸苯基醚之固有黏度(IV)係以黏度計(Schott公司製AVS500 Visco System)測定改質聚伸苯基醚在0.18g/45ml之二氯甲烷溶液(液溫25℃)中之黏度。結果，改質聚伸苯基醚之固有黏度(IV)得0.086dl/g。Also, the intrinsic viscosity (IV) of the modified polyphenylene ether in dichloromethane at 25°C was measured. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether is measured with a viscometer (AVS500 Visco System manufactured by Schott Company) in a 0.18g/45ml dichloromethane solution (liquid temperature Viscosity at 25°C). As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086 dl/g.
又，用GPC測定改質聚伸苯基醚之分子量分布。然後，從該所得之分子量分布算出重量平均分子量(Mw)。結果，Mw為2300。Also, the molecular weight distribution of the modified polyphenylene ether was measured by GPC. Then, the weight average molecular weight (Mw) was calculated from the obtained molecular weight distribution. As a result, Mw was 2300.
(硬化劑) ・硬化劑1：三聚異氰酸三烯丙酯(日本化成股份公司製之TAIC) ・硬化劑2：二乙烯苯(新日鐵住金股份公司製之DVB) (hardener) ・Hardener 1: Triallyl isocyanate (TAIC manufactured by Nippon Chemicals Co., Ltd.) ・Hardener 2: divinylbenzene (DVB manufactured by Nippon Steel & Sumitomo Metal Co., Ltd.)
(無機充填劑) ・氮化硼1：股份公司MARUKA製「AP-10S」，體積平均粒徑3.0µm・氮化硼2：Denka Co.,Ltd.製「SGP」，體積平均粒徑18µm ・二氧化矽1：Denka Co.,Ltd.製「FB-7SDC」，體積平均粒徑5µm ・氧化鋁：Denka Co.,Ltd.製「DAW-03AC」，體積平均粒徑8µm (inorganic filler) ・Boron nitride 1: "AP-10S" manufactured by MARUKA Co., Ltd., volume average particle diameter 3.0 µm ・Boron nitride 2: "SGP" manufactured by Denka Co., Ltd., volume average particle diameter 18 µm ・Silicon dioxide 1: "FB-7SDC" manufactured by Denka Co., Ltd., volume average particle diameter 5 µm ・Alumina: "DAW-03AC" manufactured by Denka Co., Ltd., volume average particle size 8µm
(磷化合物(D))
・相溶性磷化合物(D-1)1：芳香族縮合磷酸酯化合物，大八化學工業股份公司製「PX-200」，磷濃度9質量%
・相溶性磷化合物(D-1)2：環狀膦氮烯化合物，大塚化學股份公司製，「SPB-100」，磷濃度13質量%
・非相溶性磷化合物(D-2)1：二苯基膦氧化物化合物，晉一化工有限公司製，「PQ60」，磷濃度12質量%
・非相溶性磷化合物(D-2)2：次磷酸鹽化合物，Clariant Japan KK製，「OP-935」，磷濃度23質量%
(phosphorus compound (D))
・Compatible phosphorus compound (D-1) 1: Aromatic condensed phosphoric acid ester compound, "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus concentration 9% by mass
・Compatible phosphorus compound (D-1) 2: Cyclic phosphazene compound, manufactured by Otsuka Chemical Co., Ltd., "SPB-100",
(反應引發劑) ・過氧化物引發劑：PBP(1,3-雙(丁基過氧基異丙基)苯；日油股份公司製之PERBUTYL P) (reaction initiator) ・Peroxide initiator: PBP (1,3-bis(butylperoxyisopropyl)benzene; PERBUTYL P manufactured by NOF Corporation)
(苯乙烯系聚合物) ・苯乙烯系聚合物1：氫化甲基苯乙烯(乙烯/丁烯)甲基苯乙烯共聚物(股份公司Kuraray製之SEPTON V9827，重量平均分子量：92000) ・苯乙烯系聚合物2：苯乙烯・異丁烯・苯乙烯系三嵌段共聚物(股份公司Kaneka製，數量平均分子量85,000，苯乙烯之莫耳分率：30%) (styrene-based polymer) ・Styrenic polymer 1: Hydrogenated methylstyrene (ethylene/butylene) methylstyrene copolymer (SEPTON V9827 manufactured by Kuraray Co., Ltd., weight average molecular weight: 92000) ・Styrene-based polymer 2: Styrene-isobutylene-styrene-based triblock copolymer (manufactured by Kaneka Co., Ltd., number average molecular weight: 85,000, mole fraction of styrene: 30%)
(自由基化合物) ・自由基化合物1：4-苯甲醯氧基tempo，下述式所示之自由基化合物(東京化成工業股份公司製「H0878」) (free radical compound) ・Radical compound 1: 4-benzoyloxytempo, a radical compound represented by the following formula ("H0878" manufactured by Tokyo Chemical Industry Co., Ltd.)
[化學式15] [chemical formula 15]
(調製方法) 首先，將無機充填劑以外之各有機樹脂成分依表1及表2記載之組成(質量份)添加至作為溶劑之甲苯中進行混合，使固體成分濃度成為60~70質量%。將該混合物攪拌60分鐘。然後，於所得之液體中以表1及表2記載之摻混(質量份)添加各充填材，並利用珠磨機使無機充填劑分散。依上述方式進行，而獲得清漆狀樹脂組成物(清漆)。 (modulation method) First, each organic resin component other than the inorganic filler was added to toluene as a solvent according to the composition (parts by mass) described in Table 1 and Table 2, and mixed so that the solid content concentration became 60~70% by mass. The mixture was stirred for 60 minutes. Then, each filler was added to the obtained liquid in a blend (parts by mass) described in Table 1 and Table 2, and the inorganic filler was dispersed using a bead mill. In the above manner, a varnish-like resin composition (varnish) was obtained.
接著，依以下方式進行，而獲得評估基板(預浸體之硬化物)。Next, an evaluation substrate (hardened prepreg) was obtained in the following manner.
使所得之清漆浸潤至纖維質基材(玻璃布：旭化成股份公司製之#1078型，L玻璃)中後，於110℃下加熱乾燥3分鐘，藉此製出預浸體。然後，分別於層疊所得之各預浸體1、2、4及6片者之兩面貼合銅箔(古河電氣工業股份公司製「FV-WS」銅箔厚度：35µm)，以升溫速度4℃/分鐘加熱至溫度200℃，並在200℃、120分鐘、壓力3MPa之條件下進行加熱加壓，藉此作成3種板厚之覆銅積層板。The obtained varnish was impregnated into a fibrous base material (glass cloth: #1078 manufactured by Asahi Kasei Co., Ltd., L glass), and heated and dried at 110° C. for 3 minutes to prepare a prepreg. Then, attach copper foil (thickness of "FV-WS" copper foil manufactured by Furukawa Electric Co., Ltd.: 35µm) to both sides of each prepreg obtained by stacking 1, 2, 4, and 6 sheets respectively, and heat up at a rate of 4°C Heating to a temperature of 200°C per minute, and heating and pressing at 200°C, 120 minutes, and a pressure of 3MPa to make copper-clad laminates with three thicknesses.
將以上述方式調製之覆銅積層板作為評估基板，藉由以下所示之方法進行了評估。此外，在後述之熱傳導率的測定中，係使用1片預浸體之硬化物及從層疊2片預浸體的覆銅積層板去除銅箔者(預浸體之硬化物)，而在介電特性(相對介電常數)的評估試驗中，係使用從層疊4片預浸體的覆銅積層板去除銅箔者(預浸體之硬化物)。又，在後述之阻燃性的評估試驗中，係使用從層疊4片預浸體的覆銅積層板及層疊6片預浸體的覆銅積層板去除銅箔者(預浸體之硬化物)，而在g之測定、評估中，係使用從層疊4片預浸體的覆銅積層板去除銅箔者(預浸體之硬化物)。The copper-clad laminate prepared as above was used as an evaluation board, and evaluation was performed by the method shown below. In addition, in the measurement of the thermal conductivity described later, the cured product of one prepreg and the copper foil removed from the copper-clad laminate laminated with two prepregs (cured product of the prepreg) were used. In the evaluation test of the electrical characteristics (relative dielectric constant), the copper foil was removed from the copper-clad laminate laminated with 4 prepregs (prepreg cured product). In addition, in the flame retardancy evaluation test described later, the copper-clad laminates laminated with 4 prepregs and the copper-clad laminates laminated with 6 prepregs were used (hardened prepregs) ), and in the measurement and evaluation of g, the copper foil was removed from the copper-clad laminate laminated with 4 prepregs (hardened prepreg).
[介電特性(相對介電常數)] 以空腔共振器微擾法測定評估基板(預浸體之硬化物)在10GHz下的相對介電常數(Dk)。具體而言，係使用網路分析器(Keysight Technologies股份公司製之N5230A)，測定評估基板在10GHz下的相對介電常數。本實施例中之合格基準設為Dk≦4.0。 [Dielectric properties (relative permittivity)] The relative permittivity (Dk) of the evaluation substrate (hardened prepreg) at 10 GHz was measured by the cavity resonator perturbation method. Specifically, a network analyzer (N5230A manufactured by Keysight Technologies Co., Ltd.) was used to measure the relative permittivity of the evaluation substrate at 10 GHz. The pass standard in this embodiment is Dk≦4.0.
[銅箔剝離強度] 首先，為了剝離強度(銅箔剝離)試驗，使用各實施例及比較例之預浸體作成覆銅積層版(CCL)。具體而言，係層疊4片預浸體且在其兩表面貼合厚度35µm之銅箔(古河電工股份公司製「FV-WS」)後，在真空條件下，以溫度200℃、壓力3MPa之條件加熱加壓120分鐘使兩面接著銅箔，而獲得厚度510µm之覆銅積層板(CCL)(評估基板)。 [Copper foil peel strength] First, for the peel strength (copper foil peeling) test, a copper clad laminate (CCL) was produced using the prepregs of the respective examples and comparative examples. Specifically, after laminating four prepregs and laminating copper foil (Furukawa Electric Co., Ltd. "FV-WS") with a thickness of 35 µm on both surfaces, the prepreg was heated at a temperature of 200°C and a pressure of 3 MPa under vacuum conditions. Conditional heating and pressing for 120 minutes to bond copper foil on both sides to obtain a copper-clad laminate (CCL) (evaluation substrate) with a thickness of 510 µm.
然後，使用所得之CCL，依循JIS C 6481測定從絕緣層剝開銅箔的剝開強度。形成寬10mm、長100mm之圖案，利用拉伸試驗機以50mm/分鐘之速度剝開，測定當下的剝開強度(剝離強度)。測定單位為N/mm。本實施例中之合格基準設為0.40N/mm以上。Then, using the obtained CCL, the peel strength of the copper foil peeled off from the insulating layer was measured in accordance with JIS C 6481. Form a pattern with a width of 10 mm and a length of 100 mm, and use a tensile testing machine to peel off at a speed of 50 mm/min to measure the current peel strength (peel strength). The measurement unit is N/mm. The pass standard in this embodiment is set to be 0.40 N/mm or more.
[熱傳導率] 藉由依循ASTM D5470之方法測定所得之評估基板(預浸體之硬化物)的熱傳導率。具體而言，係使用熱特性評估裝置(Mentor Graphics公司製之T3Ster DynTIM Tester)，測定所得之評估基板(1片預浸體之硬化物、層疊2片預浸體之硬化物)的熱電阻與厚度，將該測定值作成圖表並以直線近似，從熱電阻與厚度增加量算出熱傳導率。本實施例中之熱傳導率的合格基準設為1.0W/m・K以上。 [Thermal conductivity] The thermal conductivity of the obtained evaluation substrate (cured product of the prepreg) was measured by following the method of ASTM D5470. Specifically, the thermal resistance and thermal resistance of the obtained evaluation substrates (cured product of one prepreg, cured product of stacking two prepregs) were measured using a thermal characteristic evaluation device (T3Ster DynTIM Tester manufactured by Mentor Graphics). Thickness, the measured value is made into a graph and approximated by a straight line, and the thermal conductivity is calculated from the thermal resistance and the thickness increase. The pass standard of the thermal conductivity in this embodiment is set at 1.0 W/m·K or more.
[玻璃轉移溫度(Tg)] 使用SEIKO INSTRUMENTS INC.製黏彈性分光計「DMS100」，測定預浸體之Tg。此時，利用彎曲模數且令頻率為10Hz來進行動態黏彈性測定(DMA)，並以在升溫速度5℃/分鐘之條件下從室溫升溫至280℃時tanδ顯示極大值之溫度為Tg。本實施例中，合格基準設為Tg≧150℃。 [Glass transition temperature (Tg)] The Tg of the prepreg was measured using a viscoelasticity spectrometer "DMS100" manufactured by SEIKO INSTRUMENTS INC. At this time, the dynamic viscoelasticity measurement (DMA) is performed using the flexural modulus and the frequency is set to 10 Hz, and the temperature at which tan δ shows the maximum value when the temperature rises from room temperature to 280°C at a heating rate of 5°C/min is Tg . In this example, the pass criterion is Tg≧150°C.
[阻燃性] 從評估基板裁切出長125mm、寬12.5mm之試片。然後，針對該試片，依循Underwriters Laboratories之“Test for Flammability of Plastic Materials-UL 94”(塑膠材料燃燒測試UL 94)進行燃燒試驗。評估基準如下。 ◎：板厚0.75mmt、板厚0.5mmt且V-0之情形 ○：板厚0.5mmt且V-0之情形 ×：在板厚0.5mmt下仍未達成V-0之情形 [flame retardant] Cut out a test piece with a length of 125 mm and a width of 12.5 mm from the evaluation substrate. Then, a flame test was performed on the test piece according to Underwriters Laboratories' "Test for Flammability of Plastic Materials-UL 94" (UL 94 for Flammability of Plastic Materials). The evaluation criteria are as follows. ◎: In the case of plate thickness 0.75mmt, plate thickness 0.5mmt and V-0 ○: When the plate thickness is 0.5mmt and V-0 ×: Case where V-0 has not yet been achieved at a plate thickness of 0.5mmt
[無機充填劑之粒度分布及峰值] 各實施例及比較例中之無機充填劑的粒度分布係藉由使用雷射繞射/散射式粒度分布測定裝置LA-960V2(股份公司堀場製作所製)測定而求得。裝置規格如下。 測定原理：米氏(Mie)散射理論 測定方式：流動測定 測定範圍：0.01µm~5000µm 光源：LD(650nm)、約5mW，LED(405mm)、約3mW 檢測器：環狀64分割矽光電二極體×1個，4ch陣列偵測器×5個，矽光偵測器×3個 折射率：1.460-0.000i [Particle size distribution and peak value of inorganic fillers] The particle size distribution of the inorganic filler in each Example and Comparative Example was determined by measurement using a laser diffraction/scattering type particle size distribution analyzer LA-960V2 (manufactured by Horiba Seisakusho Co., Ltd.). The device specifications are as follows. Measuring principle: Mie scattering theory Measurement method: flow measurement Measuring range: 0.01µm~5000µm Light source: LD (650nm), about 5mW, LED (405mm), about 3mW Detector: ring 64 split silicon photodiode × 1, 4ch array detector × 5, silicon photodetector × 3 Refractive index: 1.460-0.000i
測定部(循環系統)之規格如下。 分散：超音波探針 循環：離心泵 攪拌：攪拌葉片 分析槽(flow cell)材質：合成石英 The specifications of the measurement unit (circulation system) are as follows. Dispersion: Ultrasonic Probes Circulation: centrifugal pump Stirring: stirring blade Analysis tank (flow cell) material: synthetic quartz
粒度分布測定條件如下。The particle size distribution measurement conditions are as follows.
於分散溶劑中使用甲苯，將各測定試樣經由試料通道投入分析槽中，在攪拌狀態下進行雷射繞射/散射式粒度分布測定。Using toluene as the dispersion solvent, each measurement sample was put into the analysis tank through the sample channel, and the laser diffraction/scattering type particle size distribution measurement was performed in a stirred state.
粒度分布之解析係使用附LA-960V2之解析軟體LA-960 for Windows進行解析並算出。然後，使用測得之粒徑分布的體積比算出前述粒度分布之峰值藉此來求出。The analysis of the particle size distribution is analyzed and calculated using the analysis software LA-960 for Windows attached to LA-960V2. Then, it is obtained by calculating the peak value of the particle size distribution using the volume ratio of the measured particle size distribution.
將上述各評估之結果顯示於表1及表2。The results of the above evaluations are shown in Table 1 and Table 2.
[表1] [Table 1]
[表2] [Table 2]
(考察) 由表1可知，確認了使用本發明樹脂組成物之實施例皆可獲得介電特性低、熱傳導率及Tg高、密著性及阻燃性優異之硬化物。 (investigation) As can be seen from Table 1, it was confirmed that the examples using the resin composition of the present invention can obtain cured products with low dielectric properties, high thermal conductivity and Tg, and excellent adhesion and flame retardancy.
另一方面，如表2所示，僅使用相溶性磷化合物(D-1)作為磷化合物(D)之比較例1之試樣，無法獲得充分之Tg及阻燃性。又，僅使用非相溶性磷化合物(D-2)之比較例2試樣無法獲得充分之熱傳導率與阻燃性。無機充填劑(C)方面不含氮化硼且僅使用二氧化矽之比較例3，其熱傳導率差；而無機充填劑(C)方面不含氮化硼且僅使用氧化鋁之比較例4，無法獲得低介電特性。亦即，可知不使用氮化硼時，便無法獲得充分之熱傳導率及/或低介電特性。又，如比較例5，即便無機充填劑(C)方面使用氮化硼，但在無機充填劑(C)之粒度分布中，在粒徑1.0~50.0µm之範圍中若僅有1個峰值，便無法獲得與銅箔之充分密著性。並且，由比較例6之結果可知，即便無機充填劑(C)方面使用氮化硼，但當在粒徑1.0~50.00µm之範圍中不具有至少2個峰值時，便無法獲得充分之熱傳導率。On the other hand, as shown in Table 2, in the sample of Comparative Example 1 using only the compatible phosphorus compound (D-1) as the phosphorus compound (D), sufficient Tg and flame retardancy could not be obtained. Also, the sample of Comparative Example 2 using only the incompatible phosphorus compound (D-2) could not obtain sufficient thermal conductivity and flame retardancy. Comparative Example 3, which does not contain boron nitride as the inorganic filler (C) and only uses silicon dioxide, has poor thermal conductivity; while Comparative Example 4, which does not contain boron nitride as the inorganic filler (C) and uses only alumina , unable to obtain low dielectric properties. That is, it can be seen that sufficient thermal conductivity and/or low dielectric properties cannot be obtained without using boron nitride. Also, as in Comparative Example 5, even if boron nitride is used as the inorganic filler (C), in the particle size distribution of the inorganic filler (C), if there is only one peak in the particle size range of 1.0 to 50.0 µm, Sufficient adhesion with copper foil cannot be obtained. Also, from the results of Comparative Example 6, even if boron nitride is used as the inorganic filler (C), if there are not at least two peaks in the particle diameter range of 1.0 to 50.00 µm, sufficient thermal conductivity cannot be obtained .
本申請案係以已於2021年12月24日提申之日本專利申請案特願2021-210991為基礎，且本申請案包含其內容。This application is based on Japanese Patent Application Japanese Patent Application No. 2021-210991 filed on December 24, 2021, and this application includes the content thereof.
為了表現本發明，於前述一邊參照具體例或圖式等，一邊透過實施形態適當且充分地說明了本發明，惟應知悉，若為所屬技術領域中具有通常知識者，便可輕易做到變更及/或改良前述實施形態。因此，熟知此項技藝之人士實施之變更形態或改良形態，只要未脫離申請專利範圍所載請求項的權利範圍，即可解釋為該請求項之權利範圍涵括該變更形態或該改良形態。In order to express the present invention, the present invention has been properly and fully described through the embodiments while referring to specific examples or drawings, but it should be understood that changes can be easily made by those with ordinary knowledge in the technical field. And/or improve the aforementioned embodiments. Therefore, as long as the modified form or improved form implemented by a person familiar with the technology does not deviate from the scope of claims contained in the scope of the patent application, it can be interpreted that the scope of rights of the claimed items includes the modified form or the improved form.
產業上之可利用性 本發明在電子材料、電子器件、光學器件等的技術領域中，具有廣泛之產業上之可利用性。 Industrial availability The present invention has wide industrial applicability in the technical fields of electronic materials, electronic devices, optical devices, and the like.
1:預浸體
2:樹脂組成物或樹脂組成物之半硬化物
3:纖維質基材
11:覆金屬積層板
12:絕緣層
13:金屬箔
14:配線
21:配線基板
31:附樹脂之金屬箔
32,42:樹脂層
41:附樹脂之薄膜
43:支持薄膜
1: Prepreg
2: Resin composition or semi-hardened resin composition
3: Fibrous base material
11: Metal-clad laminate
12: Insulation layer
13: metal foil
14: Wiring
21: Wiring substrate
31: metal foil with
圖1係顯示本發明實施形態之預浸體之一例的概略截面圖。 圖2係顯示本發明實施形態之覆金屬積層板之一例的概略截面圖。 圖3係顯示本發明實施形態之配線板之一例的概略截面圖。 圖4係顯示本發明實施形態之附樹脂之金屬箔之一例的概略截面圖。 圖5係顯示本發明實施形態之附樹脂之薄膜之一例的概略截面圖。 Fig. 1 is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil according to an embodiment of the present invention. Fig. 5 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the present invention.
1:預浸體 1: Prepreg
2:樹脂組成物或樹脂組成物之半硬化物 2: Resin composition or semi-hardened resin composition
3:纖維質基材 3: Fibrous base material
Claims (22)
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| JP2021210991 | 2021-12-24 | ||
| JP2021-210991 | 2021-12-24 |
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| WO2019012954A1 (en) * | 2017-07-12 | 2019-01-17 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, film including resin, metal foil including resin, metal-clad laminate, and wiring board |
| CN112004886A (en) * | 2018-04-27 | 2020-11-27 | 三菱瓦斯化学株式会社 | Thermosetting composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
| JP2021004316A (en) * | 2019-06-26 | 2021-01-14 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, method for producing prepreg, laminate, and printed circuit board |
| US20220389189A1 (en) * | 2019-09-27 | 2022-12-08 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-cladded layered sheet, and wiring board |
| US20230257578A1 (en) * | 2020-07-17 | 2023-08-17 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, prepreg, film provided with resin, metal foil provided with resin, metal-clad laminate, and wiring board |
| JPWO2022014582A1 (en) * | 2020-07-17 | 2022-01-20 | ||
| CN112111074B (en) * | 2020-09-28 | 2023-08-18 | 常州中英科技股份有限公司 | Uniform dispersion liquid of crosslinkable hydrocarbon resin composition, prepreg prepared from uniform dispersion liquid and high-heat-conductivity thermosetting copper-clad plate prepared from uniform dispersion liquid |
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