CN117980362A - Resin composition, and printed wiring board, cured product, prepreg, and high-frequency electronic component using same - Google Patents
Resin composition, and printed wiring board, cured product, prepreg, and high-frequency electronic component using same Download PDFInfo
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- CN117980362A CN117980362A CN202280060908.4A CN202280060908A CN117980362A CN 117980362 A CN117980362 A CN 117980362A CN 202280060908 A CN202280060908 A CN 202280060908A CN 117980362 A CN117980362 A CN 117980362A
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- Prior art keywords
- resin composition
- component
- mass
- composition according
- resin
- Prior art date
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- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 212
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 125000000524 functional group Chemical group 0.000 claims abstract description 23
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 21
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 27
- 239000011256 inorganic filler Substances 0.000 claims description 25
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 239000005062 Polybutadiene Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000003505 polymerization initiator Substances 0.000 claims description 13
- 229920005992 thermoplastic resin Polymers 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 58
- 239000000047 product Substances 0.000 description 32
- 239000000377 silicon dioxide Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000945 filler Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 239000004020 conductor Substances 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 239000007822 coupling agent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 239000011229 interlayer Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000012790 adhesive layer Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000004891 communication Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920006132 styrene block copolymer Polymers 0.000 description 5
- -1 vinyl compound Chemical class 0.000 description 5
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000004727 Noryl Substances 0.000 description 3
- 229920001207 Noryl Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 238000005382 thermal cycling Methods 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 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
- 238000004566 IR spectroscopy Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 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 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- MWGMEGAYPPQWFG-UHFFFAOYSA-N [SiH4].OC(=O)C=C Chemical compound [SiH4].OC(=O)C=C MWGMEGAYPPQWFG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 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 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Provided is a resin composition which has low dielectric characteristics, good embeddability into a substrate, and excellent heat resistance. The resin composition comprises: (A) A polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal, and (B) a compound which has an isocyanurate ring structure and 2 allyl groups in 1 molecule and is liquid at 25 ℃.
Description
Technical Field
The present invention relates to a resin composition, and a printed wiring board, a cured product, a prepreg, and an electronic component for high frequency using the same.
Background
In recent years, for communication electronic devices (electronic boards) such as smart phones, tablet terminals, and communication base stations, the speed of communication has been increased, and the construction of 5G communication networks has been advanced. With such an increase in communication speed, there is a remarkable demand for low dielectric power of materials and high integration of multilayer substrates for reducing the loss of electric signals on substrates for communication electronic devices, and low dielectric resin substrates, ceramic substrates, low dielectric interlayer adhesives, and the like are used for achieving the above demand. Further, studies are being conducted on communication of high frequency signals such as 6G.
In the production of electronic devices, various resin compositions are used as adhesives and sealing materials. When the resin composition is used as the interlayer adhesive or the like, if the fluidity is low, it becomes difficult to embed the resin composition into the substrate. Therefore, in some cases, a resin composition used as an interlayer adhesive or the like is selected with attention paid to imparting low dielectric characteristics and suppressing a decrease in fluidity, and a resin having a structure with poor heat resistance is selected. For example, as a resin composition blended with low dielectric characteristics and low melt viscosity, a thermosetting resin composition containing a specific vinyl compound and a styrene/ethylene/butylene/styrene block copolymer (SEBS) has been proposed (for example, refer to patent document 1).
Prior art literature
Patent literature
Patent document 1: international publication No. WO2008/018483
Disclosure of Invention
Technical problem to be solved by the invention
As described above, the resin composition disclosed in patent document 1 has a high coefficient of thermal expansion, and is difficult to be used as an interlayer adhesive for a multilayer structure, although it is a blended resin composition having low dielectric characteristics and low melt viscosity. Here, as a means for reducing the thermal expansion coefficient of the resin composition, highly filled silica filler is exemplified.
However, in the resin composition mainly composed of a polymer elastomer disclosed in patent document 1, if the silica filler is highly filled, there is a problem that the melt viscosity becomes high and the embeddability into the substrate becomes poor.
The present invention has been made in view of the problems of the prior art as described above. The invention provides a resin composition with low dielectric property, good embedding property into a substrate and excellent heat resistance. Further, the present invention provides a printed wiring board, a cured product, a prepreg, and an electronic component for high frequency using the resin composition.
Technical means for solving the technical problems
The present invention provides a resin composition, a printed wiring board, a cured product, a prepreg, and a high-frequency electronic component shown below.
[1] A resin composition, wherein the resin composition comprises: (A) A polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal, and (B) a compound which has an isocyanuric ring structure and 2 allyl groups in1 molecule and is liquid at 25 ℃.
[2] The resin composition according to the above [1], wherein the component (A) is a thermosetting resin.
[3] The resin composition according to the above [1] or [2], wherein the molecular weight of the component (B) is 300 to 400.
[4] The resin composition according to any one of the above [1] to [3], wherein the component (A) is a polyphenylene ether represented by the following general formula (1).
[ Chemical 1]
[ Chemical 2]
[ Chemical 3]
In the above general formula (1), R 1、R2、R3、R4、R5、R6、R7 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group or a phenyl group,
- (O-X-O) -represented by the above-mentioned structural formula (2), wherein R 8、R9、R10、R14、R15 may be the same or different and is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R 11、R12、R13 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group,
- (Y-O) -is a structure in which 1 structure represented by the above structural formula (3) or 2 or more structures represented by the above structural formula (3) are arranged at random, R 16、R17 may be the same or different and is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R 18、R19 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group,
Z is an organic group having 1 or more carbon atoms, and may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom,
A. b represents an integer of 0 to 300 and at least any one is not 0, c, d represent an integer of 0 or 1.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (B) is a compound represented by the following general formula (4).
[ Chemical 4]
In the general formula (4), R is an alkyl group having 4 to 14 carbon atoms.
[6] The resin composition according to any one of the above [1] to [6], wherein the resin composition further comprises (C) an inorganic filler.
[7] The resin composition according to the above [6], wherein the nonvolatile component in the resin composition contains 50 mass% or more of the component (C) in 100 mass%.
[8] The resin composition according to any one of the above [1] to [7], wherein the resin composition further comprises (D) a polymerization initiator for initiating polymerization of the (A) component and the (B) component.
[9] The resin composition according to any one of the above [1] to [8], wherein the resin composition further comprises (E) a thermoplastic resin having a number average molecular weight of 30000 or more.
[10] The resin composition according to the above [9], wherein the nonvolatile component in the resin composition contains 1 to 50% by mass of the component (E) in 100% by mass.
[11] The resin composition according to any one of the above [1] to [10], wherein the resin composition further comprises (F) polybutadiene.
[12] The resin composition according to any one of the above [1] to [11], wherein the nonvolatile component in the resin composition comprises 15% by mass to 90% by mass of the component (A) in 100% by mass.
[13] The resin composition according to any one of the above [1] to [12], wherein the resin composition comprises 10 parts by mass to 70 parts by mass of the component (B) relative to 100 parts by mass of the component (A).
[14] A printed wiring substrate having a cured layer composed of the resin composition according to any one of [1] to [13] above.
[15] A cured product of the resin composition according to any one of the above [1] to [13 ].
[16] A prepreg, wherein the prepreg is a prepreg using the resin composition according to any one of the above [1] to [13 ].
[17] An electronic component for high frequency, wherein the electronic component for high frequency has the cured product described in [15 ].
Advantageous effects
The resin composition of the present invention achieves the effects of excellent dielectric characteristics and also excellent heat resistance. Further, the resin composition of the present invention is also high in flowability, and therefore, is excellent in embeddability into a substrate, and also has excellent film forming properties. Therefore, the resin composition of the present invention can be suitably used for printed wiring boards, cured products, prepregs, high frequency electronic components, and the like.
The printed wiring board, cured product, prepreg, and electronic component for high frequency use of the present invention have the advantages of excellent dielectric properties, heat resistance, and embedding property by using the resin composition of the present invention.
Drawings
Fig. 1 is a cross-sectional view of a multilayer wiring substrate, and is a diagram for explaining a process of breaking a conductor layer by thermal cycling.
Detailed Description
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Accordingly, it is to be understood that the following embodiments are appropriately modified and improved based on the general knowledge of those skilled in the art, without departing from the spirit of the present invention.
[ Resin composition ]
One embodiment of the resin composition of the present invention is: a resin composition, wherein the resin composition comprises: (A) A polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal, and (B) a compound which has an isocyanurate ring structure and 2 allyl groups in 1 molecule and is liquid at 25 ℃. In the following, the polyphenylene ether resin (A) having a functional group containing a carbon-carbon double bond at the terminal may be referred to as component (A). Similarly, a compound (B) having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃ may be referred to as a component (B).
The resin composition of the present embodiment is excellent in dielectric characteristics and also excellent in heat resistance. Further, the resin composition of the present embodiment is also high in fluidity, and therefore, is excellent in embeddability into a substrate, and also has excellent film forming properties. The polyphenylene ether resin as the component (A) has a functional group containing a carbon-carbon double bond at the terminal thereof, can impart low dielectric characteristics to the resin composition, and can improve fluidity upon heating. The compound as component (B) has an isocyanurate ring structure and 2 allyl groups in 1 molecule as described above, and can reduce the melt viscosity of the resin composition and improve the embeddability into wiring. In addition, the compound as the component (B) has 2 allyl groups, and thus very good low dielectric characteristics can be obtained. In addition, the resin composition of the present embodiment can obtain high heat resistance by crosslinking and curing the component (a) and the component (B).
In addition, the resin composition of the present embodiment can reduce the thermal expansion coefficient in the thickness direction of the cured product or cured layer of the resin composition. Hereinafter, the thickness direction of the cured product and the cured layer of the resin composition may be referred to as "Z direction".
For example, when the resin composition is used as an adhesive layer of a multilayer wiring board, if the thermal expansion coefficient in the thickness direction (Z direction) of a cured product of the resin composition to be the adhesive layer or the cured layer is large, a phenomenon that breakage is likely to occur in the vicinity of a through hole of the multilayer wiring board may occur. For example, fig. 1 is a sectional view of a multilayer wiring substrate, and is a diagram for explaining a process of breaking a conductor layer by thermal cycling. Fig. 1 (a) shows a state before the conductor layer breaks, and fig. 1 (b) shows a state after the conductor layer breaks due to thermal cycling. In fig. 1 (a) and (b), the arrow direction indicated by the symbol Z indicates the "thickness direction (i.e., Z direction)" of the cured product of the resin composition and the cured layer which become the adhesive layer 16.
The multilayer wiring board 10 shown in fig. 1 (a) is formed by joining 5 boards 12 (12 a to 12 e) via a conductor layer 14 and adhesive layers 16 (16 a to 16 d). The adhesive layers 16 (16 a to 16 d) are formed of, for example, cured layers obtained by curing the resin composition. The conductor layer 14 is disposed so as to cover the entire surface of the multilayer wiring board 10 and between each substrate 12 and each adhesive layer 16.
The multilayer wiring board 10 shown in fig. 1 (a) is provided with a via hole 22 for electrically connecting a plane (land) on the front surface and a plane on the back surface of the multilayer wiring board 10, and the inner wall surface of the via hole 22 is also covered with the conductor layer 14.
If the multilayer wiring substrate 10 shown in fig. 1 (a) is used in an environment where a temperature change is significant, as shown in fig. 1 (b), a break 24 may occur in the conductor layer 14. For example, if a temperature change of-55 ℃ to 125 ℃ is applied as a thermal cycle of 1 cycle to the multilayer wiring substrate 10 shown in fig. 1 (a), stress is generated due to expansion caused by the temperature change, and the breakage 24 is liable to occur in the conductor layer 14. If the thermal expansion coefficient of the adhesive layer 16 in the Z direction is large, a larger stress is generated on the conductor layer 14 covering the inner wall surface of the through hole 22, and the fracture 24 of the conductor layer 14 becomes more remarkable.
The resin composition of the present embodiment can reduce the thermal expansion coefficient in the thickness direction (i.e., the "Z direction" in fig. 1) of the cured product and the cured layer thereof, and can effectively suppress the occurrence of the fracture 24 to the conductor layer 14 as shown in fig. 1 (b).
The resin composition of the present embodiment may further contain other components such as (C) an inorganic filler, (D) a polymerization initiator, (E) a thermoplastic resin, and (F) polybutadiene, in addition to the component (a) and the component (B). Hereinafter, each of the above components may be appropriately referred to as a (C) component- (F) component.
[ (A) component ]
(A) The component (a) is a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal thereof. Examples of the functional group containing a carbon-carbon double bond include a terminal vinyl group, a vinylidene group, and an vinylidene group. (A) The component (A) is not particularly limited as long as it has a functional group containing a carbon-carbon double bond at its terminal and a polyphenylene ether is present on the skeleton. By containing the component (a), low dielectric characteristics can be imparted to the resin composition, and heat resistance and thermal expansion coefficient can be improved. The component (A) is preferably a thermosetting resin. In addition, the component (A) is particularly preferably a polyphenylene ether resin having a vinyl group at the terminal. By having a vinyl group at the terminal, low dielectric characteristics can be obtained.
(A) Examples of the component (A) include compounds having a structure represented by the following general formula (1).
[ Chemical 5]
[ Chemical 6]
[ Chemical 7]
In the above general formula (1), R 1、R2、R3、R4、R5、R6、R7 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, or a phenyl group. In addition, - (O-X-O) -is represented by the above structural formula (2), wherein in the structural formula (2), R 8、R9、R10、R14、R15 may be the same or different and is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R 11、R12、R13 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. In addition, - (Y-O) -is a structure in which 1 structure represented by the above structural formula (3) or 2 or more structures represented by the above structural formula (3) are arranged at random, wherein in the structural formula (3), R 16、R17 may be the same or different and is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R 18、R19 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, as the case may be. a. b represents an integer of 0 to 300 and at least any one is not 0, c, d represent an integer of 0 or 1. For example, a compound represented by the general formula (1) is described in Japanese patent application laid-open No. 2004-59644.
Since the compound represented by the general formula (1) has styrene functional groups at both ends, the resin composition containing such a component (a) becomes easy to cure by heating. From the viewpoint of curability, the compound represented by the general formula (1) is preferably one in which R 1～R7 is hydrogen.
In the above structural formula (2) representing the structure of- (O-X-O) -of the compound represented by the general formula (1), R 8、R9、R10、R14、R15 is preferably an alkyl group having 3 or less carbon atoms, particularly preferably a methyl group. In the structural formula (2), R 11、R12、R13 is preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, and particularly preferably a methyl group. Specifically, the following structural formula (5) can be given.
[ Chemical 8]
In the above structural formula (3) representing the structure of- (Y-O) -of the compound represented by the general formula (1), R 16、R17 is preferably an alkyl group having 3 or less carbon atoms, particularly preferably a methyl group. In the structural formula (3), R 18、R19 is preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, and particularly preferably a methyl group. Specifically, the following structural formula (6) or structural formula (7) can be mentioned.
[ Chemical 9]
Z is, for example, an alkylene group having 3 or less carbon atoms, specifically a methylene group.
A. b represents an integer of 0 to 300, preferably an integer of 0 to 30, and at least any one is not 0.
In order to control the elastic modulus of the cured product of the resin composition to be in a proper range, the compound represented by the general formula (1) preferably has a number average molecular weight of 1000 to 3000. In addition, the compound represented by the general formula (1) is suitably the following compound: a compound having functional groups containing carbon-carbon double bonds at both ends and having equivalent weight per functional group (functional group equivalent) corresponding to 1/2 of the above molecular weight, i.e., 500 to 1500. The functional group equivalent represents the degree of crosslinking density of the cured product, and if the functional group equivalent is within this range, a suitable crosslinking density can be obtained, and sufficient mechanical strength is provided, so that there is an advantage that occurrence of cracks or the like can be avoided at the time of film formation. In the present specification, the number average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using a standard curve based on standard polystyrene.
The compound represented by the general formula (1) can be produced by the method described in Japanese patent application laid-open No. 2004-59644. For example, a reaction product obtained by further reacting a polycondensate of 2,2', 3',5 '-hexamethylbiphenyl-4, 4' -diol and 2, 6-dimethylphenol with chloromethylstyrene may be used.
(A) The component (A) may be used alone or in combination of 2 or more kinds of compounds represented by the general formula (1).
The nonvolatile component in the resin composition preferably contains 15 to 90 mass% of the component (a), more preferably 17 to 80 mass%, and particularly preferably 18 to 70 mass%, of 100 mass%. If the content of the component (A) in 100 mass% of the nonvolatile component in the resin composition falls within this range, there is an advantage that the heat resistance of the resin composition and the processability such as film formation are improved. The content of the component (a) in the nonvolatile component can be measured by, for example, infrared spectrophotometry (FTIR) or gas chromatography/mass spectrometry.
In the case of containing the component (a) described so far, the component (a) is preferably contained in an amount of 15 to 95 parts by mass, more preferably 23 to 90 parts by mass, and particularly preferably 32 to 85 parts by mass, based on 100 parts by mass of the total resin components in the resin composition. If the content of the component (A) in the total of 100 parts by mass is within this range, there is an advantage that the heat resistance, film forming and other processability of the cured product of the resin composition are improved. The content of the component (a) in the resin component can be measured by, for example, infrared spectrophotometry (FTIR) or gas chromatography/mass spectrometry. The resin component in the resin composition includes, in particular, component (a), component (B), and component (E) and component (F) as optional components. Therefore, the content of the component (a) can be obtained, for example, as the content of the component (a) when the total mass of the component (a), the component (B) and other resin components is 100 parts by mass, based on the total of the resin components in the resin composition of 100 parts by mass. The content of the component (B) per 100 parts by mass of the total resin component can also be calculated as described above.
Examples of the polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal of the component (A) include "OPE-2St 1200" (number average molecular weight 1200) and "OPE-2St 2200" (number average molecular weight 2200) manufactured by Mitsubishi chemical corporation. They are polyphenylene ether resins having vinyl groups at the ends thereof.
The polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal of the component (A) may be a polyphenylene ether resin having a group represented by the following formula (8) at the terminal.
[ Chemical 10]
(Wherein, in the above formula (8), R 20 represents a hydrogen atom or an alkyl group.)
In the above formula (8), R 20 represents a hydrogen atom or an alkyl group. The alkyl group of R 20 is, for example, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom. Specifically, for example, methyl, ethyl, propyl, and the like are mentioned.
Examples of the group represented by the formula (8) include an acrylate group and a methacrylate group.
In addition, the modified polyphenylene ether having a group represented by the formula (8) preferably has a polyphenylene ether chain in the molecule, for example, a repeating unit represented by the following structural formula (9) in the molecule.
[ Chemical 11]
In the structural formula (9), m represents 1 to 50. R 22-R25 are independent of each other and may be the same or different from each other. R 22-R25 represents a hydrogen atom or an alkyl group.
The alkyl group in R 22-R25 is not particularly limited, and for example, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. Specifically, for example, methyl, ethyl, propyl, hexyl, octyl, and the like are given.
Examples of the modified polyphenylene ether having a group represented by the above formula (8) include modified polyphenylene ethers having a group represented by the above formula (8) at the terminal of a polyphenylene ether represented by the following formula (10) or formula (11). Specific examples of the modified polyphenylene ether include modified polyphenylene ethers represented by the following formula (12) or (13).
[ Chemical 12]
[ Chemical 13]
[ Chemical 14]
[ 15]
In the formulae (10) to (13), s and t are preferably, for example, the sum of s and t is 1 to 30. In addition, s is preferably 0to 20, and t is preferably 0to 20. That is, preferably, s represents 0to 20, t represents 0to 20, and the total of s and t represents 1 to 30. In the formulae (10) to (13), Y represents an alkylene group having 1 to 3 carbon atoms or a single bond, and examples of the alkylene group include a dimethylmethylene group. In the formulae (12) and (13), R 20 is the same as R 20 in the above formula (8), and represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 carbon atom is more preferable. Specifically, for example, methyl, ethyl, propyl, and the like are mentioned.
The number average molecular weight (Mn) of the modified polyphenylene ether having the group represented by the formula (8) is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and still more preferably 1000 to 3000. The number average molecular weight may be any value measured by a usual molecular weight measurement method, and specifically, a value measured by Gel Permeation Chromatography (GPC) or the like may be mentioned. In the case where the modified polyphenylene ether having a group represented by the formula (8) has a repeating unit represented by the formula (9) in the molecule, m is preferably such that the weight average molecular weight of the modified polyphenylene ether is within the above-mentioned range. Specifically, m is preferably 1 to 50.
If the number average molecular weight of the modified polyphenylene ether having the group represented by the formula (8) is within the above-mentioned numerical range, excellent dielectric characteristics derived from the polyphenylene ether are exhibited and the embeddability into a substrate is excellent.
In addition, in the modified polyphenylene ether used as the component (A), the average number of groups represented by the above formula (8) (terminal functional number) per 1 molecule of the modified polyphenylene ether at the molecular terminal is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1.5 to 3. If the number of terminal functional groups is too small, curability is deteriorated, and it tends to be difficult to obtain sufficient strength, adhesiveness, and heat resistance as a cured product. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, and for example, there is a possibility that the storage stability of the resin composition is lowered, the fluidity of the resin composition is lowered, the cured product becomes brittle, the adhesiveness is lowered, or the like. That is, if such a modified polyphenylene ether is used, the following problems may occur, for example: in multilayer molding, molding defects such as voids are generated, cracking of the substrate and delamination are likely to occur, and it is difficult to obtain a highly reliable printed wiring board.
Examples of the terminal functional group of the modified polyphenylene ether include a value represented by an average value of the groups represented by the above formula (8) per 1 molecule of all modified polyphenylene ethers present in 1 mol of the modified polyphenylene ether. 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 and calculating the decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the hydroxyl number of the polyphenylene ether before modification is the terminal functional number. The method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether can be obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to a solution of the modified polyphenylene ether and measuring the UV absorbance of the mixed solution.
The method for synthesizing the modified polyphenylene ether used as the component (A) is not particularly limited as long as the modified polyphenylene ether having the group represented by the above formula (8) at the terminal can be synthesized.
(A) The component (C) may be used alone or in combination of 2 or more kinds of modified polyphenylene ethers having a group represented by the above formula (8) at the terminal.
The content of the component (A) having the group represented by the formula (8) at the terminal thereof as described above is not particularly limited. For example, the component (a) is preferably contained in an amount of 15 to 95 parts by mass, more preferably 23 to 90 parts by mass, and particularly preferably 32 to 85 parts by mass, based on 100 parts by mass of the total resin components. If the content of the component (a) in the total 100 parts by mass of the resin components is within this range, there is an advantage that the heat resistance, film forming and other processability of the cured product of the resin composition are improved, and the toughness, adhesion and the like of the cured product are not lost.
Examples of the modified polyphenylene ether having a group represented by the above formula (8) at the terminal of the component (a) include a so-late made by SABIC, trade name "Noryl SA9000" manufactured by the company strosystem.
In addition, as described below, the present resin composition may contain an inorganic filler. When the present resin composition contains an inorganic filler, it preferably contains 40 to 90 parts by mass of the component (a), more preferably 45 to 85 parts by mass, and particularly preferably 50 to 80 parts by mass, based on 100 parts by mass of the total resin components. If it is within this range, there is an advantage that the thermal expansion coefficient of the resin composition is improved.
[ (B) component ]
(B) The component (A) is a compound having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃. By containing the component (B), the melt viscosity of the resin composition can be reduced, and the embeddability into wiring can be improved. In addition, the compound as the component (B) can obtain very good low dielectric characteristics by having 2 allyl groups. For example, in the case of using a compound having an isocyanurate ring structure and 3 allyl groups in 1 molecule instead of the component (B), a sufficiently low dielectric property cannot be obtained. Although the details are not clear, it is assumed that when a compound having 3 allyl groups is used, the compound has a three-dimensional crosslinked structure, and thus the dielectric characteristics are insufficient. On the other hand, it is presumed that if the resin composition of the present embodiment is a compound having a 2-functional allyl group as in the component (B), the dipole moment indicating a measure of molecular polarization becomes small due to the linear crosslinked structure, and thus low dielectric characteristics can be obtained. Further, although the details are not clear, it is presumed that the component (B) has an isocyanurate ring structure, and the heat resistance of the resin composition is improved. The component (B) of the resin composition of the present embodiment is a compound that is liquid at 25 ℃, and thus the embeddability is improved. On the other hand, when a compound that is solid at 25 ℃ is used as the component (B), the filming becomes difficult, which is not preferable. In particular, the component (B) is preferably a substance which reacts with the component (A) even if a polymerization initiator is not used.
(B) The molecular weight of the component (A) is preferably 300 to 400, more preferably 320 to 400. By setting the molecular weight of the component (B) within the above range, the dielectric characteristics and flowability are excellent.
(B) The component (c) is preferably a compound represented by the following general formula (4).
[ 16]
In the above general formula (4), R is an alkyl group having 4 to 14 carbon atoms, preferably an alkyl group having 8 to 14 carbon atoms, and particularly preferably an alkyl group having 10 to 12 carbon atoms.
The content of the component (B) is preferably 10 parts by mass to 70 parts by mass relative to 100 parts by mass of the component (a). With this structure, the melt viscosity of the resin composition can be reduced, the embeddability into wiring can be improved, and heat resistance can be improved. The content of the component (B) is more preferably 15 parts by mass to 65 parts by mass, and still more preferably 20 parts by mass to 60 parts by mass, based on 100 parts by mass of the component (a), although not particularly limited. Further, the nonvolatile component in the resin composition is preferably contained in an amount of 2 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 4 to 30% by mass, based on 100% by mass of the component (B). If the content ratio of the component (B) in 100 mass% of the nonvolatile components in the resin composition is within this range, the resin composition is excellent in dielectric characteristics. The content ratio of the component (B) in the nonvolatile component can be measured by, for example, an infrared spectrophotometer (FTIR), a gas chromatography mass spectrometry, or the like.
The component (B) is preferably contained in an amount of 5 to 50 parts by mass, more preferably 7 to 45 parts by mass, and particularly preferably 8 to 40 parts by mass, based on 100 parts by mass of the total resin components of the resin composition. If the content ratio of the component (B) to 100 parts by mass of the total resin components falls within this range, the film forming property and fluidity of the resin composition are good. Further, the thermosetting resin composition is preferable in that flexibility and heat resistance can be obtained.
In addition, as described below, the present resin composition may contain an inorganic filler. When the present resin composition contains an inorganic filler, it preferably contains 1 to 30 parts by mass of the component (B), more preferably 2 to 25 parts by mass, and particularly preferably 3 to 20 parts by mass, based on 100 parts by mass of the total resin components. If the content is within this range, there is an advantage that the fluidity of the resin composition can be improved and the embeddability can be improved even if the inorganic filler is contained.
The compound having an isocyanurate ring structure and 2 allyl groups in1 molecule and being liquid at 25℃as the component (B) may be referred to by the trade name "L-DAIC" manufactured by four chemical industry Co.
[ (C) component ]
(C) The components are inorganic filler. For the inorganic filler, insulation and low thermal expansion coefficient are required. As the inorganic filler, a usual inorganic filler can be used. Examples of the inorganic filler include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. The inorganic filler may be used alone or in combination of 2 or more. In particular, from the viewpoint of insulation properties, silica fillers and alumina fillers are preferable. In addition, from the viewpoint of dielectric characteristics, a silica filler is preferable. The inorganic filler may be surface-treated with a silane coupling agent having 1 or more functional groups selected from among acryl, methacryl, styryl, amino, epoxy, and vinyl groups. For example, the inorganic filler is preferably a surface-treated material having improved heat resistance, moisture resistance and dispersibility by a surface-treating agent such as an aminosilane-based coupling agent, an ureido silane-based coupling agent, an epoxy silane-based coupling agent, a mercapto silane-based coupling agent, a vinyl silane-based coupling agent, a styryl silane-based coupling agent, an acrylate silane-based coupling agent, an isocyanate silane-based coupling agent, a sulfide silane-based coupling agent, an organosilane compound and a titanate-based coupling agent. They may be used in combination of 1 or more than 2. More preferably, among the surface-treated silica fillers, a silica filler surface-treated with a vinyl silane coupling agent is preferably used. The use of the silica filler surface-treated with the vinyl silane coupling agent can improve the coefficient of thermal expansion (thickness).
The shape of the inorganic filler is not particularly limited, and examples thereof include spherical, phosphorus flake, needle-like, irregular, and the like. From the viewpoint of operability, a spherical shape is preferable. The average particle diameter is preferably 0.1 μm to 10. Mu.m, more preferably 0.1 μm to 4. Mu.m. When the average particle diameter of the inorganic filler is within this range, the embedding property into the microstructure is excellent. The average particle diameter is the particle diameter at 50% of the cumulative value in the particle size distribution at the volume basis, as measured by the laser diffraction scattering method. The average particle diameter can be measured by, for example, a laser scattering diffraction particle size distribution measuring apparatus: LS13320 (wet type) was measured by using a doctor solution コ.
In the case where the component (C) is contained, the content of the component (C) is preferably 1 to 90 parts by mass based on 100 parts by mass of the nonvolatile component in the resin composition. With this configuration, the thermal expansion coefficient can be improved satisfactorily. The content of the component (C) is more preferably 20 parts by mass to 80 parts by mass, and still more preferably 30 parts by mass to 75 parts by mass, based on 100 parts by mass of the nonvolatile component in the resin composition, although not particularly limited.
In addition, in order to reduce the coefficient of thermal expansion of the resin composition, when 50 parts by mass or more of the component (C) is contained per 100 parts by mass of the nonvolatile component in the resin composition, if the inorganic filler is highly filled, the melt viscosity of the resin composition tends to be high, and the embeddability into the substrate tends to be poor. However, by containing the compound (B) having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃, even when the inorganic filler is highly filled, the melt viscosity of the resin composition can be reduced and the embeddability into wiring can be improved.
Examples of the silica filler used for the component (C) include fused silica, ordinary silica, spherical silica, crushed silica, crystalline silica, amorphous silica, and the like, and are not particularly limited. Spherical fused silica is preferable from the viewpoints of dispersibility of the silica filler, flowability of the thermosetting resin composition, surface smoothness of the cured product, dielectric characteristics, low thermal expansion coefficient, adhesion and the like.
The method of surface-treating the silica filler with the coupling agent is not particularly limited, and examples thereof include a dry method and a wet method.
The dry method is a method for performing surface treatment as follows: the silica filler and the silane coupling agent in an appropriate amount with respect to the surface area of the silica filler are placed in a stirring device and stirred under appropriate conditions, or the silica filler is placed in the stirring device in advance and the silane coupling agent in an appropriate amount with respect to the surface area of the silica filler is added by dropping or spraying the silane coupling agent in a stock solution or a solution while stirring under appropriate conditions, and the silane coupling agent is uniformly adhered to the surface of the silica filler by stirring (is hydrolyzed) and surface-treated. Examples of the stirring device include, but are not limited to, a mixer capable of stirring and mixing at a high speed such as a screw mixer.
The wet method is a method for performing surface treatment as follows: the surface treatment is carried out by adding a silica filler to a surface treatment solution (wherein the surface treatment solution is a surface treatment solution in which a silane coupling agent having a sufficient surface area relative to the silica filler subjected to the surface treatment is dissolved in water or an organic solvent) and stirring the mixture so as to obtain a slurry, thereby allowing the silane coupling agent to sufficiently react with the silica filler, separating the silica filler from the surface treatment solution by filtration, centrifugal separation, or the like, and then drying the mixture by heating.
[ (D) component ]
(D) The component is a polymerization initiator. The polymerization initiator as the component (D) is an additive for satisfactorily starting the polymerization of the component (a) and the component (B). By containing such a component (D), the curing degree of the resin composition can be improved with respect to a certain curing temperature and time. Therefore, the resin composition of the present embodiment preferably further contains a polymerization initiator as the component (D).
(D) The polymerization initiator for the component (a) may be any one having the ability to cure the component (a) and the component (B), and conventionally known polymerization initiators may be used. Examples of the polymerization initiator include organic peroxides, inorganic peroxides, and azo compounds. Examples of the polymerization initiator of the component (D) include an organic peroxide manufactured by japan oil and fat corporation, a trade name "dock D", a trade name "dock C", and the like. The component (D) may be used alone or in combination of 2 or more.
In the case of containing the component (D), the content of the component (D) is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the nonvolatile component in the resin composition. With this configuration, heat resistance and adhesion can be improved satisfactorily. The content of the component (D) is preferably 0.1 to 8 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the nonvolatile component in the resin composition, although not particularly limited.
[ (E) component ]
(E) The component is thermoplastic resin. The thermoplastic resin as the component (E) is not particularly limited, but is preferably a thermoplastic resin having a dielectric loss tangent (tan. Delta.) of less than 0.005 in the frequency range of 1GHz to 100 GHz. This contributes to excellent dielectric characteristics of the thermosetting film formed from the resin composition of the present embodiment in a high frequency range. The "thermoplastic resin having a dielectric loss tangent (tan. Delta.) of less than 0.005 in the frequency range of 1GHz to 100 GHz" is not particularly limited, but examples thereof include styrene-based thermoplastic elastomers. Examples of the styrenic thermoplastic elastomer include block copolymers comprising a block of styrene or the like as at least one end block and an elastomer block of a conjugated diene as at least one intermediate block. Examples thereof include styrene/butadiene/styrene block copolymers (SBS), styrene/butadiene/butylene/styrene block copolymers (SBBS), styrene/ethylene/butylene/styrene block copolymers (SEBS), and styrene/ethylene/propylene/styrene block polymers (SEEPS). By including the styrene-based thermoplastic elastomer, flexibility can be imparted to the resin composition, toughness of the cured product can be maintained, adhesiveness can be improved, and dielectric characteristics can be reduced.
(E) The number average molecular weight of the component is preferably 30000 or more, more preferably 40000 or more, and further preferably 50000 or more. The number average molecular weight of the component (E) is preferably 30000 to 150000, more preferably 40000 to 120000, particularly preferably 50000 to 100000. By having the number average molecular weight within this range, solder heat resistance is improved. Although the upper limit of the number average molecular weight of the component (E) is not particularly limited, if the number average molecular weight of the thermoplastic resin is too large, the thermoplastic resin may be difficult to melt. Accordingly, the number average molecular weight of the thermoplastic resin as the component (E) is preferably 150000 or less, more preferably 120000 or less, and particularly preferably 100000 or less. The component (E) tends to have a higher molecular weight, a higher melt viscosity, and a lower embeddability into a substrate. However, by containing the compound (B) having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃, even when a thermoplastic resin having a large molecular weight is used, the melt viscosity of the resin composition can be reduced and the embeddability into wiring can be improved.
The content of the component (E) is not particularly limited, but in the case of containing the component (E), it is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, relative to 100% by mass of the nonvolatile component in the resin composition. When the content of the component (E) is within this range, the fluidity of the resin composition can be improved, and the embeddability into a substrate can be improved.
Further, the present resin composition may contain an inorganic filler, and when the present resin composition contains an inorganic filler, the content of the component (E) is preferably 1 to 60 parts by mass, more preferably 10 to 55 parts by mass, and particularly preferably 20 to 50 parts by mass, based on 100 parts by mass of the total of the resin components.
[ (F) component ]
(F) The component is polybutadiene. By including polybutadiene as the component (F), the thermal expansion coefficient in the thickness direction of the cured product or cured layer of the resin composition can be further reduced. (F) The component (B) is preferably a polybutadiene having a vinyl group in a side chain thereof, which reacts with the component (A) or the component (B). Although not clear in detail, it is assumed that the thermal expansion coefficient in the thickness direction is reduced by reacting the polybutadiene with the component (a) or the component (B) on the side chain. Therefore, by containing polybutadiene as the component (F), occurrence of the break 24 in the conductor layer 14 shown in fig. 1 (b) can be extremely effectively suppressed.
The polybutadiene as the component (F) preferably has a number average molecular weight (Mn) of 500 to 3000, more preferably 600 to 2000, still more preferably 700 to 1800. If the polybutadiene number average molecular weight (Mn) as the component (F) is within this range, the thermal expansion coefficient in the thickness direction of the cured product or cured layer of the resin composition can be further reduced.
As the polybutadiene as the component (F), there may be mentioned polybutadiene (1, 2-vinyl) manufactured by Japanese Cao, trade name "B-1000", etc.
In the case where the component (F) is contained, the content of the component (F) is preferably 1 to 20 parts by mass based on 100 parts by mass of the nonvolatile component in the resin composition. With this configuration, the thermal expansion coefficient can be set to a good value. The content of the component (F) is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the nonvolatile component in the resin composition, although not particularly limited.
[ Other Components ]
The resin composition of the present embodiment may further contain components other than the component (a) to component (F) described so far. Examples of the other components include various additives such as solvents, dispersants, silane coupling agents, antioxidants, flame retardants, and melt agents.
[ Method for producing resin composition ]
The resin composition of the present embodiment can be produced by a conventional method. The resin composition of the present embodiment can be produced by dissolving and mixing the components described above together with a solvent using, for example, a kneader, a pot mill, a three-roll mill, a rotary mixer, a twin-shaft mixer, or the like.
[ Use of resin composition ]
The resin composition of the present embodiment can be suitably used as an adhesive for electronic components or a resin composition for an adhesive film. The resin composition of the present embodiment can be suitably used as an adhesive sheet for interlayer adhesion or an interlayer adhesive for a multilayer wiring board. When the resin composition of the present embodiment is used for various applications of electronic components, the electronic components to be bonded are not particularly limited, and various printed wiring boards such as ceramic boards and organic boards, semiconductor chips, semiconductor devices, and the like can be given.
An adhesive film, an adhesive sheet for interlayer adhesion, an interlayer adhesive, and the like using the resin composition of the present embodiment are included as cured products of the resin composition in laminate boards, semiconductor devices, and the like constituting electronic components. Therefore, the cured product of the resin composition of the present embodiment is preferably contained in a laminate or a semiconductor device constituting an electronic component or the like.
The resin composition of the present embodiment can also be used as a prepreg using a cured product of the resin composition or an electronic component for high frequency having a cured product of the resin composition.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, parts,% means parts by mass and% by mass unless otherwise specified.
(Example 1-example 15, comparative example 1-comparative example 6)
[ Sample preparation ]
After the components were metered and blended so that the blending ratios (parts by mass) shown in tables 1 to 4 below were obtained, they were put into a dissolution vessel heated to 70℃and mixed under pressure for 3 hours to 6 hours while rotating at a speed of 100rpm to 400 rpm. A solution containing the resin compositions of examples 1 to 15 and comparative examples 1 to 6 was prepared as above.
In examples 1 to 15 and comparative examples 1 to 6, the following raw materials were used for preparing the solutions containing the resin compositions.
[ (A) component: polyphenylene ether resin having functional group (vinyl group) containing carbon-carbon double bond at terminal
(A1) : the trade name "OPE-2St" manufactured by Mitsubishi chemical corporation, number average molecular weight (Mn) =1200.
(A2) : the trade name "OPE-2St" manufactured by Mitsubishi chemical corporation, number average molecular weight (Mn) =2200.
(A3) : SABIC, manufactured by the company sacinc under the trade name "Noryl SA9000", number average molecular weight (Mn) =1850-1950.
[ (A') component: polyphenylene ether having no functional group containing a carbon-carbon double bond at the terminal
(A' 3): SABIC is manufactured by the company Siberian, trade name "Noryl SA90", a polyphenylene ether having a hydroxyl group at the terminal.
[ (B) component: compounds having an isocyanurate ring structure and 2 allyl groups in 1 molecule
(B1) : a compound represented by the above general formula (4) is manufactured by four chemical industry Co., ltd. Under the trade name "L-DAIC". In the general formula (4), R is an alkyl group having 4 to 14 carbon atoms.
[ (B') component: compounds other than the component (B) having an allyl group in 1 molecule ]
(B' 2): a compound having phenolic hydroxyl groups and allyl groups, which has no isocyanurate ring structure in 1 molecule, is manufactured by Dacron chemical industry Co., ltd.
(B' 3): mitsubishi chemical company, trade name "TAIC", is a compound having an isocyanuric ring structure and 3 allyl groups in 1 molecule.
[ (C) component: inorganic filler
(C1) : spherical silica surface-treated with an aminosilane coupling agent, SC4050SX (product name), manufactured by Kogyo, inc., has an average particle diameter of 1.0. Mu.m.
(C2) : spherical silica surface-treated with a vinylsilane coupling agent, 10SV-C12 (product name), manufactured by Kogyo, inc., has an average particle diameter of 1.0. Mu.m.
[ (D) component: polymerization initiator ]
(D1) : manufactured by the chemical company of solar oil, trade name "multiring D".
[ (E) component: thermoplastic resin ]
(E1) : hydrogenated styrene thermoplastic elastomer manufactured by Asahi chemical Co., ltd., trade name "Tafetete P1500", number average molecular weight (Mn) =49000.
(E2) : hydrogenated styrene thermoplastic elastomer manufactured by kuraray corporation, trade name "cell 8006", number average molecular weight (Mn) =125000.
(E3) : hydrogenated styrene thermoplastic elastomer manufactured by the company of cowrun, trade name "G1652", number average molecular weight (Mn) =53000.
[ (F) component: polybutadiene (polybutadiene)
(F1) : polybutadiene manufactured by Cao, japan under the trade name "B-1000". The side chain of polybutadiene has a vinyl group. Number average molecular weight (Mn) =1200.
[ (G) component: solvents ]
(G1) : toluene.
The column "ratio of filler in solid component (mass%)" in tables 1 to 4 shows the ratio (mass%) of component (C) in the solid component raw material used in the preparation of the resin composition. The term "ratio of filler in solid content (mass%) means the ratio of filler to nonvolatile component in the resin composition (mass%). The column "ratio (mass%) of the component (a) in the nonvolatile components" in tables 1 to 4 shows the ratio (mass%) of the component (a) in the nonvolatile components of the raw materials used in the preparation of the resin compositions. The column "ratio (mass%) of the component (B) in the nonvolatile components" in tables 1 to 4 shows the ratio (mass%) of the component (B) in the nonvolatile components of the raw materials used in the preparation of the resin composition.
The solutions containing the resin compositions of examples 1 to 15 and comparative examples 1 to 6 obtained as described above were evaluated and measured for "film forming property", "dielectric constant", "dielectric loss tangent", "coefficient of thermal expansion [10 -5/K ]", "copper foil peel strength [ N/cm ]" and "solder heat resistance (300 ℃ C..times.3 minutes)" by the methods shown below. The results are shown in tables 1 to 4.
The film-formed compositions including the resin compositions of examples 5, 8, 10 and 13 were measured for "coefficient of thermal expansion (thickness) [10 -5/K ]" by the following methods. Further, the film-formed compositions comprising the resin compositions of examples 1 to 11 and 13, comparative examples 1 to 3 and comparative example 5 were measured for "minimum melt viscosity [ Pa.s ]" and "minimum melt temperature [. Degree.C ]" by the following methods.
[ Film Forming Property ]
First, a solution containing each resin composition was applied to a PET film subjected to a peeling treatment by knife coating (nafion). Then, the solution on the PET film was dried at 80℃to 130℃to prepare a resin film having a thickness of 20 μm to 50. Mu.m. The property state of the produced resin film was visually confirmed, and evaluated based on the following evaluation criteria. The evaluation result was "good".
And (2) the following steps: excellent film.
Delta: striped, uneven films.
X: there are cracks.
[ Dielectric constant, dielectric loss tangent ]
The resin film produced in the evaluation of film forming property was cured at a temperature of 200℃for 1 hour to produce a sample for measuring dielectric constant and dielectric loss tangent. For the sample to be produced, a 10GHz resonator by a cavity resonator perturbation method (cavity resonator "method) was used to measure the dielectric constant and dielectric loss tangent. The dielectric constant is preferably less than 3.5, more preferably less than 3.0. Further, the dielectric loss tangent is preferably less than 0.0020, more preferably less than 0.0018.
[ Coefficient of thermal expansion [10 -5/K ] ]
The resin film produced in the evaluation of film forming property was laminated to a thickness of 50 μm to 100 μm and cured at a temperature of 200℃for 1 hour to produce a sample for measuring the thermal expansion coefficient. The prepared samples were measured by a stretching method using TMA (thermo-mechanical analysis apparatus), and the average thermal expansion coefficient at 100 ℃ to 110 ℃ was used as a reading (i.e., a measurement value of the thermal expansion coefficient). The measurement conditions were that after annealing to 230℃at a tensile load of 2gf at 20℃per minute, the temperature was temporarily returned to room temperature, and then the measurement was performed at 5℃per minute up to 230 ℃. The thermal expansion coefficient evaluated here is the thermal expansion coefficient in the plane direction. The coefficient of thermal expansion is preferably less than 20[10 -5/K ], more preferably less than 10[10 -5/K ].
[ Coefficient of thermal expansion (thickness) [10 -5/K ] ]
The resin film produced in the film forming property evaluation was laminated to a thickness of about 2mm, and cured at a temperature of 200℃for 1 hour to produce a sample for measuring the coefficient of thermal expansion (thickness). The prepared samples were measured by compression of TMA (thermo-mechanical analysis device) and the average thermal expansion coefficient at 100 ℃ to 110 ℃ was used as a reading (i.e., a measurement value of the thermal expansion coefficient (thickness)). The measurement conditions were that after annealing to 250℃under a compression load of 1gf at 20℃per minute, the temperature was temporarily returned to room temperature, and then the measurement was performed at 5℃per minute up to 250 ℃. The thermal expansion coefficient evaluated here is the thermal expansion coefficient in the thickness direction (i.e., Z direction). The thermal expansion coefficient in the thickness direction is preferably less than 20[10 -5/K ], more preferably less than 10[10 -5/K ].
[ Copper foil peel Strength [ N/cm ] ]
The resin film produced in the evaluation of film forming property was sandwiched between 18 μm thick copper foil and cured at 200℃for 1 hour under a pressure of 1MPa to produce a double-sided copper-clad laminate for measuring the peel strength of the copper foil. The produced double-sided copper-clad plate was cut into 1cm wide pieces, and the strength was measured when the copper foil on one side was peeled off in the 180-degree direction. The measurement conditions were a stretching speed of 50mm/min. The peel strength of the copper foil is preferably 3.0N/cm or more, more preferably 4.0N/cm or more.
[ Solder Heat resistance (300 ℃ C.). Times.3 minutes) ]
The double-sided copper clad laminate produced in the evaluation of the peel strength of copper foil was cut into 2cm square pieces, and the copper clad laminate was floated in a solder bath at 300℃for 3 minutes, and the appearance was visually confirmed, and evaluated based on the following evaluation criteria. The evaluation result was qualified when it was "PASS".
PASS: no change occurs.
X: expansion and peeling of the copper foil.
[ Minimum melt viscosity [ Pa.s ], minimum melt temperature [. Degree.C ]
The resin film produced in the evaluation of film forming property was laminated to a thickness of 200 μm to 300 μm, and the melt viscosity was measured by a rheometer. Then, the lowest melt viscosity [ Pa.s ], the lowest melt temperature [. Degree.C ] at the time of measurement was read. The measurement was performed using parallel plates having a diameter of 5mm at a load of 2gf, a strain of 1%, a frequency of 1Hz, and a speed of 5 ℃/min up to 30-160 ℃. The minimum melting temperature is preferably below 200 ℃, more preferably below 160 ℃. In addition, the minimum melt viscosity is preferably less than 10000 Pa.s, more preferably less than 5000 Pa.s.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Results (results)
As shown in tables 1 to 4, the resin compositions of examples 1 to 15 showed good results in the evaluation and measurement of "film forming property", "dielectric constant", "dielectric loss tangent", "coefficient of thermal expansion [10 -5/K ]", "copper foil peel strength [ N/cm ]", and "solder heat resistance (300 ℃ C..times.3 minutes)".
As a result of measurement of "thermal expansion coefficient (thickness) [10 -5/K ]" were 8.5[10 -5/K ] in example 5, 12.3[10 -5/K ] in example 8, 6.0[10 -5/K ] in example 10 and 6.6[10 -5/K ] in example 13.
The measurement result of the "minimum melt viscosity [ Pa.s ]" was 68 Pa.s in example 1, 1130 Pa.s in example 2, 45 Pa.s in example 3, 1166 Pa.s in example 4, 6168 Pa.s in example 5, 124 Pa.s in example 6, 8 Pa.s in example 7, 3495 Pa.s in example 8, 797 Pa.s in example 9, 9980 Pa.s in example 10, 164 Pa.s in example 11, and 5037 Pa.s in example 13. Further, comparative example 1 was 85 Pa.s, comparative example 2 was 86 Pa.s, comparative example 3 was 94 Pa.s, and comparative example 5 was 2735 Pa.s.
The measurement result of the "minimum melting temperature [. Degree.C ]" was 91℃in example 1, 120℃in example 2, 100℃in example 3, 116℃in example 4, 125℃in example 5, 100℃in example 6, 121℃in example 7, 131℃in example 8, 134℃in example 9, 127℃in example 10, 110℃in example 11 and 122 ℃. In addition, comparative example 1 was 104 ℃, comparative example 2 was 102 ℃, comparative example 3 was 102 ℃, and comparative example 5 was 141 ℃.
The resin composition of example 1 was a resin composition having a low dielectric loss tangent, excellent heat resistance, and a particularly low minimum melting temperature, in which only the component (a), the component (B), and the component (G) were blended in a solvent. The resin composition of example 6 was a resin composition having a reduced amount of component (B) compared to the resin composition of example 1, and was excellent in heat resistance and low in dielectric loss tangent even when the amount of component (B) was small. On the other hand, the resin composition of example 7 was a resin composition in which the amount of component (B) blended was increased as compared with the resin composition of example 1, and even if component (B) was added, it was a resin composition having a low dielectric loss tangent, excellent heat resistance, and a particularly low minimum melt viscosity.
The resin composition of example 2 further comprises a styrene-based thermoplastic elastomer as the component (E), and even if the component (E) is contained, the resin composition has a low dielectric loss tangent and excellent heat resistance. The resin composition of example 9 was a resin composition of a styrene-based thermoplastic elastomer having a modified component (E), and was a resin composition having a low dielectric loss tangent, heat resistance, and copper foil peel strength, which were not problematic in terms of fluidity, although the lowest melt viscosity was higher than that of example 2.
The resin composition of example 3 further contains a polymerization initiator of component (D), and even if component (D) is contained, it is a resin composition having a low dielectric loss tangent and excellent heat resistance. The resin composition of example 4 contains both the component (D) and the component (E), and is a resin composition having a low dielectric loss tangent and excellent heat resistance. The resin compositions of examples 5, 8 and 10 further contain an inorganic filler (silica filler) of component (C) in addition to components (D) and (E), and are resin compositions having a particularly excellent thermal expansion coefficient, a low dielectric loss tangent and excellent heat resistance.
The resin composition of example 11 was a resin composition having a particularly excellent coefficient of thermal expansion and minimum melt viscosity, a low dielectric loss tangent, and excellent heat resistance, in which only the component (a), the component (B), the component (C), and the component (G) were blended in a solvent. The resin composition of example 12 was a resin composition having a low dielectric loss tangent and excellent heat resistance as compared with example 1, using a polyphenylene ether resin having a number average molecular weight of 2200 as the polyphenylene ether resin of component (A). The resin composition of example 13 further comprises an inorganic filler (silica filler treated with vinyl silane) as component (C), and is a resin composition having a particularly excellent coefficient of thermal expansion (thickness), a low dielectric loss tangent and excellent heat resistance. The resin composition of example 14 contained a component (E) (styrene-based thermoplastic elastomer) different from the one used in examples 1 to 13, and showed good results in each evaluation and measurement as in examples 1 to 13 described so far. In addition, the resin composition of example 15 contains a component (a) different from the one used in examples 1 to 13, and also shows good results in each evaluation and measurement in the same manner as in examples 1 to 13.
The film forming property of example 6, in which the content ratio of the (a) component in 100 mass% of the nonvolatile component in the resin composition was 90.57 mass%, was relatively low as compared with example 1. In example 3 and example 12, in which the content of the component (a) in the nonvolatile component 100 mass% was about 70 mass%, improvement in film forming property was seen as compared with example 6, but the film forming property was also relatively lower than that in example 1. In example 8 in which the content ratio of the component (a) in the nonvolatile component 100 mass% was 17.00 mass%, the copper foil peel strength was relatively low.
The example 10 having the lowest content of the component (B) in 100 mass% of the nonvolatile component is higher than the other examples in terms of the lowest melt viscosity. Further, as can be seen from examples 1, 6 and 7, the dielectric loss tangent tends to increase as the content ratio of the component (B) in 100 mass% of the nonvolatile component increases.
In comparative examples 1 and 2, a compound having an isocyanurate ring structure and 3 allyl groups in 1 molecule was used as the component (B') instead of the component (B). The resin compositions of comparative examples 1 and 2 using such a compound were inferior in evaluation of film forming property. The resin compositions of comparative examples 1 and 2 showed high values of dielectric loss tangent.
In comparative example 3 to comparative example 5, a compound having no isocyanurate ring structure in 1 molecule but having phenolic hydroxyl group and allyl group was used as the component (B') instead of the component (B). The resin composition of comparative example 3 confirmed that the copper foil peeled off in the evaluation of solder heat resistance. In the resin composition of comparative example 3, the copper foil was also peeled during the measurement of the peel strength of the copper foil, and therefore the measurement of the peel strength of the copper foil was not performed. The resin compositions of comparative examples 4 and 5 showed high values of dielectric loss tangent. The resin compositions of comparative examples 4 and 5 have low values of peel strength of copper foil, and the copper foil is easily peeled off.
In comparative example 6, a polyphenylene ether having a hydroxyl group at the terminal was used as the component (A') instead of the component (A). In the resin composition of comparative example 6, the film-forming composition containing the resin composition was not cured, and it was difficult to produce a cured resin film. Therefore, the resin composition of comparative example 6 was not evaluated or measured other than the film forming property.
Industrial applicability
The resin composition of the present invention can be used as an adhesive for electronic parts or a resin composition for an adhesive film. The resin composition of the present invention can be used as an adhesive sheet for interlayer adhesion or an interlayer adhesive for a multilayer wiring board. The resin composition of the present invention can also be used as a prepreg using a cured product of the resin composition or as an electronic component for high frequency use having a cured product of the resin composition.
Symbol description
10. Multilayer wiring board
12. 12A, 12b, 12c, 12d, 12e substrates
14. Conductor layer
16. 16A, 16b, 16c, 16d adhesive layer
22. Through hole
24. Fracture of
Z thickness direction
Claims (17)
1. A resin composition, wherein the resin composition comprises:
(A) A polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal, and
(B) A compound having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃.
2. The resin composition according to claim 1, wherein the component (A) is a thermosetting resin.
3. The resin composition according to claim 1 or2, wherein the molecular weight of the component (B) is 300 to 400.
4. The resin composition according to any one of claim 1 to 3, wherein the component (A) is a polyphenylene ether represented by the following formula (1),
[ Chemical 1]
[ Chemical 2]
[ Chemical 3]
In the above general formula (1), R 1、R2、R3、R4、R5、R6、R7 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group or a phenyl group,
- (O-X-O) -represented by the above-mentioned structural formula (2), wherein R 8、R9、R10、R14、R15 may be the same or different and is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R 11、R12、R13 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group,
- (Y-O) -is a structure in which 1 structure represented by the above structural formula (3) or 2 or more structures represented by the above structural formula (3) are arranged at random, R 16、R17 may be the same or different and is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R 18、R19 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group,
Z is an organic group having 1 or more carbon atoms, and may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom,
A. b represents an integer of 0 to 300 and at least any one is not 0, c, d represent an integer of 0 or 1.
5. The resin composition according to any one of claims 1 to 4, wherein the component (B) is a compound represented by the following general formula (4),
[ Chemical 4]
Wherein, in the general formula (4), R is an alkyl group having 4 to 14 carbon atoms.
6. The resin composition according to any one of claims 1 to 5, wherein the resin composition further comprises (C) an inorganic filler.
7. The resin composition according to claim 6, wherein the nonvolatile component in the resin composition contains 50 mass% or more of the component (C) in 100 mass%.
8. The resin composition according to any one of claims 1 to 7, wherein the resin composition further comprises (D) a polymerization initiator that starts polymerization of the (a) component and the (B) component.
9. The resin composition according to any one of claims 1 to 8, wherein the resin composition further comprises (E) a thermoplastic resin having a number average molecular weight of 30000 or more.
10. The resin composition according to claim 9, wherein the nonvolatile component in the resin composition contains 1 to 50% by mass of the component (E) in 100% by mass.
11. The resin composition of any of claims 1-10, wherein the resin composition further comprises (F) polybutadiene.
12. The resin composition according to any one of claims 1 to 11, wherein the nonvolatile component in the resin composition contains 15 to 90 mass% of the (a) component in 100 mass%.
13. The resin composition according to any one of claims 1 to 12, wherein the resin composition comprises 10 to 70 parts by mass of the (B) component with respect to 100 parts by mass of the (a) component.
14. A printed wiring substrate, wherein the printed wiring substrate has a cured layer composed of the resin composition according to any one of claims 1 to 13.
15. A cured product, wherein the cured product is a cured product of the resin composition according to any one of claims 1 to 13.
16. A prepreg, wherein the prepreg is a prepreg using the resin composition according to any one of claims 1 to 13.
17. An electronic component for high frequency, wherein the electronic component for high frequency has the cured product according to claim 15.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021149098 | 2021-09-14 | ||
| JP2021-149098 | 2021-09-14 | ||
| PCT/JP2022/030431 WO2023042578A1 (en) | 2021-09-14 | 2022-08-09 | Resin composition, and printed wiring board, cured product, prepreg, and electronic component for high frequency in which same is used |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117980362A true CN117980362A (en) | 2024-05-03 |
Family
ID=85602754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280060908.4A Pending CN117980362A (en) | 2021-09-14 | 2022-08-09 | Resin composition, and printed wiring board, cured product, prepreg, and high-frequency electronic component using same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20240055726A (en) |
| CN (1) | CN117980362A (en) |
| TW (1) | TW202311432A (en) |
| WO (1) | WO2023042578A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024034398A1 (en) * | 2022-08-09 | 2024-02-15 | ナミックス株式会社 | Resin composition, cured product in which resin composition is used, prepreg, printed wiring board, and electronic component for high frequencies |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI404744B (en) | 2006-08-08 | 2013-08-11 | Namics Corp | Thermosetting resin composition and uncured film composed of the resin composition |
| KR20210148114A (en) * | 2019-03-28 | 2021-12-07 | 시코쿠가세이고교가부시키가이샤 | Resin composition and its use |
| TWI736897B (en) * | 2019-05-31 | 2021-08-21 | 台燿科技股份有限公司 | Resin composition and uses of the same |
| WO2022049965A1 (en) * | 2020-09-01 | 2022-03-10 | パナソニックＩｐマネジメント株式会社 | Resin composition, and prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board each obtained using said resin composition |
-
2022
- 2022-08-09 WO PCT/JP2022/030431 patent/WO2023042578A1/en active Application Filing
- 2022-08-09 KR KR1020247004698A patent/KR20240055726A/en unknown
- 2022-08-09 CN CN202280060908.4A patent/CN117980362A/en active Pending
- 2022-08-16 TW TW111130792A patent/TW202311432A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023042578A1 (en) | 2023-03-23 |
| KR20240055726A (en) | 2024-04-29 |
| TW202311432A (en) | 2023-03-16 |
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