JP2023170310A - Composition for low dielectric member - Google Patents
Composition for low dielectric member Download PDFInfo
- Publication number
- JP2023170310A JP2023170310A JP2022081973A JP2022081973A JP2023170310A JP 2023170310 A JP2023170310 A JP 2023170310A JP 2022081973 A JP2022081973 A JP 2022081973A JP 2022081973 A JP2022081973 A JP 2022081973A JP 2023170310 A JP2023170310 A JP 2023170310A
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- JP
- Japan
- Prior art keywords
- formula
- carbon atoms
- replaced
- phenyl
- low dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 102
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 83
- 125000000217 alkyl group Chemical group 0.000 claims description 75
- -1 3,4-epoxycyclohexyl Chemical group 0.000 claims description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 57
- 229910052736 halogen Inorganic materials 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 150000002367 halogens Chemical class 0.000 claims description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 28
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 125000000466 oxiranyl group Chemical group 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- 230000001588 bifunctional effect Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 22
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 22
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 21
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims description 18
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 9
- 229920003986 novolac Polymers 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000005641 methacryl group Chemical group 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 9
- 239000007869 azo polymerization initiator Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 54
- 239000000047 product Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229920001721 polyimide Polymers 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 239000004973 liquid crystal related substance Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920001955 polyphenylene ether Polymers 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 3
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical compound C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004727 Noryl Substances 0.000 description 2
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- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000007877 V-601 Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 150000004053 quinones Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PFADVMKRWMHNTC-UHFFFAOYSA-N tert-butyl (2-methylpropan-2-yl)oxycarbonyloxy carbonate Chemical compound CC(C)(C)OC(=O)OOC(=O)OC(C)(C)C PFADVMKRWMHNTC-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
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- DBQGARDMYOMOOS-UHFFFAOYSA-N methyl 4-(dimethylamino)benzoate Chemical compound COC(=O)C1=CC=C(N(C)C)C=C1 DBQGARDMYOMOOS-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- NGAVKPIEGZEJAO-UHFFFAOYSA-N naphtho[1,2-g]phthalazine Chemical compound N1=NC=C2C=C3C4=CC=CC=C4C=CC3=CC2=C1 NGAVKPIEGZEJAO-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
本発明は、電子基板や半導体パッケージ用樹脂に用いる低誘電部材を形成可能な組成物に関する。特に、低い誘電率と高い耐熱性をあわせ持ち、高周波化が進む電子デバイスにおいて速度が速く、ロスの少ない信号伝達を可能にする低誘電部材に関する。 The present invention relates to a composition capable of forming a low dielectric member used in resins for electronic substrates and semiconductor packages. In particular, the present invention relates to a low dielectric material that has both a low dielectric constant and high heat resistance, and enables high-speed and low-loss signal transmission in electronic devices, which are increasingly using higher frequencies.
近年、通信機器の5G化さらにはbeyond5Gや6G化に伴い、情報通信機器やコンピュータ等の電子デバイスや基板上での電気信号の高周波化や、アンテナが送受信する電波も高周波化しており、信号処理デバイス内で伝送速度が上がらなかったり、回路基板やアンテナ基板で信号が減衰(損失)されたりすることが問題になっている。そのため、それらの用途に使用される樹脂材料の低誘電率化、低誘電正接が求められており、従来のエポキシ樹脂やアクリル樹脂、ポリイミド(PI)シートやポリエチレンテレフタレート(PET)シートに代わり、液晶ポリマー(LCP),ポリフェニレンエーテル(PPE)、シクロオレフィンポリマー(COP)、フッ素樹脂(PTFE)などのこれまであまり使用されてこなかった樹脂や、従来の生産プロセスが活かせる改良型ポリイミド(mPI)が使用され始めている。
硬化性の低誘電樹脂は比誘電率が3.0以下、シリカや高熱伝導フィラーを含むものでは比誘電率3.5以下の材料がラインアップされており、これらの比誘電率よりも低い材料の開発が求められ、進められている。(非特許文献1)
In recent years, with the shift to 5G and beyond 5G and 6G in communication equipment, the frequency of electrical signals on electronic devices and circuit boards such as information communication equipment and computers has become higher, and the radio waves transmitted and received by antennas have also become higher frequency. The problem is that the transmission speed cannot be increased within the device, or that the signal is attenuated (loss) on the circuit board or antenna board. Therefore, resin materials used in these applications are required to have a low dielectric constant and a low dielectric loss tangent. Polymer (LCP), polyphenylene ether (PPE), cycloolefin polymer (COP), fluoropolymer (PTFE), and other resins that have not been widely used in the past, as well as improved polyimide (mPI) that can utilize conventional production processes. It is starting to be used.
Curable low dielectric resins have a dielectric constant of 3.0 or less, and those containing silica or high thermal conductivity fillers have a dielectric constant of 3.5 or less. Development is required and is underway. (Non-patent document 1)
そのような低誘電率化を進めるために、バルキーな炭化水素分子を高分子鎖中に導入したり(特許文献1、2)、シリコーン樹脂を使用したり(特許文献3、4)する検討が進められている。また、近年では吸水性や加工性など製品に必要な諸特性を満たすために、低誘電率の樹脂を組み合わせて使用する検討も進められており、例えばポリフェニレンエーテル樹脂とマレイミド樹脂を混合するような検討が多数報告されている(特許文献5、6)。
In order to achieve such a low dielectric constant, studies are being conducted on introducing bulky hydrocarbon molecules into polymer chains (
一方、現在のbeyond5Gや6Gに向けた10GHz~100THzの領域ではないが、低誘電率かつ耐熱性の高い材料としてポリシルセスキオキサン(PSQ)の開発が進められており(特許文献7)、官能基を付与し熱重合を可能にしたもの(特許文献8)や、ポリイミドに組み込んだもの(特許文献9)、ラジカル反応性に対応したもの(特許文献10)、フィラーと組み合わせ高熱伝導化したもの(特許文献11)が開発されている。
このように様々な用途で開発されてきたPSQを、10GHz以上の領域で使用される電子デバイスに適用させる試みとして、特許文献12では、低誘電基板用樹脂として、籠型のPSQを鎖状シロキサンで繋ぎ高分子化したものが検討されている。ただし、従来電子デバイスや半導体素子で使用されてきた低誘電率エポキシ樹脂やアクリル樹脂のように、他の樹脂と混合し電子デバイスを形成させることは出来ないことから、PSQを用い従来樹脂と同様に使用可能で、10GHz以上での誘電率が3.0より小さい樹脂および樹脂を形成するための組成物の開発を行った。
On the other hand, polysilsesquioxane (PSQ) is being developed as a material with low dielectric constant and high heat resistance, although it is not in the 10 GHz to 100 THz range for the current beyond 5G and 6G (Patent Document 7). Those with functional groups added to enable thermal polymerization (Patent Document 8), those incorporated into polyimide (Patent Document 9), those compatible with radical reactivity (Patent Document 10), and those combined with fillers to achieve high thermal conductivity. (Patent Document 11) has been developed.
In an attempt to apply PSQ, which has been developed for various uses, to electronic devices used in the 10 GHz or higher range,
上記のとおり、beyond5Gや6Gで使用される情報通信機器やコンピュータは高周波で駆動されるので、周辺部材に低誘電率が望まれている。また現在の半導体製造プロセスはこれまでの技術を積み重ねて成り立っているので、今までの成形プロセスで使用できる材料が好ましい。
そこで本発明は、誘電率が低く、従来のエポキシ等と同様に硬化できる部材を形成可能な組成物を提供することを課題とする。
As mentioned above, information communication equipment and computers used in beyond 5G and 6G are driven at high frequencies, so peripheral members are desired to have a low dielectric constant. Furthermore, since the current semiconductor manufacturing process is based on the accumulation of past technologies, it is preferable to use materials that can be used in conventional molding processes.
Therefore, an object of the present invention is to provide a composition that can form a member that has a low dielectric constant and can be cured in the same manner as conventional epoxy.
本発明者は、重合性基を有するシルセスキオキサン化合物を少なくとも1種含み、その構造、硬化方法、を検討することにより、比誘電率が3.0未満の低誘電率、かつ高耐熱性でこれまでの電子部品用樹脂の硬化温度と同様に200℃以下で硬化できる組成物を見出し、本発明を完成させた。 The present inventor has discovered that the present invention contains at least one type of silsesquioxane compound having a polymerizable group, and by studying its structure and curing method, it has a low dielectric constant of less than 3.0 and a high heat resistance. They discovered a composition that can be cured at 200°C or lower, which is the same as the curing temperature of conventional resins for electronic parts, and completed the present invention.
本発明の第1の態様に係る低誘電部材用組成物は、熱硬化性または光硬化性の重合性基を2個以上有する籠型のシルセスキオキサン(以下、2官能以上のシルセスキオキサンということがある。)と、硬化成分を含み、かつ該組成物にフィラーを添加しないで硬化した硬化物の硬化後の樹脂の10GHzおよび28GHzにおける比誘電率が共に3.0より低いことを特徴とする、低誘電部材用組成物。 The composition for a low dielectric member according to the first aspect of the present invention is a cage-shaped silsesquioxane (hereinafter, bifunctional or more functional silsesquioxane) having two or more thermosetting or photocurable polymerizable groups. ) and a cured product containing a curing component and without adding a filler to the composition, the dielectric constants of the cured resin at 10 GHz and 28 GHz are both lower than 3.0. A composition for low dielectric materials characterized by:
本発明の第2の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(1)および式(2)のそれぞれで表される化合物の群から選択される化合物である、
第1の態様に係る低誘電部材用組成物。
[ここに、Rは独立して、炭素数1~45のアルキル、炭素数4~8のシクロアルキル、炭素数6~16のアリール、または炭素数7~16のアリールアルキルであり;炭素数1~45のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-または-CH=CH-で置き換えられてもよく;炭素数6~16のアリールおよび炭素数7~16のアリールアルキル中のベンゼン環において、少なくとも1つの水素はハロゲンまたは炭素数1~10のアルキルで置き換えられてもよく;この炭素数1~10のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-または-CH=CH-で置き換えられてもよく;炭素数7~16のアリールアルキル中のアルキレンにおいて、炭素原子の数は1~10であり、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、Y1はそれぞれ独立して式(a)で表される基である。]
[ここに、Xは独立して、シクロペンチル、シクロヘキシル、少なくとも1つの水素がフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-が-O-で置き換えられてもよい炭素数1~10のアルキル、少なくとも1つの水素がハロゲンもしくは炭素数1~10のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~10のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキル、またはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルもしくはアリルを有する基であり;フェニルの置換基である炭素数1~10のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;フェニルアルキルのアルキレンにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、Xの少なくとも1つはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基である。]
[ここに、Rは式(1)におけるRと同じ定義を有し、Y2は式(b)で表される基または式(c)で表される基である。]
[ここに、式(b)および式(c)のそれぞれにおいて、Xは式(a)におけるXと同じ定義を有し、そして式(c)におけるZは-O-、-CH2-または単結合である。]
In the composition for a low dielectric member according to the second aspect of the present invention, the difunctional or more functional silsesquioxane is selected from the group of compounds represented by formula (1) and formula (2). is a compound,
A composition for a low dielectric member according to a first aspect.
[Here, R is independently alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 16 carbon atoms, or arylalkyl having 7 to 16 carbon atoms; In the alkyl of ~45, at least one hydrogen may be replaced by fluorine and at least one -CH 2 - may be replaced by -O- or -CH=CH-; In the benzene ring in aryl and arylalkyl having 7 to 16 carbon atoms, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; in this alkyl having 1 to 10 carbon atoms, at least one Hydrogen may be replaced by fluorine and at least one -CH 2 - may be replaced by -O- or -CH=CH-; in alkylene in arylalkyl having 7 to 16 carbon atoms, the carbon atom is from 1 to 10, and at least one -CH 2 - may be replaced by -O-; and each Y 1 is independently a group represented by formula (a). ]
[ wherein , alkyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms, and phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms; A group having phenylalkyl, oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, methacrylic, maleimide residue, vinyl or allyl consisting of ~4 alkylene; phenyl In the alkyl having 1 to 10 carbon atoms which is a substituent of , at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-; , at least one -CH 2 - may be replaced with -O-; and at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, methacryl , maleimide residue, vinyl or allyl group. ]
[Here, R has the same definition as R in formula (1), and Y 2 is a group represented by formula (b) or a group represented by formula (c). ]
[Here, in each of formula (b) and formula (c), X has the same definition as X in formula (a), and Z in formula (c) is -O-, -CH 2 - or a single It is a combination. ]
本発明の第3の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、第2の態様に記載の前記式(1)および式(2)において、Rが独立して、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、または少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;
フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素がフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-が-O-で置き換えられてもよく;
Xが独立して、炭素数1~4のアルキル、炭素数1~4のフッ素化アルキル、シクロペンチル、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキル、またはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルもしくはアリルを有する基であり、フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、
第2の態様に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの少なくとも1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基である、第1または2の態様に係る低誘電部材用組成物。
In the composition for a low dielectric member according to the third aspect of the present invention, the difunctional or more functional silsesquioxane has the formula (1) and formula (2) described in the second aspect, where R is independent. cyclohexyl, phenyl in which at least one hydrogen may be replaced with a halogen or alkyl having 1 to 4 carbon atoms, or phenyl in which at least one hydrogen may be replaced with a halogen or alkyl having 1 to 4 carbon atoms; phenylalkyl composed of alkylene having 1 to 4 carbon atoms;
In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-;
X is independently alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms; Phenylalkyl consisting of phenyl and alkylene having 1 to 4 carbon atoms, in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, or oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride A group having a residue, acrylic, methacrylic, maleimide residue, vinyl or allyl, and in the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least One -CH 2 - may be replaced by -O-; and
In each of formula (a), formula (b) and formula (c) according to the second aspect, at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide. The composition for a low dielectric member according to the first or second aspect, which is a group having a residue, vinyl or allyl.
本発明の第4の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、第2の態様に記載の前記式(1)および式(2)において、Rがシクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、または少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;
フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-が-O-で置き換えられてもよく;
第2の態様に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であって、残りのXが炭素数1~4のアルキル、炭素数1~4のフッ素化アルキル、シクロペンチル、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;
フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよい、
第1~3のいずれかの態様に係る低誘電部材用組成物。
In the composition for a low dielectric member according to the fourth aspect of the present invention, the difunctional or more functional silsesquioxane is represented by the formula (1) and formula (2) according to the second aspect, wherein R is cyclohexyl. , phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms, or phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms; 4 is a phenylalkyl composed of alkylene;
In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-;
In each of formula (a), formula (b) and formula (c) according to the second aspect, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. group, vinyl or allyl, in which the remaining phenyl which may be replaced with an alkyl group, phenyl which may have at least one hydrogen replaced with a halogen or an alkyl group having 1 to 4 carbon atoms, and phenylalkyl consisting of alkylene having 1 to 4 carbon atoms;
In the alkyl having 1 to 4 carbon atoms that is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-,
A composition for a low dielectric member according to any one of the first to third aspects.
本発明の第5の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが第2の態様に記載の前記式(1)および式(2)において、Rがシクロヘキシルまたはフェニルであり;
第2の態様に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であり、そして残りのXがメチル、エチル、t-ブチル、シクロペンチル、シクロヘキシルまたはフェニルである、
第1~4のいずれかの態様に係る低誘電部材用組成物。
In the composition for a low dielectric member according to the fifth aspect of the present invention, the difunctional or more functional silsesquioxane is represented by the formula (1) and formula (2) according to the second aspect, and R is cyclohexyl or is phenyl;
In each of formula (a), formula (b) and formula (c) according to the second aspect, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. group, vinyl or allyl, and the remaining X is methyl, ethyl, t-butyl, cyclopentyl, cyclohexyl or phenyl,
A composition for a low dielectric member according to any one of the first to fourth aspects.
本発明の第6の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが第2の態様に記載の前記式(1)および式(2)において、Rがフェニルであり;
式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であり、そして残りのXがメチルまたはフェニルである、
第1~5のいずれかの態様に係る低誘電部材用組成物。
In the composition for a low dielectric member according to the sixth aspect of the present invention, the bifunctional or more functional silsesquioxane is represented by the formula (1) and formula (2) according to the second aspect, and R is phenyl. can be;
In each of formula (a), formula (b) and formula (c), one of X has oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue, vinyl or allyl and the remaining X is methyl or phenyl,
A composition for a low dielectric member according to any one of the first to fifth aspects.
本発明の第7の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(1-1)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(1-1)において、Meはメチルを示し、Phはフェニルを示す。
The composition for a low dielectric member according to the seventh aspect of the present invention is provided by any one of the first to sixth silsesquioxanes, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (1-1). A composition for a low dielectric member according to an embodiment.
Here, in formula (1-1), Me represents methyl and Ph represents phenyl.
本発明の第8の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(1-2)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(1-2)において、Meはメチルを示し、Phはフェニルを示す。
The composition for a low dielectric member according to the eighth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (1-2). A composition for a low dielectric member according to an embodiment.
Here, in formula (1-2), Me represents methyl and Ph represents phenyl.
本発明の第9の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(2-1)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(2-1)において、Meはメチルを示し、Phはフェニルを示す。
The composition for a low dielectric member according to the ninth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (2-1). A composition for a low dielectric member according to an embodiment.
Here, in formula (2-1), Me represents methyl and Ph represents phenyl.
本発明の第10の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(2-2)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(2-2)において、Meはメチルを示し、Phはフェニルを示す。
The composition for a low dielectric member according to the tenth aspect of the present invention is provided by any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (2-2). A composition for a low dielectric member according to an embodiment.
Here, in formula (2-2), Me represents methyl and Ph represents phenyl.
本発明の第11の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(2-3)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(2-3)において、Meはメチルを示す。
The composition for a low dielectric member according to the eleventh aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (2-3). A composition for a low dielectric member according to an embodiment.
Here, in formula (2-3), Me represents methyl.
本発明の第12の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(2-4)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(2-4)において、Meはメチルを示す。
The composition for a low dielectric member according to the twelfth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (2-4). A composition for a low dielectric member according to an embodiment.
Here, in formula (2-4), Me represents methyl.
本発明の第13の態様に係る低誘電部材用組成物は、前記2官能以上のシルセスキオキサンが、式(2-5)で表される化合物である、第1~6のいずれかの態様に係る低誘電部材用組成物。
ここで、式(2-5)において、Meはメチルを示し、Phはフェニルを示す。
The composition for a low dielectric member according to the thirteenth aspect of the present invention is provided by any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (2-5). A composition for a low dielectric member according to an embodiment.
Here, in formula (2-5), Me represents methyl and Ph represents phenyl.
本発明の第14の態様に係る低誘電部材用組成物は、前記硬化成分が、アミン系硬化剤、活性エステル硬化剤、フェノール・ノボラック硬化剤、酸発生剤、リン系硬化促進剤、またはアゾ系重合開始剤であることを特徴とする、第1~13のいずれかの態様に係る低誘電部材用組成物 In the composition for a low dielectric member according to the fourteenth aspect of the present invention, the curing component is an amine curing agent, an active ester curing agent, a phenol/novolak curing agent, an acid generator, a phosphorus curing accelerator, or an azo curing agent. The composition for a low dielectric member according to any one of the first to thirteenth aspects, which is a polymerization initiator.
本発明の第15の態様に係る低誘電部材は、第1~14のいずれかの態様に係る低誘電部材用組成物が硬化した、低誘電部材。 A low dielectric member according to a fifteenth aspect of the present invention is a low dielectric member obtained by curing the composition for a low dielectric member according to any one of the first to fourteenth aspects.
本発明の第16の態様に係る電子機器は、第15の態様に係る低誘電部材と;
高周波を発信、変換、伝達、および信号処理する能力からなる群から選択される少なくとも1つの能力を有する電子デバイスと;を備えた、
電子機器。
An electronic device according to a sixteenth aspect of the present invention includes a low dielectric member according to the fifteenth aspect;
an electronic device having at least one ability selected from the group consisting of the ability to transmit, convert, transmit, and process high frequencies;
Electronics.
本発明の低誘電部材用組成物から形成された低誘電部材は、10GHz以上の高周波領域において、極めて低い誘電率と高い耐熱性を有する。さらに、熱膨張率の制御性、化学的安定性、硬度および機械的強度などの優れた特性をも有する。当該低誘電部材用組成物および低誘電部材は、例えば、低誘電基板、低誘電樹脂部品、低誘電絶縁膜およびその原料となるワニス、低誘電接着剤などに適している。 A low dielectric member formed from the composition for a low dielectric member of the present invention has an extremely low dielectric constant and high heat resistance in a high frequency region of 10 GHz or higher. Furthermore, it has excellent properties such as controllability of thermal expansion coefficient, chemical stability, hardness, and mechanical strength. The composition for a low dielectric member and the low dielectric member are suitable for, for example, a low dielectric substrate, a low dielectric resin component, a low dielectric insulating film, a varnish serving as a raw material thereof, a low dielectric adhesive, and the like.
以下、本発明の実施の形態について説明する。また、本発明は、以下の実施の形態に制限されるものではない。 Embodiments of the present invention will be described below. Further, the present invention is not limited to the following embodiments.
本発明で用いる用語について説明する。式(1)で表わされる化合物を化合物(1)と表記することがある。他の式で表される化合物についても同様に簡略化して称することがある。「少なくとも1つのAはBまたはCで置き換えられてもよい」という表現は、少なくとも1つのAがBで置き換えられる場合および少なくとも1つのAがCで置き換えられる場合に加えて、少なくとも1つのAがBで置き換えられると同時に、その他のAの少なくとも1つがCで置き換えられる場合があることを意味する。本明細書に記載される化学式において、Meはメチルであり、そしてPhはフェニルである。実施例においては、電子天秤の表示データを質量単位であるg(グラム)を用いて示した。重量%や重量比はこのような数値に基づくデータである。 The terms used in the present invention will be explained. The compound represented by formula (1) may be referred to as compound (1). Compounds represented by other formulas may also be referred to in a simplified manner. The expression "at least one A may be replaced by B or C" means that at least one A may be replaced by B or C, in addition to when at least one A is replaced by B or C. This means that at the same time that B is substituted, at least one of the other A may be substituted with C. In the chemical formulas described herein, Me is methyl and Ph is phenyl. In the examples, the display data of the electronic balance was shown using the mass unit g (gram). Weight % and weight ratio are data based on such numerical values.
[低誘電部材用組成物]
本発明の低誘電部材用組成物は、重合性シルセスキオキサン化合物(2官能以上のシルセスキオキサン)と、当該シルセスキオキサンと重合させることができる高分子またはモノマーとを共重合により硬化させることにより、当該シルセスキオキサンの大きな体積および大きな空隙率により、硬化樹脂中で誘電率の原因となる樹脂成分量を減少させることにより、10GHz以上の高周波領域においても極めて低い誘電率を保持する低誘電部材用組成物の作製が可能になる。
[Composition for low dielectric materials]
The composition for a low dielectric member of the present invention is produced by copolymerizing a polymerizable silsesquioxane compound (a bifunctional or higher functional silsesquioxane) and a polymer or monomer that can be polymerized with the silsesquioxane. By curing, the large volume and large porosity of the silsesquioxane reduce the amount of resin components that cause the dielectric constant in the cured resin, resulting in an extremely low dielectric constant even in the high frequency range of 10 GHz or higher. It becomes possible to produce a composition for a low dielectric member that maintains the properties.
本発明の第1の実施の形態に係る低誘電部材用組成物は、複数の環状シロキサンが閉じた空間を形成している籠型構造を有する基本骨格に、重合性の官能基を有する特定構造の重合性シルセスキオキサン化合物を応用し、樹脂成分の密度が低い硬化物を作製することにより作製した、低誘電率の硬化性樹脂組成物である。 The composition for a low dielectric member according to the first embodiment of the present invention has a specific structure having a polymerizable functional group in a basic skeleton having a cage structure in which a plurality of cyclic siloxanes form a closed space. This is a curable resin composition with a low dielectric constant, which is produced by applying a polymerizable silsesquioxane compound and producing a cured product with a low density of resin components.
<2官能以上のシルセスキオキサン>
2官能以上のシルセスキオキサンは、オキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリル基を2個以上有する籠型構造のシルセスキオキサンの少なくとも1つである。この籠型構造は、複数の環状シロキサンが閉じた空間を形成している構造であり、その閉じた空間の形状は特に限定されない。さらに本発明では、籠型構造の少なくとも1箇所以上が塞がれていない構造を有するシルセスキオキサン(例えばダブルデッカー型)も包含する。
<Difunctional or higher functional silsesquioxane>
Silsesquioxanes having two or more functionalities include oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residues, succinimide residues, acrylic, methacrylic, maleimide residues, and cage-type structures having two or more vinyl or allyl groups. At least one silsesquioxane. This cage-type structure is a structure in which a plurality of cyclic siloxanes form a closed space, and the shape of the closed space is not particularly limited. Furthermore, the present invention also includes a silsesquioxane having a structure in which at least one part of the cage structure is not blocked (for example, a double decker type).
このような構造の2官能以上のシルセスキオキサンの具体例として、化合物(1)および化合物(2)で示すことができる。
Specific examples of bifunctional or more functional silsesquioxanes having such a structure include Compound (1) and Compound (2).
式(1)および式(2)において、Rは炭素数1~45のアルキル、炭素数4~8のシクロアルキル、炭素数6~16のアリールおよび炭素数7~16のアリールアルキルから独立して選択される基である。即ち、式(1)および式(2)のそれぞれにおいて、8つのRは異なる2つ以上の基で構成されてもよいが、すべてが同じ基であることが好ましい。この炭素数1~45のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-または-CH=CH-で置き換えられてもよいが、隣接した-CH2-がともに-O-で置き換えられることはない。このアルキルの好ましい炭素数は1~10である。 In formula (1) and formula (2), R is independently from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 16 carbon atoms, and arylalkyl having 7 to 16 carbon atoms. is the group of choice. That is, in each of formula (1) and formula (2), the eight R's may be composed of two or more different groups, but it is preferable that all of them are the same group. In this alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O- or -CH=CH-, but adjacent Both -CH 2 - are not replaced by -O-. This alkyl preferably has 1 to 10 carbon atoms.
Rが炭素数4~8のシクロアルキルであるとき、架橋構造の基であってもよい。シクロアルキルの好ましい例はシクロペンチルおよびシクロヘキシルであり、シクロヘキシルがより好ましい。 When R is cycloalkyl having 4 to 8 carbon atoms, it may be a group with a crosslinked structure. Preferred examples of cycloalkyl are cyclopentyl and cyclohexyl, with cyclohexyl being more preferred.
Rが炭素数6~16のアリールまたは炭素数7~16のアリールアルキルであるとき、これらの基中のベンゼン環において、少なくとも1つの水素はハロゲンまたは炭素数1~10のアルキルで置き換えられてもよい。ハロゲンの例はフッ素、塩素および臭素である。この炭素数1~10のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-または-CH=CH-で置き換えられてもよいが、隣接した-CH2-がともに-O-で置き換えられることはない。このアルキルの好ましい炭素数は1~4である。炭素数7~16のアリールアルキル中のアルキレンにおいて、その炭素原子の数は1~10であり、そして少なくとも1つの-CH2-は-O-で置き換えられてもよいが、隣接した-CH2-がともに-O-で置き換えられることはない。このアルキレンの好ましい炭素数は1~4である。 When R is aryl having 6 to 16 carbon atoms or arylalkyl having 7 to 16 carbon atoms, at least one hydrogen in the benzene ring in these groups may be replaced with halogen or alkyl having 1 to 10 carbon atoms. good. Examples of halogens are fluorine, chlorine and bromine. In this alkyl having 1 to 10 carbon atoms, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O- or -CH=CH-, but adjacent Both -CH 2 - are not replaced by -O-. This alkyl preferably has 1 to 4 carbon atoms. In alkylene in arylalkyl having 7 to 16 carbon atoms, the number of carbon atoms is 1 to 10, and at least one -CH 2 - may be replaced by -O-, but adjacent -CH 2 - cannot both be replaced by -O-. The alkylene preferably has 1 to 4 carbon atoms.
このような炭素数6~16のアリールの例は、フェニル、ハロゲン化フェニル、4-メチルフェニル、4-エチルフェニル、4-ブチルフェニル、4-オクチルフェニル、2,4-ジメチルフェニル、4-メトキシフェニル、4-ブトキシフェニル、4-トリフルオロメチルフェニル、4-トリフルオロメトキシフェニル、3-クロロ-4-メチルフェニル、3,5-ジクロロ-4-メチルフェニル、および2,3-ジフルオロ-4-メトキシフェニルである。これらのうちで、フェニルが特に好ましい。 Examples of such aryl having 6 to 16 carbon atoms are phenyl, halogenated phenyl, 4-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-octylphenyl, 2,4-dimethylphenyl, 4-methoxy Phenyl, 4-butoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 3-chloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl, and 2,3-difluoro-4- It is methoxyphenyl. Among these, phenyl is particularly preferred.
前記のような炭素数7~16のアリールアルキルの例は、フェニルメチル、フェニルエチル、3-フェニルプロピル、4-フェニルブチル、4-クロロフェニルメチル、4-フルオロフェニルメチル、2-(4-フルオロフェニル)プロピル、2-(4-クロロフェニル)エチル、4-メチルフェニルメチル、2-(4-メチルフェニル)エチル、2-(2,5ジメチルフェニル)エチル、4-トリフルオロメチルフェニルメチル、2-(4-トリフルオロメチルフェニル)エチル、2-(4-エテニルフェニル)エチル、4-メトキシフェニルメチル、4-エトキシフェニルメチル、2-(4-メトキシフェニル)エチル、3-(4-メトキシフェニル)プロピル、2-クロロ-4-メチルフェニルメチル、および2,5-ジクロロ-4-メチルフェニルメチルである。 Examples of the above-mentioned arylalkyl having 7 to 16 carbon atoms include phenylmethyl, phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 4-chlorophenylmethyl, 4-fluorophenylmethyl, 2-(4-fluorophenyl ) propyl, 2-(4-chlorophenyl)ethyl, 4-methylphenylmethyl, 2-(4-methylphenyl)ethyl, 2-(2,5dimethylphenyl)ethyl, 4-trifluoromethylphenylmethyl, 2-( 4-Trifluoromethylphenyl)ethyl, 2-(4-ethenylphenyl)ethyl, 4-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2-(4-methoxyphenyl)ethyl, 3-(4-methoxyphenyl) propyl, 2-chloro-4-methylphenylmethyl, and 2,5-dichloro-4-methylphenylmethyl.
式(1)におけるY1は式(a)で表される基であり、式(2)におけるY2は式(b)または式(c)で表される基である。製造コストを考慮するとき、式(2)における2つのY2は同一の基であることが好ましいが、異なる基であっても構わない。
Y 1 in formula (1) is a group represented by formula (a), and Y 2 in formula (2) is a group represented by formula (b) or formula (c). When considering production cost, it is preferable that the two Y 2 in formula (2) are the same group, but they may be different groups.
式(a)、式(b)および式(c)のそれぞれにおいて、Xは独立してシクロペンチル、シクロヘキシル、少なくとも1つの水素がフッ素で置き換えられてもよく、そして1つの-CH2-が-O-で置き換えられてもよい炭素数1~10のアルキル、少なくとも1つの水素がハロゲンもしくは炭素数1~10のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~10のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキル、またはオキシラニル、3,4-エポキシシクロヘキシル無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルもしくはアリルを有する基である。このとき、フェニルの置換基である炭素数1~10のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく、フェニルアルキルのアルキレンにおける1つの-CH2-は-O-で置き換えられてもよい。そして、式(a)、式(b)および式(c)のそれぞれにおいて、Xの少なくとも1つはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基である。 In each of formula (a), formula (b) and formula (c), X is independently cyclopentyl, cyclohexyl, at least one hydrogen may be replaced by fluorine, and one -CH 2 - is replaced by -O - alkyl having 1 to 10 carbon atoms which may be substituted with -, phenyl which may have at least one hydrogen substituted with halogen or alkyl having 1 to 10 carbon atoms, at least one hydrogen having halogen or alkyl having 1 to 10 carbon atoms; Phenyl alkyl consisting of phenyl which may be substituted with alkyl and alkylene having 1 to 4 carbon atoms, or oxiranyl, 3,4-epoxycyclohexyl succinic anhydride residue, succinimide residue, acrylic, methacryl, maleimide residue , vinyl or allyl group. At this time, in the alkyl having 1 to 10 carbon atoms that is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-, One -CH 2 - in alkylene of phenylalkyl may be replaced with -O-. In each of formula (a), formula (b) and formula (c), at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, methacryl, maleimide. A group having a residue, vinyl or allyl.
そして、式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であって、残りのXがシクロペンチル、シクロヘキシル、少なくとも1つの水素がフッ素で置き換えられてもよく、そして1つの-CH2-が-O-で置き換えられてもよい炭素数1~10のアルキル、少なくとも1つの水素がハロゲンまたは炭素数1~10のアルキルで置き換えられてもよいフェニル、および少なくとも1つの水素がハロゲンまたは炭素数1~10のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルから選択される基であることが好ましい。 In each of formula (a), formula (b) and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue, vinyl or allyl. a group having 1 to 10 carbon atoms in which the remaining X is cyclopentyl, cyclohexyl, at least one hydrogen may be replaced with fluorine, and one -CH 2 - may be replaced with -O- alkyl, phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 10 carbon atoms, and phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 10 carbon atoms; It is preferably a group selected from phenylalkyl consisting of 1 to 4 alkylene.
式(1)および式(2)の好ましい範囲は、RとXに関して次のように表される。即ち、Rが独立して、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、または少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素がフッ素で置き換えられてもよく、そして1つの-CH2-が-O-で置き換えられてもよく;Xが独立して、炭素数1~4のアルキル、炭素数1~4のフッ素化アルキル、シクロペンチル、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキル、またはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルもしくはアリルを有する基であり;フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、式(a)、式(b)および式(c)のそれぞれにおいて、Xの少なくとも1つはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基である。 Preferred ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is independently cyclohexyl, phenyl, where at least one hydrogen may be replaced with a halogen or alkyl having 1 to 4 carbon atoms, or at least one hydrogen is replaced with a halogen or alkyl having 1 to 4 carbon atoms. is a phenylalkyl composed of optional phenyl and an alkylene having 1 to 4 carbon atoms; at least one hydrogen in the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, may be replaced with fluorine, and one -CH 2 - may be replaced by -O-; consisting of phenyl which may be replaced with halogen or alkyl having 1 to 4 carbon atoms, phenyl which may have at least one hydrogen replaced with halogen or alkyl having 1 to 4 carbon atoms, and alkylene having 1 to 4 carbon atoms. a group having phenylalkyl, oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacryl, maleimide residue, vinyl or allyl; a substituent of phenyl having 1 to 4 carbon atoms; In alkyl, at least one hydrogen may be replaced with fluorine and at least one -CH 2 - may be replaced with -O-; and in formula (a), formula (b) and formula (c ), at least one of X is a group having oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue, vinyl or allyl.
式(1)および式(2)のより好ましい範囲は、RとXに関して次のように表される。即ち、Rがシクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、または少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして1つの-CH2-が-O-で置き換えられてもよく;式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であって、残りのXが炭素数1~4のアルキル、炭素数1~4のフッ素化アルキル、シクロペンチル、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよい。 More preferable ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is cyclohexyl, phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms, or phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms. and alkylene having 1 to 4 carbon atoms; in the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and one - CH 2 - may be replaced with -O-; in each of formula (a), formula (b) and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue , acrylic, methacrylic, maleimide residue, vinyl or allyl, the remaining X is alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, at least one hydrogen is phenyl which may be replaced with halogen or alkyl having 1 to 4 carbon atoms, phenyl which may have at least one hydrogen replaced with halogen or alkyl having 1 to 4 carbon atoms, and alkylene having 1 to 4 carbon atoms; is phenylalkyl; in the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-. Good too.
式(1)および式(2)のさらに好ましい範囲は、RとXに関して次のように表される。即ち、Rがシクロヘキシルまたはフェニルであり;式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であり、そして残りのXがメチル、エチル、t-ブチル、シクロペンチル、シクロヘキシルまたはフェニルである。 More preferable ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is cyclohexyl or phenyl; in each of formula (a), formula (b), and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacryl , maleimide residue, vinyl or allyl, and the remaining X is methyl, ethyl, t-butyl, cyclopentyl, cyclohexyl or phenyl.
式(1)および式(2)の特に好ましい範囲は、RとXに関して次のように表される。即ち、Rがフェニルであり;式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であり、そして残りのXがメチルまたはフェニルである。 Particularly preferred ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is phenyl; in each of formula (a), formula (b), and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacryl, maleimide. a group having a residue, vinyl or allyl, and the remaining X is methyl or phenyl.
オキシラニル、3,4-エポキシシクロヘキシルまたは無水コハク酸残基を有する基の好ましい例を次に示す。
これらの式において、R2およびR4は炭素数1~6のアルキレンである。このアルキレンにおける1つの-CH2-は-O-または1,4-フェニレンで置き換えられてもよい。そして、R3は水素または炭素数1~6のアルキルである。
Preferred examples of groups having oxiranyl, 3,4-epoxycyclohexyl or succinic anhydride residues are shown below.
In these formulas, R 2 and R 4 are alkylene having 1 to 6 carbon atoms. One -CH 2 - in this alkylene may be replaced with -O- or 1,4-phenylene. And R 3 is hydrogen or alkyl having 1 to 6 carbon atoms.
これらのうち、オキシラニル、無水コハク酸残基、および3,4-エポキシシクロヘキシルのいずれか1つを有する基がより好ましい。 Among these, a group having any one of oxiranyl, succinic anhydride residue, and 3,4-epoxycyclohexyl is more preferred.
Xの特に好ましい例は、式(3)、式(4)および式(5)のそれぞれで表される基である。
Particularly preferred examples of X are groups represented by formula (3), formula (4) and formula (5).
アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基の好ましい例を次に示す。
Preferred examples of groups having acrylic, methacrylic, maleimide residues, vinyl or allyl are shown below.
式(6)~(11)中、Rbは、水素、ハロゲン、-CF3、または炭素数1~5のアルキルであり、式中にRbが複数ある場合は、それらが同一であっても異なっていてもよい。 In the formulas (6) to (11), R b is hydrogen, halogen, -CF 3 , or alkyl having 1 to 5 carbon atoms, and when there is more than one R b in the formula, they are the same and may also be different.
これらのうち、メタクリル、マレイミド残基、ビニルおよびアリルのいずれか1つを有する基がより好ましい。 Among these, a group having any one of methacryl, maleimide residue, vinyl, and allyl is more preferred.
化合物(1)および化合物(2)の具体例を次に示す。
式(1-1)~(2-5)において、Meはメチルを示し、Phはフェニルを示す。
Specific examples of compound (1) and compound (2) are shown below.
In formulas (1-1) to (2-5), Me represents methyl and Ph represents phenyl.
これらの2官能以上のシルセスキオキサンは、
(1-1):特許第5013127号公報
(1-2):特許第4470738号公報
(2-1):特許第5408597号公報
(2-2)(2-5):特許第4379120号公報
(2-3)(2-4):特許第5018065号公報
を参照することにより容易に得ることができる。
These bifunctional or more functional silsesquioxanes are
(1-1): Patent No. 5013127 (1-2): Patent No. 4470738 (2-1): Patent No. 5408597 (2-2) (2-5): Patent No. 4379120 ( 2-3) (2-4): Can be easily obtained by referring to Japanese Patent No. 5018065.
本発明に用いる2官能以上のシルセスキオキサンは、硬化成分(以下、硬化剤ということがある。)や反応性エラストマーなどと組み合わせて高分子鎖を形成するために2官能以上の官能基を有することが好ましく、3官能以上、または4官能以上である場合を含む。さらに、2官能以上のシルセスキオキサンの長辺の両端に官能基を有する化合物が直線的な結合を形成できるため好ましい。 The difunctional or higher functional silsesquioxane used in the present invention has a difunctional or higher functional group in order to form a polymer chain in combination with a curing component (hereinafter sometimes referred to as a curing agent) or a reactive elastomer. It is preferable to have one, including cases where it has trifunctionality or more, or tetrafunctionality or more. Furthermore, a compound having functional groups at both ends of the long side of bifunctional or more functional silsesquioxane is preferable because it can form a linear bond.
<重合性化合物>
本発明の低誘電部材用組成物は、2官能以上のシルセスキオキサンの他に、2官能以上のシルセスキオキサンに付与した重合性基と反応することができる重合性基を有する高分子または低分子化合物を構成要素としてもよい。たとえば、2官能以上のシルセスキオキサンの官能基がエポキシ基やオキセタン基の場合は、末端にアミノ基、水酸基、活性エステル構造を有する、反応性ポリフェニレンエーテルオリゴマー、反応性ポリイミドオリゴマー、反応性ポリマレイミドオリゴマー、反応性ビフェニルオリゴマー、反応性ビスフェノールオリゴマーなどを組み合わせると低誘電率かつ高耐熱性で接着性を有する樹脂を構成することができ、反応性ポリアルキルエーテル化合物、反応性EPDM化合物などと組み合わせると低誘電率でフレキシブルな樹脂を構成することができる。
2官能以上のシルセスキオキサンの官能基がアクリル基、メタクリル基、マレイミド残基、ビニル基、アリル基といったラジカル重合性の場合は、末端にアクリル基、メタクリル基、マレイミド残基、ビニル基、アリル基を有し、反応性ポリフェニレンエーテルオリゴマー、反応性ポリイミドオリゴマー、反応性ポリマレイミドオリゴマー、反応性ビフェニルオリゴマー、反応性ビスフェノールオリゴマーなどを組み合わせると、より低誘電率で高耐熱性の樹脂構成することができる。
<Polymerizable compound>
The composition for a low dielectric member of the present invention is a polymer having a polymerizable group capable of reacting with a polymerizable group imparted to the difunctional or more functional silsesquioxane, as well as a difunctional or more functional silsesquioxane. Alternatively, a low molecular compound may be used as a constituent element. For example, when the functional group of bifunctional or more functional silsesquioxane is an epoxy group or an oxetane group, reactive polyphenylene ether oligomers, reactive polyimide oligomers, reactive polyimide oligomers, and reactive polyphenylene ether oligomers, reactive polyimide oligomers, etc. By combining maleimide oligomers, reactive biphenyl oligomers, reactive bisphenol oligomers, etc., a resin with low dielectric constant, high heat resistance, and adhesive properties can be constructed, and in combination with reactive polyalkyl ether compounds, reactive EPDM compounds, etc. It is possible to construct a flexible resin with a low dielectric constant.
When the functional group of the silsesquioxane having two or more functionalities is radically polymerizable such as an acrylic group, a methacrylic group, a maleimide residue, a vinyl group, or an allyl group, an acrylic group, a methacrylic group, a maleimide residue, a vinyl group, By combining reactive polyphenylene ether oligomers, reactive polyimide oligomers, reactive polymaleimide oligomers, reactive biphenyl oligomers, reactive bisphenol oligomers, etc. that have an allyl group, a resin with a lower dielectric constant and higher heat resistance can be constructed. Can be done.
<液晶性の重合性化合物>
本発明の低誘電部材用組成物は、2官能以上のシルセスキオキサンの他に、液晶性の重合性化合物を比誘電率構成要素としてもよい。液晶性の重合性化合物(以下、重合性液晶化合物ということがある。)は、分子の直線性がよく、規則性も高いため、分子の配向方向のフォノン振動の伝導に起因する熱伝導率が高く、分子鎖の柔らかさに起因する分子振動が原因となる誘電率や誘電損失の発現が抑えられるために低誘電率かつ低誘電損失が期待できる。たとえば、特許第5084148号公報、特許第6653793号公報、特許第6902193号公報に記載の重合性液晶化合物が好ましい。
<Liquid crystalline polymerizable compound>
The composition for a low dielectric member of the present invention may include a liquid crystalline polymerizable compound as a dielectric constant component in addition to the bifunctional or higher functional silsesquioxane. Liquid crystal polymerizable compounds (hereinafter sometimes referred to as polymerizable liquid crystal compounds) have good molecular linearity and high regularity, so their thermal conductivity due to conduction of phonon vibrations in the direction of molecular orientation is low. Since the development of dielectric constant and dielectric loss caused by molecular vibration caused by the softness of molecular chains is suppressed, low dielectric constant and low dielectric loss can be expected. For example, polymerizable liquid crystal compounds described in Japanese Patent No. 5084148, Japanese Patent No. 6653793, and Japanese Patent No. 6902193 are preferred.
<その他の構成要素>
本発明の低誘電部材用組成物中の2官能以上のシルセスキオキサンに直接結合していない、すなわち図1に示した高分子鎖12に組み込まれない有機化合物(例えば重合性化合物または高分子化合物)を含んでいてもよく、重合開始剤や溶媒等を含んでいてもよい。
<Other components>
An organic compound (such as a polymerizable compound or a polymer compound), a polymerization initiator, a solvent, etc.
<結合していない高分子化合物>
本発明の低誘電部材用組成物中の2官能以上のシルセスキオキサンに直接結合していない、高分子化合物としては、膜形成性および機械的強度を低下させない化合物が好ましい。この高分子化合物は、2官能以上のシルセスキオキサンまたは硬化剤と反応しない高分子化合物であればよく、例えば2官能以上のシルセスキオキサンがオキシラニル基で硬化剤がアミノ基を有する場合は、ポリオレフィン系樹脂、ポリビニル系樹脂、シリコーン樹脂、ワックスなどが挙げられる。低誘電材料では分子鎖間に空隙があると誘電率が下がるという意味では好ましいが、毛細管現象などにより水分を吸着し、誘電特性を悪化させる場合などは、直接結合しない誘電率が低く吸水性の低い高分子化合物を添加することにより空隙を塞ぐことが好ましい。含有量は、まず結合していない重合性化合物を含まない、低誘電部材用組成物を作製し、その空隙率を測定して、その空隙率を埋められる量の高分子化合物を添加することが望ましい。
<Unbonded polymer compound>
The polymer compound that is not directly bonded to the difunctional or higher functional silsesquioxane in the composition for a low dielectric member of the present invention is preferably a compound that does not reduce film-forming properties and mechanical strength. This polymer compound may be any polymer compound that does not react with the difunctional or higher functional silsesquioxane or the curing agent. For example, if the difunctional or higher functional silsesquioxane has an oxiranyl group and the curing agent has an amino group, , polyolefin resin, polyvinyl resin, silicone resin, wax, etc. In low dielectric materials, it is preferable to have voids between molecular chains in the sense that the dielectric constant decreases, but if moisture is adsorbed due to capillarity and deteriorates dielectric properties, it is preferable to use a material with a low dielectric constant and water absorption that does not bond directly. It is preferable to fill the voids by adding a low molecular weight compound. The content can be determined by first preparing a composition for a low dielectric component that does not contain unbound polymerizable compounds, measuring its porosity, and adding an amount of the polymer compound that can fill the porosity. desirable.
<重合開始剤>
本発明の低誘電部材用組成物は重合開始剤を構成要素としてもよい。重合開始剤は、低誘電部材用組成物の重合方法に応じて、たとえば光ラジカル重合開始剤、光カチオン重合開始剤、熱ラジカル重合開始剤などを用いればよい。
<Polymerization initiator>
The composition for a low dielectric member of the present invention may include a polymerization initiator as a component. The polymerization initiator may be, for example, a photo-radical polymerization initiator, a photo-cationic polymerization initiator, a thermal radical polymerization initiator, etc., depending on the polymerization method of the composition for a low dielectric member.
光ラジカル重合開始剤としては、特に限定されず、公知のものを使用することができ、
たとえば、4-メトキシフェニル-2,4-ビス(トリクロロメチル)トリアジン、2-(4-ブトキシスチリル)-5-トリクロロメチル-1,3,4-オキサジアゾール、9-フェニルアクリジン、9,10-ベンズフェナジン、ベンゾフェノン/ミヒラーズケトン混合物、アゾビスイソブチロニトリル(AIBN)、ヘキサアリールビイミダゾール/メルカプトベンズイミダゾール混合物、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、ベンジルジメチルケタール、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、2,4-ジエチルキサントン/p-ジメチルアミノ安息香酸メチル混合物、ベンゾフェノン/メチルトリエタノールアミン混合物などが挙げられる。市販のものとしては、たとえば、チバ・スペシャリティー(株)製商品名「ダロキュアーシリーズ1173、4265」、「イルガキュアーシリーズ184、369、500、651、784、819、907、1300、1700、1800、1850、2959」、富士フイルム和光純薬工業(株)製商品名「V―59、V-65、V-70、V―601、AIBN-HP」などが挙げられる。
The photoradical polymerization initiator is not particularly limited, and known ones can be used.
For example, 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10 - Benzphenazine, benzophenone/Michler's ketone mixture, azobisisobutyronitrile (AIBN), hexaarylbiimidazole/mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/methyltriethanol Examples include amine mixtures. Commercially available products include, for example, Ciba Specialty Co., Ltd. under the trade name "DaroCure Series 1173, 4265", "IrgaCure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800". , 1850, 2959'', product names ``V-59, V-65, V-70, V-601, AIBN-HP'' manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., and the like.
光カチオン重合開始剤としては、特に限定されず、公知のものを使用することができ、たとえば、UCC(株)製商品名「サイラキューアーUVI-6990、6974」、(株)ADEKA製商品名「アデカオプトマーSP-150、152、170、172」、ローディア(株)製商品名「Photoinitiator 2074」、チバ・スペシャリティー(株)製商品名「イルガキュアー250」、みどり化学(株)製商品名「DTS-102」などが挙げられる。 The photocationic polymerization initiator is not particularly limited, and known ones can be used, such as "Cyracure UVI-6990, 6974" (trade name, manufactured by UCC Co., Ltd.), and trade name (trade name, manufactured by ADEKA Co., Ltd.). "ADEKA OPTOMER SP-150, 152, 170, 172", product name "Photoinitiator 2074" manufactured by Rhodia Co., Ltd., product name "Irgacure 250" manufactured by Ciba Specialty Co., Ltd., product manufactured by Midori Kagaku Co., Ltd. Examples include the name "DTS-102".
熱ラジカル重合開始剤の好ましい例としては、たとえば、過酸化ベンゾイル、ジイソプロピルパーオキシジカーボネート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシピバレート、ジ-t-ブチルパーオキシド(DTBPO)、t-ブチルパーオキシジイソブチレート、過酸化ラウロイル、2,2’-アゾビスイソ酪酸ジメチル(MAIB)、アゾビスイソブチロニトリル(AIBN)、アゾビスシクロヘキサンカルボニトリル(ACN)などが挙げられる。
Preferred examples of the thermal radical polymerization initiator include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxydicarbonate, and di-t-butylperoxydicarbonate. oxide (DTBPO), t-butylperoxydiisobutyrate, lauroyl peroxide,
アニオン重合、配位重合およびリビング重合用の好ましい開始剤としては、たとえば、n-C4H9Li、t-C4H9Li、R3Alなどのアルカリ金属アルキル化合物、アルミニウム化合物、遷移金属化合物などが挙げられる。
<硬化剤>
低誘電部材用組成物が、環状エーテル基を有する化合物を構成要素とする場合、硬化剤を構成要素として含有してもよい。好ましい硬化剤の例を以下に示す。
Preferred initiators for anionic, coordination and living polymerizations include, for example, alkali metal alkyl compounds such as n-C 4 H 9 Li, t-C 4 H 9 Li, R 3 Al, aluminum compounds, transition metals, etc. Examples include compounds.
<Curing agent>
When the composition for a low dielectric member contains a compound having a cyclic ether group as a constituent element, it may contain a curing agent as a constituent element. Examples of preferred curing agents are shown below.
アミン系硬化剤として、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、o-キシレンジアミン、m-キシレンジアミン、p-キシレンジアミン、トリメチルヘキサメチレンジアミン、2-メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン、イソホロンジアミン、1,3-ビスアミノメチルシクロヘキサン、ビス(4-アミノ-3-メチルシクロヘキシル)メタン、ビス(4-アミノシクロヘキシル)メタン、ノルボルネンジアミン、1,2-ジアミノシクロヘキサン、3,9-ジプロパンアミン-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-1,2-ジフェニルエタン、o-フェニレンジアミン、m-フェニレンジアミン、p-フェニレンジアミン、4,4’-ジアミノジフェニルスルホン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、ポリシクロヘキシルポリアミン、N-アミノエチルピペラジンなどが挙げられる。 As an amine curing agent, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-xylenediamine, m-xylenediamine, p-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine , 1,3-bisaminomethylcyclohexane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, 3,9-dipropanamine- 2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, o-phenylenediamine, m-phenylenediamine, Examples include p-phenylenediamine, 4,4'-diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine, and N-aminoethylpiperazine.
酸無水物系硬化剤として、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルナジック酸無水物、水素化メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、メチルシクロヘキセンテトラカルボン酸二無水物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物、エチレングリコールビスアンヒドロトリメチレート、グリセリンビス(アンヒドロトリメリテート)モノアセテート、デデセニル無水コハク酸、クロレンド酸無水物などが挙げられる。 As acid anhydride curing agents, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride Acid, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydrotrimethylate, glycerin bis(anhydrotrimellitate) ) monoacetate, dedecenyl succinic anhydride, chlorendic anhydride, etc.
フェノール系硬化剤として、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、2,3-キシレノール、2,5-キシレノール、2,6-キシレノール、3,4-キシレノール、3,5-キシレノール、m-エチルフェノール、p-エチルフェノール、2,3,5-トリメチルフェノール、2,3,6-トリメチルフェノール、o-イソプロピルフェノール、p-tert-ブチルフェノール、o-sec-ブチルフェノール、p-オクチルフェノール、2,6-ジ-tert-ブチルフェノール、レゾルシノール、1-ナフトール、2-ナフトール、ビスフェノールA、フェノールノボラック、キシリレンノボラック、ビスフェノールAノボラックなどが挙げられる。
上記以外にも特開2004-256687号公報、特開2002-226550号公報などに記載されている硬化剤も使用することができる。
As a phenolic curing agent, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, m-ethylphenol, p-ethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, o-isopropylphenol, p-tert-butylphenol, o-sec-butylphenol, p-octylphenol, 2 , 6-di-tert-butylphenol, resorcinol, 1-naphthol, 2-naphthol, bisphenol A, phenol novolak, xylylene novolak, bisphenol A novolak, and the like.
In addition to the above, curing agents described in JP-A Nos. 2004-256687 and 2002-226550 can also be used.
活性エステル系硬化剤としては、特に限定されず、公知のものを使用することができ、たとえば、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物としてDIC(株)製商品名「HPC-8000H-65T」、ナフタレン構造を含む活性エステル化合物としてDIC(株)製商品名「EXB-8150-65T」、フェノールノボラックのアセチル化物を含む活性エステル化合物として三菱ケミカル(株)製商品名「DC808」、フェノールノボラックのベンゾイル化物を含む活性エステル化合物として三菱ケミカル(株)製商品名「YLH1026」、フェノールノボラックのアセチル化物である活性エステル系硬化剤として三菱ケミカル(株)製商品名「DC808」、フェノールノボラックのベンゾイル化物である活性エステル系硬化剤として三菱ケミカル(株)製商品名「YLH1026」などが挙げられる。 The active ester curing agent is not particularly limited, and any known one can be used. For example, as an active ester compound containing a dicyclopentadiene type diphenol structure, the product name "HPC-8000H-" manufactured by DIC Corporation is used. 65T", an active ester compound containing a naphthalene structure under the trade name "EXB-8150-65T" manufactured by DIC Corporation; an active ester compound containing an acetylated product of phenol novolak under the trade name "DC808" manufactured by Mitsubishi Chemical Corporation; phenol An active ester compound containing a benzoylated novolac is the product name "YLH1026" manufactured by Mitsubishi Chemical Corporation, an active ester curing agent that is an acetylated product of phenol novolac is "DC808" manufactured by Mitsubishi Chemical Corporation, and a product name of phenol novolac is "DC808". Examples of the active ester curing agent which is a benzoylated product include the product name "YLH1026" manufactured by Mitsubishi Chemical Corporation.
また、硬化促進剤として、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン(DBU)、1,5-ジアザビシクロ[4.3.0]-5-ノネン、5,6-ジブチルアミノ-1,8-ジアザビシクロ[5.4.0]-7-ウンデセン等のシクロアミジン化合物;該シクロアミジン化合物に無水マレイン酸、1,4-ベンゾキノン、2,5-トルキノン、1,4-ナフトキノン、2,3-ジメチルベンゾキノン、2,6-ジメチルベンゾキノン、2,3-ジメトキシ-5-メチル-1,4-ベンゾキノン、2,3-ジメトキシ-1,4-ベンゾキノン、フェニル-1,4-ベンゾキノン等のキノン化合物、ジアゾフェニルメタン、フェノール樹脂などのπ結合を有する化合物を付加してなる分子内分極を有する化合物;ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の3級アミン化合物;該3級アミン化合物の誘導体;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール等のイミダゾール化合物;該イミダゾール化合物の誘導体;トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス(4-メチルフェニル)ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物;該有機ホスフィン化合物に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合を有する化合物を付加してなる分子内分極を有するリン化合物;テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、2-エチル-4-メチルイミダゾールテトラフェニルボレート、N-メチルモルホリンテトラフェニルボレート等のテトラフェニルボロン塩;該テトラフェニルボロン塩の誘導体;トリフェニルホスホニウム-トリフェニルボラン、N-メチルモルホリンテトラフェニルホスホニウム-テトラフェニルボレート等のホスフィン化合物と該テトラフェニルボロン塩との付加物などが挙げられる。 In addition, as a curing accelerator, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene, 5,6-dibutylamino Cyclamidine compounds such as -1,8-diazabicyclo[5.4.0]-7-undecene; maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc. Compounds with intramolecular polarization obtained by adding compounds with π bonds such as quinone compounds, diazophenylmethane, and phenol resins; benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. Tertiary amine compounds; derivatives of said tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of said imidazole compounds; tributylphosphine, methyldiphenylphosphine, tri- Organic phosphine compounds such as phenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; Compounds having a π bond such as maleic anhydride, the above-mentioned quinone compounds, diazophenylmethane, and phenol resins are added to the organic phosphine compound. Phosphorus compounds with intramolecular polarization formed by addition; tetraphenylboron such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. Salts; derivatives of the tetraphenylboron salt; adducts of the tetraphenylboron salt with phosphine compounds such as triphenylphosphonium-triphenylborane, N-methylmorpholinetetraphenylphosphonium-tetraphenylborate, and the like;
<溶媒>
低誘電部材用組成物は溶媒を含有してもよい。重合させる必要がある構成要素を該組成物中に含む場合、重合は溶媒中で行っても、無溶媒で行ってもよい。溶媒を含有する該組成物を基板上に、例えばスピンコート法などにより塗布した後、溶媒を除去してから光重合させてもよい。また、光硬化後適当な温度に加温して熱硬化により後処理を行ってもよい。
好ましい溶媒としては、例えば、ベンゼン、トルエン、キシレン、メシチレン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、テトラヒドロフラン、γ-ブチロラクトン、N-メチルピロリドン、ジメチルホルムアミド、ジメチルスルホキシド、シクロヘキサン、メチルシクロヘキサン、シクロペンタノン、2-ブタノン、シクロヘキサノン、酢酸2-メトキシ-1-メチルエチル(PGMEA)などが挙げられる。上記溶媒は1種単独で用いても、2種以上を混合して用いてもよい。
なお、重合時の溶媒の使用割合を限定することにはあまり意味がなく、重合効率、溶媒コスト、エネルギーコストなどを考慮して、個々のケースごとに決定すればよい。
<Solvent>
The composition for a low dielectric member may contain a solvent. When the composition contains components that need to be polymerized, the polymerization may be carried out in a solvent or without a solvent. The composition containing a solvent may be applied onto a substrate by, for example, a spin coating method, and then the solvent may be removed and then photopolymerized. Further, after photocuring, post-treatment may be performed by heating to an appropriate temperature and thermally curing.
Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone. , 2-butanone, cyclohexanone, 2-methoxy-1-methylethyl acetate (PGMEA), and the like. The above solvents may be used alone or in combination of two or more.
Note that it is not very meaningful to limit the proportion of the solvent used during polymerization, and it may be determined for each individual case, taking into account polymerization efficiency, solvent cost, energy cost, and the like.
<その他>
低誘電部材用組成物には、取扱いを容易にするために、安定剤を添加してもよい。このような安定剤としては、公知のものを制限なく使用でき、例えば、ハイドロキノン、4-エトキシフェノールおよび3,5-ジ-t-ブチル-4-ヒドロキシトルエン(BHT)などが挙げられる。
さらに、低誘電部材用組成物の粘度や色を調整するために添加剤(酸化物等)を添加してもよい。例えば、白色にするための酸化チタン、黒色にするためのカーボンブラック、粘度を調整するためのシリカの微粉末を挙げることができる。また、機械的強度をさらに増すために添加剤を添加してもよい。例えば、ガラスファイバー、カーボンファイバー、カーボンナノチューブなどの無機繊維やクロス、または高分子添加剤として、ポリビニルホルマール、ポリビニルブチラール、ポリエステル、ポリアミド、ポリイミドなどの繊維または高分子を挙げることができる。
<Others>
A stabilizer may be added to the composition for a low dielectric member in order to facilitate handling. As such stabilizers, known stabilizers can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
Furthermore, additives (oxides, etc.) may be added to adjust the viscosity and color of the composition for low dielectric members. Examples include titanium oxide to make it white, carbon black to make it black, and fine silica powder to adjust viscosity. Additionally, additives may be added to further increase mechanical strength. For example, inorganic fibers and cloths such as glass fibers, carbon fibers, and carbon nanotubes, and polymer additives include fibers and polymers such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide.
<充填剤としての無機フィラー>
低誘電部材用組成物には、熱伝導率向上、機械強度向上、粘度調整などのために、充填剤(無機フィラー)を加えることができる。たとえば、熱伝導率の高い充填剤としては、特に限定されず、公知のものを使用することができ、窒化アルミニウム、窒化ホウ素、窒化珪素などの金属窒化物、ダイアモンド、黒鉛、炭化珪素などの炭化物、酸化マグネシウム、酸化アルミニウム、酸化亜鉛、酸化珪素、酸化チタン、酸化錫、酸化ホルミニウム、酸化カルシウムなどの金属酸化物、水酸化マグネシウム、水酸化アルミニウム、などの金属水酸化物、およびコーディエライト、またはムライトなどのケイ酸塩化合物、金、銀、銅、白金、鉄、錫、鉛、ニッケル、アルミニウム、マグネシウム、タングステン、モリブデン、ステンレスなどの金属充填剤であってもよい。好ましくは、誘電率が低い、窒化ホウ素、酸化ケイ素が好ましく、特に六方晶系の窒化ホウ素(h-BN)は誘電率が低く熱伝導率が高いので好ましい。市販のものとしては、たとえば誘電正接の低い粉末状フィラーとしては、デンカ(株)製商品名「デンカ溶融シリカFB-5D、GT130MC、GT5SDC」「デンカボロンナイトライドSGP、SP-2」、(株)アドマテックス製商品名「SO-C2、SO-E1」、MOMENTIVE社製商品名「MOMENTIVETM PTX25」、機械強度を付与するための低誘電ガラスクロスとしては日東紡績(株)製商品名「NEガラス2116、3313」などが挙げられる。
<Inorganic filler as filler>
A filler (inorganic filler) can be added to the composition for a low dielectric member in order to improve thermal conductivity, improve mechanical strength, adjust viscosity, and the like. For example, fillers with high thermal conductivity are not particularly limited, and any known filler can be used, such as metal nitrides such as aluminum nitride, boron nitride, and silicon nitride, and carbides such as diamond, graphite, and silicon carbide. , metal oxides such as magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, tin oxide, forminium oxide, calcium oxide, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and cordierite, Alternatively, it may be a silicate compound such as mullite, or a metal filler such as gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, or stainless steel. Preferred are boron nitride and silicon oxide, which have a low dielectric constant, and hexagonal boron nitride (h-BN) is particularly preferred because it has a low dielectric constant and high thermal conductivity. Commercially available powder fillers with low dielectric loss tangents include Denka Fused Silica FB-5D, GT130MC, GT5SDC, Denka Boron Nitride SGP, SP-2, manufactured by Denka Co., Ltd. ) Product name “SO-C2, SO-E1” manufactured by Admatex, product name “MOMENTIVETM PTX25” manufactured by MOMENTIVE, and “NE Glass” manufactured by Nitto Boseki Co., Ltd. as a low dielectric glass cloth for imparting mechanical strength. 2116, 3313'', etc.
充填剤の形状としては、球状、無定形、繊維状、棒状、筒状、板状、中空球状などが挙げられる。充填剤の形状は、重合性液晶化合物が液晶相を発現した際の配向を妨げない形状のものが好ましい。充填剤の種類、形状、大きさ、添加量などは、目的に応じて適宜選択できる。得られる低誘電成形体が絶縁性を必要とする場合、所望の絶縁性および誘電率、誘電損失が保たれれば導電性を有する充填剤であっても構わない。好ましくは、板状結晶の窒化ホウ素を用いると、または重合性液晶化合物が板状構造に垂直に配向され易い、または重合性液晶化合物が板状構造に沿って配向され易いため好ましい。垂直に配向するか、平板に沿って配向するかは、重合性液晶化合物と、フィラーの親和性に依存する。重合性液晶化合物と微粒径の球状の酸化ケイ素を用いると溶融物や溶液の粘度を上げることができ、ケイ酸塩化合物を用いると成形体の熱膨張率を小さくできるので好ましい。
低誘電率化のためには少しでも空気の含有率を高くしたほうが、比誘電率が低くなるので、中空状のシリカや、多孔質状のシリカ、ケイ酸塩などを使用することが好ましい。また、粘度やチクソ性を調整するためは球状、または球状のシリカを使用することが好ましい。機械強度を高くする場合は、繊維状のシリカまたはケイ酸塩ガラスを用いることが好ましい。
Examples of the shape of the filler include spherical, amorphous, fibrous, rod-like, cylindrical, plate-like, and hollow spherical shapes. The shape of the filler is preferably one that does not interfere with the orientation of the polymerizable liquid crystal compound when it develops a liquid crystal phase. The type, shape, size, amount added, etc. of the filler can be appropriately selected depending on the purpose. If the obtained low dielectric molded body requires insulation, a filler having electrical conductivity may be used as long as the desired insulation, dielectric constant, and dielectric loss are maintained. It is preferable to use boron nitride in the form of plate-like crystals, or because the polymerizable liquid crystal compound is likely to be oriented perpendicularly to the plate-like structure, or the polymerizable liquid crystal compound is likely to be oriented along the plate-like structure. Whether to align vertically or along a flat plate depends on the affinity between the polymerizable liquid crystal compound and the filler. It is preferable to use a polymerizable liquid crystal compound and a spherical silicon oxide having a fine particle size to increase the viscosity of the melt or solution, and to use a silicate compound to reduce the coefficient of thermal expansion of the molded product.
In order to lower the dielectric constant, increasing the air content even a little lowers the relative dielectric constant, so it is preferable to use hollow silica, porous silica, silicate, or the like. Further, in order to adjust the viscosity and thixotropy, it is preferable to use spherical or spherical silica. When increasing mechanical strength, it is preferable to use fibrous silica or silicate glass.
球状または不定形状の充填剤の平均粒径は、0.1~200μmであることが好ましい。より好ましくは、1~100μmである。0.1μm以上であると熱伝導率がよく、200μm以下であると充填率を上げることができる。繊維状の充填剤に関しては、繊維長が長いほど引張強度は向上するが、混錬や分散は困難となる場合があるので、用途によって選択することが好ましい。分散させる場合は、繊維状充填剤の平均粒径は、0.01~200μmであることが好ましい。より好ましくは、0.1~100μmである。0.1μm以上であると熱伝導率がよく、200μm以下であると機械強度を上げることができる。
なお、本明細書において平均粒径とは、レーザー回折・散乱法による粒度分布測定に基づく。すなわち、フランホーファー回折理論およびミーの散乱理論による解析を利用して、湿式法により、粉体をある粒子径から2つに分けたとき、大きい側と小さい側が等量(体積基準)となる径をメジアン径とした。
充填剤の量は、硬化後の低誘電成形体中が5~90体積%の充填剤を含有するようにすることが好ましい。より好ましくは、20~80体積%である。20体積%以上であると高熱伝導フィラーの場合は熱伝導率が高くなり、低誘電正接フィラーの場合は誘電正接が低くなるので好ましい。80体積%以下であると低誘電成形体が脆くならず好ましい。
The average particle size of the spherical or irregularly shaped filler is preferably 0.1 to 200 μm. More preferably, it is 1 to 100 μm. If it is 0.1 μm or more, the thermal conductivity is good, and if it is 200 μm or less, the filling rate can be increased. Regarding the fibrous filler, the longer the fiber length, the better the tensile strength, but it may be difficult to knead and disperse, so it is preferable to select it depending on the application. When dispersed, the average particle size of the fibrous filler is preferably 0.01 to 200 μm. More preferably, it is 0.1 to 100 μm. If it is 0.1 μm or more, the thermal conductivity is good, and if it is 200 μm or less, the mechanical strength can be increased.
Note that in this specification, the average particle diameter is based on particle size distribution measurement using a laser diffraction/scattering method. In other words, when a powder is divided into two parts based on a certain particle size using the wet method using analysis based on Frahnhofer diffraction theory and Mie's scattering theory, the diameter at which the larger and smaller sides are equal (based on volume) is determined. was taken as the median diameter.
The amount of the filler is preferably such that the cured low dielectric molded article contains 5 to 90% by volume of the filler. More preferably, it is 20 to 80% by volume. If it is 20% by volume or more, the thermal conductivity will be high in the case of a high thermal conductivity filler, and the dielectric loss tangent will be low in the case of a low dielectric loss tangent filler, which is preferable. When the content is 80% by volume or less, the low dielectric molded body does not become brittle, which is preferable.
[低誘電樹脂]
本発明の別の実施形態である低誘電樹脂は、上述の低誘電部材用組成物の硬化物であり、低誘電部材としてシート状、フィルム状、板状、繊維状、三次元形状の部品(コネクターの絶縁部分)などに用いられるほか、そのままコート剤、接着剤や充填剤として使用することもできる。該低誘電樹脂は、上述の組成物の硬化物であるために低い誘電率を有するとともに、ポリマーとして重合性液晶化合物の重合体を用いている場合、熱伝導率、耐熱性、剛性、弾性、成形流動性、耐薬品性、及び寸法安定性等にも優れる。
[Low dielectric resin]
The low dielectric resin, which is another embodiment of the present invention, is a cured product of the above-mentioned composition for low dielectric members, and is used as a low dielectric member in the form of sheets, films, plates, fibers, three-dimensional shapes ( In addition to being used as insulation parts of connectors, etc., it can also be used as is as a coating agent, adhesive, or filler. The low dielectric resin has a low dielectric constant because it is a cured product of the above-mentioned composition, and when a polymer of a polymerizable liquid crystal compound is used as the polymer, it has good thermal conductivity, heat resistance, rigidity, elasticity, It also has excellent molding fluidity, chemical resistance, and dimensional stability.
<製造方法>
以下、低誘電部材用組成物を製造する方法、および該組成物から低誘電高耐熱基板および、低誘電高耐熱絶縁層を製造する方法について具体的に説明する。
<Manufacturing method>
Hereinafter, a method for producing a composition for a low dielectric member, and a method for producing a low dielectric, high heat resistant substrate and a low dielectric, high heat resistant insulating layer from the composition will be specifically described.
本発明の低誘電部材用組成物は、そのまま溶媒に溶解させて使用することもできる。溶液の調製は、2官能以上のシルセスキオキサン、硬化成分、必要に応じて重合性液晶化合物、溶媒、フィラー、添加剤などを加え、撹拌機を用いて組成ムラが無くなる程度まで撹拌・脱泡する。例えば、自転公転ミキサーを用い、回転数2000rpmで10分間撹拌後、回転数2200rpmで10分間脱泡する。自転公転ミキサーの他には、攪拌モーター、らいかい機、三本ロール、ボールミル、自転・公転ミル、遊星ミル、ビーズミル、ジェットミル等を用いて分散させることができる。 The composition for a low dielectric member of the present invention can also be used as it is dissolved in a solvent. To prepare the solution, add difunctional or higher functional silsesquioxane, curing component, polymerizable liquid crystal compound, solvent, filler, additives, etc. as necessary, and stir and remove using a stirrer until the composition is uniform. foam. For example, using a rotation/revolution mixer, the mixture is stirred for 10 minutes at a rotation speed of 2000 rpm, and then defoamed for 10 minutes at a rotation speed of 2200 rpm. In addition to an autorotation/revolution mixer, a stirring motor, a sieve machine, a three-roll mill, a ball mill, an autorotation/revolution mill, a planetary mill, a bead mill, a jet mill, etc. can be used for dispersion.
塗布方法には、低誘電部材用組成物を均一にコーティングするために、ウェットコーティング法を用いることが好ましい。ウェットコーティング法のうち、少量を作製する場合には簡便で均質な製膜が可能であるスピンコート法が好ましい。生産性を重視する場合には、グラビアコート法、ダイコート法、バーコート法、リバースコート法、ロールコート法、スリットコート法、ディッピング法、スプレーコート法、キスコート法、リバースキスコート法、エアーナイフコート法、カーテンコート法、インクジェット法、フレキソ印刷法、スクリーン印刷法、ロッドコート法などが好ましい。ウェットコーティング法は、これらの方法から必要とする膜厚、粘度や硬化条件等に応じて適宜選択することができる。 As the coating method, it is preferable to use a wet coating method in order to uniformly coat the composition for a low dielectric member. Among the wet coating methods, when producing a small amount, the spin coating method is preferable because it is simple and allows formation of a homogeneous film. When productivity is important, gravure coating method, die coating method, bar coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air knife coating Preferred methods include method, curtain coating method, inkjet method, flexo printing method, screen printing method, and rod coating method. The wet coating method can be appropriately selected from these methods depending on the required film thickness, viscosity, curing conditions, etc.
シートを製造する場合には、低誘電部材用組成物溶液を用いて離型処理した基材上に該組成物溶液を前記方法などでコーティングし剥離するキャスト法、構造物を製造する場合には原料粉末の混合物や、予め一部の重合性基を反応させプレポリマー化した樹脂を、金型を用い、プレス成形法、インジェクション法、各種3Dプリンター成形法(吐出積層法)などの樹脂成形法を用いることができる。成形後、金型を外して本硬化することも、金型に入れたまま本硬化することも可能である。 When manufacturing sheets, a casting method is used, in which a composition solution for low dielectric members is coated on a base material that has been subjected to mold release treatment using the method described above, and then peeled off, and when manufacturing structures. Resin molding methods such as press molding method, injection method, various 3D printer molding methods (discharge lamination method), etc. using a mold using a mixture of raw material powder or a resin that has been made into a prepolymer by reacting some polymerizable groups in advance. can be used. After molding, it is possible to remove the mold and carry out the main curing, or to carry out the main curing while remaining in the mold.
以下に、実施例を用いて、本発明を詳細に説明する。しかし本発明は、以下の実施例に記載された内容に限定されるものではない。 The present invention will be explained in detail below using examples. However, the present invention is not limited to what is described in the following examples.
本発明の実施例に用いた、低誘電部材を構成する材料は次のとおりである。 The materials constituting the low dielectric member used in the examples of the present invention are as follows.
<重合性シルセスキオキサン化合物(2官能以上のシルセスキオキサン)>
・シルセスキオキサン1:下記式(1-1)で表される化合物(JNC(株)製)
式(1-1)において、Meはメチルを示し、Phはフェニルを示す。
<Polymerizable silsesquioxane compound (bifunctional or higher functional silsesquioxane)>
・Silsesquioxane 1: Compound represented by the following formula (1-1) (manufactured by JNC Corporation)
In formula (1-1), Me represents methyl and Ph represents phenyl.
・シルセスキオキサン3:下記式(2-1)で表される化合物(JNC(株)製)
式(2-1)において、Meはメチルを示し、Phはフェニルを示す。
・Silsesquioxane 3: Compound represented by the following formula (2-1) (manufactured by JNC Corporation)
In formula (2-1), Me represents methyl and Ph represents phenyl.
・シルセスキオキサン5:下記式(2-3)で表される化合物(JNC(株)製)
式(2-3)において、Meはメチルを示す。
・Silsesquioxane 5: Compound represented by the following formula (2-3) (manufactured by JNC Corporation)
In formula (2-3), Me represents methyl.
・シルセスキオキサン6:下記式(2-4)で表される化合物(JNC(株)製)
式(2-4)において、Meはメチルを示す。
・Silsesquioxane 6: Compound represented by the following formula (2-4) (manufactured by JNC Corporation)
In formula (2-4), Me represents methyl.
・シルセスキオキサン7:下記式(2-5)で表される化合物(JNC(株)製)
式(2-5)において、Meはメチルを示し、Phはフェニルを示す。
・Silsesquioxane 7: Compound represented by the following formula (2-5) (manufactured by JNC Corporation)
In formula (2-5), Me represents methyl and Ph represents phenyl.
<硬化促進剤、開始剤>
・イミダゾール系硬化剤:2-エチル-4-メチルイミダゾール(2E4MZ)(東京化成工業(株)製商品名)
・リン系硬化促進剤:TBP-3S(北興化学工業(株)製商品名)
・アゾ系光硬化開始剤:V-601(富士フイルム和光純薬(株)製商品名)
・過酸化物系架橋剤:パーブチルP(日油(株)製商品名)
<Curing accelerator, initiator>
・Imidazole curing agent: 2-ethyl-4-methylimidazole (2E4MZ) (trade name manufactured by Tokyo Kasei Kogyo Co., Ltd.)
・Phosphorus curing accelerator: TBP-3S (trade name manufactured by Hokuko Chemical Industry Co., Ltd.)
・Azo photocuring initiator: V-601 (product name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Peroxide crosslinking agent: Perbutyl P (product name manufactured by NOF Corporation)
<その他重合性化合物>
・アミン系硬化剤:4,4’-ジアミノ-1,2-ジフェニルエタン(DDM)(富士フイルム和光純薬(株)製商品名)
・活性エステル系硬化剤:HPC-8000-65T(DIC(株)製商品名)
・反応性ポリフェニレンエーテルオリゴマー(両末端水酸基):ノリルSA90(SABIC(合)製商品名)
・反応性ポリフェニレンエーテルオリゴマー(両末端メタクリル基):ノリルSA9000(SABIC(合)製商品名)
・ビスマレイミド化合物:BМI-80(ケイ・アイ化成(株)製商品名)
・ビフェニル1:下記式(H-1)で表される化合物(JNC(株)製)
・ビフェニル型エポキシ樹脂:エピコートYX4000H(三菱ケミカル(株)製商品名)
・ビスフェノールF型エポキシ樹脂:jER807(三菱ケミカル(株)製商品名)
<Other polymerizable compounds>
・Amine curing agent: 4,4'-diamino-1,2-diphenylethane (DDM) (product name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Active ester curing agent: HPC-8000-65T (product name manufactured by DIC Corporation)
・Reactive polyphenylene ether oligomer (hydroxyl groups at both ends): Noryl SA90 (product name manufactured by SABIC (G))
・Reactive polyphenylene ether oligomer (methacrylic groups at both ends): Noryl SA9000 (trade name manufactured by SABIC (G))
・Bismaleimide compound: BМI-80 (trade name manufactured by K.I. Kasei Co., Ltd.)
・Biphenyl 1: Compound represented by the following formula (H-1) (manufactured by JNC Co., Ltd.)
・Biphenyl-type epoxy resin: Epicote YX4000H (product name manufactured by Mitsubishi Chemical Corporation)
・Bisphenol F type epoxy resin: jER807 (product name manufactured by Mitsubishi Chemical Corporation)
[実施例1]
<低誘電部材の調製>
以下に、低誘電部材の調製例を示す。
・低誘電部材用組成物溶液の準備
オキシラニルが開環していないものとし、オキシラニル基と硬化剤の水酸基の当量を合わせるように、シルセスキオキサン1を0.4503g、SA90を0.8530g、それぞれ測りとり、ガラス製の20mlスクリューキャップ瓶に投入した。その瓶に、固形分濃度が約50重量%になるように酢酸エチル1.38gを入れ、キャップをした後、ドライインキュベータで50℃にて3時間加温した。そのまま1夜室温で静置した後、2E4MZの10重量%酢酸エチル溶液を固形分100重量部に対し開始剤が2重量部になるように添加し、小型ボールミル台を用い1時間回転により攪拌し、原料溶液とした。
[Example 1]
<Preparation of low dielectric member>
An example of preparing a low dielectric member is shown below.
・Preparation of composition solution for low dielectric member Assuming that oxiranyl is not ring-opened, add 0.4503 g of
・誘電率測定用サンプルの作製
図2に示したとおり離型処理を行ったポリイミドフィルム(ニッパ(株)製J-2)に10mm幅で130μmの厚みの耐熱マスキングテープを2枚重ねにしたスペーサーを10cmの正方形状に貼りつけ、50℃に設定したホットプレートに載せ、スペーサーの内側にスポイトを用いて前記溶液を5cm×5cmの領域に全量滴下した。このまま1時間ホットプレート上で静置した後、更に真空乾燥機中50℃で3時間乾燥させ、さらに50℃の熱風乾燥機で1晩乾燥させた。
・Preparation of sample for permittivity measurement As shown in Figure 2, a spacer made of a polyimide film (J-2 manufactured by Nipper Co., Ltd.) that has been subjected to mold release treatment and two layers of heat-resistant masking tape with a width of 10 mm and a thickness of 130 μm. was pasted in a 10 cm square shape, placed on a hot plate set at 50°C, and the entire amount of the solution was dropped onto an area of 5 cm x 5 cm using a dropper inside the spacer. After leaving this as it was on a hot plate for 1 hour, it was further dried at 50° C. in a vacuum dryer for 3 hours, and further dried in a hot air dryer at 50° C. overnight.
・誘電率測定用のサンプルは50~200μmの厚みが必要なので、通常の絶縁膜よりかなり厚みを持たせないといけない。そのため、本検討では乾燥前の厚みは500μm程度の厚みになってしまうので、液の表面から溶媒が乾燥し、内部に溶媒が残ってしまうので、真空乾燥時にカルメ焼き状に発泡した。発泡した状態のまま上面にも離型剤付きポリイミドフィルムを載せ、その上下を2mm厚のアルミ板で挟み、120℃にセットした東洋精機株式会社製ミニテストプレスにセットし、脱気しながら最終的に10MPaまで加圧し、175℃まで加温したのち60分硬化させた。120℃から200℃に昇温する際は、乾燥サンプルが融解または軟化すると簡易型内を樹脂が流動するので、見かけの厚みが減り、結果として圧力が下がる。融解または軟化を確認した後、加圧→減圧を繰り返し、樹脂内の脱気を行った。
実施例1の検討では、誘電特性を測定するために厚いサンプルを作製しないといけないので発泡してしまったが、たとえば同じ樹脂組成でアミノ系シランカップリング剤を1重量%添加した溶液を用い、スピンコート法でアルミ基板上に数μmの厚みの絶縁膜を形成するような場合には、この発泡現象は観察されず綺麗な膜が得られている。
・Since the sample for dielectric constant measurement needs to be 50 to 200 μm thick, it must be much thicker than a normal insulating film. Therefore, in this study, the thickness before drying was about 500 μm, so the solvent dried from the surface of the liquid and remained inside, resulting in foaming in a carme-like shape during vacuum drying. A polyimide film with a mold release agent was placed on the top of the foamed state, and the top and bottom were sandwiched between 2 mm thick aluminum plates, and the film was placed in a mini test press made by Toyo Seiki Co., Ltd. set at 120°C, and the final product was degassed. Specifically, the pressure was increased to 10 MPa, heated to 175° C., and then cured for 60 minutes. When the temperature is raised from 120° C. to 200° C., when the dried sample melts or softens, the resin flows inside the simple mold, reducing the apparent thickness and, as a result, lowering the pressure. After confirming melting or softening, the resin was degassed by repeating pressurization and then depressurization.
In the study of Example 1, foaming occurred because a thick sample had to be prepared to measure the dielectric properties. When an insulating film several μm thick is formed on an aluminum substrate by spin coating, this bubbling phenomenon is not observed and a clean film is obtained.
<誘電特性の評価方法>
ベクトルネットワークアナライザー(アンリツ社製MS46522B-043型)に接続した、AET社製の空洞共振器(TEモード10GHz用、28GHz用)を用いて、測定用試料の、共振周波数のシフト量と減衰量を測定し、同社製ソフトウエアを用いて比誘電率(Dk)および誘電正接(Df)を計算した。データの比較時に短冊中の水分量の影響を少なくするために、相対湿度10%に設定した電子デシケーター内で1日静置し、誘電特性の評価は温度20℃にエアコンを設定した実験室で、サンプルを60分以上静置したあとで開始した。また、本サンプルは1cm角程度よりも大きくなると硬化収縮により膜にひびが入ってしまったためポリイミドフィルムから剥がさずに測定し、別途ポリイミドフィルムのみの誘電特性を測定し、AET社製の表計算シートを用いて、サンプル層のみの誘電特性を求めた。また、膜厚が厚いので柔軟性が低いサンプルではクラックが入るものが存在したが、隙間ができていない場合は誘電特性の測定にはほぼ影響はないので、そのまま測定した。一方、大きなボイドが入っているサンプルや、粉末のままの部分が残ったサンプルなどは、誘電特性の評価時に与える影響が大きいので、その部分を避けて測定した。
<Evaluation method of dielectric properties>
Using a cavity resonator manufactured by AET (for TE mode 10 GHz and 28 GHz) connected to a vector network analyzer (Model MS46522B-043 manufactured by Anritsu), the amount of shift and attenuation of the resonant frequency of the measurement sample was measured. The dielectric constant (Dk) and the dielectric loss tangent (Df) were calculated using the company's software. In order to reduce the influence of moisture content in the strips when comparing data, the strips were allowed to stand for one day in an electronic desiccator set at a relative humidity of 10%, and the dielectric properties were evaluated in a laboratory with an air conditioner set at a temperature of 20°C. , after the sample had been allowed to stand for at least 60 minutes. In addition, when this sample was larger than about 1 cm square, the film cracked due to curing shrinkage, so we measured it without removing it from the polyimide film, and separately measured the dielectric properties of the polyimide film alone. The dielectric properties of only the sample layer were determined using . In addition, some samples with low flexibility due to their thick films had cracks, but if there were no gaps, there was almost no effect on the measurement of dielectric properties, so measurements were carried out as they were. On the other hand, samples with large voids or samples with remaining powder parts have a large effect on the evaluation of dielectric properties, so these parts were avoided during measurement.
[実施例2]~[実施例9]
表1に示したように、2官能以上のシルセスキオキサン、硬化剤、開始剤、溶媒を変えた以外は実施例1と同様にサンプル作製を行い、誘電特性を評価した。
[Example 2] to [Example 9]
As shown in Table 1, samples were prepared in the same manner as in Example 1, except that the difunctional or higher functional silsesquioxane, curing agent, initiator, and solvent were changed, and the dielectric properties were evaluated.
[実施例10]
本硬化をUV硬化で行うために、溶液調製は表1に示したように、2官能以上のシルセスキオキサン、硬化剤、開始剤、溶媒を変えた以外は実施例1と同様に行い、バーコーターを用いてウエット状態での膜厚が100μmになるように製膜し、真空乾燥を行った。この際、アゾ系開始剤の熱分解が始まらないために溶媒の乾燥及び予備硬化は50℃を超えないように真空乾燥器を用いて行った。得られた未硬化膜付のポリイミドフィルムを、石英ガラスの蓋が付いた光硬化実験用のステンレス容器に入れ、5分間窒素置換した後、100mJのUV光を照射し硬化させた。硬化後のサンプルの誘電特性を評価し、実施例10とした
[Example 10]
In order to carry out the main curing by UV curing, the solution was prepared in the same manner as in Example 1, except that the difunctional or higher functional silsesquioxane, curing agent, initiator, and solvent were changed, as shown in Table 1. A film was formed using a bar coater so that the film thickness in a wet state was 100 μm, and vacuum drying was performed. At this time, in order to prevent thermal decomposition of the azo initiator, drying and preliminary curing of the solvent were performed using a vacuum dryer so as not to exceed 50°C. The obtained polyimide film with an uncured film was placed in a stainless steel container for photocuring experiments with a quartz glass lid, and after replacing the container with nitrogen for 5 minutes, it was irradiated with 100 mJ of UV light to be cured. The dielectric properties of the sample after curing were evaluated and designated as Example 10.
[比較例1]~[比較例4]
表1に示したように、2官能以上のシルセスキオキサンを、有機モノマーやオリゴマーに、硬化剤、開始剤、溶媒を適宜変更した以外は実施例1と同様にサンプル作製を行い、誘電特性を評価した。
[Comparative Example 1] to [Comparative Example 4]
As shown in Table 1, samples were prepared in the same manner as in Example 1, except that the difunctional or higher-functional silsesquioxane was replaced with an organic monomer or oligomer, and the curing agent, initiator, and solvent were changed as appropriate. was evaluated.
<誘電特性評価結果>
各サンプルの硬化条件と誘電特性の測定結果を表2にまとめる。
<Dielectric property evaluation results>
Table 2 summarizes the curing conditions and dielectric property measurement results for each sample.
実施例1~3と比較例1を比較すると、OH基が末端の硬化剤を用いた場合には、本発明の2官能以上のシルセスキオキサンを含む組成物は、市販のビフェニル型エポキシ樹脂に比べ、比誘電率(Dk)、誘電正接(Df)とも大きく低下していることが分かる。実施例1と実施例2のサンプルはボイド構造ができやすく、作成しなおしても少し空隙が出来てしまい、そこに含まれる空気込みの誘電率であるが、空隙を含んでいてもよい用途では非常に誘電率の低い材料として使用可能である。
実施例4~5と比較例2を比較すると、アミン系硬化剤を使用した場合でも、本発明の2官能以上のシルセスキオキサンを含む組成物の方が、誘電率が低く、特に誘電正接が低いことが分かる。一般にエポキシとアミン系硬化剤の組み合わせは低誘電・低損失樹脂には向かないと言われているが、一般的なDDMを使用しても、かなり低い数字が得られており、低誘電向けの硬化剤を使用すれば、さらに特性が向上すると思われる。ただし、本実施例では2官能以上のシルセスキオキサンと硬化剤のみを重合させているため、フレキシブルさを発現する組成が無い。そのため、フレキシブル性のない膜になってしまい、一部のサンプルでは、10GHzの測定後28Ghzの測定のための加工をする際に、膜にクラックが入り、基材から剥がれ落ち測定ができなかった。硬い基板上に膜を形成する場合は、問題はないが、フレキシブル性が求められる用途では、第3成分としてアルキル、エーテル、ブタジエン系エラストマーなどの柔軟な構造を有する化合物を共重合させるのがよい。
そこで低誘電向けの硬化剤として注目を集めている活性エステル系硬化剤を試してみた(実施例8、9および比較例4)。活性エステル系の硬化剤は、重合条件が難しく、たとえば同じシルセスキオキサン5を用いた実施例4と実施例9を比較すると、誘電率の絶対値はDDMの方に分があるが、実施例9では10GHzよりも28GHzの方が、誘電特性が良好となっており、より高周波領域に強い材料であるといえる。通常、誘電特性は周波数が高くなるほど悪化すると言われており、特筆できる特性である。
また、低誘電率化のためには、エポキシ樹脂よりも、ラジカル硬化系の樹脂の方が、特性が良好と言われており、マレイミドやメタクリルなどの二重結合を有する重合性基が注目されている。その例として実施例6では両末端にマレイミド基を有するビスマレイミド化合物(BМI-80)を、実施例7ではラジカル反応性であるビニル基を有するシルセスキオキサン7と、メタクリル基を有する反応性ポリフェニレンエーテルオリゴマー(SA9000)とを組み合わせてみたところ、気泡を含まない実施例4~5よりも低誘電な樹脂が得られている。また、ラジカル反応性のためUV硬化も可能であり、実施例7から透明化のためにシルセスキオキサン成分を減らし開始剤を変更した実施例10でも、シルセスキオキサン成分が少なくなった分少し比誘電率が高くなっているが、十分に低誘電な組成物が得られている。
Comparing Examples 1 to 3 and Comparative Example 1, it is found that when a curing agent with an OH group at the end is used, the composition containing a bifunctional or more functional silsesquioxane of the present invention is a commercially available biphenyl-type epoxy resin. It can be seen that both the dielectric constant (Dk) and the dielectric loss tangent (Df) are significantly reduced compared to the above. The samples of Example 1 and Example 2 tend to have a void structure, and even if they are re-created, there are some voids, and the dielectric constant is based on the air contained therein, but in applications where voids can be included. It can be used as a material with extremely low dielectric constant.
Comparing Examples 4 and 5 with Comparative Example 2, even when an amine curing agent is used, the composition containing the difunctional or more functional silsesquioxane of the present invention has a lower dielectric constant, and especially a lower dielectric loss tangent. is found to be low. It is generally said that the combination of epoxy and amine curing agents is not suitable for low dielectric and low loss resins, but even when using general DDM, considerably low numbers have been obtained, and it is suitable for low dielectric materials. It is believed that the use of a curing agent would further improve the properties. However, in this example, only the bifunctional or higher functional silsesquioxane and the curing agent are polymerized, so there is no composition that exhibits flexibility. As a result, the film was not flexible, and in some samples, the film cracked during processing for 28 GHz measurement after 10 GHz measurement, and the film peeled off from the base material, making measurements impossible. . There is no problem when forming a film on a hard substrate, but for applications that require flexibility, it is better to copolymerize a compound with a flexible structure such as an alkyl, ether, or butadiene-based elastomer as the third component. .
Therefore, we tried active ester curing agents that are attracting attention as curing agents for low dielectric applications (Examples 8 and 9 and Comparative Example 4). The polymerization conditions for active ester-based curing agents are difficult. For example, when comparing Example 4 and Example 9 using the same silsesquioxane 5, DDM has a higher absolute value of dielectric constant, but In Example 9, the dielectric properties are better at 28 GHz than at 10 GHz, and it can be said that the material is stronger in the high frequency range. It is generally said that dielectric properties deteriorate as the frequency increases, and this is a characteristic that deserves special mention.
Furthermore, in order to lower the dielectric constant, radical curing resins are said to have better properties than epoxy resins, and polymerizable groups with double bonds such as maleimide and methacrylate are attracting attention. ing. As an example, in Example 6, a bismaleimide compound (BМI-80) having a maleimide group at both ends was used, and in Example 7, a radical-reactive silsesquioxane 7 having a vinyl group and a reactive compound having a methacrylic group were used. When combined with polyphenylene ether oligomer (SA9000), a resin with lower dielectricity than Examples 4 and 5, which does not contain bubbles, was obtained. In addition, UV curing is possible due to radical reactivity, and even in Example 10, in which the silsesquioxane component was reduced and the initiator was changed for transparency from Example 7, the amount of silsesquioxane component was reduced. Although the dielectric constant is a little high, a sufficiently low dielectric composition has been obtained.
以上のように、本発明の熱硬化性または光硬化性の重合性基を2個以上有する籠型のシルセスキオキサンと、硬化成分を含む低誘電部材用組成物は、10GHz以上の高周波を取り扱う電子デバイスや電子機器の絶縁部材として好適に使用できる。 As described above, the cage-shaped silsesquioxane having two or more thermosetting or photocurable polymerizable groups of the present invention and the composition for a low dielectric member containing a curing component can be used at high frequencies of 10 GHz or higher. It can be suitably used as an insulating member for electronic devices and equipment handled.
11 シルセスキオキサンユニット(構成単位)
12 高分子鎖
13 重合性部位
21 離型剤付きポリイミドシート(A5サイズ)
22 耐熱マスキングテープ(2枚重ね)
11 Silsesquioxane unit (structural unit)
12 Polymer chain 13
22 Heat-resistant masking tape (2 layers)
Claims (16)
請求項1に記載の低誘電部材用組成物。
[ここに、Rは独立して、炭素数1~45のアルキル、炭素数4~8のシクロアルキル、炭素数6~16のアリール、または炭素数7~16のアリールアルキルであり;炭素数1~45のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-または-CH=CH-で置き換えられてもよく;炭素数6~16のアリールおよび炭素数7~16のアリールアルキル中のベンゼン環において、少なくとも1つの水素はハロゲンまたは炭素数1~10のアルキルで置き換えられてもよく;この炭素数1~10のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-または-CH=CH-で置き換えられてもよく;炭素数7~16のアリールアルキル中のアルキレンにおいて、炭素原子の数は1~10であり、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、Y1はそれぞれ独立して式(a)で表される基である。]
[ここに、Xは独立して、シクロペンチル、シクロヘキシル、少なくとも1つの水素がフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-が-O-で置き換えられてもよい炭素数1~10のアルキル、少なくとも1つの水素がハロゲンもしくは炭素数1~10のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~10のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキル、またはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルもしくはアリルを有する基であり;フェニルの置換基である炭素数1~10のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;フェニルアルキルのアルキレンにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、Xの少なくとも1つはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、スクシンイミド残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基である。]
[ここに、Rは式(1)におけるRと同じ定義を有し、Y2は式(b)で表される基または式(c)で表される基である。]
[ここに、式(b)および式(c)のそれぞれにおいて、Xは式(a)におけるXと同じ定義を有し、そして式(c)におけるZは-O-、-CH2-または単結合である。] The difunctional or more functional silsesquioxane is a compound selected from the group of compounds represented by formula (1) and formula (2), respectively.
The composition for a low dielectric member according to claim 1.
[Here, R is independently alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 16 carbon atoms, or arylalkyl having 7 to 16 carbon atoms; In the alkyl of ~45, at least one hydrogen may be replaced by fluorine and at least one -CH 2 - may be replaced by -O- or -CH=CH-; In the benzene ring in aryl and arylalkyl having 7 to 16 carbon atoms, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; in this alkyl having 1 to 10 carbon atoms, at least one Hydrogen may be replaced by fluorine and at least one -CH 2 - may be replaced by -O- or -CH=CH-; in alkylene in arylalkyl having 7 to 16 carbon atoms, the carbon atom is from 1 to 10, and at least one -CH 2 - may be replaced by -O-; and each Y 1 is independently a group represented by formula (a). ]
[ wherein , alkyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms, and phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms; A group having phenylalkyl, oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, methacrylic, maleimide residue, vinyl or allyl consisting of ~4 alkylene; phenyl In the alkyl having 1 to 10 carbon atoms which is a substituent of , at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-; , at least one -CH 2 - may be replaced with -O-; and at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, methacryl , maleimide residue, vinyl or allyl group. ]
[Here, R has the same definition as R in formula (1), and Y 2 is a group represented by formula (b) or a group represented by formula (c). ]
[Here, in each of formula (b) and formula (c), X has the same definition as X in formula (a), and Z in formula (c) is -O-, -CH 2 - or a single It is a combination. ]
フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素がフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-が-O-で置き換えられてもよく;
Xが独立して、炭素数1~4のアルキル、炭素数1~4のフッ素化アルキル、シクロペンチル、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキル、またはオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルもしくはアリルを有する基であり、フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよく;そして、
請求項2に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの少なくとも1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基である、
請求項1に記載の低誘電部材用組成物。 In the formula (1) and formula (2) according to claim 2, the bifunctional or more functional silsesquioxane is such that R is independently cyclohexyl, at least one hydrogen is a halogen or a carbon number of 1 to 4. phenyl which may be substituted with alkyl, or phenylalkyl composed of phenyl, where at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, and alkylene having 1 to 4 carbon atoms;
In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-;
X is independently alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms; Phenylalkyl consisting of phenyl and alkylene having 1 to 4 carbon atoms, in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, or oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride A group having a residue, acrylic, methacrylic, maleimide residue, vinyl or allyl, and in the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least One -CH 2 - may be replaced by -O-; and
In each of formula (a), formula (b) and formula (c) according to claim 2, at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. is a group having a group, vinyl or allyl,
The composition for a low dielectric member according to claim 1.
フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-が-O-で置き換えられてもよく;
請求項2に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であって、残りのXが炭素数1~4のアルキル、炭素数1~4のフッ素化アルキル、シクロペンチル、シクロヘキシル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニル、少なくとも1つの水素がハロゲンもしくは炭素数1~4のアルキルで置き換えられてもよいフェニルと炭素数1~4のアルキレンとで構成されるフェニルアルキルであり;
フェニルの置換基である炭素数1~4のアルキルにおいて、少なくとも1つの水素はフッ素で置き換えられてもよく、そして少なくとも1つの-CH2-は-O-で置き換えられてもよい、
請求項1に記載の低誘電部材用組成物。 In the formula (1) and formula (2) according to claim 2, the bifunctional or more functional silsesquioxane is a compound in which R is cyclohexyl and at least one hydrogen is replaced with a halogen or an alkyl having 1 to 4 carbon atoms. phenyl, which may be substituted with phenyl, or phenyl, in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, and alkylene having 1 to 4 carbon atoms;
In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-;
In each of formula (a), formula (b) and formula (c) according to claim 2, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. , vinyl or allyl, where the remaining phenyl which may be substituted with alkyl, phenyl where at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, and phenylalkyl consisting of alkylene having 1 to 4 carbon atoms;
In the alkyl having 1 to 4 carbon atoms that is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced with -O-,
The composition for a low dielectric member according to claim 1.
請求項2に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であり、そして残りのXがメチル、エチル、t-ブチル、シクロペンチル、シクロヘキシルまたはフェニルである、
請求項1に記載の低誘電部材用組成物。 In the formula (1) and formula (2) according to claim 2, in the difunctional or more functional silsesquioxane, R is cyclohexyl or phenyl;
In each of formula (a), formula (b) and formula (c) according to claim 2, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. , vinyl or allyl, and the remaining X is methyl, ethyl, t-butyl, cyclopentyl, cyclohexyl or phenyl,
The composition for a low dielectric member according to claim 1.
請求項2に記載の式(a)、式(b)および式(c)のそれぞれにおいて、Xの1つがオキシラニル、3,4-エポキシシクロヘキシル、無水コハク酸残基、アクリル、メタクリル、マレイミド残基、ビニルまたはアリルを有する基であり、そして残りのXがメチルまたはフェニルである、
請求項1に記載の低誘電部材用組成物。 The bifunctional or more functional silsesquioxane is the formula (1) and formula (2) according to claim 2, wherein R is phenyl;
In each of formula (a), formula (b) and formula (c) according to claim 2, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. , vinyl or allyl, and the remaining X is methyl or phenyl,
The composition for a low dielectric member according to claim 1.
請求項1に記載の低誘電部材用組成物。ここで、式(1-1)において、Meはメチルを示し、Phはフェニルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (1-1),
The composition for a low dielectric member according to claim 1. Here, in formula (1-1), Me represents methyl and Ph represents phenyl.
請求項1に記載の低誘電部材用組成物。ここで、式(1-2)において、Meはメチルを示し、Phはフェニルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (1-2),
The composition for a low dielectric member according to claim 1. Here, in formula (1-2), Me represents methyl and Ph represents phenyl.
請求項1に記載の低誘電部材用組成物。ここで、式(2-1)において、Meはメチルを示し、Phはフェニルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (2-1),
The composition for a low dielectric member according to claim 1. Here, in formula (2-1), Me represents methyl and Ph represents phenyl.
請求項1に記載の低誘電部材用組成物。ここで、式(2-2)において、Meはメチルを示し、Phはフェニルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (2-2),
The composition for a low dielectric member according to claim 1. Here, in formula (2-2), Me represents methyl and Ph represents phenyl.
請求項1に記載の低誘電部材用組成物。ここで、式(2-3)において、Meはメチルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (2-3),
The composition for a low dielectric member according to claim 1. Here, in formula (2-3), Me represents methyl.
請求項1に記載の低誘電部材用組成物。ここで、式(2-4)において、Meはメチルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (2-4),
The composition for a low dielectric member according to claim 1. Here, in formula (2-4), Me represents methyl.
請求項1に記載の低誘電部材用組成物。ここで、式(2-5)において、Meはメチルを示し、Phはフェニルを示す。
The bifunctional or more functional silsesquioxane is a compound represented by formula (2-5),
The composition for a low dielectric member according to claim 1. Here, in formula (2-5), Me represents methyl and Ph represents phenyl.
高周波を発信、変換、伝達、および信号処理する能力からなる群から選択される少なくとも1つの能力を有する電子デバイスと;を備えた、
電子機器。 the low dielectric member according to claim 15;
an electronic device having at least one ability selected from the group consisting of the ability to transmit, convert, transmit, and process high frequencies;
Electronics.
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