CN117500880A - Resin composition, varnish, laminated plate, printed wiring board and molded article - Google Patents
Resin composition, varnish, laminated plate, printed wiring board and molded article Download PDFInfo
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- CN117500880A CN117500880A CN202280042315.5A CN202280042315A CN117500880A CN 117500880 A CN117500880 A CN 117500880A CN 202280042315 A CN202280042315 A CN 202280042315A CN 117500880 A CN117500880 A CN 117500880A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 119
- 239000002966 varnish Substances 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims abstract description 111
- 239000011347 resin Substances 0.000 claims abstract description 111
- -1 bismaleimide compound Chemical class 0.000 claims abstract description 107
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 46
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 26
- 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 claims description 26
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004643 cyanate ester Substances 0.000 claims description 5
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- NAKOELLGRBLZOF-UHFFFAOYSA-N phenoxybenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NAKOELLGRBLZOF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000000565 sealant Substances 0.000 abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 34
- 239000003822 epoxy resin Substances 0.000 description 30
- 229920000647 polyepoxide Polymers 0.000 description 30
- 238000002156 mixing Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000945 filler Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CXISKMDTEFIGTG-UHFFFAOYSA-N [4-(1,3-dioxo-2-benzofuran-5-carbonyl)oxyphenyl] 1,3-dioxo-2-benzofuran-5-carboxylate Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(OC=2C=CC(OC(=O)C=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)=O)=C1 CXISKMDTEFIGTG-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910001647 dawsonite Inorganic materials 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JDIPZHAYUYYGSN-UHFFFAOYSA-N (4-propylphenyl) cyanate Chemical compound CCCC1=CC=C(OC#N)C=C1 JDIPZHAYUYYGSN-UHFFFAOYSA-N 0.000 description 1
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ABLCFODXAYBNID-UHFFFAOYSA-N 2-heptyl-1h-imidazole Chemical compound CCCCCCCC1=NC=CN1 ABLCFODXAYBNID-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BGDOLELXXPTPFX-UHFFFAOYSA-N 3,4-dihydro-2h-1,2-benzoxazine Chemical compound C1=CC=C2ONCCC2=C1 BGDOLELXXPTPFX-UHFFFAOYSA-N 0.000 description 1
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- KWOIWTRRPFHBSI-UHFFFAOYSA-N 4-[2-[3-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=CC(C(C)(C)C=2C=CC(N)=CC=2)=CC=1C(C)(C)C1=CC=C(N)C=C1 KWOIWTRRPFHBSI-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DRWLKECFWWDHJL-UHFFFAOYSA-N C1(C=CC(N1)=O)=O.C1(C=CC(N1)=O)=O.NCCCCCCN Chemical compound C1(C=CC(N1)=O)=O.C1(C=CC(N1)=O)=O.NCCCCCCN DRWLKECFWWDHJL-UHFFFAOYSA-N 0.000 description 1
- FPSWAZLBKMJRPL-UHFFFAOYSA-N CCC.NC1=CC=C(OC2=CC=CC=C2)C=C1 Chemical compound CCC.NC1=CC=C(OC2=CC=CC=C2)C=C1 FPSWAZLBKMJRPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 229930003836 cresol Natural products 0.000 description 1
- LKPRJIJQUNSELI-UHFFFAOYSA-N cyanic acid triazine Chemical compound OC#N.C1=CN=NN=C1 LKPRJIJQUNSELI-UHFFFAOYSA-N 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
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- 230000004907 flux Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 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
- 239000006247 magnetic powder Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- JSHBSGZCGDOXSG-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic acid Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC(C(O)=O)=C(C(O)=O)C=C1OC1=C2C=C(C(O)=O)C(C(=O)O)=C1 JSHBSGZCGDOXSG-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/121—Preparatory processes from unsaturated precursors and polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
- C08L45/02—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of coumarone-indene polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The resin composition of the present invention is obtained by melting a resin mixture containing (a) a bismaleimide compound containing an aliphatic bismaleimide compound represented by the formula (1) and an aromatic bismaleimide compound represented by the formula (2), and is a cured product that has high heat resistance and low dielectric characteristics (low relative permittivity, low dielectric loss tangent) in electronic and electric parts, and is used as a laminate, a printed wiring board, an adhesive, a sealant, a coating material, a molded article, and the like. (in the formula (1), R 1 Is an alkylene group having 6 to 12 carbon atoms. ) (in the formula (2), R 2 Is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms; x is X 1 Each independently an oxygen atom or a single bond; r is R 3 R is R 4 A hydrocarbon group having 1 to 6 carbon atoms; a and b are integers of 0 to 3 inclusive. )
Description
Technical Field
The present invention relates to a resin composition having low dielectric characteristics (low relative permittivity, low dielectric loss tangent) and used as a laminate, a printed wiring board, an adhesive, a sealant, a coating material, a molded article, etc. in electronic and electric parts.
Background
Thermosetting resins such as epoxy resins, polyimide resins, unsaturated polyester resins, and phenol resins have been used as heat-resistant resins in the field of electronic materials. These thermosetting resins are used differently according to their uses and properties. Among them, polyimide resins are widely used for applications requiring high heat resistance, because of their excellent heat resistance and wet heat resistance (heat resistance after moisture absorption). In addition, a modified polyimide resin having improved properties by a combination of other resins such as an epoxy resin and a polyimide resin is also used.
In the field of semiconductor substrates, a mounting method for directly mounting a semiconductor chip on a substrate is becoming popular. Therefore, a material used for a semiconductor is required to have high heat resistance capable of withstanding high temperature treatment or the like in a mounting process. Epoxy resins are widely used as semiconductor materials, and have been studied to meet the demand for improvement in heat resistance, and resins excellent in heat resistance have been proposed. For example, patent document 1 describes a resin composition obtained by melting a component containing a polymaleimide compound.
Prior art literature
Patent literature
Patent document 1: international publication No. WO2020/161926
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the increase in performance, capacity and speed of various electronic devices, further increase in frequency of electric signals has been advanced. The high frequency of the electric signal is advantageous for the high speed and large capacity of communication, but on the other hand, there is a concern that the reliability is lowered due to the attenuation of the signal caused by the increase of dielectric loss. Therefore, as a characteristic of a resin composition for a substrate suitable for next-generation communication to cope with high frequency, further improvement of low dielectric characteristics is demanded.
Accordingly, an object of the present invention is to provide a resin composition containing a bismaleimide compound, which further improves low dielectric characteristics. Further, it is an object of the present invention to provide a resin composition containing a bismaleimide compound which is excellent in solubility in a low-boiling solvent and curability and has excellent handleability.
Technical means for solving the problems
The resin composition of the present invention is obtained by melting a resin mixture containing (a) a bismaleimide compound, characterized in that the (a) bismaleimide compound contains: an aliphatic bismaleimide compound represented by formula (1); and an aromatic bismaleimide compound represented by formula (2).
[ chemical 1]
(in the formula (1), R 1 Is an alkylene group having 6 to 12 carbon atoms. )
[ chemical 2]
(in the formula (2), R 2 Is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms; x is X 1 Each independently an oxygen atom or a single bond; r is R 3 R is R 4 A hydrocarbon group having 1 to 6 carbon atoms; a and b are integers of 0 to 3 inclusive. )
ADVANTAGEOUS EFFECTS OF INVENTION
The resin composition contains an aliphatic bismaleimide compound and an aromatic bismaleimide compound, whereby the heat resistance of the cured product can be improved while maintaining low dielectric characteristics. Therefore, a resin composition which maintains heat resistance generally in a trade-off relationship with low dielectric characteristics and has excellent low dielectric characteristics (low relative permittivity, low dielectric loss tangent) can be provided.
Drawings
FIG. 1 is a graph showing GPC measurement results of a resin composition of example 67 having a synthesis time of 2.5 minutes.
Detailed Description
< first embodiment >, first embodiment
(resin composition)
The resin composition of the present embodiment is a resin composition obtained by melting a resin mixture containing (a) 30 to 65 parts by mass of a bismaleimide compound, (B) 5 to 25 parts by mass of a coumarone resin, and (C) 1 to 30 parts by mass of an amine compound in 100 parts by mass of a resin component of the resin mixture. Hereinafter, the components (a) to (C) and other components that may be contained in the resin composition will be described. In the present invention, the numerical ranges "a to B" mean "a or more and B or less". The compound before the respective components are melt-mixed is referred to as a "resin mixture", and the compound cooled after the melt-mixing is referred to as a "resin composition".
(A) Bismaleimide compound
The bismaleimide compound is a compound having two maleimide groups, and contains an aliphatic bismaleimide compound represented by the formula (1) shown in one of the technical means for solving the problems. By using the aliphatic bismaleimide compound, the low dielectric characteristics of the cured product of the resin composition are improved. In addition, the cured product is cured by hot pressing, and has a low water absorption rate after the cured product is in an insulated state. Therefore, the cured product can stably maintain the low dielectric characteristics immediately after the production after the lapse of time from the production.
From the viewpoint of producing a cured product having low dielectric characteristics, the aliphatic bismaleimide compound is preferably R 1 An alkylene group having 7 to 11 carbon atoms, more preferably R 1 Is an alkylene group having 9 carbon atoms. In addition, an aliphatic bismaleimide compound having a melting point of 120 ℃ or lower is preferable. Examples of such aliphatic bismaleimide compounds include: 1, 6-bismaleimide (2, 4-trimethyl) hexane, hexamethylenediamine bismaleimide, N ' -1, 2-ethylenebismaleimide, N ' -1, 3-propylenebismaleimide, N ' -1, 4-tetramethylenebismaleimide and the like. Examples of the commercially available aliphatic bismaleimide compounds include BMI-TMH (product name, manufactured by Dai and Chemie industries (Ltd.).
The bismaleimide compound also contains an aromatic bismaleimide compound represented by the formula (2) shown in one of the technical means for solving the problems. Further preferred is an aromatic bismaleimide compound having a melting point of 130℃or higher. The resin composition contains an aliphatic bismaleimide compound and an aromatic bismaleimide compound, whereby the heat resistance of the cured product can be improved while maintaining low dielectric characteristics. Further, since the solvent solubility and hardenability are good, the resin composition is excellent in handling properties, which is easily brought into an appropriate B-stage state at the time of pre-impregnation.
Examples of the aromatic bismaleimide compound represented by the formula (2) include: 4,4 '-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide and the like. Examples of the commercially available aromatic bismaleimide compounds include: BMI-1000, BMI-4000, BMI-5000, BMI-5100 (all product names, manufactured by Daand chemical industry (stock)), and the like.
From the viewpoint of heat resistance of the cured product, the composition is represented by formula (2)The aromatic bismaleimide compound shown is preferably R in formula (2) 2 Is a group represented by formula (3). Examples of such aromatic bismaleimide compounds include bisphenol A diphenyl ether bismaleimide.
[ chemical 3]
From the viewpoint of improving the low dielectric characteristics and heat resistance of the cured product and improving the solubility in a low boiling point solvent, the mass ratio of the content of the aliphatic bismaleimide compound to the content of the aromatic bismaleimide compound, namely, the aliphatic bismaleimide compound: aromatic bismaleimide compounds, preferably 3.0:7.0 to 7.0:3.0, more preferably 4.0:6.0 to 6.0:4.0, and more preferably 4.5:5.5 to 5.5:4.5.
the content of the bismaleimide compound in 100 parts by mass of the resin component of the resin mixture is 30 to 65 parts by mass. The content of the bismaleimide compound in 100 parts by mass of the resin component is more preferably 40 to 62 parts by mass, and still more preferably 50 to 60 parts by mass, from the viewpoint of achieving both high heat resistance and low dielectric characteristics of the cured product. The bismaleimide compound is used in combination of two or more. The components (B) to (I) and other components described below may be used singly or in combination of two or more.
(B) Coumarone resin
The coumarone resin is a copolymer resin with coumarone, indene and styrene as main components. Examples of the commercial products include: g-90, V-120, L-5, L-20, H-100 (all of product name, manufactured by Nissan chemical (stock)) and the like. From the viewpoint of low dielectric characteristics of the cured product, coumarone resin having a softening point of 100 ℃ or less is preferable. In the same manner, the weight average molecular weight is preferably 850 or less, more preferably 800 or less. Coumarone resins that are beaded (solid) at room temperature are preferred over coumarone resins that are liquid at room temperature.
The content of the coumarone resin in 100 parts by mass of the resin component of the resin mixture is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass, and even more preferably 13 to 18 parts by mass, from the viewpoint of high heat resistance and low dielectric characteristics of the cured product.
The content of the coumarone resin is more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, based on 100 parts by mass of the bismaleimide compound (a), in terms of the solubility in a low-boiling solvent and the stability of the dissolved state. The content of the coumarone resin is more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less, per 100 parts by mass of the bismaleimide compound, from the viewpoint of obtaining a cured product having good heat resistance.
(C) Amine compound
The aliphatic bismaleimide compound represented by the formula (1) has a problem that it does not solidify and becomes liquid after once dissolution. In order to solve the problems associated with the treatment, the resin composition of the present embodiment contains 1 to 30 parts by mass of an amine compound in 100 parts by mass of the resin component, in addition to the aliphatic bismaleimide compound. The content of the amine compound is preferably 2 to 15 parts by mass, more preferably 3 to 8 parts by mass, from the viewpoints of hardenability of the resin composition and low dielectric characteristics and heat resistance of the hardened product.
Examples of the amine compound include: aromatic amines such as diphenylamine and 1, 3-bis (3-aminophenoxy) benzene are preferably diphenylamine from the viewpoint of producing a resin composition excellent in handling properties as a prepreg. Examples of the commercial products include: diphenylamine M and diphenylamine-P (tri-well chemical fine (strand) manufacture); ODA, BODA, BAPP, HFBAPP, BAPB, TPE-M and TPE-Q (both manufactured by SeikA (strands); carboider (Kayabond) C-200S (manufactured by japan chemicals (strands)), BAN (manufactured by japan chemicals (strands)), and the like.
The diphenylamine is more preferably an aromatic amine represented by the formula (4).
[ chemical 4]
(in the formula (4), R 5 Is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms, X 1 Each independently is an oxygen atom or a single bond. )
As the bisaniline represented by the formula (4), there may be mentioned: 4,4' - [ dimethylmethylenebis (4, 1-phenoxy) ] diphenylamine, 4' - [ biphenyl-4, 4' -diylbis (oxy) ] diphenylamine, diphenylamine-M, diphenylamine-P, and the like. Among the bisanilines represented by the formula (4), commercially available products include: diphenylamine M and diphenylamine-P (tri-well chemical fine (strand) manufacture); BODA, BAPP and BAPB (manufactured by Seika (Mass)), etc.
(D) Benzoxazine compounds
The benzoxazine compound may be a compound having at least one benzoxazine ring in a molecule, and is preferably a dihydrobenzoxazine compound represented by the following general formula (5) or general formula (6), and more preferably a p-d type dihydrobenzoxazine represented by the following general formula (6).
[ chemical 5]
[ chemical 6]
(in the formula (5) and the formula (6), R 6 、R 7 Represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms. )
The content of the benzoxazine compound in 100 parts by mass of the resin component of the resin mixture is preferably 5 to 20 parts by mass, more preferably 10 to 20 parts by mass, and even more preferably 15 to 20 parts by mass, from the viewpoints of high heat resistance and low dielectric characteristics of the cured product and solubility of the resin composition in a low boiling point solvent.
The content of the benzoxazine compound is more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, relative to 100 parts by mass of the bismaleimide compound, in terms of solubility in the low-boiling solvent and stability of the state of dissolution in the low-boiling solvent. From the viewpoint of obtaining a cured product having good heat resistance, the content of the benzoxazine compound is more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less, relative to 100 parts by mass of the bismaleimide compound.
(E) Bisphenol A cyanate
Bisphenol A type cyanate is bisphenol A type cyanate (triazine) which is hardened by forming a triazine ring. The resin mixture contains bisphenol A type cyanate ester to improve the hardenability. The bisphenol a type cyanate ester includes a monomer and a (homo) polymer (polymer), but is preferably a monomer of bisphenol a type cyanate ester in view of obtaining a cured product excellent in low dielectric characteristics.
The content of bisphenol a type cyanate ester in 100 parts by mass of the resin component of the resin mixture is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, and even more preferably 0.7 to 1.3 parts by mass, from the viewpoints of low dielectric characteristics of the cured product and prevention of precipitation of components in the stage of the prepreg.
(F) Epoxy resin
The resin composition may contain an epoxy resin as needed, for example, for the purpose of supplementing various characteristics such as flame retardancy. When the epoxy resin is contained, the interlayer adhesion and insulation properties of a laminate obtained by laminating a prepreg, which is a sheet obtained by impregnating a base material with a resin composition, with the prepreg and subjecting the laminate to a pressure-heat treatment may be improved.
The epoxy resin may be a compound having an epoxy group, but is preferably a biphenyl aralkyl type epoxy resin, an epoxy resin containing a naphthalene ring, a compound having three epoxy groups, or the like, from the viewpoint of satisfying both heat resistance and low dielectric characteristics of the cured product. As the epoxy resin containing a naphthalene ring, an α -naphthol type epoxy resin is preferable. As a commercially available epoxy resin containing a naphthalene ring, ESN-475V (product name, manufactured by Nippon Kagaku Chemie (Ltd.),. Alpha. -naphthol type epoxy resin) having two epoxy groups in each naphthalene ring is exemplified. Further, as a commercially available high heat-resistant trifunctional epoxy resin, VG3101L (product name, manufactured by general Lin Taike (printc) (strand)) is exemplified.
Examples of the epoxy resin other than the above include: bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, triphenol type epoxy resin, dicyclopentadiene type epoxy resin, and the like.
Wherein the heat resistance of the cured product is improved by suppressing the content of bisphenol A type epoxy resin in the resin component of the resin mixture. Therefore, the resin mixture preferably does not contain bisphenol a epoxy resin, from the viewpoint of improving the heat resistance of the cured product. The term "bisphenol a-free epoxy resin" as used herein means that the resin mixture does not substantially contain bisphenol a-type epoxy resin in an amount that affects the properties thereof. For example, if the content of bisphenol a epoxy resin in 100 parts by mass of the resin component of the resin mixture is 1 part by mass or less, or 0.3 part by mass or less or 0.1 part by mass or less as the case may be, the properties of the resin mixture such as low dielectric characteristics will not be affected.
The content of the epoxy resin in 100 parts by mass of the resin component of the resin mixture is preferably 1 to 12 parts by mass, more preferably 2 to 10 parts by mass, and even more preferably 3 to 8 parts by mass, from the viewpoint of high heat resistance and low dielectric characteristics of the cured product.
< second embodiment >
(resin composition)
The resin composition of the present embodiment is a resin composition obtained by melting a resin mixture containing (a) a bismaleimide compound containing an aliphatic bismaleimide compound represented by formula (1) and an aromatic bismaleimide compound represented by formula (2) as one of the technical means for solving the problems. The resin composition contains an aliphatic bismaleimide compound and an aromatic bismaleimide compound, whereby the heat resistance of the cured product can be improved while maintaining the low dielectric characteristics of the cured product. The bismaleimide compound will be omitted from the description of the matters common to the first embodiment, and the following description will explain the differences.
Regarding the resin composition, from the viewpoint of improving the heat resistance of the cured product, the mass ratio of the contents of the two bismaleimide compounds in the resin mixture, that is, as the aliphatic bismaleimide compound: aromatic bismaleimide compounds, preferably 25: 55-45: 35, more preferably 27:53 to 47:38.
(H) Triallyl isocyanurate
In the resin composition, triallyl isocyanurate is contained in the resin mixture from the viewpoint of improving the solubility with respect to a low-boiling point solvent. The content of triallyl isocyanurate in 100 parts by mass of the resin component of the resin mixture is preferably 16 parts by mass to 26 parts by mass, more preferably 18 parts by mass to 24 parts by mass. By containing triallyl isocyanurate, a resin composition having high solubility in a low-boiling point solvent, which can be adjusted for a 60 mass% methyl ethyl ketone solution, is obtained. Examples of the commercially available triallyl isocyanurate include TAIC (trademark, manufactured by Mitsubishi chemical (R) and the like.
In view of improving the handleability by setting the state in the B-stage to a solid rather than a viscous solid shape, the resin composition preferably further contains an amine compound and a carboxylic dianhydride.
(C) Amine compound
The amine compound is the same as that of the first embodiment. In the case where the resin mixture contains triallylisocyanurate, the content of the amine compound in 100 parts by mass of the resin component of the resin mixture is preferably 8 to 20 parts by mass, more preferably 10 to 18 parts by mass, and even more preferably 12 to 16 parts by mass, from the viewpoint of producing a resin composition which becomes a solid in the B-stage and has high solubility in a low boiling point solvent.
(I) Carboxylic acid dianhydride
The tetracarboxylic dianhydride may be exemplified by: BPADA, 6FDA, SFDA, bzDA: egniade (ENEHYDE) (trademark, manufactured by ENEOS), TAHQ (reference example). In the case where the resin mixture contains triallylisocyanurate, the content of carboxylic dianhydride in 100 parts by mass of the resin component of the resin mixture is preferably 10 to 35 parts by mass, more preferably 15 to 30 parts by mass, and even more preferably 20 to 27 parts by mass, from the viewpoint of producing a resin composition which becomes a solid in the B-stage and has high solubility in a low boiling point solvent.
(G) Hardening accelerator
When the resin composition of the present invention described as the first embodiment and the second embodiment is used, a hardening accelerator may be added. Examples of the timing of adding the hardening accelerator include: when the resin composition is dissolved in a solvent to prepare a varnish, when the varnish is prepreg, when a substrate or a laminate is produced, or the like. The following description is common to the resin compositions of the first and second embodiments.
Examples of the hardening accelerator include: imidazoles such as dicumyl peroxide, 4' -diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptylimidazole; amines such as triethanolamine, triethylenediamine, and N-methylmorpholine; organic phosphines such as triphenylphosphine and tricresylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1, 8-diazabicyclo (5, 4, 0) undecene-7 and derivatives thereof; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt naphthenate, and cobalt octoate. Organic peroxides or azo compounds, etc. may also be used in combination as desired.
The hardening accelerator is formulated in the varnish or prepreg in such a content as to obtain a desired gelation time. For example, the hardening accelerator is used in a range of 0.01 to 5 parts by mass based on 100 parts by mass of the total resin components contained in the resin composition.
The resin composition may contain components other than the above-mentioned components (A) to (I) in the resin mixture before melt mixing. For example, an organic or inorganic filler may be used to obtain a base material for curing the resin composition to prepare a molded article. Examples of the filler include: oxides such as silica, diatomaceous earth, alumina, zinc chloride, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrite, and the like; hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite (dawsonite), and aluminum magnesium carbonate; sulfates such as calcium sulfate, barium sulfate, gypsum fiber, etc.; silicates such as calcium silicate (wollastonite), xonotlite, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based hollow spheres (silica-based ballon); nitrides such as aluminum nitride, boron nitride, and silicon nitride; carbon such as carbon black, graphite, carbon fiber, carbon hollow sphere (carbon balloon), charcoal powder, etc.; other various metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fibers, zinc borate, various magnetic powders, slag fibers, ceramic powders, and the like.
The shape of the filler is preferably spherical or scaly. Optionally, a silane coupling agent having two or more different reactive groups (one of which is a reactive group that chemically reacts with an inorganic material, and the other of which is a reactive group that chemically reacts with an organic material) in the molecule may be used together.
When an organic filler or an inorganic filler is used, the content of the filler is preferably 5.0 parts by mass to 250 parts by mass relative to 100 parts by mass of the resin component of the resin mixture.
Flame retardants may be added to the resin composition as needed. Examples of the flame retardant include: organic flame retardants such as bromine compounds such as brominated epoxy resins and phosphorus compounds such as condensed phosphoric acid esters, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, tin compounds and antimony compounds, and the like.
The content of the flame retardant is preferably a content which does not impair heat resistance or moist heat resistance of a cured product obtained by curing the resin composition and which achieves sufficient flame retardancy (for example, satisfies the V-0 condition in the UL94 standard). In the case of the organic flame retardant, for example, 1 to 20 parts by mass based on 100 parts by mass of the total resin components including the organic flame retardant in the resin composition are used; in the case of the inorganic flame retardant, 10 parts by mass to 300 parts by mass are used relative to 100 parts by mass of the total resin components.
When the resin composition is used, other additives may be added depending on the application. Examples of other additives include: synthetic rubbers such as silicone oil, thermoplastic resin, and nitrile rubber (NBR), and leveling agents. The other additive is used, for example, in an amount of 0.0001 to 5 parts by mass based on 100 parts by mass of the total of the other additive and the resin component in the resin composition.
(melt mixing step)
The resin composition of the present invention is produced by a melt-mixing step in which the resin mixture is heated and mixed in a molten state. In the melt mixing step, a usual mixing member can be used. The mixing member is preferably a kneader, a biaxial kneader, or the like. The temperature at the time of melt mixing is preferably 130 to 230 ℃, more preferably 150 to 210 ℃, and even more preferably 170 to 190 ℃ as long as the temperature at which the resin mixture melts is not less than 400 ℃.
The melt-mixing step is preferably performed under a condition that the weight average molecular weight of the resin composition obtained by heating the resin mixture is 1000 to 2500, more preferably 1200 to 1800. The time of the melt mixing step is, for example, about 0.1 to 10 minutes, but it is preferable to set the conditions such as the temperature in the melt mixing step so as to be about 0.5 to 4 minutes.
The resin composition of the present invention is obtained by cooling by natural cooling or forced cooling after the melt mixing step. The cooling method may be appropriately selected from known methods. For example, a method of naturally cooling at 0 to 40 ℃ or a method of forcibly cooling using a refrigerant may be used. Alternatively, the method may be carried out by placing the mixture in a constant temperature apparatus at 30 to 300℃after melt mixing, and then cooling the mixture. After cooling, the obtained resin composition may be used in the subsequent step as a solid resin composition.
In the melt mixing step, at least a part of the bismaleimide compound is modified by reacting the aliphatic bismaleimide compound with the aromatic bismaleimide compound and other components in the resin mixture. Thus, a resin composition having high heat resistance, low dielectric characteristics, and good solubility in a low boiling point solvent and hardenability can be produced.
The resin composition produced by the melt mixing step is preferably a component having a molecular weight of 4500-4800, in terms of improving the solubility in a low-boiling solvent. The proportion of the component having a molecular weight of 4500 to 4800 in 100% by mass of the resin composition is preferably 10% by mass to 20% by mass, more preferably 12% by mass to 18% by mass. The proportions of the components having molecular weights of 4500 to 4800 can be determined by gel permeation chromatography (gel permeation chromatography, GPC).
(varnish)
The varnish of the resin composition of the present invention is obtained by dissolving the resin composition obtained by the above-mentioned production method in a solvent having a boiling point of 120 ℃ or less and a relative dielectric constant of 10 to 30.
Examples of the solvent having a boiling point of 120 ℃ or less and a relative dielectric constant of 10 to 30 include: ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether solvents such as propylene glycol monomethyl ether, and alcohol solvents such as ethanol, 1-propanol, 2-propanol, and 1-butanol. In view of operability and the like, a ketone solvent among the exemplified solvents is preferably used. Solvents other than the solvents exemplified above may be contained.
The content of the resin composition in 100 parts by mass of the varnish is usually 40 to 80 parts by mass, preferably 50 to 70 parts by mass. The varnish can be obtained by dissolving the resin composition in a solvent at ordinary temperature (room temperature) or under heating. When the resin composition is dissolved under heating, the conditions for dissolution are, for example, about 50 to 200℃and about 0.1 to 24 hours, although the conditions depend on the boiling point of the solvent.
The prepreg is produced by coating or impregnating the base material with the varnish, and then drying the resultant to remove the solvent. As the base material, a known base material used for prepregs such as glass nonwoven fabric, glass cloth, carbon fiber cloth, organic fiber cloth, and paper can be used.
The prepreg is produced by a drying process after the varnish is applied or impregnated on the substrate, but the application method, impregnation method, and drying method are not particularly limited, and any conventionally known method can be used. The drying conditions are appropriately determined depending on the boiling point of the solvent used, and are preferably not too high. Preferably, the prepreg is dried so that the solvent remaining in 100 parts by mass of the prepreg becomes 3 parts by mass or less.
In the production of the prepreg, a filler other than the resin composition may be added to the varnish. As the filler, there may be mentioned: silica particles, alumina particles, polyphenylene ether resins, and the like. The amount of filler to be added in the preparation of the prepreg is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, based on 100 parts by mass of the resin component of the resin composition, in terms of imparting high heat resistance, low relative permittivity and low dielectric loss tangent to the cured product. Examples of commercially available silica particles and alumina particle fillers include the Admafine (product name, admatechs (manufactured by Admatechs)) series, and examples of commercially available polyphenylene ether resins include: SA90, SA120, SA9000 (product names, manufactured by SABIC contract corporation), and the like.
The resin composition of the present invention is suitable for use in a printed wiring board, and can be used as a molded article obtained by curing the resin composition. The molded article may be: a cured product obtained by curing only the resin composition, or a composite material or laminate obtained by compounding the cured product with other raw materials.
The composite material and the laminate can be obtained by: pressing 1 piece of prepreg under pressure by hot pressingHeating and curing, or laminating a plurality of prepregs and heating under pressure to integrate. The heating and pressurizing conditions in the production of the composite material are not particularly limited, and examples thereof include: the heating temperature is 100 to 300 ℃, preferably 150 to 250 ℃, more preferably 200 to 250 ℃, and the pressure is 10kg/cm 2 ～100kg/cm 2 Preferably 20kg/cm to 40kg/cm, and the heating and pressurizing time is 10 minutes to 300 minutes, preferably 30 minutes to 180 minutes.
The laminate can be used for a multilayer printed wiring board or the like by integrating a metal foil or a metal plate on one side or both sides of the laminate. The laminate may be manufactured by: the prepreg is heat-cured to be integrated by laminating a metal foil or a metal plate on one side or both sides of 1 prepreg, or laminating a metal foil or a metal plate on one side or both sides of the outermost layer of the prepreg in which a plurality of prepregs are laminated, and hot-pressing.
As the metal foil or metal plate, copper, aluminum, iron, stainless steel, or the like can be used. For example, a laminate using copper as a metal foil is a copper clad laminate (Copper Clad Laminate, CCL). The conditions for heat curing are preferably the same as those for producing a composite material. Further, a laminate for a multilayer printed wiring board may be produced using the inner core material.
The present invention can also be implemented as an adhesive, a sealant, and a coating material containing the resin composition.
Examples
Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. The test methods and raw materials used in the examples and comparative examples are as follows.
1. Test method
[ solvent solubility (methyl ethyl ketone (Methyl Ethyl Ketone, MEK) solubility) ]
60 parts by mass of a measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) were mixed at 50 ℃ or lower, ultrasonic vibration was applied for a predetermined period of time, and the dissolved state after ultrasonic vibration was evaluated visually using the following criteria.
O: the liquid was brown transparent at the time point after the application of the ultrasonic vibration for 100 minutes, and had no dissolution residue, separation, and turbidity.
X: at the time point after the application of the ultrasonic vibration for 100 minutes, there was dissolution residue, separation or turbidity.
[ glass transition Point (Tg) ]
Coefficient of thermal expansion: CTE (coefficient of thermal expansion) (ppm/. Degree.C.)
The cured product obtained by curing the resin composition was cut (cut) to a predetermined size, and the cut was used as a sample for glass transition point measurement. The glass transition point (temperature, °c) and Coefficient of Thermal Expansion (CTE) of the sample were measured using a differential scanning calorimeter (Differential Scanning Calorimeter, DSC) and TMA (Thermomechanical Analysis, thermo-mechanical analysis) methods under the following conditions.
(DSC)
The measuring machine: thermo plus EVO2 DSC8231 manufactured by the company RIGAKU
Sample weight: 5mg of
Atmosphere of gas: nitrogen (N) 2 )
Measuring temperature: 30-350 DEG C
Heating rate: 10 ℃/min.
Measurement mode: heat flux type
(TMA)
The measuring machine: thermo plus TMA8310 manufactured by RIGAKU Co
Sample size: length (longitudinal) 19mm x width (transverse) 5mm x thickness 0.1mm
Atmosphere of gas: nitrogen (N) 2 )
Measuring temperature: 30-350 DEG C
Heating rate: 10 ℃/min.
Measurement mode: stretching
[ relative permittivity (Dk), dielectric loss tangent (Df) ]
At the time point immediately after the production and after 24 hours have elapsed, the measurement was performed under 1GHz or 10GHz conditions by the cavity resonator method. By means of cavity sharing The measurement by the vibrator method was carried out under the conditions of 1GHz and 10GHz, and the results were substantially the same. As measurement samples of the relative dielectric constant (Dk) and the dielectric loss tangent (Df), copper-clad laminates (CCL) using copper as a metal foil on both surfaces of a cured product and 1 prepreg (2116E-glass, resin intrusion rate 40±10%, thickness 0.1±20%) were produced. The conditions of hot pressing at the time of heat curing and integrating the prepreg were set to a heating temperature of 230℃and a pressure of 20kg/cm 2 Heating and pressurizing for 120 minutes.
The relative dielectric constants (Dk) and dielectric loss tangents (Df) of the cured products were measured in examples 1 to 42 and comparative examples 1 to 4.
In examples 43 to 67 and comparative examples 5 to 7, the following materials were used as measurement objects, namely, copper foil was removed from CCL, and x was cut out using a die: y: z=80 mm×20mm×0.1mm, and the end of the cut member is smoothed by deburring with sandpaper or the like. The longitudinal direction of the cut member is denoted by x, the lateral direction is denoted by y, and the thickness direction is denoted by z. The dimensions in the y-direction and the z-direction were measured at three positions with a space of 20mm in the x-direction, the average value was calculated, and the values 3 bits after the decimal point were defined as the dimensions of the object to be measured in the y-direction and the z-direction.
[ Water absorption ]
The cured products of examples 66 and 67 and comparative example 6 were prepared to have a width (longitudinal) of 60mm, a length (transverse) of 60mm, and a height of 1.2mm, and the weight of the cured product obtained by the entire four sides was measured before and after storage for 48 hours at 85℃and a humidity of 85%, whereby the water absorption (%) under high temperature and high humidity conditions was evaluated.
[ State of B stage (curing) ]
The resin composition was heated to 150 to 200 ℃, stirred in this state for 3 to 5 minutes, and then the state of the resin in a state of being sufficiently cooled at room temperature was evaluated based on the following criteria.
And (2) the following steps: the resin is in the form of powder or solid and can be easily recovered.
X: the resin is in the form of a viscous solid and is difficult to recover.
2. Raw materials
(A) Polymaleimide compounds
BMI-TMH (manufactured by Dahe chemical industry (Strand) 1, 6-bismaleimide- (2, 4-trimethyl) hexane, melting point 73 ℃ C. -110 ℃ C.)
BMI-4000 (manufactured by Dahe chemical industry (Strand) bisphenol A diphenylether bismaleimide, melting point 134 ℃ C. -163 ℃ C.)
BMI-2300 (product name, manufactured by Dahe chemical industry (stock), polyphenylmethane polymaleimide, melting point 70 ℃ -145 ℃)
(B) Coumarone resin
G-90 (product name, manufactured by Nitro-chemical (strand), solid at ordinary temperature, softening point 90 ℃, weight average molecular weight 770)
(C) Amine compound
BAPP (product name, manufactured by SeikA (Strand), 2-bis [4- (4-aminophenoxy) benzene ] propane)
Bisaniline M (Tri-well chemical fine (stock) manufacture)
Caryabond (Kayabond) C-200S (product name, manufactured by Japanese chemical Co., ltd., 4' -methylenebis (2, 6-dimethylamine))
ODA (product name, manufactured by SeikA) (Strand), 4' -diaminodiphenyl ether)
BAPB (product name, manufactured by Seika (Strand), 4' -bis (4-aminophenoxy) biphenyl)
APB-N (1, 3-bis (3-aminophenoxy) benzene)
BAN (product name, manufactured by Japanese chemical Co., ltd.)
(D) Benzoxazine compounds
BZO: (P-d type) benzoxazine (manufactured by four-national chemical industry (Strand))
(E) Bisphenol A cyanate
Triazine (product name, mitsubishi gas chemistry (Strand) manufacture, CAS No.1156-51-0, monomer of bisphenol A cyanate, 2-bis (4-cyanatophenyl) propane)
(F) Epoxy resin
ESN-475V (product name, manufactured by Nippon Kagaku Chemie (Strand), alpha-naphthol aralkyl epoxy resin)
(H) Triallyl isocyanurate
Taike (TAIC) (product name, mitsubishi chemical (stock) manufacture, CAS No. 1025-15-6)
(I) Tetracarboxylic dianhydride
BPADA:4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic dianhydride
6FDA:4,4' - (hexafluoroisopropylidene) diphthalic acid tetracarboxylic dianhydride
SFDA: spiro [ fluorene-9, 9' -xanthene ] -2',3',6',7' -tetracarboxylic dianhydride
6FBPADA:5,5' - ((perfluoropropane-2, 2-diyl) bis (4, 1-phenylene)) bis (oxy)) bis (isobenzofuran-1, 3-dione)
BzDA: enihalde (ENEHYDE) (trademark manufactured by ENEOS)
TAHQ: bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylic acid) 1, 4-phenylene (CAS No. 2770-49-2)
(other ingredients: filler)
SC2500-SXJ: (product name, manufactured by Admatechs (Strand)), silica particles
(examples, comparative examples)
Resin mixtures having the proportions (parts by mass) shown in tables 1 to 8 were melt-mixed (melt-kneaded) using a biaxial mixer (kneader) to produce resin compositions. The melt-mixing step was performed under the condition that the temperature of the resin composition at the outlet of the resin composition in the biaxial mixer became 170.+ -. 10 ℃.
45 parts by mass of the resin mixture composition produced in the above manner and 55 parts by mass of the solvent were mixed at room temperature to produce a varnish of the resin composition. Tetrahydrofuran was used as a solvent in examples 1 to 22 and comparative examples 1 to 4, and methyl ethyl ketone was used as a solvent in examples 23 to 67 and comparative examples 5 to 7.
In examples 65 and 67, a varnish prepared by dispersing a filler (SC 2500-SXJ) in a proportion of 100 parts by mass relative to 100 parts by mass of the resin component of the resin composition in the varnish was impregnated into a glass cloth 2116 in a single layer to produce a (1 Ply) prepreg. In other examples 43 to 67 and comparative examples 5 to 7, prepregs were produced by directly impregnating glass cloth 2116 with varnish in a one-layer manner without adding polyphenylene ether to the varnish.
Prepregs of each example and comparative example were subjected to pressing conditions: 180 ℃ x 30kg/cm 2 X 1 hour, main hardening conditions: the cured products were cured at 230℃for 2 hours, and the glass transition point (Tg), the relative permittivity (Dk), and the dielectric loss tangent (Df) were measured for each cured product, and the measurement results are shown in tables 1 to 8. In examples 48 and 49, cracks in the resin were large at the time point of manufacturing the prepreg, and thus the resin was not the object to be measured.
TABLE 1
As shown in table 1, as the bismaleimide compound (a), by melting a resin mixture containing both the aliphatic bismaleimide compound of formula (1) and the aromatic bismaleimide compound of formula (2), the Tg of the cured product is increased as compared with the case where one of these compounds is used. The reason why Tg is improved is presumably that the use of the two bismaleimide compounds increases the molecular density, and a cured product having a strong and high-density molecular structure is obtained.
TABLE 2
-: not measured
The cured product of the resin composition using the two bismaleimide compounds shown in table 1 was excellent in heat resistance and low dielectric characteristics. However, the solvent is a high boiling point solvent such as NMP (N-Methyl-2-pyrrolidone) and the solubility in a low boiling point solvent such as Methyl ethyl ketone is low.
As shown in table 2, the resin composition was prepared by adding 16 to 23 parts by mass of triallyl isocyanurate (H) to 100 parts by mass of the resin component, and the resin composition was dissolved in a low boiling point solvent while maintaining the characteristics of a cured product excellent in heat resistance and low dielectric characteristics.
From the results shown in tables 2 and 3, it is found that the ratio of the two bismaleimide compounds needs to be within a predetermined range in order to prepare a resin composition having high solubility in a low boiling point solvent by blending triallyl (H) isocyanurate. Namely, by mixing the mass ratio in the resin mixture, i.e., the content of the aliphatic bismaleimide compound: the content of the aromatic bismaleimide compound was set to 25: 55-45: 35, a resin composition having high solubility in a low boiling point solvent can be obtained.
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As shown in tables 2 and 3, by setting the mass ratio of the two bismaleimide compounds in the resin mixture to a predetermined range, triallyl isocyanurate (H) was prepared, and resin compositions having high solubility in a low boiling point solvent were obtained. However, the resin composition has a viscous solid shape in the B-stage, and is poor in handleability.
As shown in tables 4 and 5, it was found that the resin composition was solid in the B-stage and excellent in handleability by blending 8 to 20 parts by mass of the (C) amine compound and 15 to 30 parts by mass of the (I) carboxylic dianhydride in 100 parts by mass of the resin component of the resin mixture. In addition, from the viewpoint of producing a resin composition having high solubility in a low boiling point solvent, (C) the amine compound is preferably one or more selected from the group consisting of APB-N, BAN and BAPP, and (I) the carboxylic dianhydride is preferably one or more selected from the group consisting of BPDA, 6FDA and SFDA.
TABLE 6
-: not measured
From the results shown in table 6, it can be said that the following is.
A prepreg using a resin composition obtained by melting a resin mixture containing components (A) to (C) in 100 parts by mass of the resin component of the resin mixture can be produced, which has low dielectric characteristics.
By using the diphenylamine represented by the formula (4) as the amine compound (C), a resin composition having good handleability as a prepreg can be obtained.
A resin composition obtained by melting a resin mixture containing BMI-TMH and BMI-4000 as the (A) polymaleimide compound and BAPP as the (C) amine compound is excellent in heat resistance (Tg (DSC)) and low dielectric characteristics (Df (after 24 hours)).
/>
The results shown in tables 7 and 8 can be said to be as follows.
By setting the mass ratio of BMI-TMH to BMI-4000 content to 3.0:7.0 to 7.0:3.0, and a cured product having a low CTE can be obtained.
By setting the content of G-90 in 100 parts by mass of the resin mixture to 12 parts by mass or less, the heat resistance (Tg) of the cured product can be improved.
A cured product having excellent heat resistance can be obtained regardless of the content of triazine. By containing triazine in the resin mixture, the viscosity (hardness) of the resin mixture increases, and the handleability improves.
In view of producing a cured product excellent in low dielectric characteristics, it can be said that the content of triazine in 100 parts by mass of the resin mixture is preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less.
A cured product having excellent heat resistance and low dielectric characteristics can be obtained irrespective of the content of epoxy.
The most excellent low dielectric characteristics were achieved by example 67 in which SC2500-SXJ was dispersed as a filler. It is assumed that the reason for this is that the molecular bonds formed by aggregation are blocked by the filler and eliminated, and as a result, highly dense molecular bonds can be obtained.
By using BMI-TMH and BMI-4000 as bismaleimide, a cured product having a smaller water absorption than comparative example 5 using BMI-2300 was obtained. The cured product obtained by curing the resin composition of the present invention has a small water absorption after curing by hot pressing, and therefore can stably maintain excellent low dielectric characteristics immediately after production.
[ study of production conditions ]
The optimal production conditions were studied for the resin composition of example 67 from the viewpoint of solvent solubility.
Fig. 1 shows the GPC result of the resin composition with the synthesis time set to 2.5 minutes.
The influence of the synthesis time on the properties of the resin composition is shown in table 9.
[ Synthesis conditions ]
The resin temperature is 170+/-10 DEG C
[ gel time ]
Determination of the hardening time of a hotplate at 171 ℃
[ peak area ]
The presence or absence of components having molecular weights of 4500 to 4800 is detected by GPC (gel permeation chromatography), and the ratio (%) of the peak area of the components having molecular weights of 4500 to 4800 to the total peak area is obtained when the presence or absence of components having molecular weights of 4500 to 4800 is detected.
[ weight average molecular weight ]
The weight average molecular weight of the resin composition was determined by GPC measurement.
The solvent solubility was evaluated using the following criteria.
60 parts by mass of a measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) were mixed at 50℃or lower, ultrasonic vibration was applied for a predetermined period of time, and the dissolved state after ultrasonic vibration was visually evaluated using the following criteria.
[ MEK solubility (168 hours) ]
A MEK solution of the resin was prepared by using the above method of solvent solubility (MEK solubility), left for a predetermined time, and the state of the measurement sample after left for a predetermined time was visually evaluated using the following criteria.
O: no resin precipitated at the time point after 168 hours of standing at room temperature.
X: resin precipitated at the time point after 168 hours of standing at room temperature.
TABLE 9
From the results shown in table 9, it can be said that the following is.
By extending the synthesis time, i.e., the time for melt mixing the resin mixture, the reaction proceeds and the gel time becomes shorter.
Due to the difference in synthesis time, MEK solubility in the case of long-term standing is different. By setting the synthesis time to 2.5 minutes or longer, a resin composition having good MEK solubility can be obtained.
Since the peak areas and weight average molecular weights of the components having molecular weights of 4500 to 4800, as measured by GPC, differ from each other in synthesis time, these are considered to be indicators of synthesis time for producing a resin composition having good MEK solubility.
By setting the proportion of the components having the molecular weights of 4500 through 4800 corresponding to the peak of the symbol 1 in the graph of fig. 1 to 10% to 20% of the whole, a resin composition having good MEK solubility can be obtained.
By setting the weight average molecular weight to 1100 to 2500, a resin composition having good MEK solubility can be obtained.
[ solvent solubility ]
The resin composition of example 67 (peak area 12.3%, mw=1257) having a synthesis time of 2.5 minutes was evaluated for its solubility in solvents other than MEK. As a result, PGM (propylene glycol monomethyl ether) (propylene glycol monomethyl ether), PGM-Ac (propylene glycol monomethyl ether acetate) (propylene glycol monomethyl ether acetate), DMAc (dimethyl acetamide) (dimethylacetamide), NMP (N-methyl pyrrolidone) (N-methylpyrrolidone), γ -butyrolactone, ethyl acetate, acetone, toluene, THF (tetrahydrofuran) (tetrahydrofuran), cyclohexanone, DMF (dimethylformamide) (dimethylformamide), methoxybenzene (anisole), 2- (2-butoxyethoxy) ethanol (known as ethylene glycol monoethyl ether), and 2- (2-ethoxyethoxy) ethyl acetate (ethyl carbitol acetate) were brown transparent liquids at the time point after the application of ultrasonic vibration for 100 minutes, and were free from dissolution residue, separation, turbidity, and good solubility.
Industrial applicability
The resin composition of the present invention has good solubility in a solvent, has low dielectric characteristics (low relative permittivity, low dielectric loss tangent) and high heat resistance, and is therefore useful as a raw material for adhesives, sealants, coatings, molded articles, laminates and printed wiring boards, which are suitable for various electronic devices having high performance, large capacity and high speed, and are excellent in heat resistance and low dielectric characteristics.
Claims (20)
1. A resin composition obtained by melting a resin mixture containing (A) a bismaleimide compound, characterized in that,
the (A) bismaleimide compound includes:
an aliphatic bismaleimide compound represented by formula (1); and
an aromatic bismaleimide compound represented by the formula (2),
[ chemical 1]
(in the formula (1), R 1 Alkylene having 6 to 12 carbon atoms
[ chemical 2]
(in the formula (2), R 2 Is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms; x is X 1 Each independently an oxygen atom or a single bond; r is R 3 R is R 4 A hydrocarbon group having 1 to 6 carbon atoms; a and b are each independently an integer of 0 or more and 3 or less).
2. The resin composition according to claim 1, wherein
R in the formula (1) 1 Is an alkylene group having a carbon number of 9,
r in the formula (2) 2 Is a group represented by the formula (3),
[ chemical 3]
3. The resin composition according to claim 1, wherein
The aliphatic bismaleimide compound is 1, 6-bismaleimide (2, 4-trimethyl) hexane,
the aromatic bismaleimide compound is bisphenol A diphenyl ether bismaleimide.
4. The resin composition according to claim 3, wherein
A mass ratio of the content of the aliphatic bismaleimide compound to the content of the aromatic bismaleimide compound in the resin mixture, that is, the aliphatic bismaleimide compound: the aromatic bismaleimide compound is 25: 55-45: 35.
5. The resin composition according to claim 4, wherein
The resin mixture further contains (H) triallyl isocyanurate,
the content of the triallyl isocyanurate (H) in 100 parts by mass of the resin component is 16 to 23 parts by mass.
6. The resin composition according to claim 5, wherein
The resin mixture further comprises (C) an amine compound and (I) a carboxylic dianhydride,
the content of the (C) amine compound in 100 parts by mass of the resin component is 10 to 20 parts by mass,
the content of the carboxylic dianhydride (I) in 100 parts by mass of the resin component is 15 to 30 parts by mass.
7. The resin composition according to claim 1, wherein
The resin mixture further comprises (B) a coumarone resin and (C) an amine compound,
of 100 parts by mass of the resin component of the resin mixture,
the content of the bismaleimide compound (A) is 30 to 65 parts by mass,
the content of the coumarone resin (B) is 5 to 25 parts by mass,
the content of the (C) amine compound is 1 to 30 parts by mass.
8. The resin composition according to claim 7, wherein
A mass ratio of the content of the aliphatic bismaleimide compound to the content of the aromatic bismaleimide compound, that is, the aliphatic bismaleimide compound: the aromatic bismaleimide compound is 3.0:7.0 to 7.0:3.0.
9. The resin composition according to claim 7, wherein
The (C) amine compound is diphenylamine.
10. The resin composition according to claim 7, wherein
The amine compound (C) is a diphenylamine represented by the formula (4),
[ chemical 4]
(in the formula (4), R 5 Is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms, X 1 Each independently an oxygen atom or a single bond).
11. The resin composition according to claim 7, wherein
(C) The amine compound is diphenylamine M, 4' - [ dimethylmethylenebis (4, 1-phenoxy) ] diphenylamine or (4, 4' - [ biphenyl-4, 4' -diylbis (oxy) ] diphenylamine).
12. The resin composition according to claim 7, wherein
The resin mixture further contains (D) a benzoxazine,
the content of the (D) benzoxazine in 100 parts by mass of the resin mixture is 5 to 20 parts by mass.
13. The resin composition according to claim 12, wherein
The resin mixture further contains (E) bisphenol A type cyanate ester,
the content of bisphenol A cyanate ester (E) in 100 parts by mass of the resin mixture is 0.5 to 2 parts by mass.
14. The resin composition according to claim 13, wherein
The resin mixture further contains (F) an epoxy,
The epoxy content of (F) in 100 parts by mass of the resin mixture is 1 to 9 parts by mass.
15. The resin composition according to claim 7, wherein
The weight average molecular weight of the resin composition is 1000 to 2500,
and has a molecular weight of 4500-4800, the proportion of the components is 10% -20%.
16. The resin composition according to claim 1, which is used for a printed wiring board.
17. A varnish comprising the resin composition according to claim 5 dissolved in a solvent having a boiling point of 120 ℃ or less and a dielectric constant of 10 to 30.
18. A laminated sheet produced using the resin composition according to claim 1.
19. A printed wiring board produced using the resin composition according to claim 1.
20. A molded article obtained by curing the resin composition according to claim 1.
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| JP2021-107813 | 2021-06-29 | ||
| JP2021107813 | 2021-06-29 | ||
| PCT/JP2022/015425 WO2023276379A1 (en) | 2021-06-29 | 2022-03-29 | Resin composition, varnish, laminated plate, printed wiring board, and molded product |
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| JP (1) | JPWO2023276379A1 (en) |
| KR (1) | KR20240026127A (en) |
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| JP2014105317A (en) * | 2012-11-29 | 2014-06-09 | Toho Tenax Co Ltd | Resin composition, prepreg using resin composition, and method of manufacturing resin composition |
| JP6696113B2 (en) * | 2015-04-03 | 2020-05-20 | 住友ベークライト株式会社 | Resin composition for printed wiring board, prepreg, resin substrate, metal-clad laminate, printed wiring board, and semiconductor device |
| JP6922157B2 (en) * | 2015-04-17 | 2021-08-18 | 昭和電工マテリアルズ株式会社 | Resin composition, laminated board and multi-layer printed wiring board |
| CN107227015B (en) * | 2016-03-23 | 2020-04-24 | 联茂电子股份有限公司 | Low dielectric material |
| JP2017115164A (en) * | 2017-03-30 | 2017-06-29 | Ｊｘｔｇエネルギー株式会社 | Thermosetting resin composition and epoxy resin cured product |
| JP2019157027A (en) * | 2018-03-15 | 2019-09-19 | 日立化成株式会社 | Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and method for producing the same |
| JP2019157097A (en) * | 2018-03-17 | 2019-09-19 | 帝人株式会社 | Prepreg and fiber-reinforced composite material, and method for producing same |
| CN111886267B (en) * | 2018-03-28 | 2023-08-25 | 松下知识产权经营株式会社 | Resin composition, and prepreg, resin-equipped film, resin-equipped metal foil, metal-clad laminate and wiring board using the same |
| JP7351297B2 (en) * | 2018-06-12 | 2023-09-27 | 株式会社レゾナック | Thermosetting resin composition for semiconductor encapsulation materials, semiconductor encapsulation materials, and semiconductor devices |
| CN113348195B (en) * | 2019-02-05 | 2022-05-31 | 普林科技有限公司 | Resin composition, varnish, laminate, and printed wiring board |
| CN112778701B (en) * | 2020-12-30 | 2023-02-28 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition and application thereof |
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