CN116888098A - Maleimide resin, asymmetric bismaleimide compound, curable composition, cured product, semiconductor sealing material, semiconductor sealing device, prepreg, circuit board, and laminated film - Google Patents
Maleimide resin, asymmetric bismaleimide compound, curable composition, cured product, semiconductor sealing material, semiconductor sealing device, prepreg, circuit board, and laminated film Download PDFInfo
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- CN116888098A CN116888098A CN202180086105.1A CN202180086105A CN116888098A CN 116888098 A CN116888098 A CN 116888098A CN 202180086105 A CN202180086105 A CN 202180086105A CN 116888098 A CN116888098 A CN 116888098A
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- China
- Prior art keywords
- compound
- group
- maleimide
- aromatic
- curable composition
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- 229920005989 resin Polymers 0.000 title claims abstract description 77
- 239000011347 resin Substances 0.000 title claims abstract description 77
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- -1 bismaleimide compound Chemical class 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 239000003566 sealing material Substances 0.000 title claims abstract description 23
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims description 19
- 238000007789 sealing Methods 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 125000003118 aryl group Chemical group 0.000 claims abstract description 67
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000007767 bonding agent Substances 0.000 claims abstract description 19
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 43
- 125000003545 alkoxy group Chemical group 0.000 claims description 30
- 125000005843 halogen group Chemical group 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 150000001491 aromatic compounds Chemical class 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 21
- 230000008018 melting Effects 0.000 abstract description 20
- 150000003923 2,5-pyrrolediones Chemical class 0.000 abstract description 2
- 239000005001 laminate film Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 238000005227 gel permeation chromatography Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000008065 acid anhydrides Chemical class 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 229920000767 polyaniline Polymers 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 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 7
- 239000000523 sample Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 125000005336 allyloxy group Chemical group 0.000 description 5
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 5
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 4
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000003018 phosphorus compounds Chemical class 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 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 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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 2
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical class C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- WMPGCOIUVFJFMG-UHFFFAOYSA-N 1-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)naphthalene-2,7-diol Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=C(O)C=CC2=CC=C(O)C=C21 WMPGCOIUVFJFMG-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-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
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VVQVMHASNBSOOC-UHFFFAOYSA-N 4-(hydroxymethyl)benzenesulfonic acid Chemical compound OCC1=CC=C(S(O)(=O)=O)C=C1 VVQVMHASNBSOOC-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
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- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical class OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004002 naphthaldehydes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011342 resin composition Substances 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Classifications
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Abstract
The present invention provides a maleimide resin, a maleimide compound, a curable composition containing the same, a cured product thereof, a semiconductor sealing material, a semiconductor sealing device, a prepreg, a circuit board and a laminate film, wherein the maleimide resin is a maleimide compound of a polyamine compound (C), and the polyamine compound (C) is a reaction product of a plurality of aromatic monoamine compounds (A) and a bonding agent (B). These maleimide resins and maleimide compounds have low melting points and softening points, are excellent in handleability, and the cured products have high heat resistance, and are suitably used for semiconductor sealing materials and the like.
Description
Technical Field
The present invention relates to a maleimide resin which has a low melting point, a low softening point, excellent handleability, and a cured product having high heat resistance and which can be suitably used for a semiconductor sealing material or the like; maleimide compound, curable composition containing the same, cured product thereof, semiconductor sealing material, semiconductor sealing device, prepreg, circuit board and laminated film.
Background
Since the cured product of a maleimide resin has extremely high heat resistance, it is being studied for use as a resin material in fields requiring particularly high heat resistance, such as a sealing material for power semiconductors, but it is a problem that the maleimide resin which is currently in commercial use has a high melting point and a high softening point, and is low in handleability as a material.
As a conventionally known maleimide resin, for example, a 4,4' -diphenylmethane bismaleimide type compound is widely known, but as described above, the melting point of the compound is high and the handling property as a material is poor (for example, refer to patent document 1). Further, as a maleimide resin having high handleability, a compound of 2, 2-bis [ 4- (4-maleimide phenoxy) phenyl ] propane is known, but this compound has not satisfied recent market demands in terms of physical properties of a cured product such as heat resistance (for example, refer to patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2-269716
Patent document 2: japanese patent laid-open No. 6-128225
Disclosure of Invention
Problems to be solved by the invention
Accordingly, the present invention has been made to solve the problems of providing a maleimide resin which has a low melting point, a low softening point, excellent handleability, and a cured product having high heat resistance and which can be suitably used for a semiconductor sealing material or the like; maleimide compound, curable composition containing the same, cured product thereof, semiconductor sealing material, semiconductor sealing device, prepreg, circuit board and laminated film.
Solution for solving the problem
The inventors have found as a result of intensive studies that: the present invention has been accomplished in view of the above problems, and has been made in view of the above problems, and an object of the present invention is to provide a resin composition which has a low melting point and a low softening point, is excellent in handleability, and has a high heat resistance, and can be suitably used for a semiconductor sealing material or the like.
Specifically, the present invention relates to a maleimide resin which is characterized by being a maleimide compound of a polyamine compound (C) which is a reaction product of a plurality of aromatic monoamine compounds (A) and a bonding agent (B).
The present invention also relates to an asymmetric bismaleimide compound which is a maleimide compound of an asymmetric diamine compound (C-1) obtained by bonding two different aromatic monoamine compounds (a) via a bonding agent (B).
The present invention also relates to a curable composition containing the maleimide resin or the asymmetric bismaleimide compound.
The present invention also relates to a cured product of the curable composition.
The invention also relates to a semiconductor sealing material, which uses the curable composition.
The invention also relates to a semiconductor device using the semiconductor sealing material.
The invention also relates to a prepreg using the curable composition.
The invention also relates to a circuit substrate using the prepreg.
The present invention also relates to a laminated film using the curable composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a maleimide resin which has a low melting point, a low softening point, excellent handleability, and a cured product having high heat resistance and which can be suitably used for a semiconductor sealing material or the like can be provided; maleimide compound, curable composition containing the same, cured product thereof, semiconductor sealing material, semiconductor sealing device, prepreg, circuit board and laminated film.
Drawings
FIG. 1 is a GPC chart of a maleimide resin (1) obtained in example 1.
FIG. 2 is a GPC chart of the maleimide resin (2) obtained in example 2.
FIG. 3 is a GPC chart of the maleimide resin (3) obtained in example 3.
FIG. 4 is a GPC chart of the maleimide resin (4) obtained in example 4.
FIG. 5 is a GPC chart of the maleimide resin (5) obtained in example 5.
FIG. 6 is a GPC chart of the maleimide resin (6) obtained in example 6.
FIG. 7 is a Differential Scanning Calorimetric (DSC) spectrum of the maleimide resin (1) obtained in example 1.
FIG. 8 is a Differential Scanning Calorimetric (DSC) spectrum of the maleimide resin (2) obtained in example 2.
FIG. 9 is a Differential Scanning Calorimetric (DSC) spectrum of the maleimide resin (3) obtained in example 3.
FIG. 10 is a Differential Scanning Calorimetric (DSC) spectrum of the maleimide resin (4) obtained in example 4.
FIG. 11 is a Differential Scanning Calorimetric (DSC) spectrum of the maleimide resin (5) obtained in example 5.
FIG. 12 is a Differential Scanning Calorimetric (DSC) spectrum of the maleimide resin (6) obtained in example 6.
Detailed Description
The present invention will be described in detail below.
The maleimide resin of the present invention is characterized by being a maleimide compound of a polyamine compound (C) which is a reaction product of a plurality of aromatic monoamine compounds (A) and a bonding agent (B).
If the aromatic monoamine compound (A) has an NH group on the aromatic ring 2 The compound (c) is not particularly limited in other specific structure, and various compounds can be used. Specifically, an aromatic compound such as benzene, naphthalene, anthracene, etc. has an NH on its aromatic ring 2 A compound of a group; at NH 2 Compounds having one or more other substituents on the base, and the like. Examples of the other substituent include an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, a halogen atom, an aryl group, an aralkyl group, and a hydroxyl group.
The aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, or may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like are exemplified. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the alkenyloxy group include allyloxy groups and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural part in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like are substituted on the aromatic nucleus thereof. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and structural parts in which the alkyl group, alkoxy group, halogen atom, and the like are substituted on the aromatic nucleus thereof.
Among the aromatic monoamine compounds (a), aniline or a compound having one or more of the above-mentioned other substituents on the aromatic nucleus of aniline is preferable in view of the low melting point, low softening point and excellent handleability of the obtained maleimide resin. Further, aniline, a compound having a substituent at the 2-position of aniline, and a compound having a substituent at the 2, 6-position of aniline are particularly preferable. The type of the substituent of the compound having a substituent at the 2-position of aniline and the compound having a substituent at the 2, 6-position of aniline is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, from the viewpoint of forming a maleimide resin excellent in heat resistance of a cured product.
In the present invention, as the aromatic monoamine compound (a), a plurality of kinds are used in combination. Thus, a maleimide resin having a low melting point and softening point and excellent handleability while maintaining the high heat resistance which is characteristic of the maleimide resin is formed. The number of the aromatic monoamine compound (a) to be used is not particularly limited as long as it is plural, that is, 2 or more, and it is preferably in the range of 2 to 5, more preferably 2 or 3, in combination, from the viewpoint of relatively easy production. In addition, from the viewpoint of sufficiently exhibiting the effects of low melting point, low softening point and excellent handleability, the amount of each aromatic monoamine compound (a) to be used is preferably at least 10 mass% or more, more preferably 25 mass% or more, relative to the total of the aromatic monoamine compounds (a). The upper limit value is preferably 90% or less, more preferably 75% or less. When 2 kinds of aromatic monoamine compounds (A) are used in combination, the mass ratio of the two is preferably in the range of 10/90 to 90/10. More preferably in the range of 20/80 to 80/20.
The bonding agent (B) is not particularly limited as long as it is a compound that reacts with the aromatic monoamine compound (a) to bond the aromatic rings of the aromatic monoamine compound (a) to each other, and various compounds can be used. The bonding agent (B) may be used alone or in combination of 2 or more. Specific examples of the bonding agent (B) include an aldehyde compound (B-1), a ketone compound (B-2), an aromatic compound (B-3) represented by the following general formula (B-3), an aromatic compound (B-4) represented by the following general formula (B-4), an aromatic compound (B-5) represented by the following general formula (B-5), an aromatic compound (B-6) represented by the following general formula (B-6), an aromatic compound (B-7) represented by the following general formula (B-7), an aromatic compound (B-8) represented by the following general formula (B-8), and the like.
[ in the general formulae (B-3) to (B-8), ar 1 Each independently represents an aromatic ring optionally having a substituent. R is R 1 Each independently is a hydrogen atom or a methyl group. R is R 2 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R is R 3 Each independently represents any one of an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, and an aralkyl group, and l represents an integer of 0 to 3. X is any one of hydroxyl, halogen atom and alkoxy. Y is any one of a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, and a sulfonyl group. ]
Examples of the aldehyde compound (B-1) include aliphatic aldehyde compounds such as formaldehyde and acetaldehyde; aromatic aldehyde compounds such as benzaldehyde and naphthaldehyde. One kind of them may be used alone, or 2 or more kinds may be used in combination.
Examples of the ketone compound (B-2) include aliphatic ketone compounds such as acetone, methyl ethyl ketone, and diethyl ketone; aromatic ketone compounds such as acetophenone, etc. One kind of them may be used alone, or 2 or more kinds may be used in combination.
Ar in the general formulae (B-3) to (B-6) 1 Each independently represents an aromatic ring optionally having a substituent. Specifically, phenylene, naphthylene, and structural sites having one or more various substituents on their aromatic rings are exemplified. Examples of the substituent include an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, a halogen atom, an aryl group, an aralkyl group, and a hydroxyl group. The aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like are exemplified. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the alkenyloxy group include allyloxy groups and the like. The halogen atom may be a fluorine atom or chlorine atom Atoms, bromine atoms, and the like. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural part in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like are substituted on the aromatic nucleus thereof. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and structural parts in which the alkyl group, alkoxy group, halogen atom, and the like are substituted on the aromatic nucleus thereof.
In the general formulae (B-4) and (B-6), R 2 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, and the like are exemplified.
In the general formulae (B-7) and (B-8), R 3 Each independently represents any one of an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, and an aralkyl group, and l represents an integer of 0 to 3. The aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like are exemplified. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the alkenyloxy group include allyloxy groups and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural part in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like are substituted on the aromatic nucleus thereof. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and structural parts in which the alkyl group, alkoxy group, halogen atom, and the like are substituted on the aromatic nucleus thereof.
In the general formulae (B-4), (B-6) and (B-8), X is any one of a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy.
In the general formulae (B-5) and (B-6), Y is any one of a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, and a sulfonyl group. The divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure.
Examples of the reaction step for reacting the aromatic monoamine compound (a) with the bonding agent (B) to obtain the polyamine compound (C) include a method in which a plurality of the aromatic monoamine compounds (a) and the bonding agent (B) are reacted under the condition of an acidic catalyst. In particular, from the viewpoint of easy control of the reaction, it is preferable to add the bonding agent (B) to the aromatic monoamine compound (a) in portions. The reaction may suitably be carried out in a solvent. In addition, the reaction can be efficiently performed by heating to about 50 to 200 ℃. After the completion of the reaction, the polyamine compound (C) can be obtained as an intermediate by washing with an aqueous alkali solution, distilled water or the like.
Examples of the acidic catalyst include p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, hydrochloric acid, oxalic acid, and activated clay. One kind of them may be used alone, or 2 or more kinds may be used in combination. The amount of the acid catalyst to be added is preferably in the range of 0.01 to 0.5 mole, more preferably in the range of 0.1 to 0.3 mole, based on 2 moles of the aromatic monoamine compound (a). When the molar amount cannot be defined, the ratio is preferably in the range of 1 to 50wt% relative to the total amount of the aniline compound (a), the bonding agent (B), the solvent and the acid catalyst.
Examples of the solvent include an organic solvent such as distilled water, toluene, and xylene. One of them may be used alone, or a mixture of 2 or more kinds may be prepared. The amount of the solvent is preferably in the range of 5 to 100 mass% based on the total mass of the aromatic monoamine compound (a) and the bonding agent (B).
Examples of the maleinization reaction of the polyamine compound (C) include a method in which the polyamine compound (C) and an acid anhydride are reacted under the condition of an acidic catalyst. In particular, from the viewpoint of easy control of the reaction, it is preferable to add the acid anhydride in portions to the polyamine compound (C) or to dissolve the acid anhydride in an appropriate solvent and to drop the acid anhydride. The reaction may suitably be carried out in a solvent. As a more preferable reaction step, the polyamine compound (C) and the acid anhydride are first stirred at room temperature to obtain an amic acid intermediate. Thereafter, an acid catalyst is added and the reaction is carried out by heating to 50 to 200 ℃, more preferably to 70 to 150 ℃. In this case, it is preferable to remove the moisture in the system. After the completion of the reaction, the target maleimide resin can be obtained by washing with an aqueous alkali solution, distilled water or the like.
Examples of the acid anhydride include maleic anhydride, citraconic anhydride, and 2, 3-dimethylmaleic anhydride. One kind of them may be used alone, or 2 or more kinds may be used in combination.
Examples of the acidic catalyst include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, and the like. One kind of them may be used alone, or 2 or more kinds may be used in combination. The amount of the acidic catalyst to be added is usually 0.01 to 10mol, preferably 0.03 to 3mol, based on 1g/mol of the amino equivalent of the polyaniline compound (C).
The solvent may be any solvent as long as it can dissolve the polyamine compound (C) and the acid anhydride. In particular, from the viewpoint of high solubility of the polyamine compound (C) and the acid anhydride and efficient reaction, a mixed solvent of an aprotic polar solvent such as dimethylformamide and an aprotic polar solvent such as toluene is preferably used. The nonpolar solvent includes, in addition to toluene, xylene, chlorobenzene, and the like. In addition, the aprotic polar solvent may be methyl ethyl ketone, or the like, in addition to dimethyl formaldehyde. The compounding ratio of the two and the amount of the solvent are appropriately adjusted by the solvent solubility of the polyamine compound (C) and the acid anhydride. As an example, the following method may be mentioned: the mass ratio of the nonpolar solvent to the aprotic solvent is in the range of 1/99 to 99/1, and the total solvent amount is in the range of 0.5 to 80% based on the total of the polyamine compound (C), the acid anhydride and the total solvent amount.
The molecular weight of the maleimide resin of the present invention is not particularly limited, and the reaction conditions and the like may be appropriately changed depending on the application and the like, and adjusted to a preferable value. Among them, in the case of use for a semiconductor sealing material, it is preferable to contain a low molecular weight component such as a dinuclear component represented by the following formula (1), a trinuclear component represented by the following structural formula (2), or a tetranuclear component represented by the following formulas (3-1) and (3-2) from the viewpoint of forming a resin which maintains the high heat resistance, low melting point, low softening point, and excellent handleability of a cured product.
A-B-A (1)
A-B-A-B-A (2)
A-B-A-B-A-B-A (3-1)
[ wherein A is a structural moiety derived from the aromatic monoamine compound (A) and having a maleimide group; b is a structural part derived from the bonding agent (B). Wherein A and B may be the same or different from each other. ]
The maleimide resin particularly preferably contains a dinuclear component (bismaleimide compound). The ratio of the dinuclear component (bismaleimide compound) in the maleimide resin is preferably 30% or more, more preferably 50% or more.
In the present invention, the content of the dinuclear substance in the maleimide resin is a value calculated from the area ratio of the spectrogram of Gel Permeation Chromatography (GPC). In the present invention, measurement conditions of Gel Permeation Chromatography (GPC) are described in examples. In the present invention, "number of nuclei" means: the number of structural sites derived from the aromatic monoamine compound (A) in the molecule as shown in the above formulae (1) to (3-2).
Among the dinuclear components (bismaleimide compounds), asymmetric bismaleimide compounds, which are maleimide compounds of an asymmetric diamine compound (C-1) obtained by bonding two different aromatic monoamine compounds (a) via a bonding agent (B), are preferred from the viewpoint of forming a resin excellent in handleability while maintaining high heat resistance, melting point and softening point of the cured product. Furthermore, as the aromatic monoamine compound (a), an aniline compound is preferably used, and an asymmetric bismaleimide compound represented by the following structural formula (4) is more preferably used. In the present invention, the asymmetric maleimide compound can be used by separation and purification.
[ wherein Z is a divalent organic group having 1 to 200 carbon atoms. R is R 4 Each independently is any one of aliphatic hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, halogen atom, aryl group, aralkyl group. In the formula, a plurality of R 4 Optionally the same or different. m is 0 or an integer of 1 to 4. In the formula, the structural portion α and the structural portion β surrounded by the dotted line have different structures from each other.]
Z in the structural formula (4) is a structural part derived from the bonding agent (B). Z is a divalent organic group having 1 to 200 carbon atoms, and may be a structural moiety containing other atoms such as an oxygen atom and a halogen atom if the number of carbon atoms is in the range of 1 to 200. Among them, a divalent organic group having 1 to 20 carbon atoms is more preferable. Specific examples of Z include structural parts represented by the following general formulae (Z-1) to (Z-8).
[ in the general formulae (Z-1) to (X-8), ar 1 Each independently represents an aromatic ring optionally having a substituent. R is R 3 Each independently represents any one of an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, and an aralkyl group, and l represents an integer of 0 to 3. R is R 5 Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an aromatic ring optionally having a substituent. R is R 6 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R is R 7 Is any one of a divalent aliphatic hydrocarbon group other than the group represented by the general formula (Z-1), an aromatic group optionally having a substituent, or a combination thereof. Y is any one of a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, and a sulfonyl group. n is an integer of 1 or more.]
R in the above general formula (Z-1) 5 Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an aromatic ring optionally having a substituent. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, and the like are exemplified. Examples of the optionally substituted aromatic ring include phenylene, naphthylene, and structural sites having one or more various substituents on the aromatic ring thereof. Examples of the substituent include an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, a halogen atom, an aryl group, an aralkyl group, and a hydroxyl group. The aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like are exemplified. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the alkenyloxy group include allyloxy groups and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural part in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like are substituted on the aromatic nucleus thereof. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and structural parts in which the alkyl group, alkoxy group, halogen atom, and the like are substituted on the aromatic nucleus thereof.
Ar in the general formulae (Z-2), (Z-3) and (Z-8) 1 Each independently represents an aromatic ring optionally having a substituent. Specific examples thereof include the followingAr in the general formulae (B-3) to (B-6) 1 The same groups.
R in the general formulae (Z-2) and (Z-3) 6 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, and the like are exemplified.
Y in the general formula (Z-3) is any one of a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, and a sulfonyl group. The divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure.
R in the above formula (Z-4) 3 Each independently represents any one of an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, and an aralkyl group, and l represents an integer of 0 to 3. Specific examples thereof include R in the formulae (B-7) and (B-8) 3 The same groups.
R in the above formula (Z-7) 7 Is any one of a divalent aliphatic hydrocarbon group other than the group represented by the general formula (Z-1), an aromatic group optionally having a substituent, or a combination thereof. The divalent aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure.
R in the aforementioned structural formula (4) 4 Each independently is any one of aliphatic hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, halogen atom, aryl group, aralkyl group. The aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, and may have an unsaturated bond in the structure. Specifically, methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like are exemplified. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the alkenyloxy group include allyloxy groups and the like. The halogen atom may be a fluorine atom or chlorine atomAtoms, bromine atoms, and the like. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural part in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like are substituted on the aromatic nucleus thereof. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and structural parts in which the alkyl group, alkoxy group, halogen atom, and the like are substituted on the aromatic ring thereof. In the formula, a plurality of R 4 Optionally the same or different.
Among them, from the viewpoint of forming a substance having a low melting point, a low softening point and excellent handleability of the obtained maleimide resin, it is preferable that a substituent is present on one or both sides of a carbon atom adjacent to the carbon atom substituted with a maleimide group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
The curable composition of the present application contains the maleimide resin or the asymmetric bismaleimide compound. In the curable composition of the present application, the maleimide resin or the asymmetric bismaleimide compound may be used alone as a curable component, or 1 or more other curable compounds may be used in combination.
Examples of the other curable compound include epoxy resins, phenolic resins, amine compounds, active ester resins, cyanate resins, benzoxazine resins, and compounds containing an unsaturated bond.
Examples of the epoxy resin include various bisphenol-type epoxy resins, various biphenyl-type epoxy resins, various novolak-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, phenol aralkyl-type epoxy resins, and the like. One kind of them may be used alone, or 2 or more kinds may be used in combination.
Examples of the phenolic resin include various bisphenols, various biphenyls, various novolak resins, dicyclopentadiene-phenol addition reaction resins, phenol aralkyl resins, and various arylene ether resins. One kind of them may be used alone, or 2 or more kinds may be used in combination.
The curable composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, and an emulsifier, as required.
Examples of the curing accelerator include phosphorus compounds, peroxides, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, lewis acids, amine complex salts, and the like. Among them, triphenylphosphine is preferable among phosphorus compounds, dicumyl peroxide is preferable among peroxides, 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable among tertiary amines, 2-ethyl-4-methylimidazole is preferable among imidazole compounds, and 4-dimethylaminopyridine is preferable among pyridine compounds, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.
Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and phosphoric acid amide; organic phosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphine compounds, organic nitrogen-containing phosphorus compounds, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines; silicone oil, silicone rubber, silicone resin, and other silicone flame retardants; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the content is preferably in the range of 0.1 to 20% by mass based on the solid resin component of the curable composition.
The inorganic filler is compounded, for example, when the curable composition of the present invention is used for a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, the fused silica is preferable in that more inorganic filler can be compounded. For the fused silica, either of crushed and spherical ones can be used, and in order to increase the blending amount of the fused silica and to suppress the increase in melt viscosity of the curable composition, it is preferable to mainly use spherical ones. Further, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably in the range of 0.5 to 95 parts by mass based on 100 parts by mass of the curable composition.
When the curable composition of the present invention is used for applications such as conductive paste, conductive fillers such as silver powder and copper powder can be used.
The curable composition of the present invention has a low melting point, a low softening point, excellent handleability, and a high heat resistance, and therefore, is particularly suitable for use as a semiconductor sealing material or the like, and can be widely used for electronic material applications such as printed wiring boards and resist materials, paints, adhesives, molded articles, and the like.
When the curable composition of the present invention is used for a semiconductor sealing material, it is generally preferable to compound an inorganic filler. The semiconductor sealing material can be prepared by mixing the compound using, for example, an extruder, a kneader, a roll, or the like. The method of molding the semiconductor package using the obtained semiconductor sealing material includes, for example, the following methods: the semiconductor sealing material is molded using an injection mold, a transfer molding machine, an injection molding machine, or the like, and then heated at a temperature of 50 to 250 ℃ for 1 to 10 hours, whereby a semiconductor device as a molded product can be obtained.
When the curable composition of the present invention is used for printed wiring board applications and laminate adhesive film applications, it is usually preferable to use the composition diluted with an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl glycol acetate, propylene glycol monomethyl ether acetate, and the like. The kind and amount of the organic solvent may be appropriately adjusted depending on the environment in which the curable composition is used, and for example, in the case of printed wiring board applications, a polar solvent having a boiling point of 160 ℃ or less such as methyl ethyl ketone, acetone, dimethylformamide and the like is preferably used in a proportion of 40 to 80 mass% of the nonvolatile component. In the application of the laminate adhesive film, a ketone solvent such as acetone, methyl ethyl ketone, or cyclohexanone is preferably used; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; a carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like are preferably used in a proportion of 30 to 60% by mass of nonvolatile components.
Examples of the method for producing a printed wiring board using the curable composition of the present invention include the following methods: the reinforcing base material is impregnated with the curable composition, cured to obtain a prepreg, and the prepreg is laminated with a copper foil and is heat-pressed. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass gauze. The impregnation amount of the curable composition is not particularly limited, and is preferably generally prepared so that the resin component in the prepreg is 20 to 60 mass%.
Examples
The present invention will be specifically described with reference to examples and comparative examples, and "parts" and "%" hereinafter refer to mass unless otherwise specified. In the examples of the present invention, the measurement conditions of Gel Permeation Chromatography (GPC), high Performance Liquid Chromatography (HPLC), liquid chromatography mass spectrometry (LC-MS) and amine equivalent are shown below.
< conditions for measurement by Gel Permeation Chromatography (GPC) >)
Measurement device: HLC-8320GPC manufactured by Tosoh corporation,
Column: protective column HXL-L manufactured by Tosoh corporation "
"TSK-GEL G2000HXL" manufactured by +Tosoh Corp "
"TSK-GEL G2000HXL" manufactured by +Tosoh Corp "
"TSK-GEL G3000HXL" manufactured by +Tosoh Corp "
"TSK-GEL G4000HXL" manufactured by +Tosoh Corp "
A detector: RI (differential refractometer)
And (3) data processing: GPC WorkStation EcoSEC-workbench manufactured by Tosoh Corp "
Measurement conditions: column temperature 40 DEG C
Developing solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard: the following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of "GPC station EcoSEC-workbench".
(polystyrene used)
"A-500" manufactured by Tosoh Corp "
"A-1000" manufactured by Tosoh Corp "
"A-2500" manufactured by Tosoh Corp "
"A-5000" manufactured by Tosoh corporation "
"F-1" manufactured by Tosoh Corp "
"F-2" manufactured by Tosoh Corp "
"F-4" manufactured by Tosoh Corp "
"F-10" manufactured by Tosoh Corp "
"F-20" manufactured by Tosoh Corp "
"F-40" manufactured by Tosoh Corp "
"F-80" manufactured by Tosoh Corp "
"F-128" manufactured by Tosoh corporation "
Sample: a sample (50. Mu.l) obtained by filtering a tetrahydrofuran solution having a mass% of 1.0% in terms of resin solid content with a microfilter was used.
< measurement conditions for High Performance Liquid Chromatography (HPLC) and liquid chromatography Mass Spectrometry (LC-MS) >
And (3) a controller: agilent Technologies 1260Infinity II
Column: agilent EC-C18 (4.6X10 mm, 2.7 μm)
Column temperature: 40 DEG C
Pump flow rate: 1.0 ml/min
Elution conditions: K1-Water, K2-acetonitrile
K1/K2=0/100→30/70 (concentration change in line shape 0-1.67 min)
K1/k2=30/70 (1.67-5 min)
K1/K2=30/70→90/10 (5-8 minutes)
(the ratio is the volume ratio)
Detection wavelength: UV254, 275, 300nm
MS：Agilent Technologies InfinityLab LC/MSD
< determination of amine equivalent weight >
About 2.5g of a polyaniline compound as a sample was put into a 500mL conical flask with a stopper, 7.5g of pyridine, 2.5g of acetic anhydride and 7.5g of triphenylphosphine were precisely weighed, and then a condenser was attached thereto, and the mixture was heated and refluxed for 150 minutes by an oil bath set to 120 ℃.
After cooling the mixture, 5.0mL of distilled water, 100mL of propylene glycol monomethyl ether, 75mL of tetrahydrofuran, and 0.5mol/L potassium hydroxide-ethanol solution (. About.50 mL) were added, followed by titration by potentiometric titration. Blank tests were performed by the same method, and corrections were made.
Amine equivalent (g/eq.) = (s×2,000)/(blank-a)
S: amount of sample (g)
A: consumption of 0.5mol/L Potassium hydroxide-ethanol solution (mL)
Blank: consumption of 0.5mol/L Potassium hydroxide-ethanol solution (mL) in blank test
EXAMPLE 1 Synthesis of Maleimide resin (1)
Into a 500mL eggplant-type flask equipped with a rotary evaporator were charged 52.40g (0.43 mol) of 2, 6-dimethylaniline, 64.52g (0.43 mol) of 2, 6-diethylaniline, 22.14g of distilled water and 22.73g of p-toluenesulfonic acid, and the mixture was heated to 70℃with stirring. After 30 minutes at 70℃it took 1 hour to add 34.98g (0.43 mol) of 37% formaldehyde solution 4 times and react it for 4 hours. After the reaction, air-cooled to room temperature, the reaction solution was transferred to a 2L separable flask, and diluted with 140g of toluene. The diluted solution was washed 1 time with 100g of a 10% aqueous sodium hydroxide solution and 4 times with 100g of distilled water, and concentrated under reduced pressure to obtain 109.48g of a polyaniline compound (1). The amine equivalent of the polyaniline compound (1) was 146eq/g.
To a 2L flask equipped with a thermometer, a condenser, a Dimsta water separator and a stirrer were charged 78.35g (0.54 mol in terms of amine equivalent) of a polyaniline compound (1), 231.5g of toluene and 23.3g of dimethylformamide, and the mixture was stirred at room temperature. 59.53g (0.61 mol) of maleic anhydride was charged 1 hour and 4 times, and the mixture was reacted at room temperature for 1 hour. 2.3g of p-toluenesulfonic acid monohydrate was added, and after water and toluene which had been heated and azeotroped out under reflux were cooled/separated, only toluene was returned to the system to carry out dehydration reaction for 6 hours. The solution naturally cooled to 60℃was washed 2 times with 100g of 5% aqueous sodium bicarbonate solution and 7 times with 150g of distilled water. In the process, 200g of toluene was added to improve the liquid separation ability. The mixture was concentrated under reduced pressure to obtain 105.7g of maleimide resin (1). Peaks of m+=432, 460, 488 were confirmed in LC-MS spectra. Each peak corresponds to an ammonia adduct of the following compound. The content of the binuclear component (bismaleimide compound) calculated from the area ratio of the GPC spectrum was 96%. The GPC chart of the maleimide resin (1) is shown in FIG. 1.
EXAMPLE 2 Synthesis of Maleimide resin (2)
Into a 500mL eggplant-type flask equipped with a rotary evaporator were charged 52.11g (0.43 mol) of 2-ethylaniline, 64.17g (0.43 mol) of 2, 6-diethylaniline, 22.14g of distilled water and 22.73g of p-toluenesulfonic acid, and the mixture was heated to 70℃with stirring. After 30 minutes at 70℃it took 1 hour to add 34.98g (0.43 mol) of 37% formaldehyde solution 4 times and react it for 4 hours. After the reaction, air-cooled to room temperature, the reaction solution was transferred to a 2L separable flask, and diluted with 140g of toluene. The diluted solution was washed 1 time with 100g of a 10% aqueous sodium hydroxide solution and 4 times with 100g of distilled water, and concentrated under reduced pressure to obtain 119.02g of a polyaniline compound (2). The amine equivalent of the polyaniline compound (2) was 165eq/g.
To a 2L flask equipped with a thermometer, a condenser, a Dientax water separator and a stirrer were charged 87.45g (0.53 mol in terms of amine equivalent) of a polyaniline compound (2), 231.5g of toluene and 23.3g of dimethylformamide, and the mixture was stirred at room temperature. 59.53g (0.61 mol) of maleic anhydride was charged 1 hour and 4 times, and the mixture was reacted at room temperature for 1 hour. 2.3g of p-toluenesulfonic acid monohydrate was added, and after water and toluene which had been heated and azeotroped out under reflux were cooled/separated, only toluene was returned to the system to carry out dehydration reaction for 6 hours. The solution naturally cooled to 60℃was washed 2 times with 100g of 5% aqueous sodium bicarbonate solution and 7 times with 150g of distilled water. In the process, 200g of toluene was added to improve the liquid separation ability. After concentration under reduced pressure, 123.36g of maleimide resin (2) was obtained. Peaks of m+=432, 460, 488 were confirmed in LC-MS spectra. Each peak corresponds to an ammonia adduct of the following compound. The content of the binuclear component (bismaleimide compound) calculated from the area ratio of the GPC spectrum was 56%. The GPC chart of the maleimide resin (2) is shown in FIG. 2.
EXAMPLE 3 Synthesis of Maleimide resin (3)
Into a 500mL eggplant-type flask equipped with a rotary evaporator were charged 52.11g (0.43 mol) of 2-ethylaniline, 52.11g (0.43 mol) of 2, 6-dimethylaniline, 22.14g of distilled water and 22.73g of p-toluenesulfonic acid, and the mixture was heated to 70℃with stirring. After 30 minutes at 70℃it took 1 hour to add 34.98g (0.43 mol) of 37% formaldehyde solution 4 times and react it for 4 hours. After the reaction, air-cooled to room temperature, the reaction solution was transferred to a 2L separable flask, and diluted with 140g of toluene. The diluted solution was washed 1 time with 100g of a 10% aqueous sodium hydroxide solution and 4 times with 100g of distilled water, and concentrated under reduced pressure to obtain 106.11g of a polyaniline compound (4). The amine equivalent was 147eq/g.
To a 2L flask equipped with a thermometer, a condenser, a Dientax water separator and a stirrer were charged 77.91g (0.53 mol in terms of amine equivalent) of a polyaniline compound (3), 231.5g of toluene and 23.3g of DMF, and the mixture was stirred at room temperature. 59.53g (0.61 mol) of maleic anhydride was charged 1 hour and 4 times, and the mixture was reacted at room temperature for 1 hour. 2.3g of p-toluenesulfonic acid monohydrate was added, and after water and toluene which had been heated and azeotroped out under reflux were cooled/separated, only toluene was returned to the system to carry out dehydration reaction for 6 hours. The solution naturally cooled to 60℃was washed 2 times with 100g of 5% aqueous sodium bicarbonate solution and 7 times with 150g of distilled water. In the process, 200g of toluene was added to improve the liquid separation ability. After concentration under reduced pressure, 113.09g of maleimide resin (3) was obtained. The peak of m+=432 is confirmed in LC-MS spectrum. This peak corresponds to the ammonia adduct of the following compound. The content of the binuclear component (bismaleimide compound) calculated from the area ratio of the GPC spectrum was 58%.
The GPC chart of the maleimide resin (3) is shown in FIG. 3.
( Examples 4 to 6: synthesis of maleimide resins (4) to (6) )
Maleimide resins (4) to (6) were synthesized in the same manner as in example 1, except that the types and molar numbers of the aniline compounds were changed as shown in table 1 below. GPC spectra of maleimide resins (4) to (6) are shown in FIGS. 4 to 6.
The content of the dinuclear component (bismaleimide compound) of each maleimide resin calculated from the area ratio of the GPC spectrum is shown in table 1.
In addition, from the MS spectrum of each maleimide resin, it was confirmed that: which each contain an asymmetric bismaleimide compound.
TABLE 1
( Examples 7 to 12: evaluation of maleimide resins (1) to (6) )
The melting point and softening point of each maleimide resin, td5 of the cured product, and the thermal expansion rate of the cured product were measured and evaluated in accordance with the following procedures. The evaluation results are shown in table 2.
< determination of melting Point >
The maleimide resins obtained in examples 1 to 6 were measured using differential scanning calorimetric measurement (DSC) under the following conditions, and the melting point was defined as the peak of the melting peak in the DSC curve obtained therefrom. Differential Scanning Calorimetry (DSC) spectra of maleimide resins (1) to (6) are shown in fig. 7 to 12.
Measurement device: "DSC1" manufactured by Metrele-tolidol, inc,
Sample amount: about 5mg
Temperature conditions: 10 ℃/min
< measurement of softening Point >
The softening points of the maleimide resins obtained in examples 1 to 6 were measured in accordance with JIS K7234 (Ring and ball method).
< measurement of Td5 of cured product >
The maleimide resins obtained in examples 1 to 6 were each poured into a mold of 11cm×5cm (about 1mm in thickness), cured at 200℃for 2 hours, and further cured at 250℃for 2 hours, to obtain cured products.
Td5 was measured on the obtained cured product by using TGA/DSC made by Metler-Toli Co.
Measurement device: metrele-tolidol, TGA/DSC 1
Measurement range: 40-150-600 DEG C
Heating rate: 20 ℃/min (40 ℃ C. Fwdarw.150 ℃ C.)
Hold for 15 min (150 ℃ C.)
5 ℃/min (150 ℃ C. Fwdarw.600 ℃ C.)
Atmosphere: nitrogen gas
Measurement of thermal expansion Rate of cured Material
A cured product was obtained under the same conditions as before, and the thermal expansion coefficient was measured using TMA/SS6100 manufactured by Hitachi High-Tech Science Corporation.
Measurement device: TMA/SS6100 (Hitachi High-Tech Science Corporation)
And (3) probe: quartz expansion/compression probe
Measuring the load: 88.8mN
Measuring temperature: the first operation is carried out at the temperature of r.t. -270 DEG C
The second operation is carried out at 0-270 DEG C
Heating rate: 3 ℃/min
Atmosphere: nitrogen gas
Comparative example 1
As a comparison object, 4' -diphenylmethane bismaleimide (BMI-1000 manufactured by Daihou chemical Co., ltd.) was used, and the melting point of the maleimide resin was measured in the same manner as in example. The melting point was 160 ℃. Further, since this bismaleimide compound did not melt at 150 ℃, the softening point was not measured in accordance with JIS K7234 (ring and ball method).
TABLE 2
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Claims (12)
1. A maleimide resin which is a maleimide compound of a polyamine compound (C) which is a reaction product of a plurality of aromatic monoamine compounds (A) and a bonding agent (B).
2. The maleimide resin according to claim 1, wherein the bonding agent (B) is one or more of an aldehyde compound (B-1), a ketone compound (B-2), an aromatic compound (B-3) represented by the following general formula (B-3), an aromatic compound (B-4) represented by the following general formula (B-4), an aromatic compound (B-5) represented by the following general formula (B-5), an aromatic compound (B-6) represented by the following general formula (B-6), an aromatic compound (B-7) represented by the following general formula (B-7), and an aromatic compound (B-8) represented by the following general formula (B-8),
Ar in the general formulae (B-3) to (B-8) 1 Each independently represents an aromatic ring optionally having a substituent; r is R 1 Each independently is a hydrogen atom or a methyl group; r is R 2 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms; r is R 3 Each independently is any one of aliphatic hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, halogen atom, aryl group, aralkyl group; l is an integer of 0 to 3; x is any one of hydroxyl, halogen atom and alkoxy; y is any one of a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, and a sulfonyl group.
3. The maleimide resin according to claim 1 or 2, which contains a maleimide compound of an asymmetric diamine compound (C-1) obtained by bonding two different aromatic monoamine compounds (a) via a bonding agent (B).
4. An asymmetric bismaleimide compound is a maleimide compound of an asymmetric diamine compound (C-1) obtained by bonding two different aromatic monoamine compounds (A) via a bonding agent (B).
5. The asymmetric bismaleimide compound according to claim 4 represented by the following general formula (4),
Wherein Z is a divalent organic group having 1 to 200 carbon atoms; r is R 4 Each of which is a single pieceIndependently any one of aliphatic hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, halogen atom, aryl group, aralkyl group; in the formula, a plurality of R 4 Optionally the same or different; m is 0 or an integer of 1 to 4; in the formula, the structural portion α and the structural portion β surrounded by the dotted line have different structures from each other.
6. A curable composition comprising the maleimide resin according to any one of claims 1 to 3 or the asymmetric bismaleimide compound according to claim 4 or 5.
7. A cured product of the curable composition according to claim 6.
8. A semiconductor sealing material using the curable composition according to claim 6.
9. A semiconductor device using the semiconductor sealing material according to claim 8.
10. A prepreg comprising the curable composition according to claim 6.
11. A circuit substrate using the prepreg according to claim 10.
12. A laminated film using the curable composition according to claim 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2020-212256 | 2020-12-22 | ||
| JP2020212256 | 2020-12-22 | ||
| PCT/JP2021/042356 WO2022137913A1 (en) | 2020-12-22 | 2021-11-18 | Maleimide resin, asymmetric bismaleimide compound, curable composition, cured object, semiconductor-encapsulating material, semiconductor-encapsulating device, prepreg, circuit board, and build-up film |
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| CN116888098A true CN116888098A (en) | 2023-10-13 |
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| CN202180086105.1A Pending CN116888098A (en) | 2020-12-22 | 2021-11-18 | Maleimide resin, asymmetric bismaleimide compound, curable composition, cured product, semiconductor sealing material, semiconductor sealing device, prepreg, circuit board, and laminated film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7140307B1 (en) |
| KR (1) | KR20230113611A (en) |
| CN (1) | CN116888098A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE7506026L (en) * | 1974-07-02 | 1976-01-05 | Ciba Geigy Ag | STOCK-STABLE, MATERTABLE MIXTURES. |
| CH597184A5 (en) * | 1976-04-09 | 1978-03-31 | Ciba Geigy Ag | |
| EP0385937A1 (en) | 1989-02-28 | 1990-09-05 | Ciba-Geigy Ag | Curable blends based on aromatic bismaleinimides |
| JPH02300223A (en) * | 1989-05-16 | 1990-12-12 | Mitsubishi Petrochem Co Ltd | Polyimide |
| JPH0431464A (en) * | 1990-05-25 | 1992-02-03 | Mitsubishi Petrochem Co Ltd | Curing resin composition for circuit and metal foil-clad resin board |
| JPH06128225A (en) | 1992-10-19 | 1994-05-10 | Mitsubishi Petrochem Co Ltd | Production of amorphous bismaleimide |
| KR101680274B1 (en) * | 2013-06-27 | 2016-11-29 | 제일모직 주식회사 | Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns including the patterns |
| US20220251254A1 (en) * | 2019-04-26 | 2022-08-11 | Dic Corporation | Maleimide, curable resin composition, and cured product |
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