JP2018065903A - Thermosetting resin composition - Google Patents
Thermosetting resin composition Download PDFInfo
- Publication number
- JP2018065903A JP2018065903A JP2016204408A JP2016204408A JP2018065903A JP 2018065903 A JP2018065903 A JP 2018065903A JP 2016204408 A JP2016204408 A JP 2016204408A JP 2016204408 A JP2016204408 A JP 2016204408A JP 2018065903 A JP2018065903 A JP 2018065903A
- Authority
- JP
- Japan
- Prior art keywords
- group
- resin composition
- thermosetting resin
- general formula
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 54
- -1 maleimide compound Chemical class 0.000 claims abstract description 83
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 14
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- CBLQGONGXCLTDI-UHFFFAOYSA-M dodecanoate;tetrabutylphosphanium Chemical compound CCCCCCCCCCCC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC CBLQGONGXCLTDI-UHFFFAOYSA-M 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- IDAACRIGFOMRCR-UHFFFAOYSA-M C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 IDAACRIGFOMRCR-UHFFFAOYSA-M 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 abstract description 17
- 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 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000005496 phosphonium group Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CJOAXRVQBILODR-UHFFFAOYSA-N (2,3,4,5-tetraethylphenyl)phosphane Chemical group CCC1=CC(P)=C(CC)C(CC)=C1CC CJOAXRVQBILODR-UHFFFAOYSA-N 0.000 description 1
- RXCOGDYOZQGGMK-UHFFFAOYSA-N (3,4-diaminophenyl)-phenylmethanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=CC=C1 RXCOGDYOZQGGMK-UHFFFAOYSA-N 0.000 description 1
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- FEMXBCRRAJLQAS-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-1,4-dicarboxylic acid Chemical compound C1CCCC2C(C(=O)O)CCC(C(O)=O)C21 FEMXBCRRAJLQAS-UHFFFAOYSA-N 0.000 description 1
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- UTRLJOWPWILGSB-UHFFFAOYSA-N 1-[(2,5-dioxopyrrol-1-yl)methoxymethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1COCN1C(=O)C=CC1=O UTRLJOWPWILGSB-UHFFFAOYSA-N 0.000 description 1
- VBRQKZUHWJXGLS-UHFFFAOYSA-N 1-[10-(2,5-dioxopyrrol-1-yl)decyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCCCCCN1C(=O)C=CC1=O VBRQKZUHWJXGLS-UHFFFAOYSA-N 0.000 description 1
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 description 1
- FXEKNWLZNLIDNR-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)propyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCN1C(=O)C=CC1=O FXEKNWLZNLIDNR-UHFFFAOYSA-N 0.000 description 1
- JAZKPFCQIJDBSX-UHFFFAOYSA-N 1-[3-[4-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]benzoyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=C(C=CC=2)N2C(C=CC2=O)=O)C=CC=1C(=O)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O JAZKPFCQIJDBSX-UHFFFAOYSA-N 0.000 description 1
- WXXSHAKLDCERGU-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)butyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCN1C(=O)C=CC1=O WXXSHAKLDCERGU-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- UBHKXQBETYIDCF-UHFFFAOYSA-N 1-[4-[3-[3-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]sulfonylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=CC(S(=O)(=O)C=2C=C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)C=CC=2)=C1 UBHKXQBETYIDCF-UHFFFAOYSA-N 0.000 description 1
- XOJRVZIYCCJCRD-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 XOJRVZIYCCJCRD-UHFFFAOYSA-N 0.000 description 1
- ZXZWXBTZYQSCRW-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfanylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1SC1=CC=C(N2C(C=CC2=O)=O)C=C1 ZXZWXBTZYQSCRW-UHFFFAOYSA-N 0.000 description 1
- GUIACFHOZIQGKX-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfonylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 GUIACFHOZIQGKX-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
- GHFWOKVOEMYDGO-UHFFFAOYSA-N 1-[4-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]butoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OCCCCOC1=CC=C(N2C(C=CC2=O)=O)C=C1 GHFWOKVOEMYDGO-UHFFFAOYSA-N 0.000 description 1
- LEOVPJSXLVTEPT-UHFFFAOYSA-N 1-[4-[4-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfanylphenoxy]phenyl]sulfanylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1SC(C=C1)=CC=C1OC(C=C1)=CC=C1SC1=CC=C(N2C(C=CC2=O)=O)C=C1 LEOVPJSXLVTEPT-UHFFFAOYSA-N 0.000 description 1
- KHRIGFZHBWEFPA-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]-phenylmethyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(C(C=2C=CC=CC=2)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 KHRIGFZHBWEFPA-UHFFFAOYSA-N 0.000 description 1
- AXUFKGAEDKHCBU-UHFFFAOYSA-N 1-[4-chloro-3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound ClC1=CC=C(N2C(C=CC2=O)=O)C=C1N1C(=O)C=CC1=O AXUFKGAEDKHCBU-UHFFFAOYSA-N 0.000 description 1
- XNMVBFGQPBLPKO-UHFFFAOYSA-N 1-[5-(2,5-dioxopyrrol-1-yl)pentyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCN1C(=O)C=CC1=O XNMVBFGQPBLPKO-UHFFFAOYSA-N 0.000 description 1
- XQCDLHVXAXBMGW-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)-3,5,5-trimethylhexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC(C)(C)CC(C)CCN1C(=O)C=CC1=O XQCDLHVXAXBMGW-UHFFFAOYSA-N 0.000 description 1
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 description 1
- BURPWGASPJJGEM-UHFFFAOYSA-N 1-[7-(2,5-dioxopyrrol-1-yl)heptyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCCN1C(=O)C=CC1=O BURPWGASPJJGEM-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
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- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
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- JGMHZIHMNAXXPH-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-diethoxyphosphinothioyloxy-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)ON=C(C(=O)OP(=S)(OCC)OCC)C1=CSC(N)=N1 JGMHZIHMNAXXPH-UHFFFAOYSA-N 0.000 description 1
- SBCUXVQZGCKZET-UHFFFAOYSA-N tetrabenzylphosphanium Chemical group C=1C=CC=CC=1C[P+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 SBCUXVQZGCKZET-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical group CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical group C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical group C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、熱硬化性樹脂組成物に関する。 The present invention relates to a thermosetting resin composition.
従来、複合材料用マトリックス樹脂として、高い伸度を有し補強材との接着に優れたエポキシ樹脂が広く用いられてきた。しかしながら、複合材料の採用が進められている航空、宇宙、防衛産業等の先端技術分野においては、より優れた機械的強度、耐熱性、加工性、寸法精度を有する部品を低コストで成形することが求められており、マトリックス樹脂としてビスマレイミド樹脂の利用が検討されている。 Conventionally, epoxy resins having high elongation and excellent adhesion to reinforcing materials have been widely used as matrix resins for composite materials. However, in advanced technology fields such as aviation, space, and defense industries where composite materials are being adopted, parts with superior mechanical strength, heat resistance, workability, and dimensional accuracy can be molded at low cost. Therefore, the use of bismaleimide resin as a matrix resin is being studied.
しかし、ビスマレイミド樹脂を利用するには、硬化条件として２００℃以上の高温で且つ長時間の処理が必要となり、生産性及び加工性が悪いという欠点がある。例えば、特許文献１には、ビスマレイミド化合物とベンゾオキサジン化合物の混合物の重合物（硬化物）が提案されている。しかしながら、このようなポリベンゾオキサジン変性ビスマレイミド樹脂組成物を硬化させるに当たっては、２００℃以上の加熱温度を必要とし、実用に供し難いものであった。 However, in order to use a bismaleimide resin, a high temperature of 200 ° C. or higher is required as a curing condition, and there is a disadvantage that productivity and workability are poor. For example, Patent Document 1 proposes a polymer (cured product) of a mixture of a bismaleimide compound and a benzoxazine compound. However, in order to cure such a polybenzoxazine-modified bismaleimide resin composition, a heating temperature of 200 ° C. or higher is required, which is difficult to be put into practical use.
一方、低温硬化させるため、過酸化物の使用が提案されているが、過酸化物が空気酸化により失活してしまうため、安定した品質の硬化膜が得られなかったり、窒素雰囲気下で硬化させる必要が生じる等、未だ満足すべき成果が得られていない。 On the other hand, the use of peroxide has been proposed for curing at low temperature, but the peroxide is deactivated by air oxidation, so a cured film with a stable quality cannot be obtained or cured in a nitrogen atmosphere. We have not yet achieved satisfactory results.
本発明は、優れた耐熱性を有する硬化物を形成でき、且つ低温硬化が可能な熱硬化性樹脂組成物を提供することを目的とする。 An object of this invention is to provide the thermosetting resin composition which can form the hardened | cured material which has the outstanding heat resistance, and can be cured at low temperature.
本発明者等は上記の課題を解決すべく検討を進めた結果、下記の本発明により当該課題を解決できることを見出した。
すなわち、本発明は、以下の発明を提供する。
［１］（Ａ）下記一般式（１）で表される１分子内に少なくとも２つのイミド結合を有するマレイミド化合物、及び、下記一般式（１）で表されるマレイミド化合物以外の、下記一般式（２）で表される１分子内に少なくとも２つのマレイミド基を有するマレイミド化合物からなる群より選択される１種以上のマレイミド化合物と、（Ｂ）下記一般式（３）で表されるアニオン種に１つ以上のカルボキシ基を有するホスホニウム塩と、を含有する熱硬化性樹脂組成物。
［式（１）中、Ｒ１及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示し、ｎは１〜１００の整数を示す。］
［式（２）中、Ｒ２は二価の有機基を示す。］
［式（３）中、Ｒ３〜Ｒ７は各々独立に一価の有機基を示す。］
［２］上記（Ａ）マレイミド化合物が、上記一般式（１）で表されるマレイミド化合物を少なくとも含む、上記［１］に記載の熱硬化性樹脂組成物。
［３］上記（Ｂ）ホスホニウム塩の含有量が、上記（Ａ）マレイミド化合物１００質量部に対して０．１〜５．０質量部である、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］上記一般式（３）中、上記Ｒ３〜Ｒ６は各々独立に、置換又は非置換の炭素数１〜１０の脂肪族基、置換又は非置換の芳香族基を示す、上記［１］〜［３］のいずれかに記載の熱硬化性樹脂組成物。
［５］上記一般式（３）中、上記Ｒ３〜Ｒ６は各々独立に、フェニル基、メチル基、エチル基、ｎ−プロピル基又はｎ−ブチル基を示す、上記［１］〜［４］のいずれかに記載の熱硬化性樹脂組成物。
［６］上記（Ｂ）ホスホニウム塩における上記アニオン種が、フタル酸、１，２−シクロへキシルジカルボン酸又はラウリン酸である、上記［１］〜［５］のいずれかに記載の熱硬化性樹脂組成物。
［７］上記（Ｂ）ホスホニウム塩が、テトラフェニルホスホニウム−フタル酸、テトラブチルホスホニウム−１，２−シクロへキシルジカルボン酸、及び、テトラブチルホスホニウム−ラウリン酸からなる群より選択される１種以上を含む、上記［１］〜［６］のいずれかに記載の熱硬化性樹脂組成物。
As a result of investigations to solve the above problems, the present inventors have found that the problems can be solved by the following present invention.
That is, the present invention provides the following inventions.
[1] (A) The following general formula other than the maleimide compound having at least two imide bonds in one molecule represented by the following general formula (1) and the maleimide compound represented by the following general formula (1) One or more maleimide compounds selected from the group consisting of maleimide compounds having at least two maleimide groups in one molecule represented by (2), and (B) an anionic species represented by the following general formula (3) And a phosphonium salt having one or more carboxy groups.
[In the formula (1), R 1 and Q are each independently a substituted or unsubstituted aliphatic group having 1 to 100 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, Alternatively, a substituted or unsubstituted siloxane moiety having 1 to 100 silicon atoms is shown, and n represents an integer of 1 to 100. ]
[In the formula (2), R 2 represents a divalent organic group. ]
[In the formula (3), it represents a monovalent organic group independently each R 3 to R 7. ]
[2] The thermosetting resin composition according to [1], wherein the maleimide compound (A) includes at least the maleimide compound represented by the general formula (1).
[3] The heat according to [1] or [2], wherein the content of the (B) phosphonium salt is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the (A) maleimide compound. Curable resin composition.
[4] In the above general formula (3), each of R 3 to R 6 independently represents a substituted or unsubstituted aliphatic group having 1 to 10 carbon atoms or a substituted or unsubstituted aromatic group. The thermosetting resin composition according to any one of [1] to [3].
[5] In the above general formula (3), each of R 3 to R 6 independently represents a phenyl group, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. ] The thermosetting resin composition in any one of.
[6] The thermosetting property according to any one of [1] to [5], wherein the anionic species in the (B) phosphonium salt is phthalic acid, 1,2-cyclohexyldicarboxylic acid or lauric acid. Resin composition.
[7] The phosphonium salt (B) is one or more selected from the group consisting of tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, and tetrabutylphosphonium-lauric acid. The thermosetting resin composition according to any one of the above [1] to [6].
本発明の熱硬化性樹脂組成物によれば、上記特定の（Ａ）マレイミド化合物を用いることにより、優れた耐熱性を有する硬化物を形成することができるとともに、上記特定の（Ｂ）ホスホニウム塩を（Ａ）マレイミド化合物と組み合わせて用いることにより、上記耐熱性の向上効果を維持したまま、優れた低温硬化性を得ることができる。 According to the thermosetting resin composition of the present invention, by using the specific (A) maleimide compound, a cured product having excellent heat resistance can be formed, and the specific (B) phosphonium salt. By using in combination with (A) the maleimide compound, excellent low temperature curability can be obtained while maintaining the heat resistance improving effect.
本発明によれば、優れた耐熱性を有する硬化物を形成でき、且つ低温硬化が可能な熱硬化性樹脂組成物を提供することができる。本発明の熱硬化性樹脂組成物は、優れた耐熱性を有する硬化物を形成でき、且つ低温で硬化させることができるので、その成形加工性を飛躍的に改善させることが期待される。 ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can form the hardened | cured material which has the outstanding heat resistance, and can be cured at low temperature can be provided. Since the thermosetting resin composition of the present invention can form a cured product having excellent heat resistance and can be cured at a low temperature, it is expected to dramatically improve its molding processability.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本実施形態の熱硬化性樹脂組成物は、マレイミド成分として１分子内に少なくとも２つのマレイミド基を有する（Ａ）マレイミド化合物と、硬化促進剤として（Ｂ）ホスホニウム塩と、を含有する。 The thermosetting resin composition of this embodiment contains (A) a maleimide compound having at least two maleimide groups in one molecule as a maleimide component, and (B) a phosphonium salt as a curing accelerator.
本実施形態において使用する（Ａ）マレイミド化合物は、下記一般式（１）で表される１分子内に少なくとも２つのイミド結合を有するマレイミド化合物（以下、「（Ａ−１）マレイミド化合物」という）、及び、下記一般式（１）で表されるマレイミド化合物以外の、下記一般式（２）で表される１分子内に少なくとも２つのマレイミド基を有するマレイミド化合物（以下、「（Ａ−２）マレイミド化合物」という）からなる群より選択される１種以上のマレイミド化合物である。 The maleimide compound (A) used in this embodiment is a maleimide compound having at least two imide bonds in one molecule represented by the following general formula (1) (hereinafter referred to as “(A-1) maleimide compound”). And a maleimide compound having at least two maleimide groups in one molecule represented by the following general formula (2) other than the maleimide compound represented by the following general formula (1) (hereinafter referred to as “(A-2) One or more maleimide compounds selected from the group consisting of “maleimide compounds”.
上記一般式（１）中、Ｒ１は、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示すが、分子鎖が短すぎると、柔軟性に劣り、分子鎖が長すぎると、溶剤溶解性に劣る。両者のバランスをとる観点から、Ｒ１の炭素数又はケイ素数は１０〜８０が好ましく、２０〜５０がより好ましい。 In the general formula (1), R 1 is a substituted or unsubstituted aliphatic group having 1 to 100 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, or substituted or unsubstituted Although an unsubstituted siloxane site having 1 to 100 silicon atoms is shown, if the molecular chain is too short, the flexibility is poor, and if the molecular chain is too long, the solvent solubility is poor. From the viewpoint of balancing the two, the carbon number or silicon number of R 1 is preferably 10 to 80, and more preferably 20 to 50.
上記一般式（１）中、Ｑは、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示すが、溶剤溶解性の観点から、Ｑの炭素数又はケイ素数は１〜３０が好ましい。 In the general formula (1), Q is a substituted or unsubstituted aliphatic group having 1 to 100 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, or a substituted or unsubstituted group. A substituted siloxane moiety having 1 to 100 silicon atoms is shown. From the viewpoint of solvent solubility, the carbon number or silicon number of Q is preferably 1 to 30.
上記一般式（１）中、ｎは１〜１００の整数を示すが、１〜１０の整数であってもよい。 In the general formula (1), n represents an integer of 1 to 100, but may be an integer of 1 to 10.
上記一般式（２）中、Ｒ２は二価の有機基を示すが、硬化物の耐熱性の観点から、芳香族基及び／又は脂肪族炭化水素基を有する二価の有機基であることが好ましい。 In the general formula (2), R 2 represents a divalent organic group, but is a divalent organic group having an aromatic group and / or an aliphatic hydrocarbon group from the viewpoint of heat resistance of the cured product. Is preferred.
上記一般式（１）で表される（Ａ−１）マレイミド化合物は、Ｄｅｓｉｇｎｅｒ Ｍｏｌｅｃｕｌｅｓ， Ｉｎｃ．社から商業的に入手できるが、低極性溶媒（ａ）中で、液状ジアミン化合物（ｂ）と酸二無水物（ｃ）を脱水縮合させ、得られるアミン末端ポリイミドに、酸化合物（ｄ）存在下、無水マレイン酸（ｅ）を脱水縮合させることで、合成することが可能である。 The (A-1) maleimide compound represented by the general formula (1) can be obtained from Designer Moleculars, Inc. Although it is commercially available from the company, the liquid diamine compound (b) and acid dianhydride (c) are dehydrated and condensed in the low polarity solvent (a), and the resulting amine-terminated polyimide contains an acid compound (d). Then, it can be synthesized by dehydrating and condensing maleic anhydride (e).
（Ａ−１）マレイミド化合物を合成する際に使用する低極性溶媒（ａ）としては例えば、トルエン、キシレン、メシチレン等の芳香族系溶媒、ヘキサン、シクロヘキサン等の飽和炭化水素系溶媒、原油蒸留時に得られる石油系溶媒などが挙げられるが、コスト、及び脱溶の容易さの観点から、トルエン、キシレンを使用することが好ましい。 (A-1) As a low polarity solvent (a) used when synthesizing a maleimide compound, for example, aromatic solvents such as toluene, xylene and mesitylene, saturated hydrocarbon solvents such as hexane and cyclohexane, and crude oil distillation Although the petroleum-type solvent etc. which are obtained are mentioned, It is preferable to use toluene and xylene from a viewpoint of cost and the ease of desorption.
（Ａ−１）マレイミド化合物を合成する際に使用する液状ジアミン化合物（ｂ）としては例えば、１，１０−ジアミノデカン；１，１２−ジアミノドデカン；ダイマージアミン；１，２−ジアミノ−２−メチルプロパン；１，２−ジアミノシクロヘキサン；１，２−ジアミノプロパン；１，３−ジアミノプロパン；１，４−ジアミノブタン；１，５−ジアミノペンタン；１，７−ジアミノヘプタン；１，８−ジアミノメンタン；１，８−ジアミノオクタン；１，９−ジアミノノナン；３，３’−ジアミノ−Ｎ−メチルジプロピルアミン；ジアミノマレオニトリル；１，３−ジアミノペンタン；９，１０−ジアミノフェナントレン；４，４’−ジアミノオクタフルオロビフェニル；３，５−ジアミノ安息香酸；３，７−ジアミノ−２−メトキシフルオレン；４，４’−ジアミノベンゾフェノン；３，４−ジアミノベンゾフェノン；３，４−ジアミノトルエン；２，６−ジアミノアントラキノン；２，６−ジアミノトルエン；２，３−ジアミノトルエン；１，８−ジアミノナフタレン；２，４−ジアミノトルエン；２，５−ジアミノトルエン；１，４−ジアミノアントラキノン；１，５−ジアミノアントラキノン；１，５−ジアミノナフタレン；１，２−ジアミノアントラキノン；２，４−クメンジアミン；１，３−ビスアミノメチルベンゼン；１，３−ビスアミノメチルシクロヘキサン；２−クロロ−１，４−ジアミノベンゼン；１，４−ジアミノ−２，５−ジクロロベンゼン；１，４−ジアミノ−２，５−ジメチルベンゼン；４，４’−ジアミノ−２，２’―ビストリフルオロメチルビフェニル；ビス（アミノ−３−クロロフェニ）エタン；ビス（４−アミノ−３，５−ジメチルフェニル）メタン；ビス（４−アミノ−３，５−ジエチルフェニル）メタン；ビス（４−アミノ−３−エチルジアミノフルオレン；ジアミノ安息香酸；２，３−ジアミノナフタレン；２，３−ジアミノフェノール；−５−メチルフェニル）メタン；ビス（４−アミノ−３−メチルフェニル）メタン；ビス（４−アミノ−３−エチルフェニル）メタン；４，４’−ジアミノフェニルスルホン；３，３’−ジアミノフェニルスルホン；２，２−ビス（４，（４アミノフェノキシ）フェニル）スルホン；２，２−ビス（４−（３−アミノフェノキシ）フェニル）スルホン；４，４’―オキシジアニリン；４，４’−ジアミノジフェニルスルフィド；３，４’−オキシジアニリン；２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン；１，３−ビス（４−アミノフェノキシ）ベンゼン；４，４’−ビス（４−アミノフェノキシ）ビフェニル；４，４’−ジアミノ−３，３’−ジヒドロキシビフェニル；４，４’−ジアミノ−３，３’―ジメチルビフェニル；４，４’−ジアミノ−３，３’−ジメトキシビフェニル；Ｂｉｓａｎｉｌｉｎｅ Ｍ；Ｂｉｓａｎｉｌｉｎｅ Ｐ；９，９−ビス（４−アミノフェニル）フルオレン；ｏ‐トリジンスルホン；メチレンビス（アントラニル酸）；１，３−ビス（４−アミノフェノキシ）−２，２−ジメチルプロパン；１，３−ビス（４−アミノフェノキシ）プロパン；１，４−ビス（４−アミノフェノキシ）ブタン；１，５−ビス（４−アミノフェノキシ）ブタン；２，３，５，６−テトラメチル−１，４−フェニレンジアミン；３，３’，５，５’−テトラメチルベンジジン；４，４’−ジアミノベンザニリド；２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン；ポリオキシアルキレンジアミン類（例えば、Ｈｕｎｔｓｍａｎ社の Ｊｅｆｆａｍｉｎｅ Ｄ−２３０、Ｄ４００、Ｄ−２０００及びＤ−４０００）；１，３−シクロヘキサンビス（メチルアミン）；ｍ−キシリレンジアミン；ｐ−キシリレンジアミン；ビス（４−アミノ−３−メチルシクロヘキシル）メタン；１，２−ビス（２−アミノエトキシ）エタン；３（４），８（９）−ビス（アミノメチル）トリシクロ（５．２．１．０２，６）デカン；等が挙げられるが、下記一般式（４）又は（５）で表される、炭素数３０〜４０のダイマー酸から成るジアミン化合物が好ましい。下記一般式（４）及び（５）で表されるジアミン化合物は、耐熱性及び柔軟性に優れ、また、極性の高い置換基を有さないため、低誘電特性に優れる。下記一般式（４）及び（５）で表されるジアミン化合物は、Ｃｒｏｄａ社、Ｃｏｇｎｉｓ社、ＢＡＳＦ社等から商業的に入手できる。
（Ａ−１）マレイミド化合物を合成する際に使用する酸二無水物（ｃ）としては例えば、無水ピロメリト酸；１，２，３，４−シクロブタンテトラカルボン酸二無水物；１，４，５，８−ナフタレンテトラカルボン酸二無水物；３，４，９，１０−ペリレンテトラカルボン酸二無水物；ビシクロ（２．２．２）オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物；ジエチレントリアミンペンタ酢酸二無水物；エチレンジアミン四酢酸二無水物；３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物；３，３’，４，４’−ビフェニルテトラカルボン酸二無水物；４，４’−オキシジフタリックス無水物；３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物；２，２’−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物；４，４’−ビスフェノールＡ ジフタル酸無水物；５−（２，５−ジオキシテトラヒドロ）−３−メチル−３−シクロヘキセン−１，２−ジカルボン無水物；エチレングリコールビス（トリメリット酸無水物）；ヒドロキノンジフタル酸無水物；アリルナディック酸無水物（ａｌｌｙｌ ｎａｄｉｃ ａｎｈｙｄｒｉｄｅ）；２−オクテン−１−イルコハク酸無水物；１，２，３，６−テトラヒドロフタル酸無水物；３，４，５，６−テトラヒドロフタル酸無水物等が挙げられるが、コストの観点から、無水ピロメリト酸を使用することが好ましい。 (A-1) Acid dianhydride (c) used for synthesizing the maleimide compound includes, for example, pyromellitic anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,4,5 , 8-Naphthalenetetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride; bicyclo (2.2.2) oct-7-ene-2,3,5,6-tetra Diethylenetriaminepentaacetic acid dianhydride; Ethylenediaminetetraacetic acid dianhydride; 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride; 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride; 4,4′-oxydiphthalic anhydride; 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride; 2,2′-bis (3,4-dicarboxyl Nyl) hexafluoropropane dianhydride; 4,4′-bisphenol A diphthalic anhydride; 5- (2,5-dioxytetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; ethylene Glycol bis (trimellitic anhydride); hydroquinone diphthalic anhydride; allyl nadic anhydride; 2-octen-1-ylsuccinic anhydride; 1,2,3,6-tetrahydrophthal Examples include acid anhydrides; 3,4,5,6-tetrahydrophthalic anhydride and the like. From the viewpoint of cost, it is preferable to use pyromellitic anhydride.
（Ａ−１）マレイミド化合物を合成する際に使用する酸化合物（ｄ）としては例えば、メタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸等のスルホン酸、蟻酸、酢酸、マレイン酸等の有機酸などが挙げられるが、コスト及び副反応低減の観点から、メタンスルホン酸を使用することが好ましい。 (A-1) Examples of the acid compound (d) used for synthesizing the maleimide compound include sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and organic materials such as formic acid, acetic acid and maleic acid. Examples of the acid include methanesulfonic acid from the viewpoints of cost and side reaction reduction.
本実施形態において、（Ａ−１）マレイミド化合物は、低温硬化性及び硬化物の耐熱性をより向上する観点から、下記一般式（１−１）〜（１−３）で表される化合物であってもよい。一般式（１−１）〜（１−３）中のＲ１及びｎは、一般式（１）中のＲ１及びｎと同義である。 In the present embodiment, the (A-1) maleimide compound is a compound represented by the following general formulas (1-1) to (1-3) from the viewpoint of further improving the low temperature curability and the heat resistance of the cured product. There may be. R 1 and n in the general formula (1-1) to (1-3) has the same definition as R 1 and n in the general formula (1).
一般式（１−１）〜（１−３）で表される化合物としてより具体的には、下記式（１−４）〜（１−６）で表される化合物が挙げられる。式（１−４）〜（１−６）において、ｎは１〜１００の整数を示す。 More specifically, examples of the compounds represented by the general formulas (1-1) to (1-3) include compounds represented by the following formulas (1-4) to (1-6). In formulas (1-4) to (1-6), n represents an integer of 1 to 100.
（Ａ−１）マレイミド化合物の分子量は特に限定されない。（Ａ−１）マレイミド化合物の重量平均分子量（Ｍｗ）の下限値は、１０００、２０００、３０００又は５０００であってもよい。また、（Ａ−１）マレイミド化合物のＭｗの上限値は、３００００、２００００、１２０００又は７０００であってもよい。（Ａ−１）マレイミド化合物のＭｗは、１０００〜３００００であってもよく、１５００〜２００００であってもよく、１５００〜２００００であってもよく、２０００〜１２０００であってもよく、２５００〜７０００であってもよい。 (A-1) The molecular weight of the maleimide compound is not particularly limited. (A-1) The lower limit of the weight average molecular weight (Mw) of the maleimide compound may be 1000, 2000, 3000, or 5000. Further, the upper limit value of Mw of the (A-1) maleimide compound may be 30000, 20000, 12000 or 7000. (A-1) Mw of the maleimide compound may be 1000 to 30000, 1500 to 20000, 1500 to 20000, 2000 to 12000, 2500 to 7000. It may be.
（Ａ−１）マレイミド化合物のＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定することができる。 (A-1) Mw of the maleimide compound can be measured by gel permeation chromatography (GPC) method.
なお、ＧＰＣの測定条件は下記のとおりである。
ポンプ：Ｌ−６２００型［株式会社日立ハイテクノロジーズ製］
検出器：Ｌ−３３００型ＲＩ［株式会社日立ハイテクノロジーズ製］
カラムオーブン：Ｌ−６５５Ａ−５２［株式会社日立ハイテクノロジーズ製］
ガードカラム及びカラム：ＴＳＫ Ｇｕａｒｄｃｏｌｕｍｎ ＨＨＲ−Ｌ＋ＴＳＫｇｅ
ｌ Ｇ４０００ＨＨＲ＋ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ［すべて東ソー株式会社製、商
品名］
カラムサイズ：６．０×４０ｍｍ（ガードカラム）、７．８×３００ｍｍ（カラム）
溶離液：テトラヒドロフラン
試料濃度：３０ｍｇ／５ｍＬ
注入量：２０μＬ
流量：１．００ｍＬ／分
測定温度：３０℃
The measurement conditions for GPC are as follows.
Pump: L-6200 [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolumn HHR-L + TSKge
l G4000HHR + TSKgel G2000HHR [All brand names made by Tosoh Corporation]
Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 30 ° C
上記一般式（２）で表される（Ａ−２）マレイミド化合物は、公知の方法（例えば、特公昭５１−６１５３号公報、米国特許第３０１８２９０号明細書を参照）に従って、アミン化合物（ｆ）と無水マレイン酸（ｅ）とを反応させる（マレイミド化する）ことにより合成される。 The maleimide compound (A-2) represented by the general formula (2) is converted into an amine compound (f) according to a known method (for example, see Japanese Patent Publication No. 51-6153 and US Pat. No. 3,018,290). And maleic anhydride (e) are reacted (maleimidated).
（Ａ−２）マレイミド化合物を合成する際に使用するアミン化合物（ｆ）としては例えば、エチレンジアミン；ヘキサメチレンジアミン；２，２，４−トリメチルヘキサメチレンジアミン；フェニレンジアミン類；トリレンジアミン類；４，４’−ジアミノジフェニルメタン；４，４’−ジアミノジフェニルエーテル；４，４’−ジアミノジフェニルスルホン；１，４−ビス（４−アミノフェノキシ）ベンゼン；１，４−ビス（４−アミノベンジル）ベンゼン；１，４−ビス［１−（４−アミノフェニル）−１−メチルエチル］ベンゼン；９，９−ビス［４−（４−アミノフェノキシ）フェニル］フルオレン；ビス［４−（４−アミノフェノキシ）フェニル］スルホン；１，４−ビス｛１−［４−（４−アミノフェノキシ）フェニル］−１−メチルエチル｝ベンゼン；上記一般式（４）又は（５）で表される、炭素数３０〜４０のダイマー酸から成るジアミン化合物等が挙げられる。 (A-2) Examples of the amine compound (f) used in the synthesis of the maleimide compound include ethylenediamine; hexamethylenediamine; 2,2,4-trimethylhexamethylenediamine; phenylenediamines; tolylenediamines; 4,4′-diaminodiphenyl ether; 4,4′-diaminodiphenyl sulfone; 1,4-bis (4-aminophenoxy) benzene; 1,4-bis (4-aminobenzyl) benzene; 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene; 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene; bis [4- (4-aminophenoxy) Phenyl] sulfone; 1,4-bis {1- [4- (4-aminophenoxy) phenyl] -1- Chiruechiru} benzene; represented by the above general formula (4) or (5) include diamine compounds consisting of dimer acids 30-40 carbon atoms.
このようなアミン化合物（ｆ）を使用したマレイミド化合物としては例えば、Ｎ，Ｎ’−（２，２，４−トリメチルヘキサメチレン）ビスマレイミド；Ｎ，Ｎ’−デカメチレンビスマレイミド；Ｎ，Ｎ’−オクタメチレンビスマレイミド；Ｎ，Ｎ’−ヘプタメチレンビスマレイミド；Ｎ，Ｎ’−ヘキサメチレンビスマレイミド；Ｎ，Ｎ’−ペンタメチレンビスマレイミド；Ｎ，Ｎ’−テトラメチレンビスマレイミド；Ｎ，Ｎ’−トリメチレンビスマレイミド；Ｎ，Ｎ’−エチレンビスマレイミド；Ｎ，Ｎ’−（オキシジメチレン）ビスマレイミド；１，１３−ビスマレイミド−４，７，１０−トリオキサトリデカン；１，１１−ビスマレイミド−３，６，９−トリオキサウンデカン等の脂肪族系ビスマレイミド化合物をはじめとして、Ｎ，Ｎ’−（４−メチル−１，３−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（１，３−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（１，４−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（１，２−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（１，５−ナフチレン）ビスマレイミド；Ｎ，Ｎ’−（４−クロロ−１，３−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（メチレンジ−ｐ−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（４，４’−ビフェニレン）ビスマレイミド；Ｎ，Ｎ’−（スルホニルジ−ｐ−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（オキシジ−ｐ−フェニレン）ビスマレイミド；Ｎ，Ｎ’−（３，３’−ジメチル−４，４’−ビフェニレン）ビスマレイミド；Ｎ，Ｎ’−（ベンジリデンジ−ｐ−フェニレン）ビスマレイミド；Ｎ，Ｎ’−［メチレンビス（３−クロロ−４−フェニレン）］ビスマレイミド；Ｎ，Ｎ’−［メチレンビス（３−メチル−４−フェニレン）］ビスマレイミド；Ｎ，Ｎ’−［メチレンビス（３−メトキシ−４−フェニレン）］ビスマレイミド；Ｎ，Ｎ’−（チオジ−ｐ−フェニレン）ビスマレイミド；Ｎ，Ｎ’−３，３’−ベンゾフェノンビスマレイミド；Ｎ，Ｎ’−［メチレンビス（３−メチル−５−エチル−４−フェニレン）］ビスマレイミド；Ｎ，Ｎ’−［テトラメチレンビス（オキシ−ｐ−フェニレン）］ビスマレイミド；２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン；ビス［４−（４−マレイミドフェノキシ）フェニル）］スルホン；１，４−フェニレンビス（４−マレイミドフェノキシ）；ビス［３−（４−マレイミドフェノキシ）フェニル］スルホン；ビス［４−（３−マレイミドフェノキシ）フェニル］ケトン；１，３−フェニレンビス（４−マレイミドフェノキシ）；ビス［４−（４−マレイミドフェニルチオ）フェニル］エーテル等の芳香族系マレイミド化合物が挙げられる。なお、本実施形態においては、１種類のマレイミド化合物を単独で使用してもよく、種類の異なるマレイミド化合物を組み合わせて使用してもよい。上記一般式（２）で表される（Ａ−２）マレイミド化合物は、上記一般式（１）で表される（Ａ−１）マレイミド化合物に該当しないマレイミド化合物から選ばれる。 Examples of maleimide compounds using such an amine compound (f) include N, N ′-(2,2,4-trimethylhexamethylene) bismaleimide; N, N′-decamethylene bismaleimide; N, N ′. -Octamethylene bismaleimide; N, N'-heptamethylene bismaleimide; N, N'-hexamethylene bismaleimide; N, N'-pentamethylene bismaleimide; N, N'-tetramethylene bismaleimide; N, N ' -Trimethylene bismaleimide; N, N'-ethylene bismaleimide; N, N '-(oxydimethylene) bismaleimide; 1,13-bismaleimide-4,7,10-trioxatridecane; Including aliphatic bismaleimide compounds such as bismaleimide-3,6,9-trioxaundecane, N, N -(4-Methyl-1,3-phenylene) bismaleimide; N, N '-(1,3-phenylene) bismaleimide; N, N'-(1,4-phenylene) bismaleimide; N, N'- (1,2-phenylene) bismaleimide; N, N ′-(1,5-naphthylene) bismaleimide; N, N ′-(4-chloro-1,3-phenylene) bismaleimide; N, N ′-( Methylenedi-p-phenylene) bismaleimide; N, N ′-(4,4′-biphenylene) bismaleimide; N, N ′-(sulfonyldi-p-phenylene) bismaleimide; N, N ′-(oxydi-p -Phenylene) bismaleimide; N, N '-(3,3'-dimethyl-4,4'-biphenylene) bismaleimide; N, N'-(benzylidenedi-p-phenylene) bismaleimide; N, N ' [Methylenebis (3-chloro-4-phenylene)] bismaleimide; N, N ′-[methylenebis (3-methyl-4-phenylene)] bismaleimide; N, N ′-[methylenebis (3-methoxy-4-phenylene) )] Bismaleimide; N, N ′-(thiodi-p-phenylene) bismaleimide; N, N′-3,3′-benzophenone bismaleimide; N, N ′-[methylenebis (3-methyl-5-ethyl- 4-phenylene)] bismaleimide; N, N ′-[tetramethylenebis (oxy-p-phenylene)] bismaleimide; 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane; bis [4- (4-maleimidophenoxy) phenyl)] sulfone; 1,4-phenylenebis (4-maleimidophenoxy); bis [3- (4-male Imidophenoxy) phenyl] sulfone; bis [4- (3-maleimidophenoxy) phenyl] ketone; 1,3-phenylenebis (4-maleimidophenoxy); bis [4- (4-maleimidophenylthio) phenyl] ether, etc. Aromatic maleimide compounds are exemplified. In the present embodiment, one type of maleimide compound may be used alone, or different types of maleimide compounds may be used in combination. The (A-2) maleimide compound represented by the general formula (2) is selected from maleimide compounds not corresponding to the (A-1) maleimide compound represented by the general formula (1).
本実施形態の熱硬化性樹脂組成物において、（Ａ）マレイミド化合物としては、上記一般式（１）で表される（Ａ−１）マレイミド化合物のみを使用してもよく、上記一般式（２）で表される（Ａ−２）マレイミド化合物のみを使用してもよく、（Ａ−１）マレイミド化合物及び（Ａ−２）マレイミド化合物の両方を併用してもよいが、熱硬化性樹脂組成物の低温硬化性と得られる硬化物の耐熱性とをより高水準で両立できることから、（Ａ−１）マレイミド化合物のみを使用するか、（Ａ−１）マレイミド化合物及び（Ａ−２）マレイミド化合物の両方を併用することが好ましい。いずれの場合においても、（Ａ−１）マレイミド化合物は１種を単独で又は２種以上を組み合わせて用いてもよく、（Ａ−２）マレイミド化合物は１種を単独で又は２種以上を組み合わせて用いてもよい。 In the thermosetting resin composition of the present embodiment, as the (A) maleimide compound, only the (A-1) maleimide compound represented by the general formula (1) may be used. The (A-2) maleimide compound represented by (A-2) may be used alone, or both (A-1) maleimide compound and (A-2) maleimide compound may be used in combination, but the thermosetting resin composition Since the low temperature curability of the product and the heat resistance of the resulting cured product can be compatible at a higher level, either (A-1) maleimide compound alone is used, or (A-1) maleimide compound and (A-2) maleimide It is preferable to use both compounds together. In any case, (A-1) maleimide compound may be used alone or in combination of two or more, and (A-2) maleimide compound may be used alone or in combination of two or more. May be used.
本実施形態の熱硬化性樹脂組成物において、（Ａ）マレイミド化合物に占める（Ａ−１）マレイミド化合物の割合は、熱硬化性樹脂組成物の低温硬化性と得られる硬化物の耐熱性とをより高水準で両立できることから、（Ａ）マレイミド化合物全量を基準として、３０〜１００質量％であることが好ましく、６０〜１００質量％であることがより好ましい。 In the thermosetting resin composition of the present embodiment, the ratio of the (A-1) maleimide compound to the (A) maleimide compound is the low temperature curability of the thermosetting resin composition and the heat resistance of the resulting cured product. Since it is compatible at a higher level, it is preferably 30 to 100% by mass, more preferably 60 to 100% by mass based on the total amount of the (A) maleimide compound.
本実施形態の熱硬化性樹脂組成物において、（Ａ）マレイミド化合物の含有量は、熱硬化性樹脂組成物の固形分全量を基準として６０．０〜９９．９質量％であることが好ましく、７５．０〜９９．０質量％であることがより好ましく、９０．０〜９７．０質量％であることが更に好ましい。（Ａ）マレイミド化合物の含有量が６０．０質量％以上であると、より優れた耐熱性を有する硬化物を形成できる傾向がある。（Ａ）マレイミド化合物の含有量が９９．９質量％以下であると、低温硬化性をより向上させることができる傾向がある。 In the thermosetting resin composition of the present embodiment, the content of the (A) maleimide compound is preferably 60.0 to 99.9% by mass based on the total solid content of the thermosetting resin composition, It is more preferably 75.0 to 99.0% by mass, and further preferably 90.0 to 97.0% by mass. (A) There exists a tendency which can form the hardened | cured material which has more excellent heat resistance in content of a maleimide compound being 60.0 mass% or more. (A) There exists a tendency which low temperature curability can be improved more as content of a maleimide compound is 99.9 mass% or less.
なお、本明細書において、固形分とは、常温且つ常圧条件下における不揮発成分を意味し、常温且つ常圧条件下で液状、水飴状及びワックス状のものも含む。したがって、熱硬化性樹脂組成物の固形分全量とは、熱硬化性樹脂組成物の全量から揮発性成分（溶剤等）の量を除いた量を意味する。 In the present specification, the solid content means a non-volatile component at normal temperature and normal pressure, and includes liquid, syrupy and wax-like substances at normal temperature and normal pressure. Accordingly, the total solid content of the thermosetting resin composition means an amount obtained by subtracting the amount of volatile components (such as a solvent) from the total amount of the thermosetting resin composition.
本実施形態において使用する（Ｂ）ホスホニウム塩は、下記一般式（３）で表されるアニオン種に１つ以上のカルボキシ基を有するホスホニウム塩である。
一般式（３）中、Ｒ３〜Ｒ７は各々独立に一価の有機基を示す。一般式（３）中のＲ３〜Ｒ６のリン原子に結合する基は、好ましくは芳香環もしくは複素環を有する一価の有機基又は一価の脂肪族基であり、且つリン原子と各基がＰ−Ｃ結合を形成するものであり、それらは互いに同一であっても異なっていてもよい。低温硬化性をより向上できることから、Ｒ３〜Ｒ６は各々独立に、置換又は非置換の炭素数１〜１０の脂肪族基、置換又は非置換の芳香族基であることが好ましく、フェニル基、メチル基、エチル基、ｎ−プロピル基又はｎ−ブチル基であることがより好ましい。このようなホスホニウム基としては、テトラフェニルホスホニウム基、テトラトリルホスホニウム基、テトラエチルフェニルホスホニウム基、テトラメトキシフェニルホスホニウム基、テトラナフチルホスホニウム基、テトラベンジルホスホニウム基、エチルトリフェニルホスホニウム基、ｎ−ブチルトリフェニルホスホニウム基、２−ヒドロキシエチルトリフェニルホスホニウム基、トリメチルフェニルホスホニウム基、メチルジエチルフェニルホスホニウム基、メチルジアリルフェニルホスホニウム基、テトラ−ｎ−プロピルホスホニウム基、テトラ−ｎ−ブチルホスホニウム基等が挙げられるが、これらに限定されるものではない。 In General Formula (3), R 3 to R 7 each independently represent a monovalent organic group. The group bonded to the phosphorus atom represented by R 3 to R 6 in the general formula (3) is preferably a monovalent organic group or monovalent aliphatic group having an aromatic ring or a heterocyclic ring, The groups form a P—C bond, which may be the same or different from each other. R 3 to R 6 are each independently preferably a substituted or unsubstituted aliphatic group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group, and a phenyl group. And more preferably a methyl group, an ethyl group, an n-propyl group or an n-butyl group. Examples of such phosphonium groups include tetraphenylphosphonium group, tetratolylphosphonium group, tetraethylphenylphosphonium group, tetramethoxyphenylphosphonium group, tetranaphthylphosphonium group, tetrabenzylphosphonium group, ethyltriphenylphosphonium group, n-butyltriphenyl. Examples include phosphonium group, 2-hydroxyethyltriphenylphosphonium group, trimethylphenylphosphonium group, methyldiethylphenylphosphonium group, methyldiallylphenylphosphonium group, tetra-n-propylphosphonium group, tetra-n-butylphosphonium group, It is not limited to these.
一般式（３）中のカルボキシ基を１つ以上有するアニオン種としては例えば、酢酸；プロピオン酸；酪酸；カプロン酸；エナント酸；ラウリン酸；ミリスチン酸；パルミチン酸；ステアリン酸；フタル酸；イソフタル酸；テレフタル酸；ヒドロキシイソフタル酸；マロン酸；コハク酸；グルタル酸；アジピン酸；１，３−アダマンタンジカルボン酸；アゾベンゼン−４，４’−ジカルボン酸；１，３，５−ベンゼントリカルボン酸；１，１０−ビス（４−カルボキシフェノキシ）デカン；２，２−ビス（４−カルボキシフェニル）ヘキサフルオロプロパン；ｃｉｓ−４−シクロヘキセン−１，２−ジカルボン酸；１，４−シクロヘキサンジカルボン酸；１，３−シクロヘキサンジカルボン酸；デカヒドロ−１，４−ナフタレンジカルボン酸；２，３−ピラジンジカルボン酸等が挙げられるが、これらに限定されるものではない。一般式（３）中のＲ７は、これらのアニオン種に対応する有機基（すなわち、これらのアニオン種からカルボキシ基を除いた残基）であることができる。 Examples of the anionic species having one or more carboxy groups in the general formula (3) include acetic acid; propionic acid; butyric acid; caproic acid; enanthic acid; lauric acid; myristic acid; palmitic acid; Terephthalic acid, hydroxyisophthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,3-adamantane dicarboxylic acid, azobenzene-4,4′-dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1, 10-bis (4-carboxyphenoxy) decane; 2,2-bis (4-carboxyphenyl) hexafluoropropane; cis-4-cyclohexene-1,2-dicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; -Cyclohexanedicarboxylic acid; decahydro-1,4-naphthalenedicarboxylic acid; 2 , 3-pyrazinedicarboxylic acid and the like, but are not limited thereto. R 7 in the general formula (3) can be an organic group corresponding to these anionic species (that is, a residue obtained by removing a carboxy group from these anionic species).
このようなカチオン種（ホスホニウム基）とアニオン種からなるホスホニウム塩としては例えば、テトラフェニルホスホニウム−フタル酸（カチオン種：アニオン種＝１：１、商品名「ＴＰＰ−フタル酸」、北興化学工業株式会社製）、テトラブチルホスホニウム−１，２−シクロへキシルジカルボン酸（カチオン種：アニオン種＝１：１．５、商品名「ＴＢＰ−３」、北興化学工業株式会社製）、テトラブチルホスホニウム−１，２−シクロへキシルジカルボン酸（カチオン種：アニオン種＝１：１、商品名「ＴＢＰ−３Ｓ」、北興化学工業株式会社製）、テトラブチルホスホニウム−ラウリン酸（カチオン種：アニオン種＝１：１、商品名「ＴＢＰＬＡ」、北興化学工業株式会社製）等を挙げることができる。なお、本実施形態においては、１種類のホスホニウム塩を単独で使用してもよく、種類の異なるホスホニウム塩を組み合わせて使用してもよい。 Examples of such a phosphonium salt comprising a cation species (phosphonium group) and an anion species include, for example, tetraphenylphosphonium-phthalic acid (cation species: anion species = 1: 1, trade name “TPP-phthalic acid”, Hokuko Chemical Co., Ltd. Company-made), tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid (cation species: anion species = 1: 1.5, trade name “TBP-3”, manufactured by Hokuko Chemical Co., Ltd.), tetrabutylphosphonium- 1,2-cyclohexyldicarboxylic acid (cation species: anion species = 1: 1, trade name “TBP-3S”, manufactured by Hokuko Chemical Co., Ltd.), tetrabutylphosphonium-lauric acid (cation species: anion species = 1) : 1 and trade name “TBPLA”, manufactured by Hokuko Chemical Co., Ltd.). In the present embodiment, one type of phosphonium salt may be used alone, or different types of phosphonium salts may be used in combination.
本実施形態の熱硬化性樹脂組成物において、（Ｂ）ホスホニウム塩の含有量は、（Ａ）マレイミド化合物１００質量部に対して、０．１〜５．０質量部であることが好ましく、１．０〜４．０質量部であることがより好ましく、１．５〜３．０質量部であることが更に好ましい。（Ｂ）ホスホニウム塩の含有量が５．０質量部以下であると、（Ｂ）ホスホニウム塩が高温で分解することを抑制でき、より優れた耐熱性を有する硬化物を形成できる傾向がある。（Ｂ）ホスホニウム塩の含有量が１．０質量部以上であると、低温硬化性をより向上させることができる傾向がある。 In the thermosetting resin composition of the present embodiment, the content of the (B) phosphonium salt is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the (A) maleimide compound. It is more preferable that it is 0.0-4.0 mass parts, and it is still more preferable that it is 1.5-3.0 mass parts. (B) When content of phosphonium salt is 5.0 mass parts or less, it can suppress that (B) phosphonium salt decomposes | disassembles at high temperature, and there exists a tendency which can form the hardened | cured material which has more superior heat resistance. (B) When content of a phosphonium salt is 1.0 mass part or more, there exists a tendency which can improve low-temperature curability more.
本実施形態の熱硬化性樹脂組成物の調製は、一般的に採用されている方法に準じて実施される。調製方法としては例えば、溶融混合、粉体混合、溶液混合等の方法が挙げられる。また、この際には、本実施形態の必須成分以外の成分として、例えば、着色顔料、可塑剤、溶剤、レベリング剤、有機フィラー、無機フィラー、分子量調整剤等を、本発明の効果を損なわない範囲において配合してもよい。 Preparation of the thermosetting resin composition of this embodiment is implemented according to the method generally employ | adopted. Examples of the preparation method include methods such as melt mixing, powder mixing, and solution mixing. In this case, as the components other than the essential components of the present embodiment, for example, a coloring pigment, a plasticizer, a solvent, a leveling agent, an organic filler, an inorganic filler, a molecular weight adjusting agent, etc., do not impair the effects of the present invention. You may mix | blend in the range.
本実施形態の熱硬化性樹脂組成物は、一般的に採用されている方法に準じて成形することができる。例えば、無溶剤系の例としては、溶融注型法、溶融含侵法、粉体法、ＲＴＭ法等が挙げられ、溶剤系の例としては、樹脂溶液含侵法、溶剤塗装法等を挙げることができる。 The thermosetting resin composition of the present embodiment can be molded according to a generally adopted method. For example, examples of the solventless system include a melt casting method, a melt impregnation method, a powder method, and an RTM method, and examples of a solvent system include a resin solution impregnation method and a solvent coating method. be able to.
この成形時に加熱硬化が行われ、従来技術においては２００℃以上の加熱を必要としたが、本実施形態の熱硬化性樹脂組成物を適用することにより、硬化温度の低温化を図ることができる。これにより、成形工程の簡略化（合理化）が期待される。 Heat curing is performed at the time of molding. In the prior art, heating at 200 ° C. or higher is required. However, by applying the thermosetting resin composition of this embodiment, the curing temperature can be lowered. . Thereby, simplification (rationalization) of the molding process is expected.
本実施形態の熱硬化性樹脂組成物は、無溶剤含浸性、プリプレグのタック性、ドレープ性、保存安定性を損なうことなく、ＧＦＲＰ及びＣＦＲＰ等のクラックが低減され、且つ長期間高温に曝された場合の重量減少が少ない、即ち耐熱性がより向上したマトリックス樹脂として期待される。 The thermosetting resin composition of the present embodiment has reduced cracks such as GFRP and CFRP, and is exposed to high temperatures for a long period of time without impairing solvent-free impregnation, tackiness of prepreg, drape, and storage stability. In this case, it is expected to be a matrix resin that has a small weight loss, that is, improved heat resistance.
また、本実施形態の熱硬化性樹脂組成物は、銅箔接着性、低熱膨張性、高ガラス転移温度を有し、且つ低誘電性、はんだ耐熱性、難燃性、ドリル加工性に優れる熱硬化性樹脂製のプリプレグ又は積層板用途として好適である。 Further, the thermosetting resin composition of the present embodiment has a copper foil adhesiveness, a low thermal expansion property, a high glass transition temperature, and a low dielectric property, solder heat resistance, flame resistance, and drilling workability. It is suitable for prepregs or laminates made of curable resin.
以下、本発明を実施例及び比較例によって具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.
［実施例１］
下記一般式（６）で表される１分子内に少なくとも２つのイミド結合を有するビスマレイミド化合物１００質量部と、テトラブチルホスホニウム−１，２−シクロへキシルジカルボン酸（カチオン種：アニオン種＝１：１、商品名「ＴＢＰ−３Ｓ」（以下、ＴＢＰ−３Ｓという）、北興化学工業株式会社製）１．５質量部とを均一に混合し、熱硬化性樹脂組成物を調製した。
［式中、ｎは１〜１０の整数を示す。］
[Example 1]
100 parts by mass of a bismaleimide compound having at least two imide bonds in one molecule represented by the following general formula (6), and tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid (cation species: anion species = 1) 1 and 1.5 part by mass of a trade name “TBP-3S” (hereinafter referred to as TBP-3S) manufactured by Hokuko Chemical Co., Ltd. were uniformly mixed to prepare a thermosetting resin composition.
[Wherein n represents an integer of 1 to 10. ]
［実施例２］
ＴＢＰ−３Ｓの配合量を３．０質量部に変更した以外は実施例１と同様にして、熱硬化性樹脂組成物を調製した。
[Example 2]
A thermosetting resin composition was prepared in the same manner as in Example 1 except that the amount of TBP-3S was changed to 3.0 parts by mass.
［実施例３］
ビスマレイミド化合物としてｍ−フェニレンビスマレイミド（商品名「ＢＭＩ−３０００」（以下、ＢＭＩ−３０００という）、大和化成株式会社製）１００質量部と、ＴＢＰ−３Ｓを１．５質量部とを均一に混合し、熱硬化性樹脂組成物を調製した。
[Example 3]
As a bismaleimide compound, 100 parts by mass of m-phenylene bismaleimide (trade name “BMI-3000” (hereinafter referred to as BMI-3000), manufactured by Daiwa Kasei Co., Ltd.) and 1.5 parts by mass of TBP-3S are uniformly formed. It mixed and the thermosetting resin composition was prepared.
［実施例４］
ビスマレイミド化合物としてＢＭＩ−３０００の代わりに１，６−ビスマレイミド−（２，２，４−トリメチル）ヘキサン（商品名「ＢＭＩ−ＴＭＨ」（以下、ＢＭＩ−ＴＭＨという）、大和化成株式会社製）を使用した以外は実施例３と同様にして、熱硬化性樹脂組成物を調製した。
[Example 4]
1,6-Bismaleimide- (2,2,4-trimethyl) hexane (trade name “BMI-TMH” (hereinafter referred to as BMI-TMH), manufactured by Daiwa Kasei Co., Ltd.) instead of BMI-3000 as a bismaleimide compound A thermosetting resin composition was prepared in the same manner as in Example 3 except that was used.
［実施例５］
硬化促進剤としてＴＢＰ−３Ｓの代わりにテトラブチルホスホニウム−ラウリン酸（カチオン種：アニオン種＝１：１、商品名「ＴＢＰＬＡ」、北興化学工業株式会社製）を使用した以外は実施例１と同様にして、熱硬化性樹脂組成物を調製した。
[Example 5]
Example 1 except that tetrabutylphosphonium-lauric acid (cationic species: anionic species = 1: 1, trade name “TBPLA”, manufactured by Hokuko Chemical Co., Ltd.) was used instead of TBP-3S as a curing accelerator. Thus, a thermosetting resin composition was prepared.
［比較例１］
ＴＢＰ−３Ｓを使用しない以外は実施例１と同様にして、熱硬化性樹脂組成物を調製した。
[Comparative Example 1]
A thermosetting resin composition was prepared in the same manner as in Example 1 except that TBP-3S was not used.
［比較例２］
ＴＢＰ−３Ｓを使用しない以外は実施例３と同様にして、熱硬化性樹脂組成物を調製した。
[Comparative Example 2]
A thermosetting resin composition was prepared in the same manner as in Example 3 except that TBP-3S was not used.
［比較例３］
ＴＢＰ−３Ｓを使用しない以外は実施例４と同様にして、熱硬化性樹脂組成物を調製した。
[Comparative Example 3]
A thermosetting resin composition was prepared in the same manner as in Example 4 except that TBP-3S was not used.
［比較例４］
硬化促進剤としてＴＢＰ−３Ｓの代わりにテトラブチルホスホニウムブロマイド（商品名「ＴＢＰ−ＢＢ」、北興化学工業株式会社製）を使用した以外は実施例１と同様にして、熱硬化性樹脂組成物を調製した。
[Comparative Example 4]
A thermosetting resin composition was prepared in the same manner as in Example 1 except that tetrabutylphosphonium bromide (trade name “TBP-BB”, manufactured by Hokuko Chemical Co., Ltd.) was used as a curing accelerator instead of TBP-3S. Prepared.
＜硬化温度の測定＞
各実施例及び比較例で得られた熱硬化性樹脂組成物の硬化温度を、示差走査熱量計（ＤＳＣ）により、以下の条件で測定した。すなわち、熱硬化性樹脂組成物をアルミ液体用パン（（株）リガク製）に４．５〜５．５ｍｇ計りとり、窒素流量３０ｍＬ／ｍｉｎ、昇温速度１０℃／ｍｉｎの条件で、オンセット温度及びピークトップ温度を測定した。測定装置には、（株）リガク製「Ｔｈｅｒｍｏ ｐｌｕｓ ＤＳＣ８２３０」を使用した。発熱反応が始まる温度であるオンセット温度が２００℃未満であれば、低温硬化が可能であるといえる。結果を表１に示す。
<Measurement of curing temperature>
The curing temperature of the thermosetting resin composition obtained in each example and comparative example was measured with a differential scanning calorimeter (DSC) under the following conditions. That is, 4.5 to 5.5 mg of thermosetting resin composition is measured in an aluminum liquid pan (manufactured by Rigaku Corporation), and onset under conditions of a nitrogen flow rate of 30 mL / min and a heating rate of 10 ° C./min. Temperature and peak top temperature were measured. As a measuring device, “Thermo plus DSC8230” manufactured by Rigaku Corporation was used. If the onset temperature at which the exothermic reaction starts is less than 200 ° C., it can be said that low temperature curing is possible. The results are shown in Table 1.
＜熱重量減少率の測定＞
各実施例及び比較例で得られた熱硬化性樹脂組成物をシート状に成形し、１８０℃で１時間加熱して厚み３０μｍの硬化膜を得た。得られた硬化膜から約１０ｍｇの試験片を切り出し、それをＡｌパンに入れ、窒素流量３００ｍＬ／ｍｉｎ、４０℃から５００℃までの熱重量減少をＴＧ／ＤＴＡ測定装置（株式会社日立ハイテクサイエンス製、商品名「ＴＧ／ＧＴＡ７２００」）で測定し、３００℃での熱重量減少率を求めた。結果を表１に示す。この熱重量減少率が小さいほど、耐熱性に優れている。
<Measurement of thermal weight loss rate>
The thermosetting resin compositions obtained in each Example and Comparative Example were formed into a sheet shape and heated at 180 ° C. for 1 hour to obtain a cured film having a thickness of 30 μm. About 10 mg of a test piece was cut out from the obtained cured film, put into an Al pan, a nitrogen flow rate of 300 mL / min, and a thermal weight reduction from 40 ° C. to 500 ° C. was measured with a TG / DTA measuring device (manufactured by Hitachi High-Tech Science Co., Ltd.). , Trade name “TG / GTA7200”), and the thermal weight loss rate at 300 ° C. was determined. The results are shown in Table 1. The smaller the thermal weight reduction rate, the better the heat resistance.
表１から明らかなように、アニオン種に１つ以上のカルボキシ基を有する特定のホスホニウム塩と、特定のマレイミド化合物とを含有する熱硬化性樹脂組成物（実施例）は、上記特定のホスホニウム塩を含有しない熱硬化性樹脂組成物（比較例）に比べて、ＤＳＣオンセット温度及びＤＳＣピークトップ温度が低温側にシフトし、低温硬化性に優れていることが確認された。また、実施例の熱硬化性樹脂組成物の硬化物は、優れた耐熱性を有していることが確認された。なお、比較例１の熱硬化性樹脂組成物では、オンセット温度及びピークトップ温度がそれぞれ２つ存在していた。これは、比較例１で使用したマレイミド化合物に分子量の異なるものが存在しており、それらの反応性が異なることによって、２つのピークが出たものと推察される。比較例１の熱硬化性樹脂組成物は、片方のオンセット温度及びピークトップ温度が高いため、低温硬化性に優れているとはいえない。一方、同じマレイミド化合物を用いた実施例１及び２の熱硬化性樹脂組成物では、硬化促進剤（上記特定のホスホニウム塩）を用いることにより、マレイミド化合物に分子量の異なるものが存在することによる影響がなくなり、オンセット温度及びピークトップ温度がいずれも１つであった。 As is apparent from Table 1, the thermosetting resin composition (Example) containing a specific phosphonium salt having one or more carboxy groups in the anionic species and a specific maleimide compound is the above specific phosphonium salt. DSC onset temperature and DSC peak top temperature were shifted to a low temperature side compared with a thermosetting resin composition containing no hydride (Comparative Example), and it was confirmed that the low temperature curability was excellent. Moreover, it was confirmed that the hardened | cured material of the thermosetting resin composition of an Example has the outstanding heat resistance. In the thermosetting resin composition of Comparative Example 1, there were two onset temperatures and two peak top temperatures. This is presumed that the maleimide compounds used in Comparative Example 1 have different molecular weights, and that two peaks appear due to their different reactivity. Since the thermosetting resin composition of Comparative Example 1 has a high onset temperature and peak top temperature on one side, it cannot be said that it is excellent in low-temperature curability. On the other hand, in the thermosetting resin compositions of Examples 1 and 2 using the same maleimide compound, by using a curing accelerator (the above-mentioned specific phosphonium salt), the influence due to the presence of different molecular weights in the maleimide compound. The onset temperature and the peak top temperature were both one.
本発明の熱硬化性樹脂組成物によれば、ビスマレイミド樹脂が有する優れた耐熱性（低熱重量減少率、熱酸化安定性、高温湿潤強度）、寸法安定性、加工性及び難燃性、並びに、比較的安価な材料である特長をそのままに、低温硬化を可能にし得るので、航空、宇宙、防衛産業等の先端技術分野における先進複合材料、電子機器産業、自動車産業、その他一般産業分野における複合材料の原料としての利用可能性が大である。
According to the thermosetting resin composition of the present invention, the bismaleimide resin has excellent heat resistance (low thermal weight loss rate, thermal oxidation stability, high temperature wet strength), dimensional stability, workability and flame retardancy, and Because it is possible to cure at low temperatures while maintaining the features of a relatively inexpensive material, it can be used for advanced composite materials in advanced technology fields such as aviation, space, and defense industries, as well as composites in the electronic equipment industry, automobile industry, and other general industrial fields. The applicability of the material as a raw material is great.
Claims (7)
（Ｂ）下記一般式（３）で表されるアニオン種に１つ以上のカルボキシ基を有するホスホニウム塩と、
を含有する熱硬化性樹脂組成物。
［式（１）中、Ｒ１及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示し、ｎは１〜１００の整数を示す。］
［式（２）中、Ｒ２は二価の有機基を示す。］
［式（３）中、Ｒ３〜Ｒ７は各々独立に一価の有機基を示す。］ (A) The following general formula (2) other than the maleimide compound having at least two imide bonds in one molecule represented by the following general formula (1) and the maleimide compound represented by the following general formula (1) One or more maleimide compounds selected from the group consisting of maleimide compounds having at least two maleimide groups in one molecule represented by:
(B) a phosphonium salt having one or more carboxy groups in the anionic species represented by the following general formula (3);
Containing thermosetting resin composition.
[In the formula (1), R 1 and Q are each independently a substituted or unsubstituted aliphatic group having 1 to 100 carbon atoms, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group, Alternatively, a substituted or unsubstituted siloxane moiety having 1 to 100 silicon atoms is shown, and n represents an integer of 1 to 100. ]
[In the formula (2), R 2 represents a divalent organic group. ]
[In the formula (3), it represents a monovalent organic group independently each R 3 to R 7. ]
The (B) phosphonium salt includes one or more selected from the group consisting of tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, and tetrabutylphosphonium-lauric acid, The thermosetting resin composition according to any one of claims 1 to 6.
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