WO2018021548A1 - Novel phosphonium compound - Google Patents
Novel phosphonium compound Download PDFInfo
- Publication number
- WO2018021548A1 WO2018021548A1 PCT/JP2017/027500 JP2017027500W WO2018021548A1 WO 2018021548 A1 WO2018021548 A1 WO 2018021548A1 JP 2017027500 W JP2017027500 W JP 2017027500W WO 2018021548 A1 WO2018021548 A1 WO 2018021548A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermosetting resin
- resin
- curing
- weight
- parts
- Prior art date
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- -1 phosphonium compound Chemical class 0.000 title description 36
- 229920005989 resin Polymers 0.000 claims abstract description 220
- 239000011347 resin Substances 0.000 claims abstract description 220
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 239000011342 resin composition Substances 0.000 claims abstract description 42
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 29
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims description 201
- 239000000203 mixture Substances 0.000 claims description 107
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- 239000005011 phenolic resin Substances 0.000 claims description 22
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 20
- 150000008065 acid anhydrides Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 5
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000003860 storage Methods 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 150000001450 anions Chemical group 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 5
- 125000004018 acid anhydride group Chemical group 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 120
- 239000000047 product Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 150000002989 phenols Chemical class 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 241001550224 Apha Species 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 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 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000004780 naphthols Chemical class 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 5
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- JDIPZHAYUYYGSN-UHFFFAOYSA-N (4-propylphenyl) cyanate Chemical compound CCCC1=CC=C(OC#N)C=C1 JDIPZHAYUYYGSN-UHFFFAOYSA-N 0.000 description 2
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JNCRKOQSRHDNIO-UHFFFAOYSA-N [4-[(4-cyanato-3,5-dimethylphenyl)methyl]-2,6-dimethylphenyl] cyanate Chemical compound CC1=C(OC#N)C(C)=CC(CC=2C=C(C)C(OC#N)=C(C)C=2)=C1 JNCRKOQSRHDNIO-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical class O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 2
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- UFKLQICEQCIWNE-UHFFFAOYSA-N (3,5-dicyanatophenyl) cyanate Chemical compound N#COC1=CC(OC#N)=CC(OC#N)=C1 UFKLQICEQCIWNE-UHFFFAOYSA-N 0.000 description 1
- YDCUTCGACVVRIQ-UHFFFAOYSA-N (3,6-dicyanatonaphthalen-1-yl) cyanate Chemical compound N#COC1=CC(OC#N)=CC2=CC(OC#N)=CC=C21 YDCUTCGACVVRIQ-UHFFFAOYSA-N 0.000 description 1
- UMDBGQBQDICTJC-UHFFFAOYSA-N (3-cyanatonaphthalen-1-yl) cyanate Chemical compound C1=CC=CC2=CC(OC#N)=CC(OC#N)=C21 UMDBGQBQDICTJC-UHFFFAOYSA-N 0.000 description 1
- QQZZMAPJAKOSNG-UHFFFAOYSA-N (3-cyanatophenyl) cyanate Chemical compound N#COC1=CC=CC(OC#N)=C1 QQZZMAPJAKOSNG-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
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- KYQKIQNFSSXMJR-UHFFFAOYSA-L phthalate tetraphenylphosphanium 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.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 KYQKIQNFSSXMJR-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 1
- ZMENDZUPTXLTAG-UHFFFAOYSA-M tetrabutylphosphanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCCC[P+](CCCC)(CCCC)CCCC ZMENDZUPTXLTAG-UHFFFAOYSA-M 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- BFADQASMYNGYBX-UHFFFAOYSA-N tetrakis(4-methoxyphenyl)phosphanium Chemical compound C1=CC(OC)=CC=C1[P+](C=1C=CC(OC)=CC=1)(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 BFADQASMYNGYBX-UHFFFAOYSA-N 0.000 description 1
- KOFMFKMQSQTMTM-UHFFFAOYSA-N tetrakis(4-methylphenyl)phosphanium Chemical compound C1=CC(C)=CC=C1[P+](C=1C=CC(C)=CC=1)(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 KOFMFKMQSQTMTM-UHFFFAOYSA-N 0.000 description 1
- HLNHDVOODYDVRZ-UHFFFAOYSA-M tetraphenylphosphanium;acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 HLNHDVOODYDVRZ-UHFFFAOYSA-M 0.000 description 1
- FOUUISAQGPLIMM-UHFFFAOYSA-M tetraphenylphosphanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FOUUISAQGPLIMM-UHFFFAOYSA-M 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- JWZDVHOYCNIXDA-UHFFFAOYSA-N tributyl(phenyl)phosphanium Chemical compound CCCC[P+](CCCC)(CCCC)C1=CC=CC=C1 JWZDVHOYCNIXDA-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- FCJKXDNUOQVCMT-UHFFFAOYSA-N tris(4-methoxyphenyl)-phenylphosphanium Chemical compound C1=CC(OC)=CC=C1[P+](C=1C=CC(OC)=CC=1)(C=1C=CC(OC)=CC=1)C1=CC=CC=C1 FCJKXDNUOQVCMT-UHFFFAOYSA-N 0.000 description 1
- JNFWITHIBWNJKC-UHFFFAOYSA-N tris(4-methylphenyl)-phenylphosphanium Chemical compound C1=CC(C)=CC=C1[P+](C=1C=CC(C)=CC=1)(C=1C=CC(C)=CC=1)C1=CC=CC=C1 JNFWITHIBWNJKC-UHFFFAOYSA-N 0.000 description 1
- UJGFGHBOZLCAQI-UHFFFAOYSA-N tris(phosphanyl) borate Chemical compound POB(OP)OP UJGFGHBOZLCAQI-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/313—Monocyclic acids containing more than three carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
Definitions
- the present invention provides a curing accelerator for a thermosetting resin, which has low catalytic activity at low temperatures and does not cure a thermosetting resin composition, but exhibits high catalytic activity at a desired curing temperature and can be cured in a short time.
- a thermosetting resin-based composition containing a curing accelerator for a curable resin, a thermosetting resin-based composition having excellent storage stability in one liquid, and a cured product obtained when the curing agent is an acid anhydride are colorless.
- the present invention relates to a thermosetting resin-based composition that becomes transparent.
- thermosetting resin-based composition represented by an epoxy resin or the like
- a molded body having excellent mechanical, chemical and electrical properties can be obtained.
- adhesives, paints, and casting materials they are widely used for various electrical parts such as coils, capacitors, printed boards, etc., or for insulating sealing of semiconductor elements and integrated circuits.
- epoxy resin-based compositions using an epoxy resin as a thermosetting resin are preferably used because of their excellent adhesiveness.
- the demand for high integration is high, and the structure of semiconductor packages continues to advance.
- the curing accelerator for a thermosetting resin includes “latency”, that is, a property that can efficiently cure a thermosetting resin-based composition only at a desired set temperature, that is, a low temperature. Then, the catalyst activity is low and the thermosetting resin-based composition is not cured, but a property that exhibits high catalytic activity at a desired curing temperature and can be cured in a short time is required.
- thermosetting resin-based composition for sealing materials is generally prepared and stored by mixing at a low temperature of about 100 to 120 ° C. and cured at a high temperature of 170 ° C. or higher. This is because if the curing proceeds during mixing, the fluidity deteriorates, which is not preferable. That is, it is preferable that curing is suppressed at a low temperature of about 100 to 120 ° C., and curing is performed at a high temperature of 170 ° C. or more in a short time.
- thermosetting resin-based compositions that use a thermosetting resin, a thermosetting resin curing agent, and a thermosetting resin curing accelerator are the mainstream, but these materials must be mixed immediately before use.
- thermosetting resin composition comprising a thermosetting resin and a curing accelerator for thermosetting resins has also been developed.
- This single curable thermosetting resin composition also has excellent potential, and furthermore, the single curable thermosetting resin composition in which the thermosetting resin is liquid at room temperature (one-part thermosetting resin).
- thermosetting resin is liquid at room temperature (one-part thermosetting resin).
- cured material becomes colorless and transparent is calculated
- thermosetting resin-based composition including a single-curable thermosetting resin-based composition
- the thermosetting resin curing accelerator has a low catalytic activity at low temperatures (about 100 to 120 ° C.) and the thermosetting resin.
- a thermosetting resin-based composition that does not cure the system composition but has a high catalytic activity at a desired curing temperature and can be cured in a short time, and has excellent storage stability in one liquid,
- Another object is to provide a thermosetting resin-based composition in which the cured product is colorless and transparent.
- R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group
- R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group.
- the catalyst activity is low at low temperatures and the thermosetting resin composition is not cured.
- Thermal curing that exhibits high catalytic activity at a curing temperature, can be cured in a short time, gives good storage stability in one solution, and further makes the cured product colorless and transparent when the curing agent is an acid anhydride
- the inventors have found that a functional resin composition can be obtained, and have completed the present invention.
- R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group
- a phosphonium salt consisting of one molecule of a divalent anionic residue of pyromellitic acid represented by the formula (hereinafter sometimes referred to as “phosphonium salt of the present invention”).
- R 1 to R 4 are the same or different and each is a substituent selected from a butyl group, a phenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group.
- thermosetting resin comprising at least the phosphonium salt according to any one of [1] to [4].
- thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator according to [5] and a thermosetting resin.
- thermosetting resin wherein the thermosetting resin is one or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin.
- System composition [8] The thermosetting resin composition according to [6] or [7], further including a curing agent for a thermosetting resin.
- the curing agent for thermosetting resin is one or more curing agents for thermosetting resin selected from phenol resin, polyamine, acid anhydride, and benzoxazine, [8] The thermosetting resin-based composition as described.
- thermosetting resin composition according to [8] or [9] including a master batch obtained by reacting a curing accelerator for a thermosetting resin with a curing agent for a thermosetting resin in advance. , Thermosetting resin-based composition.
- thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of [6] to [10].
- thermosetting resin-based composition containing the curing accelerator for thermosetting resins containing the phosphonium salt of the present invention as a component has lower catalytic activity at lower temperatures and thermosetting properties than when a conventional curing accelerator is used.
- the resin-based composition is not cured, but exhibits a high catalytic activity at the desired curing temperature, can be cured in a short time, and gives good storage stability in one liquid, and when an acid anhydride is used as a curing agent
- the cured product is useful because it is colorless and transparent.
- FIG. 1 is a diagram showing an IR spectrum of bis (tetraphenylphosphonium) dihydrogen pyromelolitate.
- FIG. 2 is a diagram showing an IR spectrum of bis (tetrabutylphosphonium) dihydrogen pyromellitate.
- FIG. 3 is a diagram showing an IR spectrum of the product obtained in Comparative Production Example 1.
- FIG. 4 shows the 1 H-NMR spectrum of the product obtained in Comparative Production Example 1.
- FIG. 5 is a diagram showing a 31 P-NMR spectrum of the product obtained in Comparative Production Example 1.
- the present invention relates to the following general formula (1)
- R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group
- R 1 ⁇ R 4 in phosphonium cation of the general formula (1) are the same or different and may be substituted with a linear or branched alkyl group or an alkyl group or methoxy group, having 1 to 16 carbon atoms Represents a phenyl group;
- Examples of the linear or branched alkyl group having 1 to 16 carbon atoms of R 1 to R 4 in the phosphonium cation of the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, An n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and n-dodecyl group are preferred. In particular, it is more preferable that all of R 1 to R 4 are n-butyl groups.
- a phenyl group which may be substituted with an alkyl group of R 1 to R 4 or a methoxy group is a straight chain having 1 to 4 carbon atoms. Or a branched chain, and preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, or a tert-butyl group.
- the phenyl group that may be substituted with an alkyl group or a methoxy group is preferably a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group, and particularly, all of R 1 to R 4 are phenyl groups. It is more preferable that
- Examples of the phosphonium cation of the general formula (1) include tetrabutylphosphonium cation, tetraphenylphosphonium cation, tetrakis (4-methylphenyl) phosphonium cation, tetrakis (4-methoxyphenyl) phosphonium cation, phenyltris (4-methylphenyl) phosphonium.
- the divalent anion residue of pyromellitic acid represented by the formula (2) is a divalent carboxyl anion by removing the hydrogen atoms of the 1-position, 4-position or 5-position carboxyl group of pyromellitic acid. Say things.
- a salt of the above phosphonium cation and a divalent anion residue of pyromellitic acid can be easily produced by a known method based on the description in this specification. For example, after synthesizing a dialkali metal salt of pyromellitic acid by a conventional method (solvent: water, methanol, etc.), 1 mol of tetra-substituted phosphonium halide is charged per 0.5 mol of the dialkali metal salt of pyromellitic acid. And a method for forming a salt by the formation.
- the salt may be formed by using a tetra-substituted phosphonium halide and a pyromellitic acid dialkali metal salt alone or in combination of two or more.
- a tetra-substituted phosphonium halide and a pyromellitic acid dialkali metal salt alone or in combination of two or more.
- bis (tetra-substituted phosphonium) dihydrogen pyromellitate may be formed.
- two or more kinds of bis (tetra-substituted phosphonium) dihydrogen pyromellitate may be mixed. Production examples according to this production method are described in Production Example 1.
- a salt may be formed by neutralizing 1 mol of tetrasubstituted phosphonium hydroxide with 0.5 mol of pyromellitic acid or pyromellitic anhydride. Production examples according to this production method are described in Production Example 2.
- the obtained reaction product is mixed with water, an alcohol-based organic solvent (methanol, ethanol, Propanol, butanol, etc.), ketone organic solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), ether organic solvents (tetrahydrofuran, diethyl ether, dibutyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, etc.), In addition, these may be washed with a mixed solvent and purified by recrystallization.
- an alcohol-based organic solvent methanol, ethanol, Propanol, butanol, etc.
- ketone organic solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.
- ether organic solvents tetrahydrofuran, diethyl ether, di
- the phosphonium salt obtained by these methods is usually composed mainly of a 2: 1 (molar ratio) salt of a phosphonium cation and a divalent anion residue of pyromellitic acid, and is represented by the general formula (3). .
- the anion part represents an anion residue (divalent anion residue) of pyromellitic acid represented by the formula (2), strictly speaking, a plurality of carboxyl groups or carboxyl anions.
- the carboxyl group and the carboxyl anion are actually equivalent.
- a hydrogen atom contained in a general carboxyl group has a chemical shift detected in the vicinity of 12 ppm in 1 H-NMR, whereas a hydrogen atom contained in an anion residue of pyromellitic acid described in the general formula (3) Has a very strong hydrogen bond with an adjacent oxygen atom, and thus a chemical shift in 1 H-NMR is detected around 20 ppm.
- the present invention provides a phosphonium salt (for example, the general formula (1) having two molecules of a phosphonium cation represented by the general formula (1) and one molecule of pyromellitic acid divalent anion residue represented by the formula (2). 3), a curing accelerator for thermosetting resins (hereinafter sometimes referred to as “the curing accelerator for thermosetting resins of the present invention”).
- a curing accelerator for thermosetting resins of the present invention Compared with conventional phosphonium carboxylates such as tetra-substituted phosphonium acetate and tetra-substituted phosphonium benzoate, the divalent anion residue represented by the general formula (3) is coordinated to two phosphonium cations. It is considered that a time lag until the onset of curing occurs, and low activity (latency) at low temperature and storage stability are imparted.
- the curing accelerator for a thermosetting resin of the present invention has a good potential even in a single-curing thermosetting resin composition comprising at least the curing accelerator for a thermosetting resin of the present invention and a thermosetting resin. From the preparation of the one-component single-curing, single-curing thermosetting resin composition to curing, good storage stability that can be stored at room temperature can be obtained. When the curing agent is an acid anhydride and the phosphonium salt of the general formula (3) is used as the curing accelerator, a cured product of the resin composition having excellent colorless transparency can be obtained.
- the phosphonium salt of the general formula (3) is obtained by reacting with the curing agent in advance for the purpose of facilitating homogenization.
- the master batch may be used as a curing accelerator for thermosetting resins.
- the curing accelerator for the thermosetting resin of the present invention contains solvents, fillers, additives, etc. that are usually used for the curing accelerator for thermosetting resins, as long as the effect is not affected. Further, it may be included.
- Examples of the phosphonium salt of the general formula (3) include bis (tetraphenylphosphonium) dihydrogen pyromellitate, bis [tetrakis (4-methylphenyl) phosphonium] dihydrogen pyromellitate, bis [tetrakis (4-methoxyphenyl).
- the present invention is also a thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator of the present invention and a thermosetting resin (hereinafter referred to as “single curable thermosetting of the present invention”). Sometimes referred to as “resin-based composition”).
- the present invention further relates to a thermosetting resin-based composition further including a curing agent for thermosetting resin. Hereinafter, these may be referred to as “the thermosetting resin composition of the present invention”.
- epoxy resins, maleimide resins, cyanate resins, isocyanate resins, and curing agents for thermosetting resins which are preferred examples of thermosetting resins that are components of the thermosetting resin-based composition of the present invention, will be described.
- the epoxy resin is not particularly limited, and a general-purpose epoxy resin having two or more epoxy groups in one molecule can be used.
- phenol, cresol, xylenol, catechol, resorcin, bisphenol A, Phenols such as bisphenol F and / or naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed in the presence of an acidic catalyst.
- Phenol novolak type epoxy resin orthocresol novolak type epoxy resin obtained by epoxidizing the resulting novolak resin
- bisphenol A bisphenol F, bisphenol S, alkyl-substituted or non-substituted Bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin obtained by epoxidizing substituted biphenols, stilbene phenols, etc .
- glycidyl ether type of alcohols such as butanediol, polyethylene glycol and polypropy
- the maleimide resin is not particularly limited, and a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used.
- a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used.
- These maleimide resins may be used alone or in admixture of two or more, may be used as they are, may be added with a solvent or an additive as appropriate, or may be commercially available
- the cyanate resin is not particularly limited, and a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used.
- a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used.
- 1,3-dicyanatobenzene, 1,4-disiocyanate can be used.
- cyanate resins may be used alone or in admixture of two or more, may be used as they are, may be added with a solvent, an additive or the like as appropriate, or commercially available products may be used. Good.
- the isocyanate resin is not particularly limited, and a general-purpose isocyanate resin having two or more isocyanate groups in one molecule can be used.
- polyisocyanate such as tolylene diisocyanate and diphenylmethane diisocyanate
- polypropylene examples thereof include isocyanate resins obtained by blocking terminal isocyanate groups of terminal isocyanate group oligomers obtained by reaction with polyols such as glycol and polytetramethylene glycol with phenols and alcohols.
- isocyanate resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, etc. Good.
- thermosetting resins examples include phenol resin curing agents, amine curing agents, acid anhydride curing agents, benzoxazine curing agents, dicyandiamide, and the like. Moreover, you may use thermosetting resins other than the thermosetting resin used as a main ingredient as a hardening agent for thermosetting resins.
- the phenolic resin-based curing agent is not particularly limited, and a general-purpose phenolic resin having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent can be used.
- catechol Compounds having two or more phenolic hydroxyl groups in one molecule such as resorcin, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F , Phenols such as phenylphenol and aminophenol and / or naphthols such as naphthol and dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde Novolak type phenol resins synthesized from aralkyl type phenol resins such as phenol aralkyl
- the amine curing agent is not particularly limited, and general-purpose aromatic amines, aliphatic amines and the like can be used.
- triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexa Aliphatic polyamines such as methylenediamine and 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1,2-diaminocyclohexane
- Piperazine-type polyamines such as formula polyamine, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3, 3'-diethyldipheny Methane, bis (methylthio) tol
- the acid anhydride curing agent is not particularly limited, and general-purpose acid anhydrides can be used.
- the benzoxazine-based curing agent is not particularly limited, and a general-purpose benzoxazine resin can be used.
- a general-purpose benzoxazine resin can be used.
- an Fa type benzoxazine resin obtained by reacting bisphenol F, formaldehyde and aniline, diaminodiphenylmethane.
- Pd type benzoxazine resin obtained by reacting formaldehyde with phenol.
- curing agents can be used alone or in admixture of two or more kinds, and can be used as they are, and can be used as a curing agent composition by appropriately adding a solvent, an additive or the like. It is also possible to use a commercially available product.
- thermosetting resin-based composition of the present invention requires properties that can be efficiently cured only at a desired set temperature, it is preferable to use an epoxy resin or a maleimide resin as the thermosetting resin together with the curing accelerator of the present invention. Furthermore, when a thermosetting resin curing agent is used, a phenol resin is preferably used. Moreover, when colorless and transparent are calculated
- thermosetting resin-based composition can contain various known inorganic fillers in order to reduce the linear expansion coefficient.
- examples of the inorganic filler include fused silica, crystalline silica, alumina, and aluminum nitride. These inorganic fillers may be surface-treated with a coupling agent such as a silane coupling agent.
- a coupling agent such as a silane coupling agent.
- an ion trapping agent, a release agent, a pigment such as carbon black, or the like may be added to the thermosetting resin-based composition, and a resin other than the thermosetting resin may be included.
- the content of the phosphonium salt of the general formula (3) in the thermosetting resin-based composition is less than 0.5 parts by weight, the composition may not be able to fully exert the curing power, and is more than 10 parts by weight. In this case, the storage stability of the composition may be deteriorated, so that it is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin, and this is required when the curable property is considered more strictly.
- the content is more preferably 0.7 to 5 parts by weight.
- the content of the curing agent is equivalent to the reactive group equivalent in the thermosetting resin (for example, epoxy equivalent in the resin if it is an epoxy resin) and the equivalent of the curing agent. In general, the equivalent ratio of the reactive group equivalent to the equivalent of the curing agent is set to 1.0: 0.9 to 1.0: 1.2.
- thermosetting resin-based composition of the present invention When used for a prepreg, it is preferable to have a varnish in which each component is dissolved or dispersed in an organic solvent.
- organic solvent used when producing the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide And aprotic polar solvents such as These organic solvents may be used alone or in combination of two or more, or commercially available products may be used.
- ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate
- ether solvents such as tetrahydrofuran
- aromatic hydrocarbon solvents such as toluene, xylene and mesitylene
- dimethylformamide dimethylacetamide
- N-methylpyrrolidone dimethyl sulfoxide
- aprotic polar solvents such as These organic solvents may be used alone or in combination of two or more, or commercially available products
- the method for preparing the thermosetting resin-based composition is not particularly limited, and can be prepared by mixing the above-mentioned components uniformly.
- a method in which the thermosetting resin and the phosphonium salt of the present invention are uniformly stirred and mixed at a temperature of about 20 to 150 ° C. can be exemplified.
- the solvent is exemplified as a solvent used in the production of the varnish. Solvents may be used.
- curing agent for thermosetting resins it is preferable to heat and cool the mixture of a hardening
- the viscosity of the curing agent is reduced, stirring and mixing are facilitated, and the curing agent and the curing accelerator are uniformly dispersed.
- the mixture of the curing agent and the curing accelerator can be accurately measured by pre-cooling before mixing with the thermosetting resin, and handling becomes easy.
- a master batch obtained by heating and dissolving the curing accelerator in a high concentration in the curing agent and then cooling may be used as the curing accelerator. This master batch has relatively good solubility in a curing agent.
- curing agent, a hardening accelerator, and a thermosetting resin may be mixed at once in each mixing process, or may be mixed little by little in several steps.
- a kneader such as a roll or a kneader may be used to facilitate uniform stirring and mixing.
- thermosetting resin-based composition of the present invention is desirable in that the thermosetting resin curing accelerator contained in the thermosetting resin-based composition has low catalytic activity at low temperatures and does not cure the thermosetting resin-based composition. It is a thermosetting resin-based composition that has a high catalytic activity at the curing temperature, has the potential to be cured in a short time, and is excellent in storage stability in a one-pack type.
- the latency of the thermosetting resin-based composition can be measured and evaluated by a conventional latency evaluation method.
- the gel time can be measured by a gel time measurement method based on JIS K 6910 and evaluated by the ratio of the gel time between low temperature and high temperature.
- an exothermic peak can be measured using a differential scanning calorimeter, and evaluation can be made based on a difference between an exothermic start temperature and an exothermic top temperature.
- the stability of the thermosetting resin-based composition can be measured and evaluated by a conventional stability evaluation method.
- the gel time before and after storage can be measured by a gelation time measuring method based on JIS K 6910, and evaluated by the ratio of the gel time before and after storage.
- thermosetting resin-based cured product means that the fluidity of the thermosetting resin is lost by heating the thermosetting resin-based composition under specific conditions according to the thermosetting resin-based composition.
- thermosetting resin-based cured product of the present invention refers to a hardened solid.
- thermosetting resin-based cured product of the present invention the solid material obtained by curing the thermosetting resin-based composition of the present invention may be referred to as “thermosetting resin-based cured product of the present invention”.
- the thermosetting resin-based cured product of the present invention can be obtained by heating the above-described thermosetting resin-based composition of the present invention under the conditions for curing a normal thermosetting resin-based composition. Usually, it can be obtained by heating at a curing temperature of about 100 to 250 ° C.
- thermosetting resin-based cured product of the present invention when an acid anhydride is used as a curing agent, coloring of the cured product is reduced and a colorless and transparent cured product is obtained.
- the degree of coloring of the cured product can be measured by a conventional color tone evaluation method. Examples of the color tone evaluation method include a method based on JIS-K0071-1, and the degree of coloring is indicated as a value (APHA) represented by a Hazen number. In a scene where colorless transparency is required, it is preferable that APHA is smaller, and it is practical that APHA is 50 or less.
- thermosetting resin-based composition of the present invention will be described in detail below with reference to examples and test examples, but the present invention is not limited to these.
- [ 1 H-NMR measurement] 10 mg of crystals were dissolved in about 0.5 ml of heavy DMSO, put in a ⁇ 5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE. The shift value was based on DMSO ( ⁇ 2.49 ppm).
- Pyromellitic acid dipotassium salt is prepared by dissolving 56 parts by weight of potassium hydroxide in 1.5 L of water and adding 109 parts by weight of pyromellitic anhydride to this, and then adding 419 parts by weight of tetraphenylphosphonium bromide to this. After reacting at 0 ° C. and cooling, the precipitated crystals were collected by filtration and washed with water to give bis (tetraphenylphosphonium) dihydrogen pyromellitate (hereinafter referred to as “BTPP-pyromellitic acid” represented by the following formula (4). 419 parts by weight (yield 90%). The melting point of the obtained crystal was measured and found to be 277 to 279 ° C.
- BTBP bis (tetrabutylphosphonium) dihydrogen pyromellitate
- Table 1 shows the ⁇ (ppm) values of 1 H-NMR spectrum and 31 P-NMR spectrum of the phosphonium salt according to the present invention produced according to Production Examples 1 and 2.
- thermosetting resin-based composition was performed.
- Example 1 After adding 5.0 parts by weight of BTPP-pyromellitic acid to 214 parts by weight of a phenolic resin-based curing agent MEH-7785M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), stirring and mixing for 2 minutes under heating at 150 ° C. Cooled to room temperature.
- MEH-7785M hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.
- thermosetting resin composition was obtained in the same manner as in Example 1 except that 5.0 parts by weight of BTBP-pyromellitic acid was used instead of 5.0 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was the same as in Example 1, except that 6.0 parts by weight of tetraphenylphosphonium acetate (hereinafter referred to as “TPPA”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. I got a thing.
- TPPA tetraphenylphosphonium acetate
- TPP-phthalic acid tetraphenylphosphonium hydrogen phthalate
- thermosetting property was the same as in Example 1 except that 6.9 parts by weight of tetrabutylphosphonium benzoate (hereinafter referred to as “TBP-benzoic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid.
- TBP-benzoic acid tetrabutylphosphonium benzoate
- TBP-salicylic acid tetrabutylphosphonium salicylate
- Example 1 was used except that 6.8 parts by weight of tetrabutylphosphonium hydrogen succinate (hereinafter referred to as “TBP-succinic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid.
- TBP-succinic acid tetrabutylphosphonium hydrogen succinate
- Example 1 was used except that 8.4 parts by weight of tetrabutylphosphonium hydrogen citrate (hereinafter referred to as “TBP-citric acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid.
- TBP-citric acid tetrabutylphosphonium hydrogen citrate
- Example 1 was repeated except that 7.1 parts by weight of 1,2-bis (diphenylphosphino) acetylene (hereinafter referred to as “DPPA”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. Thus, a thermosetting resin composition was obtained.
- DPPA 1,2-bis (diphenylphosphino) acetylene
- the gel time (GT) of the obtained thermosetting resin-based composition is a hot plate type gelation test manufactured by Nisshin Kagaku Co., Ltd. according to the gel time measurement method described in JIS K 6910, with the steel plate temperatures set to 150 ° C. and 175 ° C. Measurements were made using the instrument GT-D. In addition, at the steel plate temperature of 120 ° C. or lower, the resin was not sufficiently softened, so that it was difficult to determine the gelation time.
- the curing accelerator for thermosetting resin has lower catalytic activity at low temperatures and does not cure the thermosetting resin-based composition, but at the desired curing temperature. It can be said that it exhibits high catalytic activity and can be cured in a short time, that is, it has excellent potential, but in a scene where latency is required, it can be said that a gel time ratio of 2.3 or more is practical.
- Table 2 The results are shown in Table 2.
- thermosetting resin compositions of Examples 1 and 2 have a large gel time ratio (gel time at 150 ° C./gel time at 175 ° C.).
- the ratio of the gel time is large, it is predicted that the gel time is further delayed and curing is suppressed at a lower temperature of about 100 to 120 ° C. Therefore, it is clear that the thermosetting resin-based composition of the present invention is excellent in latency.
- Example 3> After adding 2.8 parts by weight of BTPP-pyromellitic acid to 54 parts by weight of phenol resin curing agent MEH-7785M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), stirring and mixing for 2 minutes under heating at 150 ° C. Cooled to room temperature. 125 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and 71 parts by weight of epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.) were added and heated at 130 ° C.
- maleimide resin BMI-2300 maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.
- epoxy resin NC-3000 epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.
- thermosetting resin-based composition (equivalent ratio of epoxy equivalent and hydroxyl equivalent of 1.0: 1.0, the total weight of epoxy resin and phenolic resin and maleimide resin) A weight ratio of 1.0: 1.0) was obtained.
- thermosetting resin composition was obtained in the same manner as in Example 7 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was obtained in the same manner as in Example 7, except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin composition was obtained in the same manner as in Example 7 except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- Example 5 Add 2.8 parts by weight of BTPP-pyromellitic acid to 83 parts by weight of epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.), stir and mix for 40 seconds under heating at 130 ° C., and then to room temperature Cooled down. To this was added 167 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed under heating at 130 ° C. for 2 minutes, cooled to room temperature, and then a thermosetting resin composition ( The weight ratio of epoxy resin to maleimide resin was 1.0: 2.0).
- thermosetting resin composition was obtained in the same manner as in Example 9 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was obtained in the same manner as in Example 9 except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was obtained in the same manner as in Example 9 except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin composition was obtained.
- ⁇ Example 7> 2.8 parts by weight of BTPP-pyromellitic acid was added to 500 parts by weight of acetone, and the mixture was stirred and mixed for 2 minutes while heating at 40 ° C.
- a system composition was obtained.
- thermosetting resin composition was obtained in the same manner as in Example 3 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin composition in the same manner as in Example 3 except that 1.6 parts by weight of triphenylphosphine (hereinafter referred to as “TPP”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. Got.
- TPP triphenylphosphine
- thermosetting resin-based composition was obtained.
- thermosetting resin-based composition was the same as in Example 3 except that 2.6 parts by weight of 2-phenylimidazole (hereinafter referred to as “2PZ”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. I got a thing.
- 2PZ 2-phenylimidazole
- Example 9 2.8 parts by weight of BTPP-pyromellitic acid was added to 500 parts by weight of THF, and the mixture was stirred and mixed for 2 minutes while heating at 40 ° C. To this was added 250 parts by weight of maleimide resin BMI-4000 (maleimide equivalent 285, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed for 2 minutes under heating at 40 ° C., and then THF was distilled off by drying to give a thermosetting resin. A system composition was obtained.
- maleimide resin BMI-4000 maleimide equivalent 285, manufactured by Daiwa Kasei Kogyo Co., Ltd.
- thermosetting resin composition was obtained in the same manner as in Example 5 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin composition was obtained in the same manner as in Example 5 except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was obtained in the same manner as in Example 5, except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was obtained in the same manner as in Example 5 except that 2.6 parts by weight of 2PZ was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was measured using a differential scanning calorimeter (DSC7020 manufactured by SII NanoTechnology) at a measurement temperature range of 30 to 350 ° C. and a temperature increase rate of 10 ° C./min. did.
- thermosetting resin-based compositions containing two types of thermosetting resins of Examples 3 to 6 and the single-curing thermosetting resin-based compositions of Examples 7 to 10 are:
- the heat generation start temperature is higher than 120 ° C., which is the temperature at the time of mixing, and the difference ( ⁇ T) between the heat generation start temperature and the heat generation top temperature is as small as 30 or less. Therefore, it is clear that the thermosetting resin-based composition of the present invention is excellent in latency.
- thermosetting resin-based cured product using an acid anhydride compound as a curing agent.
- BTPP-pyromellitic acid is added to 100 parts by weight of acid anhydride-based curing agent Ricacid MH-T (acid anhydride equivalent 168, manufactured by Shin Nippon Chemical Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride). After adding 0 part by weight and stirring and mixing for 5 minutes while heating at 60 ° C., the mixture was cooled to room temperature.
- thermosetting resin-based composition 100 parts by weight of epoxy resin jER828EL (epoxy equivalent 185, manufactured by Mitsubishi Chemical Corporation) was added, stirred and mixed for 2 minutes under heating at 60 ° C., and then cooled to room temperature to obtain a thermosetting resin-based composition. Further, the obtained thermosetting resin composition was heated at 120 ° C. for 1 hour, and further heated at 150 ° C. for 3 hours to obtain a thermosetting resin-based cured product (equivalent ratio of epoxy equivalent to acid anhydride equivalent: 1. 0: 1.1) was obtained.
- thermosetting resin composition and a cured product were obtained in the same manner as in Example 11 except that 1.0 part by weight of BTBP-pyromellitic acid was used instead of 1.0 part by weight of BTPP-pyromellitic acid. .
- thermosetting resin-based composition was the same as Example 11 except that 1.0 part by weight of tetrabutylphosphonium acetate (hereinafter referred to as “TBPA”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. Product and cured product were obtained.
- TBPA tetrabutylphosphonium acetate
- thermosetting resin system was used in the same manner as in Example 11 except that 1.0 part by weight of tetrabutylphosphonium laurate (hereinafter referred to as “TBPLA”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid.
- TPLA tetrabutylphosphonium laurate
- Example 11 was used except that 1.0 part by weight of benzyltriphenylphosphonium hydrogen phthalate (hereinafter referred to as “TPPZ-phthalic acid”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid.
- TPPZ-phthalic acid benzyltriphenylphosphonium hydrogen phthalate
- thermosetting resin-based composition is a hot plate type gelation tester GT-D manufactured by Nisshin Kagaku Co., Ltd. with a steel plate temperature of 175 ° C. according to the gel time measurement method described in JIS K 6910. Was measured using.
- the results are shown in Table 5.
- thermosetting resin-based composition The color tone of the cured product of the obtained thermosetting resin-based composition was evaluated according to the color tone evaluation method (Hazen unit color number) described in JIS K0071-1 and indicated by APHA. It can be said that the smaller the APHA, the more excellent the transparency of the cured product of the thermosetting resin-based composition, and it can be said that APHA is 50 or less in situations where colorless transparency is required. The results are shown in Table 5.
- thermosetting resin-based compositions of Examples 11 and 12 have a smaller APHA than that of Comparative Examples 19 to 22, and thus are nearly colorless and excellent in transparency.
- thermosetting resin composition An evaluation test was conducted on the storage stability of a one-component single-curing thermosetting resin composition.
- Example 13> After adding 3.0 parts by weight of BTPP-pyromellitic acid to 100 parts by weight of epoxy resin bisphenol A diglycidyl ether (Mitsubishi Chemical Co., Ltd., jER828EL, epoxy equivalent 185), stirring and mixing for 2 minutes under heating at 60 ° C. And cooled to room temperature to obtain a thermosetting resin composition.
- thermosetting resin composition was obtained in the same manner as in Example 13 except that 3.0 parts by weight of BTBP-pyromellitic acid was used instead of 3.0 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition was obtained in the same manner as in Example 13 except that 3.0 parts by weight of TBPLA was used instead of 3.0 parts by weight of BTPP-pyromellitic acid.
- thermosetting resin-based composition The gel time (GT) of the obtained thermosetting resin-based composition is in accordance with the gel time measurement method described in JIS K 6910, and the hot plate type gelation tester GT-D manufactured by Nisshin Kagaku Co., Ltd. Was measured using. Moreover, the obtained thermosetting resin-type composition was stored at 25 degreeC, and the gel time retention rate in each storage period was calculated
- thermosetting resin-based compositions of Examples 13 and 14 have a high gel time retention and excellent storage stability, and can be stored at room temperature after the composition is prepared. Become.
- thermosetting resin-based composition of the present invention has excellent curing characteristics, and the cured product has excellent transparency depending on the type of curing agent. For example, it is useful for resin sealing of various small electrical / electronic components and semiconductor components. It is.
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Abstract
A heat-curable resin composition characterized by comprising (A) a heat-curable resin, (B) a curing agent and (C) a curing accelerator that is a phosphonium salt composed of two molecules of a phosphonium cation represented by general formula (1) and one molecule of a bivalent anion residue of pyromellitic acid represented by formula (2). The heat-curable resin composition potentially has a property such that the curing accelerator has a poor catalytic activity at a lower temperature and therefore cannot cure the heat-curable resin composition at the lower temperature but exhibits a high catalytic activity at an intended curing temperature and therefore can cure the heat-curable resin composition within a short time at the intended curing temperature. The heat-curable resin composition has excellent storage stability in the form of a one-part preparation, and is colorless and transparent when the curing agent is an acid anhydride.
Description
本発明は、低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る熱硬化性樹脂用硬化促進剤、同熱硬化性樹脂用硬化促進剤を含む熱硬化性樹脂系組成物、一液における貯蔵安定性に優れた熱硬化性樹脂系組成物、ならびに硬化剤が酸無水物の場合に得られる硬化物が無色透明になる熱硬化性樹脂系組成物に関する。
The present invention provides a curing accelerator for a thermosetting resin, which has low catalytic activity at low temperatures and does not cure a thermosetting resin composition, but exhibits high catalytic activity at a desired curing temperature and can be cured in a short time. A thermosetting resin-based composition containing a curing accelerator for a curable resin, a thermosetting resin-based composition having excellent storage stability in one liquid, and a cured product obtained when the curing agent is an acid anhydride are colorless. The present invention relates to a thermosetting resin-based composition that becomes transparent.
従来、エポキシ樹脂等に代表される熱硬化性樹脂系組成物を用いると、優れた機械的、化学的および電気的性質を有する成形体等が得られるため、熱硬化性樹脂系組成物は、接着剤、塗料、注型材料としてコイル、コンデンサー、プリント基板等の各種の電気部品、あるいは半導体素子や集積回路の絶縁封止等の用途に広く使用されている。これらの用途の中で、半導体素子の絶縁封止の分野では、熱硬化性樹脂としてエポキシ樹脂を用いたエポキシ樹脂系組成物が接着性等に優れるため好適に用いられているが、半導体素子の高集積化への要求が高く、半導体パッケージの構造も進歩し続けている。
Conventionally, when a thermosetting resin-based composition represented by an epoxy resin or the like is used, a molded body having excellent mechanical, chemical and electrical properties can be obtained. As adhesives, paints, and casting materials, they are widely used for various electrical parts such as coils, capacitors, printed boards, etc., or for insulating sealing of semiconductor elements and integrated circuits. Among these uses, in the field of insulation sealing of semiconductor elements, epoxy resin-based compositions using an epoxy resin as a thermosetting resin are preferably used because of their excellent adhesiveness. The demand for high integration is high, and the structure of semiconductor packages continues to advance.
このため、封止材料等としての熱硬化性樹脂系組成物の性能も、より優れたものが要求されている。そのような状況下にあって、熱硬化性樹脂用の硬化促進剤には、熱硬化性樹脂系組成物を所望の設定温度でのみ効率良く硬化させ得る性質である「潜在性」、すなわち低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る性質が求められている。
For this reason, the performance of the thermosetting resin composition as a sealing material or the like is also required to be superior. Under such circumstances, the curing accelerator for a thermosetting resin includes “latency”, that is, a property that can efficiently cure a thermosetting resin-based composition only at a desired set temperature, that is, a low temperature. Then, the catalyst activity is low and the thermosetting resin-based composition is not cured, but a property that exhibits high catalytic activity at a desired curing temperature and can be cured in a short time is required.
これは、封止材料用途の熱硬化性樹脂系組成物は、１００～１２０℃程度の低温で混合することにより作製・貯蔵し、１７０℃以上の高温で硬化させることが一般的であり、低温で混合中に硬化が進行してしまうと、流動性悪化の要因となり好ましくないためである。つまり、１００～１２０℃程度の低温では硬化が抑制され、１７０℃以上の高温では短時間で硬化することが好ましい。
また、熱硬化性樹脂と熱硬化性樹脂用硬化剤および熱硬化性樹脂用硬化促進剤を併用する熱硬化性樹脂系組成物が主流であるが、これらの材料を使用直前に混合しなくてはならないという煩雑さ、不便さから、熱硬化性樹脂および熱硬化性樹脂用硬化促進剤からなる単独硬化型熱硬化性樹脂系組成物も開発されている。この単独硬化型熱硬化性樹脂系組成物においても潜在性に優れ、さらには、熱硬化性樹脂が常温で液体である単独硬化型の熱硬化性樹脂系組成物（一液性の熱硬化性樹脂系組成物）であって、調製してから硬化させるまでの貯蔵安定性が室温においても良好であるものも望まれている。 This is because a thermosetting resin-based composition for sealing materials is generally prepared and stored by mixing at a low temperature of about 100 to 120 ° C. and cured at a high temperature of 170 ° C. or higher. This is because if the curing proceeds during mixing, the fluidity deteriorates, which is not preferable. That is, it is preferable that curing is suppressed at a low temperature of about 100 to 120 ° C., and curing is performed at a high temperature of 170 ° C. or more in a short time.
In addition, thermosetting resin-based compositions that use a thermosetting resin, a thermosetting resin curing agent, and a thermosetting resin curing accelerator are the mainstream, but these materials must be mixed immediately before use. Due to the inconvenience and inconvenience that it should not be, a single-curing thermosetting resin composition comprising a thermosetting resin and a curing accelerator for thermosetting resins has also been developed. This single curable thermosetting resin composition also has excellent potential, and furthermore, the single curable thermosetting resin composition in which the thermosetting resin is liquid at room temperature (one-part thermosetting resin). There is also a demand for a resin-based composition that has good storage stability from preparation to curing at room temperature.
また、熱硬化性樹脂と熱硬化性樹脂用硬化剤および熱硬化性樹脂用硬化促進剤を併用する熱硬化性樹脂系組成物が主流であるが、これらの材料を使用直前に混合しなくてはならないという煩雑さ、不便さから、熱硬化性樹脂および熱硬化性樹脂用硬化促進剤からなる単独硬化型熱硬化性樹脂系組成物も開発されている。この単独硬化型熱硬化性樹脂系組成物においても潜在性に優れ、さらには、熱硬化性樹脂が常温で液体である単独硬化型の熱硬化性樹脂系組成物（一液性の熱硬化性樹脂系組成物）であって、調製してから硬化させるまでの貯蔵安定性が室温においても良好であるものも望まれている。 This is because a thermosetting resin-based composition for sealing materials is generally prepared and stored by mixing at a low temperature of about 100 to 120 ° C. and cured at a high temperature of 170 ° C. or higher. This is because if the curing proceeds during mixing, the fluidity deteriorates, which is not preferable. That is, it is preferable that curing is suppressed at a low temperature of about 100 to 120 ° C., and curing is performed at a high temperature of 170 ° C. or more in a short time.
In addition, thermosetting resin-based compositions that use a thermosetting resin, a thermosetting resin curing agent, and a thermosetting resin curing accelerator are the mainstream, but these materials must be mixed immediately before use. Due to the inconvenience and inconvenience that it should not be, a single-curing thermosetting resin composition comprising a thermosetting resin and a curing accelerator for thermosetting resins has also been developed. This single curable thermosetting resin composition also has excellent potential, and furthermore, the single curable thermosetting resin composition in which the thermosetting resin is liquid at room temperature (one-part thermosetting resin). There is also a demand for a resin-based composition that has good storage stability from preparation to curing at room temperature.
既存の熱硬化性樹脂用硬化促進剤、特にエポキシ樹脂用の硬化促進剤としては、リン系、あるいはイミダゾール系があるが、硬化力が高く、かつ電気的信頼性の高い硬化物を得ることが出来るリン系が一般的に知られており、その中でも潜在性硬化促進剤として、ホスホニウムボレート（特許文献１）、ホスホニウムカルボキシレート（特許文献２～６）、ホスホニウムチオシアネート（特許文献７）、１，２－ビス（ジフェニルホスフィノ）アセチレン（特許文献８）が挙げられるが、潜在性の観点では十分ではなかった。
Existing curing accelerators for thermosetting resins, especially curing accelerators for epoxy resins, are phosphorus-based or imidazole-based, but it is possible to obtain cured products with high curing power and high electrical reliability. Phosphorus systems that can be used are generally known. Among them, as latent curing accelerators, phosphonium borate (Patent Document 1), phosphonium carboxylate (Patent Documents 2 to 6), phosphonium thiocyanate (Patent Document 7), 1, Although 2-bis (diphenylphosphino) acetylene (Patent Document 8) is mentioned, it is not sufficient from the viewpoint of potential.
また、光半導体を封止する際は、硬化物が無色透明となるエポキシ樹脂系組成物が求められている。硬化剤として酸無水物、リン系硬化促進剤としてホスホニウムカルボキシレートを含有するエポキシ樹脂系組成物の硬化物は無色透明になることが知られている（特許文献９～１２参照）が、十分な透明性ではなかった。
さらに近年では、高耐熱用途の熱硬化性樹脂系組成物として、エポキシ樹脂とマレイミド樹脂の併用系等も種々検討されている（特許文献１３、１４参照）が、硬化促進剤の検討は十分ではなかった。 Moreover, when sealing an optical semiconductor, the epoxy resin-type composition from which hardened | cured material becomes colorless and transparent is calculated | required. It is known that a cured product of an epoxy resin-based composition containing an acid anhydride as a curing agent and a phosphonium carboxylate as a phosphorus curing accelerator becomes colorless and transparent (see Patent Documents 9 to 12). It was not transparent.
In recent years, various types of combined use of epoxy resin and maleimide resin have been studied as thermosetting resin-based compositions for high heat resistance applications (see Patent Documents 13 and 14). There wasn't.
さらに近年では、高耐熱用途の熱硬化性樹脂系組成物として、エポキシ樹脂とマレイミド樹脂の併用系等も種々検討されている（特許文献１３、１４参照）が、硬化促進剤の検討は十分ではなかった。 Moreover, when sealing an optical semiconductor, the epoxy resin-type composition from which hardened | cured material becomes colorless and transparent is calculated | required. It is known that a cured product of an epoxy resin-based composition containing an acid anhydride as a curing agent and a phosphonium carboxylate as a phosphorus curing accelerator becomes colorless and transparent (see Patent Documents 9 to 12). It was not transparent.
In recent years, various types of combined use of epoxy resin and maleimide resin have been studied as thermosetting resin-based compositions for high heat resistance applications (see Patent Documents 13 and 14). There wasn't.
本発明は、上記の従来技術に伴う問題点を解決しようとするものである。すなわち、単独硬化型熱硬化性樹脂系組成物を含む熱硬化性樹脂系組成物において、熱硬化性樹脂用硬化促進剤が、低温（１００～１２０℃程度）では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る潜在性を有し、また、一液における貯蔵安定性に優れた熱硬化性樹脂系組成物、ならびに硬化物が無色透明になる熱硬化性樹脂系組成物を提供することにある。
The present invention is intended to solve the problems associated with the above-described conventional technology. That is, in a thermosetting resin-based composition including a single-curable thermosetting resin-based composition, the thermosetting resin curing accelerator has a low catalytic activity at low temperatures (about 100 to 120 ° C.) and the thermosetting resin. A thermosetting resin-based composition that does not cure the system composition but has a high catalytic activity at a desired curing temperature and can be cured in a short time, and has excellent storage stability in one liquid, Another object is to provide a thermosetting resin-based composition in which the cured product is colorless and transparent.
このような状況に鑑み、本発明者らは鋭意検討した。その結果、下記の一般式（１）
In view of such a situation, the present inventors have intensively studied. As a result, the following general formula (1)
（式中、Ｒ１～Ｒ４は、同一または異なって、炭素数１～１６の直鎖状もしくは分岐鎖状のアルキル基、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す置換基である。）
で表されるホスホニウムカチオン２分子と、下記の式（２） (Wherein R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group) Group.)
2 molecules of phosphonium cation represented by the following formula (2)
で表されるホスホニウムカチオン２分子と、下記の式（２） (Wherein R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group) Group.)
2 molecules of phosphonium cation represented by the following formula (2)
で表されるピロメリット酸の２価のアニオン残基１分子からなるホスホニウム塩を硬化促進剤として配合することにより、低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得、また一液においては良好な貯蔵安定性を与え、さらに硬化剤が酸無水物の使用の場合に硬化物が無色透明になる熱硬化性樹脂系組成物が得られること等を見いだし、本発明を完成するに至った。
By adding a phosphonium salt consisting of one molecule of a divalent anionic residue of pyromellitic acid represented by the formula below as a curing accelerator, the catalyst activity is low at low temperatures and the thermosetting resin composition is not cured. Thermal curing that exhibits high catalytic activity at a curing temperature, can be cured in a short time, gives good storage stability in one solution, and further makes the cured product colorless and transparent when the curing agent is an acid anhydride The inventors have found that a functional resin composition can be obtained, and have completed the present invention.
すなわち、本発明は以下の内容をその要旨とするものである。
〔１〕 下記の一般式（１） That is, the gist of the present invention is as follows.
[1] The following general formula (1)
〔１〕 下記の一般式（１） That is, the gist of the present invention is as follows.
[1] The following general formula (1)
（式中、Ｒ１～Ｒ４は、同一または異なって、炭素数１～１６の直鎖状もしくは分岐鎖状のアルキル基、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す置換基である。）で表されるホスホニウムカチオン２分子と、下記の式（２）
(Wherein R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group) A phosphonium cation molecule represented by the following formula (2):
で表されるピロメリット酸の２価のアニオン残基１分子からなるホスホニウム塩（以下、「本発明のホスホニウム塩」ということがある）。
A phosphonium salt consisting of one molecule of a divalent anionic residue of pyromellitic acid represented by the formula (hereinafter sometimes referred to as “phosphonium salt of the present invention”).
〔２〕 前記一般式（１）において、Ｒ１～Ｒ４が、同一または異なって、ブチル基、フェニル基、４－メチルフェニル基、および、４－メトキシフェニル基から選ばれる置換基である、〔１〕に記載のホスホニウム塩。
[2] In the general formula (1), R 1 to R 4 are the same or different and each is a substituent selected from a butyl group, a phenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group. The phosphonium salt according to [1].
〔３〕 前記一般式（１）において、Ｒ１～Ｒ４が全てフェニル基である〔１〕に記載のホスホニウム塩である、ビス（テトラフェニルホスホニウム）ジハイドロジェンピロメリテート。
[3] Bis (tetraphenylphosphonium) dihydrogen pyromellitate, which is the phosphonium salt according to [1], wherein R 1 to R 4 are all phenyl groups in the general formula (1).
〔４〕 前記一般式（１）において、Ｒ１～Ｒ４が全てブチル基である〔１〕に記載のホスホニウム塩である、ビス（テトラブチルホスホニウム）ジハイドロジェンピロメリテート。
[4] Bis (tetrabutylphosphonium) dihydrogen pyromellitate, which is the phosphonium salt according to [1], wherein R 1 to R 4 in the general formula (1) are all butyl groups.
〔５〕 〔１〕～〔４〕のいずれかに記載のホスホニウム塩を少なくとも含む、熱硬化性樹脂用硬化促進剤。
[5] A curing accelerator for a thermosetting resin, comprising at least the phosphonium salt according to any one of [1] to [4].
〔６〕 〔５〕に記載の熱硬化性樹脂用硬化促進剤と、熱硬化性樹脂とを少なくとも含む、熱硬化性樹脂系組成物。
〔７〕 前記熱硬化性樹脂が、エポキシ樹脂、マレイミド樹脂、シアネート樹脂、および、イソシアネート樹脂から選ばれる１種または２種以上の熱硬化性樹脂である、〔６〕に記載の熱硬化性樹脂系組成物。
〔８〕 さらに熱硬化性樹脂用硬化剤を含む、〔６〕または〔７〕に記載の熱硬化性樹脂系組成物。 [6] A thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator according to [5] and a thermosetting resin.
[7] The thermosetting resin according to [6], wherein the thermosetting resin is one or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin. System composition.
[8] The thermosetting resin composition according to [6] or [7], further including a curing agent for a thermosetting resin.
〔７〕 前記熱硬化性樹脂が、エポキシ樹脂、マレイミド樹脂、シアネート樹脂、および、イソシアネート樹脂から選ばれる１種または２種以上の熱硬化性樹脂である、〔６〕に記載の熱硬化性樹脂系組成物。
〔８〕 さらに熱硬化性樹脂用硬化剤を含む、〔６〕または〔７〕に記載の熱硬化性樹脂系組成物。 [6] A thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator according to [5] and a thermosetting resin.
[7] The thermosetting resin according to [6], wherein the thermosetting resin is one or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin. System composition.
[8] The thermosetting resin composition according to [6] or [7], further including a curing agent for a thermosetting resin.
〔９〕 前記熱硬化性樹脂用硬化剤が、フェノール樹脂、ポリアミン、酸無水物、および、ベンゾオキサジンから選ばれる１種または２種以上の熱硬化性樹脂用硬化剤である、〔８〕に記載の熱硬化性樹脂系組成物。
[9] The curing agent for thermosetting resin is one or more curing agents for thermosetting resin selected from phenol resin, polyamine, acid anhydride, and benzoxazine, [8] The thermosetting resin-based composition as described.
〔１０〕 〔８〕または〔９〕に記載の熱硬化性樹脂系組成物であって、熱硬化性樹脂用硬化促進剤をあらかじめ熱硬化性樹脂用硬化剤と反応させてなるマスターバッチを含む、熱硬化性樹脂系組成物。
[10] The thermosetting resin composition according to [8] or [9], including a master batch obtained by reacting a curing accelerator for a thermosetting resin with a curing agent for a thermosetting resin in advance. , Thermosetting resin-based composition.
〔１１〕 〔６〕～〔１０〕のいずれかに記載の熱硬化性樹脂系組成物を硬化して得られる熱硬化性樹脂系硬化物。
[11] A thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of [6] to [10].
本発明のホスホニウム塩を含む熱硬化性樹脂用硬化促進剤を成分として含有する熱硬化性樹脂系組成物は、従来の硬化促進剤を用いた場合に比べ、低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得、また一液においては良好な貯蔵安定性を与え、硬化剤として酸無水物を使用の場合に、その硬化物が無色透明となるため有用である。
The thermosetting resin-based composition containing the curing accelerator for thermosetting resins containing the phosphonium salt of the present invention as a component has lower catalytic activity at lower temperatures and thermosetting properties than when a conventional curing accelerator is used. When the resin-based composition is not cured, but exhibits a high catalytic activity at the desired curing temperature, can be cured in a short time, and gives good storage stability in one liquid, and when an acid anhydride is used as a curing agent In addition, the cured product is useful because it is colorless and transparent.
以下、本発明について詳細に説明する。
＜硬化促進剤＞
本発明は、下記の一般式（１） Hereinafter, the present invention will be described in detail.
<Curing accelerator>
The present invention relates to the following general formula (1)
＜硬化促進剤＞
本発明は、下記の一般式（１） Hereinafter, the present invention will be described in detail.
<Curing accelerator>
The present invention relates to the following general formula (1)
（式中、Ｒ１～Ｒ４は、同一または異なって、炭素数１～１６の直鎖状もしくは分岐鎖状のアルキル基、または、アルキル基もしくはメトキシ基で置換してもよいフェニル基を示す置換基である。）
で表されるホスホニウムカチオン２分子と、下記の式（２） (Wherein R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group) It is a substituent.)
2 molecules of phosphonium cation represented by the following formula (2)
で表されるホスホニウムカチオン２分子と、下記の式（２） (Wherein R 1 to R 4 are the same or different and each represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may be substituted with an alkyl group or a methoxy group) It is a substituent.)
2 molecules of phosphonium cation represented by the following formula (2)
で表されるピロメリット酸の２価のアニオン残基１分子からなるホスホニウム塩である。
It is a phosphonium salt consisting of one molecule of a divalent anionic residue of pyromellitic acid represented by the formula:
一般式（１）のホスホニウムカチオンにおけるＲ１～Ｒ４は、同一または異なって、炭素数１～１６の直鎖状もしくは分岐鎖状のアルキル基、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す。
R 1 ~ R 4 in phosphonium cation of the general formula (1) are the same or different and may be substituted with a linear or branched alkyl group or an alkyl group or methoxy group, having 1 to 16 carbon atoms Represents a phenyl group;
一般式（１）のホスホニウムカチオンにおけるＲ１～Ｒ４の炭素数１～１６の直鎖状もしくは分岐鎖状のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ドデシル基であることが好ましい。特にＲ１～Ｒ４の全てが、ｎ－ブチル基であることがより好ましい。
Examples of the linear or branched alkyl group having 1 to 16 carbon atoms of R 1 to R 4 in the phosphonium cation of the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, An n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and n-dodecyl group are preferred. In particular, it is more preferable that all of R 1 to R 4 are n-butyl groups.
一般式（１）のホスホニウムカチオンにおけるＲ１～Ｒ４のアルキル基もしくはメトキシ基で置換してもよいフェニル基において、フェニル基を置換してもよいアルキル基としては炭素数１～４の直鎖状もしくは分岐鎖状であり、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、ｔｅｒｔ－ブチル基が好ましい。アルキル基もしくはメトキシ基で置換してもよいフェニル基として、より具体的には、フェニル基、４－メチルフェニル基、４－メトキシフェニル基が好ましく、特にＲ１～Ｒ４の全てが、フェニル基であることがより好ましい。
In the phosphonium cation of the general formula (1), a phenyl group which may be substituted with an alkyl group of R 1 to R 4 or a methoxy group, the alkyl group which may be substituted with a phenyl group is a straight chain having 1 to 4 carbon atoms. Or a branched chain, and preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, or a tert-butyl group. More specifically, the phenyl group that may be substituted with an alkyl group or a methoxy group is preferably a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group, and particularly, all of R 1 to R 4 are phenyl groups. It is more preferable that
一般式（１）のホスホニウムカチオンとしては、テトラブチルホスホニウムカチオン、テトラフェニルホスホニウムカチオン、テトラキス（４－メチルフェニル）ホスホニウムカチオン、テトラキス（４－メトキシフェニル）ホスホニウムカチオン、フェニルトリス（４－メチルフェニル）ホスホニウムカチオン、フェニルトリス（４－メトキシフェニル）ホスホニウムカチオン、フェニルトリブチルホスホニウムカチオン、（４－メチルフェニル）トリフェニルホスホニウムカチオン、（４－メトキシフェニル）トリフェニルホスホニウムカチオン、ブチルトリフェニルホスホニウムカチオン等が挙げられる。
Examples of the phosphonium cation of the general formula (1) include tetrabutylphosphonium cation, tetraphenylphosphonium cation, tetrakis (4-methylphenyl) phosphonium cation, tetrakis (4-methoxyphenyl) phosphonium cation, phenyltris (4-methylphenyl) phosphonium. Cation, phenyltris (4-methoxyphenyl) phosphonium cation, phenyltributylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, butyltriphenylphosphonium cation and the like.
式（２）であるピロメリット酸の２価のアニオン残基とは、ピロメリット酸の１位と、４位もしくは５位のカルボキシル基の水素原子が外れて、２価のカルボキシルアニオンとなったものをいう。
The divalent anion residue of pyromellitic acid represented by the formula (2) is a divalent carboxyl anion by removing the hydrogen atoms of the 1-position, 4-position or 5-position carboxyl group of pyromellitic acid. Say things.
上記のホスホニウムカチオンとピロメリット酸の２価のアニオン残基との塩は本明細書の記載に基づき、公知の方法により容易に製造できる。
例えば、ピロメリット酸のジアルカリ金属塩を常法で合成（溶媒は、水、メタノール等）した後、そのピロメリット酸のジアルカリ金属塩０．５モルに対してテトラ置換ホスホニウムハライドを１モル仕込み反応させることにより塩形成する方法等が挙げられる。この場合、テトラ置換ホスホニウムハライドとピロメリット酸のジアルカリ金属塩をそれぞれ単独もしくは２種類以上を使用して上記塩を形成させてもよい。２種類以上を混合する場合は、２種類以上のテトラ置換ホスホニウムハライドおよびピロメリット酸のジアルカリ金属塩同士を先に混合した後に、ビス（テトラ置換ホスホニウム）ジハイドロジェンピロメリテートを形成させてもよいし、２種類以上のビス（テトラ置換ホスホニウム）ジハイドロジェンピロメリテートを混合してもよい。本製法による製造例は、製造例１に記載した。 A salt of the above phosphonium cation and a divalent anion residue of pyromellitic acid can be easily produced by a known method based on the description in this specification.
For example, after synthesizing a dialkali metal salt of pyromellitic acid by a conventional method (solvent: water, methanol, etc.), 1 mol of tetra-substituted phosphonium halide is charged per 0.5 mol of the dialkali metal salt of pyromellitic acid. And a method for forming a salt by the formation. In this case, the salt may be formed by using a tetra-substituted phosphonium halide and a pyromellitic acid dialkali metal salt alone or in combination of two or more. When two or more types are mixed, after mixing two or more types of tetra-substituted phosphonium halides and the dialkali metal salt of pyromellitic acid, bis (tetra-substituted phosphonium) dihydrogen pyromellitate may be formed. Alternatively, two or more kinds of bis (tetra-substituted phosphonium) dihydrogen pyromellitate may be mixed. Production examples according to this production method are described in Production Example 1.
例えば、ピロメリット酸のジアルカリ金属塩を常法で合成（溶媒は、水、メタノール等）した後、そのピロメリット酸のジアルカリ金属塩０．５モルに対してテトラ置換ホスホニウムハライドを１モル仕込み反応させることにより塩形成する方法等が挙げられる。この場合、テトラ置換ホスホニウムハライドとピロメリット酸のジアルカリ金属塩をそれぞれ単独もしくは２種類以上を使用して上記塩を形成させてもよい。２種類以上を混合する場合は、２種類以上のテトラ置換ホスホニウムハライドおよびピロメリット酸のジアルカリ金属塩同士を先に混合した後に、ビス（テトラ置換ホスホニウム）ジハイドロジェンピロメリテートを形成させてもよいし、２種類以上のビス（テトラ置換ホスホニウム）ジハイドロジェンピロメリテートを混合してもよい。本製法による製造例は、製造例１に記載した。 A salt of the above phosphonium cation and a divalent anion residue of pyromellitic acid can be easily produced by a known method based on the description in this specification.
For example, after synthesizing a dialkali metal salt of pyromellitic acid by a conventional method (solvent: water, methanol, etc.), 1 mol of tetra-substituted phosphonium halide is charged per 0.5 mol of the dialkali metal salt of pyromellitic acid. And a method for forming a salt by the formation. In this case, the salt may be formed by using a tetra-substituted phosphonium halide and a pyromellitic acid dialkali metal salt alone or in combination of two or more. When two or more types are mixed, after mixing two or more types of tetra-substituted phosphonium halides and the dialkali metal salt of pyromellitic acid, bis (tetra-substituted phosphonium) dihydrogen pyromellitate may be formed. Alternatively, two or more kinds of bis (tetra-substituted phosphonium) dihydrogen pyromellitate may be mixed. Production examples according to this production method are described in Production Example 1.
また、テトラ置換ホスホニウムヒドロキシド１モルに対してピロメリット酸または無水ピロメリット酸を０．５モル用いて中和することにより塩を形成してもよい。本製法による製造例は、製造例２に記載した。
Alternatively, a salt may be formed by neutralizing 1 mol of tetrasubstituted phosphonium hydroxide with 0.5 mol of pyromellitic acid or pyromellitic anhydride. Production examples according to this production method are described in Production Example 2.
得られた反応物から純度の高い結晶を析出させ、未反応の原料および副生する無機塩を除去すること等を目的に、得られた反応物を水、アルコール系有機溶媒（メタノール、エタノール、プロパノール、ブタノール等）、ケトン系有機溶媒（アセトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルケトン等）、エーテル系有機溶媒（テトラヒドロフラン、ジエチルエーテル、ジブチルエーテル、２－メチルテトラヒドロフラン、シクロペンチルメチルエーテル、ジオキサン等）、およびこれらの混合溶媒で洗浄、再結晶精製してもよい。
なお、上記テトラ置換ホスホニウムハライド、テトラ置換ホスホニウムヒドロキシド、ピロメリット酸、無水ピロメリット酸、および溶媒はいずれも市販されているものを使用してもよい。 For the purpose of precipitating high-purity crystals from the obtained reaction product and removing unreacted raw materials and by-product inorganic salts, the obtained reaction product is mixed with water, an alcohol-based organic solvent (methanol, ethanol, Propanol, butanol, etc.), ketone organic solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), ether organic solvents (tetrahydrofuran, diethyl ether, dibutyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, etc.), In addition, these may be washed with a mixed solvent and purified by recrystallization.
Commercially available tetra-substituted phosphonium halides, tetra-substituted phosphonium hydroxides, pyromellitic acid, pyromellitic anhydride, and solvents may be used.
なお、上記テトラ置換ホスホニウムハライド、テトラ置換ホスホニウムヒドロキシド、ピロメリット酸、無水ピロメリット酸、および溶媒はいずれも市販されているものを使用してもよい。 For the purpose of precipitating high-purity crystals from the obtained reaction product and removing unreacted raw materials and by-product inorganic salts, the obtained reaction product is mixed with water, an alcohol-based organic solvent (methanol, ethanol, Propanol, butanol, etc.), ketone organic solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), ether organic solvents (tetrahydrofuran, diethyl ether, dibutyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, etc.), In addition, these may be washed with a mixed solvent and purified by recrystallization.
Commercially available tetra-substituted phosphonium halides, tetra-substituted phosphonium hydroxides, pyromellitic acid, pyromellitic anhydride, and solvents may be used.
これらの方法により得られるホスホニウム塩は、通常は、ホスホニウムカチオンとピロメリット酸の２価のアニオン残基との２：１（モル比）塩が主成分であり、一般式（３）で示される。
The phosphonium salt obtained by these methods is usually composed mainly of a 2: 1 (molar ratio) salt of a phosphonium cation and a divalent anion residue of pyromellitic acid, and is represented by the general formula (3). .
また、一般式（３）において、アニオン部は、式（２）で表されるピロメリット酸のアニオン残基（２価のアニオン残基）を示し、厳密には、複数のカルボキシル基もしくはカルボキシルアニオンのうち、ｏ－フェニレン鎖を隔てて存在するカルボキシル基およびカルボキシルアニオンがホスホニウムカチオンに配位したアニオン残基である。このとき、カルボキシル基およびカルボキシルアニオンは、実際には等価である。
In the general formula (3), the anion part represents an anion residue (divalent anion residue) of pyromellitic acid represented by the formula (2), strictly speaking, a plurality of carboxyl groups or carboxyl anions. Of these, an anion residue in which a carboxyl group and a carboxyl anion present across an o-phenylene chain are coordinated to a phosphonium cation. At this time, the carboxyl group and the carboxyl anion are actually equivalent.
一般的なカルボキシル基に含まれる水素原子は、１Ｈ－ＮＭＲにおけるケミカルシフトが１２ｐｐｍ付近に検出されるのに対し、一般式（３）に記載のピロメリット酸のアニオン残基に含まれる水素原子は、隣接する酸素原子との水素結合が非常に強いため、１Ｈ－ＮＭＲにおけるケミカルシフトが２０ｐｐｍ付近に検出される。
A hydrogen atom contained in a general carboxyl group has a chemical shift detected in the vicinity of 12 ppm in 1 H-NMR, whereas a hydrogen atom contained in an anion residue of pyromellitic acid described in the general formula (3) Has a very strong hydrogen bond with an adjacent oxygen atom, and thus a chemical shift in 1 H-NMR is detected around 20 ppm.
また、本発明は、一般式（１）で表されるホスホニウムカチオン２分子と、式（２）で表されるピロメリット酸の２価のアニオン残基１分子からなるホスホニウム塩（例えば一般式（３）で表されるホスホニウム塩）を少なくとも含む熱硬化性樹脂用硬化促進剤（以下、「本発明の熱硬化性樹脂用硬化促進剤」ということがある）である。
一般式（３）に記載の２価のアニオン残基がホスホニウムカチオン２分子に配位することが、テトラ置換ホスホニウムアセテート、テトラ置換ホスホニウムベンゾエート等、従来のホスホニウムカルボキシレートと比較し、低温時における樹脂の硬化発現までのタイムラグを生じさせ、低温時の低活性（潜在性）や貯蔵安定性の付与を引き起こしていると考えられる。 In addition, the present invention provides a phosphonium salt (for example, the general formula (1) having two molecules of a phosphonium cation represented by the general formula (1) and one molecule of pyromellitic acid divalent anion residue represented by the formula (2). 3), a curing accelerator for thermosetting resins (hereinafter sometimes referred to as “the curing accelerator for thermosetting resins of the present invention”).
Compared with conventional phosphonium carboxylates such as tetra-substituted phosphonium acetate and tetra-substituted phosphonium benzoate, the divalent anion residue represented by the general formula (3) is coordinated to two phosphonium cations. It is considered that a time lag until the onset of curing occurs, and low activity (latency) at low temperature and storage stability are imparted.
一般式（３）に記載の２価のアニオン残基がホスホニウムカチオン２分子に配位することが、テトラ置換ホスホニウムアセテート、テトラ置換ホスホニウムベンゾエート等、従来のホスホニウムカルボキシレートと比較し、低温時における樹脂の硬化発現までのタイムラグを生じさせ、低温時の低活性（潜在性）や貯蔵安定性の付与を引き起こしていると考えられる。 In addition, the present invention provides a phosphonium salt (for example, the general formula (1) having two molecules of a phosphonium cation represented by the general formula (1) and one molecule of pyromellitic acid divalent anion residue represented by the formula (2). 3), a curing accelerator for thermosetting resins (hereinafter sometimes referred to as “the curing accelerator for thermosetting resins of the present invention”).
Compared with conventional phosphonium carboxylates such as tetra-substituted phosphonium acetate and tetra-substituted phosphonium benzoate, the divalent anion residue represented by the general formula (3) is coordinated to two phosphonium cations. It is considered that a time lag until the onset of curing occurs, and low activity (latency) at low temperature and storage stability are imparted.
本発明の熱硬化性樹脂用硬化促進剤は、本発明の熱硬化性樹脂用硬化促進剤と熱硬化性樹脂とを少なくとも含む、単独硬化型の熱硬化性樹脂系組成物においても良好な潜在性が得られ、一液性の単独硬化型熱硬化性樹脂系組成物において調製してから硬化させるまでの間、室温で保存可能な良好な貯蔵安定性を得ることができる。
また、硬化剤が酸無水物の場合において、硬化促進剤に一般式（３）のホスホニウム塩を使用すると、無色透明性が優れた樹脂系組成物の硬化物が得られる。
さらに、一般式（３）のホスホニウム塩が硬化剤と均一化し難い場合等は、均一化を容易にすること等を目的として、一般式（３）のホスホニウム塩をあらかじめ硬化剤と反応させて得たマスターバッチを、熱硬化性樹脂用硬化促進剤として用いてもよい。
本発明の熱硬化性樹脂用硬化促進剤は、本発明のホスホニウム塩の他に、効果に影響しない限り、熱硬化性樹脂用硬化促進剤に通常使用される溶剤、充填剤、添加剤等をさらに含んでもよい。
なお、本発明の熱硬化性樹脂用硬化促進剤は、上記ホスホニウム塩の他に、適宜熱硬化性樹脂の硬化促進剤を併用して使用してもよい。 The curing accelerator for a thermosetting resin of the present invention has a good potential even in a single-curing thermosetting resin composition comprising at least the curing accelerator for a thermosetting resin of the present invention and a thermosetting resin. From the preparation of the one-component single-curing, single-curing thermosetting resin composition to curing, good storage stability that can be stored at room temperature can be obtained.
When the curing agent is an acid anhydride and the phosphonium salt of the general formula (3) is used as the curing accelerator, a cured product of the resin composition having excellent colorless transparency can be obtained.
Further, when it is difficult to homogenize the phosphonium salt of the general formula (3) with the curing agent, the phosphonium salt of the general formula (3) is obtained by reacting with the curing agent in advance for the purpose of facilitating homogenization. The master batch may be used as a curing accelerator for thermosetting resins.
In addition to the phosphonium salt of the present invention, the curing accelerator for the thermosetting resin of the present invention contains solvents, fillers, additives, etc. that are usually used for the curing accelerator for thermosetting resins, as long as the effect is not affected. Further, it may be included.
In addition, you may use the hardening accelerator for thermosetting resins of this invention in combination with the hardening accelerator of a thermosetting resin suitably other than the said phosphonium salt.
また、硬化剤が酸無水物の場合において、硬化促進剤に一般式（３）のホスホニウム塩を使用すると、無色透明性が優れた樹脂系組成物の硬化物が得られる。
さらに、一般式（３）のホスホニウム塩が硬化剤と均一化し難い場合等は、均一化を容易にすること等を目的として、一般式（３）のホスホニウム塩をあらかじめ硬化剤と反応させて得たマスターバッチを、熱硬化性樹脂用硬化促進剤として用いてもよい。
本発明の熱硬化性樹脂用硬化促進剤は、本発明のホスホニウム塩の他に、効果に影響しない限り、熱硬化性樹脂用硬化促進剤に通常使用される溶剤、充填剤、添加剤等をさらに含んでもよい。
なお、本発明の熱硬化性樹脂用硬化促進剤は、上記ホスホニウム塩の他に、適宜熱硬化性樹脂の硬化促進剤を併用して使用してもよい。 The curing accelerator for a thermosetting resin of the present invention has a good potential even in a single-curing thermosetting resin composition comprising at least the curing accelerator for a thermosetting resin of the present invention and a thermosetting resin. From the preparation of the one-component single-curing, single-curing thermosetting resin composition to curing, good storage stability that can be stored at room temperature can be obtained.
When the curing agent is an acid anhydride and the phosphonium salt of the general formula (3) is used as the curing accelerator, a cured product of the resin composition having excellent colorless transparency can be obtained.
Further, when it is difficult to homogenize the phosphonium salt of the general formula (3) with the curing agent, the phosphonium salt of the general formula (3) is obtained by reacting with the curing agent in advance for the purpose of facilitating homogenization. The master batch may be used as a curing accelerator for thermosetting resins.
In addition to the phosphonium salt of the present invention, the curing accelerator for the thermosetting resin of the present invention contains solvents, fillers, additives, etc. that are usually used for the curing accelerator for thermosetting resins, as long as the effect is not affected. Further, it may be included.
In addition, you may use the hardening accelerator for thermosetting resins of this invention in combination with the hardening accelerator of a thermosetting resin suitably other than the said phosphonium salt.
一般式（３）のホスホニウム塩としては、ビス（テトラフェニルホスホニウム）ジハイドロジェンピロメリテート、ビス［テトラキス（４－メチルフェニル）ホスホニウム］ジハイドロジェンピロメリテート、ビス［テトラキス（４－メトキシフェニル）ホスホニウム］ジハイドロジェンピロメリテート、ビス（テトラブチルホスホニウム）ジハイドロジェンピロメリテート、ビス[フェニルトリス（４－メチルフェニル）ホスホニウム] ジハイドロジェンピロメリテート、ビス[フェニルトリス（４－メトキシフェニル）ホスホニウム] ジハイドロジェンピロメリテート、ビス（フェニルトリブチルホスホニウム）ジハイドロジェンピロメリテート、ビス［（４－メチルフェニル）トリフェニルホスホニウム］ジハイドロジェンピロメリテート、ビス［（４－メトキシフェニル）トリフェニルホスホニウム］ジハイドロジェンピロメリテート、ビス（ブチルトリフェニルホスホニウム）ジハイドロジェンピロメリテート等が挙げられる。
Examples of the phosphonium salt of the general formula (3) include bis (tetraphenylphosphonium) dihydrogen pyromellitate, bis [tetrakis (4-methylphenyl) phosphonium] dihydrogen pyromellitate, bis [tetrakis (4-methoxyphenyl). ) Phosphonium] dihydrogen pyromellitate, bis (tetrabutylphosphonium) dihydrogen pyromellitate, bis [phenyltris (4-methylphenyl) phosphonium] dihydrogen pyromellitate, bis [phenyltris (4-methoxy) Phenyl) phosphonium] dihydrogen pyromellitate, bis (phenyltributylphosphonium) dihydrogen pyromellitate, bis [(4-methylphenyl) triphenylphosphonium] dihydrogen pyromellite , Bis [(4-methoxyphenyl) triphenylphosphonium] dihydrogen pyromellitate, bis (butyl triphenylphosphonium) dihydrogen pyromellitate and the like.
また、本発明は、本発明の熱硬化性樹脂用硬化促進剤と、熱硬化性樹脂とを少なくとも含む、熱硬化性樹脂系組成物である（以下、「本発明の単独硬化型熱硬化性樹脂系組成物」ということがある）。さらなる本発明は、さらに熱硬化性樹脂用硬化剤を含む、熱硬化性樹脂系組成物である。以下、これらを「本発明の熱硬化性樹脂系組成物」ということがある。
本発明の熱硬化性樹脂系組成物の成分である熱硬化性樹脂の好ましい例であるエポキシ樹脂、マレイミド樹脂、シアネート樹脂、イソシアネート樹脂、および熱硬化性樹脂用硬化剤について次に説明する。 The present invention is also a thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator of the present invention and a thermosetting resin (hereinafter referred to as “single curable thermosetting of the present invention”). Sometimes referred to as “resin-based composition”). The present invention further relates to a thermosetting resin-based composition further including a curing agent for thermosetting resin. Hereinafter, these may be referred to as “the thermosetting resin composition of the present invention”.
Next, epoxy resins, maleimide resins, cyanate resins, isocyanate resins, and curing agents for thermosetting resins, which are preferred examples of thermosetting resins that are components of the thermosetting resin-based composition of the present invention, will be described.
本発明の熱硬化性樹脂系組成物の成分である熱硬化性樹脂の好ましい例であるエポキシ樹脂、マレイミド樹脂、シアネート樹脂、イソシアネート樹脂、および熱硬化性樹脂用硬化剤について次に説明する。 The present invention is also a thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator of the present invention and a thermosetting resin (hereinafter referred to as “single curable thermosetting of the present invention”). Sometimes referred to as “resin-based composition”). The present invention further relates to a thermosetting resin-based composition further including a curing agent for thermosetting resin. Hereinafter, these may be referred to as “the thermosetting resin composition of the present invention”.
Next, epoxy resins, maleimide resins, cyanate resins, isocyanate resins, and curing agents for thermosetting resins, which are preferred examples of thermosetting resins that are components of the thermosetting resin-based composition of the present invention, will be described.
＜エポキシ樹脂＞
エポキシ樹脂としては、特に限定されず、１分子中に２個以上のエポキシ基を有する汎用的なエポキシ樹脂を用いることが可能であり、例えば、フェノール、クレゾール、キシレノール、カテコール、レゾルシン、ビスフェノールＡ、ビスフェノールＦ等のフェノール類および／またはナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒の存在下で縮合または共縮合させて得られるノボラック樹脂をエポキシ化したフェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、アルキル置換または非置換のビフェノール、スチルベン系フェノール類等をエポキシ化したビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂；フェノール類および／またはナフトール類とジメトキシパラキシレンやビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂等をエポキシ化したフェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテル型エポキシ樹脂；フタル酸、イソフタル酸、テトラヒドロフタル酸等のカルボン酸類のグリシジルエステル型エポキシ樹脂；アニリン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したグリシジル型またはメチルグリシジル型エポキシ樹脂；分子内のオレフィン結合をエポキシ化して得られるビニルシクロヘキセンジエポキシド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシ）シクロヘキシル－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン等の脂環型エポキシ樹脂；パラキシリレンおよび／またはメタキシリレン変性フェノール樹脂のグリシジルエーテル；テルペン変性フェノール樹脂のグリシジルエーテル；フェノール類および／またはナフトール類とジシクロペンタジエンから合成される、ジシクロペンタジエン変性フェノール樹脂、ジシクロペンタジエン型ナフトール樹脂のグリシジルエーテル；シクロペンタジエン変性フェノール樹脂のグリシジルエーテル；多環芳香環変性フェノール樹脂のグリシジルエーテル；ナフタレン環含有フェノール樹脂のグリシジルエーテル；ハロゲン化フェノールノボラック型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；トリメチロールプロパン型エポキシ樹脂；オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂；ジフェニルメタン型エポキシ樹脂；硫黄原子含有エポキシ樹脂等が挙げられる。
これらのエポキシ樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶剤や添加材等を添加してもよく、市販品を使用してもよい。 <Epoxy resin>
The epoxy resin is not particularly limited, and a general-purpose epoxy resin having two or more epoxy groups in one molecule can be used. For example, phenol, cresol, xylenol, catechol, resorcin, bisphenol A, Phenols such as bisphenol F and / or naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed in the presence of an acidic catalyst. Phenol novolak type epoxy resin, orthocresol novolak type epoxy resin obtained by epoxidizing the resulting novolak resin; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted Bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin obtained by epoxidizing substituted biphenols, stilbene phenols, etc .; synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin obtained by epoxidizing phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin, etc .; glycidyl ether type of alcohols such as butanediol, polyethylene glycol and polypropylene glycol Epoxy resin: glycidyl ester type epoxy resin of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid Glycidyl-type or methylglycidyl-type epoxy resin in which active hydrogen bonded to nitrogen atom such as aniline or isocyanuric acid is substituted with glycidyl group; vinylcyclohexene diepoxide obtained by epoxidizing intramolecular olefin bond, 3,4-epoxycyclohexyl Cycloaliphatic epoxy resins such as methyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene and / or Or glycidyl ether of metaxylylene-modified phenol resin; glycidyl ether of terpene-modified phenol resin; dicyclopentadiene-modified phenol resin synthesized from phenols and / or naphthols and dicyclopentadiene Glycidyl ether of dicyclopentadiene type naphthol resin; glycidyl ether of cyclopentadiene modified phenol resin; glycidyl ether of polycyclic aromatic ring modified phenol resin; glycidyl ether of phenol resin containing naphthalene ring; halogenated phenol novolac type epoxy resin; hydroquinone type Examples include epoxy resins; trimethylolpropane type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; diphenylmethane type epoxy resins; sulfur atom-containing epoxy resins.
These epoxy resins may be used alone or in combination of two or more, may be used as they are, may be appropriately added with a solvent, an additive, etc. Good.
エポキシ樹脂としては、特に限定されず、１分子中に２個以上のエポキシ基を有する汎用的なエポキシ樹脂を用いることが可能であり、例えば、フェノール、クレゾール、キシレノール、カテコール、レゾルシン、ビスフェノールＡ、ビスフェノールＦ等のフェノール類および／またはナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒の存在下で縮合または共縮合させて得られるノボラック樹脂をエポキシ化したフェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、アルキル置換または非置換のビフェノール、スチルベン系フェノール類等をエポキシ化したビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂；フェノール類および／またはナフトール類とジメトキシパラキシレンやビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂等をエポキシ化したフェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテル型エポキシ樹脂；フタル酸、イソフタル酸、テトラヒドロフタル酸等のカルボン酸類のグリシジルエステル型エポキシ樹脂；アニリン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したグリシジル型またはメチルグリシジル型エポキシ樹脂；分子内のオレフィン結合をエポキシ化して得られるビニルシクロヘキセンジエポキシド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシ）シクロヘキシル－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン等の脂環型エポキシ樹脂；パラキシリレンおよび／またはメタキシリレン変性フェノール樹脂のグリシジルエーテル；テルペン変性フェノール樹脂のグリシジルエーテル；フェノール類および／またはナフトール類とジシクロペンタジエンから合成される、ジシクロペンタジエン変性フェノール樹脂、ジシクロペンタジエン型ナフトール樹脂のグリシジルエーテル；シクロペンタジエン変性フェノール樹脂のグリシジルエーテル；多環芳香環変性フェノール樹脂のグリシジルエーテル；ナフタレン環含有フェノール樹脂のグリシジルエーテル；ハロゲン化フェノールノボラック型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；トリメチロールプロパン型エポキシ樹脂；オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂；ジフェニルメタン型エポキシ樹脂；硫黄原子含有エポキシ樹脂等が挙げられる。
これらのエポキシ樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶剤や添加材等を添加してもよく、市販品を使用してもよい。 <Epoxy resin>
The epoxy resin is not particularly limited, and a general-purpose epoxy resin having two or more epoxy groups in one molecule can be used. For example, phenol, cresol, xylenol, catechol, resorcin, bisphenol A, Phenols such as bisphenol F and / or naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed in the presence of an acidic catalyst. Phenol novolak type epoxy resin, orthocresol novolak type epoxy resin obtained by epoxidizing the resulting novolak resin; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted Bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin obtained by epoxidizing substituted biphenols, stilbene phenols, etc .; synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin obtained by epoxidizing phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin, etc .; glycidyl ether type of alcohols such as butanediol, polyethylene glycol and polypropylene glycol Epoxy resin: glycidyl ester type epoxy resin of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid Glycidyl-type or methylglycidyl-type epoxy resin in which active hydrogen bonded to nitrogen atom such as aniline or isocyanuric acid is substituted with glycidyl group; vinylcyclohexene diepoxide obtained by epoxidizing intramolecular olefin bond, 3,4-epoxycyclohexyl Cycloaliphatic epoxy resins such as methyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene and / or Or glycidyl ether of metaxylylene-modified phenol resin; glycidyl ether of terpene-modified phenol resin; dicyclopentadiene-modified phenol resin synthesized from phenols and / or naphthols and dicyclopentadiene Glycidyl ether of dicyclopentadiene type naphthol resin; glycidyl ether of cyclopentadiene modified phenol resin; glycidyl ether of polycyclic aromatic ring modified phenol resin; glycidyl ether of phenol resin containing naphthalene ring; halogenated phenol novolac type epoxy resin; hydroquinone type Examples include epoxy resins; trimethylolpropane type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; diphenylmethane type epoxy resins; sulfur atom-containing epoxy resins.
These epoxy resins may be used alone or in combination of two or more, may be used as they are, may be appropriately added with a solvent, an additive, etc. Good.
＜マレイミド樹脂＞
マレイミド樹脂としては、特に限定されず、１分子中に２個以上のマレイミド基を有する汎用的なマレイミド樹脂を用いることが可能であり、例えば、４，４’－ビスマレイミドジフェニルメタン、Ｎ，Ｎ’－１，３－フェニレンジマレイミド、２，２’－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、１，６’－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、ポリフェニルメタンマレイミド等が挙げられる。
これらのマレイミド樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 <Maleimide resin>
The maleimide resin is not particularly limited, and a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used. For example, 4,4′-bismaleimide diphenylmethane, N, N ′ -1,3-phenylene dimaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, polyphenylmethane maleimide and the like.
These maleimide resins may be used alone or in admixture of two or more, may be used as they are, may be added with a solvent or an additive as appropriate, or may be commercially available. Good.
マレイミド樹脂としては、特に限定されず、１分子中に２個以上のマレイミド基を有する汎用的なマレイミド樹脂を用いることが可能であり、例えば、４，４’－ビスマレイミドジフェニルメタン、Ｎ，Ｎ’－１，３－フェニレンジマレイミド、２，２’－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、１，６’－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、ポリフェニルメタンマレイミド等が挙げられる。
これらのマレイミド樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 <Maleimide resin>
The maleimide resin is not particularly limited, and a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used. For example, 4,4′-bismaleimide diphenylmethane, N, N ′ -1,3-phenylene dimaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, polyphenylmethane maleimide and the like.
These maleimide resins may be used alone or in admixture of two or more, may be used as they are, may be added with a solvent or an additive as appropriate, or may be commercially available. Good.
＜シアネート樹脂＞
シアネート樹脂としては、特に限定されず、１分子中に２個以上のシアネート基を有する汎用的なシアネート樹脂を用いることが可能であり、例えば、１，３－ジシアナトベンゼン、１，４－ジシアナトベンゼン、１，３，５－トリシアナトベンゼン、ビス（３，５－ジメチル－４－シアナトフェニル）メタン、１，３－ジシアナトナフタレン、１，４－ジシアナトナフタレン、１，６－ジシアナトナフタレン、１，８－ジシアナトナフタレン、２，６－ジシアナトナフタレン、２，７－ジシアナトナフタレン、１，３，６－トリシアナトナフタレン、４、４’－ジシアナトビフェニル、ビス（４－シアナトフェニル）メタン、２，２’－ビス（４－シアナトフェニル）プロパン、ビス（４－シアナトフェニル）エーテル、ビス（４－シアナトフェニル）チオエーテル、ビス（４－シアナトフェニル）スルホン、２、２’－ビス（４－シアナトフェニル）プロパン、ビス（３，５－ジメチル－４－シアナトフェニル）メタン、ノボラック樹脂をシアネート化したフェノールノボラック型シアネート樹脂等が挙げられる。
これらのシアネート樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。
＜イソシアネート樹脂＞
イソシアネート樹脂としては、特に限定されず、１分子中に２個以上のイソシアネート基を有する汎用的なイソシアネート樹脂を用いることが可能であり、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート等のポリイソシアネートと、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリオールとの反応で得られる末端イソシアネート基オリゴマーの末端イソシアネート基を、フェノール類、アルコール類等でブロックしたイソシアネート樹脂等が挙げられる。
これらのイソシアネート樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 <Cyanate resin>
The cyanate resin is not particularly limited, and a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used. For example, 1,3-dicyanatobenzene, 1,4-disiocyanate can be used. Anatobenzene, 1,3,5-tricyanatobenzene, bis (3,5-dimethyl-4-cyanatophenyl) methane, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-disi Anatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4- Cyanatophenyl) methane, 2,2′-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanato) Phenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2′-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, cyanate novolak resin Phenol novolac-type cyanate resin and the like.
These cyanate resins may be used alone or in admixture of two or more, may be used as they are, may be added with a solvent, an additive or the like as appropriate, or commercially available products may be used. Good.
<Isocyanate resin>
The isocyanate resin is not particularly limited, and a general-purpose isocyanate resin having two or more isocyanate groups in one molecule can be used. For example, polyisocyanate such as tolylene diisocyanate and diphenylmethane diisocyanate, and polypropylene Examples thereof include isocyanate resins obtained by blocking terminal isocyanate groups of terminal isocyanate group oligomers obtained by reaction with polyols such as glycol and polytetramethylene glycol with phenols and alcohols.
These isocyanate resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, etc. Good.
シアネート樹脂としては、特に限定されず、１分子中に２個以上のシアネート基を有する汎用的なシアネート樹脂を用いることが可能であり、例えば、１，３－ジシアナトベンゼン、１，４－ジシアナトベンゼン、１，３，５－トリシアナトベンゼン、ビス（３，５－ジメチル－４－シアナトフェニル）メタン、１，３－ジシアナトナフタレン、１，４－ジシアナトナフタレン、１，６－ジシアナトナフタレン、１，８－ジシアナトナフタレン、２，６－ジシアナトナフタレン、２，７－ジシアナトナフタレン、１，３，６－トリシアナトナフタレン、４、４’－ジシアナトビフェニル、ビス（４－シアナトフェニル）メタン、２，２’－ビス（４－シアナトフェニル）プロパン、ビス（４－シアナトフェニル）エーテル、ビス（４－シアナトフェニル）チオエーテル、ビス（４－シアナトフェニル）スルホン、２、２’－ビス（４－シアナトフェニル）プロパン、ビス（３，５－ジメチル－４－シアナトフェニル）メタン、ノボラック樹脂をシアネート化したフェノールノボラック型シアネート樹脂等が挙げられる。
これらのシアネート樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。
＜イソシアネート樹脂＞
イソシアネート樹脂としては、特に限定されず、１分子中に２個以上のイソシアネート基を有する汎用的なイソシアネート樹脂を用いることが可能であり、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート等のポリイソシアネートと、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリオールとの反応で得られる末端イソシアネート基オリゴマーの末端イソシアネート基を、フェノール類、アルコール類等でブロックしたイソシアネート樹脂等が挙げられる。
これらのイソシアネート樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 <Cyanate resin>
The cyanate resin is not particularly limited, and a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used. For example, 1,3-dicyanatobenzene, 1,4-disiocyanate can be used. Anatobenzene, 1,3,5-tricyanatobenzene, bis (3,5-dimethyl-4-cyanatophenyl) methane, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-disi Anatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4- Cyanatophenyl) methane, 2,2′-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanato) Phenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2′-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, cyanate novolak resin Phenol novolac-type cyanate resin and the like.
These cyanate resins may be used alone or in admixture of two or more, may be used as they are, may be added with a solvent, an additive or the like as appropriate, or commercially available products may be used. Good.
<Isocyanate resin>
The isocyanate resin is not particularly limited, and a general-purpose isocyanate resin having two or more isocyanate groups in one molecule can be used. For example, polyisocyanate such as tolylene diisocyanate and diphenylmethane diisocyanate, and polypropylene Examples thereof include isocyanate resins obtained by blocking terminal isocyanate groups of terminal isocyanate group oligomers obtained by reaction with polyols such as glycol and polytetramethylene glycol with phenols and alcohols.
These isocyanate resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, etc. Good.
＜硬化剤＞
熱硬化性樹脂用硬化剤としては、フェノール樹脂系硬化剤、アミン系硬化剤、酸無水物系硬化剤、ベンゾオキサジン系硬化剤、ジシアンジアミド等が挙げられる。また、主剤として用いる熱硬化性樹脂以外の熱硬化性樹脂を、熱硬化性樹脂用硬化剤として使用してもよい。 <Curing agent>
Examples of the curing agent for thermosetting resins include phenol resin curing agents, amine curing agents, acid anhydride curing agents, benzoxazine curing agents, dicyandiamide, and the like. Moreover, you may use thermosetting resins other than the thermosetting resin used as a main ingredient as a hardening agent for thermosetting resins.
熱硬化性樹脂用硬化剤としては、フェノール樹脂系硬化剤、アミン系硬化剤、酸無水物系硬化剤、ベンゾオキサジン系硬化剤、ジシアンジアミド等が挙げられる。また、主剤として用いる熱硬化性樹脂以外の熱硬化性樹脂を、熱硬化性樹脂用硬化剤として使用してもよい。 <Curing agent>
Examples of the curing agent for thermosetting resins include phenol resin curing agents, amine curing agents, acid anhydride curing agents, benzoxazine curing agents, dicyandiamide, and the like. Moreover, you may use thermosetting resins other than the thermosetting resin used as a main ingredient as a hardening agent for thermosetting resins.
フェノール樹脂系硬化剤としては、特に限定されず、一般に硬化剤として使用される１分子中に２個以上のフェノール性水酸基を有する汎用的なフェノール樹脂を用いることが可能であり、例えば、カテコール、レゾルシン、ヒドロキノン、ビスフェノールＡ、ビスフェノールＦ、置換または非置換のビフェノール等の１分子中に２個以上のフェノール性水酸基を有する化合物；フェノール、クレゾール、キシレノール、カテコール、レゾルシン、ヒドロキノン、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール類および／またはナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等から合成されるノボラック型フェノール樹脂；フェノール類および／またはナフトール類とジメトキシパラキシレンやビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂等のアラルキル型フェノール樹脂；パラキシリレンおよび／またはメタキシリレン変性フェノール樹脂；メラミン変性フェノール樹脂；テルペン変性フェノール樹脂；フェノール類および／またはナフトール類とジシクロペンタジエンから合成される、ジシクロペンタジエン型フェノール樹脂、ジシクロペンタジエン型ナフトール樹脂；シクロペンタジエン変性フェノール樹脂；多環芳香環変性フェノール樹脂；ビフェニル型フェノール樹脂；トリフェニルメタン型フェノール樹脂等が挙げられる。
The phenolic resin-based curing agent is not particularly limited, and a general-purpose phenolic resin having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent can be used. For example, catechol, Compounds having two or more phenolic hydroxyl groups in one molecule such as resorcin, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F , Phenols such as phenylphenol and aminophenol and / or naphthols such as naphthol and dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde Novolak type phenol resins synthesized from aralkyl type phenol resins such as phenol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; paraxylylene And / or metaxylylene-modified phenol resin; melamine-modified phenol resin; terpene-modified phenol resin; synthesized from phenols and / or naphthols and dicyclopentadiene, dicyclopentadiene-type phenol resin, dicyclopentadiene-type naphthol resin; cyclopentadiene Modified phenolic resin; Polycyclic aromatic ring modified phenolic resin; Biphenyl type phenolic resin; Triphenylmethane type phenolic resin It is below.
アミン系硬化剤としては、特に限定されず、汎用的な芳香族アミン、脂肪族アミン等を用いることが可能であり、例えば、トリエチレンテトラアミン、テトラエチレンペンタミン、ｍ－キシレンジアミン、トリメチルヘキサメチレンジアミン、２－メチルペンタメチレンジアミン等の脂肪族ポリアミン、イソフォロンジアミン、１，３－ビスアミノメチルシクロヘキサン、ビス（４－アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２－ジアミノシクロヘキサン等の脂環式ポリアミン、Ｎ－アミノエチルピペラジン、１，４－ビス（２－アミノ－２－メチルプロピル）ピペラジン等のピペラジン型のポリアミン、ジエチルトルエンジアミン、ジメチルチオトルエンジアミン、４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、ビス（メチルチオ）トルエンジアミン、ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ジアミノジフェニルスルホン、トリメチレンビス（４－アミノベンゾエート）、ポリテトラメチレンオキシド－ジ－ｐ－アミノベンゾエート、ポリオキシテトラメチレンビス（ｐ－アミノベンゾエート）等が挙げられる。
The amine curing agent is not particularly limited, and general-purpose aromatic amines, aliphatic amines and the like can be used. For example, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexa Aliphatic polyamines such as methylenediamine and 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1,2-diaminocyclohexane Piperazine-type polyamines such as formula polyamine, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3, 3'-diethyldipheny Methane, bis (methylthio) toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, polyoxytetramethylenebis (p -Aminobenzoate) and the like.
酸無水物系硬化剤としては、特に限定されず、汎用的な酸無水物を用いることが可能であり、例えば、ヘキサヒドロフタル酸無水物、３－メチルヘキサヒドロフタル酸無水物、４－メチルヘキサヒドロフタル酸無水物、１－メチルノルボルナン－２，３－ジカルボン酸無水物、５－メチルノルボルナン－２，３－ジカルボン酸無水物、ノルボルナン－２，３－ジカルボン酸無水物、１－メチルナジック酸無水物、５－メチルナジック酸無水物、ナジック酸無水物、フタル酸無水物、テトラヒドロフタル酸無水物、３－メチルテトラヒドロフタル酸無水物、４－メチルテトラヒドロフタル酸無水物、およびドデセニルコハク酸無水物等が挙げられる。
The acid anhydride curing agent is not particularly limited, and general-purpose acid anhydrides can be used. For example, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyl Hexahydrophthalic anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride, 5-methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, 1-methylnadic Acid anhydride, 5-methyl nadic anhydride, nadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and dodecenyl succinic anhydride Thing etc. are mentioned.
ベンゾオキサジン系硬化剤としては、特に限定されず、汎用的なベンゾオキサジン樹脂を用いることが可能であり、例えばビスフェノールＦとホルムアルデヒドとアニリンを反応させて得られるＦ－ａ型ベンゾオキサジン樹脂、ジアミノジフェニルメタンとホルムアルデヒドとフェノールを反応させて得られるＰ－ｄ型ベンゾオキサジン樹脂等が挙げられる。
The benzoxazine-based curing agent is not particularly limited, and a general-purpose benzoxazine resin can be used. For example, an Fa type benzoxazine resin obtained by reacting bisphenol F, formaldehyde and aniline, diaminodiphenylmethane. Pd type benzoxazine resin obtained by reacting formaldehyde with phenol.
これらの硬化剤は、単独で、または２種類以上を混合して使用することができ、有姿でそのまま使用してもよく、適宜溶剤や添加材等を添加し、硬化剤組成物として使用することもでき、市販品を使用してもよい。
These curing agents can be used alone or in admixture of two or more kinds, and can be used as they are, and can be used as a curing agent composition by appropriately adding a solvent, an additive or the like. It is also possible to use a commercially available product.
＜熱硬化性樹脂系組成物＞
本発明の熱硬化性樹脂系組成物に所望の設定温度でのみ効率良く硬化させ得る性質を求める場合、本発明の硬化促進剤とともに、熱硬化性樹脂としてエポキシ樹脂やマレイミド樹脂を用いることが好ましく、さらに熱硬化性樹脂用硬化剤を使用する場合はフェノール樹脂を用いることが好ましい。また、無色透明性を求める場合は、酸無水物系硬化剤を用いることが好ましい。
また、本発明の熱硬化性樹脂系組成物は、本発明の熱硬化性樹脂用硬化促進剤、熱硬化性樹脂、および熱硬化性樹脂用硬化剤の他に、効果に影響しない限り、熱硬化性樹脂系組成物に通常使用される溶剤、充填剤、添加剤等をさらに含んでもよい。
熱硬化性樹脂系組成物は、線膨張率を小さくするために、公知の各種無機充填剤を含有することができる。無機充填剤としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化アルミニウムなどが挙げられる。これらの無機充填剤は、シランカップリング剤等のカップリング剤で表面処理してもよい。
その他、熱硬化性樹脂系組成物に、イオントラップ剤、離型剤、カーボンブラック等の顔料等を添加してもよく、熱硬化性樹脂以外の樹脂を含むこともできる。
熱硬化性樹脂系組成物中の一般式（３）のホスホニウム塩の含有量は、０．５重量部より少ないと、組成物の硬化力を十分に発揮できない場合があり、１０重量部より多いと、組成物の貯蔵安定性が悪くなる場合があるため、熱硬化性樹脂１００重量部に対して０．５～１０重量部であることが好ましく、硬化性をより厳密に考慮すれば、かかる含有量を０．７～５重量部とすることが更に好ましい。さらに熱硬化性樹脂用硬化剤を使用する場合、硬化剤の含有量は、熱硬化性樹脂中の反応性基当量（例えばエポキシ樹脂であれば、樹脂中のエポキシ当量）と、硬化剤の当量との当量比を考慮して、一般的には、反応性基当量と硬化剤の当量との当量比が１．０：０．９～１．０：１．２となるようにする。 <Thermosetting resin composition>
When the thermosetting resin-based composition of the present invention requires properties that can be efficiently cured only at a desired set temperature, it is preferable to use an epoxy resin or a maleimide resin as the thermosetting resin together with the curing accelerator of the present invention. Furthermore, when a thermosetting resin curing agent is used, a phenol resin is preferably used. Moreover, when colorless and transparent are calculated | required, it is preferable to use an acid anhydride type hardening | curing agent.
In addition to the thermosetting resin curing accelerator, the thermosetting resin, and the thermosetting resin curing agent of the present invention, the thermosetting resin-based composition of the present invention can be used as long as the effect is not affected. You may further contain the solvent, filler, additive, etc. which are normally used for curable resin system composition.
The thermosetting resin-based composition can contain various known inorganic fillers in order to reduce the linear expansion coefficient. Examples of the inorganic filler include fused silica, crystalline silica, alumina, and aluminum nitride. These inorganic fillers may be surface-treated with a coupling agent such as a silane coupling agent.
In addition, an ion trapping agent, a release agent, a pigment such as carbon black, or the like may be added to the thermosetting resin-based composition, and a resin other than the thermosetting resin may be included.
If the content of the phosphonium salt of the general formula (3) in the thermosetting resin-based composition is less than 0.5 parts by weight, the composition may not be able to fully exert the curing power, and is more than 10 parts by weight. In this case, the storage stability of the composition may be deteriorated, so that it is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin, and this is required when the curable property is considered more strictly. The content is more preferably 0.7 to 5 parts by weight. Furthermore, when using a curing agent for thermosetting resin, the content of the curing agent is equivalent to the reactive group equivalent in the thermosetting resin (for example, epoxy equivalent in the resin if it is an epoxy resin) and the equivalent of the curing agent. In general, the equivalent ratio of the reactive group equivalent to the equivalent of the curing agent is set to 1.0: 0.9 to 1.0: 1.2.
本発明の熱硬化性樹脂系組成物に所望の設定温度でのみ効率良く硬化させ得る性質を求める場合、本発明の硬化促進剤とともに、熱硬化性樹脂としてエポキシ樹脂やマレイミド樹脂を用いることが好ましく、さらに熱硬化性樹脂用硬化剤を使用する場合はフェノール樹脂を用いることが好ましい。また、無色透明性を求める場合は、酸無水物系硬化剤を用いることが好ましい。
また、本発明の熱硬化性樹脂系組成物は、本発明の熱硬化性樹脂用硬化促進剤、熱硬化性樹脂、および熱硬化性樹脂用硬化剤の他に、効果に影響しない限り、熱硬化性樹脂系組成物に通常使用される溶剤、充填剤、添加剤等をさらに含んでもよい。
熱硬化性樹脂系組成物は、線膨張率を小さくするために、公知の各種無機充填剤を含有することができる。無機充填剤としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化アルミニウムなどが挙げられる。これらの無機充填剤は、シランカップリング剤等のカップリング剤で表面処理してもよい。
その他、熱硬化性樹脂系組成物に、イオントラップ剤、離型剤、カーボンブラック等の顔料等を添加してもよく、熱硬化性樹脂以外の樹脂を含むこともできる。
熱硬化性樹脂系組成物中の一般式（３）のホスホニウム塩の含有量は、０．５重量部より少ないと、組成物の硬化力を十分に発揮できない場合があり、１０重量部より多いと、組成物の貯蔵安定性が悪くなる場合があるため、熱硬化性樹脂１００重量部に対して０．５～１０重量部であることが好ましく、硬化性をより厳密に考慮すれば、かかる含有量を０．７～５重量部とすることが更に好ましい。さらに熱硬化性樹脂用硬化剤を使用する場合、硬化剤の含有量は、熱硬化性樹脂中の反応性基当量（例えばエポキシ樹脂であれば、樹脂中のエポキシ当量）と、硬化剤の当量との当量比を考慮して、一般的には、反応性基当量と硬化剤の当量との当量比が１．０：０．９～１．０：１．２となるようにする。 <Thermosetting resin composition>
When the thermosetting resin-based composition of the present invention requires properties that can be efficiently cured only at a desired set temperature, it is preferable to use an epoxy resin or a maleimide resin as the thermosetting resin together with the curing accelerator of the present invention. Furthermore, when a thermosetting resin curing agent is used, a phenol resin is preferably used. Moreover, when colorless and transparent are calculated | required, it is preferable to use an acid anhydride type hardening | curing agent.
In addition to the thermosetting resin curing accelerator, the thermosetting resin, and the thermosetting resin curing agent of the present invention, the thermosetting resin-based composition of the present invention can be used as long as the effect is not affected. You may further contain the solvent, filler, additive, etc. which are normally used for curable resin system composition.
The thermosetting resin-based composition can contain various known inorganic fillers in order to reduce the linear expansion coefficient. Examples of the inorganic filler include fused silica, crystalline silica, alumina, and aluminum nitride. These inorganic fillers may be surface-treated with a coupling agent such as a silane coupling agent.
In addition, an ion trapping agent, a release agent, a pigment such as carbon black, or the like may be added to the thermosetting resin-based composition, and a resin other than the thermosetting resin may be included.
If the content of the phosphonium salt of the general formula (3) in the thermosetting resin-based composition is less than 0.5 parts by weight, the composition may not be able to fully exert the curing power, and is more than 10 parts by weight. In this case, the storage stability of the composition may be deteriorated, so that it is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin, and this is required when the curable property is considered more strictly. The content is more preferably 0.7 to 5 parts by weight. Furthermore, when using a curing agent for thermosetting resin, the content of the curing agent is equivalent to the reactive group equivalent in the thermosetting resin (for example, epoxy equivalent in the resin if it is an epoxy resin) and the equivalent of the curing agent. In general, the equivalent ratio of the reactive group equivalent to the equivalent of the curing agent is set to 1.0: 0.9 to 1.0: 1.2.
本発明の熱硬化性樹脂系組成物をプリプレグに用いる場合、各成分が有機溶媒中に溶解または分散されたワニスの状態とすることが好ましい。
ワニスを製造する場合に用いる有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族炭化水素系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド等の非プロトン性極性溶媒等が挙げられる。これらの有機溶媒は、単独で、また２種類以上を混合してもよく、市販品を使用してもよい。 When the thermosetting resin-based composition of the present invention is used for a prepreg, it is preferable to have a varnish in which each component is dissolved or dispersed in an organic solvent.
Examples of the organic solvent used when producing the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide And aprotic polar solvents such as These organic solvents may be used alone or in combination of two or more, or commercially available products may be used.
ワニスを製造する場合に用いる有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族炭化水素系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド等の非プロトン性極性溶媒等が挙げられる。これらの有機溶媒は、単独で、また２種類以上を混合してもよく、市販品を使用してもよい。 When the thermosetting resin-based composition of the present invention is used for a prepreg, it is preferable to have a varnish in which each component is dissolved or dispersed in an organic solvent.
Examples of the organic solvent used when producing the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide And aprotic polar solvents such as These organic solvents may be used alone or in combination of two or more, or commercially available products may be used.
熱硬化性樹脂系組成物の調製方法は特に制限されず、前記各成分を均一に混合することにより調製できる。好ましい調製方法として、熱硬化性樹脂と本発明のホスホニウム塩とを温度２０～１５０℃程度で均一に攪拌混合する方法を挙げることができ、場合によっては上記ワニスの製造に用いられる溶媒として例示された溶媒を用いてもよい。また、熱硬化性樹脂用硬化剤を加える場合、硬化剤と硬化促進剤の混合物を加熱後、冷却し、続いて熱硬化性樹脂と混合し、加熱後、冷却することが好ましい。
硬化剤と硬化促進剤の混合物を加熱することにより、硬化剤の粘度を低下させ、撹拌・混合を容易にし、硬化剤と硬化促進剤が均一に分散される。
硬化剤と硬化促進剤の混合物は熱硬化性樹脂と混合する前に、予め冷却することにより正確に計量でき、取り扱いが容易になる。
硬化促進剤が硬化剤に均一化し難い場合は、硬化促進剤を硬化剤に高濃度で加熱溶解後、冷却して得られるマスターバッチを硬化促進剤として用いてもよい。このマスターバッチは、硬化剤への溶解性が比較的良好となる。 The method for preparing the thermosetting resin-based composition is not particularly limited, and can be prepared by mixing the above-mentioned components uniformly. As a preferable preparation method, a method in which the thermosetting resin and the phosphonium salt of the present invention are uniformly stirred and mixed at a temperature of about 20 to 150 ° C. can be exemplified. In some cases, the solvent is exemplified as a solvent used in the production of the varnish. Solvents may be used. Moreover, when adding the hardening | curing agent for thermosetting resins, it is preferable to heat and cool the mixture of a hardening | curing agent and a hardening accelerator, and to mix with a thermosetting resin, and to cool after heating.
By heating the mixture of the curing agent and the curing accelerator, the viscosity of the curing agent is reduced, stirring and mixing are facilitated, and the curing agent and the curing accelerator are uniformly dispersed.
The mixture of the curing agent and the curing accelerator can be accurately measured by pre-cooling before mixing with the thermosetting resin, and handling becomes easy.
When it is difficult to make the curing accelerator uniform in the curing agent, a master batch obtained by heating and dissolving the curing accelerator in a high concentration in the curing agent and then cooling may be used as the curing accelerator. This master batch has relatively good solubility in a curing agent.
硬化剤と硬化促進剤の混合物を加熱することにより、硬化剤の粘度を低下させ、撹拌・混合を容易にし、硬化剤と硬化促進剤が均一に分散される。
硬化剤と硬化促進剤の混合物は熱硬化性樹脂と混合する前に、予め冷却することにより正確に計量でき、取り扱いが容易になる。
硬化促進剤が硬化剤に均一化し難い場合は、硬化促進剤を硬化剤に高濃度で加熱溶解後、冷却して得られるマスターバッチを硬化促進剤として用いてもよい。このマスターバッチは、硬化剤への溶解性が比較的良好となる。 The method for preparing the thermosetting resin-based composition is not particularly limited, and can be prepared by mixing the above-mentioned components uniformly. As a preferable preparation method, a method in which the thermosetting resin and the phosphonium salt of the present invention are uniformly stirred and mixed at a temperature of about 20 to 150 ° C. can be exemplified. In some cases, the solvent is exemplified as a solvent used in the production of the varnish. Solvents may be used. Moreover, when adding the hardening | curing agent for thermosetting resins, it is preferable to heat and cool the mixture of a hardening | curing agent and a hardening accelerator, and to mix with a thermosetting resin, and to cool after heating.
By heating the mixture of the curing agent and the curing accelerator, the viscosity of the curing agent is reduced, stirring and mixing are facilitated, and the curing agent and the curing accelerator are uniformly dispersed.
The mixture of the curing agent and the curing accelerator can be accurately measured by pre-cooling before mixing with the thermosetting resin, and handling becomes easy.
When it is difficult to make the curing accelerator uniform in the curing agent, a master batch obtained by heating and dissolving the curing accelerator in a high concentration in the curing agent and then cooling may be used as the curing accelerator. This master batch has relatively good solubility in a curing agent.
本発明の硬化促進剤は潜在性に優れるため、混合中に熱硬化性樹脂系組成物の硬化が抑制され、熱硬化性樹脂系組成物の調製時のハンドリングがよくなる。
また、硬化剤、硬化促進剤、および熱硬化性樹脂の各成分は、各混合工程において一度に混合してもよく、または複数回に分けて少しずつ混合してもよい。また、上記溶剤や添加剤、無機充填剤等を混合する場合も、同様に、任意の時期に一度または複数回に分けて混合することができる。
なお、硬化剤と硬化促進剤との混合や熱硬化性樹脂との混合の際は、均一に攪拌・混合することを容易とするため、ロールやニーダー等の混練機等を用いてもよい。 Since the curing accelerator of the present invention is excellent in latency, curing of the thermosetting resin-based composition is suppressed during mixing, and handling during preparation of the thermosetting resin-based composition is improved.
Moreover, each component of a hardening | curing agent, a hardening accelerator, and a thermosetting resin may be mixed at once in each mixing process, or may be mixed little by little in several steps. Moreover, when mixing the said solvent, an additive, an inorganic filler, etc., it can be mixed in one time or divided into several times similarly at arbitrary times.
In mixing the curing agent and the curing accelerator or the thermosetting resin, a kneader such as a roll or a kneader may be used to facilitate uniform stirring and mixing.
また、硬化剤、硬化促進剤、および熱硬化性樹脂の各成分は、各混合工程において一度に混合してもよく、または複数回に分けて少しずつ混合してもよい。また、上記溶剤や添加剤、無機充填剤等を混合する場合も、同様に、任意の時期に一度または複数回に分けて混合することができる。
なお、硬化剤と硬化促進剤との混合や熱硬化性樹脂との混合の際は、均一に攪拌・混合することを容易とするため、ロールやニーダー等の混練機等を用いてもよい。 Since the curing accelerator of the present invention is excellent in latency, curing of the thermosetting resin-based composition is suppressed during mixing, and handling during preparation of the thermosetting resin-based composition is improved.
Moreover, each component of a hardening | curing agent, a hardening accelerator, and a thermosetting resin may be mixed at once in each mixing process, or may be mixed little by little in several steps. Moreover, when mixing the said solvent, an additive, an inorganic filler, etc., it can be mixed in one time or divided into several times similarly at arbitrary times.
In mixing the curing agent and the curing accelerator or the thermosetting resin, a kneader such as a roll or a kneader may be used to facilitate uniform stirring and mixing.
本発明の熱硬化性樹脂系組成物は、熱硬化性樹脂系組成物に含まれる熱硬化性樹脂用硬化促進剤が低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る潜在性を有し、また、一液性における貯蔵安定性に優れた熱硬化性樹脂系組成物である。
熱硬化性樹脂系組成物の潜在性は、常法の潜在性評価方法により測定・評価することができる。例えばＪＩＳ Ｋ ６９１０に準拠したゲル化時間測定方法によりゲルタイムを測定し、低温と高温のゲルタイムの比率等により評価することができる。また、例えば示差走査熱量測定装置を使用して、発熱ピークを測定し、発熱開始温度と発熱トップ温度との差等により評価することができる。
また、熱硬化性樹脂系組成物の安定性は、常法の安定性評価方法により測定・評価することができる。例えばＪＩＳ Ｋ ６９１０に準拠したゲル化時間測定方法により貯蔵前と貯蔵後のゲルタイムを測定し、貯蔵前と貯蔵後のゲルタイムの比率等により評価することができる。 The thermosetting resin-based composition of the present invention is desirable in that the thermosetting resin curing accelerator contained in the thermosetting resin-based composition has low catalytic activity at low temperatures and does not cure the thermosetting resin-based composition. It is a thermosetting resin-based composition that has a high catalytic activity at the curing temperature, has the potential to be cured in a short time, and is excellent in storage stability in a one-pack type.
The latency of the thermosetting resin-based composition can be measured and evaluated by a conventional latency evaluation method. For example, the gel time can be measured by a gel time measurement method based on JIS K 6910 and evaluated by the ratio of the gel time between low temperature and high temperature. Further, for example, an exothermic peak can be measured using a differential scanning calorimeter, and evaluation can be made based on a difference between an exothermic start temperature and an exothermic top temperature.
The stability of the thermosetting resin-based composition can be measured and evaluated by a conventional stability evaluation method. For example, the gel time before and after storage can be measured by a gelation time measuring method based on JIS K 6910, and evaluated by the ratio of the gel time before and after storage.
熱硬化性樹脂系組成物の潜在性は、常法の潜在性評価方法により測定・評価することができる。例えばＪＩＳ Ｋ ６９１０に準拠したゲル化時間測定方法によりゲルタイムを測定し、低温と高温のゲルタイムの比率等により評価することができる。また、例えば示差走査熱量測定装置を使用して、発熱ピークを測定し、発熱開始温度と発熱トップ温度との差等により評価することができる。
また、熱硬化性樹脂系組成物の安定性は、常法の安定性評価方法により測定・評価することができる。例えばＪＩＳ Ｋ ６９１０に準拠したゲル化時間測定方法により貯蔵前と貯蔵後のゲルタイムを測定し、貯蔵前と貯蔵後のゲルタイムの比率等により評価することができる。 The thermosetting resin-based composition of the present invention is desirable in that the thermosetting resin curing accelerator contained in the thermosetting resin-based composition has low catalytic activity at low temperatures and does not cure the thermosetting resin-based composition. It is a thermosetting resin-based composition that has a high catalytic activity at the curing temperature, has the potential to be cured in a short time, and is excellent in storage stability in a one-pack type.
The latency of the thermosetting resin-based composition can be measured and evaluated by a conventional latency evaluation method. For example, the gel time can be measured by a gel time measurement method based on JIS K 6910 and evaluated by the ratio of the gel time between low temperature and high temperature. Further, for example, an exothermic peak can be measured using a differential scanning calorimeter, and evaluation can be made based on a difference between an exothermic start temperature and an exothermic top temperature.
The stability of the thermosetting resin-based composition can be measured and evaluated by a conventional stability evaluation method. For example, the gel time before and after storage can be measured by a gelation time measuring method based on JIS K 6910, and evaluated by the ratio of the gel time before and after storage.
＜熱硬化性樹脂系硬化物＞
本発明において熱硬化性樹脂系硬化物とは、熱硬化性樹脂系組成物を、熱硬化性樹脂系組成物に応じた特定の条件下で加熱することによって熱硬化性樹脂の流動性がなくなり、硬化した固形物のことをいう。以下、本発明の熱硬化性樹脂系組成物を硬化した固形物を「本発明の熱硬化性樹脂系硬化物」ということがある。
本発明の熱硬化性樹脂系硬化物は、上記した本発明の熱硬化性樹脂系組成物を、通常の熱硬化性樹脂系組成物の硬化の条件下で加熱することで得ることができる。通常硬化温度１００～２５０℃程度で硬化時間３０秒～１５時間加熱により得ることができ、適宜条件を変更することも可能である。
本発明の熱硬化性樹脂系硬化物は、硬化剤として酸無水物を使用した場合に、その硬化物の着色が低減され、無色透明な硬化物となる。硬化物の着色の程度は、常法の色調評価方法により測定することができる。色調評価方法としては、例えばＪＩＳ－Ｋ００７１－１に準拠した方法が挙げられ、着色の程度は、ハーゼン式数で表した値（ＡＰＨＡ）として示される。無色透明性が求められる場面においては、ＡＰＨＡが小さいほど好ましく、ＡＰＨＡが５０以下であると実用的といえる。 <Heat-curing resin-based cured product>
In the present invention, the thermosetting resin-based cured product means that the fluidity of the thermosetting resin is lost by heating the thermosetting resin-based composition under specific conditions according to the thermosetting resin-based composition. , Refers to a hardened solid. Hereinafter, the solid material obtained by curing the thermosetting resin-based composition of the present invention may be referred to as “thermosetting resin-based cured product of the present invention”.
The thermosetting resin-based cured product of the present invention can be obtained by heating the above-described thermosetting resin-based composition of the present invention under the conditions for curing a normal thermosetting resin-based composition. Usually, it can be obtained by heating at a curing temperature of about 100 to 250 ° C. and a curing time of 30 seconds to 15 hours, and the conditions can be appropriately changed.
In the thermosetting resin-based cured product of the present invention, when an acid anhydride is used as a curing agent, coloring of the cured product is reduced and a colorless and transparent cured product is obtained. The degree of coloring of the cured product can be measured by a conventional color tone evaluation method. Examples of the color tone evaluation method include a method based on JIS-K0071-1, and the degree of coloring is indicated as a value (APHA) represented by a Hazen number. In a scene where colorless transparency is required, it is preferable that APHA is smaller, and it is practical that APHA is 50 or less.
本発明において熱硬化性樹脂系硬化物とは、熱硬化性樹脂系組成物を、熱硬化性樹脂系組成物に応じた特定の条件下で加熱することによって熱硬化性樹脂の流動性がなくなり、硬化した固形物のことをいう。以下、本発明の熱硬化性樹脂系組成物を硬化した固形物を「本発明の熱硬化性樹脂系硬化物」ということがある。
本発明の熱硬化性樹脂系硬化物は、上記した本発明の熱硬化性樹脂系組成物を、通常の熱硬化性樹脂系組成物の硬化の条件下で加熱することで得ることができる。通常硬化温度１００～２５０℃程度で硬化時間３０秒～１５時間加熱により得ることができ、適宜条件を変更することも可能である。
本発明の熱硬化性樹脂系硬化物は、硬化剤として酸無水物を使用した場合に、その硬化物の着色が低減され、無色透明な硬化物となる。硬化物の着色の程度は、常法の色調評価方法により測定することができる。色調評価方法としては、例えばＪＩＳ－Ｋ００７１－１に準拠した方法が挙げられ、着色の程度は、ハーゼン式数で表した値（ＡＰＨＡ）として示される。無色透明性が求められる場面においては、ＡＰＨＡが小さいほど好ましく、ＡＰＨＡが５０以下であると実用的といえる。 <Heat-curing resin-based cured product>
In the present invention, the thermosetting resin-based cured product means that the fluidity of the thermosetting resin is lost by heating the thermosetting resin-based composition under specific conditions according to the thermosetting resin-based composition. , Refers to a hardened solid. Hereinafter, the solid material obtained by curing the thermosetting resin-based composition of the present invention may be referred to as “thermosetting resin-based cured product of the present invention”.
The thermosetting resin-based cured product of the present invention can be obtained by heating the above-described thermosetting resin-based composition of the present invention under the conditions for curing a normal thermosetting resin-based composition. Usually, it can be obtained by heating at a curing temperature of about 100 to 250 ° C. and a curing time of 30 seconds to 15 hours, and the conditions can be appropriately changed.
In the thermosetting resin-based cured product of the present invention, when an acid anhydride is used as a curing agent, coloring of the cured product is reduced and a colorless and transparent cured product is obtained. The degree of coloring of the cured product can be measured by a conventional color tone evaluation method. Examples of the color tone evaluation method include a method based on JIS-K0071-1, and the degree of coloring is indicated as a value (APHA) represented by a Hazen number. In a scene where colorless transparency is required, it is preferable that APHA is smaller, and it is practical that APHA is 50 or less.
以下に本発明の熱硬化性樹脂系組成物を実施例および試験例により詳細に説明するが、本発明はこれらに限定されるものではない。
[１Ｈ－ＮＭＲ測定]
結晶１０ｍｇを約０．５ｍｌの重ＤＭＳＯに溶かし、φ５ｍｍの試料管に入れ、（株）ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製ＪＮＭ－ＥＣＳ４００で測定した。シフト値は、ＤＭＳＯ（δ＝２．４９ｐｐｍ）を基準とした。
[３１Ｐ－ＮＭＲ測定]
結晶１０ｍｇを約０．５ｍｌの重ＤＭＳＯに溶かし、φ５ｍｍの試料管に入れ、（株）ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製ＪＮＭ－ＥＣＳ４００で測定した。シフト値は、リン酸（δ＝０ｐｐｍ）を基準とした。
[ＩＲ測定]
ブルカー・オプティクス（株）社製ＡＬＰＨＡを用い、ＡＴＲ法で測定した。 The thermosetting resin-based composition of the present invention will be described in detail below with reference to examples and test examples, but the present invention is not limited to these.
[ 1 H-NMR measurement]
10 mg of crystals were dissolved in about 0.5 ml of heavy DMSO, put in a φ5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE. The shift value was based on DMSO (δ = 2.49 ppm).
[ 31 P-NMR measurement]
10 mg of crystals were dissolved in about 0.5 ml of heavy DMSO, put in a φ5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE. The shift value was based on phosphoric acid (δ = 0 ppm).
[IR measurement]
It measured by ATR method using ALPHA by Bruker Optics.
[１Ｈ－ＮＭＲ測定]
結晶１０ｍｇを約０．５ｍｌの重ＤＭＳＯに溶かし、φ５ｍｍの試料管に入れ、（株）ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製ＪＮＭ－ＥＣＳ４００で測定した。シフト値は、ＤＭＳＯ（δ＝２．４９ｐｐｍ）を基準とした。
[３１Ｐ－ＮＭＲ測定]
結晶１０ｍｇを約０．５ｍｌの重ＤＭＳＯに溶かし、φ５ｍｍの試料管に入れ、（株）ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製ＪＮＭ－ＥＣＳ４００で測定した。シフト値は、リン酸（δ＝０ｐｐｍ）を基準とした。
[ＩＲ測定]
ブルカー・オプティクス（株）社製ＡＬＰＨＡを用い、ＡＴＲ法で測定した。 The thermosetting resin-based composition of the present invention will be described in detail below with reference to examples and test examples, but the present invention is not limited to these.
[ 1 H-NMR measurement]
10 mg of crystals were dissolved in about 0.5 ml of heavy DMSO, put in a φ5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE. The shift value was based on DMSO (δ = 2.49 ppm).
[ 31 P-NMR measurement]
10 mg of crystals were dissolved in about 0.5 ml of heavy DMSO, put in a φ5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE. The shift value was based on phosphoric acid (δ = 0 ppm).
[IR measurement]
It measured by ATR method using ALPHA by Bruker Optics.
＜製造例１＞
水酸化カリウム５６重量部を水１．５Ｌに溶解させ、これに無水ピロメリット酸１０９重量部を加える事でピロメリット酸ジカリウム塩を作製し、これにテトラフェニルホスホニウムブロミド４１９重量部を加えて６０℃で反応させ、冷却した後、析出した結晶を濾取、水洗することにより、下記式（４）で示されるビス（テトラフェニルホスホニウム）ジハイドロジェンピロメリテート（以下、「ＢＴＰＰ－ピロメリット酸」という。）を４１９重量部（収率９０％）得た。
得られた結晶の融点を測定したところ、２７７～２７９℃であった。 <Production Example 1>
Pyromellitic acid dipotassium salt is prepared by dissolving 56 parts by weight of potassium hydroxide in 1.5 L of water and adding 109 parts by weight of pyromellitic anhydride to this, and then adding 419 parts by weight of tetraphenylphosphonium bromide to this. After reacting at 0 ° C. and cooling, the precipitated crystals were collected by filtration and washed with water to give bis (tetraphenylphosphonium) dihydrogen pyromellitate (hereinafter referred to as “BTPP-pyromellitic acid” represented by the following formula (4). 419 parts by weight (yield 90%).
The melting point of the obtained crystal was measured and found to be 277 to 279 ° C.
水酸化カリウム５６重量部を水１．５Ｌに溶解させ、これに無水ピロメリット酸１０９重量部を加える事でピロメリット酸ジカリウム塩を作製し、これにテトラフェニルホスホニウムブロミド４１９重量部を加えて６０℃で反応させ、冷却した後、析出した結晶を濾取、水洗することにより、下記式（４）で示されるビス（テトラフェニルホスホニウム）ジハイドロジェンピロメリテート（以下、「ＢＴＰＰ－ピロメリット酸」という。）を４１９重量部（収率９０％）得た。
得られた結晶の融点を測定したところ、２７７～２７９℃であった。 <Production Example 1>
Pyromellitic acid dipotassium salt is prepared by dissolving 56 parts by weight of potassium hydroxide in 1.5 L of water and adding 109 parts by weight of pyromellitic anhydride to this, and then adding 419 parts by weight of tetraphenylphosphonium bromide to this. After reacting at 0 ° C. and cooling, the precipitated crystals were collected by filtration and washed with water to give bis (tetraphenylphosphonium) dihydrogen pyromellitate (hereinafter referred to as “BTPP-pyromellitic acid” represented by the following formula (4). 419 parts by weight (yield 90%).
The melting point of the obtained crystal was measured and found to be 277 to 279 ° C.
＜製造例２＞
無水ピロメリット酸１０９重量部を水２００重量部に懸濁させ、これにテトラブチルホスホニウムヒドロキシドの４０重量％水溶液６９１重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いて脱水して得た残渣をメチルイソブチルケトン１Ｌに仕込み、析出した結晶を濾取することにより、下記式（５）で示されるビス（テトラブチルホスホニウム）ジハイドロジェンピロメリテート（以下、「ＢＴＢＰ－ピロメリット酸」という。）を３４０重量部（収率８８％）得た。
得られた結晶の融点を測定したところ、１３０～１３２℃であった。 <Production Example 2>
109 parts by weight of pyromellitic anhydride is suspended in 200 parts by weight of water, and 691 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide is added thereto for neutralization. From the resulting reaction mixture, a vacuum distillation method is used. The residue obtained by dehydration was charged into 1 L of methyl isobutyl ketone, and the precipitated crystals were collected by filtration to obtain bis (tetrabutylphosphonium) dihydrogen pyromellitate (hereinafter referred to as “BTBP”) represented by the following formula (5). -Pyromellitic acid ") was obtained in an amount of 340 parts by weight (yield 88%).
The melting point of the obtained crystal was measured and found to be 130 to 132 ° C.
無水ピロメリット酸１０９重量部を水２００重量部に懸濁させ、これにテトラブチルホスホニウムヒドロキシドの４０重量％水溶液６９１重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いて脱水して得た残渣をメチルイソブチルケトン１Ｌに仕込み、析出した結晶を濾取することにより、下記式（５）で示されるビス（テトラブチルホスホニウム）ジハイドロジェンピロメリテート（以下、「ＢＴＢＰ－ピロメリット酸」という。）を３４０重量部（収率８８％）得た。
得られた結晶の融点を測定したところ、１３０～１３２℃であった。 <Production Example 2>
109 parts by weight of pyromellitic anhydride is suspended in 200 parts by weight of water, and 691 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide is added thereto for neutralization. From the resulting reaction mixture, a vacuum distillation method is used. The residue obtained by dehydration was charged into 1 L of methyl isobutyl ketone, and the precipitated crystals were collected by filtration to obtain bis (tetrabutylphosphonium) dihydrogen pyromellitate (hereinafter referred to as “BTBP”) represented by the following formula (5). -Pyromellitic acid ") was obtained in an amount of 340 parts by weight (yield 88%).
The melting point of the obtained crystal was measured and found to be 130 to 132 ° C.
製造例１、２に準じて製造した本発明に係るホスホニウム塩の１Ｈ－ＮＭＲスペクトル、３１Ｐ－ＮＭＲスペクトルのσ（ｐｐｍ）値を、表１に示す。
Table 1 shows the σ (ppm) values of 1 H-NMR spectrum and 31 P-NMR spectrum of the phosphonium salt according to the present invention produced according to Production Examples 1 and 2.
また、製造例１、２で得られた生成物のＩＲスペクトルデータをそれぞれ、図１、２に示す。
これらのデータから、製造例１、２で得られた生成物はそれぞれ、式（４）、（５）で示される目的のホスホニウム塩であることを確認した。 In addition, IR spectrum data of the products obtained in Production Examples 1 and 2 are shown in FIGS.
From these data, it was confirmed that the products obtained in Production Examples 1 and 2 were the target phosphonium salts represented by the formulas (4) and (5), respectively.
これらのデータから、製造例１、２で得られた生成物はそれぞれ、式（４）、（５）で示される目的のホスホニウム塩であることを確認した。 In addition, IR spectrum data of the products obtained in Production Examples 1 and 2 are shown in FIGS.
From these data, it was confirmed that the products obtained in Production Examples 1 and 2 were the target phosphonium salts represented by the formulas (4) and (5), respectively.
＜比較製造例１＞
無水ピロメリット酸１０９重量部に代えて、無水フタル酸を７４重量部使用した以外は、製造例１と同様にしたところ、得られた結晶はビス（テトラフェニルホスホニウム）フタレートではなく、原料であるテトラフェニルホスホニウムブロミドであり、目的の反応は進行しなかった。
比較製造例１で得られた生成物のＩＲスペクトルデータを、図３に示す。比較製造例１で得られた生成物のＮＭＲスペクトルデータを、図４、５に示す。公知のデータベース収録の、テトラフェニルホスホニウムブロミドのスペクトルデータと、比較製造例１のスペクトルデータが一致することを確認した。
＜比較製造例２＞
無水ピロメリット酸１０９重量部に代えて、安息香酸を１２２重量部使用した以外は、製造例１と同様にしたところ、得られた結晶はテトラフェニルホスホニウムベンゾエートではなく、原料であるテトラフェニルホスホニウムブロミドであり、目的の反応は進行しなかった。
比較製造例２で得られた生成物について、ＩＲ、ＮＭＲ測定を行ったところ、比較製造例１と同じ結果が得られた。公知のデータベース収録の、テトラフェニルホスホニウムブロミドのスペクトルデータと、比較製造例２のスペクトルデータが一致することを確認した。 <Comparative Production Example 1>
Instead of 109 parts by weight of pyromellitic anhydride, 74 parts by weight of phthalic anhydride was used, and the same procedure as in Production Example 1 was carried out. The resulting crystals were not bis (tetraphenylphosphonium) phthalate but a raw material. Tetraphenylphosphonium bromide, and the target reaction did not proceed.
The IR spectrum data of the product obtained in Comparative Production Example 1 is shown in FIG. The NMR spectrum data of the product obtained in Comparative Production Example 1 are shown in FIGS. It was confirmed that the spectral data of tetraphenylphosphonium bromide recorded in a known database and the spectral data of Comparative Production Example 1 were in agreement.
<Comparative Production Example 2>
Instead of 109 parts by weight of pyromellitic anhydride, 122 parts by weight of benzoic acid was used, and the same procedure as in Production Example 1 was carried out. The resulting crystals were not tetraphenylphosphonium benzoate but tetraphenylphosphonium bromide as a raw material. The target reaction did not proceed.
When IR and NMR measurements were performed on the product obtained in Comparative Production Example 2, the same results as in Comparative Production Example 1 were obtained. It was confirmed that the spectrum data of tetraphenylphosphonium bromide recorded in a known database and the spectrum data of Comparative Production Example 2 were in agreement.
無水ピロメリット酸１０９重量部に代えて、無水フタル酸を７４重量部使用した以外は、製造例１と同様にしたところ、得られた結晶はビス（テトラフェニルホスホニウム）フタレートではなく、原料であるテトラフェニルホスホニウムブロミドであり、目的の反応は進行しなかった。
比較製造例１で得られた生成物のＩＲスペクトルデータを、図３に示す。比較製造例１で得られた生成物のＮＭＲスペクトルデータを、図４、５に示す。公知のデータベース収録の、テトラフェニルホスホニウムブロミドのスペクトルデータと、比較製造例１のスペクトルデータが一致することを確認した。
＜比較製造例２＞
無水ピロメリット酸１０９重量部に代えて、安息香酸を１２２重量部使用した以外は、製造例１と同様にしたところ、得られた結晶はテトラフェニルホスホニウムベンゾエートではなく、原料であるテトラフェニルホスホニウムブロミドであり、目的の反応は進行しなかった。
比較製造例２で得られた生成物について、ＩＲ、ＮＭＲ測定を行ったところ、比較製造例１と同じ結果が得られた。公知のデータベース収録の、テトラフェニルホスホニウムブロミドのスペクトルデータと、比較製造例２のスペクトルデータが一致することを確認した。 <Comparative Production Example 1>
Instead of 109 parts by weight of pyromellitic anhydride, 74 parts by weight of phthalic anhydride was used, and the same procedure as in Production Example 1 was carried out. The resulting crystals were not bis (tetraphenylphosphonium) phthalate but a raw material. Tetraphenylphosphonium bromide, and the target reaction did not proceed.
The IR spectrum data of the product obtained in Comparative Production Example 1 is shown in FIG. The NMR spectrum data of the product obtained in Comparative Production Example 1 are shown in FIGS. It was confirmed that the spectral data of tetraphenylphosphonium bromide recorded in a known database and the spectral data of Comparative Production Example 1 were in agreement.
<Comparative Production Example 2>
Instead of 109 parts by weight of pyromellitic anhydride, 122 parts by weight of benzoic acid was used, and the same procedure as in Production Example 1 was carried out. The resulting crystals were not tetraphenylphosphonium benzoate but tetraphenylphosphonium bromide as a raw material. The target reaction did not proceed.
When IR and NMR measurements were performed on the product obtained in Comparative Production Example 2, the same results as in Comparative Production Example 1 were obtained. It was confirmed that the spectrum data of tetraphenylphosphonium bromide recorded in a known database and the spectrum data of Comparative Production Example 2 were in agreement.
まず、熱硬化性樹脂系組成物の潜在性の評価試験を行った。
＜実施例１＞
フェノール樹脂系硬化剤のＭＥＨ－７８５１Ｍ（水酸基当量２１４、明和化成社製）２１４重量部に、ＢＴＰＰ－ピロメリット酸を５．０重量部加え、１５０℃加熱下で２分間攪拌・混合した後、室温まで冷却した。これにエポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）２８０重量部を加え、１２０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ当量と水酸基当量の当量比１．０：１．０）を得た。 First, a latent evaluation test of the thermosetting resin-based composition was performed.
<Example 1>
After adding 5.0 parts by weight of BTPP-pyromellitic acid to 214 parts by weight of a phenolic resin-based curing agent MEH-7785M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), stirring and mixing for 2 minutes under heating at 150 ° C. Cooled to room temperature. To this was added 280 parts by weight of an epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.), stirred and mixed for 2 minutes under heating at 120 ° C., then cooled to room temperature, and a thermosetting resin-based composition ( An equivalent ratio of epoxy equivalent to hydroxyl equivalent of 1.0: 1.0 was obtained.
＜実施例１＞
フェノール樹脂系硬化剤のＭＥＨ－７８５１Ｍ（水酸基当量２１４、明和化成社製）２１４重量部に、ＢＴＰＰ－ピロメリット酸を５．０重量部加え、１５０℃加熱下で２分間攪拌・混合した後、室温まで冷却した。これにエポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）２８０重量部を加え、１２０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ当量と水酸基当量の当量比１．０：１．０）を得た。 First, a latent evaluation test of the thermosetting resin-based composition was performed.
<Example 1>
After adding 5.0 parts by weight of BTPP-pyromellitic acid to 214 parts by weight of a phenolic resin-based curing agent MEH-7785M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), stirring and mixing for 2 minutes under heating at 150 ° C. Cooled to room temperature. To this was added 280 parts by weight of an epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.), stirred and mixed for 2 minutes under heating at 120 ° C., then cooled to room temperature, and a thermosetting resin-based composition ( An equivalent ratio of epoxy equivalent to hydroxyl equivalent of 1.0: 1.0 was obtained.
＜実施例２＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、ＢＴＢＰ－ピロメリット酸を５．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Example 2>
A thermosetting resin composition was obtained in the same manner as in Example 1 except that 5.0 parts by weight of BTBP-pyromellitic acid was used instead of 5.0 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、ＢＴＢＰ－ピロメリット酸を５．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Example 2>
A thermosetting resin composition was obtained in the same manner as in Example 1 except that 5.0 parts by weight of BTBP-pyromellitic acid was used instead of 5.0 parts by weight of BTPP-pyromellitic acid.
＜比較例１＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラフェニルホスホニウムアセテート（以下「ＴＰＰＡ」という。）を６．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 1>
The thermosetting resin-based composition was the same as in Example 1, except that 6.0 parts by weight of tetraphenylphosphonium acetate (hereinafter referred to as “TPPA”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. I got a thing.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラフェニルホスホニウムアセテート（以下「ＴＰＰＡ」という。）を６．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 1>
The thermosetting resin-based composition was the same as in Example 1, except that 6.0 parts by weight of tetraphenylphosphonium acetate (hereinafter referred to as “TPPA”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. I got a thing.
＜比較例２＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラフェニルホスホニウムハイドロジェンフタレート（以下「ＴＰＰ－フタル酸」という。）を５．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative example 2>
In the same manner as in Example 1, except that 5.0 parts by weight of tetraphenylphosphonium hydrogen phthalate (hereinafter referred to as “TPP-phthalic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A curable resin composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラフェニルホスホニウムハイドロジェンフタレート（以下「ＴＰＰ－フタル酸」という。）を５．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative example 2>
In the same manner as in Example 1, except that 5.0 parts by weight of tetraphenylphosphonium hydrogen phthalate (hereinafter referred to as “TPP-phthalic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A curable resin composition was obtained.
＜比較例３＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムベンゾエート（以下「ＴＢＰ－安息香酸」という。）を６．９重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 3>
The thermosetting property was the same as in Example 1 except that 6.9 parts by weight of tetrabutylphosphonium benzoate (hereinafter referred to as “TBP-benzoic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A resin-based composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムベンゾエート（以下「ＴＢＰ－安息香酸」という。）を６．９重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 3>
The thermosetting property was the same as in Example 1 except that 6.9 parts by weight of tetrabutylphosphonium benzoate (hereinafter referred to as “TBP-benzoic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A resin-based composition was obtained.
＜比較例４＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムサリチレート（以下「ＴＢＰ－サリチル酸」という。）を７．１重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative example 4>
Thermosetting as in Example 1 except that 7.1 parts by weight of tetrabutylphosphonium salicylate (hereinafter referred to as “TBP-salicylic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A functional resin-based composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムサリチレート（以下「ＴＢＰ－サリチル酸」という。）を７．１重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative example 4>
Thermosetting as in Example 1 except that 7.1 parts by weight of tetrabutylphosphonium salicylate (hereinafter referred to as “TBP-salicylic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A functional resin-based composition was obtained.
＜比較例５＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムハイドロジェンスクシネート（以下「ＴＢＰ－コハク酸」という。）を６．８重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 5>
Example 1 was used except that 6.8 parts by weight of tetrabutylphosphonium hydrogen succinate (hereinafter referred to as “TBP-succinic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A thermosetting resin composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムハイドロジェンスクシネート（以下「ＴＢＰ－コハク酸」という。）を６．８重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 5>
Example 1 was used except that 6.8 parts by weight of tetrabutylphosphonium hydrogen succinate (hereinafter referred to as “TBP-succinic acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A thermosetting resin composition was obtained.
＜比較例６＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムハイドロジェンシトレート（以下「ＴＢＰ－クエン酸」という。）を８．４重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 6>
Example 1 was used except that 8.4 parts by weight of tetrabutylphosphonium hydrogen citrate (hereinafter referred to as “TBP-citric acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A thermosetting resin composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、テトラブチルホスホニウムハイドロジェンシトレート（以下「ＴＢＰ－クエン酸」という。）を８．４重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 6>
Example 1 was used except that 8.4 parts by weight of tetrabutylphosphonium hydrogen citrate (hereinafter referred to as “TBP-citric acid”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A thermosetting resin composition was obtained.
＜比較例７＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、ブチルトリフェニルホスホニウムチオシアネート（以下「ＴＰＰＢ－ＳＣＮ」という。）を２．８重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 7>
Thermosetting as in Example 1 except that 2.8 parts by weight of butyltriphenylphosphonium thiocyanate (hereinafter referred to as “TPPPB-SCN”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A resin-based composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、ブチルトリフェニルホスホニウムチオシアネート（以下「ＴＰＰＢ－ＳＣＮ」という。）を２．８重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 7>
Thermosetting as in Example 1 except that 2.8 parts by weight of butyltriphenylphosphonium thiocyanate (hereinafter referred to as “TPPPB-SCN”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. A resin-based composition was obtained.
＜比較例８＞
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、１，２－ビス（ジフェニルホスフィノ）アセチレン（以下「ＤＰＰＡ」という。）を７．１重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 8>
Example 1 was repeated except that 7.1 parts by weight of 1,2-bis (diphenylphosphino) acetylene (hereinafter referred to as “DPPA”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. Thus, a thermosetting resin composition was obtained.
ＢＴＰＰ－ピロメリット酸５．０重量部に代えて、１，２－ビス（ジフェニルホスフィノ）アセチレン（以下「ＤＰＰＡ」という。）を７．１重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 8>
Example 1 was repeated except that 7.1 parts by weight of 1,2-bis (diphenylphosphino) acetylene (hereinafter referred to as “DPPA”) was used instead of 5.0 parts by weight of BTPP-pyromellitic acid. Thus, a thermosetting resin composition was obtained.
〔ゲルタイム測定〕
得られた熱硬化性樹脂系組成物のゲルタイム（ＧＴ）はＪＩＳ Ｋ ６９１０記載のゲル化時間測定方法に準じ、鋼板温度を１５０℃および１７５℃として、日新科学社製ホットプレート式ゲル化試験器ＧＴ―Ｄを使用して測定した。なお、鋼板温度１２０℃以下では、樹脂が十分に軟化しないため、ゲル化時間の判別は困難であった。
ゲルタイムの比率（１５０℃におけるゲルタイム／１７５℃におけるゲルタイム）が大きいほど、熱硬化性樹脂用硬化促進剤が低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る、つまり潜在性に優れるといえ、潜在性が求められる場面においては、ゲルタイムの比率が２．３以上であると実用的といえる。結果を表２に示した。 [Gel time measurement]
The gel time (GT) of the obtained thermosetting resin-based composition is a hot plate type gelation test manufactured by Nisshin Kagaku Co., Ltd. according to the gel time measurement method described in JIS K 6910, with the steel plate temperatures set to 150 ° C. and 175 ° C. Measurements were made using the instrument GT-D. In addition, at the steel plate temperature of 120 ° C. or lower, the resin was not sufficiently softened, so that it was difficult to determine the gelation time.
As the ratio of gel time (gel time at 150 ° C./gel time at 175 ° C.) is larger, the curing accelerator for thermosetting resin has lower catalytic activity at low temperatures and does not cure the thermosetting resin-based composition, but at the desired curing temperature. It can be said that it exhibits high catalytic activity and can be cured in a short time, that is, it has excellent potential, but in a scene where latency is required, it can be said that a gel time ratio of 2.3 or more is practical. The results are shown in Table 2.
得られた熱硬化性樹脂系組成物のゲルタイム（ＧＴ）はＪＩＳ Ｋ ６９１０記載のゲル化時間測定方法に準じ、鋼板温度を１５０℃および１７５℃として、日新科学社製ホットプレート式ゲル化試験器ＧＴ―Ｄを使用して測定した。なお、鋼板温度１２０℃以下では、樹脂が十分に軟化しないため、ゲル化時間の判別は困難であった。
ゲルタイムの比率（１５０℃におけるゲルタイム／１７５℃におけるゲルタイム）が大きいほど、熱硬化性樹脂用硬化促進剤が低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る、つまり潜在性に優れるといえ、潜在性が求められる場面においては、ゲルタイムの比率が２．３以上であると実用的といえる。結果を表２に示した。 [Gel time measurement]
The gel time (GT) of the obtained thermosetting resin-based composition is a hot plate type gelation test manufactured by Nisshin Kagaku Co., Ltd. according to the gel time measurement method described in JIS K 6910, with the steel plate temperatures set to 150 ° C. and 175 ° C. Measurements were made using the instrument GT-D. In addition, at the steel plate temperature of 120 ° C. or lower, the resin was not sufficiently softened, so that it was difficult to determine the gelation time.
As the ratio of gel time (gel time at 150 ° C./gel time at 175 ° C.) is larger, the curing accelerator for thermosetting resin has lower catalytic activity at low temperatures and does not cure the thermosetting resin-based composition, but at the desired curing temperature. It can be said that it exhibits high catalytic activity and can be cured in a short time, that is, it has excellent potential, but in a scene where latency is required, it can be said that a gel time ratio of 2.3 or more is practical. The results are shown in Table 2.
表２に示すように、実施例１、２の熱硬化性樹脂系組成物は、ゲルタイムの比率（１５０℃におけるゲルタイム／１７５℃におけるゲルタイム）が大きい。
当該ゲルタイムの比率が大きい場合、１００～１２０℃程度のより低温ではさらにゲルタイムが遅くなり硬化が抑制されることが予測される。よって、本発明の熱硬化性樹脂系組成物は、潜在性に優れることが明らかである。 As shown in Table 2, the thermosetting resin compositions of Examples 1 and 2 have a large gel time ratio (gel time at 150 ° C./gel time at 175 ° C.).
When the ratio of the gel time is large, it is predicted that the gel time is further delayed and curing is suppressed at a lower temperature of about 100 to 120 ° C. Therefore, it is clear that the thermosetting resin-based composition of the present invention is excellent in latency.
当該ゲルタイムの比率が大きい場合、１００～１２０℃程度のより低温ではさらにゲルタイムが遅くなり硬化が抑制されることが予測される。よって、本発明の熱硬化性樹脂系組成物は、潜在性に優れることが明らかである。 As shown in Table 2, the thermosetting resin compositions of Examples 1 and 2 have a large gel time ratio (gel time at 150 ° C./gel time at 175 ° C.).
When the ratio of the gel time is large, it is predicted that the gel time is further delayed and curing is suppressed at a lower temperature of about 100 to 120 ° C. Therefore, it is clear that the thermosetting resin-based composition of the present invention is excellent in latency.
＜実施例３＞
フェノール樹脂系硬化剤のＭＥＨ－７８５１Ｍ（水酸基当量２１４、明和化成社製）５４重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、１５０℃加熱下で２分間攪拌・混合した後、室温まで冷却した。これにマレイミド樹脂のＢＭＩ－２３００（マレイミド当量１７９、大和化成工業社製）１２５重量部とエポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）７１重量部を加え、１３０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ当量と水酸基当量の当量比１．０：１．０、エポキシ樹脂とフェノール樹脂を合算した重量とマレイミド樹脂の重量の重量比１．０：１．０）を得た。 <Example 3>
After adding 2.8 parts by weight of BTPP-pyromellitic acid to 54 parts by weight of phenol resin curing agent MEH-7785M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), stirring and mixing for 2 minutes under heating at 150 ° C. Cooled to room temperature. 125 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and 71 parts by weight of epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.) were added and heated at 130 ° C. The mixture was stirred and mixed for 2 minutes, cooled to room temperature, and the thermosetting resin-based composition (equivalent ratio of epoxy equivalent and hydroxyl equivalent of 1.0: 1.0, the total weight of epoxy resin and phenolic resin and maleimide resin) A weight ratio of 1.0: 1.0) was obtained.
フェノール樹脂系硬化剤のＭＥＨ－７８５１Ｍ（水酸基当量２１４、明和化成社製）５４重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、１５０℃加熱下で２分間攪拌・混合した後、室温まで冷却した。これにマレイミド樹脂のＢＭＩ－２３００（マレイミド当量１７９、大和化成工業社製）１２５重量部とエポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）７１重量部を加え、１３０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ当量と水酸基当量の当量比１．０：１．０、エポキシ樹脂とフェノール樹脂を合算した重量とマレイミド樹脂の重量の重量比１．０：１．０）を得た。 <Example 3>
After adding 2.8 parts by weight of BTPP-pyromellitic acid to 54 parts by weight of phenol resin curing agent MEH-7785M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), stirring and mixing for 2 minutes under heating at 150 ° C. Cooled to room temperature. 125 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and 71 parts by weight of epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.) were added and heated at 130 ° C. The mixture was stirred and mixed for 2 minutes, cooled to room temperature, and the thermosetting resin-based composition (equivalent ratio of epoxy equivalent and hydroxyl equivalent of 1.0: 1.0, the total weight of epoxy resin and phenolic resin and maleimide resin) A weight ratio of 1.0: 1.0) was obtained.
＜実施例４＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例７と同様にして熱硬化性樹脂系組成物を得た。 <Example 4>
A thermosetting resin composition was obtained in the same manner as in Example 7 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例７と同様にして熱硬化性樹脂系組成物を得た。 <Example 4>
A thermosetting resin composition was obtained in the same manner as in Example 7 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例９＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰを１．６重量部使用した以外は、実施例７と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 9>
A thermosetting resin-based composition was obtained in the same manner as in Example 7, except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰを１．６重量部使用した以外は、実施例７と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 9>
A thermosetting resin-based composition was obtained in the same manner as in Example 7, except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１０＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰ－ＭＫを４．３重量部使用した以外は、実施例７と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 10>
A thermosetting resin composition was obtained in the same manner as in Example 7 except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰ－ＭＫを４．３重量部使用した以外は、実施例７と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 10>
A thermosetting resin composition was obtained in the same manner as in Example 7 except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜実施例５＞
エポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）８３重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、１３０℃加熱下で４０秒間攪拌・混合した後、室温まで冷却した。これにマレイミド樹脂のＢＭＩ－２３００（マレイミド当量１７９、大和化成工業社製）１６７重量部を加え、１３０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ樹脂とマレイミド樹脂の重量比１．０：２．０）を得た。 <Example 5>
Add 2.8 parts by weight of BTPP-pyromellitic acid to 83 parts by weight of epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.), stir and mix for 40 seconds under heating at 130 ° C., and then to room temperature Cooled down. To this was added 167 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed under heating at 130 ° C. for 2 minutes, cooled to room temperature, and then a thermosetting resin composition ( The weight ratio of epoxy resin to maleimide resin was 1.0: 2.0).
エポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）８３重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、１３０℃加熱下で４０秒間攪拌・混合した後、室温まで冷却した。これにマレイミド樹脂のＢＭＩ－２３００（マレイミド当量１７９、大和化成工業社製）１６７重量部を加え、１３０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ樹脂とマレイミド樹脂の重量比１．０：２．０）を得た。 <Example 5>
Add 2.8 parts by weight of BTPP-pyromellitic acid to 83 parts by weight of epoxy resin NC-3000 (epoxy equivalent 274, manufactured by Nippon Kayaku Co., Ltd.), stir and mix for 40 seconds under heating at 130 ° C., and then to room temperature Cooled down. To this was added 167 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed under heating at 130 ° C. for 2 minutes, cooled to room temperature, and then a thermosetting resin composition ( The weight ratio of epoxy resin to maleimide resin was 1.0: 2.0).
＜実施例６＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例９と同様にして熱硬化性樹脂系組成物を得た。 <Example 6>
A thermosetting resin composition was obtained in the same manner as in Example 9 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例９と同様にして熱硬化性樹脂系組成物を得た。 <Example 6>
A thermosetting resin composition was obtained in the same manner as in Example 9 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１１＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰを１．６重量部使用した以外は、実施例９と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 11>
A thermosetting resin-based composition was obtained in the same manner as in Example 9 except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰを１．６重量部使用した以外は、実施例９と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 11>
A thermosetting resin-based composition was obtained in the same manner as in Example 9 except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１２＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰ－ＭＫを４．３重量部使用した以外は、実施例９と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 12>
A thermosetting resin-based composition was obtained in the same manner as in Example 9 except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰ－ＭＫを４．３重量部使用した以外は、実施例９と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 12>
A thermosetting resin-based composition was obtained in the same manner as in Example 9 except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
次に単独硬化型熱硬化性樹脂系組成物の潜在性の評価試験を行った。
＜実施例７＞
アセトン５００重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、４０℃加熱下で２分間攪拌・混合した。これにマレイミド樹脂のＢＭＩ－２３００（マレイミド当量１７９、大和化成工業社製）２５０重量部を加え、４０℃加熱下で２分間攪拌・混合した後、乾燥によりアセトンを留去し、熱硬化性樹脂系組成物を得た。 Next, the latent evaluation test of the single curable thermosetting resin composition was performed.
<Example 7>
2.8 parts by weight of BTPP-pyromellitic acid was added to 500 parts by weight of acetone, and the mixture was stirred and mixed for 2 minutes while heating at 40 ° C. To this was added 250 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed for 2 minutes under heating at 40 ° C., and then acetone was distilled off by drying to give a thermosetting resin. A system composition was obtained.
＜実施例７＞
アセトン５００重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、４０℃加熱下で２分間攪拌・混合した。これにマレイミド樹脂のＢＭＩ－２３００（マレイミド当量１７９、大和化成工業社製）２５０重量部を加え、４０℃加熱下で２分間攪拌・混合した後、乾燥によりアセトンを留去し、熱硬化性樹脂系組成物を得た。 Next, the latent evaluation test of the single curable thermosetting resin composition was performed.
<Example 7>
2.8 parts by weight of BTPP-pyromellitic acid was added to 500 parts by weight of acetone, and the mixture was stirred and mixed for 2 minutes while heating at 40 ° C. To this was added 250 parts by weight of maleimide resin BMI-2300 (maleimide equivalent 179, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed for 2 minutes under heating at 40 ° C., and then acetone was distilled off by drying to give a thermosetting resin. A system composition was obtained.
＜実施例８＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Example 8>
A thermosetting resin composition was obtained in the same manner as in Example 3 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Example 8>
A thermosetting resin composition was obtained in the same manner as in Example 3 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１３＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、トリフェニルホスフィン（以下「ＴＰＰ」という。）を１．６重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 13>
A thermosetting resin composition in the same manner as in Example 3 except that 1.6 parts by weight of triphenylphosphine (hereinafter referred to as “TPP”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. Got.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、トリフェニルホスフィン（以下「ＴＰＰ」という。）を１．６重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 13>
A thermosetting resin composition in the same manner as in Example 3 except that 1.6 parts by weight of triphenylphosphine (hereinafter referred to as “TPP”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. Got.
＜比較例１４＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、テトラフェニルホスホニウムテトラ（ｐ－トリル）ボレート（以下「ＴＰＰ－ＭＫ」という。）を４．３重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative example 14>
Example 3 was used except that 4.3 parts by weight of tetraphenylphosphonium tetra (p-tolyl) borate (hereinafter referred to as “TPP-MK”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. Thus, a thermosetting resin-based composition was obtained.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、テトラフェニルホスホニウムテトラ（ｐ－トリル）ボレート（以下「ＴＰＰ－ＭＫ」という。）を４．３重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative example 14>
Example 3 was used except that 4.3 parts by weight of tetraphenylphosphonium tetra (p-tolyl) borate (hereinafter referred to as “TPP-MK”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. Thus, a thermosetting resin-based composition was obtained.
＜比較例１５＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、２－フェニルイミダゾール（以下「２ＰＺ」という。）を２．６重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 15>
The thermosetting resin-based composition was the same as in Example 3 except that 2.6 parts by weight of 2-phenylimidazole (hereinafter referred to as “2PZ”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. I got a thing.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、２－フェニルイミダゾール（以下「２ＰＺ」という。）を２．６重量部使用した以外は、実施例３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 15>
The thermosetting resin-based composition was the same as in Example 3 except that 2.6 parts by weight of 2-phenylimidazole (hereinafter referred to as “2PZ”) was used instead of 2.8 parts by weight of BTPP-pyromellitic acid. I got a thing.
＜実施例９＞
ＴＨＦ５００重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、４０℃加熱下で２分間攪拌・混合した。これにマレイミド樹脂のＢＭＩ－４０００（マレイミド当量２８５、大和化成工業社製）２５０重量部を加え、４０℃加熱下で２分間攪拌・混合した後、乾燥によりＴＨＦを留去し、熱硬化性樹脂系組成物を得た。 <Example 9>
2.8 parts by weight of BTPP-pyromellitic acid was added to 500 parts by weight of THF, and the mixture was stirred and mixed for 2 minutes while heating at 40 ° C. To this was added 250 parts by weight of maleimide resin BMI-4000 (maleimide equivalent 285, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed for 2 minutes under heating at 40 ° C., and then THF was distilled off by drying to give a thermosetting resin. A system composition was obtained.
ＴＨＦ５００重量部に、ＢＴＰＰ－ピロメリット酸を２．８重量部加え、４０℃加熱下で２分間攪拌・混合した。これにマレイミド樹脂のＢＭＩ－４０００（マレイミド当量２８５、大和化成工業社製）２５０重量部を加え、４０℃加熱下で２分間攪拌・混合した後、乾燥によりＴＨＦを留去し、熱硬化性樹脂系組成物を得た。 <Example 9>
2.8 parts by weight of BTPP-pyromellitic acid was added to 500 parts by weight of THF, and the mixture was stirred and mixed for 2 minutes while heating at 40 ° C. To this was added 250 parts by weight of maleimide resin BMI-4000 (maleimide equivalent 285, manufactured by Daiwa Kasei Kogyo Co., Ltd.), stirred and mixed for 2 minutes under heating at 40 ° C., and then THF was distilled off by drying to give a thermosetting resin. A system composition was obtained.
＜実施例１０＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Example 10>
A thermosetting resin composition was obtained in the same manner as in Example 5 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＢＴＢＰ－ピロメリット酸を２．３重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Example 10>
A thermosetting resin composition was obtained in the same manner as in Example 5 except that 2.3 parts by weight of BTBP-pyromellitic acid was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１６＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰを１．６重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 16>
A thermosetting resin composition was obtained in the same manner as in Example 5 except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰを１．６重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 16>
A thermosetting resin composition was obtained in the same manner as in Example 5 except that 1.6 parts by weight of TPP was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１７＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰ－ＭＫを４．３重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 17>
A thermosetting resin-based composition was obtained in the same manner as in Example 5, except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、ＴＰＰ－ＭＫを４．３重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 17>
A thermosetting resin-based composition was obtained in the same manner as in Example 5, except that 4.3 parts by weight of TPP-MK was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
＜比較例１８＞
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、２ＰＺを２．６重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 18>
A thermosetting resin-based composition was obtained in the same manner as in Example 5 except that 2.6 parts by weight of 2PZ was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸２．８重量部に代えて、２ＰＺを２．６重量部使用した以外は、実施例５と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 18>
A thermosetting resin-based composition was obtained in the same manner as in Example 5 except that 2.6 parts by weight of 2PZ was used instead of 2.8 parts by weight of BTPP-pyromellitic acid.
〔ＤＳＣ測定〕
得られた熱硬化性樹脂系組成物を、示差走査熱量測定装置（エスアイアイ・ナノテクノロジー製ＤＳＣ７０２０）を使用して、測定温度範囲３０～３５０℃、昇温速度１０℃／分の条件で測定した。
検出される発熱ピークの発熱開始温度と発熱トップ温度との差（ΔＴ）が小さいほど、熱硬化性樹脂用硬化促進剤が低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る、つまり潜在性に優れるといえる。結果を表３、４に示した。 [DSC measurement]
The obtained thermosetting resin-based composition was measured using a differential scanning calorimeter (DSC7020 manufactured by SII NanoTechnology) at a measurement temperature range of 30 to 350 ° C. and a temperature increase rate of 10 ° C./min. did.
The smaller the difference (ΔT) between the exothermic start temperature and the exothermic top temperature of the detected exothermic peak is, the lower the catalyst activity at a low temperature is, the more thermosetting resin curing accelerator does not cure the thermosetting resin-based composition. It can be said that it exhibits high catalytic activity at a desired curing temperature and can be cured in a short time, that is, it has excellent potential. The results are shown in Tables 3 and 4.
得られた熱硬化性樹脂系組成物を、示差走査熱量測定装置（エスアイアイ・ナノテクノロジー製ＤＳＣ７０２０）を使用して、測定温度範囲３０～３５０℃、昇温速度１０℃／分の条件で測定した。
検出される発熱ピークの発熱開始温度と発熱トップ温度との差（ΔＴ）が小さいほど、熱硬化性樹脂用硬化促進剤が低温では触媒活性が低く熱硬化性樹脂系組成物を硬化させないが、所望の硬化温度では高い触媒活性を発揮し短時間で硬化させ得る、つまり潜在性に優れるといえる。結果を表３、４に示した。 [DSC measurement]
The obtained thermosetting resin-based composition was measured using a differential scanning calorimeter (DSC7020 manufactured by SII NanoTechnology) at a measurement temperature range of 30 to 350 ° C. and a temperature increase rate of 10 ° C./min. did.
The smaller the difference (ΔT) between the exothermic start temperature and the exothermic top temperature of the detected exothermic peak is, the lower the catalyst activity at a low temperature is, the more thermosetting resin curing accelerator does not cure the thermosetting resin-based composition. It can be said that it exhibits high catalytic activity at a desired curing temperature and can be cured in a short time, that is, it has excellent potential. The results are shown in Tables 3 and 4.
表３、４に示すように、実施例３～６の熱硬化性樹脂を２種類含む熱硬化性樹脂系組成物および実施例７～１０の単独硬化型の熱硬化性樹脂系組成物は、発熱開始温度が混合時の温度である１２０℃よりも高く、且つ、発熱開始温度と発熱トップ温度との差（ΔＴ）が３０以下と小さい。
よって、本発明の熱硬化性樹脂系組成物は、潜在性に優れることが明らかである。 As shown in Tables 3 and 4, the thermosetting resin-based compositions containing two types of thermosetting resins of Examples 3 to 6 and the single-curing thermosetting resin-based compositions of Examples 7 to 10 are: The heat generation start temperature is higher than 120 ° C., which is the temperature at the time of mixing, and the difference (ΔT) between the heat generation start temperature and the heat generation top temperature is as small as 30 or less.
Therefore, it is clear that the thermosetting resin-based composition of the present invention is excellent in latency.
よって、本発明の熱硬化性樹脂系組成物は、潜在性に優れることが明らかである。 As shown in Tables 3 and 4, the thermosetting resin-based compositions containing two types of thermosetting resins of Examples 3 to 6 and the single-curing thermosetting resin-based compositions of Examples 7 to 10 are: The heat generation start temperature is higher than 120 ° C., which is the temperature at the time of mixing, and the difference (ΔT) between the heat generation start temperature and the heat generation top temperature is as small as 30 or less.
Therefore, it is clear that the thermosetting resin-based composition of the present invention is excellent in latency.
次に、硬化剤に酸無水物系化合物を用いた熱硬化性樹脂系硬化物の透明性について評価試験を行った。
＜実施例１１＞
酸無水物系硬化剤のリカシッドＭＨ-Ｔ（酸無水物当量１６８、新日本理化社製；主成分は４－メチルヘキサヒドロフタル酸無水物）１００重量部に、ＢＴＰＰ－ピロメリット酸を１．０重量部加え、６０℃加熱下で５分間攪拌・混合した後、室温まで冷却した。これにエポキシ樹脂のｊＥＲ８２８ＥＬ（エポキシ当量１８５、三菱化学社製）１００重量部を加え、６０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物を得た。また、得られた熱硬化性樹脂系組成物を１２０℃で１時間加熱後、さらに１５０℃で３時間加熱して熱硬化性樹脂系硬化物（エポキシ当量と酸無水物当量の当量比１．０：１．１）を得た。 Next, an evaluation test was performed on the transparency of the thermosetting resin-based cured product using an acid anhydride compound as a curing agent.
<Example 11>
BTPP-pyromellitic acid is added to 100 parts by weight of acid anhydride-based curing agent Ricacid MH-T (acid anhydride equivalent 168, manufactured by Shin Nippon Chemical Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride). After adding 0 part by weight and stirring and mixing for 5 minutes while heating at 60 ° C., the mixture was cooled to room temperature. To this, 100 parts by weight of epoxy resin jER828EL (epoxy equivalent 185, manufactured by Mitsubishi Chemical Corporation) was added, stirred and mixed for 2 minutes under heating at 60 ° C., and then cooled to room temperature to obtain a thermosetting resin-based composition. Further, the obtained thermosetting resin composition was heated at 120 ° C. for 1 hour, and further heated at 150 ° C. for 3 hours to obtain a thermosetting resin-based cured product (equivalent ratio of epoxy equivalent to acid anhydride equivalent: 1. 0: 1.1) was obtained.
＜実施例１１＞
酸無水物系硬化剤のリカシッドＭＨ-Ｔ（酸無水物当量１６８、新日本理化社製；主成分は４－メチルヘキサヒドロフタル酸無水物）１００重量部に、ＢＴＰＰ－ピロメリット酸を１．０重量部加え、６０℃加熱下で５分間攪拌・混合した後、室温まで冷却した。これにエポキシ樹脂のｊＥＲ８２８ＥＬ（エポキシ当量１８５、三菱化学社製）１００重量部を加え、６０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物を得た。また、得られた熱硬化性樹脂系組成物を１２０℃で１時間加熱後、さらに１５０℃で３時間加熱して熱硬化性樹脂系硬化物（エポキシ当量と酸無水物当量の当量比１．０：１．１）を得た。 Next, an evaluation test was performed on the transparency of the thermosetting resin-based cured product using an acid anhydride compound as a curing agent.
<Example 11>
BTPP-pyromellitic acid is added to 100 parts by weight of acid anhydride-based curing agent Ricacid MH-T (acid anhydride equivalent 168, manufactured by Shin Nippon Chemical Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride). After adding 0 part by weight and stirring and mixing for 5 minutes while heating at 60 ° C., the mixture was cooled to room temperature. To this, 100 parts by weight of epoxy resin jER828EL (epoxy equivalent 185, manufactured by Mitsubishi Chemical Corporation) was added, stirred and mixed for 2 minutes under heating at 60 ° C., and then cooled to room temperature to obtain a thermosetting resin-based composition. Further, the obtained thermosetting resin composition was heated at 120 ° C. for 1 hour, and further heated at 150 ° C. for 3 hours to obtain a thermosetting resin-based cured product (equivalent ratio of epoxy equivalent to acid anhydride equivalent: 1. 0: 1.1) was obtained.
＜実施例１２＞
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、ＢＴＢＰ－ピロメリット酸を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Example 12>
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 11 except that 1.0 part by weight of BTBP-pyromellitic acid was used instead of 1.0 part by weight of BTPP-pyromellitic acid. .
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、ＢＴＢＰ－ピロメリット酸を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Example 12>
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 11 except that 1.0 part by weight of BTBP-pyromellitic acid was used instead of 1.0 part by weight of BTPP-pyromellitic acid. .
＜比較例１９＞
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、テトラブチルホスホニウムアセテート（以下「ＴＢＰＡ」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 19>
The thermosetting resin-based composition was the same as Example 11 except that 1.0 part by weight of tetrabutylphosphonium acetate (hereinafter referred to as “TBPA”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. Product and cured product were obtained.
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、テトラブチルホスホニウムアセテート（以下「ＴＢＰＡ」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 19>
The thermosetting resin-based composition was the same as Example 11 except that 1.0 part by weight of tetrabutylphosphonium acetate (hereinafter referred to as “TBPA”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. Product and cured product were obtained.
＜比較例２０＞
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、テトラブチルホスホニウムラウレート（以下「ＴＢＰＬＡ」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 20>
A thermosetting resin system was used in the same manner as in Example 11 except that 1.0 part by weight of tetrabutylphosphonium laurate (hereinafter referred to as “TBPLA”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. A composition and a cured product were obtained.
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、テトラブチルホスホニウムラウレート（以下「ＴＢＰＬＡ」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 20>
A thermosetting resin system was used in the same manner as in Example 11 except that 1.0 part by weight of tetrabutylphosphonium laurate (hereinafter referred to as “TBPLA”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. A composition and a cured product were obtained.
＜比較例２１＞
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、テトラブチルホスホニウムカチオンとビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸／メチルビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸（重量比１／４）混合物由来の混合アニオン残基との塩（以下「ＴＢＰ－ＨＮＡ」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 21>
Instead of 1.0 part by weight of BTPP-pyromellitic acid, a tetrabutylphosphonium cation and bicyclo [2.2.1] heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3 -Thermosetting in the same manner as in Example 11 except that 1.0 part by weight of a salt with a mixed anion residue (hereinafter referred to as "TBP-HNA") derived from a mixture of dicarboxylic acids (1/4 by weight) was used. Resin-based composition and cured product were obtained.
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、テトラブチルホスホニウムカチオンとビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸／メチルビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸（重量比１／４）混合物由来の混合アニオン残基との塩（以下「ＴＢＰ－ＨＮＡ」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 21>
Instead of 1.0 part by weight of BTPP-pyromellitic acid, a tetrabutylphosphonium cation and bicyclo [2.2.1] heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3 -Thermosetting in the same manner as in Example 11 except that 1.0 part by weight of a salt with a mixed anion residue (hereinafter referred to as "TBP-HNA") derived from a mixture of dicarboxylic acids (1/4 by weight) was used. Resin-based composition and cured product were obtained.
＜比較例２２＞
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、ベンジルトリフェニルホスホニウムハイドロジェンフタレート（以下「ＴＰＰＺ－フタル酸」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 22>
Example 11 was used except that 1.0 part by weight of benzyltriphenylphosphonium hydrogen phthalate (hereinafter referred to as “TPPZ-phthalic acid”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. A thermosetting resin-based composition and a cured product were obtained.
ＢＴＰＰ－ピロメリット酸１．０重量部に代えて、ベンジルトリフェニルホスホニウムハイドロジェンフタレート（以下「ＴＰＰＺ－フタル酸」という。）を１．０重量部使用した以外は、実施例１１と同様にして熱硬化性樹脂系組成物および硬化物を得た。 <Comparative Example 22>
Example 11 was used except that 1.0 part by weight of benzyltriphenylphosphonium hydrogen phthalate (hereinafter referred to as “TPPZ-phthalic acid”) was used instead of 1.0 part by weight of BTPP-pyromellitic acid. A thermosetting resin-based composition and a cured product were obtained.
〔ゲルタイム測定〕
得られた熱硬化性樹脂系組成物のゲルタイム（ＧＴ）はＪＩＳ Ｋ ６９１０記載のゲル化時間測定方法に準じ、鋼板温度を１７５℃として日新科学社製ホットプレート式ゲル化試験器ＧＴ―Ｄを使用して測定した。結果を表５に示した。 [Gel time measurement]
The gel time (GT) of the obtained thermosetting resin-based composition is a hot plate type gelation tester GT-D manufactured by Nisshin Kagaku Co., Ltd. with a steel plate temperature of 175 ° C. according to the gel time measurement method described in JIS K 6910. Was measured using. The results are shown in Table 5.
得られた熱硬化性樹脂系組成物のゲルタイム（ＧＴ）はＪＩＳ Ｋ ６９１０記載のゲル化時間測定方法に準じ、鋼板温度を１７５℃として日新科学社製ホットプレート式ゲル化試験器ＧＴ―Ｄを使用して測定した。結果を表５に示した。 [Gel time measurement]
The gel time (GT) of the obtained thermosetting resin-based composition is a hot plate type gelation tester GT-D manufactured by Nisshin Kagaku Co., Ltd. with a steel plate temperature of 175 ° C. according to the gel time measurement method described in JIS K 6910. Was measured using. The results are shown in Table 5.
〔色調評価〕
得られた熱硬化性樹脂系組成物の硬化物の色調は、ＪＩＳ Ｋ ００７１－１記載の色調評価方法（ハーゼン単位色数）に準じて評価し、ＡＰＨＡで示した。
ＡＰＨＡが小さいほど、熱硬化性樹脂系組成物の硬化物がより透明性に優れるといえ、無色透明性が求められる場面においては、ＡＰＨＡが５０以下であると実用的といえる。結果を表５に示した。 [Color evaluation]
The color tone of the cured product of the obtained thermosetting resin-based composition was evaluated according to the color tone evaluation method (Hazen unit color number) described in JIS K0071-1 and indicated by APHA.
It can be said that the smaller the APHA, the more excellent the transparency of the cured product of the thermosetting resin-based composition, and it can be said that APHA is 50 or less in situations where colorless transparency is required. The results are shown in Table 5.
得られた熱硬化性樹脂系組成物の硬化物の色調は、ＪＩＳ Ｋ ００７１－１記載の色調評価方法（ハーゼン単位色数）に準じて評価し、ＡＰＨＡで示した。
ＡＰＨＡが小さいほど、熱硬化性樹脂系組成物の硬化物がより透明性に優れるといえ、無色透明性が求められる場面においては、ＡＰＨＡが５０以下であると実用的といえる。結果を表５に示した。 [Color evaluation]
The color tone of the cured product of the obtained thermosetting resin-based composition was evaluated according to the color tone evaluation method (Hazen unit color number) described in JIS K0071-1 and indicated by APHA.
It can be said that the smaller the APHA, the more excellent the transparency of the cured product of the thermosetting resin-based composition, and it can be said that APHA is 50 or less in situations where colorless transparency is required. The results are shown in Table 5.
表５に示すように、実施例１１、１２の熱硬化性樹脂系組成物の硬化物は、比較例１９～２２に比べてＡＰＨＡが小さいため、無色透明に近く、透明性に優れている。
As shown in Table 5, the cured products of the thermosetting resin-based compositions of Examples 11 and 12 have a smaller APHA than that of Comparative Examples 19 to 22, and thus are nearly colorless and excellent in transparency.
一液性の単独硬化型熱硬化性樹脂系組成物の貯蔵安定性について評価試験を行った。
＜実施例１３＞
エポキシ樹脂のビスフェノールＡジグリシジルエーテル（三菱化学社製、ｊＥＲ８２８ＥＬ、エポキシ当量１８５）１００重量部に、ＢＴＰＰ－ピロメリット酸を３．０重量部加え、６０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物を得た。 An evaluation test was conducted on the storage stability of a one-component single-curing thermosetting resin composition.
<Example 13>
After adding 3.0 parts by weight of BTPP-pyromellitic acid to 100 parts by weight of epoxy resin bisphenol A diglycidyl ether (Mitsubishi Chemical Co., Ltd., jER828EL, epoxy equivalent 185), stirring and mixing for 2 minutes under heating at 60 ° C. And cooled to room temperature to obtain a thermosetting resin composition.
＜実施例１３＞
エポキシ樹脂のビスフェノールＡジグリシジルエーテル（三菱化学社製、ｊＥＲ８２８ＥＬ、エポキシ当量１８５）１００重量部に、ＢＴＰＰ－ピロメリット酸を３．０重量部加え、６０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物を得た。 An evaluation test was conducted on the storage stability of a one-component single-curing thermosetting resin composition.
<Example 13>
After adding 3.0 parts by weight of BTPP-pyromellitic acid to 100 parts by weight of epoxy resin bisphenol A diglycidyl ether (Mitsubishi Chemical Co., Ltd., jER828EL, epoxy equivalent 185), stirring and mixing for 2 minutes under heating at 60 ° C. And cooled to room temperature to obtain a thermosetting resin composition.
＜実施例１４＞
ＢＴＰＰ－ピロメリット酸３．０重量部に代えて、ＢＴＢＰ－ピロメリット酸を３．０重量部使用した以外は、実施例１３と同様にして熱硬化性樹脂系組成物を得た。 <Example 14>
A thermosetting resin composition was obtained in the same manner as in Example 13 except that 3.0 parts by weight of BTBP-pyromellitic acid was used instead of 3.0 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸３．０重量部に代えて、ＢＴＢＰ－ピロメリット酸を３．０重量部使用した以外は、実施例１３と同様にして熱硬化性樹脂系組成物を得た。 <Example 14>
A thermosetting resin composition was obtained in the same manner as in Example 13 except that 3.0 parts by weight of BTBP-pyromellitic acid was used instead of 3.0 parts by weight of BTPP-pyromellitic acid.
＜比較例２３＞
ＢＴＰＰ－ピロメリット酸３．０重量部に代えて、ＴＢＰＬＡを３．０重量部使用した以外は、実施例１３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 23>
A thermosetting resin-based composition was obtained in the same manner as in Example 13 except that 3.0 parts by weight of TBPLA was used instead of 3.0 parts by weight of BTPP-pyromellitic acid.
ＢＴＰＰ－ピロメリット酸３．０重量部に代えて、ＴＢＰＬＡを３．０重量部使用した以外は、実施例１３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 23>
A thermosetting resin-based composition was obtained in the same manner as in Example 13 except that 3.0 parts by weight of TBPLA was used instead of 3.0 parts by weight of BTPP-pyromellitic acid.
＜比較例２４＞
ＢＴＰＰ－ピロメリット酸３．０重量部に代えて、２－エチル－４－メチルイミダゾール（以下「２Ｅ４ＭＺ」という。）を３．０重量部使用した以外は、実施例１３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 24>
Thermosetting was carried out in the same manner as in Example 13 except that 3.0 parts by weight of 2-ethyl-4-methylimidazole (hereinafter referred to as “2E4MZ”) was used instead of 3.0 parts by weight of BTPP-pyromellitic acid. A functional resin-based composition was obtained.
ＢＴＰＰ－ピロメリット酸３．０重量部に代えて、２－エチル－４－メチルイミダゾール（以下「２Ｅ４ＭＺ」という。）を３．０重量部使用した以外は、実施例１３と同様にして熱硬化性樹脂系組成物を得た。 <Comparative Example 24>
Thermosetting was carried out in the same manner as in Example 13 except that 3.0 parts by weight of 2-ethyl-4-methylimidazole (hereinafter referred to as “2E4MZ”) was used instead of 3.0 parts by weight of BTPP-pyromellitic acid. A functional resin-based composition was obtained.
〔ゲルタイム測定および貯蔵安定性試験〕
得られた熱硬化性樹脂系組成物のゲルタイム（ＧＴ）はＪＩＳ Ｋ ６９１０記載のゲル化時間測定方法に準じ、鋼板温度を１４０℃として日新科学社製ホットプレート式ゲル化試験器ＧＴ―Ｄを使用して測定した。
また得られた熱硬化性樹脂系組成物を２５℃で保管し、各保管期間におけるゲルタイム保持率を求めた。
結果を表６に示した。 [Gel time measurement and storage stability test]
The gel time (GT) of the obtained thermosetting resin-based composition is in accordance with the gel time measurement method described in JIS K 6910, and the hot plate type gelation tester GT-D manufactured by Nisshin Kagaku Co., Ltd. Was measured using.
Moreover, the obtained thermosetting resin-type composition was stored at 25 degreeC, and the gel time retention rate in each storage period was calculated | required.
The results are shown in Table 6.
得られた熱硬化性樹脂系組成物のゲルタイム（ＧＴ）はＪＩＳ Ｋ ６９１０記載のゲル化時間測定方法に準じ、鋼板温度を１４０℃として日新科学社製ホットプレート式ゲル化試験器ＧＴ―Ｄを使用して測定した。
また得られた熱硬化性樹脂系組成物を２５℃で保管し、各保管期間におけるゲルタイム保持率を求めた。
結果を表６に示した。 [Gel time measurement and storage stability test]
The gel time (GT) of the obtained thermosetting resin-based composition is in accordance with the gel time measurement method described in JIS K 6910, and the hot plate type gelation tester GT-D manufactured by Nisshin Kagaku Co., Ltd. Was measured using.
Moreover, the obtained thermosetting resin-type composition was stored at 25 degreeC, and the gel time retention rate in each storage period was calculated | required.
The results are shown in Table 6.
表６に示すように、実施例１３、１４の熱硬化性樹脂系組成物は、ゲルタイムの保持率が高く、貯蔵安定性に優れており、組成物を調製後、室温での保存が可能となる。
As shown in Table 6, the thermosetting resin-based compositions of Examples 13 and 14 have a high gel time retention and excellent storage stability, and can be stored at room temperature after the composition is prepared. Become.
本発明の熱硬化性樹脂系組成物は硬化特性に優れ、硬化剤の種類によってその硬化物が透明性に優れるため、例えば、各種の小型の電気・電子部品や半導体部品の樹脂封止に有用である。
The thermosetting resin-based composition of the present invention has excellent curing characteristics, and the cured product has excellent transparency depending on the type of curing agent. For example, it is useful for resin sealing of various small electrical / electronic components and semiconductor components. It is.
Claims (11)
- 下記の一般式（１）
で表されるホスホニウムカチオン２分子と、下記の式（２）
2 molecules of phosphonium cation represented by the following formula (2)
- 前記一般式（１）において、Ｒ１～Ｒ４が同一または異なって、ブチル基、フェニル基、４－メチルフェニル基、および、４－メトキシフェニル基から選ばれる置換基である、請求項１に記載のホスホニウム塩。 2. The general formula (1), wherein R 1 to R 4 are the same or different and each is a substituent selected from a butyl group, a phenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group. The phosphonium salt described.
- 前記一般式（１）において、Ｒ１～Ｒ４がフェニル基である、請求項１に記載のホスホニウム塩。 The phosphonium salt according to claim 1, wherein, in the general formula (1), R 1 to R 4 are phenyl groups.
- 前記一般式（１）において、Ｒ１～Ｒ４がブチル基である、請求項１に記載のホスホニウム塩。 The phosphonium salt according to claim 1, wherein, in the general formula (1), R 1 to R 4 are butyl groups.
- 請求項１～４のいずれか一項に記載のホスホニウム塩を少なくとも含む、熱硬化性樹脂用硬化促進剤。 A curing accelerator for a thermosetting resin, comprising at least the phosphonium salt according to any one of claims 1 to 4.
- 請求項５に記載の熱硬化性樹脂用硬化促進剤と、熱硬化性樹脂とを少なくとも含む、熱硬化性樹脂系組成物。 A thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator according to claim 5 and a thermosetting resin.
- 前記熱硬化性樹脂が、エポキシ樹脂、マレイミド樹脂、シアネート樹脂、および、イソシアネート樹脂から選ばれる１種または２種以上の熱硬化性樹脂である、請求項６に記載の熱硬化性樹脂系組成物。 The thermosetting resin-based composition according to claim 6, wherein the thermosetting resin is one or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin. .
- さらに熱硬化性樹脂用硬化剤を含む、請求項６または７に記載の熱硬化性樹脂系組成物。 The thermosetting resin composition according to claim 6 or 7, further comprising a curing agent for a thermosetting resin.
- 前記熱硬化性樹脂用硬化剤が、フェノール樹脂、ポリアミン、酸無水物、および、ベンゾオキサジンから選ばれる１種または２種以上の熱硬化性樹脂用硬化剤である、請求項８に記載の熱硬化性樹脂系組成物。 The heat according to claim 8, wherein the curing agent for a thermosetting resin is one or more curing agents for a thermosetting resin selected from a phenol resin, a polyamine, an acid anhydride, and a benzoxazine. Curable resin composition.
- 請求項８または９に記載の熱硬化性樹脂系組成物であって、熱硬化性樹脂用硬化促進剤をあらかじめ熱硬化性樹脂用硬化剤と反応させてなるマスターバッチを含む、熱硬化性樹脂系組成物。 The thermosetting resin composition according to claim 8 or 9, comprising a masterbatch obtained by previously reacting a curing accelerator for a thermosetting resin with a curing agent for a thermosetting resin. System composition.
- 請求項６～１０のいずれか一項に記載の熱硬化性樹脂系組成物を硬化して得られる熱硬化性樹脂系硬化物。 A thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of claims 6 to 10.
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|---|---|---|---|---|
| JP2018065904A (en) * | 2016-10-18 | 2018-04-26 | 日立化成株式会社 | Thermosetting resin composition |
| JP2018065903A (en) * | 2016-10-18 | 2018-04-26 | 日立化成株式会社 | Thermosetting resin composition |
| JP7013643B2 (en) | 2016-10-18 | 2022-02-01 | 昭和電工マテリアルズ株式会社 | Thermosetting resin composition |
| JP2020015814A (en) * | 2018-07-25 | 2020-01-30 | 日立化成株式会社 | Thermosetting resin composition for printed wiring board, prepreg, laminate sheet, printed wiring board, and semiconductor package |
| JP2021046384A (en) * | 2019-09-20 | 2021-03-25 | 昭和電工マテリアルズ株式会社 | Phosphonium compound, and hardening accelerator |
| JP7336932B2 (en) | 2019-09-20 | 2023-09-01 | 株式会社レゾナック | Phosphonium compound and curing accelerator |
| KR20210042742A (en) * | 2019-10-10 | 2021-04-20 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same |
| KR102343438B1 (en) | 2019-10-10 | 2021-12-24 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102538165B1 (en) | 2023-05-31 |
| JP7012012B2 (en) | 2022-01-27 |
| KR20190038859A (en) | 2019-04-09 |
| JPWO2018021548A1 (en) | 2019-05-23 |
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