JP7035595B2 - Diamine compounds, resin compositions, resin films, prepregs, laminated boards, printed wiring boards and semiconductor packages - Google Patents
Diamine compounds, resin compositions, resin films, prepregs, laminated boards, printed wiring boards and semiconductor packages Download PDFInfo
- Publication number
- JP7035595B2 JP7035595B2 JP2018025383A JP2018025383A JP7035595B2 JP 7035595 B2 JP7035595 B2 JP 7035595B2 JP 2018025383 A JP2018025383 A JP 2018025383A JP 2018025383 A JP2018025383 A JP 2018025383A JP 7035595 B2 JP7035595 B2 JP 7035595B2
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- JP
- Japan
- Prior art keywords
- resin
- diamine compound
- general formula
- alkyl group
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 Diamine compounds Chemical class 0.000 title claims description 116
- 239000011342 resin composition Substances 0.000 title claims description 32
- 229920005989 resin Polymers 0.000 title claims description 29
- 239000011347 resin Substances 0.000 title claims description 29
- 239000004065 semiconductor Substances 0.000 title claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 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 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 6
- 150000004795 grignard reagents Chemical class 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- NVEBCYZIHQCMHT-UHFFFAOYSA-N 2,2-diethylhexanedioic acid Chemical compound CCC(CC)(C(O)=O)CCCC(O)=O NVEBCYZIHQCMHT-UHFFFAOYSA-N 0.000 description 5
- MXURWEKKJZUIKG-UHFFFAOYSA-N 4,9-dipropyldodecane-4,9-diamine Chemical compound CCCC(CCC)(CCCCC(CCC)(CCC)N)N MXURWEKKJZUIKG-UHFFFAOYSA-N 0.000 description 5
- HKEJLOFFDMBAEP-UHFFFAOYSA-N 4,9-dipropyldodecane-4,9-diol Chemical compound C(CC)C(CCC)(CCCCC(CCC)(O)CCC)O HKEJLOFFDMBAEP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001350 alkyl halides Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XSPUUXVSOKZZLR-UHFFFAOYSA-N 2-chloro-N-[9-[(2-chloroacetyl)amino]-4,9-dipropyldodecan-4-yl]acetamide Chemical compound ClCC(=O)NC(CCC)(CCCCC(CCC)(CCC)NC(CCl)=O)CCC XSPUUXVSOKZZLR-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-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
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、ジアミン化合物、樹脂組成物、樹脂フィルム、プリプレグ、積層板、プリント配線板及び半導体パッケージに関する。 The present invention relates to diamine compounds, resin compositions, resin films, prepregs, laminated boards, printed wiring boards and semiconductor packages.
スマートフォンに代表される通信端末のデータ通信量は増加の一途を辿っており、データ量の伝送を短時間で行うために、通信周波数の高周波数化が進んでいる。通信周波数を高くするためには伝送損失を抑制する必要があり、低誘電率及び低誘電正接を有する材料が必要とされている。
このような低誘電率及び低誘電正接を有する材料として、これまでに、多孔質ポリイミド膜（特許文献１参照）、シアナト基を有する樹脂（特許文献２参照）等が提案されている。
The amount of data communication of communication terminals represented by smartphones is steadily increasing, and the communication frequency is becoming higher in order to transmit the amount of data in a short time. In order to increase the communication frequency, it is necessary to suppress the transmission loss, and a material having a low dielectric constant and a low dielectric loss tangent is required.
As a material having such a low dielectric constant and a low dielectric loss tangent, a porous polyimide film (see Patent Document 1), a resin having a cyanato group (see Patent Document 2), and the like have been proposed so far.
特許文献１に記載の多孔質ポリイミド膜は、樹脂中に空隙を有するため、空隙に外部から異物が侵入することで絶縁信頼性が不足する懸念がある。また、特許文献２に記載のシアナト基を有する樹脂は、耐吸湿性が必ずしも十分とはいえず、さらなる改善の余地がある。このように、低誘電率及び低誘電正接とその他の特性とを両立させることは通常容易ではないため、まずは低誘電率及び低誘電正接を有する新たな材料を数多く開発し、その中から有望な材料を選択できるような状況にすることが重要である。 Since the porous polyimide film described in Patent Document 1 has voids in the resin, there is a concern that the insulation reliability may be insufficient due to foreign matter entering the voids from the outside. Further, the resin having a cyanato group described in Patent Document 2 does not always have sufficient hygroscopicity, and there is room for further improvement. As described above, it is usually not easy to achieve both low dielectric constant and low dielectric loss tangent and other characteristics. Therefore, first, we have developed many new materials with low dielectric constant and low dielectric loss tangent, and are promising among them. It is important to be in a situation where the material can be selected.
本発明は、こうした現状に鑑み、低誘電率化を可能とするジアミン化合物、該ジアミン化合物を含有してなる樹脂組成物、さらに、該樹脂組成物を用いて得られる、樹脂フィルム、プリプレグ、積層板、プリント配線板及び半導体パッケージを提供することを課題とする。 In view of these circumstances, the present invention relates to a diamine compound capable of lowering the dielectric constant, a resin composition containing the diamine compound, and a resin film, a prepreg, and a laminate obtained by using the resin composition. An object of the present invention is to provide a board, a printed wiring board, and a semiconductor package.
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、特定の構造を有するジアミン化合物であれば上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a diamine compound having a specific structure can solve the above-mentioned problems, and have completed the present invention.
すなわち、本発明は、下記［１］～［１２］に関する。
［１］下記一般式（１）で示されるジアミン化合物。
［２］前記一般式（１）中のｎが３以上の整数である、上記［１］に記載のジアミン化合物。
［３］前記一般式（１）中のＲ１～Ｒ４が炭素数２～１００のアルキル基である、上記［１］又は［２］に記載のジアミン化合物。
［４］前記一般式（１）中のＲ１～Ｒ４が直鎖状アルキル基である、上記［１］～［３］のいずれかに記載のジアミン化合物。
［５］前記一般式（１）中のＲ１～Ｒ４がいずれも同一のアルキル基である、上記［１］～［４］のいずれかに記載のジアミン化合物。
［６］上記［１］～［５］のいずれかに記載のジアミン化合物を含有してなる樹脂組成物。
［７］さらにエポキシ樹脂を含有してなる、上記［６］に記載の樹脂組成物。
［８］上記［６］又は［７］に記載の樹脂組成物を用いて形成される樹脂フィルム。
［９］上記［６］又は［７］に記載の樹脂組成物を含有してなるプリプレグ。
［１０］上記［９］に記載のプリプレグと金属箔とを含有してなる積層板。
［１１］上記［９］に記載のプリプレグ又は上記［１０］に記載の積層板を含有してなるプリント配線板。
［１２］上記［１１］に記載のプリント配線板に半導体素子を搭載してなる半導体パッケージ。
That is, the present invention relates to the following [1] to [12].
[1] A diamine compound represented by the following general formula (1).
[2] The diamine compound according to the above [1], wherein n in the general formula (1) is an integer of 3 or more.
[3] The diamine compound according to the above [1] or [2], wherein R 1 to R 4 in the general formula (1) are alkyl groups having 2 to 100 carbon atoms.
[4] The diamine compound according to any one of the above [1] to [3], wherein R 1 to R 4 in the general formula (1) are linear alkyl groups.
[5] The diamine compound according to any one of the above [1] to [4], wherein R 1 to R 4 in the general formula (1) are all the same alkyl group.
[6] A resin composition containing the diamine compound according to any one of the above [1] to [5].
[7] The resin composition according to the above [6], further containing an epoxy resin.
[8] A resin film formed by using the resin composition according to the above [6] or [7].
[9] A prepreg containing the resin composition according to the above [6] or [7].
[10] A laminated board containing the prepreg according to the above [9] and a metal foil.
[11] A printed wiring board containing the prepreg according to the above [9] or the laminated board according to the above [10].
[12] A semiconductor package in which a semiconductor element is mounted on the printed wiring board according to the above [11].
本発明のジアミン化合物によれば、樹脂組成物の硬化物の低誘電率化を達成できるため、積層板、プリント配線板及び半導体パッケージの低誘電率化が達成される。 According to the diamine compound of the present invention, the reduced dielectric constant of the cured product of the resin composition can be achieved, so that the low dielectric constant of the laminated board, the printed wiring board and the semiconductor package can be achieved.
本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。また、数値範囲の下限値および上限値は、それぞれ他の数値範囲の下限値および上限値と任意に組み合わせられる。
本明細書における記載事項を任意に組み合わせた態様も本発明に含まれる。
In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value and the upper limit value of the other numerical range, respectively.
The present invention also includes aspects in which the items described in the present specification are arbitrarily combined.
［ジアミン化合物］
本発明のジアミン化合物は、下記一般式（１）で示される。
（一般式（１）中、Ｒ１～Ｒ４は、それぞれ独立して、炭素数２以上のアルキル基を表す。Ｒ１～Ｒ４は、それぞれ同一のアルキル基であってもよいし、互いに異なるアルキル基であってもよい。ｎは、２以上の整数である。）
[Diamine compound]
The diamine compound of the present invention is represented by the following general formula (1).
(In the general formula (1), R 1 to R 4 each independently represent an alkyl group having 2 or more carbon atoms. R 1 to R 4 may be the same alkyl group, respectively, or each other. It may be a different alkyl group. N is an integer of 2 or more.)
当該構造を有する本発明のジアミン化合物［以下、ジアミン化合物（１）と称することがある。］であれば、樹脂組成物の硬化物の低誘電率化及び低誘電正接化が可能となる。当該効果が得られる正確な理由は必ずしも明らかではないが、従来知られていたジアミン化合物に比べ、ジアミン化合物（１）の自由体積（物質が実際に占める体積と、原子半径等から計算される空間占有体積との差）が大きいことに一因があるものと推察する。 The diamine compound of the present invention having this structure [hereinafter, may be referred to as a diamine compound (1). ], It is possible to reduce the dielectric constant and the dielectric loss tangent of the cured product of the resin composition. The exact reason why this effect is obtained is not always clear, but compared to the conventionally known diamine compound, the free volume of the diamine compound (1) (the space calculated from the volume actually occupied by the substance and the atomic radius, etc.) It is presumed that this is partly due to the large difference from the occupied volume.
前記Ｒ１～Ｒ４が表す炭素数２以上のアルキル基としては、例えば、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｎ－ヘキシル基、ｎ－オクチル基等が挙げられる。該アルキル基は、直鎖状アルキル基であってもよいし、分岐鎖状アルキル基であってもよいが、低誘電率化及び低誘電正接化の観点からは、好ましくは直鎖状アルキル基である。また、該アルキル基としては、低誘電率化及び低誘電正接化の観点から、好ましくは炭素数２～１００のアルキル基、より好ましくは炭素数２～５０のアルキル基、さらに好ましくは炭素数２～３０のアルキル基、特に好ましくは炭素数２～７のアルキル基、最も好ましくはｎ－プロピル基である。いずれも、自由体積の大きさが低誘電率化及び低誘電正接化に寄与しているものと推察する。
Ｒ１～Ｒ４は、それぞれ同一のアルキル基であってもよいし、互いに異なるアルキル基であってもよい。つまり、Ｒ１～Ｒ４は、全て同一のアルキル基であってもよいし、全てが異なるアルキル基であってもよいし、又は、任意の組み合わせにおいてのみ同一のアルキル基であって、その他は異なるアルキル基であってもよい。低誘電率化及び低誘電正接化の観点から、Ｒ１～Ｒ４としては、いずれも同一のアルキル基であることが好ましい。
また、Ｒ１～Ｒ４は、低誘電率化及び低誘電正接化の観点から、直鎖部位の炭素数の最大長さがそれぞれ同一であることが好ましい。Ｒ１～Ｒ４それぞれの直鎖部位の炭素数の最大長さが同一であることにより、自由体積が均一になる傾向があるためであると推察する。
Examples of the alkyl group having 2 or more carbon atoms represented by R 1 to R 4 include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and n. -Pentyl group, isopentyl group, n-hexyl group, n-octyl group and the like can be mentioned. The alkyl group may be a linear alkyl group or a branched chain alkyl group, but is preferably a linear alkyl group from the viewpoint of low dielectric constant and low dielectric loss tangent. Is. The alkyl group is preferably an alkyl group having 2 to 100 carbon atoms, more preferably an alkyl group having 2 to 50 carbon atoms, and even more preferably 2 carbon atoms, from the viewpoint of lowering the dielectric constant and lowering the dielectric constant tangent. It is an alkyl group of about 30 to, particularly preferably an alkyl group having 2 to 7 carbon atoms, and most preferably an n-propyl group. In each case, it is presumed that the size of the free volume contributes to the lower dielectric constant and the lower dielectric loss tangent.
R 1 to R 4 may be the same alkyl group or different alkyl groups from each other. That is, R 1 to R 4 may all be the same alkyl group, all may be different alkyl groups, or they may be the same alkyl group only in any combination, and the others are the same. It may be a different alkyl group. From the viewpoint of low dielectric constant and low dielectric loss tangent, it is preferable that R 1 to R 4 are all the same alkyl group.
Further, it is preferable that R 1 to R 4 have the same maximum length of carbon atoms in the linear moiety from the viewpoint of low dielectric constant and low dielectric loss tangent. It is presumed that this is because the free volume tends to be uniform because the maximum length of the carbon number of each of the linear parts of R 1 to R 4 is the same.
ｎは、括弧で囲まれたメチレン基の繰り返し数を表しており、２以上の整数である。ｎは、低誘電率化及び低誘電正接化の観点から、好ましくは２～１００の整数、より好ましくは３以上の整数、さらに好ましくは３～５０の整数、特に好ましくは３～３０の整数、最も好ましくは３～１０であり、３～６であってもよい。
例えばｎが４である場合、前記一般式（１）は下記一般式（１’）に相当し、当該一般式（１’）で示されるジアミン化合物が好ましい。
（一般式（１’）中、Ｒ１～Ｒ４及びｎは、前記説明の通りである。）
n represents the number of repetitions of the methylene group enclosed in parentheses, and is an integer of 2 or more. From the viewpoint of low dielectric constant and low dielectric loss tangent, n is preferably an integer of 2 to 100, more preferably an integer of 3 or more, still more preferably an integer of 3 to 50, and particularly preferably an integer of 3 to 30. Most preferably, it is 3 to 10, and it may be 3 to 6.
For example, when n is 4, the general formula (1) corresponds to the following general formula (1'), and the diamine compound represented by the general formula (1') is preferable.
(In the general formula (1'), R1 to R4 and n are as described above.)
以上より、最も好ましい本発明のジアミン化合物の一態様として、以下の４，９－ジ（ｎ－プロピル）ドデカン－４，９－ジアミンが挙げられる。
［樹脂組成物］
本発明は、前記本発明のジアミン化合物（１）［前記の好ましい態様を含む。］を含有してなる樹脂組成物も提供する。本発明の樹脂組成物は、ジアミン化合物（１）を含有してなるものであるため、その硬化物は低誘電率を有する。
本発明の樹脂組成物は、さらにエポキシ樹脂を含有してなるものであることが好ましい。この場合、本発明のジアミン化合物（１）とエポキシ樹脂との含有比（ジアミン化合物（１）／エポキシ樹脂）は、質量比で、好ましくは１０／９０～９０／１０、より好ましくは３０／７０～７０／３０である。
前記エポキシ樹脂としては、特に制限されるものではないが、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、α－ナフトール／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ノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物、これらにリン化合物を導入したリン含有エポキシ樹脂などが挙げられる。エポキシ樹脂は１種を単独で使用してもよいし、２種以上を併用してもよい。
[Resin composition]
The present invention includes the above-mentioned preferred embodiment of the diamine compound (1) of the present invention. ] Is also provided. Since the resin composition of the present invention contains the diamine compound (1), the cured product has a low dielectric constant.
The resin composition of the present invention preferably further contains an epoxy resin. In this case, the content ratio of the diamine compound (1) of the present invention to the epoxy resin (diamine compound (1) / epoxy resin) is preferably 10/90 to 90/10, more preferably 30/70 in terms of mass ratio. ~ 70/30.
The epoxy resin is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol. / Cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, stilben type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, Xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols, polycyclic aromatic diglycidyl ether compounds such as anthracene, etc. Examples thereof include a phosphorus-containing epoxy resin into which a phosphorus compound has been introduced. One type of epoxy resin may be used alone, or two or more types may be used in combination.
また、本発明の樹脂組成物は、通常の電子機器のプリント配線板用の絶縁樹脂組成物に配合し得る成分を含有してなるものとすることができる。当該成分としては、例えば、前記エポキシ樹脂以外の熱硬化性樹脂、エラストマー、硬化促進剤、無機充填材、有機充填材、難燃剤、機能性樹脂、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、密着性向上剤及び有機溶剤等が挙げられる。これらのうちの１種を含有していてもよいし、２種以上を含有していてもよい。 Further, the resin composition of the present invention may contain a component that can be blended in an insulating resin composition for a printed wiring board of an ordinary electronic device. Examples of the component include thermosetting resins other than the epoxy resin, elastomers, curing accelerators, inorganic fillers, organic fillers, flame retardants, functional resins, ultraviolet absorbers, antioxidants, and photopolymerization initiators. , Fluorescent whitening agent, adhesion improver, organic solvent and the like. One of these may be contained, or two or more of them may be contained.
前記エポキシ樹脂以外の熱硬化性樹脂としては、例えば、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられる。本発明の樹脂組成物が該熱硬化性樹脂を含有してなるものである場合、本発明のジアミン化合物（１）と、エポキシ樹脂及び熱硬化性樹脂と、の含有比（ジアミン化合物（１）／［エポキシ樹脂＋熱硬化性樹脂］）は、質量比で、好ましくは１０／９０～９０／１０、より好ましくは２０／８０～８０／２０である。 Examples of the thermosetting resin other than the epoxy resin include phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, and dicyclopentadiene resin. , Silicone resin, triazine resin, melamine resin and the like. When the resin composition of the present invention contains the thermosetting resin, the content ratio of the diamine compound (1) of the present invention to the epoxy resin and the thermosetting resin (diamine compound (1)). / [Epoxy resin + thermosetting resin]) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20 in terms of mass ratio.
前記エラストマーとしては、例えば、ポリブタジエン、アクリロニトリル、エポキシ変性ポリブタジエン、無水マレイン酸変性ポリブタジエン、フェノール変性ポリブタジエン及びカルボキシ変性アクリロニトリル等が挙げられる。 Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
前記硬化促進剤としては、特に限定されないが、例えば、ｐ－トルエンスルホン酸等の酸性触媒；トリエチルアミン、ピリジン、トリブチルアミン等のアミン化合物；メチルイミダゾール、フェニルイミダゾール、イソシアネートマスクイミダゾール（例えば、ヘキサメチレンジイソシアネート樹脂と２－エチル－４－メチルイミダゾールの付加反応物等）等のイミダゾール化合物；第３級アミン化合物；第４級アンモニウム化合物；トリフェニルホスフィン等のリン系化合物；ジクミルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキシン－３、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルパーオキシイソプロピルモノカーボネート、α，α’－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン等の有機過酸化物；マンガン、コバルト、亜鉛等の金属のカルボン酸塩などが挙げられる。これらの中でも、耐熱性、ガラス転移温度及び保存安定性の観点から、イミダゾール化合物、有機過酸化物、カルボン酸塩が好ましい。 The curing accelerator is not particularly limited, and is, for example, an acidic catalyst such as p-toluenesulfonic acid; an amine compound such as triethylamine, pyridine, and tributylamine; methylimidazole, phenylimidazole, isocyanate masked imidazole (for example, hexamethylene diisocyanate). Imidazole compounds such as resin and addition reaction product of 2-ethyl-4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5 -Dimethyl-2,5-bis (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, α, Organic peroxides such as α'-bis (t-butylperoxy) diisopropylbenzene; carboxylates of metals such as manganese, cobalt and zinc can be mentioned. Among these, imidazole compounds, organic peroxides, and carboxylates are preferable from the viewpoints of heat resistance, glass transition temperature, and storage stability.
前記無機充填材としては、特に限定されないが、例えば、シリカ、アルミナ、硫酸バリウム、タルク、マイカ、カオリン、ベーマイト、ベリリア、チタン酸バリウム、チタン酸カリウム、チタン酸ストロンチウム、チタン酸カルシウム、炭酸アルミニウム、水酸化マグネシウム、水酸化アルミニウム、ホウ酸アルミニウム、ケイ酸アルミニウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、炭化ケイ素、窒化ケイ素、窒化ホウ素、焼成クレー等のクレー、ガラス短繊維、ガラス粉及び中空ガラスビーズ等が挙げられる。これらは、１種を単独で使用してもよいし、２種以上を併用することもできる。 The inorganic filler is not particularly limited, and for example, silica, alumina, barium sulfate, talc, mica, kaolin, boehmite, verilia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, and the like. Magnesium hydroxide, aluminum hydroxide, aluminum borate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, zinc borate, zinc tintate, zinc oxide, titanium oxide, silicon carbide, silicon nitride, boron nitride, Examples thereof include clay such as calcined clay, short glass fibers, glass powder and hollow glass beads. These may be used alone or in combination of two or more.
前記有機充填材としては、例えば、シリコーンパウダー、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、並びにポリフェニレンエーテル等の有機物粉末などが挙げられる。
前記難燃剤としては、例えば、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、ホスファゼン、赤リン等のリン系難燃剤；三酸化アンチモン、モリブデン酸亜鉛等の無機難燃助剤；などが挙げられる。
その他、機能性樹脂、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、密着性向上剤及び有機溶剤等については、通常の電子機器のプリント配線板用の絶縁樹脂組成物に配合し得るものを使用できる。
Examples of the organic filler include silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and organic powders such as polyphenylene ether.
Examples of the flame retardant include phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, phosphazene, and red phosphorus; and inorganic flame retardants such as antimony trioxide and zinc molybdate. Flame retardants; etc.
In addition, functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion improvers, organic solvents, etc. are used in insulating resin compositions for printed wiring boards of ordinary electronic devices. You can use what can be mixed.
（１．ジアミン化合物（１）の製造方法）
本発明のジアミン化合物（１）の製造方法は特に制限されるものではないが、以下の製造方法を利用することが、常圧下で実施できる点で工業的に好ましい。
下記一般式（２）
（一般式（２）中、Ｒ１～Ｒ４は、それぞれ独立して、炭素数２以上のアルキル基を表す。Ｒ１～Ｒ４は、同一のアルキル基であってもよいし、互いに異なるアルキル基であってもよい。ｎは、２以上の整数である。）
で示されるジオール化合物を、酸触媒（例えば、硫酸）の存在下でクロロアセトニトリルと反応させることによって、下記一般式（３）
（一般式（３）中、Ｒ１～Ｒ４及びｎは、前記一般式（２）中のものと同じである。）
で示されるクロロアセトアミド化合物を得る工程［Ｉ］、及び
該クロロアセトアミド化合物をチオウレアと反応させることにより、本発明のジアミン化合物（１）を製造する工程［II］、
を有する製造方法。
(1. Method for producing diamine compound (1))
The method for producing the diamine compound (1) of the present invention is not particularly limited, but it is industrially preferable to use the following production method in that it can be carried out under normal pressure.
The following general formula (2)
(In the general formula (2), R 1 to R 4 independently represent an alkyl group having 2 or more carbon atoms. R 1 to R 4 may be the same alkyl group or are different from each other. It may be an alkyl group. N is an integer of 2 or more.)
By reacting the diol compound represented by (1) with chloroacetonitrile in the presence of an acid catalyst (for example, sulfuric acid), the following general formula (3)
(In the general formula (3), R1 to R4 and n are the same as those in the general formula (2).)
Step [I] for obtaining the chloroacetamide compound shown in the above, and step [II] for producing the diamine compound (1) of the present invention by reacting the chloroacetamide compound with thiourea.
Manufacturing method having.
（工程［Ｉ］）
工程［Ｉ］は、前記一般式（２）で示されるジオール化合物［以下、ジオール化合物（２）と称する。］から前記一般式（３）で示されるクロロアセトアミド化合物［以下、クロロアセトアミド化合物（３）と称する。］を得る工程である。
工程［Ｉ］で使用するジオール化合物（２）中のＲ１～Ｒ４及びｎは、前記一般式（１）中の定義と同じであり、且つ好ましい態様も同じである。
酸触媒としては、強酸が好ましく、硫酸がより好ましい。
酸触媒の使用量としては、特に制限されるものではないが、反応性の観点から、ジオール化合物（２）１モルに対して、好ましくは１～１５モル、より好ましくは２～１０モルである。
クロロアセトニトリルの使用量としては、特に制限されるものではないが、転化率の観点から、ジオール化合物（２）１モルに対して、好ましくは０．７～１０モル、より好ましくは１～７モルである。
工程［Ｉ］は、酢酸等の溶媒の存在下に実施することが好ましい。
(Step [I])
The step [I] is a diol compound represented by the general formula (2) [hereinafter referred to as a diol compound (2). ] To the chloroacetamide compound represented by the general formula (3) [hereinafter, referred to as the chloroacetamide compound (3). ] Is the process of obtaining.
R1 to R4 and n in the diol compound (2) used in the step [I] are the same as the definitions in the general formula (1), and the preferred embodiments are also the same.
As the acid catalyst, a strong acid is preferable, and sulfuric acid is more preferable.
The amount of the acid catalyst used is not particularly limited, but is preferably 1 to 15 mol, more preferably 2 to 10 mol, relative to 1 mol of the diol compound (2) from the viewpoint of reactivity. ..
The amount of chloroacetonitrile used is not particularly limited, but is preferably 0.7 to 10 mol, more preferably 1 to 7 mol, relative to 1 mol of the diol compound (2) from the viewpoint of conversion rate. Is.
Step [I] is preferably carried out in the presence of a solvent such as acetic acid.
工程［Ｉ］の実施態様としては、特に制限されるものではないが、次の実施態様が好ましい。具体的には、ジオール化合物（２）、クロロアセトニトリル及び溶媒を混合した混合液へ、好ましくは５℃以下（より好ましくは－１０～５℃、さらに好ましくは－１０～０℃）で酸触媒をゆっくり添加（好ましくは滴下）し、添加終了後、得られた反応混合液を常温付近に戻して攪拌を続ける実施態様である。工程［Ｉ］は常圧下で実施できる。
酸触媒の添加時間に特に制限は無いが、反応熱によって混合液の温度が急激に高まらないように調整しながらゆっくり滴下することが好ましい。好ましくは１５分以上かけて酸触媒を添加し、より好ましくは２０分以上かけて酸触媒を添加する。
酸触媒の添加終了後、得られた混合液を常温付近、例えば５～４０℃（好ましくは１０～３０℃）に戻してから攪拌を続けて十分に反応をさせる。
反応終了後、例えば、得られた反応溶液を氷水中へ注ぐことによって、クロロアセトアミド化合物（３）が固化する。ろ過等の通常の分離方法によってクロロアセトアミド化合物（３）を分離取得し、適宜、飽和炭酸水素ナトリウム水溶液、水等によって洗浄した後、乾燥させることによって、クロロアセトアミド化合物（３）が得られる。
こうして得られるクロロアセトアミド化合物（３）は、必要に応じて、有機化合物の公知の精製手段によって精製することで純度を高めることができる。
The embodiment of the step [I] is not particularly limited, but the following embodiment is preferable. Specifically, an acid catalyst is added to a mixed solution of the diol compound (2), chloroacetonitrile and a solvent at a temperature of preferably 5 ° C. or lower (more preferably -10 to 5 ° C., still more preferably -10 to 0 ° C.). In this embodiment, the mixture is slowly added (preferably dropped), and after the addition is completed, the obtained reaction mixture is returned to near room temperature and stirring is continued. Step [I] can be carried out under normal pressure.
The addition time of the acid catalyst is not particularly limited, but it is preferable to slowly drop the mixture while adjusting the temperature of the mixed solution so that the temperature of the mixed solution does not rise sharply due to the heat of reaction. The acid catalyst is preferably added over 15 minutes, more preferably over 20 minutes.
After the addition of the acid catalyst is completed, the obtained mixed solution is returned to around room temperature, for example, 5 to 40 ° C. (preferably 10 to 30 ° C.), and then stirring is continued to allow a sufficient reaction.
After completion of the reaction, for example, the obtained reaction solution is poured into ice water to solidify the chloroacetamide compound (3). The chloroacetamide compound (3) is obtained by separating and obtaining the chloroacetamide compound (3) by a usual separation method such as filtration, washing it with saturated aqueous sodium hydrogen carbonate solution, water or the like, and then drying it.
The purity of the chloroacetamide compound (3) thus obtained can be increased by purifying the organic compound by a known purification means for the organic compound, if necessary.
（工程［II］）
工程［II］は、クロロアセトアミド化合物（３）から本発明のジアミン化合物（１）を得る工程である。
チオウレアの使用量としては、特に制限されるものではないが、転化率の観点から、クロロアセトアミド化合物（３）１モルに対して、好ましくは０．７～１０モル、より好ましくは１～７モル、さらに好ましくは１～４モルである。
工程［II］は、溶媒の存在下に実施することが好ましい。溶媒としては、酢酸とエタノールの混合溶媒等が好ましい。
(Step [II])
Step [II] is a step of obtaining the diamine compound (1) of the present invention from the chloroacetamide compound (3).
The amount of thiourea used is not particularly limited, but is preferably 0.7 to 10 mol, more preferably 1 to 7 mol, based on 1 mol of the chloroacetamide compound (3) from the viewpoint of conversion rate. , More preferably 1 to 4 mol.
Step [II] is preferably carried out in the presence of a solvent. As the solvent, a mixed solvent of acetic acid and ethanol or the like is preferable.
工程［II］の実施態様としては、特に制限されるものではないが、次の実施態様が好ましい。具体的には、クロロアセトアミド化合物（３）、チオウレア及び溶媒を混合し、加熱還流して反応させる実施態様である。工程［II］は常圧下で実施できる。
反応終了後、必要に応じて得られた反応溶液を濃縮した後、水酸化ナトリウム水溶液等の塩基性水溶液を加えることによって、好ましくは反応溶液のｐＨを１４以上に調整する。次いで、ジエチルエーテル等の抽出溶媒を用いて有機物を抽出し、抽出液を、適宜、飽和食塩水等で洗浄することが好ましい。得られた抽出液を乾燥させることによって、本発明のジアミン化合物（１）が得られる。
こうして得られるジアミン化合物（１）は、必要に応じて、有機化合物の公知の精製手段によって精製することで純度を高めることができる。
The embodiment of the step [II] is not particularly limited, but the following embodiment is preferable. Specifically, it is an embodiment in which a chloroacetamide compound (3), thiourea and a solvent are mixed and heated to reflux for reaction. Step [II] can be carried out under normal pressure.
After completion of the reaction, if necessary, the obtained reaction solution is concentrated, and then a basic aqueous solution such as an aqueous sodium hydroxide solution is added to preferably adjust the pH of the reaction solution to 14 or more. Then, it is preferable to extract the organic substance using an extraction solvent such as diethyl ether and wash the extract with saturated brine or the like as appropriate. By drying the obtained extract, the diamine compound (1) of the present invention can be obtained.
The purity of the diamine compound (1) thus obtained can be increased by purifying the organic compound by a known purification means for the organic compound, if necessary.
（原料合成方法）
前記工程［Ｉ］で原料として使用するジオール化合物（２）は、下記一般式（Ａ）
（一般式（Ａ）中、ＲＡ１及びＲＡ２は、それぞれ独立に、炭素数１～１０のアルキル基を表す。ｎは、前記一般式（２）中のものと同じである。）
で示されるジアルキルエステル化合物［以下、ジアルキルエステル化合物（Ａ）と称する。］をグリニャール試薬と反応させることによって得ることができる。
(Raw material synthesis method)
The diol compound (2) used as a raw material in the step [I] has the following general formula (A).
(In the general formula ( A ), RA1 and RA2 each independently represent an alkyl group having 1 to 10 carbon atoms. N is the same as that in the general formula (2).)
The dialkyl ester compound represented by [hereinafter, referred to as a dialkyl ester compound (A). ] Can be obtained by reacting with a Grignard reagent.
前記一般式（Ａ）中、ＲＡ１及びＲＡ２が表す炭素数１～１０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基等が挙げられる。これらの中でも、炭素数１～５のアルキル基が好ましく、炭素数１～３のアルキル基がより好ましく、エチル基がより好ましい。 In the general formula ( A ), examples of the alkyl group having 1 to 10 carbon atoms represented by RA1 and RA2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and t-butyl. Group etc. can be mentioned. Among these, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and an ethyl group is more preferable.
前記原料合成に用いるグリニャール試薬は公知の方法、例えば、ハロゲン化アルキルとマグネシウムとの反応等を利用して調製できる。
グリニャール試薬の調製に用いることができるハロゲン化アルキルとしては、例えば、臭化アルキル、ヨウ化アルキル等が挙げられる。
ハロゲン化アルキルのアルキル基部位は、前記ジアミン化合物（１）及びジオール化合物（２）中のＲ１～Ｒ４に相当する。つまり、ジアルキルエステル化合物（Ａ）にグリニャール試薬を反応させることによって、Ｒ１～Ｒ４を導入する。この点から、ハロゲン化アルキルのアルキル部位の好ましい態様は、Ｒ１～Ｒ４に関する前記説明と同様である。
グリニャール試薬の調製方法に特に制限はなく、公知の方法で実施すればよい。例えば、乾燥したマグネシウム粉末に、ジエチルエーテル、テトラヒドロフラン等の有機溶媒を加え、ハロゲン化アルキルをゆっくりと添加（好ましくは滴下）した後、攪拌を続けることでグリニャール試薬を調製できる。
The Grignard reagent used for the synthesis of raw materials can be prepared by using a known method, for example, a reaction between an alkyl halide and magnesium.
Examples of the alkyl halide that can be used for preparing the Grignard reagent include alkyl bromide and alkyl iodide.
The alkyl group moiety of the alkyl halide corresponds to R 1 to R 4 in the diamine compound (1) and the diol compound (2). That is, R 1 to R 4 are introduced by reacting the dialkyl ester compound (A) with the Grignard reagent. From this point, the preferred embodiment of the alkyl moiety of the alkyl halide is the same as the above description for R1 to R4 .
The method for preparing the Grignard reagent is not particularly limited, and a known method may be used. For example, a Grignard reagent can be prepared by adding an organic solvent such as diethyl ether or tetrahydrofuran to the dried magnesium powder, slowly adding (preferably dropping) an alkyl halide, and then continuing stirring.
グリニャール反応の終了後、必要に応じて氷浴を用いて反応溶液を冷却した後、塩化アンモニウムを添加してから攪拌を続けると固体が生成する。この固体をろ過等の通常の分離手法によって分離除去してから、有機層へ塩酸を加えて混ぜ、水層をエーテル等の有機溶媒で抽出する。そして、有機層を全て合わせてから、適宜飽和炭酸水素ナトリウム水溶液、飽和食塩水等で洗浄し、得られた有機層を乾燥させた後、有機溶媒を留去することによって、ジオール化合物（２）を得ることができる。
こうして得られるジオール化合物（２）は、必要に応じて、有機化合物の公知の精製手段によって精製することで純度を高めることができる。
After completion of the Grignard reaction, if necessary, the reaction solution is cooled using an ice bath, ammonium chloride is added, and stirring is continued to form a solid. After separating and removing this solid by a usual separation method such as filtration, hydrochloric acid is added to the organic layer and mixed, and the aqueous layer is extracted with an organic solvent such as ether. Then, after all the organic layers are combined, the mixture is appropriately washed with saturated aqueous sodium hydrogen carbonate solution, saturated brine, etc., the obtained organic layer is dried, and then the organic solvent is distilled off to distill off the diol compound (2). Can be obtained.
The purity of the diol compound (2) thus obtained can be increased by purifying the organic compound by a known purification means for the organic compound, if necessary.
（２．ジアミン化合物（１）のその他の製造方法）
上記製造方法の他にも、前記一般式（２）で示されるジオール化合物を高圧化でアンモニアと反応させることにより、ジアミン化合物（１）を製造することもできる。当該方法を利用する場合には、耐圧設備が必要となる。
また、前記ジオール化合物（２）の代わりに、原料としてジニトロ化合物を使用し、ニトロ基をアミノ基に変換する方法により、ジアミン化合物（１）を製造することもできる。
(2. Other methods for producing the diamine compound (1))
In addition to the above production method, the diamine compound (1) can also be produced by reacting the diol compound represented by the general formula (2) with ammonia at high pressure. When using this method, pressure-resistant equipment is required.
Further, the diamine compound (1) can also be produced by using a dinitro compound as a raw material instead of the diol compound (2) and converting the nitro group into an amino group.
［プリプレグ］
本発明は、本発明の樹脂組成物を含有してなるプリプレグも提供する。
プリプレグの製造方法に特に制限はなく、公知のプリプレグの製造方法を採用することができる。例えば、樹脂組成物を繊維基材に含浸又は塗布した後、加熱等により半硬化（Ｂステージ化）させることにより製造してもよく、樹脂組成物を離型フィルムに塗布した後、加熱等により半硬化（Ｂステージ化）させて樹脂組成物をフィルム状に形成して樹脂フィルムを得、該樹脂フィルムを繊維基材にラミネートすることにより製造してもよい。このように、本発明は、本発明の樹脂組成物を用いて形成される樹脂フィルムも提供する。
半硬化（Ｂステージ化）させる際の加熱温度は、溶剤除去の工程と同時に行うため、有機溶剤の除去効率が良好である有機溶剤の沸点以上の温度が好ましく、具体的には、好ましくは８０～２００℃、より好ましくは１４０～１８０℃である。
[Prepreg]
The present invention also provides a prepreg containing the resin composition of the present invention.
The method for producing a prepreg is not particularly limited, and a known method for producing a prepreg can be adopted. For example, it may be produced by impregnating or applying the resin composition to the fiber substrate and then semi-curing (B-staged) by heating or the like, or by applying the resin composition to the release film and then heating or the like. It may be produced by semi-curing (B-stage) to form a resin composition into a film to obtain a resin film, and laminating the resin film on a fiber substrate. As described above, the present invention also provides a resin film formed by using the resin composition of the present invention.
Since the heating temperature for semi-curing (B-stage) is performed at the same time as the solvent removing step, a temperature above the boiling point of the organic solvent, which has good removal efficiency of the organic solvent, is preferable, and specifically, 80 is preferable. It is about 200 ° C., more preferably 140 to 180 ° C.
プリプレグ全体の厚さは、内層回路の厚さ等に応じて適宜調整すればよいが、成形性及び作業性の観点から、１０～７００μｍが好ましく、１０～５００μｍがより好ましく、１０～２５０μｍがさらに好ましく、１０～１５０μｍが特に好ましい。 The thickness of the entire prepreg may be appropriately adjusted according to the thickness of the inner layer circuit and the like, but from the viewpoint of moldability and workability, 10 to 700 μm is preferable, 10 to 500 μm is more preferable, and 10 to 250 μm is further preferable. It is preferable, and 10 to 150 μm is particularly preferable.
［積層板］
本発明は、本発明のプリプレグを含有してなる積層板も提供する。
具体的には、本発明のプリプレグの両面に回路形成用の金属箔を設置することによって、積層板（金属箔が設置された積層板は、特に金属張積層板と称される。）が得られる。該金属箔の金属としては、銅、金、銀、ニッケル、白金、モリブデン、ルテニウム、アルミニウム、タングステン、鉄、チタン、クロム、又はこれらの金属元素のうちの少なくとも１種を含む合金であることが好ましい。合金としては、銅系合金、アルミニウム系合金、鉄系合金が好ましい。銅系合金としては、銅－ニッケル合金等が挙げられる。鉄系合金としては、鉄－ニッケル合金（４２アロイ）等が挙げられる。これらの中でも、金属としては、銅、ニッケル、４２アロイがより好ましく、入手容易性及びコストの観点からは、銅がさらに好ましい。金属箔の厚みとしては、特に制限されないが、３～２１０μｍであってもよく、好ましくは５～１４０μｍである。
[Laminate board]
The present invention also provides a laminated board containing the prepreg of the present invention.
Specifically, by installing metal foils for circuit formation on both sides of the prepreg of the present invention, a laminated plate (a laminated plate on which the metal foil is installed is particularly referred to as a metal-clad laminated plate) can be obtained. Be done. The metal of the metal foil may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. preferable. As the alloy, copper-based alloys, aluminum-based alloys, and iron-based alloys are preferable. Examples of the copper-based alloy include copper-nickel alloys. Examples of the iron-based alloy include iron-nickel alloys (42 alloys). Among these, copper, nickel, and 42 alloy are more preferable as the metal, and copper is further preferable from the viewpoint of availability and cost. The thickness of the metal foil is not particularly limited, but may be 3 to 210 μm, preferably 5 to 140 μm.
［プリント配線板］
本発明は、本発明のプリプレグ又は本発明の積層板を含有してなるプリント配線板も提供する。
本発明のプリント配線板は、前記金属張積層板に配線パターンを形成することによって、プリント配線板を製造することができる。配線パターンの形成方法としては特に限定されるものではないが、サブトラクティブ法、フルアディティブ法、セミアディティブ法（ＳＡＰ：Semi Additive Process）又はモディファイドセミアディティブ法（ｍ－ＳＡＰ：modified Semi Additive Process）等の公知の方法が挙げられる。
[Printed wiring board]
The present invention also provides a printed wiring board containing the prepreg of the present invention or the laminated board of the present invention.
The printed wiring board of the present invention can manufacture a printed wiring board by forming a wiring pattern on the metal-clad laminated board. The method for forming the wiring pattern is not particularly limited, but is limited to a subtractive method, a full additive method, a semi-additive method (SAP: Semi Additive Process), a modified semi-additive method (m-SAP: modified Semi Additive Process), etc. A known method of the above can be mentioned.
［半導体パッケージ］
本発明は、本発明のプリント配線板に半導体素子を搭載してなる半導体パッケージも提供する。本発明の半導体パッケージは、本発明のプリント配線板の所定の位置に、半導体チップ、メモリ等を搭載して製造することができる。
[Semiconductor package]
The present invention also provides a semiconductor package in which a semiconductor element is mounted on the printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory, or the like at a predetermined position on the printed wiring board of the present invention.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明を制限するものではない。 Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
製造例１〔アジピン酸ジエチルの製造〕
冷却管を取り付けた内容積２Ｌの三口フラスコにアジピン酸２００ｇ及びエタノール１，２００ｍＬを加え、０℃で硫酸２０ｍＬをゆっくりと加えた。反応溶液を還流させながら終夜撹拌した後、溶液を１／３程度にまで濃縮し、飽和炭酸水素ナトリウム水溶液４００ｍＬに反応混合物を徐々に注いだ。ｐＨが中性であることを確認し、水層を酢酸エチル４００ｍＬで３回抽出し、全ての有機層を合わせて、飽和炭酸水素ナトリウム６００ｍＬ、飽和食塩水６００ｍＬで洗浄した。得られた有機層をＮａ２ＳＯ４で乾燥した後、溶媒を留去することで、アジピン酸ジエチル２６０ｇを得た。なお、アジピン酸ジエチルの同定は、ＮＭＲ分析によって行なった。
Production Example 1 [Production of diethyl adipic acid]
200 g of adipic acid and 1,200 mL of ethanol were added to a three-necked flask having an internal volume of 2 L equipped with a cooling tube, and 20 mL of sulfuric acid was slowly added at 0 ° C. After stirring overnight while refluxing the reaction solution, the solution was concentrated to about 1/3, and the reaction mixture was gradually poured into 400 mL of a saturated aqueous sodium hydrogen carbonate solution. After confirming that the pH was neutral, the aqueous layer was extracted 3 times with 400 mL of ethyl acetate, and all the organic layers were combined and washed with 600 mL of saturated sodium hydrogen carbonate and 600 mL of saturated brine. The obtained organic layer was dried over Na 2 SO 4 , and then the solvent was distilled off to obtain 260 g of diethyl adipic acid. The identification of diethyl adipic acid was performed by NMR analysis.
（アジピン酸ジエチルの同定）
１Ｈ－ＮＭＲ（５００ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：４．１３（ｑ、４Ｈ、Ｊ＝７．３Ｈｚ）、２．３４－２．３１（ｍ、４Ｈ）、１．６８－１．６５（ｍ、４Ｈ）、１．２６（ｔ、６Ｈ、Ｊ＝７．３Ｈｚ）
１３Ｃ－ＮＭＲ（１２５ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：１７７．３、６０．２、 ３３．９、 ２４．４、 １４．２
(Identification of diethyl adipic acid)
1 1 H-NMR (500 MHz, CDCl 3 , TMS, ppm) δ: 4.13 (q, 4H, J = 7.3 Hz), 2.34-2.31 (m, 4H), 1.68-1. 65 (m, 4H), 1.26 (t, 6H, J = 7.3Hz)
13 C-NMR (125 MHz, CDCl 3 , TMS, ppm) δ: 177.3, 60.2, 33.9, 24.4, 14.2
製造例２〔４，９－ジプロピルドデカン－４，９－ジオールの製造〕
玉栓、冷却管、滴下ロート及び三方コックを取り付けた内容積５Ｌの三口フラスコに、マグネシウム１０７ｇを加えてよく乾燥させた。窒素置換をしたのち、乾燥したテトラヒドロフラン（ＴＨＦ）３００ｍＬをマグネシウムの表面が隠れるぐらいまで加えた後、臭化プロピル２０ｍＬを加え、グリニャール反応の開始を確認した。
ＴＨＦ１，７００ｍＬを加えた後、臭化プロピル３６４ｍＬを穏やかに還流する程度の速度で滴下した。滴下終了後、反応溶液を還流しながら終夜撹拌した。
水浴を用いて反応溶液を室温に冷やし、製造例１で合成したアジピン酸ジエチル１３３ｍＬを１時間かけて滴下した。滴下終了後、反応溶液を還流しながら終夜撹拌した。反応終了後、氷浴を用いて反応溶液を冷却した後、塩化アンモニウム２００ｍＬを加え、反応溶液に固体が生成するまでよく撹拌した。固体を吸引ろ過で濾別し、得られた有機層に１Ｎ塩酸２，０００ｍＬを加えて水層と有機層とに分離させ、水層をエーテル１，０００ｍＬで２回抽出した。得られた有機層を合わせて、飽和炭酸水素ナトリウム水溶液２，０００ｍＬ及び飽和食塩水２，０００ｍＬで洗浄し、有機層を硫酸ナトリウムで乾燥した。次いで、有機溶媒を留去することで、４，９－ジプロピルドデカン－４，９－ジオール１５５ｇを得た。なお、４，９－ジプロピルドデカン－４，９－ジオールの同定は、ＮＭＲ分析によって行なった。
Production Example 2 [Production of 4,9-dipropyldodecane-4,9-diol]
107 g of magnesium was added to a three-necked flask having an internal volume of 5 L and equipped with a ball stopper, a cooling tube, a dropping funnel and a three-way cock, and the flask was thoroughly dried. After the nitrogen substitution, 300 mL of dried tetrahydrofuran (THF) was added until the surface of magnesium was hidden, and then 20 mL of propyl bromide was added to confirm the start of the Grignard reaction.
After adding 1,700 mL of THF, 364 mL of propyl bromide was added dropwise at such a rate as to gently reflux. After completion of the dropping, the reaction solution was stirred overnight while refluxing.
The reaction solution was cooled to room temperature using a water bath, and 133 mL of diethyl adipic acid synthesized in Production Example 1 was added dropwise over 1 hour. After completion of the dropping, the reaction solution was stirred overnight while refluxing. After completion of the reaction, the reaction solution was cooled using an ice bath, 200 mL of ammonium chloride was added, and the mixture was stirred well until a solid was formed in the reaction solution. The solid was filtered off by suction filtration, 2,000 mL of 1N hydrochloric acid was added to the obtained organic layer to separate it into an aqueous layer and an organic layer, and the aqueous layer was extracted twice with 1,000 mL of ether. The obtained organic layers were combined, washed with 2,000 mL of saturated aqueous sodium hydrogen carbonate solution and 2,000 mL of saturated brine, and the organic layer was dried over sodium sulfate. Then, the organic solvent was distilled off to obtain 155 g of 4,9-dipropyldodecane-4,9-diol. The identification of 4,9-dipropyldodecane-4,9-diol was performed by NMR analysis.
（４，９－ジプロピルドデカン－４，９－ジオールの同定）
１Ｈ－ＮＭＲ（５００ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：１．４３－１．３６（ｍ、６Ｈ）、１．３２－１．２５（ｍ、６Ｈ）、０．９０（ｔ、６Ｈ、Ｊ＝８．０Ｈｚ）
１３Ｃ－ＮＭＲ（１２５ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：７４．４、４１．７、 ３９．２、 ２４．１、 １６．７、 １４．７
(Identification of 4,9-dipropyldodecane-4,9-diol)
1 1 H-NMR (500 MHz, CDCl 3 , TMS, ppm) δ: 1.43-1.36 (m, 6H), 1.32-1.25 (m, 6H), 0.90 (t, 6H, J = 8.0Hz)
13 C-NMR (125 MHz, CDCl 3 , TMS, ppm) δ: 74.4, 41.7, 39.2, 24.1, 16.7, 14.7
実施例１
（工程［Ｉ］）
フラスコに、製造例２で得た４，９－ジプロピルドデカン－４，９－ジオール２９ｇ、クロロアセトニトリル２５ｍＬ、酢酸５０ｍＬを加え、フラスコを氷浴につけてから、硫酸３２ｍＬを３０分かけて滴下した。滴下終了後、溶液を室温に戻し、終夜撹拌した。
反応終了後、氷水４００ｍＬ中に反応溶液を注ぎ、生成した固体を吸引ろ過した。得られた固体を飽和炭酸水素ナトリウム水溶液２００ｍＬで２回、水２００ｍＬで２回洗浄し、空気中で２日乾燥して、Ｎ，Ｎ’－（４，９－ジプロピルドデカン－４，９－ジイル）ビス（２－クロロアセトアミド）３４ｇを得た。なお、生成物の同定は、ＮＭＲ分析によって行なった。
Example 1
(Step [I])
To the flask, 29 g of 4,9-dipropyldodecane-4,9-diol obtained in Production Example 2, 25 mL of chloroacetonitrile, and 50 mL of acetic acid were added, the flask was placed in an ice bath, and then 32 mL of sulfuric acid was added dropwise over 30 minutes. .. After completion of the dropping, the solution was returned to room temperature and stirred overnight.
After completion of the reaction, the reaction solution was poured into 400 mL of ice water, and the produced solid was suction-filtered. The obtained solid was washed twice with 200 mL of saturated aqueous sodium hydrogen carbonate solution and twice with 200 mL of water, dried in air for 2 days, and N, N'-(4,9-dipropyldodecane-4,9-). 34 g of diyl) bis (2-chloroacetamide) was obtained. The product was identified by NMR analysis.
（Ｎ，Ｎ’－（４，９－ジプロピルドデカン－４，９－ジイル）ビス（２－クロロアセトアミド）の同定）
１Ｈ－ＮＭＲ（５００ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：５．９９（ｂｒ、２Ｈ）、３．９１（ｓ、４Ｈ）、１．７０－１．６０（ｍ、１２Ｈ）、１．２５－１．１９（ｍ、１２Ｈ）、０．９０（ｔ、１２Ｈ、Ｊ＝６．０Ｈｚ）
１３Ｃ－ＮＭＲ（１２５ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：１６４．４、５９．６、 ４２．９、 ３７．７、 ３５．３、 ２３．７、１６．５、 １４．４
(Identification of N, N'-(4,9-dipropyldodecane-4,9-diyl) bis (2-chloroacetamide))
1 1 H-NMR (500 MHz, CDCl 3 , TMS, ppm) δ: 5.99 (br, 2H), 3.91 (s, 4H), 1.70-1.60 (m, 12H), 1.25 -1.19 (m, 12H), 0.90 (t, 12H, J = 6.0Hz)
13 C-NMR (125 MHz, CDCl 3 , TMS, ppm) δ: 164.4, 59.6, 42.9, 37.7, 35.3, 23.7, 16.5, 14.4
（工程［II］）
フラスコに上記工程［Ｉ］で製造したＮ，Ｎ’－（４，９－ジプロピルドデカン－４，９－ジイル）ビス（２－クロロアセトアミド）２５ｇ、チオウレア１０ｇ、エタノール３５０ｍＬ及び酢酸７０ｍＬを加え、一昼夜、加熱還流した。
反応終了後、１／３まで加熱濃縮を行い、６Ｎ水酸化ナトリウム水溶液を用いてｐＨを１４以上にした。その後、ジエチルエーテル２５０ｍＬで３回有機物を抽出し、抽出液を合わせて飽和食塩水５００ｍＬで３回洗浄した。抽出液を固体の水酸化ナトリウムで乾燥後、溶液を除去することで、４，９－ジプロピルドデカン－４，９－ジアミン１５ｇを得た。なお、生成物の同定は、ＮＭＲ分析によって行なった。
(Step [II])
To the flask, 25 g of N, N'-(4,9-dipropyldodecane-4,9-diyl) bis (2-chloroacetamide) prepared in the above step [I], 10 g of thiourea, 350 mL of ethanol and 70 mL of acetic acid were added. It was heated and refluxed all day and night.
After completion of the reaction, the mixture was heated and concentrated to 1/3, and the pH was adjusted to 14 or higher using a 6N aqueous sodium hydroxide solution. Then, the organic matter was extracted 3 times with 250 mL of diethyl ether, and the extracts were combined and washed 3 times with 500 mL of saturated brine. The extract was dried with solid sodium hydroxide and then the solution was removed to obtain 15 g of 4,9-dipropyldodecane-4,9-diamine. The product was identified by NMR analysis.
（４，９－ジプロピルドデカン－４，９－ジアミンの同定）
１Ｈ－ＮＭＲ（５００ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：１．２０－１．１８（ｍ、２８Ｈ）、０．８９－０．０８（ｍ、１２Ｈ）
１３Ｃ－ＮＭＲ（１２５ＭＨｚ、ＣＤＣｌ３、ＴＭＳ、ｐｐｍ）δ：５３．６、４２．７、 ４０．３、 ２３．２、 １６．７、 １４．８
(Identification of 4,9-dipropyldodecane-4,9-diamine)
1 1 H-NMR (500 MHz, CDCl 3 , TMS, ppm) δ: 1.20-1.18 (m, 28H), 0.89-0.08 (m, 12H)
13 C-NMR (125 MHz, CDCl 3 , TMS, ppm) δ: 53.6, 42.7, 40.3, 23.2, 16.7, 14.8
以上の様にして得た４，９－ジプロピルドデカン－４，９－ジアミン４．０ｇと、ビスフェノールＡ型エポキシ樹脂（ｊＥＲ（登録商標）８２８、三菱ケミカル株式会社製）５．２ｇとを室温で１０分間混合して樹脂組成物を得た。
（誘電特性の評価方法）
下側に銅箔を配置した厚さ１ｍｍのテフロン（登録商標）板であって、長さ１５ｃｍ及び幅５ｃｍがくり抜かれたテフロン（登録商標）板のそのくり抜かれた部分に前記樹脂組成物を入れ、その上に銅箔を配置した。その後、１００℃、６０分、１．０ＭＰａのプレス条件で成型し、両側の銅箔を過硫酸アンモニウムで除去することによって、評価用樹脂板を作製した。
該評価用樹脂板を長さ１００ｍｍ及び幅２ｍｍに切り出し、ネットワークアナライザー（アジレント・テクノロジーＡ株式会社製、商品名：Ｅ８３６４Ｂ）と１ＧＨｚ用空洞共振器（株式会社関東電子応用開発製）を用いて、空洞共振摂動法にて１ＧＨｚの比誘電率を測定した。比誘電率が低いほど、誘電特性に優れることを示す。結果を表１に示す。
4.0 g of 4,9-dipropyldodecane-4,9-diamine obtained as described above and 5.2 g of bisphenol A type epoxy resin (jER® 828, manufactured by Mitsubishi Chemical Corporation) were added at room temperature. Was mixed for 10 minutes to obtain a resin composition.
(Evaluation method of dielectric properties)
A 1 mm thick Teflon (registered trademark) plate with a copper foil placed on the lower side, and the resin composition is applied to the hollowed out portion of the Teflon (registered trademark) plate having a length of 15 cm and a width of 5 cm. I put it in and placed a copper foil on it. Then, it was molded at 100 ° C. for 60 minutes under the pressing conditions of 1.0 MPa, and the copper foils on both sides were removed with ammonium persulfate to prepare a resin plate for evaluation.
The evaluation resin plate was cut into a length of 100 mm and a width of 2 mm, and a network analyzer (manufactured by Agilent Technologies A Co., Ltd., trade name: E8364B) and a cavity resonator for 1 GHz (manufactured by Kanto Electronics Applied Development Co., Ltd.) were used. The relative permittivity of 1 GHz was measured by the cavity resonance permittivity method. The lower the relative permittivity, the better the dielectric property. The results are shown in Table 1.
比較例１
ペンタメチレンジアミン（東京化成工業株式会社製）１．９ｇと、ビスフェノールＡ型エポキシ樹脂（ｊＥＲ（登録商標）８２８、三菱ケミカル株式会社製）７．８ｇを室温で１０分間混合して樹脂組成物を得た。この際、ペンタメチレンジアミンとビスフェノールＡ型エポキシ樹脂の前記混合量は、実施例１で使用した４，９－ジプロピルドデカン－４，９－ジアミンとビスフェノールＡ型エポキシ樹脂の官能基の当量比とほぼ同じになるように調整されたものである。
該樹脂組成物を用いて、実施例１と同様にして誘電特性の評価を行った。結果を表１に示す。
Comparative Example 1
1.9 g of pentamethylenediamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 7.8 g of bisphenol A type epoxy resin (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation) are mixed at room temperature for 10 minutes to prepare a resin composition. Obtained. At this time, the mixed amount of pentamethylenediamine and the bisphenol A type epoxy resin is the equivalent ratio of the functional groups of the 4,9-dipropyldodecane-4,9-diamine and the bisphenol A type epoxy resin used in Example 1. It has been adjusted to be almost the same.
Using the resin composition, the dielectric property was evaluated in the same manner as in Example 1. The results are shown in Table 1.
表１より、実施例１の樹脂組成物では、比較例１の樹脂組成物よりも比誘電率が小さくなった。誘電正接についても同様の傾向になるものと推察される。
比較例１で用いたペンタメチレンジアミンよりも、本発明のジアミン化合物（１）の自由体積が大きいことが、このような結果が得られた一因であると考える。
From Table 1, the resin composition of Example 1 had a smaller relative permittivity than the resin composition of Comparative Example 1. It is presumed that the same tendency will occur for the dielectric loss tangent.
It is considered that the fact that the free volume of the diamine compound (1) of the present invention is larger than that of the pentamethylenediamine used in Comparative Example 1 is one of the reasons for obtaining such a result.
本発明のジアミン化合物（１）を用いると誘電特性を向上させることができるため、プリント配線板及び半導体パッケージの材料として有用である。 Since the diamine compound (1) of the present invention can improve the dielectric property, it is useful as a material for a printed wiring board and a semiconductor package.
Claims (12)
（一般式（１）中、Ｒ１～Ｒ４は、それぞれ独立して、炭素数２～７のアルキル基を表す。Ｒ１～Ｒ４は、それぞれ同一のアルキル基であってもよいし、互いに異なるアルキル基であってもよい。ｎは、３～６の整数である。） The diamine compound represented by the following general formula (1).
(In the general formula (1), R 1 to R 4 independently represent an alkyl group having 2 to 7 carbon atoms. R 1 to R 4 may be the same alkyl group, respectively. Alkyl groups different from each other may be used. N is an integer of 3 to 6 ).
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| US4277621A (en) * | 1978-10-18 | 1981-07-07 | Ciba-Geigy Corporation | Substituted 11-amino-undeca-4,8-dienal and 11-amino-undecanal derivatives and processes for their preparation |
| US4252936A (en) * | 1979-01-24 | 1981-02-24 | The United States Of America As Represented By The United States Department Of Energy | Use of 2,5-dimethyl-2,5-hexane diamine as a curing agent for epoxy resins |
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| Balizer, Edward; Duffy, James V.，The effects of steric hindrance on sub-glass transitions in epoxy polymers，Polymer，1992年，33(10),，2114-22 |
| REGISTRY（STN）[online]，1992.07.10[検索日 2021.09.03]CAS登録番号 142312-99-0 |
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