WO2013141247A1 - 活性エステル樹脂、熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム - Google Patents
活性エステル樹脂、熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム Download PDFInfo
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- WO2013141247A1 WO2013141247A1 PCT/JP2013/057853 JP2013057853W WO2013141247A1 WO 2013141247 A1 WO2013141247 A1 WO 2013141247A1 JP 2013057853 W JP2013057853 W JP 2013057853W WO 2013141247 A1 WO2013141247 A1 WO 2013141247A1
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- WIPO (PCT)
- Prior art keywords
- acid
- resin
- carbon atoms
- dicarboxylic acid
- group
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims description 173
- 239000011347 resin Substances 0.000 title claims description 173
- 150000002148 esters Chemical class 0.000 title claims description 126
- 239000011342 resin composition Substances 0.000 title claims description 71
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 66
- 239000004065 semiconductor Substances 0.000 title claims description 14
- 239000000463 material Substances 0.000 title description 15
- 238000005538 encapsulation Methods 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 176
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 145
- 125000003118 aryl group Chemical group 0.000 claims abstract description 122
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 115
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 92
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 78
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 56
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 40
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 125000001424 substituent group Chemical group 0.000 claims abstract description 28
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 26
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 20
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- -1 aromatic monocarboxylic acid Chemical class 0.000 claims description 103
- 239000005011 phenolic resin Substances 0.000 claims description 87
- 150000004820 halides Chemical class 0.000 claims description 80
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 77
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 58
- 239000003822 epoxy resin Substances 0.000 claims description 57
- 229920000647 polyepoxide Polymers 0.000 claims description 57
- 238000004519 manufacturing process Methods 0.000 claims description 43
- 229920003986 novolac Polymers 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 25
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 23
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 13
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000003566 sealing material Substances 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 239000002966 varnish Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000003014 reinforcing effect Effects 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 68
- 239000003063 flame retardant Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 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 26
- 239000010410 layer Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000001723 curing Methods 0.000 description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 16
- 150000002989 phenols Chemical class 0.000 description 16
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 15
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000002313 adhesive film Substances 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 7
- 239000011810 insulating material Substances 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000010680 novolac-type phenolic resin Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 235000003441 saturated fatty acids Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 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 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 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
- 150000007973 cyanuric acids Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000007033 dehydrochlorination reaction Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000000434 field desorption mass spectrometry Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 3
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-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
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 2
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
Images
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
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- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
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- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0243—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing phosphorus
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- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/04—Chemically modified polycondensates
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
- H05K3/0067—Laminating printed circuit boards onto other substrates, e.g. metallic substrates onto an inorganic, non-metallic substrate
-
- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Definitions
- the present invention provides a thermosetting resin composition that exhibits excellent flame retardancy, heat resistance, and low dielectric loss tangent in the cured product, and has excellent performance in solvent solubility, the cured product, and the cured product.
- the present invention relates to an active ester resin, and the thermosetting resin composition semiconductor sealing material, prepreg, circuit board, and build-up film.
- Epoxy resin compositions containing an epoxy resin and a curing agent as an essential component exhibit excellent heat resistance and insulation in the cured product, and are widely used in electronic component applications such as semiconductors and multilayer printed boards. .
- thermosetting resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for a signal with a higher speed and a higher frequency. It is desired.
- a technique is known in which an active ester compound obtained by arylesterifying a phenolic hydroxyl group in a phenol novolac resin is used as a curing agent for an epoxy resin (described below).
- Patent Document 1 an active ester compound obtained by arylesterifying a phenolic hydroxyl group in a phenol novolac resin is used as a curing agent for an epoxy resin (described below).
- multilayer printed circuit board insulating materials are also required to have extremely high heat resistance, and the activity obtained by aryl esterifying the phenolic hydroxyl group in the phenol novolac resin described above In the ester compound, the crosslink density of the cured product is lowered due to the introduction of the aryl ester structure, and the heat resistance of the cured product is insufficient. Thus, it was difficult to achieve both heat resistance and low dielectric constant / low dielectric loss tangent.
- the resin itself has a flame-retardant effect without using an additive-based halogen flame retardant.
- halogen-free flame retardant systems There is a growing demand for so-called halogen-free flame retardant systems.
- the active ester compound obtained by arylesterifying the phenolic hydroxyl group in the phenol novolak resin described above has many pendant aromatic hydrocarbon groups that easily burn in the molecular structure, although the dielectric properties are good. Therefore, the cured product is inferior in flame retardancy, and the above halogen-free flame retardant system cannot be constructed.
- thermosetting resin composition that can combine excellent heat resistance and flame retardancy while having a low dielectric constant and low dielectric loss tangent in the cured product
- An object of the present invention is to provide a cured product, an active ester resin that exhibits these performances, a semiconductor sealing material obtained from the composition, a prepreg, a circuit board, and a buildup film.
- the phosphorus atom-containing phenol substance has a part or all of the hydroxyl groups of the substance, an aromatic dicarboxylic acid, an acid anhydride thereof or an aromatic dicarboxylic acid. Or a dihydride of a saturated dicarboxylic acid having 2 to 6 carbon atoms, an acid anhydride thereof, or a saturated dicarboxylic acid having 2 to 6 carbon atoms so that the hydroxyl group forms an ester bond.
- the resulting active ester resin has been found to have excellent characteristics in heat resistance and flame retardancy while having a low dielectric constant and low positive tangent in the cured product, and the present invention has been completed.
- the present invention reacts an aromatic aldehyde (a1) having an alkoxy group as a substituent on an aromatic nucleus with an organophosphorus compound (a2) having a P—H group or a P—OH group in the molecular structure.
- the phosphorus atom-containing compound (i) thus obtained is further reacted with a phenol substance (a3) to obtain a phosphorus atom-containing phenol substance (A1), and then the obtained phosphorus atom-containing phenol substance (A1) Dicarboxylic acid, its anhydride or dihalide of aromatic dicarboxylic acid, or saturated dicarboxylic acid having 2 to 6 carbon atoms, its anhydride, or dihalide of saturated dicarboxylic acid having 2 to 6 carbon atoms (A2) Is reacted so that part or all of the hydroxyl groups of the phenolic substance (A1) form an ester bond.
- a3 a phosphorus atom-containing phenol substance
- A1 Dicarboxylic acid, its anhydride or dihalide of aromatic dicarboxylic acid, or saturated dicarboxylic acid having 2 to 6 carbon atoms, its anhydride, or dihalide of saturated dicarboxylic acid having 2 to 6 carbon atoms
- A2
- the present invention further relates to a novel active ester resin obtained by the above production method.
- the present invention further includes the following structural formula (I)
- Ar represents a benzene ring or a naphthalene ring
- Fc represents a hydrogen atom or a hydroxyl group
- Z represents the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3
- the present invention relates to a novel active ester resin characterized by having a resin structure that is knotted through the ester residue (A2).
- the present invention further has a novolac type phenolic resin structure, and as substituents on the aromatic nucleus, the following structural formulas z1 to z4
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
- a phenol resin (A1y) having a structural part selected from the group consisting of the partial structures represented by the following: an aromatic dicarboxylic acid, an acid anhydride thereof, or a dihalide of an aromatic dicarboxylic acid, or saturated with 2 to 6 carbon atoms Reaction with a dicarboxylic acid, its acid anhydride, or a dihalide (A2) of a saturated dicarboxylic acid having 2 to 6 carbon atoms such that a part or all of the hydroxyl groups of the phenol resin (A1y) form an ester bond.
- a novel active ester resin having a resin structure in which two hydroxyl groups are knotted through the ester residue (A2).
- the present invention further includes the following structural formula (II)
- R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Z represents a hydrogen atom or the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus
- at least one of Z is a structural moiety selected from the partial structures represented by the structural formulas z1 to z4.
- the present invention relates to a novel active ester resin characterized by having a resin structure in which two hydroxyl groups are knotted through the ester residue (A2).
- the present invention further relates to a curable resin composition comprising an active ester resin (A) and an epoxy resin (B) as essential components, wherein the active ester resin (A) is the above-described novel active ester resin.
- the present invention relates to a thermosetting resin composition.
- the present invention further relates to a cured product obtained by curing the thermosetting resin composition.
- the present invention further relates to a semiconductor sealing material containing the active ester resin (A), the epoxy resin (B), and an inorganic filler (C).
- the present invention further includes impregnating a reinforcing substrate with a composition containing the active ester resin (A), the epoxy resin (B), and the organic solvent (D), and semi-curing the resulting impregnated substrate. It relates to the prepreg obtained.
- the composition containing the active ester resin (A), the epoxy resin (B) and the organic solvent (D) is shaped into a plate shape, and a copper foil is heat-press molded. It is related with the circuit board obtained by this.
- the present invention further comprises a build-up film, wherein a composition containing the active ester resin (A), the epoxy resin (B), and the organic solvent (D) is applied onto a base film and dried. About.
- thermosetting resin composition capable of combining excellent heat resistance and flame retardancy while having a low dielectric constant and low dielectric loss tangent, the cured product, and these
- An active ester resin exhibiting performance, a semiconductor sealing material obtained from the composition, a prepreg, a circuit board, and a buildup film can be provided.
- FIG. 1 is a GPC chart of the phenol resin (A1-1) obtained in Production Example 1.
- FIG. 2 is a 13 C-NMR chart of the phenol resin (A1-1) obtained in Production Example 1.
- FIG. 3 is an FD-MS spectrum of the phenol resin (A1-1) obtained in Production Example 1.
- 4 is a GPC chart of the phenol resin (A1-2) obtained in Production Example 2.
- FIG. 5 is a GPC chart of the phenol resin (A1-3) obtained in Production Example 3.
- FIG. 6 is a GPC chart of the phenol resin (A1′-1) obtained in Comparative Production Example 2.
- FIG. 7 is a GPC chart of the phenol resin (A1′-2) obtained in Comparative Production Example 3.
- FIG. 1 is a GPC chart of the phenol resin (A1-1) obtained in Production Example 1.
- FIG. 2 is a 13 C-NMR chart of the phenol resin (A1-1) obtained in Production Example 1.
- FIG. 3 is an FD-MS spectrum of
- FIG. 8 is a GPC chart of the active ester resin (A-1) obtained in Example 1.
- FIG. 9 is the FD-MS spectrum of the active ester resin (A-1) obtained in Example 1.
- FIG. 10 is a 13 C-NMR chart of the active ester resin (A-1) obtained in Example 1.
- the production method of the present invention comprises an aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus, and an organophosphorus compound (a2) having a P—H group or a P—OH group in the molecular structure.
- a phosphorus atom-containing compound (i) obtained by reacting with a phenol substance (a3) to obtain a phosphorus atom-containing phenol substance (A1), an aromatic dicarboxylic acid, and its acid anhydride Or a dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms, an acid anhydride thereof, or a dihalide of a saturated dicarboxylic acid having 2 to 6 carbon atoms (A2). ) Are reacted so that part or all of the hydroxyl groups possessed by them form an ester bond.
- the active ester resin obtained by the production method of the present invention has a specific phosphorus atom-containing structure in the molecular main skeleton, it can impart excellent heat resistance and flame retardancy to the cured product, and aryl in the resin structure. Since it has a carbonyloxy structure site or an alkylcarbonyloxy structure site, the cured product can have excellent dielectric properties such as low dielectric constant and low dielectric loss tangent.
- an active ester resin having a phenolic hydroxyl group in an arylcarbonyloxylated or alkylcarbonyloxylated resin structure of a polyfunctional phenolic hydroxyl group-containing resin has a heat resistance due to the arylcarbonyloxy group or the alkylcarbonyloxy group. It is worthy of special mention that in the present invention, such a decrease in heat resistance and flame retardancy is hardly observed.
- aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus used in the present invention is, for example, benzaldehyde, o-tolualdehyde, p-tolualdehyde, o-ethylaldehyde, p-ethylaldehyde, p-isopropyl.
- aromatic aldehyde substituents such as benzaldehyde, naphthaldehyde, anthracene aldehyde, etc. include those having an alkoxy group. Specifically, the following structural formula (a1-1)
- R 5 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3)
- an aromatic aldehyde (a1-1) represented by the following structural formula (a1-2)
- R 5 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3)
- the aromatic aldehyde (a1-1) is preferable, and the compound having a value of n of 1 is more preferable. preferable.
- the aromatic aldehyde (a1) used in the present invention has an alkoxy group as a substituent on the aromatic nucleus, the aromatic aldehyde (a1) and an organic phosphorus compound having a P—H group or a P—OH group
- the reactivity of the hydroxyl group of the phosphorus atom-containing compound (i), which is a reaction product with (a2), is excellent, and the phosphorus atom-containing compound (i) can be converted into a phenolic substance (a3) without using any catalyst. Reacts to the aromatic nucleus inside.
- the alkoxy group of the aromatic aldehyde (a1) is preferably a methoxy group or an ethoxy group, and the aromatic aldehyde is preferably benzaldehyde or naphthaldehyde.
- the organophosphorus compound (a2) having a P—H group or a P—OH group to be reacted with the aromatic aldehyde (a1) in the molecular structure is specifically represented by the following structural formula (a2-1) or structural formula ( a2-2)
- Xa is a hydrogen atom or a hydroxyl group
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom or a carbon atom.
- the compound represented by these is mentioned.
- examples of the alkyl group having 1 to 5 carbon atoms constituting R 1 , R 2 , R 3 and R 4 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, An n-pentyl group may be mentioned.
- a compound in which Xa is a hydrogen atom is preferable.
- an organic phosphorus compound represented by the structural formula (a2-1) is preferable because a cured product of the obtained active ester resin is excellent in flame retardancy.
- the reaction of the aromatic aldehyde (a1) and the organophosphorus compound (a2) can be performed, for example, under a temperature condition of 80 to 180 ° C.
- the reaction can be carried out without a catalyst.
- it can carry out in presence of non-ketone type organic solvents, such as an alcohol type organic solvent and a hydrocarbon type organic solvent.
- the phosphorus atom-containing compound (i) obtained by such a method includes, for example, a compound represented by the structural formula (a1-1) as the aromatic aldehyde (a1) and a structural formula (a2) as the organic phosphorus compound (a2).
- a1-1 the structural formula represented by the aromatic aldehyde (a1)
- a structural formula (a2) as the organic phosphorus compound (a2).
- the compound represented by a2-1) or the structural formula (a2-2) specifically, the following structural formulas x1 to x4 are used.
- R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group
- R5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is an integer of 1 to 3.
- the compound represented by the structural formula x1 or x2 is preferable because it is particularly excellent in reactivity with the phenol substance (a3), and the active ester resin finally obtained is particularly excellent in flame retardancy. Therefore, the compound represented by the structural formula x1 is preferable.
- the phenol substance (a3) used in the present invention is phenol, cresol, xylenol, ethylphenol, isopropylphenol, t-butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chloro.
- Monohydric phenols such as phenol, bromophenol, naphthol; dihydric phenols such as catechol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; bisphenol A, bisphenol F, Bisphenols such as bisphenol S; phenol novolac resins, cresol novolac resins, bisphenol A novolac resins Bisphenol S novolak resin, alpha-naphthol novolak resin, beta-naphthol novolak resin, dihydroxynaphthalene novolak resin, other structural formula (A3-a)
- a novolac-type phenolic resin such as a novolac resin represented by:
- Phenols are knotted via an aliphatic cyclic hydrocarbon group selected from the group consisting of dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborn-2-ene, ⁇ -pinene, ⁇ -pinene, and limonene.
- Phenolic resin having a defined molecular structure; structural formula (A3-b)
- Rb is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and lb is an integer of 0 to 10 in terms of repeating units);
- A3-c The following structural formula (A3-c),
- Rg is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and lg is an integer of 0 to 10 in terms of a repeating unit);
- A3-h The following structural formula (A3-h)
- each Rh is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- each Ri is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- Multivalent naphthol represented by:
- polyfunctional phenol containing the structural portion represented by the partial structural formula A3-j in the molecular structure is more specifically the following structural formulas (A3-j2) and (A3-j3)
- the alternating copolymer structure which makes the structure represented by repeating unit a repeating unit is mentioned.
- the phenolic hydroxyl group-containing aromatic hydrocarbon group can take various structures, specifically, phenol, naphthol, and the following structural formulas Ph1 to Ph16:
- An aromatic hydrocarbon group formed from a compound having an alkyl group as a substituent on these aromatic nuclei is preferable from the viewpoint of excellent dielectric performance.
- each structure is a monovalent aromatic hydrocarbon group when the structure is located at the molecular end.
- those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.
- the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (An) contained in the phenol resin structure is a monovalent or polyvalent aromatic having an alkoxy group as a substituent on the condensed polycyclic aromatic nucleus.
- a hydrocarbon group specifically, an alkoxyquinaphthalene structure represented by the following structural formulas An1 to An12.
- each structure is a monovalent aromatic hydrocarbon group when the structure is located at the molecular end.
- those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.
- the divalent hydrocarbon group (M) selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group is, for example, an methylene group or an alkylidene group as an ethylidene group.
- 1,1-propylidene group, 2,2-propylidene group, dimethylene group, propane-1,1,3,3-tetrayl group, n-butane-1,1,4,4-tetrayl group, n-pentane- A 1,1,5,5-tetrayl group may be mentioned.
- Examples of the methylene group containing an aromatic hydrocarbon structure include those having the following structures M1 to M8.
- a methylene group is preferable from the viewpoint of excellent dielectric effect.
- dihydric phenol, novolac type phenol resin, and aralkyl type phenol resin have curability and solubility in organic solvents when the obtained active ester resin is used as a curing agent for epoxy resin. It is preferable because it becomes good, and particularly when the finally obtained active ester resin is used as a curing agent for an epoxy resin of an epoxy resin composition for a printed wiring board, it has excellent solvent solubility and moisture resistance. -From the point which is excellent in a flame retardance, a novolak-type phenol resin and an aralkyl type phenol resin are preferable.
- the novolac type phenolic resin preferably has a melt viscosity at 150 ° C.
- the melt viscosity in the range of 0.1 to 300 dPa ⁇ s is preferable from the viewpoint of excellent moisture resistance, heat resistance and heat resistance reliability in the cured product of the finally obtained active ester resin.
- the dihydric phenol is excellent in heat resistance in a cured product of an active ester resin from which dihydroxynaphthalene such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene is finally obtained. It is preferable from the point.
- the reaction of the phosphorus atom-containing compound (i), which is a reaction product of the aromatic aldehyde (a1) and the organophosphorus compound (a2), with the phenol substance (a3) is carried out at a temperature of 140 to 200 ° C. Can be done.
- the reaction between the phosphorus atom-containing compound (i) and the phenol substance (a3) is extremely high in reactivity and does not require a catalyst, but may be used as appropriate.
- catalysts examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid etc. are mentioned.
- the amount used is preferably less than 5.0% by mass with respect to the total weight of the charged raw materials.
- the reaction rate of the phosphorus atom-containing compound (i) and the phenolic substance (a3) is not particularly limited. Rather, because of its good reactivity, the intended flame retardancy and heat resistance
- the amount of modification of the phosphorus atom-containing compound (i) with respect to the phenolic substance (a3) can be arbitrarily controlled according to the performance level of the property or the application.
- the reaction is such that the phosphorus atom-containing compound (i) does not remain in the reaction product, specifically, the reaction point on the aromatic nucleus of the phenolic substance (a3) is less than the equivalent. It is preferable to make it.
- the phosphorus atom-containing compound (i) is modified into a novolac type phenol resin or an aralkyl type phenol resin preferably used as the phenol substance (a3), the phosphorus atom content is 4.0 to 7. A range of 0% by mass is preferable from the viewpoint of excellent heat resistance and flame retardancy.
- the desired product can be obtained by dehydration and drying if necessary.
- the phosphorus atom-containing phenol substance (A1) obtained in this manner the phosphorus atom-containing compound (i), which is an unreacted component, hardly remains.
- the phosphorus atom-containing compound (i) is modified into a novolac type phenol resin or an aralkyl type phenol resin, and the phosphorus atom content is adjusted to a range of 4.0 to 7.0% by mass, The residual amount of the phosphorus atom-containing compound (i) is below the detection limit of GPC in the phosphorus atom-containing phenol resin.
- the molecular structure of the phosphorus atom-containing phenol substance (A1) thus obtained can be arbitrarily designed by selecting the above-described raw material components. Specifically, for example, the following structural formula (I )
- Ar represents a benzene ring or a naphthalene ring
- Fc represents a hydrogen atom or a hydroxyl group
- Z represents the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3
- R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Z represents a hydrogen atom or the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus
- at least one of Z is a structural moiety selected from the partial structures represented by the structural formulas z1 to z4.
- a cured product having particularly excellent heat resistance can be obtained.
- a partial structure represented by z1 or z2 is preferable, and a structure represented by the structural formula z1 is particularly preferable.
- the aromatic dicarboxylic acid used as (A2), its acid anhydride or dihalide of aromatic dicarboxylic acid is, for example, phthalic acid, isophthalic acid, terephthalic acid
- Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, acid anhydrides of phthalic acid, and acid fluorides and acids of the aromatic dicarboxylic acids Examples thereof include acid halides such as chloride, acid bromide
- saturated dicarboxylic acids having 2 to 6 carbon atoms, acid anhydrides thereof, or dihalides of saturated dicarboxylic acids having 2 to 6 carbon atoms are specifically oxalic acid, malonic acid, succinic acid, glutaric acid, Examples thereof include saturated dicarboxylic acids such as adipic acid, acid anhydrides of these saturated dicarboxylic acids, and acid halides such as acid fluorides, acid chlorides, acid bromides, and acid iodides of these saturated dicarboxylic acids.
- aromatic dicarboxylic acids, their anhydrides or dihalides of aromatic dicarboxylic acids, or saturated dicarboxylic acids having 2 to 6 carbon atoms, their anhydrides, or dihalides of saturated dicarboxylic acids having 2 to 6 carbon atoms (A2 ) May be used alone or in combination of two or more.
- aromatic dicarboxylic acids, acid anhydrides or aromatic dicarboxylic acids can be obtained because an active ester resin having higher heat resistance and flame retardancy and excellent dielectric properties such as low dielectric constant and low dielectric loss tangent can be obtained.
- the dihalide is more preferable, and isophthalic acid chloride and terephthalic acid chloride are particularly preferable since the reactivity with the phenolic hydroxyl group in the phosphorus atom-containing phenol compound (A1) is good.
- the reaction with a dihalide (A2) of a saturated dicarboxylic acid of 6 to 6 specifically includes a phenol substance (A1) and an aromatic dicarboxylic acid, its acid anhydride or dihalide of an aromatic dicarboxylic acid, or 2 carbon atoms.
- the reaction ratio of the saturated dicarboxylic acid with dihalide (A2) is such that the resulting active ester resin has high solvent solubility, so that the phenolic hydroxyl group in (A1) and the carboxyl group in (A2) ( Or equivalent ratio to [halide) [OH in (A1)] / [carboxyl group (or halide) in (A2)] is a ratio of 1.00 / 0.01 to 1.00 / 0.40. It is preferable.
- the cured film of the resulting active ester resin has higher heat resistance and flame retardancy, so that [OH in (A1)] / [carboxyl group (or halide) in (A2)]. Is more preferably 1.00 / 0.05 to 1.00 / 0.35.
- alkali catalyst examples include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.
- each raw material component is preferably dissolved in an organic solvent and used for the reaction.
- organic solvent used here include toluene and dichloromethane.
- the molecular structure of the active ester resin thus obtained can be arbitrarily designed by selecting the above-described raw material components. Specifically, for example, the following structural formula (I)
- Ar represents a benzene ring or a naphthalene ring
- Fc represents a hydrogen atom or a hydroxyl group
- Z represents the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
- a phenol resin (A1y) having a structural part selected from the group consisting of the partial structures represented by the following: an aromatic dicarboxylic acid, an acid anhydride thereof, or a dihalide of an aromatic dicarboxylic acid, or saturated with 2 to 6 carbon atoms Reaction with a dicarboxylic acid, its acid anhydride, or a dihalide (A2) of a saturated dicarboxylic acid having 2 to 6 carbon atoms such that a part or all of the hydroxyl groups of the phenol resin (A1y) form an ester bond.
- a novel active ester resin (Ay-1) characterized in that it has a resin structure in which two hydroxyl groups are knotted through the ester residue of (A2),
- R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Z represents a hydrogen atom or the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus
- at least one of Z is a structural moiety selected from the partial structures represented by the structural formulas z1 to z4.
- the active ester resin (Ax-1), (Ay-1) or (Az-1) a cured product having particularly excellent heat resistance can be obtained among the partial structures represented by the structural formulas z1 to z4. Therefore, the partial structure represented by the structural formula z1 or z2 is preferable, and the partial structure represented by the structural formula z1 is particularly preferable.
- the proportion of all phenolic hydroxyl groups in which an ester bond is formed is that the resulting active ester resin has a high glass transition temperature. It is preferably in the range of 1 to 40 mol%. Among them, the range of 5 to 35 mol% is more preferable because the cured film of the resulting active ester resin has higher heat resistance and flame retardancy.
- the phosphorus atom-containing phenolic substance (A1) ) May be substituted with an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms, an acid anhydride thereof, or 2 to 6 carbon atoms.
- the dihalide of saturated dicarboxylic acid (A2) is reacted so as to form an ester bond, and part or all of the other hydroxyl groups of the phosphorus atom-containing phenolic substance (A1) are converted to aromatic monocarboxylic acids or their Forms an ester bond with a halide, or a saturated fatty acid having 2 to 6 carbon atoms, the halide or an acid anhydride (A3) of the saturated fatty acid It is preferably reacted as.
- the aromatic monocarboxylic acids or their halides are specifically Specifically, benzoic acid, or alkyl benzoic acid such as phenyl benzoic acid, methyl benzoic acid, ethyl benzoic acid, n-propyl benzoic acid, i-propyl benzoic acid and t-butyl benzoic acid, 1-naphthoic acid, 2 -Naphthoic acid, phenyl naphthoic acid, methyl naphthoic acid, ethyl naphthoic acid, alkyl naphthoic acid such as n-propyl naphthoic acid, i-propyl naphthoic acid and t-butyl naphthoic acid, and their acid fluorides, acid chlorides
- saturated fatty acid having 2 to 6 carbon atoms, a halide thereof, or an acid anhydride of the saturated fatty acid include acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, and their acid fluorides and acids.
- acid halides such as chloride, acid bromide and acid iodide, or acid anhydrides of acetic acid, propionic acid, butyric acid, pentanoic acid and hexanoic acid.
- aromatic monocarboxylic acids or their halides, saturated fatty acids having 2 to 6 carbon atoms, their halides or acid anhydrides (A3) of the saturated fatty acids may be used alone or in combination of two or more. May be.
- an aromatic monocarboxylic acid or a halide thereof is more preferable because an active ester resin having higher heat resistance and flame retardancy and excellent dielectric properties such as low dielectric constant and low dielectric loss tangent is obtained. Since the reactivity with the phenolic hydroxyl group in the contained phenol compound (A1) becomes good, a benzoic acid chloride or an alkylbenzoic acid base is particularly preferable.
- a method of reacting the acid anhydride or dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms, the acid anhydride or a dihalide of saturated dicarboxylic acid having 2 to 6 carbon atoms (A2) Specifically, the phenol substance (A1), an aromatic monocarboxylic acid or its halide, a saturated fatty acid having 2 to 6 carbon atoms, its halide or an acid anhydride (A3) of the saturated fatty acid, and an aromatic Dicarboxylic acid, its anhydride or dihalide of aromatic dicarboxylic acid, or saturated dicarboxylic acid having 2 to 6 carbon atoms
- the phenol compound (A1) and an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, a saturated dicarboxylic acid having 2 to 6 carbon atoms, an acid anhydride thereof, or an acid anhydride having 2 to 6 carbon atoms After reacting with a dihalide (A2) of a saturated dicarboxylic acid, an aromatic monocarboxylic acid or its halide, or a saturated fatty acid having 2 to 6 carbon atoms, its halide, or an acid anhydride (A3) of the saturated fatty acid is reacted.
- Method 3 hereinafter abbreviated as “method 3”) and the like.
- the method 1 includes a phosphorus atom-containing phenol compound (A1), an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms, Acid anhydride or dihalide (A2) of saturated dicarboxylic acid having 2 to 6 carbon atoms and aromatic monocarboxylic acid or halide thereof, saturated fatty acid having 2 to 6 carbon atoms, halide thereof or acid of said saturated fatty acid.
- A3 phosphorus atom-containing phenol compound
- A1 an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms
- the ratio of each reaction component is the aromatic dicarboxylic acid, its acid anhydride or dihalide of aromatic dicarboxylic acid, or the saturation of 2 to 6 carbon atoms with respect to the hydroxyl group in the phosphorus atom-containing phenol resin (A1).
- the equivalent ratio [OH / carboxyl group (or halide)] of the saturated fatty acid, its halide, or the carboxyl group in the acid anhydride (A3) of the saturated fatty acid or its halide is 1.0 / 0.5 to 1.
- a range of 0 / 1.0 is preferable because the obtained active ester resin has high heat resistance and flame retardancy.
- the dielectric constant and dielectric loss tangent of the cured film of the resulting active ester resin are lower, it is more preferably in the range of 1.0 / 0.7 to 1.0 / 1.0.
- a range of 0.0 / 0.8 to 1.0 / 1.0 is particularly preferable.
- the ratio of the dicarboxylic acid dihalide (A2) to the aromatic monocarboxylic acid or halide thereof, or the saturated fatty acid having 2 to 6 carbon atoms, the halide or acid anhydride (A3) of the saturated fatty acid is Since it is excellent, aromatic dicarboxylic acid, its acid anhydride or dihalide of aromatic dicarboxylic acid, or saturated dicarboxylic acid having 2 to 6 carbon atoms, its acid anhydride, or saturated dicarboxylic acid having 2 to 6 carbon atoms.
- Aromatic monocarboxylic acid or its halide, or carbon source for the carboxyl group in dihalide (A2) or its halide The equivalent ratio [(A2) / (A3)] of the saturated fatty acid of formula 2-6, its halide, or the carboxyl group or its halide in the anhydride (A3) of the saturated fatty acid is from 0.99 / 0.01 to A range of 0.60 / 0.40 is preferable.
- the equivalent ratio [(A2) / (A3)] of the carboxyl group or its halide in the acid anhydride (A3) of the fatty acid is in the range of 0.95 / 0.05 to 0.65 / 0.35. More preferred.
- the method 2 includes a phosphorus atom-containing phenol resin (A1), an aromatic monocarboxylic acid or a halide thereof, a saturated fatty acid having 2 to 6 carbon atoms, a halide thereof, or an acid anhydride of the saturated fatty acid. (A3) in the presence of a basic catalyst, and then the obtained intermediate and an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, or a C 2-6 carbon atom. Examples thereof include a method in which a saturated dicarboxylic acid, an acid anhydride thereof, or a dihalide (A2) of a saturated dicarboxylic acid having 2 to 6 carbon atoms is reacted under a basic catalyst.
- the method 2 includes a phosphorus atom-containing phenol resin (A1), an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms, After reacting an acid anhydride or a dihalide (A2) of a saturated dicarboxylic acid having 2 to 6 carbon atoms in the presence of a basic catalyst, the resulting intermediate, an aromatic monocarboxylic acid or a halide thereof Or a method of reacting a saturated fatty acid having 2 to 6 carbon atoms, a halide thereof or an acid anhydride (A3) of the saturated fatty acid in the presence of a basic catalyst.
- A1 phosphorus atom-containing phenol resin
- A2 an aromatic dicarboxylic acid, an acid anhydride thereof or a dihalide of an aromatic dicarboxylic acid, or a saturated dicarboxylic acid having 2 to 6 carbon atoms
- each reaction component is the aromatic dicarboxylic acid, its anhydride or dihalide of aromatic dicarboxylic acid, or the number of carbon atoms of 2 to 6 with respect to the hydroxyl group in the phosphorus atom-containing phenol resin (A1).
- 6 equivalent fatty acid [OH / carboxyl group (or halide)] of the saturated fatty acid, its halide, or the carboxyl group in the acid anhydride (A3) of the saturated fatty acid or its halide is 1.0 / 0.5 to
- the range of 1.0 / 1.0 is preferable because the obtained active ester resin has high heat resistance and flame retardancy. Furthermore, since the dielectric constant and dielectric loss tangent of the cured film of the resulting active ester resin are lower, it is more preferably in the range of 1.0 / 0.7 to 1.0 / 1.0. A range of 0.0 / 0.8 to 1.0 / 1.0 is particularly preferable.
- an aromatic dicarboxylic acid, an acid anhydride thereof, or a dihalide of an aromatic dicarboxylic acid a saturated dicarboxylic acid having 2 to 6 carbon atoms, an acid anhydride thereof, or 2 to 6 carbon atoms.
- the ratio of the dihalide (A2) of the saturated dicarboxylic acid to the aromatic monocarboxylic acid or its halide, or the saturated fatty acid having 2 to 6 carbon atoms, the halide or the acid anhydride (A3) of the saturated fatty acid is Aromatic dicarboxylic acid, its acid anhydride or dihalide of aromatic dicarboxylic acid, or saturated dicarboxylic acid having 2 to 6 carbon atoms, its acid anhydride, or saturated dicarboxylic acid having 2 to 6 carbon atoms.
- Aromatic monocarboxylic acid or its halide, or charcoal with respect to the carboxyl group or its halide in dihalide (A2) of acid The equivalent ratio [(A2) / (A3)] of the saturated fatty acid having 2 to 6 atoms, its halide or the carboxyl group or its halide in the anhydride (A3) of the saturated fatty acid is 0.99 / 0.01 It is preferably in the range of ⁇ 0.60 / 0.40.
- the equivalent ratio [(A2) / (A3)] of the carboxyl group or its halide in the acid anhydride (A3) of the fatty acid is in the range of 0.95 / 0.05 to 0.65 / 0.35. More preferred.
- alkali catalyst examples include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.
- each raw material component is dissolved in an organic solvent and used for the reaction.
- organic solvent used here include toluene, methyl isobutyl ketone, and dichloromethane.
- method 1 is preferable in that simpler production is possible.
- the molecular structure of the active ester resin thus obtained can be arbitrarily designed by selecting the above-mentioned raw material components. Specifically, for example, the following structural formula (I)
- Ar represents a benzene ring or a naphthalene ring
- Fc represents a hydroxyl group
- Z represents the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3
- An acid, an acid anhydride thereof, or a dihalide (A2) of a saturated dicarboxylic acid having 2 to 6 carbon atoms is reacted so as to form an ester bond, so that two structural sites (i) have the above structure (A2).
- Active ester resin having a resin structure obtained by reacting a saturated fatty acid, a halide thereof or an acid anhydride (A3) of the saturated fatty acid so as to form an ester bond Ax-2) and,
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3
- A1y having a structural part selected from the group consisting of the partial structure represented by the following: aromatic dicarboxylic acid, acid anhydride thereof or dihalide of aromatic dicarboxylic acid, or carbon atom
- Two structural sites (i) are reacted with a saturated dicarboxylic acid of 2-6, its anhydride, or a dihalide (A2) of a saturated dicarboxylic acid of 2-6 carbon atoms so as to form an ester bond.
- R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Z represents a hydrogen atom or the following structural formulas z1 to z4.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R represents an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus
- at least one of Z is a structural moiety selected from the partial structures represented by the structural formulas z1 to z4.
- a saturated dicarboxylic acid having 2 to 6 atoms, an acid anhydride thereof, or a dihalide of a saturated dicarboxylic acid having 2 to 6 carbon atoms is reacted so as to form an ester bond.
- the active ester resin (Ax-2), (Ay-2) or (Az-2) a cured product having particularly excellent heat resistance can be obtained among the partial structures represented by the structural formulas z1 to z4. Therefore, the partial structure represented by the structural formula z1 or z2 is preferable, and the partial structure represented by the structural formula z1 is particularly preferable.
- the proportion of all phenolic hydroxyl groups in which an ester bond is formed is such that the obtained active ester resin has high heat resistance and flame retardancy. Therefore, it is preferably 50 mol% or more. Furthermore, since the dielectric constant and dielectric loss tangent of the cured coating film of the resulting active ester resin are lower, it is more preferably in the range of 70 mol% or more, and particularly preferably in the range of 80 mol%. .
- an aromatic dicarboxylic acid an acid anhydride thereof, a dihalide of an aromatic dicarboxylic acid, or a carbon atom
- the ratio of the saturated dicarboxylic acid having 2 to 6 or its acid anhydride or the dihalide (A2) of the saturated dicarboxylic acid having 2 to 6 carbon atoms forming an ester bond is in the range of 1 to 40 mol%
- the ratio of the aromatic monocarboxylic acid or its halide, or the saturated fatty acid having 2 to 6 carbon atoms, the halide or the acid anhydride of the saturated fatty acid (A3) formed an ester bond is in the range of 60 to 98 mol%.
- the dielectric constant and dielectric loss tangent are lower, among the phenolic hydroxyl groups forming ester bonds, aromatic dicarboxylic acids, their acid anhydrides or dihalides of aromatic dicarboxylic acids, or carbon atoms of 2 to
- the ratio of the saturated dicarboxylic acid of 6 or its acid anhydride or the dihalide (A2) of saturated dicarboxylic acid having 2 to 6 carbon atoms forming an ester bond is in the range of 5 to 35 mol%, and is aromatic.
- the ratio of the monocarboxylic acid or its halide, or the saturated fatty acid having 2 to 6 carbon atoms, the halide or the acid anhydride (A3) of the saturated fatty acid formed with an ester bond is in the range of 65 to 95 mol%. Is more preferable.
- the active ester resin described in detail above has a high solubility in an organic solvent and becomes a material suitable for a circuit board varnish, and also has a softening point from the point of being able to express flame retardant performance that has not existed before.
- the range is preferably from 80 to 200 ° C, more preferably from 90 to 170 ° C.
- the active ester resin when the active ester resin is applied to a circuit board, it is preferable to further reduce the functional group concentration in the epoxy resin to improve the dielectric properties and moisture resistance after curing.
- the functional group equivalent is 240 to 400 g / eq. Based on the total number of functional groups of the arylcarbonyloxy group and the phenolic hydroxyl group. In the range of 300 to 370 g / eq. More preferably, it is the range.
- thermosetting resin composition of the present invention comprises an active ester resin (A) and an epoxy resin (B) as essential components, and the active ester resin (A) is the above-described active ester resin of the present invention. is there.
- Examples of the epoxy resin (B) used in the thermosetting resin composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and polyhydroxynaphthalene type epoxy resin.
- Phenol novolac type epoxy resin cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, Naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde Dehydro resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resins.
- epoxy resins tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, and novolac type epoxy resin are used in that a cured product having excellent flame retardancy can be obtained.
- a dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties and moisture resistance can be obtained.
- a novolac type epoxy resin is particularly preferable because a cured product having an excellent balance between dielectric properties and flame retardancy can be obtained.
- the compounding amount of the active ester resin (A) and the epoxy resin (B) in the thermosetting resin composition of the present invention is that the active ester resin (
- the ratio of the epoxy groups in the epoxy resin (B) is 0.8 to 1.2 equivalents relative to 1 equivalent in total of the hydroxyl groups in A) and the ester bond sites present on the aromatic nucleus.
- the ester bond site present on the aromatic nucleus means that the hydroxyl group present in the structural formula (I) is an aromatic monocarboxylic acid or a halide thereof, or a saturated fatty acid having 2 to 6 carbon atoms, or a halide thereof.
- part produced by esterifying by reaction with the acid anhydride of the said saturated fatty acid is pointed out.
- the thermosetting resin composition of the present invention may use a curing agent for epoxy resin in combination.
- epoxy resin curing agents that can be used here include curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.
- examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, and guanidine derivative.
- the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine.
- acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride.
- Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin Aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol -Cresol-condensed novolak resin, biphenyl-modified phenolic resin (polyhydric
- phenol novolac resins cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyls.
- Resins, naphthol aralkyl resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because of their excellent flame retardancy. .
- the amount used is preferably in the range of 10 to 50% by mass from the viewpoint of dielectric properties.
- a curing accelerator can be appropriately used in combination with the thermosetting resin composition of the present invention.
- Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
- dimethylaminopyridine and imidazole are preferable from the viewpoint of excellent heat resistance, dielectric characteristics, solder resistance, and the like.
- triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines.
- DBU -[5.4.0] -undecene
- the thermosetting resin composition of the present invention described in detail above is characterized by exhibiting excellent solvent solubility. Therefore, the thermosetting resin composition preferably contains an organic solvent (C) in addition to the above components.
- the organic solvent (C) that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc.
- a polar solvent having a boiling point of 160 ° C.
- the organic solvent (C) for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.
- esters such as cellosolve and butyl carbitol
- aromatic hydrocarbons such as toluene and xylene
- dimethylformamide dimethylacetamide
- N-methylpyrrolidone etc.
- nonvolatile content 30 to 60 mass. It is preferable to use it in the ratio which becomes%.
- thermosetting resins can be used in combination with the thermosetting resin composition of the present invention.
- examples of other thermosetting resins that can be used here include cyanate ester compounds, vinylbenzyl compounds, acrylic compounds, maleimide compounds, and the like.
- the amount used is not particularly limited as long as the effects of the present invention are not impaired, but 1 to 80% by weight based on the thermosetting resin composition of the present invention. It is preferable that it is the range of these.
- thermosetting resin composition is a non-halogen flame retardant that substantially does not contain a halogen atom in order to exert flame retardancy, for example, in the field of printed wiring boards, as long as the reliability is not lowered. May be blended.
- non-halogen flame retardants examples include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants.
- the flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.
- the phosphorus flame retardant either inorganic or organic can be used.
- the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .
- the red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like.
- the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide
- a method of double coating with a resin may be used.
- organic phosphorus compound examples include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7 -Dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and the like, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.
- general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9
- the blending amount thereof is appropriately selected depending on the type of the phosphorus flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy.
- the active ester resin (A) In the case where 100 parts by mass of a thermosetting resin composition containing all of epoxy resin (B), non-halogen flame retardant, and other fillers and additives, red phosphorus is used as a non-halogen flame retardant. It is preferably blended in the range of 1 to 2.0 parts by weight, and when an organophosphorus compound is used, it is preferably blended in the range of 0.1 to 10.0 parts by weight, particularly 0.5 to It is preferable to mix
- the phosphorous flame retardant when using the phosphorous flame retardant, may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.
- nitrogen-based flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.
- triazine compound examples include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, guanylmelamine sulfate, melem sulfate, melam sulfate, etc.
- examples thereof include an aminotriazine sulfate compound, aminotriazine-modified phenol resin, and aminotriazine-modified phenol resin further modified with tung oil, isomerized linseed oil, and the like.
- cyanuric acid compound examples include cyanuric acid and melamine cyanurate.
- the amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. In the range of 0.05 to 10 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of resin (A), epoxy resin (B), non-halogen flame retardant and other fillers and additives. It is preferable to mix, and it is particularly preferable to mix in the range of 0.1 to 5 parts by mass.
- a metal hydroxide, a molybdenum compound or the like may be used in combination.
- the silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.
- the amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. In the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition containing the resin (A), the epoxy resin (B), the non-halogen flame retardant, and other fillers and additives. It is preferable to mix. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.
- inorganic flame retardant examples include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.
- metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.
- the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide.
- metal carbonate compound examples include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
- the metal powder examples include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
- boron compound examples include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
- the low-melting-point glass include, for example, Shipley (Bokusui Brown), hydrated glass SiO 2 —MgO—H 2 O, PbO—B 2 O 3 system, ZnO—P 2 O 5 —MgO system, P 2 O 5 —B 2 O 3 —PbO—MgO system, P—Sn—O—F system, PbO—V 2 O 5 —TeO 2 system, Al 2 O 3 —H 2 O system, lead borosilicate system, etc.
- the glassy compound can be mentioned.
- the blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy.
- organic metal salt flame retardant examples include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.
- the amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of organometallic salt-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. For example, 0.005 to 10 mass in 100 mass parts of thermosetting resin composition containing all of active ester resin (A), epoxy resin (B), non-halogen flame retardant and other fillers and additives. It is preferable to blend in the range of parts.
- an inorganic filler can be blended as necessary.
- the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
- fused silica When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica.
- the fused silica can be used in either a crushed shape or a spherical shape.
- the filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total amount of the thermosetting resin composition.
- electroconductive fillers such as silver powder and copper powder, can be used.
- thermosetting resin composition of the present invention various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be added as necessary.
- thermosetting resin composition of the present invention can be obtained by uniformly mixing the above-described components.
- the thermosetting resin composition of the present invention containing the active ester resin (A), the epoxy resin (B), and, if necessary, a curing accelerator according to the present invention is easily cured by a method similar to a conventionally known method. It can be a thing.
- the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.
- thermosetting resin composition of the present invention includes hard printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, semiconductor sealing materials , Conductive paste, adhesive film for build-up, resin casting material, adhesive and the like.
- hard printed wiring board materials insulating materials for electronic circuit boards, and adhesive film for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate.
- circuit boards such as hard printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulation materials for build-up boards because of their high flame resistance, high heat resistance, low thermal expansibility, and solvent solubility. It is preferable to use it for a material and a semiconductor sealing material.
- the circuit board of the present invention is manufactured by obtaining a varnish obtained by diluting a thermosetting resin composition in an organic solvent, laminating it into a plate shape, laminating it with a copper foil, and heating and pressing it.
- a varnish-like thermosetting resin composition containing the organic solvent is further blended with an organic solvent to form a varnish, and this is impregnated into a reinforcing base material.
- the reinforcing substrate examples include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, this method is first a cured product by heating the varnish-like thermosetting resin composition at a heating temperature according to the type of solvent used, preferably 50 to 170 ° C. Get a prepreg. At this time, the mass ratio of the thermosetting resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60 mass%. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and heat-pressed at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, A target circuit board can be obtained.
- thermosetting resin composition of the present invention In order to manufacture a flexible wiring board from the thermosetting resin composition of the present invention, an active ester resin (A), an epoxy resin (B), and an organic solvent are blended, and a coating machine such as a reverse roll coater or a comma coater is used. Is applied to the electrically insulating film. Subsequently, it is heated at 60 to 170 ° C. for 1 to 15 minutes using a heater to volatilize the solvent, and the adhesive composition is B-staged. Next, the metal foil is thermocompression bonded to the adhesive using a heating roll or the like. In this case, the pressure for pressure bonding is preferably 2 to 200 N / cm, and the temperature for pressure bonding is preferably 40 to 200 ° C.
- the process may be completed here. However, if complete curing is required, post-curing is preferably performed at 100 to 200 ° C. for 1 to 24 hours.
- the thickness of the adhesive composition film after final curing is preferably in the range of 5 to 100 ⁇ m.
- thermosetting resin composition of the present invention As a method for obtaining an interlayer insulating material for a buildup substrate from the thermosetting resin composition of the present invention, for example, the thermosetting resin composition appropriately blended with rubber, filler or the like is sprayed on a wiring board on which a circuit is formed. After applying using a coating method, a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness
- the plating method electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent.
- a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern.
- the through-hole portion is formed after the outermost resin insulating layer is formed.
- a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil is heat-pressed at 170 to 250 ° C. on a wiring board on which a circuit is formed, thereby forming a roughened surface and performing plating treatment. It is also possible to produce a build-up substrate by omitting the process.
- thermosetting resin composition of the present invention an active ester resin (A), an epoxy resin (B), and a compounding agent such as an inorganic filler are extruded as necessary.
- silica is usually used as the inorganic filler.
- the semiconductor encapsulant of the present invention is blended in the thermosetting resin composition by blending the inorganic filler in a proportion of 70 to 95% by mass. It becomes a stopping material.
- the composition is molded by casting or using a transfer molding machine, injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device as a molded product. The method of obtaining is mentioned.
- the method for producing an adhesive film for buildup from the thermosetting resin composition of the present invention is, for example, a multilayer print by applying the thermosetting resin composition of the present invention on a support film to form a resin composition layer.
- the method of setting it as the adhesive film for wiring boards is mentioned.
- the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and simultaneously with the circuit board lamination. It is important to exhibit fluidity (resin flow) capable of filling the via hole or through hole in the circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics.
- the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable that the resin can be filled in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.
- the method for producing the above-mentioned adhesive film is prepared by preparing the varnish-like thermosetting resin composition of the present invention, applying the varnish-like composition to the surface of the support film, and further heating.
- it can be produced by drying the organic solvent by hot air blowing or the like to form the layer ( ⁇ ) of the thermosetting resin composition.
- the thickness of the layer ( ⁇ ) to be formed is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer is preferably 10 to 100 ⁇ m.
- the said layer ((alpha)) may be protected with the protective film mentioned later.
- a protective film By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
- the above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil.
- the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.
- the thickness of the support film is not particularly limited, but is usually 10 to 150 ⁇ m, preferably 25 to 50 ⁇ m.
- the thickness of the protective film is preferably 1 to 40 ⁇ m.
- the support film described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.
- the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer ( ⁇ ) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that ⁇ ) is in direct contact with the circuit board.
- the laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.
- the lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.
- thermosetting resin composition of the present invention when using the thermosetting resin composition of the present invention as a conductive paste, for example, a method of dispersing fine conductive particles in the thermosetting resin composition to form a composition for an anisotropic conductive film, room temperature And a liquid paste resin composition for circuit connection and an anisotropic conductive adhesive.
- thermosetting resin composition of the present invention can also be used as a resist ink.
- a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are blended into the thermosetting resin composition, and a pigment, talc, and filler are further added for resist ink.
- cured material After making it into a composition, after apply
- the composition obtained by the above method may be heated in a temperature range of about 20 to 250 ° C.
- thermosetting resin composition excellent in environmental properties that exhibits high flame retardancy without using a halogen-based flame retardant it is possible to obtain a thermosetting resin composition excellent in environmental properties that exhibits high flame retardancy without using a halogen-based flame retardant.
- the excellent dielectric properties of these cured products can realize high-speed operation speed of high-frequency devices.
- the phenolic hydroxyl group-containing resin can be easily and efficiently produced by the production method of the present invention, and a molecular design corresponding to the target level of performance described above becomes possible.
- melt viscosity and softening point measurement at 180 ° C. GPC measurement, 13 C-NMR, and FD-MS spectrum were measured under the following conditions.
- GPC Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (Differential refraction diameter) Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular
- a phenol resin (A1-1) having a repeating unit as a repeating unit was obtained.
- the phenol resin (A1-1) obtained had a hydroxyl group equivalent of 228 g / equivalent, a melt viscosity at a softening point of 148 ° C. and 180 ° C. of 400 dPa ⁇ s.
- the GPC chart of the obtained phenol resin (A1-1) is shown in FIG. 1, the C 13 NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. From the C 13 NMR chart, the 77 ppm hydroxymethylene peak disappeared, and a peak indicating the formation of a methine skeleton in the vicinity of 55.3 ppm was detected.
- Production Example 2 490 g of phenol resin (A1-2) was prepared in the same manner as in Production Example 1, except that 161.2 g (1.55 mol) of phenol novolac resin was changed to 248 g (1.55 mol) of 2,7-dihydroxynaphthalene. Got.
- the obtained phenol compound (A1-2) had a hydroxyl group equivalent of 250 g / equivalent, a melt viscosity at a softening point of 140 ° C. and 180 ° C. of 300 dPa ⁇ s.
- a GPC chart of the resulting phenol resin (A1-2) is shown in FIG.
- Production Example 3 340 g of phenol resin (A1-3) was obtained in the same manner as in Production Example 1, except that 161.2 g (1.55 mol) of phenol novolac resin was changed to 259 g (1.55 mol) of phenylaralkyl resin. .
- the phenol resin (A1-3) obtained had a hydroxyl group equivalent of 232 g / equivalent, a melt viscosity at a softening point of 102 ° C. and 180 ° C. of 1.0 dPa ⁇ s.
- a GPC chart of the resulting phenol resin (A1-3) is shown in FIG.
- Comparative production example 1 A flask equipped with a thermometer, cooling tube, fractionating tube, nitrogen gas inlet tube, and stirrer was charged with 216 g (1.0 mol) of HCA and 71 g (1.0 mol) of a 42 mass% formalin aqueous solution, and the temperature was raised to 100 ° C. Warmed and allowed to react for 4 hours. The precipitated solid was then filtered off and washed with acetone to give 2- (6-oxide-6H-dibenz ⁇ c, e> ⁇ 1,2> oxa-phosphorin-6-yl) methanol (hereinafter referred to as “ODOPM”). Abbreviated.) 245 g was obtained. The melting point of the obtained ODOPM was 152 to 154 ° C.
- Comparative production example 2 An eggplant flask was charged with 144 g (1.0 mol) of phenol novolac resin, and the temperature was raised to 100 ° C. with stirring in a nitrogen stream. After raising the temperature, 230 g (1.0 mol) of ODOPM obtained in Comparative Production Example 1 was added, heated to 140 ° C. and maintained for 12 hours. The mixture was then cooled to room temperature, filtered and dried to obtain a phenol resin (A1′-1). A GPC chart of the resulting phenol resin (A1′-1) is shown in FIG.
- Comparative production example 3 A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was charged with 144 g (1.0 mol) of phenol novolac resin, 216 g (1.0 mol) of HCA, and 216 g of toluene, and 110 ° C. The solution was heated up and dissolved. Next, 122 g (1.0 mol) of p-hydroxybenzaldehyde was charged, the temperature was raised to 180 ° C., and the mixture was reacted at 180 ° C. for 8 hours. After filtration and drying, 335 g of phenol resin (A1′-2) was obtained. . The melting point of the obtained phenol resin (A1′-2) was 286 ° C. A GPC chart of the resulting phenol resin (A1′-2) is shown in FIG.
- Example 1 A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 228 g of the phenol resin (A1-1) obtained in Production Example 1 and 980 g of methyl isobutyl ketone, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 10.1 g (0.05 mol) of isophthalic acid chloride and 126 g (0.9 mol) of benzoyl chloride were charged, and the inside of the system was controlled to 60 ° C. or lower while performing a nitrogen gas purge, and a 20% sodium hydroxide aqueous solution. 240 g was added dropwise over 3 hours. Thereafter, stirring was continued for 1.0 hour under these conditions.
- the esterification rate with respect to the phenolic hydroxyl group was 100%, and the functional group equivalent calculated from the charged raw material composition was 328 g / equivalent.
- the functional group equivalent of the active ester resin (A) is a value calculated for the ester bond site present on the aromatic nucleus in the active ester resin (A).
- FIG. 8 shows a GPC chart of the obtained active ester resin (A-1)
- FIG. 9 shows an MS spectrum
- FIG. 10 shows a 13 C-NMR chart.
- the obtained active ester resin (A-1) was obtained from each of the phenol resins (A1-1).
- Example 2 Except for changing 10.1 g (0.05 mol) of isophthalic acid chloride to 30 g (0.15 mol) of isophthalic acid chloride and 126 g (0.9 mol) of benzoyl chloride to 98 g (0.7 mol) of benzoyl chloride.
- An active ester resin (A-2) was obtained in the same manner as in Example 1.
- the softening point of this active ester resin (A-2) was 157 ° C.
- the esterification rate with respect to the phenolic hydroxyl group was 100%, and the functional group equivalent calculated from the charged raw material composition was 320 g / equivalent.
- Example 3 A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 250 g of the phenol compound (A1-2) obtained in Production Example 2 and 1000 g of methyl isobutyl ketone, and the system was purged with nitrogen under reduced pressure. Dissolved. Next, 10.1 g (0.05 mol) of isophthalic acid chloride and 126 g (0.9 mol) of benzoyl chloride were charged, and then the inside of the system was controlled to 60 ° C. or lower while purging with nitrogen gas, and 20% water 240 g of an aqueous sodium oxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions.
- the esterification rate with respect to the phenolic hydroxyl group was 100%, and the functional group equivalent calculated from the charged raw material composition was 350 g / equivalent.
- the obtained active ester resin (A-3) was obtained from each of the phenol compounds (A1-2). It was confirmed that benzoyl chloride reacted with dehydrochlorination on the resin component.
- Example 4 A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 232 g of phenol resin (A1-3) obtained in Production Example 3 and 995 g of methyl isobutyl ketone, and the system was purged with nitrogen under reduced pressure. Dissolved. Next, 10.1 g (0.05 mol) of isophthalic acid chloride and 119 g (0.85 mol) of benzoyl chloride were charged, and then the inside of the system was controlled to 60 ° C. or lower while purging with nitrogen gas, and 20% hydroxylation was performed. 240 g of aqueous sodium solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions.
- the esterification rate with respect to the phenolic hydroxyl group was 95%, and the functional group equivalent calculated from the charged raw material composition was 327 g / equivalent.
- the obtained active ester resin (A-4) was obtained from each of the phenol resins (A1-3). It was confirmed that benzoyl chloride reacted with dehydrochlorination on the resin component.
- Comparative Example 1 A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 104 g of phenol resin (A1′-1) obtained in Comparative Production Example 2 and 600 g of methyl isobutyl ketone, and the system was under reduced pressure nitrogen. Replaced and dissolved. Next, 126 g (0.9 mol) of benzoyl chloride was added, and then the inside of the system was controlled to 60 ° C. or lower while purging with nitrogen gas, and 205 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed.
- Comparative Example 2 The phenol resin (A1′-2) obtained in Comparative Production Example 3 was tried to react with benzoyl chloride by the same method as in the example, but the phenol resin (A1′-2) was dissolved in methyl isobutyl ketone. The reaction product could not be obtained.
- Comparative Example 3 228 g of phenol resin (A1-1) was changed to 105 g of phenol novolac resin (“TD-2090” manufactured by DIC, hydroxyl equivalent: 105 g / eq), and 205 g of 20% aqueous sodium hydroxide solution was replaced with 189 g of 20% aqueous sodium hydroxide solution. 188 g of active ester resin (A′-2) was obtained in the same manner as in Example 1 except that The functional group equivalent calculated from the raw material composition charged was 199 grams / equivalent.
- Thermosetting Resin Composition According to the formulation shown in Table 1 below, active ester resin (A), epoxy resin (B) [phenol novolac epoxy resin (“N-770” epoxy equivalent by DIC Corporation: 183 g / eq) )], 0.05 phr of a curing catalyst (dimethylaminopyridine) is added, and methyl ethyl ketone is blended so that the non-volatile content (NV) of each composition is finally 58% by mass. I adjusted things. Next, a laminate was prepared by curing under the following conditions, and heat resistance, dielectric properties and flame retardancy were evaluated by the following methods. The results are shown in Table 1.
- ⁇ Laminate production conditions > Base material: Glass cloth “# 2116” (210 ⁇ 280 mm) manufactured by Nitto Boseki Co., Ltd. Number of plies: 6 Condition of prepreg: 160 ° C Curing conditions: 200 ° C., 40 kg / cm 2 for 1.5 hours, post-molding plate thickness: 0.8 mm
- A-1 Active ester resin (A-1) obtained in Example 1 A-2: Active ester resin (A-2) obtained in Example 2 A-3: Active ester resin (A-3) obtained in Example 3 A-4: Active ester resin (A-4) obtained in Example 4
- A′-1 Active ester resin (A′-1) obtained in Comparative Example 1 A′-2: Active ester resin obtained in Comparative Example 3 (A′-2)
- N-770 phenol novolac type epoxy resin (“N-770” manufactured by DIC Corporation, epoxy equivalent: 183 g / eq.) * 1: Maximum combustion time (seconds) in one flame contact * 2: Total burning time of 5 test pieces (seconds)
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Abstract
Description
で表される部分構造からなる群から選択される構造部位である。]
で表される構造部位(i)を有するフェノール化合物(A1x)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記構造部位(i)中に存在する水酸基がエステル結合を形成するように反応させ、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂に関する。
で表される部分構造からなる群から選択される構造部位を有するフェノール樹脂(A1y)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記フェノール樹脂(A1y)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂に関する。
からなる群から選択され、かつ、Zの少なくとも一つは前記構造式z1~z4で表される部分構造から選択される構造部位である。]
で表される部分構造からなる群から選択される構造部位(ii)を有するフェノール樹脂(A1z)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記フェノール樹脂(A1z)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂に関する。
本発明の製造方法は、前記した通り、アルコキシ基を芳香核上の置換基として有する芳香族アルデヒド(a1)と、P-H基又はP-OH基を分子構造中に有する有機リン化合物(a2)とを反応させて得られるリン原子含有化合物(i)を、更に、フェノール物質(a3)と反応させてリン原子含有フェノール物質(A1)を得、これと、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記フェノール物質(A1)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させることを特徴とするものである。
で表される化合物が挙げられる。ここで、R1、R2、R3、R4を構成する炭素原子数1~5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、t-ブチル基、n-ペンチル基が挙げられる。
のいずれか一つで表されるものが挙げられる。
で表される部分構造からなる群から選択される構造部位である。]
で表される構造部位(i)を有するフェノール化合物(A1x)や、
で表される部分構造からなる群から選択される構造部位を有するフェノール樹脂(A1y)、
からなる群から選択され、かつ、Zの少なくとも一つは前記構造式z1~z4で表される部分構造から選択される構造部位である。]
で表される部分構造からなる群から選択される構造部位(ii)を有するフェノール樹脂(A1z)等が挙げられる。
で表される部分構造からなる群から選択される構造部位である。]
で表される構造部位(i)を有するフェノール化合物(A1x)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記構造部位(i)中に存在する水酸基がエステル結合を形成するように反応させ、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂(Ax-1)や、
で表される部分構造からなる群から選択される構造部位を有するフェノール樹脂(A1y)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記フェノール樹脂(A1y)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂(Ay-1)、
(上記構造式z1~z4中、R1、R2、R3、R4は、それぞれ独立的に、水素原子、炭素原子数1~5のアルキル基、塩素原子、臭素原子、フェニル基、アラルキル基を表し、R5は水素原子又は炭素原子数1~5のアルキル基を表し、Rは炭素原子1~4のアルキル基を表し、nは芳香核上の置換基ORの数であり1~3である。)
からなる群から選択され、かつ、Zの少なくとも一つは前記構造式z1~z4で表される部分構造から選択される構造部位である。]
で表される部分構造からなる群から選択される構造部位(ii)を有するフェノール樹脂(A1z)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記フェノール樹脂(A1z)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された脂構造を有することを特徴とする新規活性エステル樹脂(Az-1)等が挙げられる。
(上記構造式z1~z4中、R1、R2、R3、R4は、それぞれ独立的に、水素原子、炭素原子数1~5のアルキル基、塩素原子、臭素原子、フェニル基、アラルキル基を表し、R5は水素原子又は炭素原子数1~5のアルキル基を表し、Rは炭素原子1~4のアルキル基を表し、nは芳香核上の置換基ORの数であり1~3である。)
で表される部分構造からなる群から選択される構造部位である。]
で表される構造部位(i)を有するフェノール化合物(A1x)が有する水酸基の一方と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、エステル結合を形成するように反応させて、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有し、かつ、前記構造部位(i)中に存在する水酸基のもう一方と、芳香族モノカルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物(A3)とを、エステル結合を形成するように反応させて得られる樹脂構造を有する活性エステル樹脂(Ax-2)や、
で表される部分構造からなる群から選択される構造部位を有するフェノール樹脂(A1y)が有する水酸基の一部と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、エステル結合を形成するように反応させ、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有し、かつ、前記フェノール樹脂(A1y)が有する他の水酸基の一部乃至全部と、芳香族カルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物(A3)とを、エステル結合を形成するように反応させて得られる樹脂構造を有する新規活性エステル樹脂(Ay-2)、
からなる群から選択され、かつ、Zの少なくとも一つは前記構造式z1~z4で表される部分構造から選択される構造部位である。]
で表される部分構造からなる群から選択される構造部位(ii)を有するフェノール樹脂(A1z)水酸基の一部と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライドとを、エステル結合を形成するように反応させ、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有し、かつ、前記フェノール樹脂が有する他の水酸基の一部乃至全部と、芳香族カルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物とを、エステル結合を形成するように反応させて得られる樹脂構造を有する活性エステル樹脂(Az-2)等が挙げられる。
2)軟化点測定法:JIS K7234に準拠した。
3)GPC:
測定装置 :東ソー株式会社製「HLC-8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折径)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
4)13C-NMR:日本電子株式会社製「NMR GSX270」により測定した。
5)FD-MS :日本電子株式会社製 二重収束型質量分析装置「AX505H(FD505H)」により測定した。
温度計、冷却管、分留管、撹拌器を取り付けたフラスコに、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド以下、「HCA」と略記する)を124g(0.59モル)、p-アニスアルデヒド78.7g(0.59モル)、フェノールノボラック樹脂161.2g(1.55モル)を仕込み、90℃の温度条件下、窒素を吹き込みながら撹拌した。その後、140℃に昇温して4時間攪拌した後、160℃に昇温して4時間、更に180℃に加熱して2時間撹拌した。その後、水を加熱減圧下で除去し、下記構造単位A及び構造単位B
フェノールノボラック樹脂161.2g(1.55モル)を、2,7-ジヒドロキシナフタレン248g(1.55モル)に変えた以外は、製造例1と同様の方法により、フェノール樹脂(A1-2)490gを得た。得られたフェノール化合物(A1-2)の水酸基当量は250グラム/当量、軟化点140℃、180℃での溶融粘度は300dPa・sであった。得られたフェノール樹脂(A1-2)のGPCチャートを図4に示す。
フェノールノボラック樹脂161.2g(1.55モル)を、フェニルアラルキル樹脂259g(1.55モル)に変えた以外は、製造例1と同様の方法により、フェノール樹脂(A1-3)340gを得た。得られたフェノール樹脂(A1-3)の水酸基当量は232グラム/当量、軟化点102℃、180℃での溶融粘度は1.0dPa・sであった。得られたフェノール樹脂(A1-3)のGPCチャートを図5に示す。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、HCA216g(1.0モル)、42質量%ホルマリン水溶液71g(1.0モル)を仕込み、100℃まで昇温し、4時間反応させた。次いで析出した固体をろ別し、アセトンで洗浄して2-(6-オキシド-6H-ジベンズ<c,e><1,2>オキサ-ホスフォリン-6-イル)メタノール(以下、「ODOPM」と略記する。)245gを得た。得られたODOPMの融点は152~154℃であった。
ナスフラスコに、フェノールノボラック樹脂144g(1.0モル)を仕込み、窒素気流下、攪拌しながら100℃に昇温した。昇温後、比較製造例1で得たODOPM230g(1.0モル)を添加し、140℃に加熱して12時間維持した。次いで、その混合物を室温まで冷却し、ろ過後に乾燥して、フェノール樹脂(A1’-1)を得た。得られたフェノール樹脂(A1’-1)のGPCチャートを図6に示す。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、フェノールノボラック樹脂144g(1.0モル)、HCA216g(1.0モル)、及びトルエン216gを仕込み、110℃まで昇温して加熱溶解させた。次いで、p-ヒドロキシベンズアルデヒド122g(1.0モル)を仕込み、180℃まで昇温し180℃で8時間反応させた後、ろ過、乾燥を経て、フェノール樹脂(A1’-2)を335g得た。得られたフェノール樹脂(A1’-2)の融点は286℃であった。得られたフェノール樹脂(A1’-2)のGPCチャートを図7に示す。
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに、前記製造例1で得たフェノール樹脂(A1-1)228gとメチルイソブチルケトン980gを仕込み、系内を減圧窒素置換し溶解させた。次いで、イソフタル酸クロライド10.1g(0.05モル)および塩化ベンゾイル126g(0.9モル)を仕込み、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液240gを3時間かけて滴下した。その後、この条件下で1.0時間撹拌を続けた。反応終了後、静置分液して水層を取り除いた。更に反応物が溶解しているメチルイソブチルケトン相に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のPHが7になるまでこの操作を繰り返した。デカンタ脱水で水分を除去した後、減圧脱水でメチルイソブチルケトンを除去し、活性エステル樹脂(A-1)を得た。この活性エステル樹脂(A-1)の軟化点は140℃であった。また、フェノール性水酸基に対するエステル化率は100%、仕込んだ原料組成より計算される官能基当量は328グラム/当量であった。ここで、活性エステル樹脂(A)の官能基当量は、活性エステル樹脂(A)中、芳香核上に存在するエステル結合部位について計算した値である。
得られた活性エステル樹脂(A-1)のGPCチャートを図8に、MSスペクトルを図9に、13C-NMRチャートを図10に示す。製造例1で得たフェノール樹脂(A1-1)と比較して、そのMSスペクトルの推移から、得られた活性エステル樹脂(A-1)は、フェノール樹脂(A1-1)に含まれるそれぞれの樹脂成分にイソフタル酸クロライド及び塩化ベンゾイルが脱塩酸を伴い反応したものであることが確認された。また、得られた活性エステル(A-1)の13C-NMRには、エステル基由来のカルボニルの炭素の存在を示すピークが165ppm確認に確認された。
イソフタル酸クロライド10.1g(0.05モル)をイソフタル酸クロライド30g(0.15モル)に、塩化ベンゾイル126g(0.9モル)を、塩化ベンゾイル98g(0.7モル)に変えた以外は実施例1と同様の方法により活性エステル樹脂(A-2)を得た。この活性エステル樹脂(A-2)の軟化点は157℃であった。また、フェノール性水酸基に対するエステル化率は100%、仕込んだ原料組成より計算される官能基当量は320グラム/当量であった。
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに、製造例2で得たフェノール化合物(A1-2)250gとメチルイソブチルケトン1000gを仕込み、系内を減圧窒素置換し溶解させた。次いで、イソフタル酸クロライド10.1g(0.05モル)、及び塩化ベンゾイル126g(0.9モル)を仕込み、その後、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液240gを3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているメチルイソブチルケトン相に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のPHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去した後、減圧脱水でメチルイソブチルケトンを除去し、活性エステル樹脂(A-3)を得た。この活性エステル樹脂(A-3)の軟化点は143℃であった。また、フェノール性水酸基に対するエステル化率は100%、仕込んだ原料組成より計算される官能基当量は350グラム/当量であった。製造例2で得たフェノール化合物(A1-2)と比較して、そのMSスペクトルの推移から、得られた活性エステル樹脂(A-3)は、フェノール化合物(A1-2)に含まれるそれぞれの樹脂成分に塩化ベンゾイルが脱塩酸を伴い反応したものであることが確認された。
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに、製造例3で得たフェノール樹脂(A1-3)232gとメチルイソブチルケトン995gを仕込み、系内を減圧窒素置換し溶解させた。次いで、イソフタル酸クロライド10.1g(0.05モル)、及び塩化ベンゾイル119g(0.85モル)を仕込みその後、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液240gを3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているメチルイソブチルケトン相に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のPHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去した後、減圧脱水でメチルイソブチルケトンを除去し、活性エステル樹脂(A-4)を得た。この活性エステル樹脂(A-4)の軟化点は100℃であった。また、フェノール性水酸基に対するエステル化率は95%、仕込んだ原料組成より計算される官能基当量は327グラム/当量であった。製造例3で得たフェノール樹脂(A1-3)と比較して、そのMSスペクトルの推移から、得られた活性エステル樹脂(A-4)は、フェノール樹脂(A1-3)に含まれるそれぞれの樹脂成分に塩化ベンゾイルが脱塩酸を伴い反応したものであることが確認された。
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに、比較製造例2で得たフェノール樹脂(A1’-1)104gとメチルイソブチルケトン600gを仕込み、系内を減圧窒素置換し溶解させた。次いで、塩化ベンゾイル126g(0.9モル)を仕込みその後、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液205gを3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているメチルイソブチルケトン相に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のPHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去した後、減圧脱水でメチルイソブチルケトンを除去し、活性エステル樹脂(A’-1)を得た。この活性エステル樹脂(A’-1)の軟化点は100℃であった。また、フェノール性水酸基に対するエステル化率は100%、仕込んだ原料組成より計算される官能基当量は197グラム/当量であった。比較製造例2で得たフェノール樹脂(A1’-1)と比較して、そのMSスペクトルの推移から、得られた活性エステル樹脂(A’-1)は、フェノール樹脂(A1’-1)に含まれるそれぞれの樹脂成分に塩化ベンゾイルが脱塩酸を伴い反応したものであることが確認された。
比較製造例3で得たフェノール樹脂(A1’-2)について、実施例と同様の方法により塩化ベンゾイルとの反応を行おうとしたが、フェノール樹脂(A1’-2)がメチルイソブチルケトンに溶解せず、反応物を得る事ができなかった。
フェノール樹脂(A1-1)228gを、フェノールノボラック樹脂(DIC社製「TD-2090」、水酸基当量:105g/eq)105gに変え、20%水酸化ナトリウム水溶液205gを、20%水酸化ナトリウム水溶液189gに変えた以外は実施例1と同様の方法により、活性エステル樹脂(A’-2)188gを得た。仕込んだ原料組成より計算される官能基当量は199グラム/当量であった。
下記、表1記載の配合に従い、活性エステル樹脂(A)、エポキシ樹脂(B)[フェノールノボラック型エポキシ樹脂(DIC社製「N-770」エポキシ当量:183g/eq)]、硬化触媒(ジメチルアミノピリジン)0.05phrを加え、最終的に各組成物の不揮発分(N.V.)が58質量%となるようにメチルエチルケトンを配合して、熱硬化性樹脂組成物を調整した。
次いで、下記の如き条件で硬化させて積層板を試作し、下記の方法で耐熱性、誘電特性及び難燃性を評価した。結果を表1に示す。
基材:日東紡績株式会社製 ガラスクロス「#2116」(210×280mm)
プライ数:6 プリプレグ化条件:160℃
硬化条件:200℃、40kg/cm2で1.5時間、成型後板厚:0.8mm
粘弾性測定装置(DMA:レオメトリック社製固体粘弾性測定装置RSAII、レクタンギュラーテンション法;周波数1Hz、昇温速度3℃/min)を用いて、弾性率変化が最大となる(tanδ変化率が最も大きい)温度をガラス転移温度として評価した。
T288:試験法はIPC TM650に準拠し評価した。
JIS-C-6481に準拠し、アジレント・テクノロジー株式会社製ネットワークアナライザ「E8362C」を用い空洞共振法にて、絶乾後23℃、湿度50%の室内に24時間保管した後の試験片の1GHzでの誘電率および誘電正接を測定した。
UL-94試験法に準拠し、厚さ0.8mmの試験片5本用いて燃焼試験を行った。
A-1:実施例1で得られた活性エステル樹脂(A-1)
A-2:実施例2で得られた活性エステル樹脂(A-2)
A-3:実施例3で得られた活性エステル樹脂(A-3)
A-4:実施例4で得られた活性エステル樹脂(A-4)
A’-1:比較例1で得られた活性エステル樹脂(A’-1)
A’-2:比較例3で得られた活性エステル樹脂(A’-2)
N-770:フェノールノボラック型エポキシ樹脂(DIC(株)製「N-770」、エポキシ当量:183g/eq.)
*1:1回の接炎における最大燃焼時間(秒)
*2:試験片5本の合計燃焼時間(秒)
Claims (21)
- アルコキシ基を芳香核上の置換基として有する芳香族アルデヒド(a1)と、P-H基又はP-OH基を分子構造中に有する有機リン化合物(a2)とを反応させて得られるリン原子含有化合物(i)を、更に、フェノール物質(a3)と反応させてリン原子含有フェノール物質(A1)を得、次いで、得られたリン原子含有フェノール物質(A1)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記フェノール物質(A1)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させることを特徴とする活性エステル樹脂の製造方法。
- 前記リン原子含有フェノール物質(A1)が有する水酸基の一部を、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とエステル結合を形成するように反応させ、かつ、前記リン原子含有フェノール物質(A1)が有する他の水酸基の一部乃至全部を、芳香族モノカルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物(A3)とエステル結合を形成するように反応させることを特徴とする活性エステル樹脂の製造方法。
- 前記芳香族アルデヒド(a1)が、該芳香族アルデヒド(a1)中のアルコキシ基としてメトキシ基又はエトキシ基を有するものである請求項1記載の製造方法。
- 前記フェノール物質(a3)が、2価フェノール、又は多官能型フェノール樹脂である請求項1記載の製造方法。
- 前記多官能型フェノール樹脂が、ノボラック型フェノール樹脂又はアラルキル型フェノール樹脂である請求項5記載の製造方法。
- 前記2価フェノールが、ジヒドロキシナフタレンである請求項5記載の製造方法。
- 請求項1~7の何れか1つに記載の製造方法によって得られた分子構造を有することを特徴とする新規活性エステル樹脂。
- 下記構造式(I)
で表される構造部位(i)を有するリン原子含有フェノール化合物(A1x)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記構造部位(i)中に存在する水酸基がエステル結合を形成するように反応させ、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂。 - 前記構造式(I)中のFcが水酸基であり、前記構造部位(i)中に存在する水酸基の一方と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、エステル結合を形成するように反応させ、2つの構造部位(i)が前記(A2)のエステル残基を介して結節された樹脂構造を有し、かつ、前記構造部位(i)中に存在する水酸基のもう一方と、芳香族モノカルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物(A3)とを、エステル結合を形成するように反応させて得られる樹脂構造を有する請求項9記載の活性エステル樹脂。
- ノボラック型フェノール樹脂構造を有し、かつ、その芳香核上の置換基として、下記構造式z1~z4
で表される部分構造からなる群から選択される構造部位を有するリン原子含有フェノール樹脂(A1y)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記リン原子含有フェノール樹脂(A1y)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂。 - 前記活性エステル樹脂が、前記リン原子含有フェノール樹脂(A1y)が有する水酸基の一部と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、エステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有し、かつ、前記フェノール樹脂(A1y)が有する他の水酸基の一部乃至全部と、芳香族モノカルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物(A3)とを、エステル結合を形成するように反応させて得られる樹脂構造を有するものである請求項11記載の活性エステル樹脂。
- 下記構造式(II)
(上記構造式z1~z4中、R1、R2、R3、R4は、それぞれ独立的に、水素原子、炭素原子数1~5のアルキル基、塩素原子、臭素原子、フェニル基、アラルキル基を表し、R5は水素原子又は炭素原子数1~5のアルキル基を表し、Rは炭素原子1~4のアルキル基を表し、nは芳香核上の置換基ORの数であり1~3である。)からなる群から選択され、かつ、Zの少なくとも一つは前記構造式z1~z4で表される部分構造から選択される構造部位である。]
で表される部分構造からなる群から選択される構造部位(ii)を有するリン原子含有フェノール樹脂(A1z)と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、前記リン原子含有フェノール樹脂(A1z)が有する水酸基の一部乃至全部がエステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有することを特徴とする新規活性エステル樹脂。 - 前記活性エステル樹脂が、前記リン原子含有フェノール樹脂(A1z)が有する水酸基の一部と、芳香族ジカルボン酸、その酸無水物若しくは芳香族ジカルボン酸のジハライド、又は炭素原子数2~6の飽和ジカルボン酸、その酸無水物、若しくは炭素原子数2~6の飽和ジカルボン酸のジハライド(A2)とを、エステル結合を形成するように反応させ、2つの水酸基が前記(A2)のエステル残基を介して結節された樹脂構造を有し、かつ、前記フェノール樹脂(A1z)が有する他の水酸基の一部乃至全部と、芳香族モノカルボン酸若しくはそのハライド、又は炭素原子数2~6の飽和脂肪酸、そのハライド若しくは前記飽和脂肪酸の酸無水物(A3)とを、エステル結合を形成するように反応させて得られる樹脂構造を有するものである請求項13記載の活性エステル樹脂。
- 活性エステル樹脂(A)とエポキシ樹脂(B)とを必須成分とする硬化性樹脂組成物であって、前記活性エステル樹脂(A)が、請求項4~14のいずれか一つに記載の活性エステル樹脂であることを特徴とする熱硬化性樹脂組成物。
- 前記活性エステル樹脂(A)と、前記エポキシ樹脂(B)との配合比率が、エポキシ樹脂(B)中のエポキシ基の合計1当量に対して、活性エステル樹脂(A)中の水酸基と、芳香核上に存在するエステル結合部位との合計が0.7~1.5当量となる割合である請求項15記載の硬化性樹脂組成物。
- 請求項15記載の熱硬化性樹脂組成物を硬化させてなる硬化物。
- 請求項15記載の熱硬化性樹脂組成物における前記活性エステル樹脂(A)及び前記エポキシ樹脂(B)に加え、更に無機質充填材(C)を組成物中70~95質量%となる割合で含有する熱硬化性樹脂組成物からなることを特徴とする半導体封止材料。
- 請求項15記載の熱硬化性樹脂組成物を有機溶剤(D)に希釈したものを補強基材に含浸し、得られる含浸基材を半硬化させることによって得られるプリプレグ。
- 請求項15記載の熱硬化性樹脂組成物を有機溶剤に希釈したワニスを得、これを板状に賦形したものと銅箔とを加熱加圧成型することにより得られる回路基板。
- 請求項15記載の熱硬化性樹脂組成物を有機溶剤に希釈したものを基材フィルム上に塗布し、乾燥させることを特徴とするビルドアップフィルム。
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WO2015188377A1 (zh) * | 2014-06-13 | 2015-12-17 | 广东生益科技股份有限公司 | 一种苯氧基环三磷腈活性酯、无卤树脂组合物及其用途 |
WO2019124062A1 (ja) * | 2017-12-21 | 2019-06-27 | パナソニックIpマネジメント株式会社 | プリプレグ、基板、金属張積層板、半導体パッケージ及びプリント回路板 |
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