JP5228328B2 - Low melt viscosity phenol novolac resin, process for producing the same, and cured epoxy resin using the same - Google Patents
Low melt viscosity phenol novolac resin, process for producing the same, and cured epoxy resin using the same Download PDFInfo
- Publication number
- JP5228328B2 JP5228328B2 JP2007022723A JP2007022723A JP5228328B2 JP 5228328 B2 JP5228328 B2 JP 5228328B2 JP 2007022723 A JP2007022723 A JP 2007022723A JP 2007022723 A JP2007022723 A JP 2007022723A JP 5228328 B2 JP5228328 B2 JP 5228328B2
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- Prior art keywords
- phenol
- melt viscosity
- formaldehyde
- formula
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 83
- 239000003822 epoxy resin Substances 0.000 title claims description 55
- 229920000647 polyepoxide Polymers 0.000 title claims description 55
- 229920003986 novolac Polymers 0.000 title claims description 49
- 238000000034 method Methods 0.000 title description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 117
- -1 phenol compound Chemical class 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000000155 melt Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 65
- 239000005011 phenolic resin Substances 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000003795 chemical substances by application Substances 0.000 description 23
- 150000002989 phenols Chemical class 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000006482 condensation reaction Methods 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000006839 xylylene group Chemical group 0.000 description 7
- 125000004849 alkoxymethyl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 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 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910002026 crystalline silica Inorganic materials 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- FYFNKGINBOBCKR-UHFFFAOYSA-N 1,4-bis(ethoxymethyl)benzene Chemical compound CCOCC1=CC=C(COCC)C=C1 FYFNKGINBOBCKR-UHFFFAOYSA-N 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- UQWJRHXJJRTQCX-UHFFFAOYSA-N 1-(ethoxymethyl)-4-[4-(ethoxymethyl)phenyl]benzene Chemical group C1=CC(COCC)=CC=C1C1=CC=C(COCC)C=C1 UQWJRHXJJRTQCX-UHFFFAOYSA-N 0.000 description 1
- UIMJANTUJQGSEX-UHFFFAOYSA-N 2,2'-biphenyldimethanol Chemical group OCC1=CC=CC=C1C1=CC=CC=C1CO UIMJANTUJQGSEX-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- DDIFJMOHITYIGU-UHFFFAOYSA-N 3-[4-[4-(3-hydroxypropyl)phenyl]phenyl]propan-1-ol Chemical group C1=CC(CCCO)=CC=C1C1=CC=C(CCCO)C=C1 DDIFJMOHITYIGU-UHFFFAOYSA-N 0.000 description 1
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical compound CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- QEYKYHBKQHGNPQ-UHFFFAOYSA-N [4-[2-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=CC=C1CO QEYKYHBKQHGNPQ-UHFFFAOYSA-N 0.000 description 1
- SFHGONLFTNHXDX-UHFFFAOYSA-N [4-[4-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=C(CO)C=C1 SFHGONLFTNHXDX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
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- 150000002460 imidazoles Chemical class 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は、各種バインダー、コーティング材、積層材、成形材料等に有用な低溶融粘度フェノールノボラック樹脂、その製造方法およびそれを用いたエポキシ硬化物に関する。特に半導体封止用、プリント基板絶縁用、電子回路銅張積層板あるいは航空機用構造材料に好ましく適用できる繊維強化複合材料などのエポキシ硬化剤に好適な、低溶融粘度、高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化及び難燃性を兼ね備えた低溶融粘度フェノールノボラック樹脂及びその製造方法に関する。 The present invention relates to a low melt viscosity phenol novolak resin useful for various binders, coating materials, laminated materials, molding materials, and the like, a production method thereof, and an epoxy cured product using the same. Low melt viscosity, high glass transition temperature, low moisture absorption, particularly suitable for epoxy curing agents such as semiconductor sealing, printed circuit board insulation, electronic circuit copper-clad laminates, or fiber reinforced composite materials that can be preferably applied to aircraft structural materials The present invention relates to a low melt viscosity phenol novolak resin that has both high performance, high adhesion, heat resistance, rapid curing and flame retardancy, and a method for producing the same.
電子材料、特に半導体封止用、プリント基板絶縁用などのエポキシ樹脂硬化剤として、各種のフェノール系重合体、例えばフェノールノボラック型樹脂、フェノールアラルキル樹脂等が使用されている。しかし近年、半導体パッケージの小型・薄型化、多ピン化、高密度実装化に伴い、より高性能な樹脂が求められている。
さらに近年電気・電子分材料分野においてはその発展に伴い、低粘度化をはじめ耐熱性、耐湿性、密着性等の一層の向上が求められている。これらの要求に対しエポキシ樹脂組成物について多くの提案がなされてはいるが、未だ充分とはいえない。特に電子回路基板材料において、実装ハンダ処置時のクラックなど吸湿が原因の不良が大きな問題であり、低吸湿性材料への要求が強い。低吸湿率化のためにはフィラーの高充填化が必要であり、この高充填化には、樹脂の低粘度化が必要である。一方、比強度、比弾性率に優れる炭素繊維を強化繊維に、該炭素繊維と濡れ性、接着性が良好なエポキシ樹脂をマトリックス樹脂に使用する炭素繊維強化複合材料においても、低粘度で、耐熱性を有する樹脂が求められている。
Various phenolic polymers, such as phenol novolac resins and phenol aralkyl resins, are used as an epoxy resin curing agent for electronic materials, particularly for semiconductor encapsulation and printed circuit board insulation. However, in recent years, with the miniaturization and thinning of semiconductor packages, the increase in the number of pins, and the high density mounting, higher performance resins are required.
Further, in recent years, with the development in the field of electrical and electronic materials, further improvement in heat resistance, moisture resistance, adhesion, etc., as well as lowering of viscosity, has been demanded. Many proposals for epoxy resin compositions have been made to meet these requirements, but they are still not sufficient. In particular, in electronic circuit board materials, defects due to moisture absorption such as cracks during mounting solder treatment are a major problem, and there is a strong demand for low moisture absorption materials. In order to reduce the moisture absorption rate, it is necessary to increase the filling of the filler. To increase the filling, it is necessary to reduce the viscosity of the resin. On the other hand, carbon fiber reinforced composite materials that use carbon fibers with excellent specific strength and specific elastic modulus as reinforcing fibers and epoxy resins with good wettability and adhesion with the carbon fibers as matrix resins also have low viscosity and heat resistance. Resins having properties are demanded.
ＢＧＡ（Ｂａｌｌ ＧｒｉｄＡｒｒａｙ）などの片面封止パッケージに用いた場合、パッケージの反りが小さいという優れた性能を有する。しかし最近の半導体パッケージでは、例えばＢＧＡの場合、さらなるファインピッチ化や一括封止タイプになり、反りが小さいことの他に流動性が高いこと、基板表面との密着性が良いことなどが求められている。また低溶融粘度であれば流動性や密着性が向上し、フィラーも多く配合できるので半田耐熱性や耐水性の面でも有利になる。即ちこれら封止材への要求特性を満たすために、低溶融粘度、高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化、及び難燃性を兼ね備えた低溶融粘度フェノールノボラック樹脂の出現が強く望まれている。 When used in a single-side sealed package such as BGA (Ball GridArray), it has an excellent performance that the warpage of the package is small. However, in recent semiconductor packages, for example, in the case of BGA, it becomes a finer pitch and a package type, and it is required to have high fluidity and good adhesion to the substrate surface in addition to small warpage. ing. Further, if the melt viscosity is low, the fluidity and adhesion are improved, and a large amount of filler can be added, which is advantageous in terms of solder heat resistance and water resistance. That is, in order to satisfy the required properties for these encapsulants, a low melt viscosity phenol novolac resin that combines low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, fast curing, and flame retardancy. The appearance of is strongly desired.
またビルドアップ基板の層間絶縁材にも、耐水性に優れ、高ガラス転移温度で接着性のよいエポキシ樹脂組成物が望まれており、これを達成するために、元々耐水性や保存安定性に優れたフェノール系硬化剤で、低溶融粘度、高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化、及び難燃性を兼ね備えたものが望まれている。 In addition, epoxy resin compositions with excellent water resistance and high adhesiveness at high glass transition temperatures are also desired for interlayer insulation materials for build-up substrates. To achieve this, water resistance and storage stability are inherently improved. An excellent phenolic curing agent having low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid curing, and flame retardancy is desired.
電子材料用樹脂材料にはエポキシ樹脂が多く用いられ、そのエポキシ樹脂の硬化剤としては各種のフェノ−ルノボラック縮合体、アミン類、酸無水物が使用される。特に半導体（ＩＣ）封止用エポキシ樹脂の硬化剤としては、耐熱性、信頼性の面からフェノ−ル性ノボラック縮合体が主に用いられる。近年、ＩＣの高集積化、パッケ−ジの小型、薄型化、また表面実装方式の適用が進み、その封止用材料には耐熱衝撃性および表面実装作業時のソルダリング耐熱性を一層向上させることが要求されている。ソルダリング耐熱性を左右する大きな要因として、封止用樹脂材料の吸湿性が挙げられる。すなわち、吸湿した封止用材料は表面実装作業時の高温下で水分の気化による内圧が発生し、内部剥離やパッケ−ジクラックが発生してソルダリング耐熱性が劣る。したがって、エポキシ樹脂硬化剤として使用されるフェノ−ル性ノボラック縮合体は低吸湿性であることが特に要求される。 Epoxy resins are often used as resin materials for electronic materials, and various phenol novolac condensates, amines, and acid anhydrides are used as curing agents for the epoxy resins. In particular, as a curing agent for epoxy resin for semiconductor (IC) sealing, phenolic novolak condensates are mainly used in terms of heat resistance and reliability. In recent years, ICs have been highly integrated, packages have become smaller and thinner, and surface mounting methods have been applied, and the sealing material has further improved thermal shock resistance and soldering heat resistance during surface mounting operations. It is requested. A major factor affecting the soldering heat resistance is the hygroscopicity of the sealing resin material. That is, the moisture-absorbing sealing material generates an internal pressure due to vaporization of water at a high temperature during the surface mounting operation, causes internal peeling and package cracks, and has poor soldering heat resistance. Therefore, the phenolic novolak condensate used as an epoxy resin curing agent is particularly required to have low hygroscopicity.
プリント基板絶縁用のエポキシ樹脂ワニスは、プリプレグ製造時の取り扱い性を考慮すると、その粘度が低い方が好ましく、有機溶剤の使用量も少ない程よい。しかしながら、この分野で使用されるこれまでのエポキシ樹脂溶液の粘度は、十分に満足できるほど低くすることができないか、あるいは有機溶剤の使用量を少なくすることが難しいという問題点がある。 The epoxy resin varnish for insulating a printed circuit board preferably has a lower viscosity in view of handling at the time of prepreg production, and the smaller the amount of organic solvent used, the better. However, there is a problem that the viscosity of the epoxy resin solution used so far in this field cannot be sufficiently lowered or it is difficult to reduce the amount of the organic solvent used.
一方、封止用材料の吸湿性を低下させる方法として、封止用樹脂材料に充填される非吸湿性のシリカなどの充填材を増量する方法がある。この場合、ベ−スの樹脂材料の粘度が高いと充填材の高充填性が損なわれるので、硬化剤として用いるフェノール性ノボラック縮合体の粘度が低いことが望まれる。また、封止用材料には耐熱性、高強度、強靱性、難燃性、接着強さなどが求められる。封止用エポキシ樹脂の硬化剤としてフェノ−ルノボラック縮合体を用いた従来の封止用樹脂材料では、吸湿性が比較的高く、また他の物性の面からも十分に満足できるものではなかった。 On the other hand, as a method of reducing the hygroscopicity of the sealing material, there is a method of increasing the amount of filler such as non-hygroscopic silica filled in the sealing resin material. In this case, if the viscosity of the base resin material is high, the high filling property of the filler is impaired. Therefore, it is desired that the phenolic novolak condensate used as the curing agent has a low viscosity. In addition, the sealing material is required to have heat resistance, high strength, toughness, flame retardancy, adhesive strength, and the like. Conventional sealing resin materials using a phenol novolak condensate as a curing agent for the sealing epoxy resin have a relatively high hygroscopicity and are not sufficiently satisfactory from the viewpoint of other physical properties.
そこで、低吸湿性、耐熱性、接着性、難燃性などを向上させるために各種のフェノ−ルノボラック縮合体が提案されている。例えば、ｏ−クレゾ−ルなどのアルキルフェノ−ル類を用いたノボラック縮合体、また、１−ナフト−ルなどのナフト−ル類を用いたノボラック縮合体がある（例えば、特許文献１から３参照）。また、フェノ−ルの縮合剤としてジ（ヒドロキシプロピル）ビフェニルを用いたフェノ−ル性化合物が開示されており（特許文献４参照）、ビス（メトキシメチル）ビフェニル混合物を用いたフェノ−ルノボラック縮合体を提案している（特許文献５参照）。さらに、ホルムアルデヒドを有効に利用した電子部品封止用エポキシ樹脂成型材料（特許文献６参照）が開示されている。
しかし、さらに一層の吸湿性、耐熱性、接着特性、難燃性、速硬化、などが向上した材料が望まれている。
Accordingly, various phenol novolak condensates have been proposed in order to improve low moisture absorption, heat resistance, adhesion, flame retardancy, and the like. For example, there are novolak condensates using alkylphenols such as o-cresol and novolak condensates using naphthols such as 1-naphthol (for example, Patent Documents 1 to 3). reference). Further, a phenolic compound using di (hydroxypropyl) biphenyl as a phenol condensing agent is disclosed (see Patent Document 4), and a phenol novolak condensate using a bis (methoxymethyl) biphenyl mixture. (Refer to Patent Document 5). Furthermore, an epoxy resin molding material for electronic component sealing (see Patent Document 6) that effectively uses formaldehyde is disclosed.
However, a material having further improved hygroscopicity, heat resistance, adhesive properties, flame retardancy, rapid curing, etc. is desired.
本発明の課題は、低溶融粘度、高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化、及び難燃性などに優れ、特に電気および電子産業用、電子部品の封止用、積層板材料用のエポキシ樹脂用として好適に用いられる新規なフェノール樹脂およびこのフェノール樹脂をエポキシ化したエポキシ化ノボラック縮合体およびそれをエポキシ樹脂用硬化剤と反応して得られたエポキシ樹脂硬化物を提供することにある。 The object of the present invention is excellent in low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, fast curing, flame retardancy, etc., especially for electrical and electronic industries, for sealing electronic parts , A novel phenol resin suitably used as an epoxy resin for laminate materials, an epoxidized novolak condensate obtained by epoxidizing this phenol resin, and a cured epoxy resin obtained by reacting it with a curing agent for epoxy resin Is to provide.
しかし、低吸湿化のためＯＨ当量を上げるために、ビフェニル基の導入率を上げると、溶融粘度が上昇する。その結果、溶融粘度の上昇により流動性が悪く、そのため成形上のトラブルを引き起こす。溶融粘度を下げるために分子量を小さくしたりすると、ガラス転移温度が下がるとともに成形時の硬化性が低下する。すなわち、低吸湿性、低溶融粘度、硬化性と高ガラス転移温度の両立は原理的に難しいとされている。 However, if the introduction rate of the biphenyl group is increased in order to increase the OH equivalent to reduce moisture absorption, the melt viscosity increases. As a result, the fluidity is poor due to an increase in melt viscosity, which causes a molding trouble. When the molecular weight is decreased to lower the melt viscosity, the glass transition temperature is lowered and the curability at the time of molding is lowered. That is, it is considered that it is difficult in principle to achieve both low hygroscopicity, low melt viscosity, curability and high glass transition temperature.
本発明者らは、上記アラルキル型のフェノール樹脂の低吸湿性、高密着性、耐熱性物性を生かし、かつ溶融粘度が低いフェノール系硬化剤を得るために鋭意検討した結果、分子内にアルキレン型重合体単位と、フェノールノボラック重合体単位を共に有し、両者の重合度の比を特定範囲にすることにより、低溶融粘度で速硬化で、低吸湿性、高密着性、耐熱性の優れたフェノールノボラック樹脂が得られることを見出し本発明を完成した。 As a result of intensive investigations to obtain a phenolic curing agent that makes use of the low hygroscopicity, high adhesion, and heat-resistant physical properties of the above aralkyl type phenolic resin and has a low melt viscosity, the present inventors have found that an alkylene type in the molecule. It has both polymer units and phenol novolac polymer units, and by setting the ratio of the degree of polymerization to a specific range, it has a low melt viscosity, quick curing, low moisture absorption, high adhesion, and excellent heat resistance. The present invention was completed by finding that a phenol novolac resin can be obtained.
すなわち本発明は、下記一般式（１）で表わされ、１５０℃における溶融粘度が１００〜１０００ｍＰａ・ｓ、または、２００℃での溶融粘度が１０〜１９００ｍＰａ・ｓである低溶融粘度フェノールノボラック樹脂である。 That is, the present invention is a low melt viscosity phenol novolac resin represented by the following general formula (1) and having a melt viscosity at 150 ° C. of 100 to 1000 mPa · s or a melt viscosity at 200 ° C. of 10 to 1900 mPa · s. It is.
下記一般式（１）： The following general formula (1):
で示されるビフェニリレン基及びキシリレン基から選ばれる少なくとも１の架橋基を表し、Ｒ１、Ｒ２及びＲ３は、同一でも異なっていてもよく、それぞれ、水素又は、ヒドロキシ基又は炭素数１から６個のアルキル基であり、ｐ、ｑ及びｒは、それぞれ０〜２の整数である。）
で表わされ、ｍ／ｎは０．０４〜２０であり、１５０℃における溶融粘度が１００〜１０００ｍＰａ・ｓ、または、２００℃における溶融粘度が１０〜１９５０ｍＰａ・ｓである低溶融粘度フェノールノボラック樹脂である。
And represents at least one bridging group selected from a biphenylylene group and a xylylene group, and R 1 , R 2 and R 3 may be the same or different, and each represents hydrogen, a hydroxy group, or a carbon number of 1 to 6 It is an alkyl group, and p, q, and r are integers of 0-2, respectively. )
A low melt viscosity phenol novolac resin having a melt viscosity at 150 ° C. of 100 to 1000 mPa · s, or a melt viscosity at 200 ° C. of 10 to 1950 mPa · s. It is.
また、本発明は、フェノール類、一般式（１）のＲを構成する架橋体及びホルムアルデヒドを、酸触媒の存在下で縮合させることを特徴とする上記式（１）で示される低溶融粘度フェノールノボラック樹脂の製造方法である。 The present invention also provides a low melt viscosity phenol represented by the above formula (1), characterized in that phenols, a crosslinked product constituting R in the general formula (1) and formaldehyde are condensed in the presence of an acid catalyst. This is a method for producing a novolac resin.
さらに、本発明は、上記一般式（１）で示される低溶融粘度フェノールノボラック樹脂を含むエポキシ樹脂硬化物である。 Furthermore, this invention is an epoxy resin hardened | cured material containing the low melt viscosity phenol novolak resin shown by the said General formula (1).
本発明の低溶融粘度フェノールノボラック樹脂は、分子内に４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋基を含有するフェノール樹脂及びメチレン架橋基を含有するフェノール樹脂の重合単位を共に有し、両者の重合度の比が特定の範囲である構造としたことにより、エポキシ硬化剤に好適な、低溶融粘度、高ガラス転移温度、低吸湿性、高密着性、耐熱性、及び難燃性を兼ね備えた樹脂である。
本発明の樹脂は、ＢＧＡ等、最新の半導体封止材料に対応でき、エポキシ硬化剤としても利用できる。
The low melt viscosity phenol novolak resin of the present invention has 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4-xylylene group in the molecule, It has both polymer units of a phenol resin containing a crosslinking group such as 1,2-xylylene group or 1,3-xylylene group and a phenol resin containing a methylene crosslinking group, and the ratio of the degree of polymerization of both is in a specific range. By having such a structure, it is a resin having low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, and flame retardancy suitable for an epoxy curing agent.
The resin of the present invention can correspond to the latest semiconductor sealing materials such as BGA, and can also be used as an epoxy curing agent.
本発明の低溶融粘度フェノールノボラック樹脂は、上記一般式（１）で示されるＲがビフェニリレン架橋基及び／またはキシリレン架橋基を含有するフェノール樹脂の重合単位をトータルでｎ個、メチレン架橋基を含有するフェノールノ樹脂の重合単位をトータルでｍ個有する共重合タイプのフェノール樹脂であり、一般式（１）における各重合単位の重合度比ｍ／ｎが０．０４〜２０、好ましくは０．０５〜９、より好ましくは０．１〜６であり、かつ、１５０℃における溶融粘度が１００〜１０００ｍＰａ・ｓまたは２００℃での溶融粘度が１０〜１９００ｍＰａ・ｓのフェノール樹脂である。
好ましい範囲は、該フェノール樹脂の平均分子量（重合度：使用するフェノール類と一般式（１）のＲを構成する架橋体及びホルムアルデヒドとの合計使用量とのモル比により異なる）により異なる。
使用するフェノール類と一般式（１）のＲを構成する架橋体及びホルムアルデヒドとの合計使用量とのモル比が、１．３〜２．０倍モル未満の場合のフェノール樹脂では、２００℃での溶融粘度は１００〜１６００ｍＰａ・ｓであり、さらに好ましくは２００〜１２００ｍＰａ・ｓである。
使用するフェノール類と一般式（１）のＲを構成する架橋体及びホルムアルデヒドとの合計使用量とのモル比が、２．０以上〜３．０倍モル未満の場合のフェノール樹脂では、２００℃での溶融粘度は、１５〜５０ｍＰａ・ｓであり、さらに好ましくは２０〜４０ｍＰａ・ｓである。
使用するフェノール類と一般式（１）のＲを構成する架橋体及びホルムアルデヒドとの合計使用量とのモル比が３．０以上〜１０倍モルの場合、好ましくは３．０以上〜５倍モルの場合のフェノール樹脂では、２００℃での溶融粘度は、１０〜２０ｍＰａ・ｓであり、さらに好ましくは１０〜１５ｍＰａ・ｓである。
The low melt viscosity phenol novolak resin of the present invention contains a total of n polymerization units of a phenol resin in which R represented by the general formula (1) contains a biphenylylene crosslinkable group and / or a xylylene crosslinkable group, and a methylene crosslinkable group Copolymer type phenolic resin having a total of m polymerization units of phenolic resin, and the polymerization degree ratio m / n of each polymerization unit in the general formula (1) is 0.04 to 20, preferably 0.05. And a phenol resin having a melt viscosity at 150 ° C. of 100 to 1000 mPa · s or a melt viscosity at 200 ° C. of 10 to 1900 mPa · s.
The preferred range varies depending on the average molecular weight of the phenol resin (degree of polymerization: depending on the molar ratio between the phenols used and the total amount of the cross-linked product and formaldehyde constituting R in the general formula (1)).
In a phenol resin in which the molar ratio of the phenols used and the total amount of the cross-linked product and formaldehyde constituting R in the general formula (1) is 1.3 to 2.0 times less, at 200 ° C. Has a melt viscosity of 100 to 1600 mPa · s, more preferably 200 to 1200 mPa · s.
In the case of a phenol resin in which the molar ratio of the phenols to be used and the total amount used of the crosslinked body and formaldehyde constituting R in the general formula (1) is 2.0 or more and less than 3.0 times mole, The melt viscosity at is from 15 to 50 mPa · s, more preferably from 20 to 40 mPa · s.
When the molar ratio of the phenols used and the total amount used of the cross-linked product and formaldehyde constituting R in the general formula (1) is 3.0 to 10 times mol, preferably 3.0 to 5 times mol In the case of the phenol resin, the melt viscosity at 200 ° C. is 10 to 20 mPa · s, more preferably 10 to 15 mPa · s.
本発明の低溶融粘度フェノール樹脂は、ｍ／ｎが０．０４未満では溶融粘度を下げる効果が不十分で流動性が良くならず好ましくない。 If the m / n is less than 0.04, the low melt viscosity phenol resin of the present invention is not preferable because the effect of lowering the melt viscosity is insufficient and the fluidity is not improved.
本発明で使用するフェノール類は、一般式（１）で記載のとおり、ベンゼン環に水酸基を少なくとも１個有し、Ｒ１、Ｒ２及びＲ３は、同一でも異なっていてもよく、それぞれ水素又は、ヒドロキシ基又は炭素数１から６個のアルキル基であり、ｐ、ｑ及びｒは、それぞれ０〜２の整数からなる化合物群である。
これらのフェノール類は、単独でも２種以上を混合して用いても何ら問題はない。
具体的なフェノール類としては、例えばフェノール、クレゾール、エチルフェノール、プロピルフェノール、ブチルフェノール、ヘキシルフェノール、ノニルフェノール、キシレノール、ブチルメチルフェノール等の１価フェノールの他、カテコール、レゾルシン、ハイドロキノン等の２価フェノールも挙げられるが、特にフェノールが好ましい。
The phenols used in the present invention have at least one hydroxyl group on the benzene ring as described in the general formula (1), and R 1 , R 2 and R 3 may be the same or different, Or it is a hydroxyl group or a C1-C6 alkyl group, and p, q, and r are a compound group which consists of an integer of 0-2, respectively.
There is no problem even if these phenols are used alone or in combination of two or more.
Specific phenols include, for example, monohydric phenols such as phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, nonylphenol, xylenol, and butylmethylphenol, as well as dihydric phenols such as catechol, resorcin, and hydroquinone. Among them, phenol is particularly preferable.
本発明でメチレン架橋基を形成する化合物としては、ホルムアルデヒドが好適に挙げられる。さらにホルムアルデヒドの形態としては、特に制限はないが、ホルムアルデヒド水溶液、及びパラホルムアルデヒド、トリオキサンなど酸存在下で分解してホルムアルデヒドとなる重合物を用いることもできる。
好ましくは、取り扱いの容易なホルムアルデヒド水溶液であり、市販品の４２％ホルムアルデヒド水溶液をそのまま使用できる。
As the compound that forms a methylene crosslinking group in the present invention, formaldehyde is preferably exemplified. Furthermore, the form of formaldehyde is not particularly limited, but a formaldehyde aqueous solution and a polymer that decomposes in the presence of an acid such as paraformaldehyde and trioxane to formaldehyde can also be used.
A formaldehyde aqueous solution that is easy to handle is preferable, and a commercially available 42% formaldehyde aqueous solution can be used as it is.
本発明で使用する架橋基Ｒは、次式（２）で表される４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等があげられる。
これらの異性体においては、単独でも混合しても使用することができる。
The bridging group R used in the present invention is a 4,4′-biphenylylene group, a 2,4′-biphenylylene group, a 2,2′-biphenylylene group and / or 1,4 represented by the following formula (2). -Xylylene group, 1,2-xylylene group, 1,3-xylylene group, and the like.
These isomers can be used alone or in combination.
具体的には、４，４’−ジ（ハロゲノメチル）ビフェニル、２，４’−ジ（ハロゲノメチル）ビフェニル、２，２’−ジ（ハロゲノメチル）ビフェニル、４，４’−ジ（アルコキシメチル）ビフェニル、２，４’−ジ（アルコキシメチル）ビフェニル、２，２’−ジ（アルコキシメチル）ビフェニル、１，４−ジ（ハロゲノメチル）ベンゼン、１，４−ジ（アルコキシメチル）ベンゼン、１，２−ジ（ハロゲノメチル）ベンゼン、１，２−ジ（アルコキシメチル）ベンゼン、１，３−ジ（ハロゲノメチル）ベンゼンおよび１，３−ジ（アルコキシメチル）ベンゼンを用いることにより導かれる。
あるいは、４，４’−ジ（ヒドロキシメチル）ビフェニル、２，４’−ジ（ヒドロキシメチル）ビフェニル、２，２’−ジ（ヒドロキシメチル）ビフェニル、１，４−ジ（ヒドロキシメチル）ベンゼン、１，３−ジ（ヒドロキシメチル）ベンゼンおよび１，２−ジ（ヒドロキシメチル）ベンゼンを用いることもできる。
ここで、ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素が挙げられるが、塩素が好ましい。アルコキシル基としては、特に制限はないが、炭素数１〜６個の脂肪族アルコキシが好ましい。具体的には、メトキシおよびエトキシが挙げられる。
好ましい具体的な化合物としては、４，４’−ジ（クロロメチル）ビフェニル、４，４’−ジ（メトキシメチル）ビフェニル、４，４’−ジ（エトキシメチル）ビフェニル、１，４−ジ（クロロメチル）ベンゼン、１，４−ジ（メトキシメチル）ベンゼン及び１，４−ジ（エトキシメチル）ベンゼンが挙げられる。
これら、（１）式中のＲを構成する架橋体としては、ビフェニリレン基および／又はキシリレン基を単一でも混合して使用することも何ら問題ではない。
しかし、混合して使用する場合では、その混合比率は、ビフェニリレン基１モルに対して２０〜５０モル％でキシリレン基を使用するのが好ましい。
Specifically, 4,4′-di (halogenomethyl) biphenyl, 2,4′-di (halogenomethyl) biphenyl, 2,2′-di (halogenomethyl) biphenyl, 4,4′-di (alkoxymethyl) ) Biphenyl, 2,4′-di (alkoxymethyl) biphenyl, 2,2′-di (alkoxymethyl) biphenyl, 1,4-di (halogenomethyl) benzene, 1,4-di (alkoxymethyl) benzene, 1 , 2-di (halogenomethyl) benzene, 1,2-di (alkoxymethyl) benzene, 1,3-di (halogenomethyl) benzene and 1,3-di (alkoxymethyl) benzene.
Alternatively, 4,4′-di (hydroxymethyl) biphenyl, 2,4′-di (hydroxymethyl) biphenyl, 2,2′-di (hydroxymethyl) biphenyl, 1,4-di (hydroxymethyl) benzene, 1 , 3-Di (hydroxymethyl) benzene and 1,2-di (hydroxymethyl) benzene can also be used.
Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine, with chlorine being preferred. Although there is no restriction | limiting in particular as an alkoxyl group, A C1-C6 aliphatic alkoxy is preferable. Specific examples include methoxy and ethoxy.
Preferred specific compounds include 4,4′-di (chloromethyl) biphenyl, 4,4′-di (methoxymethyl) biphenyl, 4,4′-di (ethoxymethyl) biphenyl, 1,4-di ( Chloromethyl) benzene, 1,4-di (methoxymethyl) benzene and 1,4-di (ethoxymethyl) benzene.
As the cross-linked product constituting R in the formula (1), it is not a problem to use a single biphenylylene group and / or xylylene group in combination.
However, in the case of using a mixture, it is preferable to use the xylylene group at a mixing ratio of 20 to 50 mol% with respect to 1 mol of the biphenylylene group.
［低溶融粘度フェノール樹脂の製造］
一般式（１）で示される低溶融粘度フェノールノボラック樹脂の製造方法は、酸触媒存在下、一定量のフェノール類に対して、ｎ倍モルのＲ、即ち４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等とｍ倍モルのホルムアルデヒドを同時に添加して１段の縮合反応で行なうことができる。
この場合は（１）式中のＲを構成する架橋体及びホルムアルデヒドの合計１モルに対し、フェノールを１．３〜１０倍モル、好ましくは１．３〜５倍モルの範囲で使用すると共に、反応温度を低温（一例として１００℃前後）にてフェノール類とホルムアルデヒドの反応を優先的に行ない、主として低分子量のメチレン架橋基のフェノール樹脂を形成させ、次いで昇温または触媒を増量してメチレン架橋基フェノール樹脂、（１）式中のＲを構成する架橋体及びフェノールを反応させる方式を採用するのが好ましい。
用いる酸触媒としては、特に限定はなく、塩酸、蓚酸、硫酸、リン酸、パラトルエンスルホン酸など公知のものを単独であるいは２種以上併用して使用することができるが、硫酸、蓚酸又はパラトルエンスルホン酸が特に好ましい。
縮合反応の温度は、低温条件としては５０〜１２０℃、好ましくは８０〜１１０℃であり、昇温時での反応温度は１３０〜２３０℃、好ましくは１５０〜２００℃である。
縮合反応の時間は、反応温度や使用する触媒の種類および量により変動するが、１〜２４時間程度である。
反応圧力は、通常、常圧下にて行うが、若干の加圧下あるいは減圧下にて実施しても何ら問題はない。
（１）式中のＲを構成する架橋体とホルムアルデヒドの合計１モルに対しフェノールの使用量を１．３倍モル未満にするなど上述の反応条件を大きく逸脱した場合には高分子量で溶融粘度の高いフェノールノボラック樹脂が得られる傾向があり好ましくない。
また、フェノールの使用量を１０倍モルより多く使用すると２核体以下の低分子量成分が増加し、Ｔｇの低下、機械強度の低下が生じるなど物性を低下させ傾向が認められやはり好ましくない。また、フェノール使用量が増加しコスト高、環境負荷の面で問題となり好ましくない。
[Production of low melt viscosity phenol resin]
A method for producing a low melt viscosity phenol novolak resin represented by the general formula (1) comprises n-fold moles of R, that is, 4,4′-biphenylylene group or 2 , 4'-biphenylylene group, 2,2'-biphenylylene group and / or 1,4-xylylene group, 1,2-xylylene group, 1,3-xylylene group, etc. and m times mole of formaldehyde are added simultaneously Thus, it can be carried out by a one-stage condensation reaction.
In this case, phenol is used in a range of 1.3 to 10 times mol, preferably 1.3 to 5 times mol for a total of 1 mol of the crosslinked body constituting R in formula (1) and formaldehyde, The reaction between phenols and formaldehyde is preferentially performed at a low reaction temperature (eg, around 100 ° C. as an example) to form a phenol resin mainly of low molecular weight methylene crosslinking groups, and then the temperature is increased or the catalyst is increased to increase the methylene crosslinking. It is preferable to employ a method in which a base phenol resin, a cross-linked body constituting R in the formula (1), and phenol are reacted.
The acid catalyst to be used is not particularly limited, and known ones such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid can be used alone or in combination of two or more. Toluenesulfonic acid is particularly preferred.
The temperature of the condensation reaction is 50 to 120 ° C., preferably 80 to 110 ° C. as a low temperature condition, and the reaction temperature at the time of temperature rise is 130 to 230 ° C., preferably 150 to 200 ° C.
The time for the condensation reaction varies depending on the reaction temperature and the type and amount of the catalyst used, but is about 1 to 24 hours.
The reaction pressure is usually carried out under normal pressure, but there is no problem even if it is carried out under slight pressure or reduced pressure.
(1) In the case where the amount of phenol used is less than 1.3 times the mole of the total of 1 mol of the cross-linked product constituting R in the formula and formaldehyde, the molecular weight is high and the melt viscosity High phenol novolac resin tends to be obtained, which is not preferable.
On the other hand, if the amount of phenol used is more than 10-fold mol, low molecular weight components of 2 or less nuclei are increased, and Tg and mechanical strength tend to be lowered. In addition, the amount of phenol used is increased, which is not preferable because of high costs and environmental impact.
そのため、本発明の低溶融粘度フェノール樹脂は、フェノール類、ホルムアルデヒド、（１）式中のＲを構成する４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋体の添加順序に制限はないが、一括で同時に添加することが、経済性、生産性の観点からは望ましい。 Therefore, the low melt viscosity phenol resin of the present invention includes phenols, formaldehyde, 4,4′-biphenylylene group or 2,4′-biphenylylene group or 2,2′- which constitutes R in the formula (1). There is no restriction on the order of addition of a crosslinked product such as a biphenylylene group and / or 1,4-xylylene group, 1,2-xylylene group or 1,3-xylylene group, but it is economical to add them all at once. This is desirable from the viewpoint of productivity.
別法としては、架橋基ホルムアルデヒドと（１）式中のＲを構成する４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋体の添加順序をずらす方法も挙げられる。
具体的には、酸触媒の存在下で、予めフェノール類とホルムアルデヒドを縮合させ、次いで（１）式中のＲを構成する４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋体を添加して縮合させる２段の縮合反応で製造することもできる。このような２段の縮合反応では、２段目の反応において新たにフェノール類を添加することができる。ただし、この場合も１段反応の場合と同様にフェノール類を過剰に使用することが好ましい。２段目の反応において追加する（１）式中のＲを構成する架橋体及びフェノール類は、１〜２段反応のトータルで仕込む（１）式中のＲを構成する架橋体とホルムアルデヒドの合計１モルに対して、１〜２段のトータルで仕込むフェノールが１．３モル倍以上、好ましくは２．３〜５倍モルの範囲で使用することが重要である。このような２段反応で行なうと、アルキレン基含有架橋基型フェノール樹脂及びメチレン架橋基含有フェノール樹脂の各重合単位の重合度、すなわちｎ及びｍの分布が狭くなり、分子量のコントロールが容易となり、所望の溶融粘度の重合体が得やすいので、本発明の目的のためには好ましい。
しかしながら、フェノール類、（１）式中のＲを構成する４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋体の反応の後に、ホルムアルデヒドを添加する場合、フェノール類がトータルで仕込む（１）式中のＲを構成する架橋体とホルムアルデヒドの合計１モルに対して１．３倍モル付近で合成すると高分子化が進み、低粘度化が進まず、好ましくないケースが起こる場合もある。
Alternatively, the bridging group formaldehyde and the 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4 constituting R in the formula (1) A method of shifting the addition order of a crosslinked product such as a -xylylene group, a 1,2-xylylene group, or a 1,3-xylylene group is also included.
Specifically, in the presence of an acid catalyst, phenols and formaldehyde are condensed in advance, and then 4,4′-biphenylylene group or 2,4′-biphenylylene group constituting R in the formula (1) It is produced by a two-stage condensation reaction in which a 2,2′-biphenylylene group and / or 1,4-xylylene group, a 1,2-xylylene group, or a 1,3-xylylene group or the like is added and condensed. You can also. In such a two-stage condensation reaction, phenols can be newly added in the second-stage reaction. However, in this case as well, it is preferable to use an excessive amount of phenols as in the case of the one-stage reaction. The cross-linked product and phenol constituting R in the formula (1) added in the second-stage reaction are charged in the total of the first and second-stage reactions (1) The total of the cross-linked product constituting R and R in the formula It is important that the phenol charged in a total of 1 to 2 stages is used in an amount of 1.3 mol times or more, preferably 2.3 to 5 times mol per mol. When carried out in such a two-stage reaction, the degree of polymerization of each polymer unit of the alkylene group-containing crosslinkable phenol resin and the methylene crosslinkable group-containing phenol resin, that is, the distribution of n and m becomes narrow, and the control of the molecular weight becomes easy. It is preferred for the purposes of the present invention because a polymer of the desired melt viscosity is easily obtained.
However, phenols, 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4-xylylene group constituting R in the formula (1) When formaldehyde is added after the reaction of a crosslinked product such as 1,2-xylylene group or 1,3-xylylene group, phenol is charged in total and the crosslinked product constituting R in formula (1) and formaldehyde When the synthesis is carried out in the vicinity of 1.3 times the total amount of 1 mol, polymerization proceeds and the viscosity does not decrease, and an unfavorable case may occur.
２段階の縮合反応は、１段の縮合反応条件に準じて実施することができる。
前記１段縮合反応及び２段縮合反応における酸触媒の使用量は、その種類によっても異なるが、蓚酸の場合は０．１〜２．０重量％程度、硫酸の場合は０．０５〜０．５重量％程度、またパラトルエンスルホン酸の場合は０．０２〜０．１重量％程度使用するのがよい。とくに２段縮合反応を行う場合では、２段目のビフェニリレン基またはキシリレン基含有架橋基をフェノール類及びメチレン架橋基フェノール樹脂と反応させる際には、硫酸又はパラトルエンスルホン酸を使用することが好ましい。また、反応温度はとくに限定はないが、６０〜１６０℃程度の範囲に設定するのが好ましい。より好ましくは、８０〜１４０℃である。
The two-stage condensation reaction can be carried out according to the one-stage condensation reaction conditions.
The amount of the acid catalyst used in the one-stage condensation reaction and the two-stage condensation reaction varies depending on the type, but in the case of oxalic acid, it is about 0.1 to 2.0% by weight, and in the case of sulfuric acid, 0.05 to 0.00. About 5% by weight, and in the case of paratoluenesulfonic acid, it is preferable to use about 0.02 to 0.1% by weight. In particular, when a two-stage condensation reaction is performed, it is preferable to use sulfuric acid or paratoluenesulfonic acid when the second-stage biphenylylene group or xylylene group-containing crosslinking group is reacted with phenols and a methylene crosslinking group phenol resin. . The reaction temperature is not particularly limited, but is preferably set in the range of about 60 to 160 ° C. More preferably, it is 80-140 degreeC.
酸触媒の存在下で縮合反応させた後、未反応のフェノール類及び酸触媒を除去することにより、本発明の低溶融粘度フェノールノボラック樹脂を得ることができる。
フェノール類の除去方法は、減圧下あるいは不活性ガスを吹き込みながら熱をかけ、フェノール類を蒸留し系外へ除去する方法が一般的である。酸触媒の除去は、水洗などの洗浄による方法が挙げられる。
After the condensation reaction in the presence of the acid catalyst, the unreacted phenols and the acid catalyst are removed, whereby the low melt viscosity phenol novolak resin of the present invention can be obtained.
As a method for removing phenols, a method is generally used in which heat is applied under reduced pressure or while blowing an inert gas to distill the phenols out of the system. The removal of the acid catalyst includes a method such as washing with water.
本発明の低溶融粘度フェノール樹脂の製造方法において、原料のフェノール類、４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等架橋基及びホルムアルデヒドの使用量をコントロールすることにより、所望の１５０℃または２００℃における溶融粘度を有する樹脂を得ることができる。 In the method for producing a low melt viscosity phenol resin of the present invention, the raw material phenols, 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4- A resin having a desired melt viscosity at 150 ° C. or 200 ° C. can be obtained by controlling the amount of xylylene group, 1,2-xylylene group, cross-linking group such as 1,3-xylylene group and formaldehyde used. .
本発明のフェノール樹脂は、分子内に４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋基を含有するフェノール樹脂の重合単位と、メチレン架橋基を含有するフェノール樹脂の重合単位を特定の割合で共に有する構造であり、それによりエポキシ硬化剤に好適な、低溶融粘度、高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化、及び難燃性を兼ね備えた樹脂となっている。 The phenol resin of the present invention contains 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4-xylylene group or 1,2- A structure having both a polymer unit of a phenol resin containing a cross-linking group such as a xylylene group or a 1,3-xylylene group and a polymer unit of a phenol resin containing a methylene cross-link group in a specific ratio, thereby epoxy curing It is a resin having a low melt viscosity, a high glass transition temperature, a low hygroscopic property, a high adhesion, a heat resistance, a rapid curing, and a flame retardancy suitable for the agent.
本発明のフェノール樹脂は、バインダー、コーティング材、積層材、成形材料等の用途に広く使用できるが、特に低溶融粘度で、しかも高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化、及び難燃性を有するところから、特に半導体封止用、プリント基板絶縁用などのエポキシ硬化剤に適している。 The phenolic resin of the present invention can be widely used in applications such as binders, coating materials, laminates, molding materials, etc., but it has a particularly low melt viscosity and high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, high speed. From the viewpoint of curing and flame retardancy, it is particularly suitable for epoxy curing agents for semiconductor encapsulation, printed circuit board insulation, and the like.
［エポキシ樹脂硬化物］
本発明のフェノール樹脂は、エポキシ樹脂用硬化剤として用いることができる。エポキシ樹脂硬化物はフェノール樹脂とエポキシ樹脂及び硬化促進剤を混合し、１００〜２５０℃の温度範囲で硬化させることにより得られる。
[Hardened epoxy resin]
The phenol resin of the present invention can be used as a curing agent for epoxy resins. The cured epoxy resin can be obtained by mixing a phenol resin, an epoxy resin, and a curing accelerator and curing them in a temperature range of 100 to 250 ° C.
エポキシ樹脂としては、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂などのグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ハロゲン化エポキシ樹脂など、分子中にエポキシ基を二個以上有するエポキシ樹脂が挙げられる。これらエポキシ樹脂は単独で使用しても、２種類以上を併用してもよい。 Examples of the epoxy resin include glycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, and glycidyl. Examples thereof include an epoxy resin having two or more epoxy groups in the molecule, such as an ester type epoxy resin, a glycidylamine type epoxy resin, and a halogenated epoxy resin. These epoxy resins may be used alone or in combination of two or more.
［硬化促進剤］
硬化促進剤としては、エポキシ樹脂をフェノール系硬化剤で硬化させるための公知の硬化促進剤を用いることが出来る。このような硬化促進剤としては例えば有機ホスフィン化合物およびそのボロン塩、３級アミン、４級アンモニウム塩、イミダゾール類及びそのテトラフェニルボロン塩などを挙げることができるが、この中でも、硬化性や耐湿性の点から、トリフェニルホスフィン及び１，８−ジアザビシクロ（５，４，０）ウンデセン−７（ＤＢＵ）が好ましい。また、より高流動性にするためには、加熱により活性が発現する熱潜在性の硬化促進剤がより好ましく、テトラフェニルホスフォニウム・テトラフェニルボレートなどのテトラフェニルホスフォニウム誘導体が好ましい。
[Curing accelerator]
As a hardening accelerator, the well-known hardening accelerator for hardening an epoxy resin with a phenol type hardening | curing agent can be used. Examples of such curing accelerators include organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and their tetraphenylboron salts, and among them, curability and moisture resistance. From this point, triphenylphosphine and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) are preferable. In order to achieve higher fluidity, a heat-latent curing accelerator that exhibits activity by heating is more preferable, and tetraphenylphosphonium derivatives such as tetraphenylphosphonium and tetraphenylborate are preferable.
［その他添加剤］
本発明のエポキシ樹脂組成物には、必要に応じて、無機充填剤、離型剤、着色剤、難燃剤、低応力剤等を、添加または予め反応して用いることができる。とくに半導体封止用に使用する場合は、無機充填剤の添加は必須である．このような無機充填剤の例として、非晶性シリカ、結晶性シリカ、アルミナ、ガラス、珪酸カルシウム、石膏、炭酸カルシウム、マグネサイト、クレー、タルク、マイカ、マグネシア、硫酸バリウムなどを挙げることができるが、とくに非晶性シリカ、結晶性シリカなどが好ましい．これら添加剤の使用量は、従来の半導体封止用エポキシ樹脂組成物における使用量と同様でよい。
[Other additives]
In the epoxy resin composition of the present invention, an inorganic filler, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance as necessary. Especially when used for semiconductor encapsulation, the addition of inorganic fillers is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia, barium sulfate and the like. However, amorphous silica, crystalline silica and the like are particularly preferable. The usage-amount of these additives may be the same as the usage-amount in the conventional epoxy resin composition for semiconductor sealing.
本発明のアルキル型樹脂は適当量のフェノールノボラック樹脂単位を有し、エポキシ樹脂硬化剤として用いた場合、高ガラス転移温度、低吸湿性、高密着性、耐熱性、速硬化、及び難燃性を維持し、しかも低粘度化を実現させることができる。 The alkyl type resin of the present invention has an appropriate amount of phenol novolac resin unit, and when used as an epoxy resin curing agent, has a high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid curing, and flame retardancy. In addition, a low viscosity can be realized.
次に、本発明のフェノールノボラック樹脂をエピクロルヒドリンと反応させてエポキシ樹脂とする方法については、例えば、該フェノールノボラック樹脂に過剰のエピクロルヒドリンを加え、水酸化ナトリウムや水酸化カリウム等のアルカリ金属水酸化物の存在下に４０〜１５０℃、好ましくは５０〜１２０℃の範囲で１〜１０時間程度反応させる方法が挙げられる。この場合、エピクロルヒドリンの使用量は、該フェノールノボラック樹脂の水酸基当量に対して２〜１５倍モル、好ましくは２〜１０倍モルである。また、使用するアルカリ金属水酸化物の使用量は、該フェノールノボラック樹脂の水酸基当量に対して０．８〜１．２倍モル、好ましくは０．９〜１．１倍モルである。
反応後の後処理については、反応終了後、過剰のエピクロルヒドリンを蒸留除去し、残留物をメチルイソブチルケトン等の有機溶剤に溶解し、ろ過し水洗して無機塩を除去し、次いで有機溶剤を留去することにより、目的とするエポキシ樹脂を得ることができる。
Next, regarding the method of reacting the phenol novolak resin of the present invention with epichlorohydrin to obtain an epoxy resin, for example, adding an excess epichlorohydrin to the phenol novolak resin and then alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. In the presence of, a method of reacting in the range of 40 to 150 ° C., preferably 50 to 120 ° C. for about 1 to 10 hours can be mentioned. In this case, the usage-amount of epichlorohydrin is 2-15 times mole with respect to the hydroxyl equivalent of this phenol novolak resin, Preferably it is 2-10 times mole. Moreover, the usage-amount of the alkali metal hydroxide to be used is 0.8-1.2 times mole with respect to the hydroxyl equivalent of this phenol novolak resin, Preferably it is 0.9-1.1 times mole.
Regarding post-treatment after the reaction, excess epichlorohydrin is distilled off after completion of the reaction, the residue is dissolved in an organic solvent such as methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the organic solvent is distilled off. By leaving, the target epoxy resin can be obtained.
このようにして得られたエポキシ樹脂と該フェノールノボラック樹脂を硬化剤として新たなエポキシ樹脂組成物とすることができる。 A new epoxy resin composition can be obtained by using the epoxy resin thus obtained and the phenol novolac resin as a curing agent.
得られたエポキシ樹脂組成物には、必要に応じて、無機充填材、離型剤、着色剤、カップリング剤、難燃剤等を添加または予め反応して用いることができる。特に半導体封止用途に使用する場合、無機充填材の添加は必須となる。このような無機充填材の例として、非晶性シリカ、結晶性シリカ、アルミナ、珪酸カルシウム、炭酸カルシウム、タルク、マイカ、硫酸バリウムなどをあげることができるが、特に非晶性シリカ、結晶性シリカなどが好ましい。また、これら添加剤の配合割合は公知の半導体封止用エポキシ樹脂組成物における割合と同様でよい。
半導体封止用として使用された組成物は、半導体装置として半導体製品の一部品として使用される。
The obtained epoxy resin composition can be used by adding or reacting in advance with an inorganic filler, a release agent, a colorant, a coupling agent, a flame retardant, or the like, if necessary. In particular, when used for semiconductor sealing applications, the addition of an inorganic filler is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, calcium silicate, calcium carbonate, talc, mica, barium sulfate, etc., and particularly amorphous silica and crystalline silica. Etc. are preferable. Moreover, the mixture ratio of these additives may be the same as the ratio in the well-known epoxy resin composition for semiconductor sealing.
The composition used for semiconductor encapsulation is used as a part of a semiconductor product as a semiconductor device.
以下に実施例を挙げて、本発明を具体的に説明する。なお本発明で得られたフェノール樹脂の評価方法を示す。 The present invention will be specifically described below with reference to examples. In addition, the evaluation method of the phenol resin obtained by this invention is shown.
（１）１５０℃溶融粘度：ＩＣＩ溶融粘度計を用い、１５０℃でのフェノール樹脂の溶融粘度を測定した。
（２）２００℃溶融粘度：ＩＣＩ溶融粘度計を用い、２００℃でのフェノール樹脂の溶融粘度を測定した。
ＩＣＩ粘度の測定方法は以下の通り。
ＩＣＩコーンプレート粘度計 ＭＯＤＥＬ ＣＶ−１Ｓ ＴＯＡ工業（株）
ＩＣＩ粘度計のプレート温度を１５０℃（２００℃）に設定し、試料を所定量、秤量する。
プレート部に秤量した樹脂を置き、上部よりコーンで押えつけ、９０ｓｅｃ放置する。
コーンを回転させて、そのトルク値をＩＣＩ粘度として読み取る。
(1) 150 ° C. melt viscosity: The melt viscosity of a phenol resin at 150 ° C. was measured using an ICI melt viscometer.
(2) 200 ° C. melt viscosity: The melt viscosity of a phenol resin at 200 ° C. was measured using an ICI melt viscometer.
The measuring method of ICI viscosity is as follows.
ICI Cone Plate Viscometer MODEL CV-1S TOA Industrial Co., Ltd.
The plate temperature of the ICI viscometer is set to 150 ° C. (200 ° C.), and a predetermined amount of the sample is weighed.
Place the weighed resin on the plate, press it with the cone from the top, and leave it for 90 seconds.
The cone is rotated and its torque value is read as ICI viscosity.
表１に示した条件で合成したフェノール樹脂（実施例および比較例）を硬化剤として使用した場合、対するエポキシ樹脂は、ＪＥＲ（株）製ＹＸ−４０００（エポキシ等量１８７ｇ／ｅｑ）のテトラメチルビフェノール型エポキシ樹脂であり、硬化促進剤としてトリフェニルホスフィン（ＴＰＰと略記することもある。）を使用した。
本発明の低溶融粘度フェノール樹脂および上記エポキシ樹脂を、フェノール水酸基当量とエポキシ当量比が１：１となるように配合し、ＴＰＰ触媒は、該配合のエポキシ樹脂重量に対して０．２ｗｔ％仕込んだ。これらを、１７５℃に加熱して溶融混合し、真空脱泡した後に１５０℃の金型（厚さ４ｍｍ）に注型し、１５０℃、３時間で硬化させた後、さらに１８０℃、５時間かけて硬化して成形体を試作した。
得られた成形体（硬化物）の各種物性の試験方法は次の通り。
（３）Ｔｇ：ＴＭＡ法（Ｔｈｅｒｍａｌ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ、熱機械分析法）（昇温速度５℃／分）
（４）吸水率：２４時間煮沸法、
（５）残炭率
残炭率と酸素指数は比例関係があり、一般的に難燃性の高い樹脂は残炭率が高いと言われている（非特許文献１参照）。該文献を参照し、難燃性の指標として残炭率を測定した。
測定方法
上記配合で硬化させた成形体を１．５ｃｍ角の切断し、重量を測定する。
切断したサンプルをルツボに入れ、８００℃の電気炉で１時間、還元焼成する。
冷却後、サンプルの重量を測定する。
さらに８００℃の電気炉で２時間かけ灰化させ、その重量を測定する。
下記式より残炭率を求める
残炭率＝ 焼成後の重量-灰化後の重量
試料の重量
When phenol resins (Examples and Comparative Examples) synthesized under the conditions shown in Table 1 are used as curing agents, the epoxy resin is tetramethyl of YX-4000 (epoxy equivalent 187 g / eq) manufactured by JER Corporation. It is a biphenol type epoxy resin, and triphenylphosphine (sometimes abbreviated as TPP) was used as a curing accelerator.
The low melt viscosity phenol resin of the present invention and the above epoxy resin are blended so that the phenol hydroxyl group equivalent ratio and the epoxy equivalent ratio are 1: 1, and the TPP catalyst is charged at 0.2 wt% with respect to the weight of the epoxy resin of the blend. It is. These were melt-mixed by heating to 175 ° C., vacuum degassed, cast into a 150 ° C. mold (thickness 4 mm), cured at 150 ° C. for 3 hours, and then further 180 ° C. for 5 hours. A molded product was produced by curing.
Test methods for various physical properties of the obtained molded body (cured product) are as follows.
(3) Tg: TMA method (Thermal Mechanical Analysis, thermomechanical analysis method) (heating rate 5 ° C./min)
(4) Water absorption rate: 24 hours boiling method,
(5) Residual coal rate The residual coal rate and the oxygen index are proportional to each other, and it is generally said that a resin with high flame retardancy has a high residual coal rate (see Non-Patent Document 1). With reference to this document, the residual carbon ratio was measured as an index of flame retardancy.
Measuring method The molded body cured by the above blending is cut into 1.5 cm square and the weight is measured.
The cut sample is put in a crucible and reduced and fired in an electric furnace at 800 ° C. for 1 hour.
After cooling, the sample is weighed.
Further, ashing is performed in an electric furnace at 800 ° C. for 2 hours, and the weight is measured.
Obtain the remaining charcoal rate from the following formula
Residual coal rate = weight after firing-weight after ashing
Sample weight
（６）ゲルタイム測定
エポキシ樹脂とフェノール樹脂を１：１の当量になるように試験管に仕込み、さらにＴＰＰをエポキシに対して０．１２ｗｔ％になるよう計量し、試験管に仕込む。
湯温を１７５℃に設定したゲルタイマー（東芝時間計 ＳＦ０−３０４Ｍ）に試験管を設置し、ＳＵＳ攪拌棒を使い、１秒間に１回転で攪拌する。
はじめは粘度が低く液状であるが、一定時間経過すると、樹脂の粘度が
急激に上昇し、ゲル状となる。この時間をゲルタイムとする。
この時間が速いほど、硬化性が良好という指標になる。
(6) Measurement of gel time An epoxy resin and a phenol resin are charged into a test tube so as to have an equivalent of 1: 1, and TPP is weighed so as to be 0.12 wt% with respect to the epoxy and charged into a test tube.
A test tube is installed in a gel timer (Toshiba hour meter SF0-304M) in which the hot water temperature is set to 175 ° C., and a SUS stir bar is used to stir at one rotation per second.
Initially, the viscosity is low and liquid, but after a certain period of time, the viscosity of the resin rapidly increases and becomes a gel. This time is defined as gel time.
The faster this time, the better the curability.
実施例１
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール２７４．４８ｇ（２．９２モル）、４，４’−ジ（メトキシメチル）ビフェニル（以下、４，４’−ＢＭＭＢと略記する。）３８７．２ｇ（１．６モル）、４２％ホルマリン水溶液２８．２８ｇ（０．４０モル）、５０％硫酸水溶液０．１４ｇを仕込み、１００℃で３時間反応させた。
その後、反応温度を１２５℃に保ちながら２時間反応させその後１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより４３１ｇのフェノールノボラック樹脂（２００℃溶融粘度：１６００ｍＰａ・ｓ）を得た。
Example 1
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 274.48 g (2.92 mol) of phenol, 4,4′-di (methoxymethyl) biphenyl (hereinafter 4,4′-BMMB) was added. 387.2 g (1.6 mol), 42% formalin aqueous solution 28.28 g (0.40 mol) and 50% sulfuric acid aqueous solution 0.14 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 431 g of phenol novolac resin (200 ° C. melt viscosity: 1600 mPa · s).
実施例２
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール２７４．４８ｇ（２．９２モル）、４，４’−ＢＭＭＢ２９０．４０ｇ（１．２モル）、４２％ホルマリン水溶液５７．１４ｇ（０．８モル）、５０％硫酸水溶液０．１４ｇを仕込み、１００℃で３時間反応させた。
その後、反応温度を１２５℃に保ちながら２時間反応させその後１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより３９３ｇのフェノールノボラック樹脂（２００℃溶融粘度：１１００ｍＰａ・ｓ）を得た。
Example 2
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 274.48 g (2.92 mol), 4,4′-BMMB 290.40 g (1.2 mol), 42% formalin aqueous solution 57 .14 g (0.8 mol) and 50% sulfuric acid aqueous solution 0.14 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 393 g of a phenol novolac resin (200 ° C. melt viscosity: 1100 mPa · s).
実施例３
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール２７４．４８ｇ（２．９２モル）、４，４’−ＢＭＭＢ１９３．６４ｇ（０．８モル）、４２％ホルマリン水溶液８５．７１ｇ（１．２モル）、５０％硫酸水溶液０．１４ｇを仕込み、１００℃で３時間反応させた。
その後、反応温度を１２５℃に保ちながら２時間反応させその後１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより２６４ｇのフェノールノボラック樹脂（２００℃溶融粘度：１０８０ｍＰａ・ｓ）を得た。
Example 3
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 274.48 g (2.92 mol), 4,4′-BMMB 193.64 g (0.8 mol), 42% formalin aqueous solution 85 .71 g (1.2 mol) and 50% sulfuric acid aqueous solution 0.14 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off under reduced pressure to obtain 264 g of phenol novolac resin (200 ° C. melt viscosity: 1080 mPa · s).
実施例４
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４７３．７６ｇ（５．０４モル）、４，４’−ＢＭＭＢ ２９０．４ｇ（１．２モル）、４２％ホルマリン水溶液５７．１４ｇ（０．８モル）、５０％硫酸水溶液０．１４ｇを仕込み、１００℃で３時間反応させた。
その後、反応温度を１２５℃に保ちながら２時間反応させその後１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより４２１ｇのフェノールノボラック樹脂（２００℃溶融粘度：３１ｍＰａ・ｓ）を得た。
Example 4
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 473.76 g (5.04 mol) of phenol, 290.4 g (1.2 mol) of 4,4′-BMMB, 42% formalin aqueous solution 57.14 g (0.8 mol) and 50% sulfuric acid aqueous solution 0.14 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 421 g of a phenol novolac resin (200 ° C. melt viscosity: 31 mPa · s).
実施例５
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４７３．７６ｇ（５．０４モル）、４，４’−ＢＭＭＢ １９３．６ｇ（０．８モル）、４２％ホルマリン水溶液８５．７１ｇ（１．２モル）、５０％硫酸水溶液０．１４ｇを仕込み、１００℃で３時間反応させた。
その後、反応温度を１２５℃に保ちながら２時間反応させその後１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより３９３ｇのフェノールノボラック樹脂（２００℃溶融粘度：２３ｍＰａ・ｓ）を得た。
Example 5
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, phenol 473.76 g (5.04 mol), 4,4′-BMMB 193.6 g (0.8 mol), 42% formalin aqueous solution 85.71 g (1.2 mol) and 50% sulfuric acid aqueous solution 0.14 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 393 g of a phenol novolac resin (200 ° C. melt viscosity: 23 mPa · s).
実施例６
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４０４．２ｇ（４．３０モル）、４，４’−ジ（クロロメチル）ビフェニル（以下、４，４’−ＢＣＭＢと略記する。）１５０．７０ｇ（０．６モル）を仕込み１００℃で３時間反応させ、その後４２％ホルマリン水溶液２８．５７ｇ（０．４モル）を添加し、その後、１００℃で３時間反応させた。
その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより２５１ｇのフェノールノボラック樹脂（２００℃溶融粘度：１２ｍＰａ・ｓ）を得た。
Example 6
To a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 404.2 g (4.30 mol) of phenol, 4,4′-di (chloromethyl) biphenyl (hereinafter, 4,4′-BCMB) was added. 150.70 g (0.6 mol) is charged and reacted at 100 ° C. for 3 hours, followed by addition of 28.57 g (0.4 mol) of 42% formalin aqueous solution, and then reaction at 100 ° C. for 3 hours. I let you.
Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 251 g of phenol novolac resin (200 ° C. melt viscosity: 12 mPa · s).
実施例７
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４０４．２ｇ（４．３０モル）、４２％ホルマリン水溶液２８．５７ｇ（０．４モル）、３７％０．１１ｇを仕込み、１００℃で３時間反応させた。
その後４，４’−ＢＣＭＢ １５０．７０ｇ（０．６モル）を分割添加し、１００℃で３時間反応させた。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより２４０ｇのフェノールノボラック樹脂（２００℃溶融粘度：１１ｍＰａ・ｓ）を得た。
Example 7
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 404.2 g (4.30 mol) of phenol, 28.57 g (0.4 mol) of 42% formalin aqueous solution, and 0.11 g of 37% were added. The mixture was charged and reacted at 100 ° C. for 3 hours.
Thereafter, 150.70 g (0.6 mol) of 4,4′-BCMB was added in portions and reacted at 100 ° C. for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 240 g of a phenol novolac resin (200 ° C. melt viscosity: 11 mPa · s).
実施例８
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４０４.２ｇ（４．３０モル）、４，４’−ＢＣＭＢ１５０．７０ｇ（０．６モル）、４２％ホルマリン水溶液２８．５７ｇ（０．４モル）を仕込み、１００℃で３時間反応させた。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することにより２５０ｇのフェノールノボラック樹脂（２００℃溶融粘度：１２ｍＰａ・ｓ）を得た。
Example 8
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, phenol 404.2 g (4.30 mol), 4,4′-BCMB 150.70 g (0.6 mol), 42% formalin aqueous solution 28 .57 g (0.4 mol) was charged and reacted at 100 ° C. for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 250 g of a phenol novolac resin (200 ° C. melt viscosity: 12 mPa · s).
比較例１
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４１１．７２ｇ（４．３８モル）、４，４’−ＢＭＭＢ ７２６ｇ（３．０モル）５０％硫酸水溶液０．２１ｇを仕込み、１２５℃で３時間反応させた。
その後、１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することによりフェノールノボラック樹脂（２００℃溶融粘度：１９５０ｍＰａ・ｓ）を得た。
Comparative Example 1
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 411.72 g (4.38 mol), 4,4′-BMMB 726 g (3.0 mol) 50% sulfuric acid aqueous solution 0.21 g And reacted at 125 ° C. for 3 hours.
Then, it heated up at 165 degreeC and reacted for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain a phenol novolac resin (200 ° C. melt viscosity: 1950 mPa · s).
比較例２
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール２３６．９ｇ（２．５２モル）、４，４’−ＢＭＭＢ ２４２ｇ（１．０モル）５０％硫酸水溶液０．２０ｇを仕込み、１２５℃で３時間反応させた。
その後、１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することによりフェノールノボラック樹脂（２００℃溶融粘度：４３ｍＰａ・ｓ）を得た。
Comparative Example 2
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 236.9 g (2.52 mol), 4,4′-BMMB 242 g (1.0 mol) 50% sulfuric acid aqueous solution 0.20 g And reacted at 125 ° C. for 3 hours.
Then, it heated up at 165 degreeC and reacted for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off under reduced pressure to obtain a phenol novolac resin (200 ° C. melt viscosity: 43 mPa · s).
比較例３
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール４０４．２ｇ（４．３モル）、４，４’−ＢＭＭＢ ２４２ｇ（１．０モル）５０％硫酸水溶液０．２０ｇを仕込み、１２５℃で３時間反応させた。
その後、１６５℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、得られた反応溶液を冷却し、水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することによりフェノールノボラック樹脂（２００℃溶融粘度：１８ｍＰａ・ｓ）を得た。
Comparative Example 3
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, phenol 404.2 g (4.3 mol), 4,4′-BMMB 242 g (1.0 mol) 50% sulfuric acid aqueous solution 0.20 g And reacted at 125 ° C. for 3 hours.
Then, it heated up at 165 degreeC and reacted for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off under reduced pressure to obtain a phenol novolac resin (200 ° C. melt viscosity: 18 mPa · s).
比較例４
撹拌装置、コンデンサー、及び窒素ガス導入管を備えたガラス製反応釜に、フェノール２８２．０ｇ（３．００モル）、４２％ホルマリン水溶液１４５．７１ｇ（２．０４モル）蓚酸０．２５ｇを仕込み、１００℃で３時間反応させた。
その後水洗を３回行った。油層を分離し、減圧蒸留により未反応フェノールを留去することによりフェノールノボラック樹脂（２００℃溶融粘度：５５ｍＰａ・ｓ）を得た。
Comparative Example 4
A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 282.0 g (3.00 mol) of phenol, 145.71 g (2.04 mol) of 42% formalin aqueous solution, and 0.25 g of oxalic acid, The reaction was carried out at 100 ° C. for 3 hours.
Thereafter, washing with water was performed three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain a phenol novolac resin (200 ° C. melt viscosity: 55 mPa · s).
実施例１〜８および比較例１〜４で得られたフェノールノボラック樹脂の合成条件、該フェノール樹脂の特性と上記の方法で成形体にした硬化物の物性特性を表１にまとめて示した。 Table 1 summarizes the synthesis conditions of the phenol novolac resins obtained in Examples 1 to 8 and Comparative Examples 1 to 4, the characteristics of the phenol resins, and the physical properties of the cured products obtained by the above methods.
Claims (3)
で表わされる構成単位からなり、ｍ／ｎは０．０４〜２０であり、In which m / n is 0.04 to 20,
（Ａ）ホルムアルデヒドと（Ｂ）下記式（３） (A) Formaldehyde and (B) the following formula (3)
す。）で示される化合物、と（Ｃ）フェノール化合物とを縮合させて得られ、The ), And (C) a phenol compound are condensed,
使用する（Ｃ）フェノール化合物と（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物との合計使用量とのモル比［（Ｃ）フェノール化合物／（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物］が１．３〜２．０倍モル未満の場合で、２００℃での溶融粘度が１００〜１６００ｍＰａ・ｓ、 Molar ratio of (C) phenol compound to be used and (A) formaldehyde and (B) total use amount of the compound represented by the formula (3) [(C) phenol compound / (A) formaldehyde and (B) above When the compound represented by the formula (3) is less than 1.3 to 2.0 times mol, the melt viscosity at 200 ° C. is 100 to 1600 mPa · s,
使用する（Ｃ）フェノール化合物と（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物との合計使用量とのモル比［（Ｃ）フェノール化合物／（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物］が２．０以上〜３．０倍モル未満の場合で、２００℃での溶融粘度が、１５〜５０ｍＰａ・ｓ、または、 Molar ratio of (C) phenol compound to be used and (A) formaldehyde and (B) total use amount of the compound represented by the formula (3) [(C) phenol compound / (A) formaldehyde and (B) above When the compound represented by the formula (3) is 2.0 or more and less than 3.0 times mol, the melt viscosity at 200 ° C. is 15 to 50 mPa · s, or
使用する（Ｃ）フェノール化合物と（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物との合計使用量とのモル比［（Ｃ）フェノール化合物／（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物］が３．０以上〜１０倍モルの場合で、２００℃での溶融粘度が、１０〜２０ｍＰａ・ｓである、 Molar ratio of (C) phenol compound to be used and (A) formaldehyde and (B) total use amount of the compound represented by the formula (3) [(C) phenol compound / (A) formaldehyde and (B) above In the case where the compound represented by the formula (3) is 3.0 to 10 times mol, the melt viscosity at 200 ° C. is 10 to 20 mPa · s.
ことを特徴とする低溶融粘度フェノールノボラック樹脂と、エポキシ樹脂とを含有するエポキシ樹脂組成物。An epoxy resin composition containing a low melt viscosity phenol novolac resin and an epoxy resin.
で表わされる構成単位からなり、ｍ／ｎは０．０４〜２０であり、
（Ａ）ホルムアルデヒドと（Ｂ）下記式（３）
す。）で示される化合物、と（Ｃ）フェノール化合物とを縮合させて得られ、
使用する（Ｃ）フェノール化合物と（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物との合計使用量とのモル比［（Ｃ）フェノール化合物／（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物］が１．３〜２．０倍モル未満の場合で、２００℃での溶融粘度が１００〜１６００ｍＰａ・ｓ、
使用する（Ｃ）フェノール化合物と（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物との合計使用量とのモル比［（Ｃ）フェノール化合物／（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物］が２．０以上〜３．０倍モル未満の場合で、２００℃での溶融粘度が、１５〜５０ｍＰａ・ｓ、または、
使用する（Ｃ）フェノール化合物と（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物との合計使用量とのモル比［（Ｃ）フェノール化合物／（Ａ）ホルムアルデヒド及び（Ｂ）前記式（３）で示される化合物］が３．０以上〜１０倍モルの場合で、２００℃での溶融粘度が、１０〜２０ｍＰａ・ｓである、
ことを特徴とする低溶融粘度フェノールノボラック樹脂成分を含有するエポキシ樹脂硬化物。
The following general formula (1):
In which m / n is 0.04 to 20,
(A) Formaldehyde and (B) the following formula (3)
The ), And (C) a phenol compound are condensed,
Molar ratio of (C) phenol compound to be used and (A) formaldehyde and (B) total use amount of the compound represented by the formula (3) [(C) phenol compound / (A) formaldehyde and (B) above When the compound represented by the formula (3) is less than 1.3 to 2.0 times mol, the melt viscosity at 200 ° C. is 100 to 1600 mPa · s,
Molar ratio of (C) phenol compound to be used and (A) formaldehyde and (B) total use amount of the compound represented by the formula (3) [(C) phenol compound / (A) formaldehyde and (B) above When the compound represented by the formula (3) is 2.0 or more and less than 3.0 times mol, the melt viscosity at 200 ° C. is 15 to 50 mPa · s, or
Molar ratio of (C) phenol compound to be used and (A) formaldehyde and (B) total use amount of the compound represented by the formula (3) [(C) phenol compound / (A) formaldehyde and (B) above In the case where the compound represented by the formula (3) is 3.0 to 10 times mol, the melt viscosity at 200 ° C. is 10 to 20 mPa · s.
An epoxy resin cured product containing a low melt viscosity phenol novolak resin component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007022723A JP5228328B2 (en) | 2007-02-01 | 2007-02-01 | Low melt viscosity phenol novolac resin, process for producing the same, and cured epoxy resin using the same |
Applications Claiming Priority (1)
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| JP2010070471A (en) * | 2008-09-17 | 2010-04-02 | Air Water Inc | Phenolic polymer, method of producing the same, and use therefor |
| KR101609014B1 (en) * | 2009-01-30 | 2016-04-04 | 메이와가세이가부시키가이샤 | Epoxy resin composition, process for producing the epoxy resin composition, and cured object formed therefrom |
| JP5515583B2 (en) * | 2009-10-02 | 2014-06-11 | 宇部興産株式会社 | Phenolic resin, epoxy resin and cured epoxy resin |
| JP5968227B2 (en) * | 2010-12-27 | 2016-08-10 | 旭化成株式会社 | Photosensitive resin composition for alkali development, cured relief pattern, and semiconductor device |
| JP5752574B2 (en) * | 2011-11-29 | 2015-07-22 | 明和化成株式会社 | Phenol novolac resin and epoxy resin composition using the same |
| CN103988127B (en) * | 2011-12-09 | 2019-04-19 | 旭化成株式会社 | Photosensitive polymer combination, the manufacturing method of cured relief pattern, semiconductor device and display body device |
| WO2013125620A1 (en) * | 2012-02-23 | 2013-08-29 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof |
| WO2014203867A1 (en) * | 2013-06-18 | 2014-12-24 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon formaldehyde resin, modified aromatic hydrocarbon formaldehyde resin, and epoxy resin, and method for producing said resins |
| WO2014203868A1 (en) * | 2013-06-18 | 2014-12-24 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon formaldehyde resin, modified aromatic hydrocarbon formaldehyde resin, and epoxy resin, and method for producing said resins |
| JP7326708B2 (en) * | 2018-07-06 | 2023-08-16 | エア・ウォーター・パフォーマンスケミカル株式会社 | Method for producing phenolic resin |
| EP4335886A1 (en) * | 2021-05-06 | 2024-03-13 | DIC Corporation | Phenolic resin, epoxy resin, curable resin composition, cured article, fiber-reinforced composite material, and fiber-reinforced resin molded article |
| WO2023153160A1 (en) * | 2022-02-14 | 2023-08-17 | Dic株式会社 | Phenolic resin, epoxy resin, curable resin composition, cured product, fiber-reinforced composite material, and fiber-reinforced resin molded article |
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| JPH04142324A (en) * | 1990-10-02 | 1992-05-15 | Nippon Steel Chem Co Ltd | Production of modified phenol/aralkyl resin |
| JP3587570B2 (en) * | 1994-10-20 | 2004-11-10 | 三井化学株式会社 | Benzylated polyphenols, their epoxy resins, their production methods and uses |
| JP3636409B2 (en) * | 1996-10-30 | 2005-04-06 | 日本化薬株式会社 | Phenolic resins, epoxy resins, epoxy resin compositions and cured products thereof |
| JP4385831B2 (en) * | 2004-04-05 | 2009-12-16 | 宇部興産株式会社 | Phenol resin mixture for rubber composition addition |
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