JPWO2008047613A1 - Epoxy resin and method for producing the same, and epoxy resin composition and cured product using the same - Google Patents
Epoxy resin and method for producing the same, and epoxy resin composition and cured product using the same Download PDFInfo
- Publication number
- JPWO2008047613A1 JPWO2008047613A1 JP2008539743A JP2008539743A JPWO2008047613A1 JP WO2008047613 A1 JPWO2008047613 A1 JP WO2008047613A1 JP 2008539743 A JP2008539743 A JP 2008539743A JP 2008539743 A JP2008539743 A JP 2008539743A JP WO2008047613 A1 JPWO2008047613 A1 JP WO2008047613A1
- Authority
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- Japan
- Prior art keywords
- epoxy resin
- resin composition
- present
- cured product
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 118
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 118
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 28
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 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 17
- 238000006243 chemical reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- -1 phosphate ester Chemical class 0.000 description 11
- 238000006735 epoxidation reaction Methods 0.000 description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001721 transfer moulding Methods 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 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
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 2
- 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 class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 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
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- ZLCSFXXPPANWQY-UHFFFAOYSA-N 3-ethyltoluene Chemical compound CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- YGYPMFPGZQPETF-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C=2C=C(C)C(O)=C(C)C=2)=C1 YGYPMFPGZQPETF-UHFFFAOYSA-N 0.000 description 2
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 101100066651 Escherichia phage K1E GP90 gene Proteins 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
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- 238000004382 potting Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
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- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
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- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本発明は、下記式（１）：（式中、Ｐ、Ｒおよびｍはそれぞれ独立して存在し、Ｐは炭素数１〜６のアルキル基を、Ｒは水素もしくは炭素数１〜６のアルキル基を、ｍは０〜３の整数を表す。また、ｎは繰り返し数である。）で表されるフェノール樹脂であって、水酸基当量が１６０〜２３０ｇ／ｅｑであるフェノール樹脂をエポキシ化して得た、低吸水性、低誘電性、難燃性及び耐熱性に優れる硬化物を与えることが可能なエポキシ樹脂を提供するものである。また、本発明は、上記のエポキシ樹脂及び硬化剤を含有するエポキシ樹脂組成物と、該エポキシ樹脂組成物を硬化してなる硬化物とを提供するものである。In the present invention, the following formula (1): (wherein P, R and m are each independently present, P is an alkyl group having 1 to 6 carbon atoms, R is hydrogen or an alkyl having 1 to 6 carbon atoms) M represents an integer of 0 to 3. Also, n is the number of repetitions.) Obtained by epoxidizing a phenol resin having a hydroxyl group equivalent of 160 to 230 g / eq. In addition, the present invention provides an epoxy resin capable of providing a cured product excellent in low water absorption, low dielectric property, flame retardancy and heat resistance. Moreover, this invention provides the epoxy resin composition containing said epoxy resin and a hardening | curing agent, and the hardened | cured material formed by hardening | curing this epoxy resin composition.
Description
本発明は、エポキシ樹脂及びその製造方法、並びに該エポキシ樹脂を含有するエポキシ樹脂組成物及び該エポキシ樹脂組成物の硬化物に関し、特に低吸水性及び低誘電性を有する硬化物を与えることが可能なエポキシ樹脂に関するものである。 The present invention relates to an epoxy resin, a method for producing the same, an epoxy resin composition containing the epoxy resin, and a cured product of the epoxy resin composition, and in particular, can provide a cured product having low water absorption and low dielectric properties. It relates to an epoxy resin.
エポキシ樹脂は、種々の硬化剤で硬化されることにより、一般に機械的性質、耐水性、耐薬品性、耐熱性、電気的性質などに優れた硬化物となり、接着剤、塗料、積層板、成型材料、注型材料、レジストなどの幅広い分野に利用されている。 Epoxy resins are cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists.
近年、電気電子機器の急速な発展に伴い、電気電子部品の高密度化・高集積化が急速に進められてきている。例えば、パッケージ材料においては鉛フリーの半田耐熱材が求められ、その硬化物に対して、優れた耐熱性・吸水性が熱望されている。 In recent years, with the rapid development of electrical and electronic equipment, the density and integration of electrical and electronic parts have been rapidly advanced. For example, lead-free solder heat-resistant materials are required for package materials, and excellent heat resistance and water absorption are desired for the cured products.
また、基板、特に高密度に積層された基板に使用される素材においては優れた電気絶縁性が要求されており、その硬化物には低誘電性が求められている。 In addition, excellent electrical insulation is required for a material used for a substrate, particularly a substrate laminated at a high density, and a low dielectric property is required for the cured product.
さらに、電気電子部品の難燃剤としてハロゲン系エポキシ樹脂と三酸化アンチモンが多用されているが、これらを使用した製品はその廃棄後の不適切な処理により、ダイオキシン等の有害物質の発生に寄与することが指摘されている。上記の問題を解決する方法の一つとして、リン原子を骨格に有するエポキシ樹脂が提案されている。特に、通常のリン酸エステルタイプの化合物を使用しなくても、樹脂骨格を選ぶことで従来のエポキシ樹脂に比べ難燃性に優れたものが開発されてきている。現在、特に一般に「ハロゲンフリー、リンフリー」と呼ばれる、難燃剤を使用せずに難燃性を発現するような樹脂骨格の探索がなされている。 In addition, halogen-based epoxy resins and antimony trioxide are frequently used as flame retardants for electrical and electronic parts, but products using these contribute to the generation of harmful substances such as dioxins due to inappropriate treatment after disposal. It has been pointed out. As one method for solving the above problem, an epoxy resin having a phosphorus atom in the skeleton has been proposed. In particular, even if a normal phosphate ester type compound is not used, a resin having excellent flame retardancy compared to conventional epoxy resins has been developed by selecting a resin skeleton. At present, a search for a resin skeleton, which is generally called “halogen-free, phosphorus-free” and exhibits flame retardancy without using a flame retardant, has been made.
これらの要求を満たす難燃性エポキシ樹脂としてはフェノールアラルキル型エポキシ樹脂が挙げられるが、近年の高度な要求性能に対応しきれておらず、更なる特性の向上が期待されている。（特開２００６−０６３２０７号公報及び特開２００１−１７２４７３号公報参照。） Examples of flame retardant epoxy resins that satisfy these requirements include phenol aralkyl type epoxy resins, but they have not been able to meet the recent high performance requirements, and further improvements in properties are expected. (See JP 2006-063207 and JP 2001-172473.)
そこで、本発明の目的は、上記従来技術の問題を解決し、難燃性及び耐熱性に優れる上、低吸水性及び低誘電性を有する硬化物を与えることが可能なエポキシ樹脂及びその製造方法を提供することにある。また、本発明の他の目的は、かかるエポキシ樹脂を含有するエポキシ樹脂組成物及びその硬化物を提供することにある。 Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide an epoxy resin capable of providing a cured product having low water absorption and low dielectric properties, as well as excellent flame retardancy and heat resistance, and a method for producing the same Is to provide. Another object of the present invention is to provide an epoxy resin composition containing such an epoxy resin and a cured product thereof.
本発明者らは、上記したような実状に鑑み、鋭意検討した結果、１,３-アルキル置換ベンゼン由来の骨格、例えばキシレン骨格を有する変性エポキシ樹脂を用いることにより、低吸水性、低誘電性、難燃性及び耐熱性に優れた硬化物が得られることを見出し、本発明を完成させるに至った。 As a result of intensive investigations in view of the above-described actual situation, the present inventors have achieved low water absorption and low dielectric properties by using a modified epoxy resin having a skeleton derived from 1,3-alkyl-substituted benzene, for example, a xylene skeleton. The present inventors have found that a cured product excellent in flame retardancy and heat resistance can be obtained, and have completed the present invention.
即ち、本発明の要旨構成は次のとおりである。 That is, the gist configuration of the present invention is as follows.
１．下記式（１）：
２．上記１に記載のエポキシ樹脂及び硬化剤を含有するエポキシ樹脂組成物。 2. 2. An epoxy resin composition comprising the epoxy resin according to 1 and a curing agent.
３．上記２に記載のエポキシ樹脂組成物を硬化してなる硬化物。 3. A cured product obtained by curing the epoxy resin composition described in 2 above.
４．下記式（１）：
本発明によれば、１,３-アルキル置換ベンゼン由来の骨格を有するフェノール樹脂をエポキシ化することにより、低吸水性及び低誘電性を有する硬化物を与えることが可能なエポキシ樹脂及びその製造方法を提供することができる。また、かかるエポキシ樹脂を含有した、電気・電子材料、成型材料、注型材料、積層材料、塗料、接着剤、レジスト用途などの広範囲の用途に有用なエポキシ樹脂組成物及びその硬化物を提供することができる。 According to the present invention, an epoxy resin capable of providing a cured product having low water absorption and low dielectric properties by epoxidizing a phenol resin having a skeleton derived from 1,3-alkyl-substituted benzene, and a method for producing the same Can be provided. Also provided are epoxy resin compositions containing such epoxy resins, useful for a wide range of applications such as electrical / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resist applications, and cured products thereof. be able to.
本発明のエポキシ樹脂は、下記式（１）：
式（１）において、Ｐは炭素数１〜６のアルキル基であり、該アルキル基は直鎖状、枝分れ状、環状のいずれであってもよい。該アルキル基としては、メチル基、エチル基、ブチル基、プロピル基、ペンチル基、ヘキシル基、シクロヘキシル基等が挙げられ、これらの中でも、メチル基が特に好ましい。また、Ｒは水素原子又は炭素数１〜６のアルキル基であり、該アルキル基は直鎖状、枝分れ状、環状のいずれであってもよい。該アルキル基としては、メチル基、エチル基、ブチル基、プロピル基、ペンチル基、ヘキシル基、シクロヘキシル基等が挙げられるが、最も好適なＲは水素原子である。更に、繰り返し数ｎは通常１〜４０の整数であり、好ましくは１〜２０の整数であり、更に好ましくは１〜５の整数であり、特に好ましくは１〜２の整数である。 In the formula (1), P is an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a propyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Among these, a methyl group is particularly preferable. R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a propyl group, a pentyl group, a hexyl group, and a cyclohexyl group, and the most preferable R is a hydrogen atom. Furthermore, the repetition number n is an integer of 1-40 normally, Preferably it is an integer of 1-20, More preferably, it is an integer of 1-5, Most preferably, it is an integer of 1-2.
式（１）で表されるフェノール樹脂は、例えば１，３−アルキル置換ベンゼン（ｍ−キシレン、１−メチル−３−エチルベンゼン、１，３−ジエチルベンゼン等）とホルムアルデヒドとを酸性触媒（硫酸、硝酸等の無機強酸、ｐ−トルエンスルホン酸、キシレンスルホン酸等の有機スルホン酸やシュウ酸等の有機酸等）により反応させた後、更に、フェノール類（フェノール又はアルキル置換フェノール）と反応させることで合成できる。なお、本発明で原料として使用できるフェノール樹脂は、上記式（１）で表されるフェノール樹脂が主成分であれば、該樹脂を合成する過程で副生する他の芳香族アルデヒド樹脂を含んでいてもよく、これらの混合物として水酸基当量が１６０〜２３０ｇ／ｅｑであればよく、１８０〜２１０ｇ／ｅｑであるものが好ましい。また、上記式（１）におけるｎは、通常１〜４０の整数を表す。 The phenol resin represented by the formula (1) is, for example, a 1,3-alkyl-substituted benzene (m-xylene, 1-methyl-3-ethylbenzene, 1,3-diethylbenzene, etc.) and formaldehyde as an acidic catalyst (sulfuric acid, nitric acid). By reacting with a strong inorganic acid such as p-toluenesulfonic acid, organic sulfonic acid such as xylene sulfonic acid, or organic acid such as oxalic acid, and then further reacting with phenols (phenol or alkyl-substituted phenol). Can be synthesized. In addition, if the phenol resin represented by the above formula (1) is a main component, the phenol resin that can be used as a raw material in the present invention includes other aromatic aldehyde resins by-produced in the process of synthesizing the resin. The mixture may have a hydroxyl group equivalent of 160 to 230 g / eq, preferably 180 to 210 g / eq. Moreover, n in the said Formula (1) represents the integer of 1-40 normally.
以下に本発明のエポキシ樹脂の合成方法の一例を記載する。本発明のエポキシ樹脂は、前述の式（１）で表されるフェノール樹脂を使用し、エピハロヒドリンと反応させることでエポキシ化（グリシジル化）する。 An example of the method for synthesizing the epoxy resin of the present invention will be described below. The epoxy resin of the present invention is epoxidized (glycidylated) by using the phenol resin represented by the above formula (1) and reacting with epihalohydrin.
上記エポキシ化反応において使用するエピハロヒドリンとしては、エピクロルヒドリン、α-メチルエピクロルヒドリン、γ-メチルエピクロルヒドリン、エピブロモヒドリン等が挙げられ、本発明においては工業的に入手が容易なエピクロルヒドリンが好ましい。エピハロヒドリンの使用量は、上記式（１）で表されるフェノール樹脂の水酸基１モルに対し通常２〜２０モルであり、好ましくは４〜１０モルである。 Examples of the epihalohydrin used in the epoxidation reaction include epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like. In the present invention, epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 2-20 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin represented by the said Formula (1), Preferably it is 4-10 mol.
上記エポキシ化反応においては、アルカリ金属水酸化物を用いることが好ましい。該アルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられる。なお、アルカリ金属水酸化物を、固形物として利用してもよいし、その水溶液として使用してもよい。例えば、アルカリ金属水酸化物を水溶液として使用する場合においては、アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に、減圧下又は常圧下で連続的に水及びエピハロヒドリンを留出させ、更に分液して水を除去し、エピハロヒドリンを反応系内に連続的に戻す方法によりエポキシ化反応を行うことができる。アルカリ金属水酸化物の使用量は、上記式（１）で表されるフェノール樹脂の水酸基１モルに対して通常０．９〜３．０モルであり、好ましくは１．０〜２．０モルであり、より好ましくは１．０〜１．５モルである。 In the epoxidation reaction, an alkali metal hydroxide is preferably used. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. In addition, you may utilize an alkali metal hydroxide as a solid substance, and may use it as the aqueous solution. For example, when alkali metal hydroxide is used as an aqueous solution, an aqueous solution of alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or normal pressure. Then, liquid separation is performed to remove water, and the epoxidation reaction can be carried out by continuously returning the epihalohydrin to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-3.0 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin represented by the said Formula (1), Preferably it is 1.0-2.0 mol. More preferably, it is 1.0-1.5 mol.
上記エポキシ化反応においては、反応を促進するためにテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の４級アンモニウム塩を触媒として添加することが好ましい。４級アンモニウム塩の使用量は、上記式（１）で表されるフェノール樹脂の水酸基１モルに対し通常０．１〜１５ｇであり、好ましくは０．２〜１０ｇである。 In the epoxidation reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst in order to accelerate the reaction. The usage-amount of a quaternary ammonium salt is 0.1-15g normally with respect to 1 mol of hydroxyl groups of the phenol resin represented by the said Formula (1), Preferably it is 0.2-10g.
上記エポキシ化反応においては、さらに、メタノール、エタノール、イソプロピルアルコール等のアルコール類、ジメチルスルホン、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン等の非プロトン性極性溶媒などを添加して反応を行うことが反応進行上好ましい。 In the epoxidation reaction, it is preferable to carry out the reaction by adding an alcohol such as methanol, ethanol or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran or dioxane. .
上記アルコール類を使用する場合、その使用量は、エピハロヒドリンの使用量に対し通常２〜５０質量％であり、好ましくは４〜２０質量％である。一方、非プロトン性極性溶媒を用いる場合においては、その使用量はエピハロヒドリンの使用量に対し通常５〜１００質量％であり、好ましくは１０〜８０質量％である。 When using the said alcohol, the usage-amount is 2-50 mass% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-20 mass%. On the other hand, when an aprotic polar solvent is used, the amount used is usually 5 to 100% by mass, preferably 10 to 80% by mass, based on the amount of epihalohydrin used.
上記エポキシ化反応において、反応温度は通常３０〜９０℃であり、好ましくは３５〜８０℃である。一方、反応時間は通常０．５〜１０時間であり、好ましくは１〜８時間である。これらのエポキシ化反応の反応物は、水洗後、または水洗無しに加熱減圧下でエピハロヒドリンや溶媒等を除去することにより精製され得る。また、更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、回収した反応物をトルエン、メチルイソブチルケトンなどの溶剤に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて、副生成物の閉環反応を行ない、副生成物であるハロヒドリンの閉環を確実なものにすることもできる。この場合、アルカリ金属水酸化物の使用量は、エポキシ化に使用した上記式（１）で表されるフェノール樹脂の水酸基１モルに対して通常０．０１〜０．３モルであり、好ましくは０．０５〜０．２モルである。また、反応温度は通常５０〜１２０℃であり、反応時間は通常０．５〜２時間である。 In the epoxidation reaction, the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. On the other hand, reaction time is 0.5 to 10 hours normally, Preferably it is 1 to 8 hours. The reaction product of these epoxidation reactions can be purified by removing epihalohydrin, a solvent, or the like under heating and reduced pressure after washing with water or without washing with water. In addition, in order to make an epoxy resin with less hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. In addition, a ring-closing reaction of the by-product can be performed to ensure the ring-closing of the by-product halohydrin. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol with respect to 1 mol of the hydroxyl group of the phenol resin represented by the above formula (1) used for epoxidation, preferably 0.05 to 0.2 mol. Moreover, reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.
上記エポキシ化反応においては、反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下溶剤を留去することにより本発明のエポキシ樹脂を得ることができる。なお、本発明のエポキシ樹脂は、エピハロヒドリンとしてエピクロルヒドリンを用いることにより上記式（１）で表されるフェノール樹脂を主成分とするフェノール樹脂をエポキシ化（グリシジル化）して得られるエポキシ樹脂が好ましく、具体的には、下記式（２）：
本発明のエポキシ樹脂は、各種樹脂原料、例えばエポキシアクリレートおよびその誘導体、オキサゾリドン系化合物、環状カーボネート化合物等の原料として使用できる。 The epoxy resin of the present invention can be used as a raw material for various resin raw materials such as epoxy acrylate and derivatives thereof, oxazolidone compounds, and cyclic carbonate compounds.
以下、本発明のエポキシ樹脂組成物について記載する。本発明のエポキシ樹脂組成物は、上記した本発明のエポキシ樹脂と、硬化剤とを必須成分として含有することを要する。本発明のエポキシ樹脂組成物においては、上記した本発明のエポキシ樹脂を単独で、または本発明のエポキシ樹脂を他のエポキシ樹脂と併用して使用することができる。本発明のエポキシ樹脂を他のエポキシ樹脂と併用する場合、エポキシ樹脂の全体に占める本発明のエポキシ樹脂の含有率は、３０質量％以上が好ましく、４０質量％以上が特に好ましい。ただし、本発明のエポキシ樹脂組成物において、本発明のエポキシ樹脂を改質剤として使用する場合は、エポキシ樹脂の全体に占める本発明のエポキシ樹脂の含有率が、１〜３０質量％であることが好ましい。 Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention needs to contain the above-described epoxy resin of the present invention and a curing agent as essential components. In the epoxy resin composition of the present invention, the above-described epoxy resin of the present invention can be used alone, or the epoxy resin of the present invention can be used in combination with other epoxy resins. When using together the epoxy resin of this invention with another epoxy resin, 30 mass% or more is preferable and, as for the content rate of the epoxy resin of this invention which occupies for the whole epoxy resin, 40 mass% or more is especially preferable. However, in the epoxy resin composition of the present invention, when the epoxy resin of the present invention is used as a modifier, the content of the epoxy resin of the present invention in the entire epoxy resin is 1 to 30% by mass. Is preferred.
本発明のエポキシ樹脂と併用し得る他のエポキシ樹脂としては、例えば、ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂などが挙げられる。具体的には、ビスフェノールＡ、ビスフェノールＳ、チオジフェノール、フルオレンビスフェノール、テルペンジフェノール、４，４’−ビフェノール、２，２’−ビフェノール、３，３’，５，５’−テトラメチル−[１，１’−ビフェニル]−４，４’−ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｏ−ヒドロキシベンズアルデヒド、ｐ−ヒドロキシアセトフェノン、ｏ−ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール、４，４’−ビス（クロルメチル）−１，１’−ビフェニル、４，４’−ビス（メトキシメチル）−１，１’−ビフェニル、１，４−ビス（クロロメチル）ベンゼン、１，４−ビス（メトキシメチル）ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類、アルコール類から誘導されるグリシジルエーテル化物、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等の固形または液状エポキシ樹脂が挙げられるが、これらに限定されるものではない。これらの樹脂は、単独で用いてもよく、２種以上併用してもよい。 Examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. . Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These resins may be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物が含有する硬化剤としては、例えば、アミン系化合物、アミド系化合物、酸無水物系化合物、フェノール系化合物などが挙げられる。使用できる硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミンなどのアミン系化合物；ジシアンジアミド、リノレン酸の２量体とエチレンジアミンより合成されるポリアミド樹脂などのアミド系化合物；無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸などの酸無水物系化合物；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、テトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類等のビスフェノール類；テルペンジフェノール、４，４’−ビフェノール、２，２’−ビフェノール、３，３’，５，５’−テトラメチル−［１，１’−ビフェニル］−４，４’−ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン等の多価フェノール系化合物；フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｏ−ヒドロキシベンズアルデヒド、ｐ−ヒドロキシアセトフェノン、ｏ−ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール等との重縮合物及びこれらの変性物；上記のフェノール類と４，４’−ビス（クロロメチル）−１，１’−ビフェニル、４，４’−ビス（メトキシメチル）−１，１’−ビフェニル、１，４’−ビス（クロロメチル）ベンゼン、１，４’−ビス（メトキシメチル）ベンゼン等との重縮合物であるフェノールアラルキル樹脂及びこれらの変性物、その他イミダゾール、トリフルオロボラン−アミン錯体、グアニジン誘導体、テルペンとフェノール類の縮合物などが挙げられるが、これらの中でも、本発明のエポキシ樹脂と同系の骨格を有するフェノールアラルキル樹脂が好ましい。これら硬化剤は、単独で用いてもよく、２種以上を用いてもよい。 Examples of the curing agent contained in the epoxy resin composition of the present invention include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. Specific examples of curing agents that can be used include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; amides such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine. Compounds: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Acid anhydride compounds; bisphenols such as halogenated bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and tetrabromobisphenol A Terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin , Naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, etc .; phenols (phenol, alkyl-substituted phenol, naphthol, alkyl) Substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, fluorine Polycondensates with furals and the like and modified products thereof; the above phenols and 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1 Phenol aralkyl resins which are polycondensates with '-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, etc., and their modified products, other imidazoles, trifluoroborane -An amine complex, a guanidine derivative, a condensate of terpene and phenol, and the like, among these, a phenol aralkyl resin having a skeleton similar to the epoxy resin of the present invention is preferable. These curing agents may be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物において、硬化剤の含有量は、エポキシ樹脂全体（本発明のエポキシ樹脂及び他のエポキシ樹脂、以下同じ）のエポキシ基１当量に対して０．７〜１．２当量が好ましい。エポキシ基１当量に対して、硬化剤の含有量が０．７当量未満であるか、１．２当量を超えると、いずれの場合においてもエポキシ樹脂組成物の硬化が不完全となり、良好な硬化物性が得られないおそれがある。 In the epoxy resin composition of the present invention, the content of the curing agent is 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the entire epoxy resin (the epoxy resin of the present invention and other epoxy resins, the same shall apply hereinafter). Is preferred. When the content of the curing agent is less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, the curing of the epoxy resin composition becomes incomplete in any case, and good curing is achieved. Physical properties may not be obtained.
本発明のエポキシ樹脂組成物は、更に硬化促進剤を含有することができる。使用できる硬化促進剤の具体例としては、２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾ−ル類、２−（ジメチルアミノメチル）フェノール、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等のホスフィン類、オクチル酸スズ等の金属化合物等が挙げられる。硬化促進剤の含有量は、必要に応じて適宜選択されるが、エポキシ樹脂の合計（本発明のエポキシ樹脂及び他のエポキシ樹脂、以下同じ）１００質量部に対して０．１〜５．０質量部であることが好ましい。 The epoxy resin composition of the present invention can further contain a curing accelerator. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. Although content of a hardening accelerator is suitably selected as needed, it is 0.1-5.0 with respect to 100 mass parts of total of the epoxy resin (the epoxy resin of this invention and other epoxy resins, and the same below). It is preferable that it is a mass part.
本発明のエポキシ樹脂組成物には、必要に応じてバインダー樹脂を配合することもできる。バインダー樹脂としては、ブチラール系樹脂、アセタール系樹脂、アクリル系樹脂、エポキシ−ナイロン系樹脂、ＮＢＲ（アクリロニトリル−ブタジエンゴム）−フェノール系樹脂、エポキシ−ＮＢＲ系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、シリコーン系樹脂などが挙げられるが、これらに限定されるものではない。バインダー樹脂の含有量は、必要に応じて適宜選択されるが、エポキシ樹脂組成物の硬化物の難燃性、耐熱性を損なわない範囲であることが好ましく、エポキシ樹脂の合計１００質量部に対して通常０．０５〜５０質量部であり、好ましくは０．０５〜２０質量部である。 A binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. As binder resins, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR (acrylonitrile-butadiene rubber) -phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicones Examples thereof include, but are not limited to, resins. Although content of binder resin is suitably selected as needed, it is preferable that it is the range which does not impair the flame retardance and heat resistance of the hardened material of an epoxy resin composition, and is with respect to a total of 100 mass parts of epoxy resin. The amount is usually 0.05 to 50 parts by mass, preferably 0.05 to 20 parts by mass.
また、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を添加することができる。無機充填剤としては、結晶シリカ、溶融シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、タルク等の粉体またはこれらを球形化したビーズ等が挙げられるが、これらに限定されるものではない。これら無機充填剤は、単独で用いてもよく、２種以上を併用してもよい。これら無機充填剤の含有量は、本発明のエポキシ樹脂組成物中において０〜９５質量％が好ましいが、難燃性及び機械性強度の観点から、５０〜９５質量％が更に好ましく、７０〜９５質量％が特に好ましい。更に、本発明のエポキシ樹脂組成物には、シランカップリング剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、顔料等の種々の配合剤、各種熱硬化性樹脂を添加することができる。 Moreover, an inorganic filler can be added to the epoxy resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These inorganic fillers may be used alone or in combination of two or more. The content of these inorganic fillers is preferably 0 to 95% by mass in the epoxy resin composition of the present invention, but is more preferably 50 to 95% by mass from the viewpoint of flame retardancy and mechanical strength, and 70 to 95%. Mass% is particularly preferred. Furthermore, the epoxy resin composition of the present invention includes a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, and various thermosetting resins. can do.
本発明のエポキシ樹脂組成物は、本発明のエポキシ樹脂と、硬化剤と、必要に応じて適宜選択した各種成分とを、必要に応じて押出機、ニーダ、ロール等を用いて均一に混合することにより得ることができる。また、本発明のエポキシ樹脂組成物の硬化物は、従来知られている方法と同様の方法により、上記エポキシ樹脂組成物を硬化することで容易に得ることができる。具体的には、例えば、本発明のエポキシ樹脂と、硬化剤と、必要に応じて適宜選択した各種成分（硬化促進剤、無機充填剤等）とを、必要に応じて押出機、ニーダ、ロール等を用いて均一になるまで充分に混合しエポキシ樹脂組成物を得、そのエポキシ樹脂組成物を溶融した後、注型又はトランスファー成型機などを用いて成型し、さらに８０〜２００℃で２〜１０時間加熱することにより、本発明のエポキシ樹脂組成物の硬化物を得ることができる。 The epoxy resin composition of the present invention uniformly mixes the epoxy resin of the present invention, a curing agent, and various components appropriately selected as necessary using an extruder, a kneader, a roll, or the like. Can be obtained. Moreover, the hardened | cured material of the epoxy resin composition of this invention can be easily obtained by hardening | curing the said epoxy resin composition by the method similar to the method known conventionally. Specifically, for example, the epoxy resin of the present invention, a curing agent, and various components appropriately selected as necessary (a curing accelerator, an inorganic filler, etc.), an extruder, a kneader, and a roll as necessary. Etc. are sufficiently mixed until uniform to obtain an epoxy resin composition, and after melting the epoxy resin composition, it is molded using a casting or transfer molding machine, and further at 80 to 200 ° C. The cured product of the epoxy resin composition of the present invention can be obtained by heating for 10 hours.
また、本発明のエポキシ樹脂組成物の硬化物は、上記したエポキシ樹脂組成物をトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の溶剤に溶解させ、エポキシ樹脂組成物のワニスとし、次いでそのワニスをガラス繊維、カ−ボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させて加熱乾燥して得たプリプレグを熱プレス成形することにより得ることができる。なお、エポキシ樹脂組成物のワニスに使用される溶剤の使用量は、上記エポキシ樹脂組成物と該溶剤の混合物中で通常１０〜７０質量％であり、好ましくは１５〜７０質量％である。 In addition, the cured product of the epoxy resin composition of the present invention is obtained by dissolving the above epoxy resin composition in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and drying by heating is prepared by hot press molding. Can be obtained. In addition, the usage-amount of the solvent used for the varnish of an epoxy resin composition is 10-70 mass% normally in the mixture of the said epoxy resin composition and this solvent, Preferably it is 15-70 mass%.
また、本発明のエポキシ樹脂をフィルム型のエポキシ樹脂組成物の改質剤として使用する場合、具体的には、Ｂ−ステージにおける柔軟性等を向上させることができる。このようなフィルム型のエポキシ樹脂組成物は、例えば、上記したエポキシ樹脂組成物のワニスを剥離フィルム上に塗布し、加熱下で溶剤を除去することにより、シート状の接着剤として得られる。このシート状の接着剤は、多層基板などにおける層間絶縁層として使用することができる。 Moreover, when using the epoxy resin of this invention as a modifier of a film type epoxy resin composition, the softness | flexibility etc. in a B-stage can be improved specifically ,. Such a film-type epoxy resin composition is obtained as a sheet-like adhesive by, for example, applying the varnish of the above-described epoxy resin composition on a release film and removing the solvent under heating. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
本発明のエポキシ樹脂組成物及びその硬化物は、接着剤、封止材等、様々な用途に使用することができる。上記接着剤としては、土木用、建築用、自動車用、一般事務用、医療用の接着剤の他、電子材料用の接着剤が挙げられる。また、電子材料用の接着剤として、具体的には、ビルドアップ基板等の多層基板の層間接着剤、ダイボンディング剤、アンダーフィル等の半導体用接着剤、ＢＧＡ補強用アンダーフィル、異方性導電性フィルム（ＡＣＦ）、異方性導電性ペースト（ＡＣＰ）等の実装用接着剤等が挙げられる。 The epoxy resin composition and cured product thereof of the present invention can be used for various applications such as adhesives and sealing materials. Examples of the adhesive include an adhesive for electronic materials in addition to an adhesive for civil engineering, construction, automobile, general office work, and medical use. In addition, as adhesives for electronic materials, specifically, interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfill, BGA reinforcing underfill, anisotropic conductivity Mounting adhesives such as conductive film (ACF) and anisotropic conductive paste (ACP).
また、上記封止材としては、コンデンサ、トランジスタ、ダイオード、発光ダイオード、ＩＣ、ＬＳＩなどに用いるポッティング、ディッピング、トランスファーモールド封止、ＩＣ、ＬＳＩ類のＣＯＢ、ＣＯＦ、ＴＡＢなどに用いるポッティング封止、フリップチップなどに用いるアンダーフィル、ＢＧＡ、ＣＳＰなどのＩＣパッケージ類実装時の封止（補強用アンダーフィル）などを挙げることができる。 Further, as the sealing material, potting, dipping, transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings used for ICs, LSIs such as COB, COF, TAB, Examples include underfill used for flip chips and the like, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.
＜＜実施例＞＞
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。なお、以下において特に断りのない限り、組成表示における「部」は質量部を示す。また、エポキシ当量及び軟化点は、以下の方法で測定した。<< Example >>
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In addition, unless otherwise indicated below, "part" in a composition display shows a mass part. Moreover, the epoxy equivalent and the softening point were measured by the following methods.
（１）エポキシ当量
ＪＩＳ Ｋ−７２３６に記載された方法で測定した。単位はｇ／ｅｑである。(1) Epoxy equivalent It measured by the method described in JIS K-7236. The unit is g / eq.
（２）軟化点
ＪＩＳ Ｋ−７２３４に記載された方法で測定した。単位は℃である。(2) Softening point It measured by the method described in JIS K-7234. The unit is ° C.
（参考合成例１）
特開２００４−２７７７１７号公報に記載の方法に従い、下記式（ｂ）：
According to the method described in JP-A-2004-277717, the following formula (b):
詳細には、撹拌機、還流冷却管、撹拌装置を備えたフラスコに、ＸＬＣ−３Ｌ１００部と、エピクロルヒドリン２６８部とを加え、１２０℃まで昇温し、溶解し、この溶液中に４０質量％水酸化ナトリウム水溶液５８部を３時間かけて徐々に滴下した。滴下中、共沸してくる水はディーンスターク水分離器により系外に排出し、エピクロルヒドリンは系内に戻しながら反応を行った。反応温度を１００〜１１５℃に保ちながら行った。滴下終了後、さらに還流を続けて、水の留出がなくなってから更に１時間、１１５℃〜１２０℃において熟成を行い、反応を終了とした。次に、反応液を室温まで冷却し、生成した塩を濾過により除去した後、エピクロルヒドリンを最大で１４０℃の加熱・減圧下の条件で、留去し、上記式（ｂ）で表されるフェノールアラルキル樹脂のエポキシ化物（粗製）を得た。このようにして得られた粗フェノールアラルキル型エポキシ化物を、メチルイソブチルケトン４０６部に溶解させ、均一の溶液とした。この溶液に２％リン酸水素二ナトリウム水溶液２９０部を加え、５０℃において２時間撹拌を行った後、分液し、更に１１６部の純水にて水洗を３回行った。メチルイソブチルケトンを最大で１５０℃の加熱・減圧下の条件で留去した。残渣として精製されたフェノールアラルキル樹脂のエポキシ化物（エポキシ樹脂（ｂ））１３０部を得た。得られたエポキシ樹脂（ｂ）のエポキシ当量は２３８ｇ／ｅｑであり、軟化点は５２．０℃であった。 Specifically, 100 parts of XLC-3L and 268 parts of epichlorohydrin are added to a flask equipped with a stirrer, a reflux condenser, and a stirrer, heated to 120 ° C. and dissolved, and 40% by mass water is added to the solution. 58 parts of an aqueous sodium oxide solution was gradually added dropwise over 3 hours. During the dropwise addition, water azeotropically was discharged out of the system by a Dean-Stark water separator, and epichlorohydrin was reacted while returning to the system. The reaction temperature was kept at 100 to 115 ° C. After completion of the dropwise addition, the mixture was further refluxed, and after completion of the distillation of water, aging was carried out at 115 ° C. to 120 ° C. for 1 hour to complete the reaction. Next, the reaction solution is cooled to room temperature, and the formed salt is removed by filtration. Then, epichlorohydrin is distilled off under heating and reduced pressure at a maximum of 140 ° C. to obtain a phenol represented by the above formula (b). An epoxidized aralkyl resin (crude) was obtained. The crude phenol aralkyl type epoxidized product thus obtained was dissolved in 406 parts of methyl isobutyl ketone to obtain a uniform solution. To this solution, 290 parts of a 2% aqueous solution of disodium hydrogenphosphate was added, stirred for 2 hours at 50 ° C., then separated, and further washed with 116 parts of pure water three times. Methyl isobutyl ketone was distilled off under heating and reduced pressure at a maximum of 150 ° C. 130 parts of an epoxidized phenol aralkyl resin (epoxy resin (b)) purified as a residue was obtained. The epoxy equivalent of the obtained epoxy resin (b) was 238 g / eq, and the softening point was 52.0 ° C.
（実施例１）
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら、下記式（３）：
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while the following formula (3):
（実施例２および比較例1）
実施例１で得られたエポキシ樹脂（ａ）、比較例として参考合成例１で得られたエポキシ樹脂（ｂ）、硬化剤としてＫＡＹＡＨＡＲＤ ＧＰＨ−６５（日本化薬株式会社製，ＯＨ当量１９９ｇ／ｅｑ，軟化点６５．０℃，ビフェニル−フェノール縮合型のフェノールアラルキル樹脂）、及び硬化促進剤としてＴＰＰ（トリフェニルホスフィン，北興化学工業株式会社製）を用い、表１に示す配合処方（質量部）で、本発明及び比較用のエポキシ樹脂組成物を調製した。該エポキシ樹脂組成物を、トランスファー成型（１７５℃、６０秒）により樹脂成型体とし、これをさらに１６０℃で２時間、さらに１８０℃で８時間かけて硬化させた。(Example 2 and Comparative Example 1)
Epoxy resin (a) obtained in Example 1, epoxy resin (b) obtained in Reference Synthesis Example 1 as a comparative example, KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., OH equivalent 199 g / eq) as a curing agent , Softening point 65.0 ° C., biphenyl-phenol condensation type phenol aralkyl resin), and TPP (triphenylphosphine, manufactured by Hokuko Chemical Co., Ltd.) as a curing accelerator, the formulation shown in Table 1 (parts by mass) Thus, the present invention and comparative epoxy resin compositions were prepared. The epoxy resin composition was formed into a resin molding by transfer molding (175 ° C., 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.
このようにして得られた硬化物の吸水率、誘電率を、下記の方法で測定した。結果を表２に示す。 The water absorption and dielectric constant of the cured product thus obtained were measured by the following methods. The results are shown in Table 2.
（３）吸水試験
硬化物を直径５ｃｍ×厚み４ｍｍの円盤状の試験片とし、該試験片を（ａ）１００℃の水中で２４時間煮沸した後の重量増加率（％）と、（ｂ）８５℃、相対湿度８５％の条件下で２４時間浸漬した後の重量増加率（％）と、（ｃ）１２１℃、相対湿度１００％の条件下で２４時間浸漬した後の重量増加率（％）とを求めた。(3) Water absorption test The cured product was a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm, and (a) the weight increase rate (%) after boiling the test piece in water at 100 ° C. for 24 hours, (b) Weight increase rate (%) after immersion for 24 hours under conditions of 85 ° C. and relative humidity 85%, and (c) Weight increase rate after immersion for 24 hours under conditions of 121 ° C. and relative humidity 100% (%) )
（４）誘電率測定
誘電正接測定治具として、１ＧＨｚ空洞共振機（関東電子応用開発株式会社製）を使用し、誘電率を測定した。(4) Dielectric Constant Measurement A dielectric constant was measured by using a 1 GHz cavity resonator (manufactured by Kanto Electronics Application Development Co., Ltd.) as a dielectric loss tangent measurement jig.
（実施例３および比較例２）
実施例１で得られたエポキシ樹脂（ａ）、比較例として参考合成例１で得られたエポキシ樹脂（ｂ）、硬化剤としてＫＡＹＡＨＡＲＤ ＧＰＨ−６５、硬化促進剤としてＴＰＰ、無機充填剤としてＭＳＲ−２２１２（株式会社龍森製）、ワックスとしてカルナバ１号（株式会社セラリカＮＯＤＡ製）、及びカップリング剤としてＫＢＭ−３０３（信越化学工業株式会社製）を用い、表３に示す配合処方（質量部）で、本発明及び比較用のエポキシ樹脂組成物を調製した。該エポキシ樹脂組成物を、トランスファー成型（１７５℃、６０秒）により樹脂成型体とし、これをさらに１６０℃で２時間、さらに１８０℃で８時間かけて硬化させた。(Example 3 and Comparative Example 2)
Epoxy resin (a) obtained in Example 1, epoxy resin (b) obtained in Reference Synthesis Example 1 as a comparative example, KAYAHARD GPH-65 as a curing agent, TPP as a curing accelerator, MSR- as an inorganic filler 2212 (manufactured by Tatsumori Co., Ltd.), Carnauba No. 1 (manufactured by Celerica NODA Co., Ltd.) as the wax, and KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the coupling agent, the formulation shown in Table 3 (parts by weight The epoxy resin composition for the present invention and for comparison was prepared. The epoxy resin composition was formed into a resin molding by transfer molding (175 ° C., 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.
このようにして得られた硬化物の難燃性を、下記の方法で測定した。結果を表４に示す。 The flame retardancy of the cured product thus obtained was measured by the following method. The results are shown in Table 4.
（５）難燃性
ＵＬ−９４に準拠して、厚み０．８ｍｍと１．６ｍｍの試験片について、トータル燃焼時間を測定した。なお、トータル燃焼時間は、自己消火するまでの時間である。(5) Flame retardance Based on UL-94, the total combustion time was measured about the test piece of thickness 0.8mm and 1.6mm. The total combustion time is the time until self-extinguishing.
（実施例４）
実施例１で得られたエポキシ樹脂（ａ）、硬化剤として上記式（３）で表されるキシレンホルムアルデヒド樹脂（ザイスター ＧＰ９０，フドー株式会社製，ＯＨ当量１９７ｇ／ｅｑ，軟化点８５℃）、及び硬化促進剤としてＴＰＰを用い、表５に示す配合処方（質量部）で、本発明のエポキシ樹脂組成物を調製した。該エポキシ樹脂組成物を、トランスファー成型（１７５℃、６０秒）により樹脂成型体とし、これをさらに１６０℃で２時間、さらに１８０℃で８時間かけて硬化させた。Example 4
The epoxy resin (a) obtained in Example 1, the xylene formaldehyde resin represented by the above formula (3) as a curing agent (Zyster GP90, manufactured by Fudou Co., Ltd., OH equivalent 197 g / eq, softening point 85 ° C.), and Using TPP as a curing accelerator, the epoxy resin composition of the present invention was prepared with the formulation (parts by mass) shown in Table 5. The epoxy resin composition was formed into a resin molding by transfer molding (175 ° C., 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.
このようにして得られた硬化物の吸水率、誘電率を、実施例２と同様にして測定した。結果を表６に示す。 The water absorption and dielectric constant of the cured product thus obtained were measured in the same manner as in Example 2. The results are shown in Table 6.
本発明のエポキシ樹脂組成物の硬化物は、比較例のエポキシ樹脂組成物の硬化物と比較して、表２に示したように低吸水性で且つ低誘電性であり、また、表４に示したように燃焼時間の短い難燃性を有する硬化物であることが分かる。さらに、表６の結果から、本発明のエポキシ樹脂と主骨格が同じフェノールアラルキル樹脂を硬化剤として含有するエポキシ樹脂組成物は、その硬化物に更なる低吸水性及び低誘電性を付与できることが明らかとなった。 The cured product of the epoxy resin composition of the present invention has a low water absorption and a low dielectric property as shown in Table 2 as compared with the cured product of the epoxy resin composition of the comparative example. It can be seen that the cured product has flame retardancy with a short burning time as shown. Furthermore, from the results of Table 6, an epoxy resin composition containing a phenol aralkyl resin having the same main skeleton as the epoxy resin of the present invention as a curing agent can impart further low water absorption and low dielectric properties to the cured product. It became clear.
本発明のエポキシ樹脂組成物及びその硬化物は、これらの特性を生かすことにより、電気・電子材料分野、特に半導体封止、基板に有用である。 The epoxy resin composition and the cured product thereof of the present invention are useful in the field of electric / electronic materials, particularly in semiconductor encapsulation and substrates, by taking advantage of these characteristics.
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